POLYMERS FUNCTIONALIZED WITH NITRILE COMPOUNDS CONTAINING A PROTECTED AMINO GROUP
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.
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 .