Macromolecular Corrosion (McIn) Inhibitors: Structures, Methods Of Making And Using The Same

Abstract

Disclosed are multifunctional compounds represented by structural formula (I): methods of producing compounds represented by structural formula (I) and their use in inhibiting corrosion in corrodible material.

What is claimed is: 
     
         1 . A compound having Structural Formula I: 
       
         
           
           
               
               
           
         
         wherein: 
         X is: 
       
       
         
           
           
               
               
           
         
         each R 1  is H, independently an optionally substituted C 1 -C 20  alkyl group, an optionally substituted C 1 -C 10  alkyl group, a tertiary carbon group, a methyl group, a methoxy group, an optionally substituted aryl group, and optionally substituted alkoxy group, an optionally substituted carbonyl group, an optionally substituted alkoxycarbonyl group, an optionally-CH(R′″)(R′″COOH) wherein each R′″ independently C 1 -C 10  linear or branched alkyl chain, —OH, —SH or —NH 2  or an optionally substituted carbocyclic or heterocyclic non-aromatic ring; 
         i=0, 1, 2, 3; 
         j=0 or 1; 
         n is an integer from 1 to 1000, or an integer from 1 to 100, or an integer from 1 to 50, or an integer from 1 to 25, or an integer from 1 to 15, or preferably an integer from 1 to 10; 
         when n=1, then j=0; 
         when n>1 then j=1; 
         each R 2  and R 3  is independently H, a C1-C8 linear or branched or cyclic alkyl chain, an optionally substituted C 1 -C 20  alkyl group, an optionally substituted C 1 -C 10  alkyl group, a tertiary carbon group, a methyl group, a methoxy group, an optionally substituted aryl group, and optionally substituted alkoxy group, an optionally substituted carbonyl group, an optionally substituted alkoxycarbonyl group, or —CH(R′″)(R′″COOH); 
         R is a C 1 -C 24  linear or branched alkyl chain, alkenyl chain, or an isomerized structure or a mixture of isomerized (A) and (B): 
       
       
         
           
           
               
               
           
         
         wherein R a  is a C 1 -C 24  alkenyl linear or branched chain. 
       
     
     
         2 . The compound of  claim 1 , wherein:
 n=1;   j=0;   R is a mixture of isomerized structures of   
       
         
           
           
               
               
           
         
       
       and
 R d  is a C1-C24 linear or branched alkyl chain 
 
     
     
         3 . The compound of  claim 1 , wherein:
 [X] is   
       
         
           
           
               
               
           
         
       
       and the compound is represented by structural Formula II: 
       
         
           
           
               
               
           
         
         wherein: 
         each R 2 , R 3  independently is H, methyl, or a C 1 -C 8  linear or branched or cyclic alkyl chain, 
         R is a C 1 -C 24  linear or branched alkyl chain, an isomerized alkenyl chain or a mixture of isomerized alkenyl chains represented by: 
       
       
         
           
           
               
               
           
         
         wherein R d  is a linear or branched C 1 -C 24  alkyl chain; or 
         an isomerized structure or a mixture of isomerized (A) and (B) 
       
       
         
           
           
               
               
           
         
         wherein R a  is a C 1 -C 24  linear or branched alkenyl chain, an alkenyl chain portion of octenyl succinic anhydride (OSA); dodecenyl succinic anhydride (DDSA); octadecenyl succinic anhydride (ODSA); or polyisobutylene succinic anhydride (PIBSA) having a molecular weight between 300 and 1500. 
       
     
     
         4 . The compound of  claim 3 , wherein each R 2 , R 3  is H and j=1, wherein the compound structure is represented by Structural formula III: 
       
         
           
           
               
               
           
         
       
       wherein,
 R 1  is selected from the group consisting of 
 
       
         
           
           
               
               
           
         
         an isomerized alkyl acid chain or a mixture of isomerized alkyl acid chains as shown below 
       
       
         
           
           
               
               
           
         
       
     
     
         5 . The compound of  claim 4 , wherein i is 1 and compound is represented by Structural Formula IV 
       
         
           
           
               
               
           
         
       
     
     
         6 . The compound of  claim 5 , wherein R 1  is H, CH 3 , OCH 3 , or a linear or branched C 1 -C 9  alkyl chain. 
     
     
         7 . The compound of  claim 1  wherein, wherein n=1, j=0, is represented by the structural formula: 
       
         
           
           
               
               
           
         
         wherein [X] is 
       
       
         
           
           
               
               
           
         
         R is an isomerized alkenyl chain represented by 
       
       
         
           
           
               
               
           
         
       
       or mixtures thereof; and
 each R d  is a linear or branched C—C alkyl chain 
 
     
     
         8 . The compound of  claim 7 , wherein, R is isomerized alkenyl chain represented by 
       
         
           
           
               
               
           
         
         or their isomer mixtures (1)-(8); and 
         each R d  is a C 1 -C 24  alkyl chain. 
       
     
     
         9 . The compound of  claim 7  wherein n=1, j=0, and the compound is represented by: 
       
         
           
           
               
               
           
         
         wherein R d  is a linear or branched C 1 -C 24  alkyl chain; 
       
       an isomerized structure or a mixture of isomerized (A) and (B) 
       
         
           
           
               
               
           
         
         wherein R a  is a C 1 -C 24  linear or branched alkenyl chain, an alkenyl chain portion of octenyl succinic anhydride (OSA); dodecenyl succinic anhydride (DDSA); octadecenyl succinic anhydride (ODSA); or polyisobutylene succinic anhydride (PIBSA) having a molecular weight from 300 to 1500; and 
       
       R 1  is selected from the group consisting of 
       
         
           
           
               
               
           
         
         an isomerized alkyl acid chain or a mixture of isomerized alkyl acid chains as shown below: 
       
       
         
           
           
               
               
           
         
       
       and 
       wherein the substituted phenol is not phenol, 2,4-dimethyl phenol or resorcinol if R a  is an alkenyl chain portion of OSA, DDSA, ODSA, or PIBSA. 
     
     
         10 . The compound of  claim 9 , wherein
 i=1; and   R 1  is H, CH 3 , OCH 3 , or a linear or branched C 1 -C 12  alkyl chain.   
     
     
         11 . A mixture of a compound represented by following structural formulas: 
       
         
           
           
               
               
           
         
         wherein 
         each R 5  and R 6  is independently a H, methyl, or a C 1 -C 24  linear or branched or cyclic alkyl chain; 
         Each n and n′ is independently 1 to 15, preferably 4 to 10; 
         in particular, a compound containing the following isomer structures: 
       
       
         
           
           
               
               
           
         
         wherein each R 5 , R d  independently is a linear or branched C 1 -C 24  alkyl chain. 
       
     
     
         12 . A method of producing a compound having Structural Formula I: 
       
         
           
           
               
               
           
         
         wherein 
         X is 
       
       
         
           
           
               
               
           
         
         each R 1  is H, independently an optionally substituted C 1 -C 20  alkyl group, an optionally substituted C 1 -C 10  alkyl group, a tertiary carbon group, a methyl group, a methoxy group, an optionally substituted aryl group, and optionally substituted alkoxy group, an optionally substituted carbonyl group, an optionally substituted alkoxycarbonyl group, an optionally-CH(R′″)(R′″COOH) wherein each R′″ independently C 1 -C 10  linear or branched alkyl chain, —OH, —SH or —NH 2  or an optionally substituted carbocyclic or heterocyclic non-aromatic ring. 
         I=0, 1, 2, 3; 
         j=0 or 1; 
         n is an integer from 1 to 1000 or 1 to 100, 1 to 50 or 1 to 25, 1 to 15, or preferably 1 to 10, 
         when n=1, then j=0; 
         when n>1 then j=1; 
         each R 2  and R 3  is independently H, a C1-C8 linear or branched or cyclic alkyl chain, an optionally substituted C 1 -C 20  alkyl group, an optionally substituted C 1 -C 10  alkyl group, a tertiary carbon group, a methyl group, a methoxy group, an optionally substituted aryl group, and optionally substituted alkoxy group, an optionally substituted carbonyl group, an optionally substituted alkoxycarbonyl group, or —CH(R′″)(R′″COOH) 
         R is a C 1 -C 24  linear or branched alkyl chain, alkenyl chain, or an isomerized structure or a mixture of isomerized (A) and (B): 
       
       
         
           
           
               
               
           
         
         wherein R a  is a C 1 -C 24  alkenyl linear or branched chain, the method comprising: 
         (a) reacting X in a solvent with an aldehyde selected from the group of formaldehyde, acetaldehyde, valeraldehyde, butyraldehyde, isovalrealdehyde, 2-methyl butanal, benzaldehyde, cyclohexanecarbaldehyde, 3-methylcyclohexanecrabaldehyde, glyceraldehyde, glucose aldehyde, 
         (b) Reacting the product in (a) with an alkyl acyl chloride, an oleoyl chloride, or alkenyl succinic anhydride selected from the group of octenyl succinic anhydride (OSA), dodecenyl succinic anhydride (DDSA); octadecenyl succinic anhydride (ODSA); polyisobutylene succinic anhydride (PIBSA) having a molecular weight from 300 to 1500; 
         (c) Reacting the product of (b) with maleic anhydride if the reactant used in (b) is an oleoyl chloride, and then finally, 
         (d) Reacting the succinic anhydride group of product in (c) is reacting with a C 1 -C 24  linear or branched or cyclic alcohol. 
       
     
     
         13 . The method of  claim 12 , wherein the compound is represented by 
       
         
           
           
               
               
           
         
         wherein, 
         R is a C 1 -C 24  linear or branched alkyl chain, an isomerized alkenyl chain or a mixture of isomerized alkenyl chains represented by 
       
       
         
           
           
               
               
           
         
         wherein R d  is a linear or branched C 1 -C 24  alkyl chain; or 
         an isomerized structure or a mixture of isomerized (A) and (B) 
       
       
         
           
           
               
               
           
         
         wherein R a  is a C 1 -C 24  linear or branched alkenyl chain, an alkenyl chain portion of OSA, octenyl succinic anhydride; DDSA, dodecenyl succinic anhydride; ODSA, octadecenyl succinic anhydride; PIBSA, polyisobutylene succinic anhydride (low molecular weight, 300-1500 molecular weight, and 
         R 1  is selected from the group consisting of 
       
       
         
           
           
               
               
           
         
         n is an integer from 1 to 1000 or 1 to 100, 1 to 50 or 1 to 25, 1 to 15, or preferably to 10, 
         a method comprising: 
         (a) Reacting in a solvent at reflux a phenol having the following formula: 
       
       
         
           
           
               
               
           
         
       
       wherein R 1  is selected from the group consisting of 
       
         
           
           
               
               
           
         
         an isomerized alkyl acid chain or a mixture of isomerized alkyl acid chains as shown below 
       
       
         
           
           
               
               
           
         
         with 
         formaldehyde, 
         (b) The product in (a) is reacting with an oleoyl chloride or alkyl acyl chloride at ice temperature to room temperature for 1 hour to 24 hours, or an alkenyl succinic anhydride is selected from the group of OSA, octenyl succinic anhydride; DDSA, dodecenyl succinic anhydride; ODSA, octadecenyl succinic anhydride; PIBSA, polyisobutylene succinic anhydride (low molecular weight, 300-1500 molecular weight) at 80° C. to 150° C. for 1 to 24 hours, 
         (c) The product in (b) is reacting with maleic anhydride at 170° C.-210° C. for 1 hour to hours if the reactant used in (b) is an oleoyl chloride, and then finally 
         (d) The succinic anhydride group of product in (c) is reacting with a C 1 -C 24  linear or branched or cyclic alcohol at 80° C. to 150° C., if the reactant used in (b) is an oleoyl chloride. 
       
     
     
         14 . The method of  claim 13  wherein a substituted phenol is selected from the group of 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         preferably 
         phenol, ortho-cresol, a mixture of o-,m-, and p-cresol, 2-methoxy phenol, or a C 1 -C 12  linear or branched alkyl chain. 
       
     
     
         15 . The method of  claim 14  wherein the aldehydes is formaldehyde or acetaldehyde. 
     
     
         16 . The method of  claim 12  wherein a product comprises structural isomers if an alkenyl chain is attached to the substituted phenol. 
     
     
         17 . A method of making a compound in  claim 7  having the following a mixture of isomeric structures: 
       
         
           
           
               
               
           
         
         wherein [X] is 
       
       
         
           
           
               
               
           
         
         R is an isomerized alkenyl chain represented by 
       
       
         
           
           
               
               
           
         
         wherein R d  independently is a linear or branched C 1 -C 24  alkyl chain, the method comprising:
 a) reacting in a solvent or in bulk an oleic acid with a C 1 -C 24  linear or branched or cyclic alcohol, 
 b) the product in (a) is reacting with a maleic anhydride at 170° C.-210° C. for 1 hour to hours, and finally 
 c) c. the succinic anhydride group of product in (b) is reacting with an X—OH selected from a group of a substituted phenol, ethylene glycol, hexanediol, neopentyl glycol, diethanolamine, trimethylolpropane, glycerol, triethanolamine, pentaeryrthritol, di-pentaeryrthritol at 80° C. to 150° C. 
 
       
     
     
         18 . The method of  claim 17  having the following a mixture of isomeric structures: 
       
         
           
           
               
               
           
         
         wherein each R 5 , R d  independently is a linear or branched C 1 -C 24  alkyl chain, the method comprising:
 a) reacting in a solvent or in bulk an oleic acid with a C 1 -C 24  linear or branched or cyclic alcohol using an acidic catalyst selected from sulfuric acid, para-toluene sulfonic acid, solid phase catalysts, and phosphoric acid. 
 b) the product in (a) is reacting with a maleic anhydride at 170° C.-210° C. for 1 hour to hours, and finally 
 c) the succinic anhydride group of product in (b) is reacting with a C 1 -C 24  linear or branched or cyclic alcohol at 80° C. to 150° C. for 1 to 24 hours. 
 
       
     
     
         19 . A method of preventing corrosion in a corrodible material, comprising combining the corrodible material with a compound represented by the following structural formula: 
       
         
           
           
               
               
           
         
       
       wherein 
       X is 
       
         
           
           
               
               
           
         
       
       Each R 1  is H, independently an optionally substituted C 1 -C 20  alkyl group, an optionally substituted C 1 -C 10  alkyl group, a tertiary carbon group, a methyl group, a methoxy group, an optionally substituted aryl group, and optionally substituted alkoxy group, an optionally substituted carbonyl group, an optionally substituted alkoxycarbonyl group, an optionally-CH(R′″)(R′″COOH) wherein each R′″ independently C 1 -C 10  linear or branched alkyl chain, —OH, —SH or —NH 2  or an optionally substituted carbocyclic or heterocyclic non-aromatic ring. 
       i=0 or 1 or 2 or 3; 
       j=0 or 1; 
       n is an integer from 1 to 1000 or 1 to 100, 1 to 50 or 1 to 25, 1 to 15, or preferably 1 to 10,
 when n=1, then j=0; 
 when n>1 then j=1; 
 
       Each R 2 , R 3 , is H, independently a C1-C8 linear or branched or cyclic alkyl chain, independently an optionally substituted C 1 -C 20  alkyl group, an optionally substituted C 1 -C 10  alkyl group, a tertiary carbon group, a methyl group, a methoxy group, an optionally substituted aryl group, and optionally substituted alkoxy group, an optionally substituted carbonyl group, an optionally substituted alkoxycarbonyl group, an optionally-CH(R′″)(R′″COOH) 
       R is a C 1 -C 24  linear or branched alkyl chain, alkenyl chain, or an isomerized structure or a mixture of isomerized (A) and (B): 
       
         
           
           
               
               
           
         
       
       wherein R a  is a C 1 -C 24  alkenyl linear or branched chain. 
     
     
         20 . The method of  claim 19  wherein the corrodible material is a bio-oil or modified bio-oil, vegetable oil and/or animal fat, polyolesters, synthetic or bio poly alpha olefins (PAO), polyalkylene glycols (PAG), biobased esters like polyol esters and estolides, petroleum based Group I, II, III, IV, and V oil, or mixture thereof, lubricants, biolubricants, biobased lubricants, gasoline, kerosene, diesel, grease, and biodiesel oil, hydraulic oil, turbine oil, transformer oil, elevator oil, 2-stroke engine oil, engine oil, and water based paints, cements, metal surfaces of, iron, steel, copper, aluminum, and alloys; plastics, bioplastics, polyolefins, nylons, polyamides, elastomers, thermoplastic elastomers, natural and synthetic polymers and copolymers. 
     
     
         21 . A composition comprising:
 a) a compound according to  claim 1 ; and   b) a bio-oil or modified bio-oil, a vegetable oil and/or animal fat, a polyolester, a synthetic or bio poly alpha olefin (PAO), a polyalkylene glycols (PAG), a biobased ester like polyol ester and estolides, a petroleum based Group I, II, III, IV, and V oil, or mixture thereof; and   c) one or more of an antioxidant, a metal deactivator, rust inhibitor, copper corrosion inhibitor, viscosity index modifier, pour point depressant, a dispersing agent, a detergent, an extreme-pressure, a dye, a seal swell agent, a demulsifier, or an anti-foaming additive.   
     
     
         22 . The composition of  claim 21 , wherein the composition is an additive package comprising additives one or more of an antioxidant, a metal deactivator, rust inhibitor, copper corrosion inhibitor, viscosity index modifier, pour point depressant, dispersing agent, detergent, an extreme-pressure, a dye, a seal swell agent, a demulsifier, and an anti-foaming additive; each additive present is mixed into a carrier oil selected from a group of petroleum, bio-based, bio-oil to formulate a fluid including gasoline, diesel, biodiesel, a base stock oil selected from the group of a bio-oil, a biobased oil, petroleum oil, Group I, Group II, Group III, Group IV oil, Group V or mixture thereof or to a already formulated lubricating oil for enhancing further the fluid or lubricant performance. 
     
     
         23 . A process for the inhibition of the metal corrosion due to contact with the fluid which comprises incorporating into the fluid an effective corrosion inhibiting amount of a compound of Structure (I) of  claim 1 .