Method for producing rubber compositions with disaggregated carbon nanotubes

Patent metadata

Field	Value
Publication number	US-11814523-B2
Application number	US-201916961674-A
Country	US
Kind code	B2
Filing date	Jan 14, 2019
Priority date	Jan 12, 2018
Publication date	Nov 14, 2023
Grant date	Nov 14, 2023

Abstract

Methods for producing a cross-linkable rubber composition that comprises a masterbatch are disclosed. The masterbatch comprising a base masterbatch and the method includes forming the base masterbatch by adding a diene rubber to an internal mixer; adding a total quantity of a solid agglomerated material that includes carbon nanotubes into the mixing chamber; and mixing the diene elastomer and the solid agglomerated material. To ensure adequate distribution and dispersion of the material, the base masterbatch has a minimum Mooney viscosity ML(1+4)100 of at least 85 MU.

First claim

What is claimed is:

1. A method for producing a cross-linkable rubber composition that comprises a masterbatch, the masterbatch comprising a base masterbatch, the method comprising:
forming the base masterbatch by adding a diene rubber within a mixing chamber of an internal mixer; adding a total quantity of a solid agglomerated material into the mixing chamber; and mixing the diene elastomer and the solid agglomerated material in the mixing chamber,
wherein the solid agglomerated material comprises disaggregated carbon nanotubes consisting of a continuous network of carbon nanotubes, the continuous network comprising 1) voids and 2) aggregates of carbon nanotubes having a d 50 mean size of less than 5 μm, the voids and the aggregates together being in an amount that is less than 60% of a predetermined surface area, such percentage as determined by electron microscopy image analysis, the remainder being the disaggregated carbon nanotubes in the continuous network that do not comprise a clearly defined shape and being in an amount that is at least 40% of the predetermined surface area, and wherein the base masterbatch has a minimum Mooney viscosity ML(1+4)100 of at least 85 MU; and
continuing to mix the base masterbatch until it has reached a first predetermined temperature.

2. The method of claim 1 , wherein the first predetermined temperature is between 120° C. and 190° C.

3. The method of claim 1 , wherein the minimum Mooney viscosity is 95 MU.

4. The method of claim 1 , wherein after the step of continuing to mix the base masterbatch until it has reached a first predetermined temperature, the method further comprises:
dropping the masterbatch from the internal mixer;
cooling the masterbatch; and
adding at least a portion of the masterbatch into the mixing chamber, the portion of the masterbatch providing a predetermined amount of the solid agglomerated material required in the cross-linkable rubber composition.

5. The method of claim 1 , wherein the total quantity of the solid agglomerated material is sufficient to provide the minimum Mooney viscosity.

6. The method of claim 1 , wherein the total quantity of the solid agglomerated material in the base masterbatch is between 15 phr and 100 phr.

7. The method of claim 1 , wherein the minimum Mooney viscosity if 90 MU.

8. The method of claim 1 , wherein the cross-linkable rubber composition comprises between 1 phr and 75 phr of the solid agglomerated material.

9. The method of claim 1 , wherein the diene rubber is a highly unsaturated rubber selected from natural rubber, a synthetic rubber or combinations thereof.

10. The method of claim 1 , wherein the amount of the voids and the aggregates is less than 10% and the remainder is at least 90%.

11. The method of claim 1 , wherein the solid agglomerated material is of a form that is spheres, cylinders, flakes, granules, bricks or combinations thereof, wherein a smallest diameter of the form is greater than 1 mm.

12. The method of claim 1 , wherein the disaggregated carbon nanotubes of the continuous network are multi-walled.

13. The method of claim 1 , wherein the disaggregated carbon nanotubes of the continuous network are oxidized.

14. The method of claim 1 , wherein the step of adding a total quantity of a solid agglomerated material into the mixing chamber optionally further comprises:
adding a portion of the total quantity of the solid agglomerated material into the mixing chamber and mixing with the diene rubber;
repeating the step of adding a portion of the total quantity and mixing with the diene rubber until the total quantity has been added.

15. The method of claim 14 , wherein the total quantity of the solid agglomerated material is added within the first 50% of a total mixing time period, the total mixing time period being between the step of adding a portion of the total quantity of the solid agglomerated material into the mixing chamber and continuing to mix the base masterbatch until it has reached a first predetermined temperature.

16. The method of claim 1 , further comprising:
optionally adding one or more additional components of the base masterbatch to the mixing chamber and mixing it with the diene rubber and the solid agglomerated material, wherein the base masterbatch minimum Mooney viscosity is maintained and wherein the one or more additional components are selected from predetermined components of a non-productive phase of the cross-linkable rubber composition.

17. The method of claim 16 , wherein after the step of continuing to mix the base masterbatch until it has reached a first predetermined temperature, the method further comprises:
optionally adding one or more additional component of the masterbatch to the mixing chamber and mixing it with the base masterbatch, wherein maintaining the minimum Mooney viscosity is not required and wherein the one or more additional components are selected from predetermined components of a non-productive phase of the cross-linkable rubber composition.

18. The method of claim 1 , after the step of continuing to mix the base masterbatch until it has reached a first predetermined temperature or after the step of adding the masterbatch into the internal mixer, further comprising:
adding additional predetermined components of a non-productive phase of the cross-linkable rubber composition into the mixing chamber;
mixing the additional predetermined components with the masterbatch until it has reached a second predetermined temperature;
dropping the non-productive phase of the cross-linkable rubber composition; and
cooling the non-productive phase; and then
mixing a curing agent into the non-productive phase to form the productive phase;
cooling the cross-linkable rubber composition.

19. The method of claim 18 , further comprising:
forming a tire component from the cross-linkable rubber composition.

Assignees

• Michelin & Cie

Inventors

• Pappas Christopher
• Mehlem Jeremy John
• Khripin Constantine

Classifications

• C08L9/06 Primary

  Copolymers with styrene · CPC title

• B60C1/0016

  Compositions of the tread · CPC title

• B60C11/0008

  characterised by the tread rubber · CPC title

• C08F236/06

  Butadiene · CPC title

• C08F236/08

  Isoprene · CPC title