US2012296041A1PendingUtilityA1

Polymers functionalized with nitrile compounds containing a protected amino group

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Assignee: LUO STEVENPriority: Jan 22, 2010Filed: Jan 24, 2011Published: Nov 22, 2012
Est. expiryJan 22, 2030(~3.5 yrs left)· nominal 20-yr term from priority
Inventors:Steven Luo
B60C 1/00C08F 8/30C08F 8/34C08C 19/44C08C 19/22C08K 3/04C08F 8/42C08F 36/06C08C 19/25C08L 15/00C08F 212/08
57
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Claims

Abstract

A method for preparing a functionalized polymer, the method comprising the steps of: (i) polymerizing monomer with an anionic initiator to form a reactive polymer; and (ii) reacting the reactive polymer with a nitrile compound containing a protected amino group, where the protected amino group is directly attached to a moiety selected from the group consisting of acyclic moieties, heterocyclic moieties, and non-aromatic cyclic moieties.

Claims

exact text as granted — not AI-modified
1 . A method for preparing a functionalized polymer, the method comprising the steps of:
 (i) polymerizing monomer with an anionic initiator to form a reactive polymer; and   (ii) reacting the reactive polymer with a nitrile compound containing a protected amino group, where the protected amino group is directly attached to a moiety selected from the group consisting of acyclic moieties, heterocyclic moieties, and non-aromatic cyclic moieties.   
     
     
         2 . The method of  claim 1 , where the protected amino group is selected from the group consisting of bis(trihydrocarbylsilyl)amino, bis(dihydrocarbylhydrosilyl)amino, 1-aza-disila-1-cyclohydrocarbyl, (trihydrocarbylsilyl)(hydrocarbyl)amino, (dihydrocarbylhydrosilyl)(hydrocarbyl)amino, 1-aza-2-sila-1-cyclohydrocarbyl, dihydrocarbylamino, and 1-aza-1-cyclohydrocarbyl groups. 
     
     
         3 . The method of  claim 1 , where the nitrile compound containing a protected amino group derives from a nitrile compound selected from the group consisting of arenecarbonitrile compounds, alkanecarbonitrile compounds, alkenecarbonitrile compounds, alkynecarbonitrile compounds, cycloalkanecarbonitrile compounds, cycloalkenecarbonitrile compounds, cycloalkynecarbonitrile compounds, and heterocyclic nitrile compounds. 
     
     
         4 . The method of  claim 1 , where the anionic initiator is an organolithium compound and the monomer includes conjugated diene monomer and optionally monomer copolymerizable therewith. 
     
     
         5 . The method of  claim 1 , where both the cyano group and the protected amino group of the nitrile compound containing a protected amino group are directly attached to a moiety selected from the group consisting of acyclic moieties, heterocyclic moieties, and non-aromatic cyclic moieties. 
     
     
         6 . The method of  claim 1 , where the nitrile compound containing a protected amino group is an arenecarbonitrile compound containing a protected amino group selected from the group consisting of [bis(trihydrocarbylsilyl)amino]arenecarbonitrile, [bis(dihydrocarbylhydrosilyl)amino]arenecarbonitrile, (1-aza-disila-1-cyclohydrocarbyl)arenecarbonitrile, [(trihydrocarbylsilyl)(hydrocarbyl)amino]arenecarbonitrile, [(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]arenecarbonitrile, (1-aza-2-sila-1-cyclohydrocarbyl)arenecarbonitrile, (dihydrocarbylamino)arenecarbonitrile, and (1-aza-1-cyclohydrocarbyl)arenecarbonitrile. 
     
     
         7 . The method of  claim 1 , where the nitrile compound containing a protected amino group is an alkanecarbonitrile compound containing a protected amino group selected from the group consisting of [bis(trihydrocarbylsilyl)amino]alkanecarbonitrile, [bis(dihydrocarbylhydrosilyl)amino]alkanecarbonitrile, (1-aza-disila-1-cyclohydrocarbyl)alkanecarbonitrile, [(trihydrocarbylsilyl)(hydrocarbyl)amino]alkanecarbonitrile, [(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]alkanecarbonitrile, (1-aza-2-sila-1-cyclohydrocarbyl)alkanecarbonitrile, (dihydrocarbylamino)alkanecarbonitrile, and (1-aza-1-cyclohydrocarbyl)alkanecarbonitrile. 
     
     
         8 . The method of  claim 1 , where the nitrile compound containing a protected amino group is an alkenecarbonitrile compound containing a protected amino group selected from the group consisting of [bis(trihydrocarbylsilyl)amino]alkenecarbonitrile, [bis(dihydrocarbylhydrosilyl)amino]alkenecarbonitrile, (1-aza-disila-1-cyclohydrocarbyl)alkenecarbonitrile, [(trihydrocarbylsilyl)(hydrocarbyl)amino]alkenecarbonitrile, [(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]alkenecarbonitrile, (1-aza-2-sila-1-cyclohydrocarbyl)alkenecarbonitrile, (dihydrocarbylamino)alkenecarbonitrile, and (1-aza-1-cyclohydrocarbyl)alkenecarbonitrile. 
     
     
         9 . The method of  claim 1 , where the nitrile compound containing a protected amino group is an alkynecarbonitrile compound containing a protected amino group selected from the group consisting of [bis(trihydrocarbylsilyl)amino]alkynecarbonitrile, [bis(dihydrocarbylhydrosilyl)amino]alkynecarbonitrile, (1-aza-disila-1-cyclohydrocarbyl)alkynecarbonitrile, [(trihydrocarbylsilyl)(hydrocarbyl)amino]alkynecarbonitrile, [(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]alkynecarbonitrile, (1-aza-2-sila-1-cyclohydrocarbyl)alkynecarbonitrile, (dihydrocarbylamino)alkynecarbonitrile, and (1-aza-1-cyclohydrocarbyl)alkynecarbonitrile. 
     
     
         10 . The method of  claim 1 , where the nitrile compound containing a protected amino group is a cycloalkanecarbonitrile compound containing a protected amino group selected from the group consisting of [bis(trihydrocarbylsilyl)amino]cycloalkanecarbonitrile, [bis(dihydrocarbylhydrosilyl)amino]cycloalkanecarbonitrile, (1-aza-disila-1-cyclohydrocarbyl)cycloalkanecarbonitrile, [(trihydrocarbylsilyl)(hydrocarbyl)amino]cycloalkanecarbonitrile, [(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]cycloalkanecarbonitrile, (1-aza-2-sila-1-cyclohydrocarbyl)cycloalkanecarbonitrile, (dihydrocarbylamino)cycloalkanecarbonitrile, and (1-aza-1-cyclohydrocarbyl)cycloalkanecarbonitrile. 
     
     
         11 . The method of  claim 1 , where the nitrile compound containing a protected amino group is a cycloalkenecarbonitrile compound containing a protected amino group selected from the group consisting of [bis(trihydrocarbylsilyl)amino]cycloalkenecarbonitrile, [bis(dihydrocarbylhydrosilyl)amino]cycloalkenecarbonitrile, (1-aza-disila-1-cyclohydrocarbyl)cycloalkenecarbonitrile, [(trihydrocarbylsilyl)(hydrocarbyl)amino]cycloalkenecarbonitrile, [(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]cycloalkenecarbonitrile, (1-aza-2-sila-1-cyclohydrocarbyl)cycloalkenecarbonitrile, (dihydrocarbylamino)cycloalkenecarbonitrile, and (1-aza-1-cyclohydrocarbyl)cycloalkenecarbonitrile. 
     
     
         12 . The method of  claim 1 , where the nitrile compound containing a protected amino group is a cycloalkynecarbonitrile compound containing a protected amino group selected from the group consisting of [bis(trihydrocarbylsilyl)amino]cycloalkynecarbonitrile, [bis(dihydrocarbylhydrosilyl)amino]cycloalkynecarbonitrile, (1-aza-disila-1-cyclohydrocarbyl)cycloalkynecarbonitrile, [(trihydrocarbylsilyl)(hydrocarbyl)amino]cycloalkynecarbonitrile, [(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]cycloalkynecarbonitrile, (1-aza-2-sila-1-cyclohydrocarbyl)cycloalkynecarbonitrile, (dihydrocarbylamino)cycloalkynecarbonitrile, and (1-aza-1-cyclohydrocarbyl)cycloalkynecarbonitrile. 
     
     
         13 . The method of  claim 1 , where the nitrile compound containing a protected amino group is a heterocyclic nitrile compound containing a protected amino group selected from the group consisting of [bis(trihydrocarbylsilyl)amino]heterocyclic nitrile, [bis(dihydrocarbylhydrosilyl)amino]heterocyclic nitrile, (1-aza-disila-1-cyclohydrocarbyl)heterocyclic nitrile, [(trihydrocarbylsilyl)(hydrocarbyl)amino]heterocyclic nitrile, [(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]heterocyclic nitrile, (1-aza-2-sila-1-cyclohydrocarbyl)heterocyclic nitrile, (dihydrocarbylamino)heterocyclic nitrile, and (1-aza-1-cyclohydrocarbyl)heterocyclic nitrile. 
     
     
         14 . A method for preparing a functionalized polymer, the method comprising the steps of:
 (i) polymerizing monomer with an anionic initiator to form a reactive polymer; and   (ii) reacting the reactive polymer with a nitrile compound containing a protected amino group defined by the formula I:   
       
         
           
           
               
               
           
         
         where R 1  is a divalent organic group, and R 2  and R 3  are each independently a monovalent organic group or a hydrolyzable group, or R 2  and R 3  join to form a divalent organic group, with the proviso that R 1  is an acyclic divalent organic group, a heterocyclic divalent organic group, a non-aromatic cyclic divalent organic group that is devoid of heteroatoms, or a divalent organic group containing an aromatic ring that is devoid of heteroatoms so long as, where R 1  is a divalent organic group containing an aromatic ring that is devoid of heteroatoms, the protected amino group is not directly attached to the aromatic ring. 
       
     
     
         15 . The method of  claim 14 , where the nitrile compound containing a protected amino group is defined by the formula II: 
       
         
           
           
               
               
           
         
         where R 1  and R 5  are each independently a divalent organic group, and R 4  and R 6  are each independently a bond or a hydrolyzable group, with the proviso that R 1  is an acyclic divalent organic group, a heterocyclic divalent organic group, a non-aromatic cyclic divalent organic group that is devoid of heteroatoms, or a divalent organic group containing an aromatic ring that is devoid of heteroatoms so long as, where R 1  is a divalent organic group containing an aromatic ring that is devoid of heteroatoms, the protected amino group is not directly attached to the aromatic ring. 
       
     
     
         16 . The method of  claim 14 , where the nitrile compound containing a protected amino group is defined by the formula III: 
       
         
           
           
               
               
           
         
         where R 1  is a divalent organic group, R 3  is a monovalent organic group or a hydrolyzable group, each R 7  is independently a hydrogen atom or a monovalent organic group, or R 3  and one R 7  join to form a divalent organic group, with the proviso that R 1  is an acyclic divalent organic group, a heterocyclic divalent organic group, a non-aromatic cyclic divalent organic group that is devoid of heteroatoms, or a divalent organic group containing an aromatic ring that is devoid of heteroatoms so long as, where R 1  is a divalent organic group containing an aromatic ring that is devoid of heteroatoms, the protected amino group is not directly attached to the aromatic ring. 
       
     
     
         17 . The method of  claim 16 , where the nitrile compound containing a protected amino group is defined by the formula IV: 
       
         
           
           
               
               
           
         
         where R 1  and R 8  are each independently a divalent organic group, and each R 7  is independently a hydrogen atom or a monovalent organic group, with the proviso that R 1  is an acyclic divalent organic group, a heterocyclic divalent organic group, a non-aromatic cyclic divalent organic group that is devoid of heteroatoms, or a divalent organic group containing an aromatic ring that is devoid of heteroatoms so long as, where R 1  is a divalent organic group containing an aromatic ring that is devoid of heteroatoms, the protected amino group is not directly attached to the aromatic ring. 
       
     
     
         18 . The method of  claim 14 , where the nitrile compound containing a protected amino group is defined by the formula V: 
       
         
           
           
               
               
           
         
         where R 1  is a divalent organic group, and R 9  and R 10  are each independently a hydrogen atom or a monovalent organic group, or at least one R 9  and at least one R 10  join to form a divalent organic group, with the proviso that R 1  is an acyclic divalent organic group, a heterocyclic divalent organic group, a non-aromatic cyclic divalent organic group that is devoid of heteroatoms, or a divalent organic group containing an aromatic ring that is devoid of heteroatoms so long as, where R 1  is a divalent organic group containing an aromatic ring that is devoid of heteroatoms, the protected amino group is not directly attached to the aromatic ring. 
       
     
     
         19 . The method of  claim 18 , where the nitrile compound containing a protected amino group is defined by the formula VI: 
       
         
           
           
               
               
           
         
         where R 1  and R 11  are each independently a divalent organic group, and R 9  and R 10  are each independently a hydrogen atom or a monovalent organic group, with the proviso that R 1  is an acyclic divalent organic group, a heterocyclic divalent organic group, a non-aromatic cyclic divalent organic group that is devoid of heteroatoms, or a divalent organic group containing an aromatic ring that is devoid of heteroatoms so long as, where R 1  is a divalent organic group containing an aromatic ring that is devoid of heteroatoms, the protected amino group is not directly attached to the aromatic ring. 
       
     
     
         20 . The method of  claim 14 , where the anionic initiator is an organolithium compound and the monomer includes conjugated diene monomer and optionally monomer copolymerizable therewith. 
     
     
         21 . The method of  claim 14 , where said step of reacting produces a reaction product that is subsequently protonated. 
     
     
         22 . A functionalized polymer containing a protected amino group, the functionalized polymer being defined by the formula VII: 
       
         
           
           
               
               
           
         
         where π is a polymer chain of a polydiene or a copolymer of conjugated diene and co-monomer having a medium or low cis-1,4-linkage content, R 1  is a divalent organic group, and R 2  and R 3  are each independently a monovalent organic group or a hydrolyzable group, or R 2  and R 3  join to form a divalent organic group, with the proviso that R 1  is an acyclic divalent organic group, a heterocyclic divalent organic group, a non-aromatic cyclic divalent organic group that is devoid of heteroatoms, or a divalent organic group containing an aromatic ring that is devoid of heteroatoms so long as, where R 1  is a divalent organic group containing an aromatic ring that is devoid of heteroatoms, the protected amino group is not directly attached to the aromatic ring. 
       
     
     
         23 . A functionalized polymer containing an amino group, the functionalized polymer being defined by the formula VIII: 
       
         
           
           
               
               
           
         
         where π is a polymer chain of a polydiene or a copolymer of conjugated diene and co-monomer having a medium or low cis-1,4-linkage content, R 1  is a divalent organic group, and R 12  and R 13  are each independently a monovalent organic group or a hydrogen atom, or R 12  and R 13  join to form a divalent organic group, with the proviso that R 1  is an acyclic divalent organic group, a heterocyclic divalent organic group, a non-aromatic cyclic divalent organic group that is devoid of heteroatoms, or a divalent organic group containing an aromatic ring that is devoid of heteroatoms so long as, where R 1  is a divalent organic group containing an aromatic ring that is devoid of heteroatoms, the amino group is not directly attached to the aromatic ring. 
       
     
     
         24 . A tire component including the vulcanized residue of the functionalized polymer of  claim 22 . 
     
     
         25 . A tire component including the vulcanized residue of the functionalized polymer of  claim 23 .

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