Aspartic ester functional compounds

Abstract

A functional aspartate prepared by A) reacting an aziridine with a Michael-acceptor molecule to form an aziridinyl aspartate, and B) reacting the aziridinyl aspartate with an active hydrogen containing compound to form the functional aspartate. The functional aspartate can be used in adhesive, sealant or coating compositions that also include an isocyanate functional material. The composition can be used in a method of bonding a first substrate to a second substrate that includes applying a coating of the above-identified adhesive composition to at least one surface of the first substrate or the second substrate, and contacting a surface of the first substrate with a surface of the second substrate, where at least on of the contacting surfaces has the coating applied thereto. The composition can also be used to coat substrates.

1 . A functional dialkyl aspartate according to the formula:  
       
         
           
           
               
               
           
         
       
       wherein 
 R 1  and R 2  are independently C 1 -C 8  linear, branched or cyclic alkyl,  
 each occurrence of R 3  is independently selected from H, C 1 -C 20  linear, branched, or cyclic alkyl, aryl, alkaryl or aralkyl,  
 Y is a linking group selected from the group consisting of —O—, —S—, —NR 5 —, 
 —O—P(O) 2 —O—, —P(O) 2 —O—, —S(O) 2 —O—,  
                     
 and a group resulting from the removal of an acidic hydrogen from a carbon that is positioned adjacent to one or more electron withdrawing groups according to one of the formulas  
                     
 wherein  
 R 5  is H or C 1 -C 3  linear or branched alkyl,  
 W 1  is an electron withdrawing group selected from the group consisting of nitrile, R 11 —CO—, nitro, 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,  
 W 2  is a ketone,  
 R 11  is selected from H. —OH, C 1 -C 24  linear, branched or cyclic alkyl, aryl, alkaryl, or aralkyl, which may contain one or more hetero atoms selected from O, S, and/or N,  
 R 12  is C 1 -C 24  linear, branched or cyclic alkylene, arylene, alkarylene, or aralkylene, which may contain one or more hetero atoms selected from O, S, and/or N, and  
 
 R 4  is a linking group selected from the group consisting of 
 C 1 -C 24  linear, branched or cyclic alkylene, arylene, alkarylene, or aralkylene,  
 —(—[CHR 7 —] n —O-)p-R 8 —, wherein R 7  is C 1 -C 3  linear or branched alkyl or aklylol, 
 n is 1 to 4, and  
 p is 1 to 1,000, 
                     
 
 wherein q is 1 to 1,000, and each occurrence of R 8  is independently selected from C 1 -C 24  linear, branched or cyclic alkylene, alkenylene, arylene, alkarylene, or aralkylene, optionally including substituent hydroxyl, carboxylic acid, or C 1 -C 8  linear, branched or cyclic carboxylic acid ester groups,  
                     
 wherein r is 1 to 10,000, 
 R 9  is C 1 -C 3  linear or branched alkyl,  
 X is —OR 10  or —NR 5   2 , where R 5  is as defined above,  
 R 10  is H or C 1 -C 24  linear, branched or cyclic alkyl, aryl, alkaryl, and aralkyl,  
 
 and combinations thereof, and  
 
 Z is selected from the group consisting of —H, —OR 10 , —R 4 —OR 10 , —NR 5   2 , 
 R 4 —NR 5   2 , —SH, —R 4 —SH,  
                     
 
 
     
     
         2 . The functional aspartate of  claim 1 , wherein the group Z-R 4 —Y— is a polyester radical.  
     
     
         3 . The functional aspartate of  claim 2 , wherein the polyester is a carboxylic acid functional polyester.  
     
     
         4 . The functional aspartate of  claim 1 , wherein the group Z-R 4 —Y— is a polyether radical.  
     
     
         5 . The functional aspartate of  claim 4 , wherein the polyether is a hydroxyl functional polyether.  
     
     
         6 . The functional aspartate of  claim 1 , wherein the group Z-R 4 —Y— is a polyacrylate radical.  
     
     
         7 . The functional aspartate of  claim 6 , wherein the poly(meth)acrylate is a carboxylic acid functional poly(meth)acrylate.  
     
     
         8 . The functional aspartate of  claim 1 , wherein the group Z-R 4 —Y— is a monoester radical of a C 1 -C 24  linear, branched or cyclic alkyl, alkenyl, aryl, alkaryl, or aralkyl dicarboxylic acid.  
     
     
         9 . The functional aspartate of  claim 8 , wherein the dicarboxylic acid is selected from the group consisting of adipic acid, malonic acid, succinic acid, maleic acid, fumaric acid, pentanedioc acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonadioic acid, and mixtures thereof.  
     
     
         10 . A method of preparing a functional aspartate comprising: 
 A) reacting an aziridine with a Michael-acceptor molecule to form an aziridinyl aspartate, and    B) reacting the aziridinyl aspartate with an active hydrogen containing compound to form the functional aspartate.    
     
     
         11 . The method of  claim 10 , wherein the aziridine is selected from unsubstituted aziridine, 2-methyl aziridine, 2-ethyl aziridine, 2-n-propyl aziridine, and 2-isopropyl aziridine.  
     
     
         12 . The method of  claim 10 , wherein the Michael-acceptor molecule is selected from the group consisting of 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, maleimidee, 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.  
     
     
         13 . The method of  claim 10 , wherein the active hydrogen containing compound is a C 1 -C 24  linear, branched or cyclic alkylene, alkenylene, arylene, alkarylene, or aralkylene, a polyether, a polyester, or a poly(meth)acrylic molecule containing two or more functional groups selected from the group consisting of hydroxyl, carboxylic acid, thiol, amine, phosphoric acid, sulfonic acid, acidic CH groups, and combinations thereof.  
     
     
         14 . The method of  claim 10 , wherein a catalyst is used in A).  
     
     
         15 . The method of  claim 10 , wherein a catalyst is used in B).  
     
     
         16 . A functional aspartate prepared according to the method of  claim 10 .  
     
     
         17 . An adhesive, sealant or coating composition comprising: 
 i) the functional dialkyl aspartate of  claim 1 , and    ii) an isocyanate functional material.    
     
     
         18 . The composition of  claim 17 , wherein the isocyanate functional material is a polyisocyanate containing from 2 to 6 isocyanate groups.  
     
     
         19 . The composition of  claim 18 , wherein the polyisocyanate has a structure according to the formula:  
         OCN—R 17 —NCO  
       wherein 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.  
     
     
         20 . The composition of  claim 18 , wherein the polyisocyanate is selected from the group consisting of 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, .α,α,α′,α′-tetramethyl-1,3-diisocyanate, α,α,α′,α′-1,4-xylylene diisocyanate, 1-isocyanato-1-methyl-4(3)-isocyanatomethyl cyclohexane, 2,4-hexahydrotoluylene diisocyanate, 2,6-hexahydrotoluylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluylene diisocyanate, 2,6-toluylene diisocyanate, 2,4-diphenyl-methane diisocyanate, 4,4′-diphenyl-methane diisocyanate, 1,5-diisocyanato naphthalene and mixtures thereof.  
     
     
         21 . The composition of  claim 17 , further comprising one or more materials selected from the group consisting of 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.  
     
     
         22 . The composition according to  claim 17  comprising iii) an amine chain extender.  
     
     
         23 . The composition according to  claim 22 , wherein the amine is 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.  
     
     
         24 . The composition of  claim 17  as a two-component composition, wherein a first component comprises i) and a second component comprises ii).  
     
     
         25 . The composition according to  claim 24 , wherein the first component further comprises iii) an amine chain extender.  
     
     
         26 . A method of applying a composition to a substrate comprising mixing component i) and component ii) of  claim 24 .  
     
     
         27 . A method of bonding a first substrate to a second substrate comprising 
 applying a coating of the composition of  claim 17  to at least one surface of the first substrate or the second substrate, and    contacting a surface of the first substrate with a surface of the second substrate, wherein at least on of the contacting surfaces has the coating applied thereto.    
     
     
         28 . The method of  claim 27 , wherein one or both of the first substrate and the second substrate comprises a substrate selected from the group consisting of wood, metals, plastics, paper, canvas, ceramics, stone, glass, and concrete.  
     
     
         29 . The method of  claim 28 , wherein the metal comprises iron or aluminum.  
     
     
         30 . The method of  claim 28 , wherein the plastic is selected from the group consisting of poly(ethylene), poly(propylene), poly(ethylene terephthalate), and mixtures thereof.  
     
     
         31 . The method of  claim 27 , wherein the first substrate and the second substrate are contacted at a temperature of from 0° C. to 150° C.  
     
     
         32 . The method of  claim 27 , wherein the first substrate and the second substrate are contacted at a pressure of from atmospheric pressure to 500 psi.  
     
     
         33 . An assembly made according to  claim 27  comprising at least the first substrate and the second substrate bonded together.  
     
     
         34 . A method of coating a substrate comprising applying the composition of  claim 17  to at least a portion of a surface of the substrate.  
     
     
         35 . A coated substrate prepared according to the method of  claim 34 .  
     
     
         36 . An adhesive, sealant or coating composition comprising: 
 i) the functional aspartate of  claim 16 , and    ii) an isocyanate functional material.    
     
     
         37 . The composition according to  claim 36  comprising iii) an amine chain extender.  
     
     
         38 . The composition according to  claim 37 , wherein the amine is 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.  
     
     
         39 . The composition of  claim 36 , wherein the isocyanate functional material is a polyisocyanate containing from 2 to 6 isocyanate groups.  
     
     
         40 . The composition of  claim 36  as a two-component composition, wherein a first component comprises i) and a second component comprises ii).  
     
     
         41 . A method of applying a composition to a substrate comprising mixing component i) and component ii) of  claim 36 .  
     
     
         42 . The method according to  claim 41 , wherein component i) includes an amine chain extender.  
     
     
         43 . The composition of  claim 37 , wherein the isocyanate functional material is a polyisocyanate containing from 2 to 6 isocyanate groups.  
     
     
         44 . The composition of  claim 37  as a two-component composition, wherein a first component comprises i) and iii) and a second component comprises ii).  
     
     
         45 . A method of applying a composition to a substrate comprising mixing component i), component ii) and component iii) of  claim 37 .  
     
     
         46 . A method of bonding a first substrate to a second substrate comprising 
 applying a coating of the composition of  claim 36  to at least one surface of the first substrate or the second substrate, and    contacting a surface of the first substrate with a surface of the second substrate, wherein at least on of the contacting surfaces has the coating applied thereto.    
     
     
         47 . An assembly made according to  claim 46  comprising at least the first substrate and the second substrate bonded together.  
     
     
         48 . A method of coating a substrate comprising applying the composition of  claim 36  to at least a portion of a surface of the substrate.  
     
     
         49 . A coated substrate prepared according to the method of  claim 48 .  
     
     
         50 . The composition of  claim 36 , wherein the isocyanate functional material comprises one or more polyisocyanate adducts containing biuret, urethane, uretdione, allophanate, isocyanurate, and/or iminooxadiazinedione groups.