Polymers functionalized with heterocyclic imines
A method for preparing a functionalized polymer, the method comprising the steps of: (i) polymerizing monomer to form a reactive polymer, and (ii) reacting the reactive polymer with an imine compound containing a heterocyclic group and a hydrocarbyloxy-substituted or silyloxy-substituted aryl group.
1. A method for preparing a functionalized polymer, the method comprising the steps of:
(i) polymerizing monomer to form a reactive polymer, and
(ii) reacting the reactive polymer with an imine compound containing a heterocyclic group and a hydrocarbyloxy-substituted or silyloxy-substituted aryl group;
where the imine compound containing a heterocyclic group and a hydrocarbyloxy-substituted or silyloxy-substituted aryl group is defined by the formula I:
where Θ is a heterocyclic group, R 1 is a bond or a divalent organic group, R 2 is a hydrogen atom or a monovalent organic group, R 3 is a bond or divalent organic group, each R 4 is independently a hydrogen atom, a halogen atom, a monovalent organic group, a hydrocarbyloxy group, or a silyloxy group, or where two or more R 4 groups join to form a divalent, trivalent or tetravalent organic group, with the proviso that at least one R 4 is a hydrocarbyloxy or silyloxy group.
2. The method of claim 1 , where the imine compound containing a heterocyclic group and a hydrocarbyloxy-substituted or silyloxy-substituted aryl group is defined by the formula II:
where Θ is a heterocyclic group, R 1 is a bond or a divalent organic group, R 2 is a hydrogen atom or a monovalent organic group, R 3 is a bond or divalent organic group, each R 4 is independently a hydrogen atom, a halogen atom, a monovalent organic group, a hydrocarbyloxy group, or a silyloxy group, or where two or more R 4 groups join to form a divalent, trivalent or tetravalent organic group, and R 5 is a hydrocarbyl or silyl group.
3. The method of claim 2 , where the imine compound containing a heterocyclic group and a hydrocarbyloxy-substituted or silyloxy-substituted aryl group is defined by the formula III:
where Θ is a heterocyclic group, R 1 is a bond or a divalent organic group, R 2 is a hydrogen atom or a monovalent organic group, R 3 is a bond or divalent organic group, each R 4 is independently a hydrogen atom, a halogen atom, a monovalent organic group, a hydrocarbyloxy group, or a silyloxy group, or where two or more R 4 groups join to form a divalent, trivalent or tetravalent organic group, and each R 6 is independently a hydrogen atom or a monovalent organic group.
4. The method of claim 1 , where the imine compound containing a heterocyclic group and a hydrocarbyloxy-substituted or silyloxy-substituted aryl group contains an oxygen-containing heterocyclic group.
5. The method of claim 1 , where the imine compound containing a heterocyclic group and a hydrocarbyloxy-substituted or silyloxy-substituted aryl group contains a sulfur-containing heterocyclic group.
6. The method of claim 1 , where the imine compound containing a heterocyclic group and a hydrocarbyloxy-substituted or silyloxy-substituted aryl group contains a nitrogen-containing saturated heterocyclic group.
7. The method of claim 1 , where the imine compound containing a heterocyclic group and a hydrocarbyloxy-substituted or silyloxy-substituted aryl group contains a nitrogen-containing unsaturated heterocyclic group that does not contain a carbon-nitrogen double bond.
8. The method of claim 1 , where the imine compound containing a heterocyclic group and a hydrocarbyloxy-substituted or silyloxy-substituted aryl group contains a nitrogen-containing unsaturated heterocyclic group that contains one carbon-nitrogen double bond.
9. The method of claim 1 , where the imine compound containing a heterocyclic group and a hydrocarbyloxy-substituted or silyloxy-substituted aryl group contains a nitrogen-containing unsaturated heterocyclic group that contains two carbon-nitrogen double bonds.
10. The method of claim 1 , where the imine compound containing a heterocyclic group and a hydrocarbyloxy-substituted or silyloxy-substituted aryl group contains a nitrogen-containing unsaturated heterocyclic group that contains three carbon-nitrogen double bonds.
11. The method of claim 1 , where the imine compound containing a heterocyclic group and a hydrocarbyloxy-substituted or silyloxy-substituted aryl group contains a nitrogen-containing unsaturated heterocyclic group that contains four carbon-nitrogen double bonds.
12. The method of claim 1 , where the imine compound containing a heterocyclic group and a hydrocarbyloxy-substituted or silyloxy-substituted aryl group contains a nitrogen-containing unsaturated heterocyclic group that contains at least one second distinct heteroatom.
13. The method of claim 1 , where the monomer includes conjugated diene monomer.
14. The method of claim 13 , where said step of polymerizing employs a coordination catalyst.
15. The method of claim 14 , where the coordination catalyst is a lanthanide-based catalyst.
16. The method of claim 15 , where the lanthanide-based catalyst includes (a) a lanthanide-containing compound, (b) an alkylating agent, and (c) a halogen source.
17. The method of claim 16 , where the alkylating agent includes an aluminoxane and an organoaluminum compound represented by the formula AlR n X 3-n , where each R, which may be the same or different, is a monovalent organic group that is attached to the aluminum atom via a carbon atom, where each X, which may be the same or different, is a hydrogen atom, a halogen atom, a carboxylate group, an alkoxide group, or an aryloxide group, and where n is an integer of 1 to 3.
18. The method of claim 14 , where said step of polymerizing monomer takes place within a polymerization mixture including less than 20% by weight of organic solvent.
19. The method of claim 13 , where said step of polymerizing employs an anionic initiator.
20. The method of claim 19 , where the anionic initiator is an organolithium compound.
21. A method for preparing a functionalized polymer, the method comprising the steps of:
(i) polymerizing conjugated diene monomer, and optionally monomer copolymerizable therewith, to form a polymer having a reactive chain end; and
(ii) reacting the reactive chain end of the polymer with an imine compound containing a heterocyclic group and a hydrocarbyloxy-substituted or silyloxy-substituted aryl group;
where the imine compound containing a heterocyclic group and a hydrocarbyloxy-substituted or silyloxy-substituted aryl group is defined by the formula I:
where Θ is a heterocyclic group, R 1 is a bond or a divalent organic group, R 2 is a hydrogen atom or a monovalent organic group, R 3 is a bond or divalent organic group, each R 4 is independently a hydrogen atom, a halogen atom, a monovalent organic group, a hydrocarbyloxy group, or a silyloxy group, or where two or more R 4 groups join to form a divalent, trivalent or tetravalent organic group, with the proviso that at least one R 4 is a hydrocarbyloxy or silyloxy group.
22. A functionalized polymer prepared by the steps of:
(i) polymerizing conjugated diene monomer, and optionally monomer copolymerizable therewith, to form a polymer having a reactive chain end; and
(ii) reacting the reactive chain end of the polymer with an imine compound containing a heterocyclic group and a hydrocarbyloxy-substituted or silyloxy-substituted aryl group;
where the imine compound containing a heterocyclic group and a hydrocarbyloxy-substituted or silyloxy-substituted aryl group is defined by the formula I:
where Θ is a heterocyclic group, R 1 is a bond or a divalent organic group, R 2 is a hydrogen atom or a monovalent organic group, R 3 is a bond or divalent organic group, each R 4 is independently a hydrogen atom, a halogen atom, a monovalent organic group, a hydrocarbyloxy group, or a silyloxy group, or where two or more R 4 groups join to form a divalent, trivalent or tetravalent organic group, with the proviso that at least one R 4 is a hydrocarbyloxy or silyloxy group.
23. A tire component prepared by employing the functionalized polymer of claim 22 .
24. A method for preparing a functionalized polymer, the method comprising the steps of:
(i) polymerizing monomer to form a reactive polymer, and
(ii) reacting the reactive polymer with an imine compound containing a heterocyclic group and a hydrocarbyloxy-substituted or silyloxy-substituted aryl group; where the hydrocarbyloxy-substituted or silyloxy-substituted aryl group contains a hydrocarbyloxy or silyloxy substituent at the 2 position.