# US 10,370,460 B1 · Process for producing functionalized polymers

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- Number: US 10,370,460 B1
- Document ID: US10370460B1
- Status: Granted
- Kind: B1
- Application number: 15/159,114
- Filed: 2016-05-19
- Granted: 2019-08-06
- Earliest claimed: 2015-05-20
- Assignees: Bridgestone Corporation
- Applicants: Bridgestone Corporation
- Inventors: Kevin Michael McCauley; Timothy Leonard Tartamella; Zachary Aaron Bush
- Web page: https://patentgrep.com/patent/US10370460B1

## CPC

- 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 2/38: Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation}
- C08F 8/30: Introducing nitrogen atoms or nitrogen-containing groups
- C08F 4/52: selected from boron, aluminium, gallium, indium, thallium or rare earths (C08F4/14 takes precedence)
- C08F 4/545: {rare earths being present, e.g. triethylaluminium + neodymium octanoate}
- C08F 36/04: conjugated
- C08K 5/16: Nitrogen-containing compounds {(C08K5/0091 takes precedence)}
- C08K 5/34: Heterocyclic compounds having nitrogen in the ring
- C08C: TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)

## Abstract

A method for producing a functionalized polymer, the method comprising the steps of: (i) preparing a bulk polymerization system including a reactive polymer by introducing a lanthanide-based catalyst and a conjugated diene monomer; (ii) adding a heterocyclic nitrile compound the polymerization system including the reactive polymer to prepare polymerization system including a functionalized polymer; and (iii) adding a protic compound to the polymerization system including a functionalized polymer where the ratio of water or protic hydrogen atoms in the protic compound to the lanthanide atoms in the lanthanide-based catalyst is at least 1500 to 1.

## Claims

### Claim 1

A continuous method for preparing a functionalized polymer, the method comprising the steps of:
(i) in a first zone, continuously polymerizing conjugated diene monomer with a lanthanide-based catalyst within a polymerization mixture that includes less than 20% by weight of solvent based on the total weight of the polymerization mixture to produce a reactive polymer,
(ii) continuously transferring the reactive polymer to a second zone and adding a heterocyclic nitrile compound to prepare a functionalized polymer;
(iii) continuously transferring the functionalized polymer to a third zone and adding a quenching agent, where the ratio of water or protic hydrogen atoms in the quenching agent to the lanthanide atoms in the lanthanide-based catalyst is from about 1500 to 1 to about 3000:1; and
(iv) continuously transferring the functionalized polymer to a devolatizer.

### Claim 2 (depends on 1)

The method of claim 1, where the quenching agent is selected from the group consisting of alcohols, carboxylic acids, inorganic acids, water, and mixtures thereof.

### Claim 3 (depends on 2)

The method of claim 2, where the quenching agent is an alcohol.

### Claim 4 (depends on 2)

The method of claim 2, where the quenching agent is a carboxylic acid.

### Claim 5 (depends on 2)

The method of claim 2, where the quenching agent is water.

### Claim 6 (depends on 2)

The method of claim 2, where the quenching agent is an inorganic acid.

### Claim 7 (depends on 1)

The method of claim 1, where the ratio of water or protic hydrogen atoms in the quenching agent to the lanthanide atoms in the lanthanide-based catalyst is at least 1900 to 1.

### Claim 8 (depends on 1)

The method of claim 1, where the polymerization mixture includes less than 5% by weight of solvent based on the total weight of the polymerization mixture.

### Claim 9 (depends on 1)

The method of claim 1, where the heterocyclic nitrile compound is defined by the formula θ-C≡N or θ-R—C≡N, where θ is a heterocyclic group and R is a divalent organic group.

### Claim 10 (depends on 9)

The method of claim 9, where the heterocyclic group is aromatic.

### Claim 11 (depends on 10)

The method of claim 10, where the heterocyclic group is pyridine.

### Claim 12 (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 13 (depends on 12)

The method of claim 12, 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 14

A continuous method for the production of functionalized polydienes, comprising:
(i) continuously charging a mixture of one or more conjugated diene monomer, lanthanide-based catalyst system, and less than 20% weight percent organic solvent based on the total weight of the monomer, catalyst and solvent, into a reactor;
(ii) continuously polymerizing the monomer to a conversion of up to 20% by weight of the monomer to form a mixture of reactive polymer and monomer;
(iii) continuously removing the mixture of reactive polymer and monomer from the reactor and functionalizing the reactive polymer with a heterocyclic nitrile compound prior to a total monomer conversion of 25% by weight to form a mixture of functionalized polymer and monomer;
(iv) continuously quenching the mixture of functionalized polymer and monomer with a quenching agent, where the ratio of water or protic hydrogen atoms in the quenching agent to the lanthanide atoms in the lanthanide-based catalyst is from about 1500 to 1 to about 3000:1; and
(v) continuously recovering the monomer from the mixture of functionalized polymer and monomer.

### Claim 15 (depends on 14)

The method of claim 14, where the ratio of water or protic hydrogen atoms in the quenching agent to the lanthanide atoms in the lanthanide-based catalyst is at least 1900 to 1.

### Claim 16 (depends on 14)

The method of claim 14, where the polymerization mixture includes less than 5% by weight of solvent based on the total weight of the polymerization mixture.

### Claim 17 (depends on 14)

The method of claim 14, where the heterocyclic nitrile compound is defined by the formula θ-C≡N or θ-R—C≡N, where θ is a heterocyclic group and R is a divalent organic group.

### Claim 18 (depends on 14)

The method of claim 14, where the step of functionalizing the reactive polymer with a heterocyclic nitrile compound and the step of quenching the mixture of functionalized polymer and monomer take place in separate zones.

### Claim 19 (depends on 1)

The method of claim 1, where the functionalized polymer is characterized by a decrease in Mooney viscosity (ML1+4 @100° C.) after 24 hours aging under atmospheric conditions of less than 10%.

### Claim 20 (depends on 14)

The method of claim 14, where the functionalized polydiene is characterized by a decrease in Mooney viscosity (ML1+4 @100° C.) after 24 hours aging under atmospheric conditions of less than 10%.

### Claim 21 (depends on 1)

The method of claim 1, further comprising the step of adding an antioxidant to the third zone, wherein the amount of antioxidant added is from about 0.2% to about 1% by weight of the functionalized polymer.

### Claim 22 (depends on 14)

The method of claim 14, in conjunction with said step of continuously quenching the mixture, introducing an antioxidant to the functionalized polymer, wherein the amount of antioxidant added is from about 0.2% to about 1% by weight of the functionalized polydiene.