Polymers functionalized with nitrile compounds containing a protected amino group

Patent metadata

Field	Value
Publication number	US-9469710-B2
Application number	US-201514607173-A
Country	US
Kind code	B2
Filing date	Jan 28, 2015
Priority date	Jan 22, 2010
Publication date	Oct 18, 2016
Grant date	Oct 18, 2016

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.

First claim

What is claimed is:

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, where the protected amino group includes a hydrolyzable group.

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, and 1-aza-2-sila-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, and (1-aza-2-sila-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) carbyl)amino]alkanecarbonitrile, and (1-aza-2-sila-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, and (1-aza-2-sila-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, and (1-aza-2-sila-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, and (1-aza-2-sila-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, and (1-aza-2-sila-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, and (1-aza-2-sila-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, and (1-aza-2-sila-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 at least one of R 2 , R 3 , or the divalent organic group formed by joining R 2 and R 3 is a hydrolyzable group, and with the further 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

Assignees

• Bridgestone Corp

Inventors

• Luo Steven
• Suzuki Eiju
• Brumbaugh Dennis R

Classifications

• B60C1/00 Primary

  Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition · CPC title

• C08K3/04

  Carbon · CPC title

• C08C19/44

  of polymers containing metal atoms exclusively at one or both ends of the skeleton · CPC title

• C08F8/30 Primary

  Introducing nitrogen atoms or nitrogen-containing groups · CPC title

• C08F8/42

  Introducing metal atoms or metal-containing groups · CPC title