# US 8,785,566 B2 · Polymers functionalized with polycyano compounds

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- Number: US 8,785,566 B2
- Document ID: US8785566B2
- Status: Granted
- Kind: B2
- Application number: 13/146,042
- Filed: 2010-01-22
- Published: 2011-11-24
- Granted: 2014-07-22
- Earliest claimed: 2009-01-23
- Assignees: Bridgestone Corporation
- Applicants: Steven Luo
- Inventors: Steven Luo
- Web page: https://patentgrep.com/patent/US8785566B2

## CPC

- C08F 8/30: Introducing nitrogen atoms or nitrogen-containing groups
- B60C 1/0016: {Compositions of the tread}
- C08C 19/22: Incorporating nitrogen atoms into the molecule
- C08C 19/44: of polymers containing metal atoms exclusively at one or both ends of the skeleton
- C08F 136/06: Butadiene
- C08F 236/10: with vinyl-aromatic monomers
- C08K 3/013: Fillers, pigments or reinforcing additives
- C08L 9/00: Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L 15/00: Compositions of rubber derivatives (C08L11/00, C08L13/00 take precedence)
- C08K 3/04: Carbon
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- B60C: VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- C08C: TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

A method for preparing a functionalized polymer, the method comprising the steps of polymerizing monomer to form a reactive polymer, and reacting the reactive polymer with a polycyano compound.

## Claims

### Claim 1

A method for preparing a functionalized polymer, the method comprising the steps of:
(i) polymerizing monomer consisting of conjugated diene monomer with a lanthanide-based catalyst system to form a polymer having a reactive chain end and a cis-1,4-linkage content of at least 60%; and
(ii) reacting the reactive chain end with a polycyano compound, where the polycyano compound is defined by the formula N≡C—R1—C≡N, where R1 is an acyclic divalent organic group that may or may not include one or more heteroatoms or R1 is a cyclic divalent organic group that is devoid of heteroatoms.

### Claim 2 (depends on 1)

The method of claim 1, where the polycyano compound includes two or more cyano groups.

### Claim 3 (depends on 1)

The method of claim 1, where the polycyano compound is selected from the group consisting of (polycyano)arene, (polycyano)alkane, (polycyano)alkene, (polycyano)alkyne, (polycyano)cycloalkane, (polycyano)cycloalkene, and (polycyano)cycloalkyne compounds.

### Claim 4 (depends on 3)

The method of claim 3, where the (polycyano)arene compound is selected from the group consisting of dicyanoarene, tricyanoarene, and tetracyanoarene compounds.

### Claim 5 (depends on 3)

The method of claim 3, where the (polycyano)alkane compound is selected from the group consisting of dicyanoalkane, tricyanoalkane, and tetracyanoalkane compounds.

### Claim 6 (depends on 3)

The method of claim 3, where the (polycyano)alkene compound is selected from the group consisting of dicyanoalkene, tricyanoalkene, and tetracyanoalkene compounds.

### Claim 7 (depends on 3)

The method of claim 3 where the (polycyano)alkyne compound is selected from the group consisting of dicyanoalkyne, tricyanoalkyne, tetracyanoalkyne compounds.

### Claim 8 (depends on 3)

The method of claim 3, where the (polycyano)cycloalkane compound is selected from the group consisting of dicyanocycloalkane, tricyanocycloalkane, and tetracyanocycloalkane compounds.

### Claim 9 (depends on 3)

The method of claim 3, where the (polycyano)cycloalkene compound is selected from the group consisting of dicyanocycloalkene, tricyanocycloalkene, and tetracyanocycloalkene compounds.

### Claim 10 (depends on 1)

The method of claim 1, where said step of reacting produces a reaction product that is subsequently protonated.

### Claim 11 (depends on 1)

The method of claim 1, where the lanthanide-based catalyst includes (a) a lanthanide-containing compound, (b) an alkylating agent, and (c) a halogen source.

### Claim 12 (depends on 11)

The method of claim 11, where the alkylating agent includes an aluminoxane and an organoaluminum compound represented by the formula AlRnX3-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.

### Claim 13 (depends on 1)

The method of claim 1, where said step of polymerizing monomer takes place within a polymerization mixture including less than 20% by weight of organic solvent.

### Claim 14 (depends on 3)

The method of claim 3, where the polycyano compound is a (polycyano)arene compound selected from the group consisting of 1,2-dicyanobenzene (phthalonitrile), 1,3-dicyanobenzene (isophthalodinitrile or isophthalonitrile), 1,4-dicyanobenzene (terephthalonitrile), 1,2-dicyanonaphthalene, 1,3-dicyanonaphthalene, 1,4-dicyanonaphthalene, 1,5-dicyanonaphthalene, 1,6-dicyanonaphthalene, 1,7-dicyanonaphthalene, 1,8-dicyanonaphthalene, 2,3-dicyanonaphthalene, 2,4-dicyanonaphthalene, 1,1′-biphenyl)-4,4′-dicarbonitrile, 1,2-dicyanoanthracene, 1,3-dicyanoanthracene, 1,4-dicyanoanthracene, 1,8-dicyanoanthracene, 1,9-dicyanoanthracene, 2,3-dicyanoanthracene, 2,4-dicyanoanthracene, 9,10-dicyanoanthracene, 9,10-dicyanophenanthrene, 1,2-dicyanoindene, 1,4-dicyanoindene, 2,6-dicyanoindene, 1,2-dicyanoazulene, 1,3-dicyanoazulene, 4,5-dicyanoazulene, 1,8-dicyanofluorene, 1,9-dicyanofluorene, 4,5-dicyanofluorene, 2,6-dicyanotoluene, 2-cyanophenylacetonitrile, 4-cyanophenylacetonitrile, 1,3,5-tricyanobenzene, 1,2,4-tricyanobenzene, 1,2,5-tricyanobenzene, 1,4,6-tricyanoindene, 1,3,7-tricyanonaphthalene, 1,2,4,5-tetracyanobenezene, and 1,3,5,6-tetracyanonaphthalene.

### Claim 15 (depends on 3)

The method of claim 3, where the polycyano compound is a (polycyano)alkane selected from the group consisting of malononitrile, 1,2-dicyanoethane (succinonitrile), 1,2-dicyano-1,2-diphenylethane, 1,3-dicyanopropane (glutaronitrile), 2-methylglutaronitrile, 1,2-dicyanopropane, dimethylmalononitrile, diphenylmalononitrile, 1,4-dicyanobutane (adiponitrile), 1,5-dicyanopentane (pimelonitrile), 1,6-dicyanohexane (suberonitrile), 1,7-dicyanoheptane, 1,8-dicyanooctane (sebaconitrile), 3,3′-thiodipropionitrile, 1,1,3-tricyanopropane, 1,1,2-tricyanopropane, 1,1,4-tricyanobutane, 1,1,5-tricyanopentane, 1,1,6-tricyanohexane, 1,3,5-tricyanohexane, 1,2,5-tricyanoheptane, 2,4,6-tricyanooctane, tris(2-cyanoethyl)amine, 1,1,3,3-tetracyanopropane, 1,1,4,4-tetracyanobutane, 1,1,6,6,-tetracyanohexane, and 1,2,4,5-tetracyanohexane.

### Claim 16 (depends on 3)

The method of claim 3, where the polycyano compound is a (polycyano)alkene selected from the group consisting of fumaronitrile, 1,3-dicyanopropene, cis-1,4-dicyano-2-butene, trans-1,4-dicyano-2-butene, 2-methyleneglutaronitrile, benzylidenemalononitrile, 1,1,2-tricyanoethylene, 1,1,3-tricyanopropene, 1,1,4-tricyano-2-butene, 1,1,5-tricyano-2-pentene, tetracyanoethylene, 7,8,8-tetracyanoquinodimethane, and 1,1,4,4-tetracyano-2-butene.

### Claim 17 (depends on 3)

The method of claim 3, where the polycyano compound is a (polycyano)alkyne selected from the group consisting of 3,3-dicyanopropyne, 3,4-dicyano-1-butyne, 3,4-dicyano-1-pentyne, 3,4-dicyano-1-pentyne, 3,5-dicyano-1-pentyne, 3,4-dicyano-1-hexyne, 3,5-dicyano-1-hexyne, 3,6-dicyano-1-hexyne, 4,5-dicyano-1-hexyne, 4,6-dicyano-1-hexyne, 5,6-dicyano-1-hexyne, 1,3,3-tricyanopropyne, 1,3,4-tricyano-1-butyne, 1,3,4-tricyano-1-pentyne, 1,3,4-tricyano-1-pentyne, 1,3,5-tricyano-1-pentyne, 1,4,5-tricyano-1-pentyne, 3,4,5-tricyano-1-hexyne, 3,4,6-tricyano-1-hexyne, 3,5,6-tricyano-1-hexyne, 3,4,5-tricyano-1-hexyne, and 1,1,4,4-tetracyano-2-butyne.

### Claim 18 (depends on 3)

The method of claim 3, where the polycyano compound is a (polycyano)cycloalkane selected from the group consisting of 1,2-dicyanocyclobutane, 1,2-dicyanocyclopentane, 1,3-dicyanocyclopentane, 1,2-dicyanocyclohexane, 1,3-dicyanocyclohexane, 1,4-dicyanocyclohexane, 1,2-dicyanocycloheptane, 1,3-dicyanocycloheptane, 1,4-dicyanocycloheptane, 1,2-dicyanocyclooctane, 1,3-dicyanocyclooctane, 1,4-dicyanocyclooctane, 1,5-dicyanocyclooctane, 1,2,4-tricyanocyclohexane, 1,3,4-tricyanocyclohexane, 1,2,4-tricyanocycloheptane, 1,3,4-tricyanocycloheptane, 1,2,4-tricyanocyclooctane, 1,2,5-tricyanocyclooctane, 1,3,5-tricyanocyclooctane, 1,2,3,4-tetracyanocyclohexane, 2,2,4,4-tetracyclohexane, 1,2,3,4-tetracyanocycloheptane, 1,1,4,4-tetracyanocycloheptane, 1,2,3,4-tetracyanocyclooctane, 1,2,3,5-tetracyanocyclooctane, 3,3-dimethylcyclopropane-1,1,2,2-tetracyanocarbonitrile, and spiro(2.4) heptane-1,1,2,2-tetracarbonitrile.

### Claim 19 (depends on 3)

The method of claim 3, where the polycyano compound is a (polycyano)cycloalkene selected from the group consisting of 1,2-dicyanocyclopentene, 1,3-dicyanocyclopentene, 1,4-dicyanocyclopentene, 1,2-dicyanocyclohexene, 1,3-dicyanohexene, 1,4-dicyanocyclohexene, 3,6-dicyanocyclohexene, 1,2-dicyanocycloheptene, 1,3-dicyanocycloheptene, 1,4-dicyanocycloheptene, 1,6-dicyanocyclooctene, 3,4-dicyanocycloheptene, 1,2,3-tricyanocyclopentene, 1,2,4-tricyanocyclopentene, 1,2,4-tricyanocyclohexene, 1,3,5-tricyanocyclohexene, 1,2,4-tricyanocycloheptene, 1,3,4-tricyanocycloheptene, 1,2,3-tricyanocyclooctene, 1,2,5-tricyanocyclooctene, 1,2,3,4-tetracyanocyclohexene, 3,3,4,4-tetracyanocyclohexene, 1,2,4,5-tetracyanocycloheptene, 3,3,4,4-tetracyanocycloheptene, 1,2,3,4-tetracyanocyclooctene, 3,3,4,4-tetracyanocyclooctene, tricyclo[4.2.2.0(2,5)]deca-3,9-diene-7,7,8,8-tetracarbonitrile, 1,2,6,7-tetracyanocyclooctene, tricyclo[4.2.2.0(2,5)]deca-3,9-diene-7,7,8,8-tetracarbonitrile, 3-methyltricyclo[4.2.2.0(2,5)]deca-3,9-diene-7,7,8,8-tetracarbonitrile, 3-phenyltricyclo[4.2.2.0(2,5)]deca-3,9-diene-7,7,8,8-tetracarbonitrile, 3,4-dimethyltricyclo[4.2.2.0 (2,5)]deca-3,9-diene-7,7,8,8-tetracarbonitrile, bicyclo[7.2.0]undeca-2,4,7-triene-10,10,11,11-tetracarbonitrile, bicyclo[2.2.1]hept-5-ene-2,2,3,3-tetracarbonitrile, and tetracyclo[8.2.2.0(2,9).0(3,8)]tetradeca-3 (8),13-diene-11,11,12,12-tetracarbonitrile.

### Claim 20

A method for preparing a functionalized polymer, the method comprising the steps of:
(i) polymerizing monomer consisting of conjugated diene monomer with a lanthanide-based catalyst system to form a polymer having a pseudo-living chain end; and
(ii) reacting the polymer having a pseudo-living chain end with a polycyano compound, where the polycyano compound is defined by the formula N≡C—R1—C≡N, where R1 is an acyclic divalent organic group that may or may not include one or more heteroatoms or R1 is a cyclic divalent organic group that is devoid of heteroatoms.

### Claim 21 (depends on 1)

The method of claim 1, where the conjugated diene monomer is 1,3-butadiene, and where said polymer is polybutadiene.