Explosive emulsion compositions containing modified copolymers of isoprene, butadiene, and/or styrene

Abstract

The invention provides explosive emulsion compositions which include polymers of conjugated dienes and/or aryl-substituted olefins which have been hydrogenated, functionalized, and optionally modified. The explosive emulsion compositions include a copolymer of two different conjugated dienes. The polymers may be selectively hydrogenated to produce polymers which have highly controlled amounts of unsaturation, permitting highly selective functionalization.

What is claimed is:  
     
         1 . An explosive emulsion composition comprising: a copolymer of a first conjugated diene and a second conjugated diene, wherein: 
 said first conjugated diene comprises at least one relatively more substituted conjugated diene having at least five carbon atoms and the formula:                          wherein R 1 —R 6  are each independently hydrogen or a hydrocarbyl group, provided that at least one of R 1 —R 6  is a hydrocarbyl group, provided that after polymerization, the unsaturation of the polymerized conjugated diene of formula (1) has the formula:                          wherein R I , R II , R III  and R IV  are each independently hydrogen or a hydrocarbyl group, provided that either both R I  and R II  are hydrocarbyl groups or both R III  and R IV  are hydrocarbyl groups; and    said second conjugated diene comprises at least one relatively less substituted conjugated diene different from the first conjugated diene and having at least four carbon atoms and the formula:                          wherein R 7 -R 12  are each independently hydrogen or a hydrocarbyl group, provided that after polymerization, the unsaturation of the polymerized conjugated diene of formula (3) has the formula:                          wherein R V , R VI , R VII  and R VIII  are each independently hydrogen or a hydrocarbyl group, provided that one of R V  or R VI  is hydrogen, one of R VII  or R VIII  is hydrogen, and at least one of R V , R VI , R VII  and R VIII  is a hydrocarbyl group; and    wherein said copolymer has been functionalized by a method comprising:    selectively hydrogenating said copolymer to provide a selectively hydrogenated copolymer; and    functionalizing said selectively hydrogenated copolymer to provide a functionalized copolymer having at least one polar functional group.    
     
     
         2 . The explosive emulsion composition of  claim 1 , wherein said copolymer is in an amount in the range of from 0.05 to 2.0% by weight based on the total weight of explosive emulsion composition.  
     
     
         3 . The explosive emulsion composition of  claim 1 , wherein said copolymer is in an amount in the range of from 0.1 to 1.5% by weight based on the total weight of explosive emulsion composition.  
     
     
         4 . The explosive emulsion composition of  claim 1 , wherein said copolymer is in an amount in the range of from 0.1 to 1% by weight based on the total weight of explosive emulsion composition.  
     
     
         5 . The explosive emulsion composition of  claim 1 , further comprising oxidizer in an amount in the range of 40 to 95% by weight based on the total weight of the explosive emulsion composition.  
     
     
         6 . The explosive emulsion composition of  claim 5 , wherein said oxidizer is ammonium nitrate.  
     
     
         7 . The explosive emulsion composition of  claim 1 , further comprising water in an amount in the range of 5 to 50% by weight based on the total weight of the explosive emulsion composition.  
     
     
         8 . The explosive emulsion composition of  claim 1 , further comprising oil in an amount in the range of 4 to 30% by weight based on the total weight of the explosive emulsion composition.  
     
     
         9 . The explosive emulsion composition of  claim 1 , wherein said first and second conjugated dienes are polymerized as a block copolymer comprising at least two alternating blocks:  
       (I) x -(B) y  or (B) y —(I) x    
       wherein: 
 the block (I) comprises at least one polymerized conjugated diene of formula (1);  
 the block (B) comprises at least one polymerized conjugated diene of formula (3);  
 x is the number of polymerized monomer units in block (I) and is at least 1, and y is the number of polymerized monomer units in block (B) and is at least 25.  
 
     
     
         10 . The explosive emulsion composition of  claim 1 , wherein said first conjugated diene is included in said polymer in an amount of from 1% to about 25% wt.; and said second conjugated diene is included in said polymer in an amount of from 75% wt. to 99% wt.  
     
     
         11 . The explosive emulsion composition of  claim 1 , wherein after the selectively hydrogenating step, the Iodine Number for residual unsaturation of formula (2) is from 50% to 100% of the Iodine Number prior to the selectively hydrogenating step.  
     
     
         12 . The explosive emulsion composition of  claim 1 , wherein after the selectively hydrogenating step, the Iodine Number for residual unsaturation of formula (4) is from 0% to 10% of Iodine Number prior to the selectively hydrogenating step.  
     
     
         13 . The explosive emulsion composition of  claim 1 , wherein the conjugated diene of formula (1) comprises isoprene and the conjugated diene of formula (3) comprises 1,3-butadiene.  
     
     
         14 . The explosive emulsion composition of  claim 13 , wherein each of the (B) blocks has from 30% to 90% of 1,2-subunits.  
     
     
         15 . The explosive emulsion composition of  claim 1 , wherein said functionalizing step provides a functionalized polymer having at least one functional group selected from the group consisting of halogen groups, hydroxyl groups, epoxy groups, sulfonic acid groups, mercapto groups, carboxylic acid derivative groups, and mixtures thereof.  
     
     
         16 . The explosive emulsion composition of  claim 15 , wherein said carboxylic acid derivative groups are derived from maleic anhydride.  
     
     
         17 . The explosive emulsion composition of  claim 1 , wherein said functionalized copolymer is modified by reaction with a Lewis base selected from the group consisting of a monoamine, polyamine, polyhydroxy compound, reactive polyether, or a combination thereof.  
     
     
         18 . The explosive emulsion composition of  claim 17 , wherein said polyamine comprises an aminopropylmorpholine.  
     
     
         19 . An explosive emulsion composition comprising: 
 a copolymer of a first conjugated diene, a second conjugated diene and an aryl-substituted olefin, wherein: 
 said first conjugated diene comprises at least one relatively more substituted conjugated diene having at least five carbon atoms and the formula:  
                     
 wherein R 1 -R 6  are each independently hydrogen or a hydrocarbyl group, provided that at least one of R 1 -R 6  is a hydrocarbyl group, provided that after polymerization, the unsaturation of the polymerized conjugated diene of formula (1) has the formula:  
                     
 wherein R I , R II , R III  and R IV  are each independently hydrogen or a hydrocarbyl group, provided that either both R I  and R II  are hydrocarbyl groups or both R III  and R IV  are hydrocarbyl groups; and  
 said second conjugated diene comprises at least one relatively less substituted conjugated diene different from the first conjugated diene and having at least four carbon atoms and the formula:  
                     
 wherein R 7 -R 12  are each independently hydrogen or a hydrocarbyl group, provided that after polymerization, the unsaturation of the polymerized conjugated diene of formula (3) has the formula:  
                     
 wherein R V , R VI , R VII  and R VIII  are each independently hydrogen or a hydrocarbyl group, provided that one of R V  or R VI  is hydrogen, one of R VII  or R VIII  is hydrogen, and at least one of R V , R VI , R VII  and R VIII  is a hydrocarbyl group; and  
 wherein said copolymer has been functionalized by a method comprising: 
 selectively hydrogenating said copolymer to provide a selectively hydrogenated copolymer; and  
 functionalizing said selectively hydrogenated copolymer to provide a functionalized copolymer having at least one polar functional group.  
 
   
     
     
         20 . The explosive emulsion composition of  claim 19 , wherein said aryl-substituted olefin is selected from the group consisting of styrene, alkylated styrene, vinyl naphthalene and alkylated vinyl naphthalene.  
     
     
         21 . The explosive emulsion composition of  claim 20 , wherein said aryl-substituted olefin is styrene.  
     
     
         22 . The explosive emulsion composition of  claim 19 , wherein said functionalizing step provides a functionalized polymer having at least one functional group selected from the group consisting of halogen groups, hydroxyl groups, epoxy groups, sulfonic acid groups, mercapto groups, carboxylic acid derivative groups, and mixtures thereof.  
     
     
         23 . The explosive emulsion composition of  claim 19 , wherein said carboxylic acid derivative groups comprise maleic anhydride.  
     
     
         24 . The explosive emulsion composition of  claim 19 , wherein said first and second conjugated dienes are polymerized as a block copolymer comprising at least two alternating blocks:  
       (I) x -(B) y  or (B) y -(I) x    
       wherein: 
 the block (I) comprises at least one polymerized conjugated diene of formula (1);  
 the block (B) comprises at least one polymerized conjugated diene of formula (3);  
 x is the number of polymerized monomer units in block (I) and is at least 1, and y is the number of polymerized monomer units in block (B) and is at least 25.  
 
     
     
         25 . The explosive emulsion composition of  claim 24 , wherein said block (I) and/or block (B) comprises the aryl-substituted olefin incorporated randomly or as block.