Chain extended functionalized initiators and methods of preparing and using the same

Abstract

The present invention provides protected functionalized polymerization initiators having less than one molar equivalent chain extension agent introduced therein to provide hydrocarbon solubility.

1 . A polymerization initiator comprising a compound of the formula  
       
         
           
           
               
               
           
         
       
       wherein: 
 M is an alkali metal selected from the group consisting of lithium, sodium and potassium;  
 Q is a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more conjugated diene hydrocarbons, one or more alkenylsubstituted aromatic compounds, or mixtures of one or more dienes with one or more alkenylsubstituted aromatic compounds into the M-Z linkage;  
 Z is a branched or straight chain hydrocarbon connecting group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups;  
 T is selected from the group consisting of oxygen, sulfur, and nitrogen groups and mixtures thereof;  
 (A-R 1  R 2  R 3 ) m  is a protecting group in which A is an element selected from Group IVa of the Periodic Table of the Elements, and R 1 , R 2 , and R 3  are independently defined as hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl and substituted cycloalkyl;  
 l is an integer from 1 to 7;  
 n is >0 and <1; and  
 m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen.  
 
     
     
         2 . The initiator of  claim 1 , wherein M is lithium.  
     
     
         3 . The initiator of  claim 1 , wherein said conjugated diene is selected from the group consisting of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene (piperylene), myrcene, 2-methyl-3ethyl- 1,3-butadiene, 2-methyl-3ethyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-hexadiene, 1,3-heptadiene, 3-methyl-1,3heptadiene, 1,3-octadiene, 3-butyl-1,3 -octadiene, 3 ,4-dimethyl- 1,3 -hexadiene, 3 -n-propyl- 1,3 -pentadiene, 4,5-diethyl-1,3-octadiene, 2,4-diethyl-1,3-butadiene, 2,3-di-n-propyl-1,3-butadiene, 2-methyl-3-isopropyl-1,3-butadiene, and mixtures thereof.  
     
     
         4 . The initiator of  claim 1 , wherein said alkenylsubstituted aromatic compound is selected from the group consisting of styrene, alpha-methylstyrene, vinyltoluene, 2-vinylpyridine, 4-vinylpyridine, 1-vinylnaphthalene, 2-vinylnaphthalene, 1-alpha-methylvinylnaphthalene, 2-alpha-methylvinylnaphathalene, 1,2-diphenyl-4-methyl-1-hexene, alkyl, cycloalkyl, aryl, alkaryl and aralkyl derivatives thereof and mixtures thereof.  
     
     
         5 . The initiator of  claim 4 , wherein Q comprises isoprene.  
     
     
         6 . The initiator of  claim 1 , wherein T is oxygen.  
     
     
         7 . The initiator of  claim 1 , wherein T is nitrogen.  
     
     
         8 . The initiator of  claim 1 , wherein T is sulfur.  
     
     
         9 . The initiator of  claim 1 , wherein A is carbon.  
     
     
         10 . The initiator of  claim 1 , wherein A is silicon.  
     
     
         11 . The initiator of  claim 1 , wherein said initiator is 3-(hexamethyleneimino)-1-propyllithium extended with 0.05 to 0.95 equivalents isoprene.  
     
     
         12 . The initiator of  claim 1 , wherein said initiator is 3-(pyrrolidino)-1-propyllithium chain extended with 0.05 to 0.95 equivalents isoprene.  
     
     
         13 . The initiator of  claim 1 , wherein said initiator is 3-(1,1-dimethylethoxy)-1-propyllithium chain extended with 0.05 to 0.95 equivalents isoprene.  
     
     
         14 . The initiator of  claim 1 , wherein said initiator is 2,2-dimethyl-3-trimethylsiloxy-1-propyllithium chain extended with 0.05 to 0.95 equivalents isoprene.  
     
     
         15 . The initiator of  claim 1 , wherein said compound has the formula M-Q n -Z-T-(A-R 1 R 2  R 3 ) m .  
     
     
         16 . The initiator of  claim 1 , wherein said compound has the formula  
       
         
           
           
               
               
           
         
       
     
     
         17 . A hydrocarbon composition comprising one or more protected functionalized chain extended anionic polymerization initiators of the formula  
       
         
           
           
               
               
           
         
       
       wherein: 
 M is an alkali metal selected from the group consisting of lithium, sodium and potassium;  
 Q is a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more conjugated diene hydrocarbons, one or more alkenylsubstituted aromatic compounds, or mixtures of one or more dienes with one or more alkenylsubstituted aromatic compounds into the M-Z linkage;  
 Z is a branched or straight chain hydrocarbon connecting group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups;  
 T is selected from the group consisting of oxygen, sulfur, and nitrogen groups and mixtures thereof; (A-R 1 , R 2 , R 3 ) m  is a protecting group in which A is an element selected from Group IVa of the Periodic Table of the Elements, and R 1 , R 2 , and R 3  are independently defined as hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl and substituted cycloalkyl;  
 l is an integer from 1 to 7;  
 n is >0 and <1; and  
 m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen.  
 
     
     
         18 . The composition of  claim 17 , wherein said initiator has the formula M-Q n -Z-T-(A-R 1 R 2  R 3 ) m .  
     
     
         19 . The composition of  claim 17 , wherein said initiator has the formula  
       
         
           
           
               
               
           
         
       
     
     
         20 . The composition of  claim 17 , further comprising at least one additional polymerization initiator.  
     
     
         21 . The composition of  claim 20 , wherein said at least one additional initiator comprises one or more non-chain extended compounds of the formula  
       
         
           
           
               
               
           
         
       
       wherein: 
 M is an alkali metal selected from the group consisting of lithium, sodium and potassium;  
 Z is a branched or straight chain hydrocarbon connecting group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups;  
 T is selected from the group consisting of oxygen, sulfur, and nitrogen groups and mixtures thereof;  
 (A-R 1  R 2  R 3 ) m  is a protecting group in which A is an element selected from Group IVa of the Periodic Table of the Elements, and R 1 , R 2 , and R 3  are independently defined as hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl and substituted cycloalkyl;  
 l is an integer from 1 to 7; and  
 m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen.  
 
     
     
         22 . The composition of  claim 20 , wherein said at least one additional initiator comprises one or more chain extended compounds of the formula  
       
         
           
           
               
               
           
         
       
       wherein: 
 M is an alkali metal selected from the group consisting of lithium, sodium and potassium;  
 Q is a saturated or unsaturated hydrocarbyl group derived by incorporation of one or more conjugated diene hydrocarbons, one or more alkenylsubstituted aromatic compounds, or mixtures of one or more dienes with one or more alkenylsubstituted aromatic compounds into the M-Z linkage;  
 Z is a branched or straight chain hydrocarbon connecting group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups;  
 T is selected from the group consisting of oxygen, sulfur, and nitrogen groups and mixtures thereof;  
 (A-R 1  R 2  R 3 ) m  is a protecting group in which A is an element selected from Group IVa of the Periodic Table of the Elements, and R 1 , R 2 , and R 3  are independently defined as hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl and substituted cycloalkyl;  
 l is an integer from 1 to 7;  
 n is an integer from 1 to 5; and  
 m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen.  
 
     
     
         23 . The composition of  claim 17 , wherein said composition optionally includes a polymerization promoter.  
     
     
         24 . The composition of  claim 17 , wherein M is lithium.  
     
     
         25 . The composition of  claim 17 , wherein said conjugated diene is selected from the group consisting of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene (piperylene), myrcene, 2-methyl-3ethyl-1,3-butadiene, 2-methyl-3ethyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-hexadiene, 1,3-heptadiene, 3-methyl-1,3-heptadiene, 1,3-octadiene, 3-butyl-1,3-octadiene, 3,4-dimethyl-1,3-hexadiene, 3-n-propyl-1,3-pentadiene, 4,5-diethyl-1,3-octadiene, 2,4-diethyl-1,3-butadiene, 2,3-di-n-propyl-1,3-butadiene, 2-methyl-3-isopropyl-1,3-butadiene, and mixtures thereof.  
     
     
         26 . The composition of  claim 17 , wherein said alkenylsubstituted aromatic compound is selected from the group consisting of styrene, alpha-methylstyrene, vinyltoluene, 2-vinylpyridine, 4-vinylpyridine, 1-vinylnaphthalene, 2-vinylnaphthalene, 1-alpha-methylvinylnaphthalene, 2-alpha-methylvinylnaphathalene, 1,2-diphenyl-4-methyl-1-hexene, alkyl, cycloalkyl, aryl, alkaryl and aralkyl derivatives thereof and mixtures thereof.  
     
     
         27 . The composition of  claim 26 , wherein Q comprises isoprene.  
     
     
         28 . The composition of  claim 17 , wherein T is oxygen.  
     
     
         29 . The composition of  claim 17 , wherein T is nitrogen.  
     
     
         30 . The composition of  claim 17 , wherein T is sulfur.  
     
     
         31 . The composition of  claim 17 , wherein A is carbon.  
     
     
         32 . The composition of  claim 17 , wherein A is silicon.  
     
     
         33 . The composition of  claim 17 , wherein said initiator is 3-(hexamethyleneimino)-1-propyllithium chain extended with 0.05 to 0.95 equivalents isoprene.  
     
     
         34 . The composition of  claim 17 , wherein said initiator is 3-(pyrrolidino)-1-propyllithium chain extended with 0.05 to 0.95 equivalents isoprene.  
     
     
         35 . The composition of  claim 17 , wherein said initiator is 3-(1,1-dimethylethoxy)-1-propyllithium chain extended with 0.05 to 0.95 equivalents isoprene.  
     
     
         36 . The composition of  claim 17 , wherein said initiator is 2,2-dimethyl-3-trimethylsiloxy-l-proypyllithium chain extended with 0.05 to 0.95 equivalents isoprene.  
     
     
         37 . The composition of  claim 17 , wherein said hydrocarbon solvent is selected from the group consisting of alkanes, cycloalkanes, aromatic solvents and mixtures thereof.  
     
     
         38 . The composition of  claim 37 , wherein said solvent is cyclohexane.  
     
     
         39 - 90 . (Cancelled)