Novel multifunctional initiators for anionic polymerization and polymers therefrom

Abstract

The embodiments of the invention relate to a multifunctional lithiated amine-containing compound comprising at least two molecules of lithiated amine in a molecule of the compound. In one embodiment, the compound has a formula where x is an integer of 1 or more, Q is (a) an element selected from the group consisting of O, S, N, P and Si or (b) an alkylene group having from 1 to 20 methylene groups, and R 1 and R 2 are the same or different and are selected from the group consisting of alkyls, cycloalkyls and aralkyls containing from 1 to 20 carbon atoms. In another embodiment, the compound comprises cyclic lithio amines and has a formula: where x is 1 or more, R 3 , R 4 and R 5 are the same or different and represent alkylene groups containing from 3 to 20 carbon atoms.

1 . A multifunctional lithiated amine-containing compound comprising at least two molecules of lithiated amine in a molecule of the compound, wherein the compound does not contain any active hydrogen that can react with carbon-lithium or nitrogen-lithium species. 
     
     
         2 . The compound of  claim 1  having a formula: 
       
         
           
           
               
               
           
         
         where x is an integer of 1 or more, Q is (a) an element selected from the group consisting of O, S, N, P and Si or (b) an alkylene group having from 1 to 20 methylene groups, and R 1  and R 2  are the same or different and are selected from the group consisting of alkyls, cycloalkyls and aralkyls containing from 1 to 20 carbon atoms. 
       
     
     
         3 . The compound of  claim 1 , comprising cyclic lithio amines and having a formula: 
       
         
           
           
               
               
           
         
         where x is 1 or more, R 3 , R 4  and R 5  are the same or different and represent alkylene groups containing from 3 to 20 carbon atoms. 
       
     
     
         4 . The compound of  claim 2 , wherein nitrogen forms part of a ring. 
     
     
         5 . The compound of  claim 2 , wherein the formula is: 
       
         
           
           
               
               
           
         
         wherein Q divalent. 
       
     
     
         6 . The compound of  claim 2 , wherein the formula is: 
       
         
           
           
               
               
           
         
         wherein Q is trivalent. 
       
     
     
         7 . The compound of  claim 2 , wherein the formula is: 
       
         
           
           
               
               
           
         
         wherein Q is tetravalent. 
       
     
     
         8 . The compound of  claim 2 , wherein Q is a dendrimer or a nano-material, wherein the dendrimer or the nano-material has a plurality of sites for forming chemical bonds. 
     
     
         9 . The compound of  claim 1 , wherein at least of one of the at least two molecules of lithiated amine comprises a functionalized piperidine, a functionalized piperazine, or a functionalized pyrrolidine. 
     
     
         10 . The compound of  claim 2 , wherein the formula represents Li-4,4′-trimethylenedipiperidine-Li. 
     
     
         11 . A polymer comprising multifunctional lithiated amine-containing compound comprising at least two molecules of lithiated amine in a molecule of the compound, wherein the compound does not contain any active hydrogen that can react with carbon-lithium or nitrogen-lithium species. 
     
     
         12 . The polymer of  claim 11 , further comprising butadiene or styrene and a polymerization terminator. 
     
     
         13 . The polymer of  claim 12 , further comprising both styrene and butadiene. 
     
     
         14 . The polymer of  claim 13 , wherein the polymer has tan δ measured by a rotorless shear rheometer of less than 0.1 for shear rate sweeps performed at a strain set between 2 to 14% strain. 
     
     
         15 . The polymer of  claim 11 , wherein the compound has a formula 
       
         
           
           
               
               
           
         
         where x is an integer of 1 or more, Q is (a) an element selected from the group consisting of O, S, N, P and Si or (b) an alkylene group having from 1 to 20 methylene groups, and R 1  and R 2  are the same or different and are selected from the group consisting of alkyls, cycloalkyls and aralkyls containing from 1 to 20 carbon atoms. 
       
     
     
         16 . The polymer of  claim 11 , the compound comprising cyclic lithio amines and having a formula: 
       
         
           
           
               
               
           
         
         where x is 1 or more, R 3 , R 4  and R 5  are the same or different and represent alkylene groups containing from 3 to 20 carbon atoms. 
       
     
     
         17 . A method of manufacturing a multifunctional lithiated amine-containing compound comprising at least two molecules of lithiated amine in a molecule of the compound, the method comprising reacting lithium or a lithium-containing compound with an amine-containing compound having at least two nitrogen atoms, wherein the compound does not contain any active hydrogen that can react with carbon-lithium or nitrogen-lithium species. 
     
     
         18 . The method of  claim 18 , wherein the amine-containing compound is 4,4′-trimethylenedipiperidine. 
     
     
         19 . A method of preparing a polymer by employing anionic polymerization comprising: (i) providing monomer including conjugated dienes; (ii) providing a polymerization medium including a non-polar solvent; (iii) providing an initiator comprising a multifunctional lithiated amine-containing compound comprising at least two molecules of lithiated amine in a molecule of the compound, wherein the compound does not contain any active hydrogen that can react with carbon-lithium or nitrogen-lithium species; and (iv) contacting the monomer and initiator within the polymerization medium. 
     
     
         20 . The method of  claim 19 , wherein the initiator is generated in-situ during the preparation of the polymer. 
     
     
         21 . The method of  claim 19 , wherein the anionic polymerization is a mono-modal living polymerization. 
     
     
         22 . The method of  claim 19 , wherein the contacting the monomer and initiator within the polymerization medium results in a living polymer, and further comprising the step of contacting the living polymer with a polymerization terminator. 
     
     
         23 . The method of  claim 19 , wherein the compound has a formula 
       
         
           
           
               
               
           
         
         where x is an integer of 1 or more, Q is (a) an element selected from the group consisting of O, S, N, P and Si or (b) an alkylene group having from 1 to 20 methylene groups, and R 1  and R 2  are the same or different and are selected from the group consisting of alkyls, cycloalkyls and aralkyls containing from 1 to 20 carbon atoms. 
       
     
     
         24 . The method of  claim 19 , the compound comprising cyclic lithio amines and having a formula: 
       
         
           
           
               
               
           
         
         where x is 1 or more, R 3 , R 4  and R 5  are the same or different and represent alkylene groups containing from 3 to 20 carbon atoms. 
       
     
     
         25 . A tire component comprising a vulcanizate residue of the polymer of  claim 12 .