Polyamine-based corrosion inhibitors

Abstract

Compounds having N-oxide, quaternary ammonium, and/or betaine functionality according to formulas (1)-(4) are effective corrosion inhibitors, suitable for use in any of a variety of applications such as automotive cooling systems, heating boilers, drilling of oil wells, and the handling, transportation and storage of crude petroleum and various petroleum fractions. The groups R 1 -R 5 may be certain hydrocarbyl groups. In formulas (1) and (3), R 3 may also be (CH 2 ) p —COO − in which p is either 1 or 2, and R 2 may also be (CH 2 ) p —COO − in formulas (3) and (4). In the compounds of formulas (1) and (2), R 2 may also be a polyhydroxyalkyl group of formula (A), shown below.

1 . A compound according to formula (1)  
       
         
           
           
               
               
           
         
       
       wherein R 1  is selected from the group consisting of C 4 -C 18  branched alkyl, linear alkyl, alkenyl, cycloalkyl, aryl, alkaryl, and aralkyl; R 2  is selected from the group consisting of C 1 -C 8  alkyl, alkenyl, cycloalkyl, aryl, alkaryl, aralkyl, and moieties of formula (A)  
       
         
           
           
               
               
           
         
       
       R 3  is C 1 -C 8  alkyl, alkenyl, cycloalkyl, aryl, alkaryl, or (CH 2 ) p —COO −  in which p is either 1 or 2; n is an integer from 2 to 14; m is an integer from 0 to 2; R 4  is H, α-D-glucopyranosyl, β-D-pyranosyl, or β-D-galactopyranosyl; and X −  is Cl − , Br − , I − , OH − , CH 3 COO − , 1/2 SO 4   −2 , or 1/3 PO 4   −3 , provided that the number of X −  moieties in formula (1) is reduced by one for each R 3  that is (CH 2 ) p —COO − ; further provided that R 1  is not linear-alkyl when R 3  is not (CH 2 ) p —COO − .  
     
     
         2 . The compound of  claim 1 , wherein R 1  is a moiety of formula (A).  
     
     
         3 . The compound of  claim 1 , wherein R 1  is dodecyl.  
     
     
         4 . The compound of  claim 1 , wherein R 1  is cocoalkyl.  
     
     
         5 . The compound of  claim 1 , wherein R 1  is tallow.  
     
     
         6 . The compound of  claim 1 , wherein R 2  is 1-deoxyglucityl.  
     
     
         7 . The compound of  claim 1 , wherein R 2  is methyl or ethyl.  
     
     
         8 . The compound of  claim 1 , wherein R 3  is (CH 2 ) p —COO − .  
     
     
         9 . The compound of  claim 1 , wherein n is 2 or 6.  
     
     
         10 . A compound according to formula (2)  
       
         
           
           
               
               
           
         
       
       wherein R 1  is selected from the group consisting of C 4 -C 18  branched alkyl, linear alkyl, alkenyl, cycloalkyl, aryl, alkaryl, and aralkyl; R 2  is selected from the group consisting of C 1 -C 8  alkyl, alkenyl, cycloalkyl, aryl, alkaryl, aralkyl, and moieties of formula (A)  
       
         
           
           
               
               
           
         
       
       n is an integer from 2 to 14; m is an integer from 0 to 2; and R 4  is H, α-D-glucopyranosyl, β-D-pyranosyl, or β-D-galactopyranosyl.  
     
     
         11 . The compound of  claim 10 , wherein R 1  is dodecyl.  
     
     
         12 . The compound of  claim 10 , wherein R 1  is cocoalkyl.  
     
     
         13 . The compound of  claim 10 , wherein R 1  is tallow.  
     
     
         14 . The compound of  claim 10 , wherein R 2  is methyl or ethyl.  
     
     
         15 . The compound of  claim 10 , wherein R 2  is a moiety of formula (A).  
     
     
         16 . The compound of  claim 10 , wherein R 2  is 1-deoxyglucityl.  
     
     
         17 . The compound of  claim 16 , wherein R 1  is selected from the group consisting of butyl, hexyl, octyl, and dodecyl.  
     
     
         18 . The compound of  claim 10 , wherein n is 2 or 6.  
     
     
         19 . A compound according to formula (3)  
       
         
           
           
               
               
           
         
       
       wherein R 1  is C 3 -C 12  branched alkyl, linear alkyl, alkenyl, cycloalkyl, or aryl-substituted branched or linear alkyl; R 2  and R 3  are each individually selected from the group consisting of C 1 -C 4  alkyl, benzyl, C 3 -C 5  alkenyl, and (CH 2 ) p —COO −  in which p is either 1 or 2, provided that not both of R 2  and R 3  are (CH 2 ) p —COO − ; R 4  and R 5  are chosen independently from C 2 -C 6  alkylene; n is an integer from 0 to 4; and X −  is Cl − , Br − , I − , OH − , CH 3 COO − , 1/2 SO 4   −2 , or 1/3 PO 4   −3 , provided that the number of X moieties in formula (3) is reduced by one for each R 3  that is (CH 2 ) p —COO − ; further provided that, if n is 0 and R 4  is (CH 2 ) 2 , then either R 1  is not linear alkyl or R 3  is (CH 2 ) p —COO − , or both.  
     
     
         20 . The compound of  claim 19 , wherein R 1  is branched C 3 -C 12  alkyl.  
     
     
         21 . The compound of  claim 19 , wherein R 3  is (CH 2 ) p —COO − .  
     
     
         22 . The compound of  claim 19 , wherein R 4  and R 5  are both (CH 2 ) 2 .  
     
     
         23 . The compound of  claim 19 , wherein R 4  and R 5  are both (CH 2 ) 3 .  
     
     
         24 . The compound of  claim 19 , wherein R 4  and R 5  are both (CH 2 ) 6 .  
     
     
         25 . The compound of  claim 19 , wherein R 4  and R 5  are both (CH 2 ) 3 CH(CH 3 )CH 2 .  
     
     
         26 . A compound according to formula (4)  
       
         
           
           
               
               
           
         
       
       wherein R 1  is C 3 -C 12  branched alkyl, linear alkyl, alkenyl, cycloalkyl, or aralkyl; R 2  is selected from the group consisting of C 1 -C 4  alkyl, benzyl, C 3 -C 5  alkenyl, and (CH 2 ) p —COO −  in which p is either 1 or 2; R 4  and R 5  are chosen independently from C 2 -C 6  alkylene; and n is an integer from 0 to 4; provided that n is ≧1 if R 2  is not (CH 2 ) p —COO − .  
     
     
         27 . The compound of  claim 26 , wherein R 4  and R 5  are both (CH 2 ) 2 .  
     
     
         28 . The compound of  claim 26 , wherein R 4  and R 5  are both (CH 2 ) 3 .  
     
     
         29 . The compound of  claim 26 , wherein R 4  and R 5  are both (CH 2 ) 6 .  
     
     
         30 . The compound of  claim 26 , wherein R 4  and R 5  are both (CH 2 ) 3 CH(CH 3 )CH 2 .  
     
     
         31 . A method of reducing corrosion of a metal surface, comprising contacting the metal surface with a corrosive medium comprising a corrosion inhibitor according to any of: 
 a) formula (1):                          wherein R 1  is selected from the group consisting of C 4 -C 18  branched alkyl, linear alkyl, alkenyl, cycloalkyl, aryl, alkaryl, and aralkyl; R 2  is selected from the group consisting of C 1- C 8  alkyl, alkenyl, cycloalkyl, aryl, alkaryl, aralkyl, and moieties of formula (A)                          R 3  is C 1 -C 8  alkyl, alkenyl, cycloalkyl, aryl, alkaryl, or (CH 2 ) p —COO −  in which p is either 1 or 2; n is an integer from 2 to 14; m is an integer from 0 to 2; R 4  is H, α-D-glucopyranosyl, β-D-pyranosyl, or β-D-galactopyranosyl; and X −  is Cl − , Br − , I − , OH − , CH 3 COO − , 1/2 SO 4   −2 , or 1/3 PO 4   −3 , provided that the number of X −  moieties in formula (1) is reduced by one for each R 3  that is (CH 2 ) p —COO − ; further provided that R 1  is not linear alkyl when R 3  is not (CH 2 ) p —COO − ;    b) formula (2):                          wherein R 1  is selected from the group consisting of C 4 -C 18  branched alkyl, linear alkyl, alkenyl, cycloalkyl, aryl, alkaryl, and aralkyl; R 2  is selected from the group consisting of C1-C8 alkyl, alkenyl, cycloalkyl, aryl, alkaryl, aralkyl, and moieties of formula (A)                          n is an integer from 2 to 14; m is an integer from 0 to 2; and R 4  is H, α-D-glucopyranosyl, β-D-pyranosyl, or β-D-galactopyranosyl;    c) formula (3):                          wherein R 1  is C 3 -C 12  branched alkyl, linear alkyl, alkenyl, cycloalkyl, or aryl-substituted branched or linear alkyl; R 2  and R 3  are each individually selected from the group consisting of C 1 -C 4  alkyl, benzyl, C 3 -C 5  alkenyl, and (CH 2 ) p —COO −  in which p is either 1 or 2, provided that not both of R 2  and R 3  are (CH 2 ) p —COO − ; R 4  and R 5  are chosen independently from C 2 -C 6  alkylene; n is an integer from 0 to 4; and X −  is Cl − , Br − , I − , OH − , CH 3 COO − , 1/2 SO 4   −2 , or 1/3 PO 4   −3 , provided that the number of X −  moieties in formula (3) is reduced by one for each R 3  that is (CH 2 ) p —COO − ; further provided that, if n is 0 and R 4  is (CH 2 ) 2 , then either R 1  is not linear alkyl or R 3  is (CH 2 ) p —COO − , or both; and    d) formula (4):                          wherein R 1  is C 3 -C 12  branched alkyl, linear alkyl, alkenyl, cycloalkyl, or aralkyl; R 2  is selected from the group consisting of C 1 -C 4  alkyl, benzyl, C 3 -C 5  alkenyl, and (CH 2 ) p —COO −  in which p is either 1 or 2; R 4  and R 5  are chosen independently from C 2 -C 6  alkylene; and n is an integer from 0 to 4; provided that n is ≧1 if R 2  is not (CH 2 ) p —COO − .