Water-soluble phenylenediamine compositions and methods for stabilizing ethylenically unsaturated compounds and monomers

Abstract

Compositions and methods for inhibiting polymerization of ethylenically unsaturated monomers are provided. The compositions include a water-soluble phenylenediamine composition.

What is claimed is:  
     
         1 . A composition comprising one or more compounds of the following formula:  
       
         
           
           
               
               
           
         
         wherein at least one of R 1 , R 2 , and R 3  is  
         
           
             
             
                 
                 
             
           
         
         R 1 , R 2  and R 3  are independently selected from H, alkyl, hydroxyalkyl, —O—R 6 , —S—R 6 , —C(O)R 6 , —C(S)R 6 , —N—(R 7 )(R 8 ), aryl, and  
         
           
             
             
                 
                 
             
           
         
         R 5  is selected from the group consisting of H, alkyl, hydroxyalkyl, O, S, —O—R 6 , —S—R 6 , —N—(R 7 )(R 8 ), and aryl;  
         Z comprises one or more substituents selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heterocyclo, —CN, —NO 2 , —O—R 6 , —S—R 6 , and —N(R 7 )(R 8 ); and  
         R 6 , R 7  and R 8  are independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl and heterocyclo.  
       
     
     
         2 . The composition of  claim 1 , wherein at least one of said compounds corresponds to the following formula:  
       
         
           
           
               
               
           
         
       
     
     
         3 . The composition of  claim 1 , wherein said composition is water-soluble.  
     
     
         4 . The composition of  claim 1 , further comprising a solvent.  
     
     
         5 . The composition of  claim 1 , further comprising a solvent selected from the group consisting of water and an organic solvent.  
     
     
         6 . The composition of  claim 1 , further comprising a second polymerization inhibitor composition.  
     
     
         7 . The composition of  claim 6 , wherein said second polymerization inhibitor composition is a phenylenediamine of the following formula:  
       
         
           
           
               
               
           
         
       
       wherein R a , R b  and R c  are independently selected from the group consisting of H, C 1 -C 18  alkyl, hydroxyalkyl, —O—R 6 , —S—R 6 , —N—(R 7 )(R 8 ), and aryl.  
     
     
         8 . The composition of  claim 1 , wherein said composition comprises a compound of the following formula:  
       
         
           
           
               
               
           
         
       
     
     
         9 . The composition of  claim 1 , wherein said composition comprises at least one of the following compounds:  
       
         
           
           
               
               
           
         
       
     
     
         10 . The composition of  claim 1 , wherein said composition comprises at least one of the following compounds:  
       
         
           
           
               
               
           
         
       
     
     
         11 . A composition resistant to polymerization comprising: 
 (a) an ethylenically unsaturated monomer, and    (b) one or more water-soluble compounds of the following formula:                          wherein at least one of R 1 , R 2 , and R 3  is                          R 1 , R 2  and R 3  are independently selected from H, C 1 -C 18  alkyl, hydroxyalkyl, —O—R 6 , —S—R 6 , —N—(R 7 )(R 8 ), aryl, and                          R 5  is selected from the group consisting of H, alkyl, hydroxyalkyl, —O—R 6 , —S—R 6 , —N—(R 7 )(R 8 ), and aryl;    Z comprises one or more substituents selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heterocyclo, —CN, —NO 2 , —O—R 6 , —S—R 6 , and —N(R 7 )(R 8 );    R 6 , R 7  and R 8  are independently selected form the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl and heterocyclo; and wherein    said composition is water-soluble.    
     
     
         12 . The composition of  claim 11 , further comprising a solvent.  
     
     
         13 . A method of preparing a water-soluble phenylenediamine composition comprising the step of reacting a phenylenediamine compound of the following formula:  
       
         
           
           
               
               
           
         
       
       wherein at least one of R 1 , R 2  and R 3  is H and 
 R 1 , R 2  and R 3  are independently selected from the group consisting of, alkyl, hydroxyalkyl, —O—R 6 , —S—R 6 , —C(O)R 6 , —C(S)R 6 , —N—(R 7 )(R 8 ), and aryl;  
 Z comprises one or more substituents selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heterocyclo, —CN, —NO 2 , —O—R 6 , —S—R 6 , and —N(R 7 )(R 8 ); and  
 R 6 , R 7  and R 8  are independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl and heterocyclo,  
 with a heterocyclic compound of the following formula:  
                     
 wherein R 5  is selected from the group consisting of H, alkyl, hydroxyalkyl, —O—R 6 , —S—R 6 , —N—(R 7 )(R 8 ), and aryl.  
 
     
     
         14 . A method of preparing a water-soluble phenylenediamine composition comprising the step of reacting 1,4-phenylenediamine with a heterocyclic compound of the following formula:  
       
         
           
           
               
               
           
         
         wherein R 5  is selected from the group consisting of H, alkyl, hydroxyalkyl, —O—R 6 , —S—R 6 , —N—(R 7 )(R 8 ), and aryl.  
       
     
     
         15 . The method of  claim 14 , wherein said heterocyclic compound comprises a member selected from the group consisting of propylene oxide and butylene oxide.  
     
     
         16 . The method of  claim 14 , wherein said water-soluble phenylenediamine retains at least one unsubstituted “—NH” group.  
     
     
         17 . A method of reducing or inhibiting fouling and deposit formation during hydrocarbon processing comprising the step of administering to a hydrocarbon stream at or upstream of a location where said fouling and/or said deposit formation may occur an effective amount of one or more water-soluble compounds of the following formula:  
       
         
           
           
               
               
           
         
         wherein at least one of R 1 , R 2 , and R 3  is  
         
           
             
             
                 
                 
             
           
         
         R 1 , R 2  and R 3  are independently selected from H, C 1 -C 18  alkyl, hydroxyalkyl, —O—R 6 , —S—R 6 , —N—(R 7 )(R 8 ), aryl, and  
         
           
             
             
                 
                 
             
           
         
         R 5  is selected from the group consisting of H, alkyl, hydroxyalkyl, —O—R 6 , —S—R 6 , —N—(R 7 )(R 8 ), and aryl;  
         Z comprises one or more substituents selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heterocyclo, —CN, —NO 2 , —O—R 6 , —S—R 6 , and —N(R 7 )(R 8 );  
         R 6 , R 7  and R 8  are independently selected form the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl and heterocyclo; and wherein  
         said composition is water-soluble.  
       
     
     
         18 . The method of  claim 17 , further comprising the step of mixing said water-soluble compounds with a solvent prior to said administering.  
     
     
         19 . A reaction product of a phenylenediamine compound of the following formula:  
       
         
           
           
               
               
           
         
         wherein at least one of R 1 , R 2  and R 3  is H;  
         R 1 , R 2  and R 3  are independently selected from the group consisting of, alkyl, hydroxyalkyl, —O—R 6 , —S—R 6 , —C(O)R 6 , —C(S)R 6 , —N—(R 7 )(R 8 ), and aryl;  
         Z comprises one or more substituents selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heterocyclo, —CN, —NO 2 , —O—R 6 , —S—R 6 , and —N(R 7 )(R 8 ); and  
         R 6 , R 7  and R 8  are independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl and heterocyclo,  
         with a heterocylic compound of the following formula:  
         
           
             
             
                 
                 
             
           
         
         wherein R 5  is selected from the group consisting of H, alkyl, hydroxyalkyl, —O—R 6 , —S—R 6 , —N—(R 7 )(R 8 ), and aryl.  
       
     
     
         20 . The reaction product of  claim 19 , wherein said phenylenediamine compound is 1,4-phenylenediamine.  
     
     
         21 . The product of  claim 19 , wherein said product retains at least one unsubstituted “—NH” group.