Carbon nanostructure preblends and their applications

• US 9,550,907 B2
• Filed: 02/27/2015
• Issued: 01/24/2017
• Est. Priority Date: 02/27/2015
• Status: Active Grant

• Current Assignee: Gates Corporation The
• Original Assignee: Gates Corporation The
• Inventors: Burlett, Donald James, Richter, Henning, Sivarajan, Ramesh, Vejins, Viktor
• Primary Examiner(s): CHIN, HUI H
• Application Number:
  US14/633,458
• Publication Number:
  US 20160251534A1
• Time in Patent Office: 697 Days
• Field of Search: 524/495
• US Class Current: 1/1
• CPC Class Codes: C01B 2202/02 Single-walled nanotubes
• CPC Class Codes: C01B 2202/06 Multi-walled nanotubes
• CPC Class Codes: C01B 32/05 Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
• CPC Class Codes: C01B 32/152 Fullerenes
• CPC Class Codes: C01B 32/168 After-treatment
• CPC Class Codes: C01B 32/174 Derivatisation; Solubilisation; Dispersion in solvents
• CPC Class Codes: C01P 2002/82 by IR- or Raman-data
• CPC Class Codes: C01P 2004/03 obtained by SEM
• CPC Class Codes: C01P 2004/13 Nanotubes
• CPC Class Codes: C01P 2004/133 Multiwall nanotubes
• CPC Class Codes: C01P 2004/84 one phase coated with the other
• CPC Class Codes: C08J 2300/26 Elastomers
• CPC Class Codes: C08J 2323/16 Ethene-propene or ethene-propene-diene copolymers
• CPC Class Codes: C08J 2323/20 having four to nine carbon atoms
• CPC Class Codes: C08J 2323/22 Copolymers of isobutene; butyl rubber
• CPC Class Codes: C08J 3/20 Compounding polymers with additives, e.g. colouring
• CPC Class Codes: C08J 3/22 using masterbatch techniques
• CPC Class Codes: C08J 3/223 Packed additives
• CPC Class Codes: C08K 2201/011 Nanostructured additives
• CPC Class Codes: C08K 3/04 Carbon
• CPC Class Codes: C08K 3/041 : Carbon nanotubes
• CPC Class Codes: C08K 3/042 : Graphene or derivatives, e.g. graphene oxides
• CPC Class Codes: C08K 3/045 : Fullerenes
• CPC Class Codes: C08K 5/03 : aromatic , e.g. C6H5-CH2-Cl
• CPC Class Codes: C08L 23/16 : Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
• CPC Class Codes: C09C 1/0081 : Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound C09C1/0015, C09C1/0078 take precedence
• CPC Class Codes: C09C 1/44 : Carbon
• CPC Class Codes: C09C 1/46 : Graphite C09C1/0015 takes precedence
• CPC Class Codes: C09C 1/48 : Carbon black
• CPC Class Codes: C09C 1/58 : Agglomerating, pelleting, or the like by wet methods
• CPC Class Codes: C09D 123/16 : Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02E 60/13 : Energy storage using capacitors

Abstract

A method for preparing a “preblend” of nano-structured carbon, such as nanotubes, fullerenes, or graphene, and a particulate solid, such as carbon black, graphitic particles or glassy carbon involving wet-mixing and followed by optional drying to remove the liquid medium. The preblend may be in the form of a core-shell powder material with the nano-structured carbon as the shell on the particulate solid core. The preblend may provide particularly improved dispersion of single-wall nanotubes in ethylene-α-olefin elastomer compositions, resulting in improved reinforcement from the nanotubes. The improved elastomer compositions may show simultaneous improvement in both modulus and in elongation at break. The elastomer compositions may be formed into useful rubber articles.

Claims

1. A preblend composition comprising carbon nanostructures and a particulate solid, said preblend composition prepared by wet-mixing said carbon nanostructures and said particulate solid in a liquid medium, wherein the preblend composition comprises solid core particles of said particulate solid coated with a shell of said carbon nanostructures forming a core-shell material;

and

wherein the core particles are carbon black particles.

2. The preblend composition of claim 1 wherein the preblend further comprises a nanotube network with carbon black particles dispersed therein.

3. The preblend composition of claim 1 wherein the carbon nanostructures are nanotubes.

4. The preblend composition of claim 1 wherein the core particles are regular or irregular in shape and have a size in the range of 20 nm to 20 μ

m in terms of average longest dimension.

5. The preblend composition of claim 1 wherein the carbon nanostructures consist of one or more from the group consisting of fullerenes, single-walled carbon nanotubes, multi-walled carbon nanotubes, and their chemical derivatives.

6. The preblend composition of claim 1 wherein the shell coating on the core particles cover a surface area in the range of 50-100% of the total surface area of the core particles.

7. A method for dispersing carbon nanostructures in a polymer comprising:

wet-mixing in a liquid medium a blend comprising said carbon nanostructures and a particulate solid;

drying said blend to form a preblend of the carbon nanostructures and the particulate for adding to a polymer in a conventional compounding process;

wherein said preblend forms a core-shell structure comprising a shell of said carbon nanostructures coating a core comprising a particle of said particulate solid; and

wherein said particulate solid is carbon black.

8. The method of claim 7 wherein said liquid medium is an organic liquid.

9. The method of claim 7 wherein said liquid medium comprises substituted aromatic molecules, alkyl substituted aromatics, halogenated substituted molecules, halogenated alkanes, partially hydrogenated aromatics, alkylamines, cyclic ethers, o-dichlorobenzene, xylene, benzene, dimethylformamide, ethylene chloride, chloroform, 1,2,4-trimethylbenzene, 1,2,3,4-tetramethylbenzene, tetrahydrofuran, 1,2-dibromobenzene, 1,1,2,2-tetrachloroethane, 1,2,3,4-tetrahydronaphthalene, octadecylamine, acetone and mixtures thereof.

10. The method of claim 7 wherein said liquid medium is water or water stabilized by means of surfactant with such surfactant being at least one member selected from the group consisting of sodium cholate, sodium octylbenzene sulfonate, sodium butylbenzene sulfonate, sodium benzoate, sodium dodecyl sulfate, C₈H₁₇C₆H₄(OCH₂CH₂)n-OH wherein n˜

10, dodecyltrimethylammonium bromide, dextrin, and polystyrene-polyethylene oxide diblock copolymer.

11. The method of claim 7 wherein the nano-structured carbon comprises carbon nanotubes (“

CNT”

), and wherein said preblend further comprises particles of the particulate solid intermixed with a network of said CNT.

12. The method of claim 11 wherein said CNT are single-wall carbon nanotubes.

13. The method of claim 11 wherein said CNT are multi-wall carbon nanotubes.

14. The method of claim 7 further comprising mixing said preblend into a polymer composition.

15. The method of claim 14 wherein the primary polymer in the polymer composition is an ethylene-α

-olefin elastomer.

16. The method of claim 15 wherein the α

-olefin of the ethylene-a-olefin elastomer is propylene, butylene or octene.

17. The method of claim 14 further comprising making a rubber article comprising said polymer composition.

18. The method of claim 17 wherein said rubber article is a belt, hose, tire, or vibration control component.

19. A method for dispersing carbon nanotubes (“

CNT”

) in an elastomer comprising;

obtaining a preblend of CNT and carbon black which was formed by wet-mixing the CNT and the carbon black in a liquid medium followed by drying, wherein said preblend comprises a core-shell structure comprising a shell of said CNT coating a core comprising said carbon black;

mixing said preblend into said elastomer with other ingredients to form an elastomer composition.

20. The method of claim 19 further comprising making an elastomeric article comprising said elastomer composition.

21. The method of claim 20 wherein said elastomeric article is a belt, hose, tire, or vibration control component.

22. The method of claim 20 wherein said elastomeric article is a power transmission belt.

23. The method of claim 19 wherein the weight ratio of the carbon black to the CNT in the preblend is in the range of 4:

1 to 20;

1.

24. The method of claim 19 wherein the preblend further comprises particles of the carbon black intermixed within a network of the CNT.

25. The method of claim 19 wherein the preblend further comprises a nanotube network with carbon black particles dispersed therein.

26. A preblend composition comprising carbon nanostructures and a particulate solid, said preblend composition prepared by wet-mixing said carbon nanostructures and said particulate solid in a liquid medium followed by drying, wherein the preblend composition comprises solid core particles of said particulate solid coated with a shell of said carbon nanostructures forming a core-shell material;

and

wherein the core particles are carbon black particles.

27. The preblend composition of claim 26 wherein the preblend further comprises a nanotube network with carbon black particles dispersed therein.

28. The preblend composition of claim 26 wherein the core particles comprise carbon black particles and the carbon nanostructures comprise nanotubes.

29. The core-shell material of claim 26 wherein the core particles are regular or irregular in shape and have a size in the range of 20 nm to 20 μ

m in terms of average longest dimension.

30. The composition of claim 26 wherein the carbon nanostructures consist of one or more from the group consisting of fullerenes, single-walled carbon nanotubes, multi-walled carbon nanotubes, and their chemical derivatives.

31. The core-shell material of claim 26 wherein the shell coating on the core particles cover a surface area in the range of 50-100% of the total surface area of the core particles.

32. A method comprising:

dispersing carbon nanostructures in a liquid medium to form a dispersion;

blending the dispersion with a particulate solid to form a blend; and

drying said blend to form a preblend;

wherein the preblend comprises a core-shell material comprising a core of particles of said particulate solid coated with a shell of said carbon nanostructures; and

wherein the particulate solid is carbon black.

33. The method of claim 32 further comprising adding the preblend to a polymer in a compounding process.

34. The method of claim 32 further comprising using the preblend as part of a battery electrode or as part of an electrolyte medium in a super capacitor.

35. The method of claim 32 further comprising using the preblend in an electrolyte medium, paint, coating, or slurry.