Sulfonate esters as latent acid catalysts

Abstract

The present invention is directed towards novel sulfonic acid esters as catalysts for crosslinking of polymers having hydroxyl, carboxyl, and amide functional groups with a crosslinking agent and resin compositions containing the same. The present invention provides polymeric film coatings which have superior hardness, impact resistance, adhesion, improved blister resistance, salt spray characteristics and flexibility. These catalysts are especially effective in coil primer formulations containing calcium ion exchange anticorrosive pigments, where traditional blocked acid catalysts are ineffective.

1 . A curable coating composition comprising a total solids content of at least 50 percent, said coating composition being capable of acid catalyzed crosslinking and containing at least one active hydrogen-containing resin, at least one curing agent present externally and/or internally as a part of the active hydrogen-containing resin, optionally, at least one basic anticorrosive pigment, and a catalytic amount of at least one non-ionic ester of a sulfonic acid having the following structural formula (s): 
       
         
           
           
               
               
           
         
       
       wherein,
 Z is an organic radical selected from the group consisting of linear, branched, saturated or unsaturated alkyl having from 1 to 40 carbon atoms, a cycloalkyl having from 5 to 40 carbon atoms, an aryl having from 6 to 40 carbon atoms, an aralkyl group having from 7 to 9 carbon atoms, which aralkyl optionally may be substituted with an alkyl having from 1 to 36 carbon atoms, said organic radical is connected to the sulfur atom by a carbon atom; 
 E is 
 
       
         
           
           
               
               
           
         
       
       or a cycloalkyl having from 3 to 20 carbon atoms;
 R 1 , R 2 , R 3 , R 4  and R 5  are independently hydrogen or an organic radical; 
 W is selected from the group consisting of alkylene having from 1 to 18 carbon atoms and alkenylene having from 2 to 18 carbon atoms; 
 Y is selected from the group consisting of alkylene having from 1 to 18 carbon atoms, hydroxyl substituted alkylene having from 1 to 18 carbon atoms, alkenylene having from 2 to 18 carbon atoms, and hydroxyl substituted alkenylene having from 2 to 18 carbon atom; 
 subscript n equals 2 to 20; 
 T is a n-valent radical selected from the group consisting of alkane or alkene having up to about 200 carbon atoms, an n-valent radical of a cycloalkane or cycloalkene having from 5 to 12 carbon atoms, an n-valent radical of a bicyclic or tricyclic hydrocarbon having from 7 to 12 carbon atoms or an n-valent radical of an aryl, alkyl substituted aryl or aralkyl hydrocarbon having from 6 to 15 carbon atoms, with the provisos that when n is 2, T is an alkylene having from 2 to 40 carbon atoms, a cycloalkylene having from 6 to 10 carbon atoms or an alkylenearylenealkylene having from 8 to 10 carbon atoms, when n is 3, T is an alkanetriyl having from 3 to 6 carbon atoms, and when n is 4, T is an alkanetetrayl having from 4 to 6 carbon atoms; 
 Y′ is a radical independently selected from the group consisting of alkyl having from 1 to 20 carbon atoms, cycloalkyl having from 3 to 20 carbon atoms, aryl having from 6 to 18 carbon atoms, halogen, alkoxy, hydroxyl, and aryloxy; 
 R is independently selected from the group consisting of hydrogen, alkyl having from 1 to 20 carbon atoms, cycloalkyl having from 3 to 20 carbon atoms, aryl having from 6 to 18 carbon atoms; 
 R 6  is independently selected from the group consisting of alkyl having from 1 to 100 carbon atoms, cycloalkyl having from 3 to 20 carbon atoms, hydroxyalkyl, and hydroxycycloalkyl; 
 y′ is an integer from 0 to 4, w is an integer from 0 to 2, and x is an integer from 1 to 3, with the proviso that when w is 0, y′ is an integer from 1 to 4 and x is an integer from 2 to 3 and when y′ is 0, w is an integer from 1 to 2 and x is an integer from 1 to 3; 
 R 10  is H or an alkyl group having from 1 to 40 carbon atoms, 
 x′ is an integer from 0 to 2; 
 R′ is 
 
       
         
           
           
               
               
           
         
         R 11  and R 12  independently are the same or different and are linear or branched alkyl group having from 6 to 40 carbons; 
         y″ is 0 to 3, z is 0 to 3, and y″+z is 1 to 4; 
         R 51 , R 52 , R 53  and R 54  are independently selected from the group consisting of hydrogen or linear or branched hydrocarbyl groups having from about 9 to about 40 carbon atoms, with the proviso that l, m, n′ and p are integers from 0 to 4 and the sum of l+m+n′+p is at least 1 and R 51 , R 52 , R 53  and R 54  are independently hydrogen when either l, m, n′, or p is 0. 
       
     
     
         2 . The composition of  claim 1  wherein R 1  of Formula (I) is selected from the group consisting of hydrogen, carboalkoxy, alkyl having from 3 to 20 carbon atoms, aryl having from 6 to 18 carbon atoms, and cycloalkyl having from 3 to 20 carbon atoms. 
     
     
         3 . The composition of  claim 1  wherein R 2  of Formula (I) is selected from the group consisting of hydrogen, carboalkoxy, alkyl having from 3 to 20 carbon atoms, aryl having from 6 to 18 carbon atoms, and cycloalkyl having from 3 to 20 carbon atoms. 
     
     
         4 . The composition of  claim 1  wherein R 3  of Formula (I) is selected from the group consisting of hydrogen, carboalkoxy, acyloxy, N-alkylcarbamyloxy, N-arylcarbamyloxy, alkyl having from 3 to 20 carbon atoms, aryl having from 6 to 18 carbon atoms, and cycloalkyl having from 3 to 20 carbon atoms. 
     
     
         5 . The composition of  claim 1  wherein R 4  of Formula (I) is selected from the group consisting of hydrogen, carboalkoxy, acyloxy, N-alkylcarbamyloxy, N-arylcarbamyloxy, alkyl having from 3 to 20 carbon atoms, aryl having from 6 to 18 carbon atoms, and cycloalkyl having from 3 to 20 carbon atoms. 
     
     
         6 . The composition of  claim 1  wherein R 5  of Formula (I) is selected from the group consisting hydrogen, carboalkoxy, acyloxy, N-alkylcarbamyloxy, N-arylcarbamyloxy, alkyl having from 3 to 20 carbon atoms, aryl having from 6 to 18 carbon atoms, and cycloalkyl having from 3 to 20 carbon atoms. 
     
     
         7 . The composition of  claim 1  wherein when n is greater than 4, T is an oligomeric functional hydrocarbon moiety. 
     
     
         8 . The composition of  claim 7  wherein T is a polyolefin from derived at least one of the of the following polybutene, polyisobutylenes, poly(ethylene-vinyl alcohol) copolymer, poly(ethylene-vinyl alcohol-vinyl acetate) copolymer, poly(ethylene-acrylic acid) copolymer, poly(ethylene-methyl acrylate) copolymer, poly(ethylene-methacrylic acid) copolymer, poly(ethylene-methyl methacrylate) copolymer, poly(ethylene-vinyl alcohol-methacrylic acid) copolymer, poly(ethylene-ethyl acrylate-maleic anhydride) copolymer, poly(ethylene-butyl acrylate-maleic anhydride) copolymer, polyethylene-maleic anhydride graft copolymer, poly(ethylene-glycidyl methacrylate) copolymer, polyethylene monoalcohol, and polyethylene monocarboxylic acid. 
     
     
         9 . The composition of  claim 8  wherein the polyolefin has a molecular weight (average weight) M n  from about 300 to about 500 000. 
     
     
         10 . The composition of  claim 1  wherein Z comprises a radical selected from the group consisting of an aliphatic hydrocarbon having from 1 to 20 carbon atoms, an aromatic radical, and a heterocyclic radical. 
     
     
         11 . The composition of  claim 10  wherein E is 
       
         
           
           
               
               
           
         
       
     
     
         12 . The composition of  claim 1  wherein R 1 , R 2 , R 3 , R 4 , R 5  are independently sulfonate substituted alkyls. 
     
     
         13 . The composition of  claim 1  wherein the active hydrogen-containing resin comprises a polymeric polyol having a hydroxyl functionality of at least two. 
     
     
         14 . The composition of  claim 13  wherein the polymeric polyol is selected from the group consisting of hydrocarbon polyols, ester polyols, ether polyols, polyester polyols, polyether polyols, amide polyols, polyamide, polyols, acrylic polyols, urethane polyols, polyurethane polyols, cyclic nitrogen-containing polyols, urea polyols, polyurea polyols and mixtures thereof. 
     
     
         15 . The composition of  claim 1  wherein the curing agent comprises an aminoplast resin. 
     
     
         16 . The composition of  claim 15  wherein the aminoplast resin comprises a melamine-formaldehyde condensation product. 
     
     
         17 . The composition of  claim 15  wherein the aminoplast resin comprises an at least partially alkylated melamine-formaldehyde condensation product. 
     
     
         18 . The composition of  claim 17  wherein the aminoplast resin comprises at least partially methylated. 
     
     
         19 . The composition of  claim 17  wherein the polymeric polyol comprises a polyester polyol. 
     
     
         20 . The composition of  claim 17  wherein the polymeric polyol comprises an acrylic polyol. 
     
     
         21 . The composition of  claim 17  wherein the polymeric polyol comprises a polyurethane polyol. 
     
     
         22 . The composition of  claim 1  wherein Z is selected from the group consisting of, methyl, ethyl, phenyl, tolyl, p-tolyl, benzyl, alkylbenzyl o-carbomethyoxyphenyl, naphthyl, and didodecylnaphthyl and dinonylnaphthyl. 
     
     
         23 . The composition of  claim 1  wherein the basic anticorrosive pigment comprises an oxyaminophosphate salt of magnesium or an oxyaminophosphate salt of magnesium modified with a calcium salt or a calcium ion exchange anticorrosive pigment. 
     
     
         24 . The composition of  claim 17  wherein R 1  and R 2  are independently selected from the group consisting of hydrogen, propyl, isopropyl, 1-isobutyryloxy-2-methyl-2-propyl, and carboethoxy; and R 3 , R 4 , and R 5  are independently selected from the group consisting of hydrogen, methanesulfonyloxymethyl, N-butylcarbamyloxy, para-toluenesulfonyloxymethyl, isobutyrloxymethyl and ortho-carbomethoxybenzenesulfonyloxymethyl. 
     
     
         25 . The composition of  claim 1  wherein the sulfonic acid ester comprises at least one compound selected from the group consisting of dodecyl dodecylbenzene sulfonate; dodecyl didodecyl naphthalene sulfonate; 2,2,4-trimethyl-1,3-pentanediyl bis(ortho-carbomethoxybenzenesulfonate); dodecyl dinonyl naphthalene sulfonate; di(octyl)dinonyl naphthalene disulfonate; octyl dinonyl naphthalene sulfonate; di(dodecyl)dinonyl naphthalene disulfonate; octyl dodecylbenzene sulfonate; octyl didodecyl naphthalene sulfonate; cyclohexyl toluene sulfonate; octyl tolene sulfonate; dodecyl toluene sulfonate; hexyl, cyclohexyl, bis hexylene, decyl, -tetradecyl, hexadecyl, octadecyl, 1-methyl-4-(1-methyethenyl)-cyclohexyl, bicyclo-(3,3,0)-oct-1-yl, bicycle-(2,2,1)hepta-2,5-diyl, norbornyl, bis dicyclopentyl; dodecylbenzene sulfonate, hexyl, cyclohexyl, bis hexylene, decyl, -tetradecyl, hexadecyl, octadecyl, 1-methyl-4-(1-methyethenyl)-cyclohexyl, bicyclo-(3,3,0)-oct-1-yl, bicycle-(2,2,1)hepta-2,5-diyl, norbornyl, bis dicyclopentyl; didodecyl naphthalene sulfonate; hexyl, cyclohexyl, his hexylene, decyl, -tetradecyl, hexadecyl, octadecyl, 1-methyl-4-(1-methyethenyl)-cyclohexyl, bicyclo-(3,3,0)-oct-1-yl, bicycle-(2,2,1)hepta-2,5-diyl, norbornyl, his dicyclopentyl dinonyl naphthalene sulfonate; dihexyl, dicyclohexyl, bis hexylene, didecyl, ditetradecyl, dihexadecyl, dioctadecyl, di(1-methyl-4-(1-methyethenyl)-cyclohexyl), di(bicyclo-(3,3,0)-oct-1-yl, bicycle-(2,2,1)hepta-2,5-diyl), dinorbornyl, bis(dicyclopentyl)dinonyl naphthalene disulfonate; hexyl, cyclohexyl, bis hexylene, decyl, -tetradecyl, hexadecyl, octadecyl, 1-methyl-4-(1-methyethenyl)-cyclohexyl, bicyclo-(3,3,0)-oct-1-yl, bicycle-(2,2,1)hepta-2,5-diyl, norbornyl, bis dicyclopentyl toluene sulfonate; hexyl, cyclohexyl, bis hexylene, octyl, dodecyl, decyl, -tetradecyl, hexadecyl, octadecyl, 1-methyl-4-(1-methyethenyl)-cyclohexyl, bicyclo-(3,3,0)-oct-1-yl, bicycle-(2,2,1)hepta-2,5-diyl, norbornyl, bis dicyclopentyl methane sulfonate; dicyclohexyl toluene 2,4-disulfonate; dicyclohexyl 1,3-xylene-4,6-disulfonate; tricyclohexyl 3,5-disulfonylbenzoate; 2,2,4-trimethyl-1,3-pentanediyl bis(orthocarbomethoxybenzenesulfonate); 2,2,4-trimethyl-1,3-pentanediyl dimethane sulfonate; 1-carboethoxy ethyl methanesulfonate; cyclohexyl ortho-carbomethoxybenzenesulfonate; 4-tert-butylcyclohexyl para-toluene sulfonate; 2-(N-cyclohexylcarbamyloxy)cyclohexyl para-toluenesulfonate; and hydrogenated bisphenol A mono-para-toluenesulfonate. 
     
     
         26 . The composition of  claim 1  wherein the amount of catalyst ranges from about 0.1 to about 20 percent by weight based on the resinous components of the composition. 
     
     
         27 . The composition of  claim 24  wherein the amount of anticorrosive pigment ranges from about 1.0 to about 20 percent by weight based on resinous components of the composition. 
     
     
         28 . The composition of  claim 1  wherein said composition is sprayable. 
     
     
         29 . The composition of  claim 1  wherein the at least one active hydrogen-containing resin comprises a silicon containing resin. 
     
     
         30 . A base coating comprising the composition of  claim 1 . 
     
     
         31 . A primer coating comprising the composition of  claim 1 . 
     
     
         32 . A clear coating comprising the composition of  claim 1 . 
     
     
         33 . The cured composition of  claim 1 . 
     
     
         34 . A process for coating a substrate with high solids, organic solvent based, sprayable coating composition, comprising the steps of:
 a) spraying a substrate electrostatically with an organic solvent based, sprayable coating composition having a total solids content of at least 50 percent, comprising:
 i) an active hydrogen-containing resin; 
 ii) a curing agent present either externally and/or internally as a part of the active hydrogen-containing resin; 
 iii) catalytic amount of the catalyst of  claim 1 ; and, optionally, 
 iv) an anticorrosive pigment; and 
   b) baking the coated substrate of step (a) at a temperature of about 80° C. to about 350° C. to form a cured coating.   
     
     
         35 . A method for forming a multi-layer coating comprising:
 i) applying, sequentially, a layer of a primer coating composition, applying a layer of a base coating composition, and applying a layer of a clear coating composition on a substrate; and   ii) curing, simultaneously, in a single bake all of the applied three layers,   
       wherein at least one of the coating compositions comprises a catalytic amount of the catalyst of  claim 1 . 
     
     
         36 . A non-ionic ester of a sulfonic acid comprising at least one of the following structural formula(s): 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein, 
         Z is an organic radical selected from the group consisting of linear, branched, saturated or unsaturated alkyl having from 1 to 40 carbon atoms, a cycloalkyl having from 5 to 40 carbon atoms, an aryl having from 6 to 40 carbon atoms, an aralkyl group having from 7 to 9 carbon atoms, which aralkyl optionally may be substituted with an alkyl having from 1 to 36 carbon atoms, said organic radical is connected to the sulfur atom by a carbon atom;
 subscript n equals 2 to 20; 
 T is a n-valent radical selected from the group consisting of alkane or alkene having up to about 200 carbon atoms, an n-valent radical of a cycloalkane or cycloalkene having from 5 to 12 carbon atoms, an n-valent radical of a bicyclic or tricyclic hydrocarbon having from 7 to 12 carbon atoms or an n-valent radical of an aryl, alkyl substituted aryl or aralkyl hydrocarbon having from 6 to 15 carbon atoms, with the provisos that when n is 2, T is an alkylene having from 2 to 12 carbon atoms, a cycloalkylene having from 6 to 10 carbon atoms or an alkylenearylenealkylene having from 8 to 10 carbon atoms, when n is 3, T is an alkanetriyl having from 3 to 6 carbon atoms, and when n is 4, T is an alkanetetrayl having from 4 to 6 carbon atoms; 
 R 10  is H or an alkyl group having from 1 to 40 carbon atoms, R 11  and R 12  independently are the same or different and are linear or branched alkyl group having from 6 to 40 carbons; 
 R′ is 
 
       
       
         
           
           
               
               
           
         
         
           x′ is an integer from 0 to 2; 
           y″ is 0 to 3, z is 0 to 3, and y″+z is 1 to 4; 
           R 51 , R 52 , R 53  and R 54  are independently selected from the group consisting of hydrogen or linear or branched hydrocarbyl groups having from about 9 to about 40 carbon atoms, with the proviso that l, m, n′ and p are integers from 0 to 4 and the sum of l+m+n′+p is at least 1 and R 51 , R 52 , R 53  and R 54  are independently hydrogen when either l, m, n′, or p is 0. 
         
       
     
     
         37 . The sulfonic acid of  claim 36  wherein T is a polyolefin derived from at least one of the of the following polybutene, polyisobutylenes, poly(ethylene-vinyl alcohol) copolymer, poly(ethylene-vinyl alcohol-vinyl acetate) copolymer, poly(ethylene-acrylic acid) copolymer, poly(ethylene-methyl acrylate) copolymer, poly(ethylene-methacrylic acid) copolymer, poly(ethylene-methyl methacrylate) copolymer, poly(ethylene-vinyl alcohol-methacrylic acid) copolymer, poly(ethylene-ethyl acrylate-maleic anhydride) copolymer, poly(ethylene-butyl acrylate-maleic anhydride) copolymer, polyethylene-maleic anhydride graft copolymer, poly(ethylene-glycidyl methacrylate) copolymer, polyethylene monoalcohol, and polyethylene monocarboxylic acid. 
     
     
         38 . The sulfonic acid of  claim 36  wherein said sulfonic acid comprises at least one compound selected from the group consisting of dodecyl dodecylbenzene sulfonate; dodecyl didodecyl naphthalene sulfonate; 2,2,4-trimethyl-1,3-pentanediyl bis(ortho-carbomethoxybenzenesulfonate); dodecyl dinonyl naphthalene sulfonate; di(octyl)dinonyl naphthalene disulfonate; octyl dinonyl naphthalene sulfonate; di(dodecyl)dinonyl naphthalene disulfonate; octyl dodecylbenzene sulfonate; octyl didodecyl naphthalene sulfonate; cyclohexyl toluene sulfonate; octyl tolene sulfonate; dodecyl toluene sulfonate; hexyl, cyclohexyl, bis hexylene, decyl, tetradecyl, hexadecyl, octadecyl, 1-methyl-4-(1-methyethenyl)-cyclohexyl, bicyclo-(3,3,0)-oct-1-yl, bicycle-(2,2,1)hepta-2,5-diyl, norbornyl, bis dicyclopentyl; dodecylbenzene sulfonate, hexyl, cyclohexyl, bis hexylene, decyl, -tetradecyl, hexadecyl, octadecyl, 1-methyl-4-(1-methyethenyl)-cyclohexyl, bicyclo-(3,3,0)-oct-1-yl, bicycle-(2,2,1) hepta-2,5-diyl, norbornyl, bis dicyclopentyl; didodecyl naphthalene sulfonate; hexyl, cyclohexyl, bis hexylene, decyl, -tetradecyl, hexadecyl, octadecyl, 1-methyl-4-(1-methyethenyl)-cyclohexyl, bicyclo-(3,3,0)-oct-1-yl, bicycle-(2,2,1)hepta-2,5-diyl, norbornyl, bis dicyclopentyl dinonyl naphthalene sulfonate; dihexyl, dicyclohexyl, bis hexylene, didecyl, ditetradecyl, dihexadecyl, dioctadecyl, di(1-methyl-4-(1-methyethenyl)-cyclohexyl), di(bicyclo-(3,3,0)-oct-1-yl, bicycle-(2,2,1)hepta-2,5-diyl), dinorbornyl, bis(dicyclopentyl)dinonyl naphthalene disulfonate; hexyl, cyclohexyl, bis hexylene, decyl, -tetradecyl, hexadecyl, octadecyl, 1-methyl-4-(1-methyethenyl)-cyclohexyl, bicyclo-(3,3,0)-oct-1-yl, bicycle-(2,2,1)hepta-2,5-diyl, norbornyl, bis dicyclopentyl toluene sulfonate; and hexyl, cyclohexyl, bis hexylene, octyl, dodecyl, decyl, tetradecyl, hexadecyl, octadecyl, 1-methyl-4-(1-methyethenyl)-cyclohexyl, bicyclo-(3,3,0)-oct-1-yl, bicycle-(2,2,1)hepta-2,5-diyl, norbornyl, bis dicyclopentyl methane sulfonate.