Composition and method for inhibiting polymerization and polymer growth

Abstract

A method for inhibiting the premature polymerization and the polymer growth of ethylenically unsaturated monomers is disclosed wherein the method comprises adding to said monomers an effective amount of at least one hydrogen donor or electron acceptor. In a preferred embodiment, the hydrogen donor or electron acceptor is used in combination with a stable nitroxyl free radical.

1 . A method for inhibiting the premature polymerization and the polymer growth of ethylenically unsaturated monomers comprising adding to said monomers an effective amount of at least one inhibitor that is an electron acceptor selected from the group consisting of quinones, quinone imines, quinone methides, and acetylenes.  
     
     
         2 . The method of  claim 1  wherein the inhibitor is of the structure  
       
         
           
           
               
               
           
         
       
       wherein 
 X and Y are independently selected from the group consisting of oxygen, NR 110 , and CR 124 R 125 ;  
 R 120 , R 121 , R 122 , and R 123  are independently selected from the group consisting of hydrogen, alkyl, aryl, cycloalkyl, heterocyclic, substituted alkyl, substituted aryl, OR 110 , NR 110 R 111 , SR 110 , NO, NO 2 , CN, COR 112 , and halogen, or R 120  and R 121  can be taken together and/or R 122  and R 123  can be taken together to form one or two ring structures, respectively, either of which can be of five to seven members;  
 R 124  and R 125  are independently selected from the group consisting of hydrogen, alkyl, aryl, cycloalkyl, heterocyclic, substituted alkyl, substituted aryl, OR 110 , NR 110 R 111 , SR 110 , NO 2 , NO, CN, COR 112 , halogen, and/or can be taken together to form a ring structure of five to seven members;  
 R 110  and R 111  are independently selected from the group consisting of hydrogen, alkyl, aryl, benzyl, cyclic, heterocyclic, substituted alkyl or aryl where the substituents are C, O, N, S, or P, and COR 102 , or R 110  and R 111  can be taken together to form a ring structure of five to seven members;  
 R 112  is R 102 , OR 102 , or NR 102 R 103 ; and  
 R 102  and R 103  are independently selected from the group consisting of hydrogen, alkyl, aryl, benzyl, cyclic, heterocyclic, and substituted alkyl or aryl where the substituents are C, O, N, S, or P, or R 102  and R 103  can be taken together to form a ring structure of five to seven members.  
 
     
     
         3 . The method of  claim 2  wherein X and Y are oxygen.  
     
     
         4 . The method of  claim 2  wherein X is oxygen and Y is CR 124 R 125 .  
     
     
         5 . The method of  claim 2  wherein X is oxygen and Y is NR 110 .  
     
     
         6 . The method of  claim 2  wherein X and Y are NR 110 .  
     
     
         7 . The method of  claim 2  wherein X is NR 110  and Y is CR 124 R 125 .  
     
     
         8 . The method of  claim 1  wherein the inhibitor is of the structure  
         R 126 —C≡C—R 127    
       wherein 
 R 126  and R 127  are independently selected from the group consisting of hydrogen, alkyl, aryl, cycloalkyl, heterocyclic, substituted alkyl, substituted aryl, OR 110 , NR 010 R 111 , SR 110 , NO 2 , NO, CN, COR 112 , and halogen;  
 R 110  and R 111  are independently selected from the group consisting of hydrogen, alkyl, aryl, benzyl, cyclic, heterocyclic, substituted alkyl or aryl where the substituents are C, O, N, S, or P, and COR 102  or R 110  and R 111  can be taken together to form a ring structure of five to seven members;  
 R 12  is R 102 , OR 102 , or NR 102 R 103 ; and  
 R 102  and R 103  are independently selected from the group consisting of hydrogen, alkyl, aryl, benzyl, cyclic, heterocyclic, and substituted alkyl or aryl where the substituents are C, O, N, S, or P, or R 102  and R 103  can be taken together to form a ring structure of five to seven members.  
 
     
     
         9 . The method of  claim 1  wherein the inhibitor is selected from the group consisting of phenylacetylene, 2,5-di-t-butyl-1,4-benzoquinone, 2,6-di-t-butyl-1,4-benzoquinone, 1,4-benzoquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 2,6-di-t-butyl-4-(phenylmethylene)-2,5-cyclohexadiene-1-one, 2,6-di-t-butyl-4-(phenylimino)-2,5-cyclohexadiene-1-one, and ethyl 3,4-bis-(3,5-di-t-butyl-4-one-2,5-cyclohexadienylidene)-hexane-1,6-dioate.  
     
     
         10 . A method for inhibiting the premature polymerization and the polymer growth of ethylenically unsaturated monomers comprising adding to said monomers 
 A) at least one first inhibitor that is an electron acceptor selected from the group consisting of quinones, quinone imines, quinone methides, and acetylenes, and    B) at least one second inhibitor having the following structural formula:                          wherein 
 R 1  and R 4  are independently selected from the group consisting of hydrogen, alkyl, and heteroatom-substituted alkyl;  
 R 2  and R 3  are independently selected from the group consisting of alkyl and heteroatom-substituted alkyl; and  
 X 1  and X 2  
 (1) are independently selected from the group consisting of halogen, cyano, amido, —S—C 6 H 5 , carbonyl, alkenyl, alkyl of 1 to 15 carbon atoms, COOR 7 , —S—COR 7 , and —OCOR 7 , wherein R 7  is alkyl or aryl, or  
 (2) taken together, form a ring structure with the nitrogen.  
 
   
     
     
         11 . The method of  claim 10  wherein the first inhibitor is of the structure  
       
         
           
           
               
               
           
         
       
       wherein 
 X and Y are independently selected from the group consisting of oxygen, NR 110 , and CR 124 R 125 ;  
 R 120 , R 121 , R 122 , and R 123  are independently selected from the group consisting of hydrogen, alkyl, aryl, cycloalkyl, heterocyclic, substituted alkyl, substituted aryl, OR 110 , NR 110 R 111 , SR 110 , NO, NO 2 , CN, COR 112 , and halogen, or R 120  and R 121  can be taken together and/or R 122  and R 123  can be taken together to form one or two ring structures, respectively, either of which can be of five to seven members;  
 R 124  and R 125  are independently selected from the group consisting of hydrogen, alkyl, aryl, cycloalkyl, heterocyclic, substituted alkyl, substituted aryl, OR 110 , NR 110 R 111 , SR 110 , NO 2 , NO, CN, COR 112 , halogen, and/or can be taken together to form a ring structure of five to seven members;  
 R 110  and R 111  are independently selected from the group consisting of hydrogen, alkyl, aryl, benzyl, cyclic, heterocyclic, substituted alkyl or aryl where the substituents are C, O, N, S, or P, and COR 102 , or R 110  and R 111  can be taken together to form a ring structure of five to seven members;  
 R 112  is R 102 , OR 102 , or NR 102 R 103 ; and  
 R 102  and R 103  are independently selected from the group consisting of hydrogen, alkyl, aryl, benzyl, cyclic, heterocyclic, and substituted alkyl or aryl where the substituents are C, O, N, S, or P, or R 102  and R 103  can be taken together to form a ring structure of five to seven members.  
 
     
     
         12 . The method of  claim 11  wherein X and Y are oxygen.  
     
     
         13 . The method of  claim 11  wherein X is oxygen and Y is CR 124 R 125 .  
     
     
         14 . The method of  claim 11  wherein X is oxygen and Y is NR 110 .  
     
     
         15 . The method of  claim 11  wherein X and Y are NR 110 .  
     
     
         16 . The method of  claim 11  wherein X is NR 110  and Y is CR 124 R 125 .  
     
     
         17 . The method of  claim 10  wherein the first inhibitor is of the structure  
         R 126 —C≡C—R 127    
       wherein 
 R 126  and R 127  are independently selected from the group consisting of hydrogen, alkyl, aryl, cycloalkyl, heterocyclic, substituted alkyl, substituted aryl, OR 110 , NR 110 , R 111 , SR 110 , NO 2 , NO, CN, COR 112 , and halogen;  
 R 110  and R 111  are independently selected from the group consisting of hydrogen, alkyl, aryl, benzyl, cyclic, heterocyclic, substituted alkyl or aryl where the substituents are C, O, N, S, or P, and COR 102  or R 110  and R 111  can be taken together to form a ring structure of five to seven members;  
 R 112  is R 102 , OR 102 , or NR 102 R 103 ; and  
 R 102  and R 103  are independently selected from the group consisting of hydrogen, alkyl, aryl, benzyl, cyclic, heterocyclic, and substituted alkyl or aryl where the substituents are C, O, N, S, or P, or R 102  and R 103  can be taken together to form a ring structure of five to seven members.  
 
     
     
         18 . The method of  claim 10  wherein the first inhibitor is selected from the group consisting of phenylacetylene, 2,5-di-t-butyl-1,4-benzoquinone, 2,6-di-t-butyl-1,4-benzoquinone, 1,4-benzoquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 2,6-di-t-butyl-4-(phenylmethylene)-2,5-cyclohexadiene-1-one, 2,6-di-t-butyl-4-(phenylimino)-2,5-cyclohexadiene-1-one, and ethyl 3,4-bis-(3,5-di-t-butyl-4-one-2,5-cyclohexadienylidene)-hexane-1,6-dioate.  
     
     
         19 . The method of  claim 10  wherein the second inhibitor is of the structure  
       
         
           
           
               
               
           
         
       
       wherein R 1  and R 4  are independently selected from the group consisting of hydrogen, alkyl, and heteroatom-substituted alkyl and R 2  and R 3  are independently selected from the group consisting of alkyl and heteroatom-substituted alkyl, and the  
       
         
           
           
               
               
           
         
       
       portion represents the atoms necessary to form a five-, six-, or seven-membered heterocyclic ring.  
     
     
         20 . The method of  claim 19  wherein the second inhibitor comprises one or more nitroxyls selected from the group consisting of: 
 N,N-di-tert-butylnitroxide;    N,N-di-tert-amylnitroxide;    N-tert-butyl-2-methyl-1-phenyl-propylnitroxide;    N-tert-butyl-1-diethylphosphono-2,2-dimethylpropylnitroxide;    2,2,6,6-tetramethyl-piperidinyloxy;    4-amino-2,2,6,6-tetramethyl-piperidinyloxy;    4-hydroxy-2,2,6,6-tetramethyl-piperidinyloxy;    4-oxo-2,2,6,6-tetramethyl-piperidinyloxy;    4-dimethylamino-2,2,6,6-tetramethyl-piperidinyloxy;    4-ethanoyloxy-2,2,6,6-tetramethyl-piperidinyloxy;    2,2,5,5-tetramethylpyrrolidinyloxy;    3-amino-2,2,5,5-tetramethylpyrrolidinyloxy;    2,2,4,4-tetramethyl-1-oxa-3-azacyclopentyl-3-oxy;    2,2,4,4-tetramethyl-1-oxa-3-pyrrolinyl-1-oxy-3-carboxylic acid;    2,2,3,3,5,5,6,6-octamethyl-1,4-diazacyclohexyl-1,4-dioxy;    4-bromo-2,2,6,6-tetramethyl-piperidinyloxy;    4-chloro-2,2,6,6-tetramethyl-piperidinyloxy;    4-iodo-2,2,6,6-tetramethyl-piperidinyloxy;    4-fluoro-2,2,6,6-tetramethyl-piperidinyloxy;    4-cyano-2,2,6,6-tetramethyl-piperidinyloxy;    4-carboxy-2,2,6,6-tetramethyl-piperidinyloxy;    4-carbomethoxy-2,2,6,6-tetramethyl-piperidinyloxy;    4-carbethoxy-2,2,6,6-tetramethyl-piperidinyloxy;    4-cyano-4-hydroxy-2,2,6,6-tetramethyl-piperidinyloxy;    4-methyl-2,2,6,6-tetramethyl-piperidinyloxy;    4-carbethoxy-4-hydroxy-2,2,6,6-tetramethyl-piperidinyloxy;    4-hydroxy-4-(1-hydroxypropyl)-2,2,6,6-tetramethyl-piperidinyloxy;    4-methyl-2,2,6,6-tetramethyl-1,2,5,6-tetrahydropyridine-1-oxyl;    4-carboxy-2,2,6,6-tetramethyl-1,2,5,6-tetrahydropyridine-1-oxyl;    4-carbomethoxy-2,2,6,6-tetramethyl-1,2,5,6-tetrahydropyridine-1-oxyl;    4-carbethoxy-2,2,6,6-tetramethyl-1,2,5,6-tetrahydropyridine-1-oxyl;    4-amino-2,2,6,6-tetramethyl-1,2,5,6-tetrahydropyridine-1-oxyl;    4-amido-2,2,6,6-tetramethyl-1,2,5,6-tetrahydropyridine-1-oxyl;    3,4-diketo-2,2,5,5-tetramethylpyrrolidinyloxy;    3-keto-4-oximino-2,2,5,5-tetramethylpyrrolidinyloxy;    3-keto-4-benzylidine-2,2,5,5-tetramethylpyrrolidinyloxy;    3-keto-4,4-dibromo-2,2,5,5-tetramethylpyrrolidinyloxy;    2,2,3,3,5,5-hexamethylpyrrolidinyloxy;    3-carboximido-2,2,5,5-tetramethylpyrrolidinyloxy;    3-oximino-2,2,5,5-tetramethylpyrrolidinyloxy;    3-hydroxy-2,2,5,5-tetramethylpyrrolidinyloxy;    3-cyano-3-hydroxy-2,2,5,5-tetramethylpyrrolidinyloxy;    3-carbomethoxy-3-hydroxy-2,2,5,5-tetramethylpyrrolidinyloxy;    3-carbethoxy-3-hydroxy-2,2,5,5-tetramethylpyrrolidinyloxy;    2,2,5,5-tetramethyl-3-carboxamido-2,5-dihydropyrrole-1-oxyl;    2,2,5,5-tetramethyl-3-amino-2,5-dihydropyrrole-1-oxyl;    2,2,5,5-tetramethyl-3-carbethoxy-2,5-dihydropyrrole-1-oxyl;    2,2,5,5-tetramethyl-3-cyano-2,5-dihydropyrrole-1-oxyl;    bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)succinate;    bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)adipate;    bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;    bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)n-butylmalonate;    bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)phthalate;    bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)isophthalate;    bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)terephthalate;    bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)hexahydroterephthalate;    N,N′-bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)adipamide;    N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-caprolactam;    N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-dodecylsuccinimide;    2,4,6-tris-[N-butyl-N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)]-s-triazine; and    4,4′-ethylenebis(1-oxyl-2,2,6,6-tetramethylpiperazin-3-one).