HK1094188B - Adhesive, sealant or coating composition containing aspartic ester functional compounds - Google Patents

Description

Adhesive, sealant or coating compositions containing aspartate-functional compounds

Technical Field

The present invention relates to functional aspartate compounds and their use in adhesive, sealant and coating compositions.

Technical Field

Aspartates represent a unique class of reactants in adhesives, coatings and sealants. The reactivity is generally between the slow typical polyols and the fast reacting primary and secondary amines.

U.S. patent nos. 5412056, 5623045, 5126170 and 5821326 disclose coating compositions wherein the binder is a two-component system comprising a polyisocyanate component and an isocyanate-reactive component. The latter component comprises at least one aspartic acid diester group formed by reacting an amine with a maleic or fumaric diester.

EP 0667362a1 discloses coating compositions comprising a polyisocyanate component, a component comprising at least one aspartic diester group formed by reacting an amine with a maleic or fumaric diester, and a water-absorbing zeolite.

Adhesives are commonly used to join or secure two or more adherends. An adherend is considered to be any two or more materials, or pieces of material, to be joined together, including wood, metal, plastic, paper, ceramic, stone, glass, concrete, and the like. Adhesives used for these purposes are based on a variety of technologies including elastomer/solvent/resin mixtures, epoxies, latexes, polyurethanes, silicones, cyanoacrylates, acrylates, hot melts, and the like. Such adhesives have one or more disadvantages, such as they contain toxic and often flammable solvents, they are incompatible with one or more types of adherends, they have long cure times, and in many cases they form bonds of insufficient strength.

For coatings applied to substrates, it is often required in many cases to establish the desired appearance by applying multiple coating layers, the last of which may be a pigmented or unpigmented topcoat. Unfortunately, as the article comprising the coated substrate ages, the appearance of the coated surface of the substrate is impaired by the scratches that normally occur as a result of "abrasion and tearing".

Sealants are typically films, often comprising plastics, that are applied to one or more surfaces of one or more substrates to prevent liquids or gases from permeating through the film. The sealant may be used to protect the substrate from exposure, or is also commonly used to protect against exposure of through-hole defects in the substrate or between gaps (which may exist between substrates).

Various adhesive, coating and sealant applications often require high molecular weight compounds comprising aspartates. However, the corresponding precursors often react slowly, resulting in long processing times, poor conversion of the desired product and/or impure products.

Furthermore, the use of established amine-maleic/fumarate synthetic pathways does not allow the desired functionality and/or molecular structure to be achieved in aspartate materials. This limits the possible aspartate containing materials to be used for formulation.

U.S. Pat. No.2569200 discloses polyvalent alkylidene iminates and methods of preparation.

The art has identified a need for alternative synthetic routes that provide a greater range of molecular structures and functional groups for aspartate containing compounds that can be efficiently prepared.

Disclosure of Invention

The present invention relates to functional dialkyl aspartates of the general formula:

in the formula, R¹And R²Each is C₁-C₈A linear, branched or cyclic alkyl group,

R³independently at each occurrence is selected from H, C₁-C₂₀A linear, branched or cyclic alkyl, aryl, alkaryl or aralkyl group,

y is a linking group selected from-O-, -S-, -NR⁵-，

-O-P(O)₂-O-，-P(O)₂-O-，-S(O)₂-O-，And

a group formed by removing an acidic hydrogen from a carbon adjacent to one or more electron withdrawing groups represented by one of the following general formulae:

or

In the formula, R⁵Is H or C₁-C₃A linear or branched alkyl group,

W¹is an electron-withdrawing group selected from the group consisting of nitrile, R¹¹-CO-, nitro, carboxylic acid and its corresponding salt, C of carboxylic acid₁-C₂₄A linear, branched or cyclic alkyl, alkenyl, aryl, alkylaryl or arylalkyl ester, and C₁-C₂₄A linear, branched or cyclic alkylsulfonyl group,

W²is a ketone, and the compound is a ketone,

R¹¹selected from H, -OH, C₁-C₂₄A linear, branched or cyclic alkyl, aryl, alkaryl or aralkyl group, which may contain one or more heteroatoms selected from O, S and/or N,

R¹²is C₁-C₂₄Straight, branched or cyclic alkylene, arylene, alkarylene or aryleneAralkyl groups, which may contain one or more heteroatoms selected from O, S and/or N,

R⁴is a linking group selected from C₁-C₂₄Linear, branched or cyclic alkylene, arylene, alkarylene or aralkylene, - (- [ CHR)⁷-]_n-O-)_p-R⁸-, in the formula, R⁷Is C₁-C₃A straight or branched alkyl or alkanol group,

n is a number of 1 to 4,

p is a number from 1 to 1000,

wherein q is 1 to 1000, R⁸Independently at each occurrence is selected from C₁-C₂₄Straight, branched or cyclic alkylene, alkenylene, arylene, alkarylene or aralkylene, optionally containing substituent hydroxyl, carboxylic acid or C₁-C₈A linear, branched or cyclic carboxylate group,

wherein r is 1 to 10000,

R⁹is C₁-C₃A linear or branched alkyl group,

x is-OR¹⁰-or-NR⁵ ₂Wherein R is⁵As has been described above, in the above-mentioned,

R¹⁰is H or C₁-C₂₄-linear, branched or cyclic alkyl, aryl, alkaryl and aralkyl groups,

and a combination thereof,

z is selected from-H, -OR¹⁰、-R⁴-OR¹⁰、-NR⁵ ₂、-R⁴-NR⁵ ₂、-SH、-R⁴-SH，

And

the invention also relates to a method for preparing functional aspartates and to functional aspartates obtained by said method. The method comprises the following steps:

A) reacting an aziridine with a Michael-acceptor molecule to form an aziridinyl aspartate,

B) reacting the aziridinyl aspartate with an active hydrogen-containing compound to form the functional aspartate.

The invention also relates to an adhesive, sealant or coating composition comprising:

i) the above-mentioned functional aspartic esters, and

ii) an isocyanate functional material.

Detailed Description

Other than in the operating examples, or where otherwise indicated, all numbers or expressions referring to quantities of ingredients, reaction conditions, and the like, in the specification and claims are to be understood as modified in all instances by the term "about". Various numerical ranges are disclosed in this patent application. Since these ranges are continuous, they include every value between the minimum and maximum values. Unless indicated otherwise, the various numerical ranges set forth herein are approximations.

As used herein, the term "alkyl" refers to the general formula C_sH_2s+1Shown inWherein s is the number of carbon atoms or a range thereof. The term "substituted alkyl" refers to an alkyl group having one or more hydrogens replaced with a non-carbon atom or group, non-limiting examples of which include halides, amines, alcohols, oxygen (e.g., ketone or aldehyde groups), and thiols.

As used herein, the term "cyclic alkyl" or "cycloalkyl" refers to the formation of the general formula C_sH_2s-1A monovalent radical of an aliphatic hydrocarbon chain of the depicted ring, wherein s is the number of carbon atoms or a range. The term "substituted cycloalkyl" refers to a cycloalkyl group containing one or more heteroatoms; non-limiting examples of ring structures are-O-, -NR-, and-S-; 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 (e.g., ketone or aldehyde groups), and thiols. R represents an alkyl group of 1 to 24 carbon atoms.

As used herein, the term "aryl" refers to a monovalent group of an aromatic hydrocarbon. Aromatic hydrocarbons include those carbon-based cyclic compounds containing conjugated double bonds, containing 4t +2 electrons in the resulting cyclic conjugated pi-orbital system, where t is an integer of at least 1. As used herein, an aryl group may comprise an aromatic monocyclic ring structure, one or more fused aromatic ring structures, covalently linked aromatic ring structures, wherein any or all of the ring structures may comprise heteroatoms. Non-limiting examples of such heteroatoms included in the aromatic ring structure include O, N and S.

As used herein, the term "alkylene" refers to a carbon chain length of C₁(acyclic) or C₄(in this case cyclic) to C₂₅Is usually C₂-C₁₂And (3) an acyclic or cyclic divalent hydrocarbon which may be substituted or unsubstituted, and may contain a substituent. As a non-limiting example, the alkylene group may be a lower alkyl group having 1 to 12 carbon atoms. By way of non-limiting illustration, "propylene" includes n-propylene and isopropylene; likewise, "butylene" includes n-butylene, isobutylene and t-butylene.

In this context, the terms "(meth) acrylic" and "(meth) acrylate" include the corresponding derivatives of acrylic acid and methacrylic acid, without any limitation.

As used herein, the term "cure" includes crosslinking of the adhesive, sealant or coating composition components and formation of a film as a result of evaporation of water and other solvents and diluents, if present, while the resulting film imparts physical and chemical properties such as bond strength and peel strength.

As used herein, the term "cross-linking" refers to the formation of short chain molecules that link two longer molecular chains by reaction between two or more functional groups on the short chain.

The present invention relates to the preparation of functional dialkyl aspartates ("aspartates") and aspartates prepared using the method. Embodiments of the invention include a method comprising:

A) reacting an aziridine with a Michael-acceptor molecule to form an aziridinyl aspartate,

B) reacting the aziridinyl aspartate with an active hydrogen-containing compound to form the functional aspartate.

In the present invention, the term "aziridine" refers to a compound of the general formula I:

in the formula, R³¹And R³²Independently at each occurrence is selected from H, C₁-C₂₀A linear, branched or cyclic alkyl, aryl, alkaryl or aralkyl group; in some cases, H, C₁-C₃A linear or branched alkyl group; in other cases selected from H, C₁-C₂Straight or branched chain alkyl. In an embodiment of the invention, R³²Is H, and at least one occurrence of R³¹Is H. In another embodiment of the present invention, the nitrogen isThe propylidine is selected from the group consisting of unsubstituted aziridine (aziridine),

2-methylaziridine, 2-ethylaziridine, 2-n-propylziridine and 2-isopropylziridine.

In the present invention, the term "Michael-acceptor molecule" refers to a molecule that contains one or more Electron Withdrawing Groups (EWG) that make the carbon in a carbon-carbon double bond electropositive and in a good position for nucleophilic attack. Any suitable Michael-acceptor molecule, or polymer comprising a Michael-acceptor in the backbone, can be used in the present invention. Non-limiting examples of Michael-acceptor groups on the polymer backbone are the maleate groups represented by the following general formula:

in the formula, R^pAnd R^p’Independently is C₁-C₂₀Straight, branched or cyclic alkyl, aryl, alkaryl or aralkyl groups, and s and t are independently from 1 to 1000, in some cases from 1 to 500, and in other cases from 1 to 100.

In embodiments of the invention, suitable Michael-acceptor molecules include, but are not limited to, those comprising a carbon-carbon double bond and one or more EWGs selected from ketones, nitriles, nitro, carboxylic acids and their corresponding salts, C of a carboxylic acid₁-C₂₄Linear, branched or cyclic alkyl, alkenyl, aryl, alkylaryl or arylalkyl esters and C₁-C₂₄Linear, branched or cyclic alkylsulfonyl.

In a particular embodiment of the invention, suitable Michael-acceptor molecules include, but are not limited to, C of maleic acid₁-C₈Straight, branched or cyclic dialkyl esters, C of fumaric acid₁-C₈Straight, branched or cyclic dialkyl esters, maleimides, C₁-C₈Straight, branched or cyclic N-alkyl maleimides, monoamides of maleic acid, monoamides of fumaric acid, diamides of maleic acid,Diamides of fumaric acid, C of maleic acid₁-C₈C of straight, branched or cyclic N-alkylamides and fumaric acid₁-C₈Straight, branched or cyclic N-alkyl amides.

As used herein, the term "active hydrogen-containing compound" refers to a compound that contains a hydrogen atom that is sufficiently acidic to allow the compound to undergo a ring-opening reaction of the aziridine moiety.

In an embodiment of the present invention, the active hydrogen-containing compound includes, but is not limited to, a C containing two or more functional groups selected from hydroxyl, carboxylic acid, thiol, amine, phosphoric acid, sulfonic acid CH group, and combinations thereof₁-C₂₄A linear, branched or cyclic alkylene, alkenylene, arylene, alkarylene or aralkylene, polyether, polyester or poly (meth) acrylic molecule.

As used herein, the terms "(meth) acrylic acid" and "(meth) acrylate" refer to compounds that include or are derived from methacrylic acid and its corresponding ester, amide, and salt and acrylic acid and its corresponding ester, amide, and salt moieties.

In an embodiment of the invention, the active hydrogen-containing compound includes at least one active hydrogen-containing group, in some cases an average of at least 1.5, and in other cases at least 2 active hydrogen-containing groups.

In an embodiment of the invention, the active hydrogen-containing compound has the following general formula II:

Z-R⁴-Y’ (II)

wherein Y' is selected from the group consisting of-OH, -SH, -NR⁵H、-COOH、-O-P(O)₂-OH、-P(O)₂-OH、-S(O)₂-OH and a group comprising an acidic hydrogen on a carbon adjacent to one or more electron withdrawing groups as shown in one of the following formulae III and/or IV:

in the formula, R⁵Is H or C₁-C₃A linear or branched alkyl group,

W¹is an electron-withdrawing group selected from the group consisting of nitrile, R¹¹-CO-, nitro, carboxylic acid and its corresponding salt, C of carboxylic acid₁-C₂₄A linear, branched or cyclic alkyl, alkenyl, aryl, alkylaryl or arylalkyl ester, and C₁-C₂₄A linear, branched or cyclic alkylsulfonyl group,

W²is a ketone, and the compound is a ketone,

R¹¹selected from H, -OH, C₁-C₂₄A linear, branched or cyclic alkyl, aryl, alkaryl or aralkyl group, which may contain one or more heteroatoms selected from O, S and/or N,

R¹²is C₁-C₂₄A linear, branched or cyclic alkylene, arylene, alkarylene or aralkylene group, which may contain one or more heteroatoms selected from O, S and/or N,

in the general formula II, R⁴Is a linking group selected from C₁-C₂₄Linear, branched or cyclic alkylene, arylene, alkarylene or aralkylene, - (- [ CHR)⁷-]_n-O-)_p-R⁸-, in the formula, R⁷Is C₁-C₃A straight or branched alkyl or alkanol group,

n is 1 to 4, in some cases 2 or 3,

p is 1 to 1000, in some cases 1 to 500, in other cases 2 to 250, in some cases 2 to 100, in other cases 2 to 50,

and

wherein q is 1-1000, in some cases 1-500, in other cases 2-250, in some cases 2-100, in other cases 2-50, R⁸Independently at each occurrence is selected from C₁-C₂₄Straight, branched or cyclic alkylene, alkenylene, arylene, alkarylene or aralkylene, optionally containing substituent hydroxyl, carboxylic acid or C₁-C₈A linear, branched or cyclic carboxylate group,

wherein r is 1 to 10000, in some cases 1 to 500, in other cases 2 to 250, in some cases 2 to 100, in other cases 2 to 50,

R⁹is C₁-C₃A linear or branched alkyl group,

x is-OR¹⁰-or-NR⁵ ₂Wherein R is⁵As has been described above, in the above-mentioned,

R¹⁰is H or C₁-C₂₄-linear, branched or cyclic alkyl, aryl, alkaryl and aralkyl groups,

and combinations thereof.

Furthermore, in the general formula II,

z is selected from-H, -OR¹⁰、-R⁴-OR¹⁰、-NR⁵ ₂、-R⁴-NR⁵ ₂、-SH、-R⁴-SH，

And

in the formula, R⁴、R⁵And R¹⁰As mentioned above, R¹And R²Independently is C₁-C₈In some cases, C₂-C₆Linear, branched or cyclic alkyl groups or a portion of the polymer backbone.

A particular embodiment of the invention relates to functional aspartates, where Z-R⁴-Y-is a polyester group. Aspects of this embodiment relate to the case when the polyester is a carboxylic acid functional polyester.

In another embodiment of the invention, the group Z-R in the active hydrogen containing compound of formula II⁴-Y' -is a polyether group in a functional aspartate. In some aspects of this embodiment, the polyether is a hydroxyl functional polyether.

Other embodiments of the present invention relate to compositions comprising z-R of formula II⁴-Y' active hydrogen compounds, wherein the radical Z-R⁴-Y' is a poly (meth) acrylate containing one or more active hydrogen groups. In some aspects of this embodiment, the poly (meth) acrylate is a carboxylic acid functional polyacrylate.

In other embodiments of the invention, the active hydrogen-containing compound of formula II comprises a group Z-R⁴-Y', which is C₁-C₂₄Linear, branched or cyclic alkyl, alkenyl, aryl, alkaryl or aralkyl dicarboxylic acids. In some aspects of this embodiment, the dicarboxylic acid is selected from adipic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acidPimelic acid, suberic acid, azelaic acid and mixtures thereof.

In another embodiment, the Michael-acceptor molecule is a diester or diamide of maleic acid, where each ester or amide group is independently C₁-C₈In some cases, C₂-C₆The linear, branched or cyclic alkyl, aziridine are shown in formula I and the active hydrogen containing compound is shown in formula II, wherein Y' is a carboxylic acid.

In embodiments of the invention, a catalyst may be used to prepare the functional dialkyl aspartate. Suitable catalysts can be used in A) or B).

In a particular embodiment of the invention, the catalyst used in a) is selected from metal salts of saturated or unsaturated carboxylic acids, metal alcoholates (including but not limited to sodium methylate, aluminum ethylate), and metal salts of basic amides (including but not limited to sodium amides).

In a particular embodiment of the invention, the catalyst used in B) can be selected from Bronstead acids or Lewis acids. Non-limiting examples of Lewis acids that may be used as catalysts include tris (pentafluorophenyl) borane, metal halides such as CuCl₂·2H₂O or BiCl₃And trifluoromethanesulfonates of suitable metals (abbreviated TF) such as Yb (OTF)₃、LiNTF₂、Sn(OTF)₂Or Cu (OTF)₂. Non-limiting examples of Bronstead acids that can be used as catalysts include hydrochloric acid, sulfuric acid, and perchloric acid. In some aspects of this embodiment, a heterogeneous catalyst may be used, the catalyst comprising silica gel and/or montmorillonite.

As a non-limiting embodiment for preparing the functional aspartates of the present invention, the Michael-acceptor molecule and the aziridine of formula I are mixed at a temperature of less than 30 deg.C and stirred for 30 minutes to 24 hours. Vacuum is applied to remove unreacted aziridine, and/or an electrophile is used to react with the aziridine and remove the aziridine. The reaction provides aziridine aspartate, which is mixed with an acid functional polyether (active hydrogen containing compound) and stirred for 4-24 hours. Completion of the reaction is determined by chromatography, gel permeation chromatography (as non-limiting examples).

Embodiments of the present invention relate to functional dialkyl aspartates produced by the process of the present invention. Particular embodiments of the present invention relate to functional dialkyl aspartates of the general formula V:

in the formula, R¹And R²Independently is C₁-C₈Linear, branched or cyclic alkyl, R³Independently at each occurrence is selected from H, C₁-C₂₀A linear, branched or cyclic alkyl, aryl, alkaryl or aralkyl group.

And in formula V, Y is a linking group selected from the group consisting of-O-, -S-, -NR⁵-，-O-P(O)₂-O-、-P(O)₂-O-、-S-(O)₂-O-、

And

groups of formula III or formula IV wherein W is a group formed by removing an acidic hydrogen (H) from the carbon adjacent to one or more electron withdrawing groups, as shown in formulas IIIa and Iva¹And W²As described above:

in the formula V, R⁴Is the above linker and Z is the above group.

A particular embodiment of the present invention relates to functional aspartates, where the group Z-R⁴-Y-is a polyester group. One of this embodimentThese aspects relate to the case when the polyester is a carboxylic acid functional polyester.

In another embodiment of the invention, the group Z-R⁴-Y-is a polyether group in a functional aspartate. In some aspects of this embodiment, the polyether is a hydroxyl functional polyether.

Another embodiment of the present invention relates to functional aspartates, where Z-R⁴the-Y-group is a poly (meth) acrylate group. In some aspects of this embodiment, the poly (meth) acrylate is a carboxylic acid functional polyacrylate.

In another embodiment of the present invention, the functional aspartate comprises a group Z-R⁴-Y-, which is C₁-C₂₄Monoester groups of linear, branched or cyclic alkyl, alkenyl, aryl, alkaryl or aralkyl dicarboxylic acids. In some aspects of this embodiment, the dicarboxylic acid is selected from the group consisting of adipic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and mixtures thereof.

In a particular embodiment of the invention, the functional aspartate of the formula V corresponds to formula Va:

in the formula, Z, R⁴、R³²、R³¹、R¹And R²As mentioned above, X may be O or NR⁵As described above.

Embodiments of the present invention relate to adhesive, sealant or coating compositions comprising:

i) one or more functional dialkyl aspartates as described above, and

ii) an isocyanate functional material.

In an embodiment of the present invention, the isocyanate functional material may be a polyisocyanate containing 2 to 6 isocyanate groups. In a specific embodiment, the polyisocyanate has a structure represented by formula VI:

OCN-R¹⁷-NCO (VI)

in the formula, R¹⁷Is selected from C₂-C₂₄Linear, branched and cyclic alkylene, arylene and aralkylene groups, which may optionally contain one or more isocyanate groups.

In another embodiment of the present invention, the polyisocyanate may be selected from the group consisting of 1, 4-tetramethylene diisocyanate, 1, 6-hexamethylene diisocyanate, 2, 4-trimethyl-1, 6-hexamethylene diisocyanate, 1, 12-dodecamethylene diisocyanate, cyclohexane-1, 3-diisocyanate and cyclohexane-1, 4-diisocyanate, 1-isocyanato-2-isocyanatomethylcyclopentane, 1-isocyanato-3-isocyanatomethyl-3, 5, 5-trimethylcyclohexane, bis- (4-isocyanatocyclohexyl) -methane, 2, 4' -dicyclohexylmethane diisocyanate, 1, 3-bis- (isocyanatomethyl) -cyclohexane and 1, 4-bis- (isocyanatomethyl) -cyclohexane, bis- (4-isocyanato-3-methyl-cyclohexyl) -methane, α, α, α ', α' -tetramethyl-1, 3-diisocyanate, α, α, α ', α' -1, 4-xylylene diisocyanate, 1-isocyanato-1-methyl-4 (3) -isocyanatomethylcyclohexane, 2, 4-hexahydrotolylene diisocyanate, 2, 6-hexahydrotolylene diisocyanate, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 2, 4-diphenyl-methane diisocyanate, 2, 3-tolylene diisocyanate, 2-tolyl, 4, 4' -diphenyl-methane diisocyanate, 1, 5-diisocyanatonaphthalene, and mixtures thereof.

In another embodiment of the invention, the polyisocyanates include one or more polyisocyanate adducts containing biuret, urethane, uretdione (uretdione), allophanate, isocyanurate, and/or iminooxadiazinedione (iminooxadiazinedione) groups.

Non-limiting examples of biuret group-containing polyisocyanates include those prepared using coreactants such as water, tertiary alcohols, primary and secondary monoamines, and primary and/or secondary diamines, as described in U.S. Pat. Nos. 3124605, 3358010, 3644490, 3862973, 3903126, 3903127, 4051165, 4147714, or 4220749, the relevant portions of which are incorporated herein by reference. These polyisocyanates have an NCO content of 18 to 22% by weight and an average NCO functionality of 3 to 3.5.

Non-limiting examples of urethane-containing groups include those prepared by the methods described in U.S. Pat. No.3183112 (relevant portions of which are incorporated herein by reference), in the case of diisocyanates, by reacting an excess of polyisocyanate and low molecular weight diols and polyols (molecular weight less than 400), such as trimethylolpropane, glycerol, 1, 2-dihydroxypropane, and mixtures thereof. The polyisocyanates containing urethane groups 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, such as a trialkylphosphine catalyst, which may be used in admixture with other aliphatic and/or cycloaliphatic polyisocyanates, especially the isocyanurate group-containing polyisocyanates described above.

Non-limiting examples of allophanate group-containing polyisocyanates include those prepared in accordance with the procedures described in U.S. Pat. Nos. 3769318, 4160080 and 4177342, the relevant portions of which are incorporated herein by reference. The allophanate group-containing polyisocyanates have an NCO content of 12 to 21% by weight and an average NCO functionality of 2 to 4.5.

Non-limiting examples of polyisocyanates containing isocyanurate and allophanate groups include those made according to the processes described in U.S. Pat. Nos. 5124427, 5208334 and 5235018, the relevant portions of which are incorporated herein by reference. Such polyisocyanates contain monoisocyanurate groups and monoallophanate groups in a ratio of about 10:1 to 1:10, and in some cases 5:1 to 1: 7.

Non-limiting examples of polyisocyanates containing iminooxadiazinedione and optionally containing isocyanurate groups include those prepared in the presence of specific fluorine-containing catalysts as described in U.S. Pat. No.5914383, the relevant portions of which are incorporated herein by reference. These polyisocyanates typically 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.

In embodiments of the invention, the adhesive, sealant or coating composition may comprise (iii) an amine chain extender. In a particular aspect of this embodiment, the amine chain extender comprises C₁-C₂₄A linear, branched or cyclic alkyl, aryl, alkaryl or aralkyl difunctional amine, optionally containing one or more-O-, -NH-or-S-heteroatoms.

In an embodiment of the invention, the adhesive, sealant or coating composition may be a two-component composition, wherein the first component comprises i) and the second component comprises ii). In a particular aspect of this embodiment, the first component further comprises (iii) an amine chain extender.

In an embodiment of the invention, the adhesive, sealant or coating composition comprises one or more materials selected from leveling agents, wetting agents, flow control agents, antiskinning agents, antifoaming agents, fillers, adhesion promoters, viscosity modifiers, plasticizers, pigments, dyes, uv absorbers, thermal stabilizers, antioxidants and mixtures thereof.

Non-limiting examples of plasticizers useful 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 and trioctyl phosphate, polypropylene glycol adipate, polybutylene glycol adipate, and the like. Such plasticizers may be used alone or in combination of two or more.

Non-limiting examples of adhesion promoters useful in the present invention include epoxy resins, phenolic resins, silane and aminosilane coupling agents known in the art, alkyl titanates, and/or aromatic polyisocyanates.

Non-limiting examples of curing catalysts (for curing) useful in the present invention include phthalate esters, e.g., tetrabutyl titanate and tetrapropyl titanate; organotin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate and tin naphthenate; lead octoate; amine-based compounds and salts and carboxylates of these compounds, for example, butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2, 4, 6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine and 1, 3-diazabicyclo (5, 4, 6) undecene-7 (DBU), low molecular weight polyamide resins (prepared by reaction between an excess of polyamine and a polybasic acid); reaction products between excess polyamines and epoxides; and known silanol condensing catalysts such as silane coupling agents containing an amino group (e.g., gamma-aminopropyltrimethoxysilane and N- (. beta. -aminoethyl) aminopropylmethyldimethoxysilane). These compounds may be used alone or in combination.

Non-limiting examples of leveling agents useful in the present invention include cellulose, e.g., nitrocellulose and cellulose acetate butyrate.

Non-limiting examples of wetting agents useful in the present invention include glycols, silanes, anionic surfactants, and any other wetting agent known in the art.

Non-limiting examples of flow control agents useful in the present inventionExamples include polyacrylates, nonionic fluorinated alkyl ester surfactants, nonionic alkylaryl polyether alcohols, silicones, and the like, and are available under the trade name RESIFLOWThose available from Estron chemical, Inc., Parsippany, N.J., under the trade name BenzoneThose available from DSM, Inc. as MODAFLOWThose available from Monasanto and sold under the trade name SURFYNOLThose commercially available from Airproducts, Bethlehem, PA.

Non-limiting examples of anti-skinning agents useful in the present invention include lecithin, oximes (non-limiting examples being butyraldehyde oxime, methyl ethyl ketoxime), hydroquinone (non-limiting example being 2, 5-di-t-butylhydroquinone), and the methyl esters of hydroquinone and anthraquinone.

Non-limiting examples of defoamers useful in the present invention include those known under the trade name FOAMEXThose available from Rohm and Haas company, Philadelphia, Pa, and under the BYK trade nameThose available from BYK-ChemieUSA, Wallinpford, CT and under the trade name Foam BrakeThose available from BASF corp, mount olive, NJ.

Non-limiting examples of fillers useful in the present invention include fumed silica, precipitated 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, fireclay, clay, titanium dioxide, bentonite, organic bentonite, iron oxide, zinc oxide, activated zinc white, and fibrous fillers such as glass fibers or filaments. The filler may have any suitable particle size, and in embodiments of the present invention, the filler particle size is from 5nm to 10 μm, in some cases from 10nm to 5 μm, and in other cases from 25nm to 1 μm.

Non-limiting examples of viscosity modifiers useful in the present invention include alkali soluble, acid soluble and hydrophobically modified alkali soluble or acid soluble emulsion polymers with ACRYSOLThose commercially available from Rohm Hass Company, cellulosics, modified cellulosics, natural gums such as xanthan gum, and the like.

Non-limiting examples of pigments useful in the present invention include silica, calcium carbonate, magnesium carbonate, titanium oxide, iron oxide, and carbon black.

Non-limiting examples of dyes useful in the present invention include mordant dyes, i.e., dyes made from plants, insects, and algae, and direct dyes, non-limiting examples being those based on benzidine or benzidine derivatives.

Non-limiting examples of the ultraviolet light absorbers used in the present invention include benzotriazole-based ultraviolet light absorbers, salicylate-based ultraviolet light absorbers, benzophenone-based ultraviolet light absorbers, hindered amine-based light stabilizers, and nickel-based light stabilizers.

Non-limiting examples of heat stabilizers useful in the present invention include HCL scavengers (a non-limiting example of which is epoxidized soybean oil), beta-thiodipropionate (non-limiting examples of which are lauryl, stearyl, myristyl or tridecyl esters), mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (. beta. -dodecylmercapto) propionate, and lead phosphate.

Non-limiting examples of antioxidants useful in the present invention include 2, 6-di-tert-butylphenol, 2, 4-di-tert-butylphenol, 2, 6-di-tert-butyl-4-methylphenol, 2, 5-di-tert-butylhydroquinone, n-octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate]2, 2 '-methylenebis (4-methyl-6-tert-butylphenol), 4' -butylidenebis (3-methyl-6-tert-butylphenol), 4 '-thiobis (3-methyl-6-tert-butylphenol), N' -diphenyl-p-phenylenediamine, 6-ethoxy-2, 2, 4-trimethyl-1, 2-dihydroquinone and also under the trade name IRGANOXAntioxidants available from Ciba specialty Chemicals, Basel, Switzerland.

The present invention also provides a method of joining a first adherend or substrate to a second adherend or substrate. The method comprises the following steps:

applying the above adhesive composition comprising components i), ii) and optionally iii) to at least a portion of the surface of a first adherend and optionally to at least a portion of the surface of a second adherend;

contacting a first adherend surface comprising an adhesive composition with a second adherend surface, the at least one contacting surface having the applied composition, thereby forming a bonded assembly;

curing the adhesive composition in the bonded assembly.

The method of connecting provides an assembly. The assembly includes a first adherend and a second adherend, each of which includes one or more materials selected from wood, metal, plastic, paper, ceramic, inorganic, stone, glass, and concrete.

In a particular embodiment of the invention, the metal comprises iron or aluminum. In another embodiment of the present invention, the plastic comprises polyethylene, polypropylene, polyethylene terephthalate, and mixtures thereof.

In an embodiment of the invention, the first substrate and the second substrate are contacted at a temperature of 0-150 ℃. The first substrate and the second substrate may also be contacted at a pressure of from atmospheric pressure to 500 psi.

Embodiments of the present invention also relate to assemblies made by the above methods, wherein at least a first adherend or substrate and a second adherend or substrate are bonded together.

Other embodiments of the present invention are directed to an adhesive, sealant or coating composition comprising

i) The functional aspartate according to claim 16,

ii) the above isocyanate functional materials, and optionally

iii) the amine chain extender described above.

Another embodiment of the present invention relates to a method of coating a substrate comprising applying the above-described coating composition comprising components i), ii) and optionally iii) to at least a portion of the surface of the substrate. The invention also provides a coated substrate prepared according to the method. Thus, the substrate may be, but is not limited to, one or more materials selected from wood, metal, plastic, paper, ceramic, mineral, stone, glass, concrete. In particular embodiments, the substrate may include wood, metals such as ferrous and aluminum substrates, and plastics.

The coating composition may be applied by conventional means such as brushing, dipping, flow coating, spraying, and the like. Upon application to a substrate, the composition coalesces to form a substantially continuous film on the substrate. The liquid in the film is removed by heating or air drying, thereby forming a film on the surface of the substrate.

A further embodiment of the present invention relates to a coating composition which is a two-component composition, wherein the first component comprises i) and optionally iii) and the second component comprises ii).

Embodiments of the present invention relate to a method of applying a composition to a substrate comprising mixing together component i) and component ii) as described above.

The present invention is more particularly described in the following examples that are intended for purposes of illustration only and many modifications and alterations will be apparent to those skilled in the art. All parts and percentages are by weight unless otherwise indicated.

Example 1

This example illustrates the synthesis of diethyl 2- (2-methyl-1-aziridinyl) succinate, an intermediate in accordance with the present invention. Using a round bottom flask with thermocouple, stirrer, nitrogen inlet, feed funnel and cold finger, 8.08g (0.1415mol) of 2-methylaziridine and diethyl maleate (24.36g, 0.1415mol) were mixed while maintaining the temperature below 30 ℃ and stirred overnight. Vacuum was applied to remove unreacted 2-methylaziridine. Gas Chromatography (GC) was used to judge completion of the reaction.

Examples 2 to 9

An aspartate functional compound was prepared by mixing the product of example 1 and an active hydrogen containing compound in an equivalent ratio of 1:1 of the product of example 1 and the active hydrogen compound in a round bottom flask equipped with a stirrer at room temperature. The completion of the reaction was confirmed using GPC and GC. Specific examples are listed in the following table.

(ii) manually combining the aspartate-functional compound and a polyisocyanate: (N-3000) in a ratio of NCO: NH ═ 1: 1. The Shore A and Shore D hardness were determined in accordance with DIN53505 and ASTM D2240. In that4444(Instron Corp., Canton, Mass.) tensile strength and elongation at break were determined in accordance with DIN/ISO 527.

The following table shows specific results.

Examples	Active hydrogen compound	Shore A	Shore B	Tensile strength	Elongation (%)
						2	Polyester A	56	8	149	144
3	Polyester B	66	13	587	112
						4	Adipic acid	--	55	1351	144
5	Adipic acid	--	63	2247	140
						6	Polyether A	32	--	419	224
7	Polyether B	76	--	2552	80
						8	Polyether C	54	--	924	111
9	Polyether D	80	--	2240	45

¹Polyester of adipic acid, 1, 6-hexanediol and neopentyl glycol, number average molecular weight (Mn) 1030

²Polyesters of adipic acid, 1, 6-hexanediol, neopentyl glycol and trimethylolpropane, Mn 1275

³As described in U.S. patent No.6384175, a polyether is prepared by reacting a polyether (hydroxyl functionality of 2, Mn-425,9121, available from Bayer) and hexahydrophthalic anhydride

⁴As described in U.S. patent No.6384175, a polyether is prepared by reacting a polyether (hydroxyl functionality of 5.8, Mn 859,4030, available from Bayer)) and hexahydrophthalic anhydride

⁵As described in U.S. patent No.6384175, a polyether is prepared by reacting a polyether (hydroxyl functionality of 3, Mn 439,4035, available from Bayer)) and hexahydrophthalic anhydride

⁶As described in U.S. patent No.6384175, a polyether is prepared by reacting a polyether (hydroxyl functionality of 5, Mn 625,4034, available from Bayer) and sixAcid functional polyethers prepared by reaction of hydrophthalic anhydride

Examples 10 to 12

An aspartate-functional compound is prepared by mixing the product prepared in example 1 with two active hydrogen containing compounds as described above. The aspartate-functional compound and the isocyanate were then mixed by hand as described above at a ratio of NCO: NH ═ 1:1N-3300. The evaluation was carried out as described above, and the results are shown in the following table.

⁷Acid-terminated polyesters made from adipic acid, hexanediol, neopentyl glycol, and trimethylolpropane.

NH1420 available from Bayer Corporation, Pittsburgh, Pa

⁹Imine functional polyamines

Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.

Claims (9)

1. An adhesive, sealant or coating composition comprising:

i) a functional dialkyl aspartate of the formula:

and

ii) an isocyanate functional material;

wherein, in the above formula, R¹And R²Independently is C₁-C₈Straight chainAn alkyl group;

each R³Independently selected from H, C₁-C₂₀A linear alkyl group;

Z-R⁴-Y-is selected from: a carboxylic acid functional polyester; a hydroxyl functional polyether; carboxylic acid functional poly (meth) acrylates; and C₁-C₂₄Monoester groups of linear, branched or cyclic alkyl, alkenyl, aryl, alkaryl or aralkyl dicarboxylic acids.

2. The composition of claim 1, wherein the isocyanate functional material is a polyisocyanate comprising from 2 to 6 isocyanate groups.

3. The composition of claim 2, wherein the polyisocyanate has a structure represented by the general formula:

OCN-R¹⁷-NCO

in the formula, R¹⁷Is selected from C₂-C₂₄Linear, branched and cyclic alkylene, arylene and aralkylene groups, which may optionally contain one or more isocyanate groups.

4. The composition of claim 2, wherein the polyisocyanate is selected from the group consisting of 1, 4-tetramethylene diisocyanate, 1, 6-hexamethylene diisocyanate, 2, 4-trimethyl-1, 6-hexamethylene diisocyanate, 1, 12-dodecamethylene diisocyanate, cyclohexane-1, 3-diisocyanate and cyclohexane-1, 4-diisocyanate, 1-isocyanato-2-isocyanatomethylcyclopentane, 1-isocyanato-3-isocyanatomethyl-3, 5, 5-trimethylcyclohexane, bis- (4-isocyanatocyclohexyl) -methane, 2, 4' -dicyclohexylmethane diisocyanate, 1, 3-bis- (isocyanatomethyl) -cyclohexane and 1, 4-bis- (isocyanatomethyl) -cyclohexane, bis- (4-isocyanato-3-methyl-cyclohexyl) -methane, α, α, α ', α' -tetramethyl-1, 3-diisocyanate, α, α ', α' -1, 4-xylylene diisocyanate, 1-isocyanato-1-methyl-4 (3) -isocyanatomethylcyclohexane, 2, 4-hexahydrotoluylene diisocyanate, 2, 6-hexahydrotoluylene diisocyanate, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, 2, 4-toluylene diisocyanate, 2, 6-toluene diisocyanate, 2, 4-diphenyl-methane diisocyanate, 4' -diphenyl-methane diisocyanate, 1, 5-diisocyanatonaphthalene, and mixtures thereof.

5. The composition of claim 1, wherein the composition further comprises one or more materials selected from the group consisting of leveling agents, wetting agents, flow control agents, anti-skinning agents, anti-foaming agents, fillers, adhesion promoters, viscosity modifiers, plasticizers, pigments, dyes, ultraviolet absorbers, thermal stabilizers, antioxidants, and mixtures thereof.

6. The composition of claim 1 comprising iii) an amine chain extender.

7. The composition of claim 6, wherein the amine is C₁-C₂₄A linear, branched or cyclic alkyl, aryl, alkaryl or aralkyl difunctional amine, optionally containing one or more-O-, -NH-or-S-heteroatoms.

8. The composition of claim 1 which is a two-component composition wherein the first component comprises i) and the second component comprises ii).

9. The composition of claim 8, wherein the first component further comprises iii) an amine chain extender.