CN116262841A

CN116262841A - Conductive rubber composition and article comprising the same

Info

Publication number: CN116262841A
Application number: CN202211612200.3A
Authority: CN
Inventors: R·V·丹尼斯-佩尔彻; 赵军令; A·P·默里
Original assignee: Goodyear Tire and Rubber Co
Current assignee: Goodyear Tire and Rubber Co
Priority date: 2021-12-15
Filing date: 2022-12-15
Publication date: 2023-06-16

Abstract

The invention discloses a conductive rubber composition and an article comprising the same. Described herein are conductive rubber compositions comprising a rubber component and one or more conductive carbon compounds. In another aspect, the conductive rubber composition may be prepared by first adding one or more conductive carbon components to the polymer phase, thereby creating a filler network in the continuous polymer phase in the finished product. In a further aspect, the conductive carbon component may be or include one or more of the following: carbon black, short carbon fibers, graphite powder, or graphene powder. After mixing, the conductive rubber composition may optionally be vulcanized. The conductive rubber composition has good mechanical properties and resistivity, and can be processed using existing equipment.

Description

Conductive rubber composition and article comprising the same

Technical Field

The present invention relates to the field of rubber, and more particularly to an electrically conductive rubber composition and an article comprising the same.

Background

Many applications in the computing, military, medical equipment, telecommunications and transportation fields require conductive rubber compounds. Although several approaches have been proposed to obtain rubber compositions meeting the different needs of these industries, maintaining acceptable mechanical reinforcing properties has proven difficult.

Rubber is an electrically insulating material. In order to make the rubber conductive, a continuous path of conductive particles must be created in the rubber. However, the conductive filler significantly affects the electrical and mechanical properties of the rubber.

In addition, conductive carbon compounds are difficult to mix with high molecular weight rubbers and other polymers. Non-uniform mixing may in turn result in a non-uniform distribution of conductive carbon in articles made from the composition, which can affect the conductivity of the rubber compositions as well as their mechanical strength. Long carbon fibers can provide the required mechanical strength, but lack elasticity and may fracture.

Despite the progress made in the development of conductive rubbers, there is still a lack of conductive rubber compositions which have acceptable mechanical properties, can be processed with existing equipment, and maintain their conductivity without degradation over time. The present disclosure meets these and other needs.

Disclosure of Invention

Described herein is a conductive rubber composition comprising a rubber component and one or more conductive carbon compounds, wherein the conductive rubber composition has an uncured or cured resistance at 23 ℃ of less than about 10 megaohms (mΩ) when formed into a wire of about 10 inches (254 mm) length and 2 mm diameter. In another aspect, the conductive rubber composition may be prepared by first adding one or more conductive carbon components to the polymer phase, thereby creating a filler network in the continuous polymer phase in the finished product. In a further aspect, the conductive carbon component may be or include one or more of the following: carbon black, short carbon fibers, graphite powder, or graphene powder. After mixing, the conductive rubber composition may optionally be vulcanized. The conductive rubber composition has good mechanical properties and resistivity, and can be processed using existing equipment. Also disclosed are articles comprising the conductive rubber composition.

The invention discloses the following embodiments:

1. a conductive rubber composition comprising a rubber component and one or more conductive carbon components, wherein the conductive rubber composition has an uncured or cured resistance of less than about 10M Ω at 23 ℃ when formed into a wire that is about 10 inches (254 millimeters) long and 2 millimeters in diameter.

2. The conductive rubber composition of claim 1, wherein the rubber component comprises Natural Rubber (NR), polyisoprene rubber (IR), styrene Butadiene Rubber (SBR), polybutadiene rubber (BR), butyl or halogenated butyl rubber, ethylene propylene rubber (EM), ethylene propylene diene monomer rubber (EPDM), neoprene rubber (CR), nitrile rubber (NBR), hydrogenated acrylonitrile butadiene rubber (HNBR), silicone rubber (MQ), thermoplastic rubber, or any combination thereof.

3. The conductive rubber composition of scheme 2, wherein the butyl or halogenated butyl rubber comprises isobutylene-isoprene rubber (IIR), brominated isobutylene-isoprene rubber (BIIR), chlorinated isobutylene-isoprene rubber (CIIR), brominated isobutylene-co-p-methylstyrene rubber (BIMS), or any combination thereof.

4. The conductive rubber composition according to claim 1, wherein the conductive rubber composition comprises a blend of two or more rubber components.

5. The conductive rubber composition according to the scheme 1, wherein the rubber component comprises about 5X 10 ⁴ Da to about 3X 10 ⁷ Molecular weight of Da (M _w ）。

6. The conductive rubber composition of claim 1, wherein the rubber component comprises a mooney viscosity UML of about 0.01 to about 150 or a mooney viscosity UMS of about 2 to about 150.

7. The conductive rubber composition of claim 1, wherein the rubber component comprises a glass transition temperature of about-110 ℃ to about 30 ℃.

8. The conductive rubber composition according to the scheme 1, wherein the rubber component comprises a molecular weight distribution (M _w /M _n ）。

9. The conductive rubber composition of claim 1, wherein the one or more conductive carbon components comprise carbon black, short carbon fibers, graphite powder, graphene powder, or any combination thereof.

10. The conductive rubber composition of claim 1, wherein the one or more conductive carbon components are present in an amount of about 20 phr to about 150 phr.

11. The conductive rubber composition of scheme 1, wherein the one or more conductive carbon components comprise a polymer having an average particle size of about 5 nm to about 100 nm and about 20 m ² /g to about 1700 m ² Carbon black with BET surface area per gram.

12. The conductive rubber composition of claim 1, wherein the one or more conductive carbon components comprise carbon fibers, wherein the carbon fibers comprise chopped carbon fiber yarns, multi-walled carbon nanotubes (MWCNTs), single-walled carbon nanotubes (SWCNTs), or any combination thereof.

13. The conductive rubber composition according to claim 12, wherein the short carbon fibers have a diameter of about 1 nm to about 1000 nm and about 1 μm to about 1 x 10 ⁴ Length of μm.

14. The conductive rubber composition of claim 1, wherein the one or more carbon components comprise a blend of carbon black and short carbon fibers.

15. The conductive rubber composition of claim 14, wherein in the blend the short carbon fibers are from about 5 phr to about 80 phr and the carbon black is from about 15 phr to about 70 phr.

16. The conductive rubber composition of claim 1, further comprising at least one additional component selected from the group consisting of antioxidants, antiozonants, oils, zinc oxide, fatty acids, sulfur, accelerators, scorch retarders, or any combination thereof.

17. The conductive rubber composition according to claim 1, wherein the conductive rubber composition has a tensile strength of about 2 MPa to about 30 MPa.

18. The conductive rubber composition according to the scheme 1, wherein the conductive rubber composition has an elongation at break of about 200% to about 800%.

19. An article comprising the conductive rubber composition according to scheme 1.

20. The article of claim 19, wherein the article comprises a tire, a tire chimney, a wire, a sensor, a hose, an electromagnetic interference shielding gasket, a weatherable sealing material, an adhesive article, or any combination thereof.

Other systems, methods, features, and advantages of the disclosure will be or become apparent to one with skill in the art upon examination of the following figures and detailed description. It is intended that all such additional systems, methods, features and advantages be included within this description, be within the scope of the present disclosure, and be protected by the accompanying claims. Furthermore, all optional and preferred features and modifications of the described embodiments are applicable to all aspects of the disclosure taught herein. Furthermore, the various features of the dependent claims, as well as all optional and preferred features and modifications of the embodiments, are combinable and interchangeable with each other.

Detailed Description

In one aspect, disclosed herein is a conductive rubber composition comprising a rubber component and one or more conductive carbon compounds. In another aspect, the conductive rubber composition may be prepared by first adding one or more conductive carbon components to the polymer phase, thereby creating a filler network in the continuous polymer phase in the finished product. In a further aspect, the conductive carbon component may be or include one or more of the following: carbon black, short carbon fibers, graphite powder, or graphene powder. After mixing, the conductive rubber composition may optionally be vulcanized. The conductive rubber composition has acceptable mechanical properties and conductivity and can be processed using existing equipment.

Definition of the definition

As used herein, "comprising" is to be interpreted as specifying the presence of the stated features, integers, steps or components as referred to, but does not preclude the presence or addition of one or more features, integers, steps or components, or groups thereof. In addition, in the case of the optical fiber, the terms "pass", "comprising", "including", "containing", and "including" are used to denote "pass", "include", "contain", "include", "are used to indicate" pass "," through "," by "are used to indicate" pass "," include "and" include "are used to include the" include "included)", "related to" (related to) ", and" for example "are each used in their open, non-limiting sense, and may be used interchangeably. Furthermore, the term "comprising" is intended to include examples and aspects encompassed by the terms "consisting essentially of … …" and "consisting of … …". Similarly, the term "consisting essentially of … …" is intended to include examples encompassed by the term "consisting of … …".

As used in the specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a conductive carbon compound," "a rubber component," or "an oil" includes, but is not limited to, mixtures or combinations of two or more such conductive carbon compounds, rubber components, or oils, and the like.

It should be noted that ratios, concentrations, amounts, and other numerical data may be expressed herein in a range format. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It will also be understood that there are many values disclosed herein, and that each value is also disclosed herein as "about" that particular value in addition to the value itself. For example, if the value "10" is disclosed, then "about 10" is also disclosed. Ranges may be expressed herein as from "about" one particular value, and/or to "about" another particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms a further aspect. For example, if a value of "about 10" is disclosed, "10" is also disclosed.

When a range is expressed, further aspects include from the one particular value and/or to the other particular value. For example, where the range includes one or two boundaries, ranges excluding either or both of those included boundaries are also included in the present disclosure, e.g., the phrase "x to y" includes ranges from "x" to "y" as well as ranges greater than "x" and less than "y". The range may also be expressed as an upper limit, such as "about x, y, z, or less," and should be interpreted to include the specific ranges of "about x," "about y," and "about z," as well as ranges of "less than x," less than y, "and" less than z. Likewise, the phrase "about x, y, z, or greater" should be construed to include the specific ranges of "about x", "about y", and "about z" as well as ranges of "greater than x", "greater than y", and "greater than z". Further, the phrase "about 'x' to 'y'" wherein 'x' and 'y' are numerical values includes "about 'x' to about 'y'".

It is to be understood that such range format is used for convenience and brevity and thus should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For purposes of illustration, a numerical range of "about 0.1% to 5%" should be interpreted to include not only the explicitly recited values of about 0.1% to about 5%, but also include individual values (e.g., about 1%, about 2%, about 3%, and about 4%) and sub-ranges (e.g., about 0.5% to about 1.1%, about 5% to about 2.4%, about 0.5% to about 3.2%, and about 0.5% to about 4.4%) within the indicated range, as well as other possible sub-ranges.

The terms "about," "approximately," "equal to or about" and "substantially" as used herein mean that the relevant amount or value may be the exact value or a value that provides an equivalent result or effect to that described in the claims or taught herein. That is, it is to be understood that the amounts, dimensions, formulations, parameters, and other quantities and characteristics are not nor need they be exact, but may be approximated and/or larger or smaller as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, as well as other factors known to those of skill in the art, in order to achieve an equivalent result or effect. In some cases, the value that provides the equivalent result or effect cannot be reasonably determined. In such cases, it is generally understood that "about" and "equal to or about" as used herein refers to nominal values that indicate a variation of ±10%, unless otherwise indicated or inferred. Generally, an amount, dimension, formulation, parameter, or other quantity or characteristic is "about," "approximately," or "equal to or about," whether or not explicitly stated as such. It is to be understood that, unless specifically stated otherwise, where "about", "approximately" or "equal to or about" is used before a quantitative value, the parameter also includes the particular quantitative value itself.

The term "effective amount" as used herein refers to an amount sufficient to effect the desired change in a physical property of a composition or material. For example, an "effective amount" of a conductive carbon compound refers to an amount sufficient to achieve a desired improvement in properties (e.g., achieve a desired level of resistivity) that are modulated by the formulation components. The particular level expressed in weight percent of the composition required as an effective amount will depend on a variety of factors including the amount and type of rubber component, the molecular weight of the rubber component, the form and size of the conductive carbon compound, and the end use of any article made using the conductive rubber composition.

The term "optional" or "optionally" as used herein means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

"resistance" refers to how strongly a material, such as conductive rubber, can resist the flow of electrical current. Materials with high resistance are better insulators, while materials with low resistance are better conductors. The resistance may be measured using a standard meter, such as a FLUKE 117 true value multimeter.

"elongation at break" refers to the percentage of the original length of a rubber or elastomeric material to the length to which the material extends at break when an extension or tensile force is applied to the material.

"fiber" is a natural or artificial unit of matter that forms the basic element of a filament, characterized by a length that is at least 10 times its diameter or width.

"modulus" refers to the tensile force (e.g., 10% modulus, 50% modulus, etc.) at a particular elongation value when a stretching or elongating motion is applied to a rubber or elastomeric material.

"Mooney viscosity" refers to the shear torque against the rotation of a cylindrical metal disc or rotor with a cylindrical cavity embedded in rubber and is reported in arbitrary Mooney units. An exemplary procedure for determining mooney viscosity can be found in standard test method ASTM D1646.

"Phr" refers to parts by weight of the corresponding material per 100 parts by weight of rubber or elastomer.

"storage modulus (G')" is a measure of the deformation energy stored in an elastic manner in a viscoelastic material. In some aspects, a material with a higher degree of crosslinking will have a greater storage modulus.

"T25" refers to the cure time required for the rubber composition to reach 25% of the ultimate elastic torque and is expressed in minutes with reference to a given temperature. Meanwhile, "T90" is the time required for the rubber composition to reach 90% of the ultimate elastic torque value. T25 and T90 may be measured using a rotor-less rheometer (moving die rheometer) and/or a rubber processing analyzer.

"Zwick rebound" refers to a test of the elasticity of a material. In this test, a force is applied to the material. The fully elastic material stores energy from the force and releases energy when the force is removed. The fully plastic material absorbs the supplied energy. Rubber materials typically have Zwick rebound values that reflect the degree of plasticity and elasticity, and Zwick rebound values typically vary with temperature.

As used herein, "oil absorption value" refers to the cubic centimeter or milliliter of dibutyl phthalate (DBP) or paraffinic oil absorbed by 100 grams of carbon black under a standard set of conditions.

Unless otherwise indicated, the pressures referred to herein are based on atmospheric pressure (i.e., one atmosphere).

Rubber component

In one aspect, the conductive rubber compositions disclosed herein include a rubber component. In a further aspect, the rubber component may be Natural Rubber (NR), polyisoprene rubber (IR), styrene Butadiene Rubber (SBR), polybutadiene rubber (BR), butyl or halogenated butyl rubber, ethylene propylene rubber (EM), ethylene propylene diene monomer rubber (EPDM), neoprene rubber (CR), nitrile rubber (NBR), hydrogenated acrylonitrile butadiene rubber (HNBR), silicone rubber (MQ), thermoplastic rubber, or any combination thereof. In a further aspect, the butyl or halogenated butyl rubber may be isobutylene-isoprene rubber (IIR), brominated isobutylene-isoprene rubber (BIIR), chlorinated isobutylene-isoprene rubber (CIIR), brominated isobutylene-co-p-methylstyrene rubber (BIMS), or any combination thereof. In another aspect, the thermoplastic rubber may be poly (styrene-butadiene-styrene) rubber (SBS), thermoplastic elastomer rubber (TPE), melt Processable Rubber (MPR), or any combination thereof. In one aspect, the thermoplastic elastomer rubber may be a thermoplastic polyurethane rubber.

In one aspect, the conductive rubber composition comprises a blend of two or more rubber components. In one aspect, and without wishing to be bound by theory, a conductive system based on a polymer blend may achieve high conductivity at lower filler content, thereby alleviating the difficulty of blending carbon compounds in the polymer and reducing material costs.

Molecular weight

In one aspect, the rubber component may have a weight of about 5X 10 ⁴ Da to about 3X 10 ⁷ Da. Or about 3X 10 ⁵ Da to about 5X 10 ⁶ Da. Or about 5X 10 ⁴ Da、6 × 10 ⁴ Da、7 × 10 ⁴ Da、8 × 10 ⁴ Da、9 × 10 ⁴ Da、1 × 10 ⁵ Da、2 × 10 ⁵ Da、3 × 10 ⁵ Da、4 × 10 ⁵ Da、5 × 10 ⁵ Da、6 × 10 ⁵ Da、7 × 10 ⁵ Da、8 × 10 ⁵ Da、9 × 10 ⁵ Da、1 × 10 ⁶ Da、2 × 10 ⁶ Da、3 × 10 ⁶ Da、4 × 10 ⁶ Da、5 × 10 ⁶ Da、6 × 10 ⁶ Da、7 × 10 ⁶ Da、8 × 10 ⁶ Da、9 × 10 ⁶ Da、1 × 10 ⁷ Da、2 × 10 ⁷ Da. Or about 3X 10 ⁷ Da, or a combination of any of the foregoing values, or a molecular weight (M) covering a range of any of the foregoing values _w ）。

Molecular weight distribution

In another aspect, the rubber component may have a molecular weight distribution (M) of from about 1 to about 10, or from about 2.1 to about 10, or from about 3.9 to about 8.2, or from about 1, 1.25, 1.5, 1.75, 2, 2.1, 2.25, 2.5, 2.75, 3, 3.25, 3.5, 3.75, 4, 4.25, 4.5, 4.75, 5, 5.25, 5.5, 5.75, 6, 6.25, 6.5, 6.75, 7, 7.25, 7.5, 7.75, 8, 8.25, 8.5, 8.75, 9.25, 9.5, 9.75, or about 10, or a combination of any of the foregoing values, or a range covering any of the foregoing values _w /M _n ）。

Mooney viscosity

In one aspect, the rubber component has a mooney viscosity UML of about 0.01 to about 150, or about 0.01, 0.05, 0.1, 0.5, 1, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, or about 150, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In another aspect, the rubber component has a mooney viscosity UMS of about 2 to about 150, or about 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, or about 150, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

_g Glass transition temperature [ ]T）

In one aspect, the rubber component has a glass transition temperature of from about-110 ℃ to about 30 ℃, or from about-75 ℃ to about-25 ℃, or from about-110, -105, -100, -95, -90, -85, -80, -75, -70, -65, -60, -55, -50, -45, -40, -35, -30, -25, -20, -15, -10, -5, 0, 5, 10, 15, 20, 25, or about 30 ℃, or a combination of any of the foregoing values, or ranges encompassing any of the foregoing values.

Exemplary rubber Components

In one aspect, in the disclosed conductive rubber composition, the rubber component comprises a polymer having a molecular weight of about 3X 10 ⁴ Da to about 3X 10 ⁷ Da and a glass transition temperature of about-75 ℃ to about-65 ℃.

In one aspect, in the disclosed conductive rubber composition, the rubber component comprises a polymer having a molecular weight of about 2X 10 ⁵ Da to about 8X 10 ⁵ Da. Synthetic cis-1, 4-polyisoprene rubber having a Mooney viscosity UML of about 75 and a glass transition temperature of about-70℃to about-60 ℃.

In one aspect, in the disclosed conductive rubber composition, the rubber component comprises a polymer having a molecular weight of about 1X 10 ⁵ Da to about 4X 10 ⁵ Da. Emulsion polymerized styrene-butadiene rubber having a Mooney viscosity of about 50 UML and a glass transition temperature of about-60 ℃ to about-50 ℃.

In one aspect, in the disclosed conductive rubber composition, the rubber component comprises a polymer having a molecular weight of about 7X 10 ⁴ Da to about 8X 10 ⁴ Da. A solution polymerized styrene-butadiene rubber having a mooney viscosity UML of about 2.6 and a glass transition temperature of about-30 ℃ to about-20 ℃.

Exemplary suitable rubber components include, but are not limited to, the following: TSR20 natural rubber, RSS natural rubber, NATSYN 2200, PLF1502, exp SBR, and combinations thereof. In one aspect, TSR20 (technical grade rubber) natural rubber is a block rubber (Block rubber) available from a variety of manufacturers consisting essentially of cis-1, 4-polyisoprene and having a temperature of-70℃ T of (2) _g A molecular weight distribution of 4.59 to 8.11, a mooney viscosity (UML) of 88 to 99.2, and a maximum impurity (dirt) of 20%. On the other hand, RSS (# 2 ribbed smoke film (Ribbed Smoked Sheet Rubber)) natural rubber is a form of raw natural rubber available from many manufacturers and has a T of-70℃ _g Molecular weight distribution of 1.35 to 2.36 and mooney viscosity (UMS) of 80 to 142. In any of these aspects, the natural rubber may have a molecular weight in the range of about 1X 10 ⁷ Da to about 3X 10 ⁷ Da. In yet another aspect, NATSYN 2200 (Goodyear Chemical, akron OH) is a synthetic high cis polyisoprene containing non-contaminating antioxidants (non-staining antioxidant) and having T at-64 DEG C _g 、2.04 × 10 ⁵ M of Da _n 、7.31 × 10 ³ M of Da _w Molecular weight distribution of 3.575 and mooney viscosity (UML) of 75. In one aspect, PLF1502 (PLIOFLEX 1502, goodyear Chemical, akron OH) is an emulsion polymerized styrene-butadiene copolymer (23.5% styrene, 12% vinyl, 55% trans, 10% cis) having a T of-55 DEG C _g 、1.01 × 10 ⁵ M of Da _n 、4.03 × 10 ⁵ M of Da _w Molecular weight distribution of 3.99 and Mooney viscosity (UML) of 50, contains a non-contaminating antioxidant. In one aspect, exp SBR is a tentative Li-solution based styrene-butadiene rubber having a T of-26 degrees Celsius _g 、7.39 × 10 ⁴ M of Da _n 、7.39 × 10 ⁴ M of Da _w A molecular weight distribution of 1.00 and a Mooney viscosity (UML) of 2.63.

Carbon compounds

In one aspect, the conductive rubber compositions disclosed herein comprise a conductive carbon component. Exemplary conductive carbon components are described below.

In one aspect, the one or more carbon components may be present in an amount of about 20 phr to about 150 phr, or about 30 phr to about 100 phr, or about 40 phr to about 80 phr, or about 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, or about 150 phr, or a combination of any of the foregoing values, or ranges comprising any of the foregoing values.

Carbon black

In one aspect, the conductive carbon component may be or include carbon black. In another aspect, the carbon black can have an average particle size of about 5 nm to about 100 nm, or about 5 nm to about 50 nm, or about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or about 100 nm, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

In one aspect, the carbon black can have a molecular weight of about 20 m ² /g to about 1700 m ² /g, or about 50 m ² /g to about 1500 m ² /g, or about 20, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, or about 1700 m ² /g, or a combination of any of the foregoing values, or a BET surface area covering a range of any of the foregoing values.

In another aspect, the carbon black can have a molecular weight of about 20 to about 1200 m ² /g, or about 100 m ³ /g to about 300 m ³ /g, or about 150 m ³ /g to about 200 m ³ /g, or about 20, 25, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, or about 1200 m ³ /g, or a combination of any of the foregoing values, or an outer surface area based on statistical thickness method (STSA) covering a range of any of the foregoing values.

In another aspect, the carbon black can have an oil absorption value of about 500 mL/100 g to about 20 mL/100 g, or about 500 mL/100 g to about 80 mL/100 g, or about 500, 450, 400, 350, 300, 250, 200, 150, 100, or about 80 mL/100 g, or a combination of any of the foregoing values, or a range comprising any of the foregoing values.

Exemplary suitable carbon blacks include, but are not limited to, the following: n299 ASTM grade carbon black, PRINTEX XE2B (Orion Engineered Carbons, luxembourg), PROPEL X22 (Cabot Corporation, boston MA), or any combination thereof. In one aspect, PRINTEX XE2B has a pass standard An oil absorption value of 410 mL/100 g as measured by test method ASTM D2414, 1100 m as measured by ASTM D6556 ² BET surface area per gram and average primary particle size of 30 nm based on ASTM D3849. In another aspect, PROPEL X22 has an iodine value of 230 mg/g according to Standard test method ASTM D1510, 173 m according to Standard test method ASTM D6556 ² Per gram of external surface area based on statistical thickness method (STSA), compressed sample oil absorption value (COAN) of 100 mL/100 g according to standard test method ASTM D3493 and coloration of 150% ITRB according to standard test method ASTM D3265. Additional useful carbon BLACKs include BLACK PEARLS 2000 carbon BLACK and Vulcan XC-72 (BOTH FROM Cabot Corporation, boston MA), CONDUCTEX 975 and CONDUCTEX SC (Columbian Chemicals, hamilton ON Canada), and PRINTEX XE2, PRINTEX L and PRINTEX L6 (Orion Engineered Carbons, luxembourg).

Short carbon fiber

In one aspect, the conductive carbon component may be or include short carbon fibers. In an aspect, the short carbon fibers may be carbon fibers, chopped carbon fiber yarns, multi-walled carbon nanotubes (MWCNTs), single-walled carbon nanotubes (SWCNTs), or any combination thereof. In one aspect, the short carbon fibers have a diameter of about 1 nm to about 1000 nm, or about 150 nm to about 600 nm, or about 1, 10, 25, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, or about 1000 nm, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

In another aspect, the short carbon fibers may have a length of about 1 μm to about 1X 10 ⁴ μm, or about 1, 100, 500, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, or about 10,000 μm, or a combination of any of the foregoing, or a length covering a range of any of the foregoing.

In yet another aspect, the short carbon fibers may have an average transverse aspect ratio (lateral length to thickness ratio) of about 10:1 to about 10,000:1, or about 10:1, 50:1, 100:1, 500:1, 1000:1, 2000:1, 3000:1, 4000:1, 5000:1, 6000:1, 7000:1, 8000:1, 9000:1, or about 10,000:1, or a combination of any of the foregoing, or a range covering any of the foregoing.

Exemplary short carbon fibers useful herein have diameters (depending on the grade) of about 150 to about 600 nm, about 120-190 m ² BET surface area per gram and length of greater than 1. Mu.m.

Blends of

In some aspects, the carbon component may comprise a blend. In one aspect, the one or more carbon components consist of a blend of carbon black and graphite powder, or a blend of carbon black and graphene powder.

In another aspect, the one or more carbon components include a blend of carbon black and short carbon fibers. In one aspect, and without wishing to be bound by theory, a blend comprising carbon black and short carbon fibers may provide additional advantages in terms of the conductivity of the mixture. In one aspect, carbon black can improve inter-fiber contact by forming particle bridges, while carbon fibers can aid in the transport of electrons over long distances, creating a continuous path for electrical conduction in the disclosed compositions. In some aspects, a blend comprising carbon black and short carbon fibers may result in a different conductive network structure being formed in the blend of polymers than a rubber composition based on a single polymer.

Further in this aspect, the short carbon fiber may be from about 5 phr to about 80 phr, or from about 20 phr to about 40 phr, or may be from about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or about 80 phr, or a combination of any of the foregoing values, or a range of any of the foregoing values, and the carbon black may be from about 15 phr to about 70 phr, or from about 10 phr to about 60 phr, or about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, or about 70 phr, or a combination of any of the foregoing values, or a range of any of the foregoing values.

In one aspect, the conductive carbon component can include ASTM N299 grade carbon black and have a diameter of about 1 nm to about 1000 nm and a diameter of about 1 μm to about 1X 10 ⁴ Short carbon fibers of length μm.

In another aspect, the conductive carbon componentMay include carbon black having an oil absorption value of about 100 mL/100 g and having a diameter of about 1 nm to about 1000 nm and a diameter of about 1 μm to about 1 x 10 ⁴ Short carbon fibers of length μm.

In another aspect, the conductive carbon component can include carbon black having an average particle size of about 30 nm and having a diameter of about 1 nm to about 1000 nm and about 1 μm to about 1×10 ⁴ Short carbon fibers of length μm.

Additional component

In one aspect, the conductive rubber compositions disclosed herein may additionally contain one or more additional components in addition to those components already described. In one aspect, the additional component may be selected from antioxidants and/or antiozonants, oils, zinc oxide, fatty acids, sulfur, accelerators, scorch retarders (retarders), and combinations thereof.

Antioxidants and/or antiozonants

In one aspect, the conductive rubber compositions disclosed herein comprise at least one antioxidant, at least one antiozonant, or any combination thereof. In one aspect, the antiozonants may protect the rubber composition from ozone (O ₃ ) Attack. In another aspect, the antiozonant may be a material, such as wax, that migrates to the surface of the rubber article to protect the article from ozone. Suitable examples of antiozonants include, but are not limited to, antiozite 67P (Vanderbilt Chemicals, LLC, norwalk CT USA). In one aspect, the antioxidant is a non-contaminating antioxidant. In another aspect, the antioxidant can be an amine antioxidant, a diphenylamine antioxidant, a polymeric dihydroquinoline, or any combination thereof. In yet another aspect, the antioxidant or antiozonant may be present in the composition in an amount of about 1 phr to about 2 phr, or in an amount of about 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or about 2 phr, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

Oil (oil)

In one aspect, the conductive rubber composition comprises an oil. In another aspect, the oil is a standard rubber processing oil, such as an aromatic rubber processing oil, a paraffinic rubber processing oil, a naphthenic rubber processing oil, or any combination thereof. In one aspect, the rubber processing oil can improve the dispersion of the filler and the flow characteristics of the rubber composition during processing. In one aspect, the oil may be present in an amount of about 4 phr to about 30 phr, or in an amount of about 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or about 30 phr, or a combination of any of the foregoing values, or a range comprising any of the foregoing values.

Zinc oxide

In one aspect, the conductive rubber composition disclosed herein comprises zinc oxide. In another aspect, zinc oxide is an activator useful in the vulcanization of rubber. In one aspect, the zinc oxide is present in the conductive rubber composition from about 1 phr to about 5 phr, or from about 1, 2, 3, 4, or about 5 phr, or a combination of any of the foregoing values, or ranges comprising any of the foregoing values. In one aspect, the zinc oxide is present in an amount of about 3 phr.

Fatty acid

In one aspect, the conductive rubber compositions disclosed herein comprise fatty acids. In another aspect, the fatty acid may be stearic acid, palmitic acid, oleic acid, or any combination thereof. In a further aspect, the fatty acid may be present in the conductive rubber composition in an amount of about 1 phr to about 5 phr, or in an amount of about 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.25, 2.5, 2.75, 3, 3.25, 3.5, 3.75, 4, 4.25, 4.5, 4.75, or about 5 phr, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

Sulfur (S)

In one aspect, the conductive rubber composition disclosed herein comprises sulfur. In another aspect, sulfur may be present in an amount of from 0.5 to about 5 phr, or from about 0.5 to about 3 phr, or from about 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or about 5 phr, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, sulfur is present in an amount of about 1.8 phr. In one aspect, sulfur may be used to form crosslinks between rubber chains during the vulcanization process.

Accelerating agent

In one aspect, the conductive rubber composition includes an accelerator. In one aspect, the accelerator may be a sulfenamide sulfur cure accelerator. In another aspect, the accelerator is present in an amount of about 0.5 to about 5 phr, or about 1 to about 2 phr, or about 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or about 5 phr, or a combination of any of the foregoing values, or a range comprising any of the foregoing values. In one aspect, the accelerator is present at about 1.2 phr.

Scorch retarder

In one aspect, the conductive rubber composition includes a scorch retarder. In another aspect, the scorch retarder may be N- (cyclohexylthio) phthalimide. In yet another aspect, the scorch retarder may be present in an amount of about 0.05 to about 0.5 phr, or about 0.1 phr to about 0.3 phr, or about 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, or about 0.5 phr, or a combination of any of the foregoing values, or ranges comprising any of the foregoing values.

In one aspect, scorch retarder may be used to prevent premature vulcanization during rubber processing. An exemplary scorch retarder may be vangard PVI (Vanderbilt Chemicals, LLC, norwalk CT USA).

Method for preparing conductive rubber composition

In one aspect, the disclosed conductive rubber compositions may be prepared by mixing one or more additives into the rubber or polymer base of the rubber composition. In a further aspect, the polymer base of the rubber or rubber composition is heated to soften the rubber or polymer base sufficiently to allow mixing of the additives into the rubber composition. In yet another aspect, additives are discussed herein, and include one or more of antioxidants or antiozonants, oils, zinc oxide, fatty acids, sulfur, accelerators, scorch retarders, and one or more conductive carbon components.

In one aspect, the additives may be mixed into the rubber composition sequentially or simultaneously. In some aspects, a masterbatch may be prepared that includes a non-reactive additive such as a conductive carbon component to ensure adequate mixing of the conductive carbon component before vulcanization begins. In a further aspect, a vulcanization additive (e.g., sulfur, zinc oxide) may be added to the masterbatch after preparation of the masterbatch.

In some aspects, the rubber composition may be further shaped prior to or during the early stages of vulcanization by a process including, but not limited to, extrusion, calendaring, molding, casting, another rubber processing process, or any combination thereof.

In some aspects, processing aids, such as waxes, including but not limited to microcrystalline waxes and paraffins, if used, may be used in a range of, for example, about 1 phr to about 5 phr, or about 1 phr to about 3 phr, or about 1, 2, 3, 4, or about 5 phr, or a combination of any of the foregoing values, or ranges encompassing any of the foregoing values.

In another aspect, the resin (typically as a tackifier) may be incorporated into the rubber composition, where the tackifier or resin is a compound such as a synthetic hydrocarbon and natural resin, if used, ranging, for example, from about 1 phr to 5 phr or from about 1 phr to about 3 phr, or from about 1, 2, 3, 4, or about 5 phr, or a combination of any of the foregoing values, or ranges subsumed therein.

In some aspects, the curing agent may be present as sulfur with one or more sulfur curing accelerators. In another aspect, for sulfur and accelerator curing agent(s), the amount of sulfur used may be, for example, from about 0.5 phr to about 5 phr, or from about 0.5 to about 3 phr, or at about 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or about 5 phr, or a combination of any of the foregoing values, or ranges covering any of the foregoing values; and the accelerator(s) (typically of the sulfenamide type) is used in a range of about 0.5 phr to about 5 phr, or about 1 phr to about 2 phr, or in a range of about 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or about 5 phr, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

In yet another aspect, the components of the composition, including the elastomer but not the sulfur and accelerator curing agent, are typically first mixed together in a series of at least two sequential mixing stages, although sometimes a mixing stage may be used to a temperature ranging, for example, from about 145 ℃ to about 185 ℃, or about 145, 150, 155, 160, 165, 170, 175, 180, or about 185 ℃, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values, and such a mixing stage is typically referred to as a non-productive mixing stage. In a further aspect, sulfur and an accelerator, and optionally one or more scorch retarder and optionally one or more antidegradant, are mixed therewith in a second stage, commonly referred to as a productive mixing stage, to a temperature of, for example, about 90 ℃ to about 120 ℃, or about 90, 95, 100, 105, 110, 115, or about 120 ℃, or a combination of any of the foregoing values, or a range covering any of the foregoing values. Such mixing procedures are well known to those skilled in the art.

Properties of the conductive rubber composition

Uncured storage modulus

In one aspect, the disclosed conductive rubber composition can have an uncured storage modulus at 15% strain, 100 ℃ and 0.83 Hz of about 185 kPa to about 1100 kPa, or about 185, 200, 300, 400, 500, 600, 700, 800, 900, 1000, or about 1100 kPa, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In a further aspect, the uncured storage modulus can be measured using a rubber processing analyzer.

Storage modulus

In one aspect, the disclosed conductive rubber compositions can have a storage modulus at 1% strain, 100 ℃ and 11 Hz of about 1.1 MPa to about 4 MPa, or about 1.1, 1.5, 2, 2.5, 3, 3.5, or about 4 MPa, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

In one aspect, the disclosed conductive rubber composition can have a storage modulus at 10% strain, 100 ℃ and 11 Hz of about 0.8 MPa to about 3 MPa, or about 0.8, 1, 1.2, 1.4, 1.6, 1.8, 2, 2.2, 2.4, 2.6, 2.8, or about 3 MPa, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

In one aspect, the disclosed conductive rubber compositions can have a storage modulus at 50% strain, 100 ℃ and 11 Hz of about 0.35 MPa to about 1 MPa, or about 0.35, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or about 1 MPa, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

In any of these aspects, the storage modulus can be measured using a rubber processing analyzer.

Modulus of

In one aspect, the disclosed conductive rubber composition can have a 10% modulus of about 0.4 MPa to about 2.5 MPa, or about 0.4, 0.5, 1, 1.5, 2, or about 2.5 MPa, or a combination of any of the foregoing values, or a range covering any of the foregoing values.

In another aspect, the disclosed conductive rubber composition can have a 50% modulus of about 1.25 MPa to about 3.5 MPa, or about 1.25, 1.5, 2, 2.5, 3, or about 3.5 MPa, or a combination of any of the foregoing values, or ranges covering any of the foregoing values.

In yet another aspect, the disclosed conductive rubber composition can have a 100% modulus of about 2 MPa to about 5.2 MPa, or about 2, 2.5, 3, 3.5, 4, 4.5, 5, or about 5.2 MPa, or a combination of any of the foregoing values, or a range covering any of the foregoing values.

In one aspect, the disclosed conductive rubber composition can have a modulus of 200% from about 3 MPa to about 12 MPa, or about 3, 4, 5, 6, 7, 8, 9, 10, 11, or about 12 MPa, or a combination of any of the foregoing values, or a range covering any of the foregoing values.

In one aspect, the disclosed conductive rubber composition can have a 300% modulus of about 4 MPa to about 13.5 MPa, or about 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or about 13.5 MPa, or a combination of any of the foregoing values, or ranges covering any of the foregoing values.

In any of these aspects, modulus can be measured using a tensile test based on ASTM D412.

Tensile strength Degree of

In one aspect, the conductive rubber compositions disclosed herein can have a tensile strength of greater than about 2 MPa, or about 2 MPa to about 30 MPa, or about 2, 2.5, 3, 3.5, 4, 4.5, 5, 10, 15, 20, 25, or about 30 MPa, or a combination of any of the foregoing values, or ranges covering any of the foregoing values. In one aspect, tensile strength may be measured using a tensile test based on ASTM D412.

Elongation at break

In one aspect, the conductive rubber compositions disclosed herein can have an elongation at break of greater than about 200%, or about 200% to about 800%, or about 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, or about 800%, or a combination of any of the foregoing values, or ranges covering any of the foregoing values. In one aspect, elongation at break may be measured using a tensile test based on ASTM D412.

Cured or uncured resistor

In one aspect, the conductive rubber compositions disclosed herein can be formed into wires. In another aspect, the wire may be about 10 inches (254 millimeters) long and about 2 millimeters in diameter. In a further aspect, such a wire may have an upper limit of about 5 ohms (Ω) to about 10 megaohms (mΩ), or about 5 Ω to about 100 kiloohms (kΩ), or about 5 Ω, 25 Ω, 50 Ω, 75 Ω, 100 Ω, 200 Ω, 300 Ω, 400 Ω, 500 Ω, 600 Ω, 700 Ω, 800 Ω, or 900 Ω, or 1 k Ω, 5 k Ω, 10 k Ω, 20 k Ω, 30 k Ω, 40 k Ω, 50 k Ω, 60 k Ω, 70 k Ω, 80 k Ω, 90 k Ω, 100 k Ω, 200 k Ω, 300 k Ω, 400 k Ω, 500 k Ω, 600 k Ω, 700 k Ω, 800 k Ω, or 900 k Ω, or 1 k Ω, 2 k Ω, 3 k Ω, 4 k Ω, 5 k Ω, 6 k Ω, 527 Ω, 8 Ω, 9 Ω, or any combination of any of the foregoing or any range of values that may not be cured, including any of the foregoing values. In one aspect, the resistance can be measured using a standard multimeter. In another aspect, the conductive rubber composition has a resistivity of less than about 800 Ω ∈m, or about 10, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, or about 800 Ω ∈m, or a combination of any of the foregoing values, or ranges covering any of the foregoing values.

In one aspect, the conductivity and/or resistance of the conductive rubber in the disclosed compositions is enhanced when the surface area, particle size, and structure (e.g., porosity) of the carbon component is high.

T25 and T90

In one aspect, the conductive rubber compositions disclosed herein can have a T25 measured at 150 ℃ for 60 minutes using a spinless rheometer standard test of from about 1 minute to about 30 minutes, or about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or about 30 minutes, or a combination of any of the foregoing values, or a range covering any of the foregoing values.

In another aspect, the conductive rubber compositions disclosed herein can have a T90 of about 5 minutes to about 60 minutes, or about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or about 60 minutes, or a combination of any of the foregoing values, or a range covering any of the foregoing values, measured using a rotor-less rheometer standard test at 150 ℃ for 60 minutes.

In one aspect, T25 and T90 may be measured using rubber processing analyzer and/or rotor-less rheometer standard tests (employing ASTM D5289 and/or ISO 6502).

Zwick rebound

In one aspect, the conductive rubber composition may have a Zwick rebound at 23 ℃ of about 30 to about 60, or about 30, 35, 40, 45, 50, 55, or about 60, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

In another aspect, the conductive rubber composition may have a Zwick rebound at 100 ℃ of about 45 to about 75, or about 45, 50, 55, 60, 65, 70, or about 75, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

In one aspect, zwick rebound can be measured using standard test method DIN 53512 for elastomers and rubbers, ISO 4662 for rubbers, or BS 903.

Final torque

In one aspect, the disclosed conductive rubber composition has a final torque measured at 150 ℃ for 60 minutes of about 10 dN ∈m to about 45 dN ∈m, or about 10, 15, 20, 25, 30, 35, 40, or about 45 dN ∈m, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the final torque may be measured using a rotor-less rheometer to perform tests according to ASTM D5289 and/or ISO 6502.

2 point Reversion (version) time

In one aspect, the disclosed conductive rubber compositions have a 2-point reversion time measured at 150 ℃ for 60 minutes of about 0.1 minutes to about 40 minutes, or about 0.1, 0.5, 1, 5, 10, 15, 20, 25, 30, 35, or about 40 minutes, or a combination of any of the foregoing values, or ranges covering any of the foregoing values. In one aspect, the 2-point reversion time may be measured using a rotor-less rheometer to perform tests according to ASTM D5289 and/or ISO 6502.

Exemplary methods for evaluating properties of the disclosed conductive rubbers are provided in the embodiments.

Article comprising conductive rubber composition

In one aspect, provided herein are articles comprising the conductive rubber compositions disclosed herein. In another aspect, the article may be a tire, a tire chimney (wire), a wire, a sensor, a hose, an electromagnetic interference shielding gasket, a weather resistant sealing material, an adhesive article (adhesive), or any combination thereof. The conductive rubber compositions described herein have excellent resistance properties while using a smaller amount of carbon component. The composition also has good mechanical properties, which reduce the degradation rate of articles (e.g., tires) made therefrom. Thus, articles incorporating the conductive compositions described herein have good electrical and mechanical properties.

Many modifications and other embodiments of the disclosed compositions and methods will come to mind to one skilled in the art to which the disclosed compositions and methods pertain having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. Therefore, it is to be understood that the disclosure is not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. The skilled person will recognize many variations and adaptations of the aspects described herein. Such variations and adaptations are intended to be included in the teachings of the present disclosure and are covered by the claims herein.

Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

As will be apparent to those of skill in the art upon reading the present disclosure, each of the individual embodiments described and illustrated herein has discrete components and features that can be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present disclosure.

Any recited method may be performed in the order of recited events or in any other order that is logically possible. That is, unless explicitly stated otherwise, it is in no way intended that any method or aspect set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not specifically state that a step is limited to a particular order in a claim or in the specification, it is in no way intended that the order be inferred in any respect. This applies to any possible non-explicit basis of interpretation, including logic relating to the arrangement of steps or operational flows, simple meanings derived from grammatical organization or punctuation, or the number or type of aspects described in the specification.

All publications mentioned herein are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the publications are cited. The disclosure of the publications discussed herein is provided solely for its application prior to the filing date of the present application. Nothing herein is to be construed as an admission that the invention is not entitled to antedate such publication by virtue of prior invention. Further, the dates of publication provided herein may be different from the actual publication dates, which may need to be independently confirmed.

While aspects of the disclosure may be described and claimed in terms of specific legal categories (e.g., system legal categories), this is for convenience only and it will be appreciated by those skilled in the art that each aspect of the disclosure may be described and claimed in terms of any legal category.

It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only, and is not intended to be limiting. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed compositions and methods belong. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the specification and relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

Before describing various aspects of the present disclosure, the following definitions are provided and should be used unless otherwise indicated. Additional terms may be defined elsewhere in this disclosure.

Having now described aspects of the present disclosure, in general, the following examples describe some additional aspects of the present disclosure. While aspects of the present disclosure are described in connection with the following embodiments and the corresponding text and drawings, it is not intended to limit aspects of the present disclosure to this description. On the contrary, the intent is to cover all alternatives, modifications and equivalents as included within the spirit and scope of the disclosure.

Aspects of the invention

The present disclosure may be described in terms of the following numbered aspects, which should not be confused with the claims.

Aspect 1. An electrically conductive rubber composition comprising a rubber component and one or more electrically conductive carbon components, wherein the electrically conductive rubber composition has an uncured or cured resistance of less than about 10M Ω at 23 ℃ when formed into a wire of about 10 inches (254 millimeters) length and 2 millimeters diameter.

Aspect 2. The conductive rubber composition of aspect 1, wherein the rubber component comprises Natural Rubber (NR), polyisoprene rubber (IR), styrene Butadiene Rubber (SBR), polybutadiene rubber (BR), butyl or halogenated butyl rubber, ethylene propylene rubber (EM), ethylene propylene diene monomer rubber (EPDM), neoprene rubber (CR), nitrile rubber (NBR), hydrogenated acrylonitrile butadiene rubber (HNBR), silicone rubber (MQ), thermoplastic rubber, or any combination thereof.

Aspect 3 the conductive rubber composition of aspect 2, wherein the butyl or halogenated butyl rubber comprises isobutylene-isoprene rubber (IIR), brominated isobutylene-isoprene rubber (BIIR), chlorinated isobutylene-isoprene rubber (CIIR), brominated isobutylene-co-p-methylstyrene rubber (BIMS), or any combination thereof.

Aspect 4. The conductive rubber composition of aspect 2, wherein the thermoplastic rubber comprises poly (styrene-butadiene-styrene) rubber (SBS), thermoplastic elastomer rubber (TPE), melt Processible Rubber (MPR), or any combination thereof.

The conductive rubber composition of aspect 5, aspect 4, wherein the thermoplastic elastomer rubber comprises a thermoplastic polyurethane rubber (TPU).

Aspect 6. The conductive rubber composition according to any one of aspects 2 to 5, wherein the conductive rubber composition comprises a blend of two or more rubber components.

Aspect 7 the conductive rubber composition of any of the preceding aspects, wherein the rubber component comprises about 5X 10 ⁴ Da to about 3X 10 ⁷ Molecular weight of Da (M _w ）。

Aspect 8 the conductive rubber composition of any of the preceding aspects, wherein the rubber component comprises about 3X 10 ⁵ Da to about 5X 10 ⁶ Molecular weight of Da (M _w ）。

Aspect 9. The conductive rubber composition of any of the preceding aspects, wherein the rubber component comprises a mooney viscosity UML of about 0.01 to about 150.

Aspect 10. The conductive rubber composition of any of the preceding aspects, wherein the rubber component comprises a mooney viscosity UMS of about 2 to about 150.

Aspect 11. The conductive rubber composition of any of the preceding aspects, wherein the rubber component comprises a glass transition temperature of about-110 ℃ to about-30 ℃.

Aspect 12. The conductive rubber composition of any of the preceding aspects, wherein the rubber component comprises a glass transition temperature of about-75 ℃ to about-30 ℃.

Aspect 13 the conductive rubber composition of any of the preceding aspects, wherein the one or more conductive carbon components comprise carbon black, short carbon fibers, graphite powder, graphene powder, or any combination thereof.

Aspect 14. The conductive rubber composition of any of the preceding aspects, wherein the one or more carbon components are present in an amount of about 20 phr to about 150 phr.

Aspect 15. The conductive rubber composition of aspect 14, wherein the one or more carbon components are present in an amount of from about 30 phr to about 100 phr.

Aspect 16. The conductive rubber composition of aspect 14, wherein the one or more carbon components are present in an amount of from about 40 phr to about 80 phr.

The electrically conductive rubber composition of any of aspects 17, aspects 13-16, wherein the one or more carbon components comprise carbon black having an average particle size of from about 5 nm to about 100 nm.

The conductive rubber composition of aspect 18, aspect 17, wherein the one or more carbon components comprise carbon black having an average particle size of from about 5 nm to about 50 nm.

Aspect 19 the conductive rubber composition of any of the preceding aspects, wherein the rubber component comprises a molecular weight distribution (M) of about 2.1 to about 10 _w /M _n ）。

Aspect 20 the conductive rubber composition of any of the preceding aspects, wherein the rubber component comprises a molecular weight distribution (M) of about 3.9 to about 8.2 _w /M _n ）。

Aspect 21 the electroconductive rubber composition according to any one of aspects 13 to 20, whichThe one or more carbon components comprise a carbon having a molecular weight of about 20 m ² /g to about 1700 m ² Carbon black with BET surface area per gram.

Aspect 22 the conductive rubber composition of aspect 21, wherein the one or more carbon components comprise a rubber composition having a molecular weight of about 50 m ² /g to about 1500 m ² Carbon black with BET surface area per gram.

Aspect 23 the conductive rubber composition of any of aspects 13-22, wherein the one or more carbon components comprise a composition having a molecular weight of about 20 m ³ /g to about 1200 m ³ Per gram of carbon black based on the external surface area of the statistical thickness method (STSA).

Aspect 24 the conductive rubber composition of aspect 23, wherein the one or more carbon components comprise a rubber composition having a molecular weight of about 100 m ³ /g to about 300 m ³ Per gram of carbon black based on the external surface area of the statistical thickness method (STSA).

The electrically conductive rubber composition of any of aspects 13-24, wherein the one or more carbon components comprise carbon black having an Oil Absorption Number (OAN) of about 500 mL/100 g to about 80 mL/100 g.

Aspect 26 the conductive rubber composition of aspect 25, wherein said one or more carbon components comprises carbon black having an Oil Absorption Number (OAN) of from about 500 mL/100 g to about 100 mL/100 g.

Aspect 27 the conductive rubber composition of any one of aspects 13-26, wherein the short carbon fibers comprise carbon fibers, chopped carbon fiber yarns, multi-walled carbon nanotubes (MWCNTs), single-walled carbon nanotubes (SWCNTs), or any combination thereof.

Aspect 28 the conductive rubber composition of aspect 27, wherein the short carbon fibers have a diameter of about 1 nm to about 1000 nm.

Aspect 29 the conductive rubber composition of aspect 28, wherein said short carbon fibers have a diameter of about 150 nm to about 600 nm.

The conductive rubber composition of any one of aspects 30, 27-29, wherein the short carbon fibers have a particle size of about 1 μm to about 1X 10 ⁴ Length of μm.

The conductive rubber composition of any of aspects 28-30, wherein the short carbon fibers have an average cross-machine direction aspect ratio of from about 10:1 to about 10,000:1.

Aspect 32 the conductive rubber composition of any of aspects 13-31, wherein the one or more carbon components comprises a blend of carbon black and graphite powder.

Aspect 33 the conductive rubber composition of any one of aspects 13-31, wherein the one or more carbon components comprises a blend of carbon black and graphene powder.

Aspect 34 the conductive rubber composition of any of aspects 13-31, wherein the one or more carbon components comprises a blend of carbon black and short carbon fibers.

Aspect 35 the conductive rubber composition of aspect 34, wherein in the blend the short carbon fibers are from about 5 phr to about 80 phr and the carbon black is from about 15 phr to about 70 phr.

Aspect 36 the conductive rubber composition of aspect 34, wherein in the blend the short carbon fibers are from about 20 phr to about 40 phr and the carbon black is from about 10 phr to about 60 phr.

Aspect 37 the conductive rubber composition of any of the preceding aspects, further comprising at least one antioxidant, at least one antiozonant, or any combination thereof.

Aspect 38 the conductive rubber composition of aspect 37, wherein the antioxidant comprises an amine antioxidant, a diphenylamine antioxidant, a polymeric dihydroquinoline, or any combination thereof.

Aspect 39. The conductive rubber composition of aspects 37 or 38, wherein the antioxidant is present in an amount of about 1 phr to about 2 phr.

Aspect 40. The conductive rubber composition of any of the preceding aspects, further comprising at least one additional component selected from the group consisting of oils, zinc oxide, fatty acids, sulfur, accelerators, scorch retarders, or any combination thereof.

Aspect 41 the conductive rubber composition of aspect 40, wherein the oil comprises an aromatic rubber process oil, a paraffinic rubber process oil, a naphthenic rubber process oil, or any combination thereof.

Aspect 42. The conductive rubber composition of aspects 40 or 41, wherein the oil is present in an amount of about 4 phr to about 30 phr.

Aspect 43 the conductive rubber composition of aspect 40, wherein said zinc oxide is present in an amount of about 3 phr.

Aspect 44 the conductive rubber composition of aspect 40, wherein the fatty acid comprises stearic acid, palmitic acid, oleic acid, or any combination thereof.

Aspect 45 the conductive rubber composition of aspects 40 or 44, wherein the fatty acid is present in an amount of about 1 phr to about 5 phr.

Aspect 46. The conductive rubber composition of aspect 40, wherein said sulfur is present in an amount of about 0.5 phr to about 5 phr.

Aspect 47 the conductive rubber composition of aspect 40, wherein the accelerator comprises a sulfenamide.

Aspect 48. The conductive rubber composition of aspects 40 or 47, wherein the accelerator is present in an amount of about 0.5 phr to about 5 phr.

Aspect 49 the conductive rubber composition of aspect 40, wherein the scorch retarder comprises N- (cyclohexylthio) phthalimide.

Aspect 50. The conductive rubber composition of aspects 40 or 49, wherein the scorch retarder is present in an amount of about 0.05 phr to about 0.5 phr.

Aspect 51 the conductive rubber composition of any one of aspects 1 to 50, wherein the rubber component comprises a rubber composition having a molecular weight of about 3X 10 ⁴ Da to about 3X 10 ⁷ Da and a glass transition temperature of about-75 ℃ to about-65 ℃.

Aspect 52 the conductive rubber composition of any one of aspects 1 to 50, wherein the rubber component comprises a rubber composition having a weight of about 2X 10 ⁵ Da to about 8X 10 ⁵ A molecular weight of Da, a mooney viscosity UML of about 75 and a glass transition temperature of about-70 ℃ to about-60 ℃.

Aspect 53 the conductive rubber composition of any one of aspects 1 to 50, wherein the rubber component comprises a rubber composition having a molecular weight of about 1X 10 ⁵ Da to about 4X 10 ⁵ An emulsion polymerized styrene-butadiene rubber having a molecular weight of Da, a Mooney viscosity UML of about 50 and a glass transition temperature of about-60 ℃ to about-50 ℃.

Aspect 54 the conductive rubber composition of any one of aspects 1 to 50, wherein the rubber component comprises a rubber composition having a weight of about 7X 10 ⁴ Da to about 8X 10 ⁴ A solution polymerized styrene-butadiene rubber having a molecular weight of Da, a mooney viscosity UML of about 2.6 and a glass transition temperature of about-30 ℃ to about-20 ℃.

Aspect 55 the conductive rubber composition of any one of aspects 1-50, wherein the conductive carbon component comprises carbon black having an average particle size of about 5 nm to about 100 nm.

Aspect 56 the conductive rubber composition of any of aspects 1-50, wherein the conductive carbon component comprises a polymer having an average particle size of about 5 nm to about 50 nm and about 20 m ² /g to about 1500 m ² Carbon black of average surface area per gram.

Aspect 57 the conductive rubber composition of any of aspects 1-50, wherein the conductive carbon component comprises ASTM N299 grade carbon black and has a diameter of about 1 nm to about 1000 nm and about 1 μm to about 1 x 10 ⁴ Short carbon fibers of length μm.

Aspect 58 the conductive rubber composition of any of aspects 1-50, wherein the conductive carbon component comprises carbon black having an oil absorption value of about 100 mL/100 g and having a diameter of about 1 nm to about 1000 nm and a diameter of about 1 μm to about 1 x 10 ⁴ Short carbon fibers of length μm.

Aspect 59 the conductive rubber composition of any one of aspects 1-50, wherein the conductive carbon component comprises carbon black having an average particle size of about 30 nm and having a diameter of about 1 nm to about 1000 nm and a diameter of about 1 μm to about 1 x 10 ⁴ Short carbon fibers of length μm.

Aspect 60 the conductive rubber composition of any one of the preceding aspects, wherein the conductive rubber composition has an uncured storage modulus at 15% strain, 100 ℃ and 0.83 Hz of about 185 kPa to about 1100 kPa.

Aspect 61. The conductive rubber composition of any one of the preceding aspects, wherein the conductive rubber composition has a storage modulus at 1% strain, 100 ℃ and 11 Hz of about 1.1 MPa to about 4 MPa.

Aspect 62. The conductive rubber composition of any one of the preceding aspects, wherein the conductive rubber composition has a storage modulus at 10% strain, 100 ℃ and 11 Hz of about 0.8 MPa to about 3 MPa.

Aspect 63. The conductive rubber composition of any of the preceding aspects, wherein the conductive rubber composition has a storage modulus at 50% strain, 100 ℃ and 11 Hz of about 0.35 MPa to about 1 MPa.

Aspect 64. The conductive rubber composition of any of the preceding aspects, wherein the conductive rubber composition has a 10% modulus of about 0.4 MPa to about 2.5 MPa.

Aspect 65 the conductive rubber composition of any of the preceding aspects, wherein the conductive rubber composition has a 50% modulus of about 1.25 MPa to about 3.5 MPa.

Aspect 66. The conductive rubber composition of any of the preceding aspects, wherein the conductive rubber composition has a 100% modulus of about 2 MPa to about 5.2 MPa.

Aspect 67. The conductive rubber composition of any of the preceding aspects, wherein the conductive rubber composition has a 200% modulus of about 3 MPa to about 12 MPa.

Aspect 68. The conductive rubber composition of any of the preceding aspects, wherein the conductive rubber composition has a 300% modulus of about 4 MPa to about 13.5 MPa.

Aspect 69. The conductive rubber composition of any of the preceding aspects, wherein the conductive rubber composition has a tensile strength of greater than about 2 MPa.

Aspect 70. The conductive rubber composition of any one of the preceding aspects, wherein the conductive rubber composition has a tensile strength of about 4.5 MPa to about 30 MPa.

Aspect 71 the conductive rubber composition of any one of the preceding aspects, wherein the conductive rubber composition has an elongation at break of greater than about 200%.

Aspect 72. The conductive rubber composition of any one of the preceding aspects, wherein the conductive rubber composition has an elongation at break of about 300% to about 800%.

Aspect 73 the conductive rubber composition of any one of the preceding aspects, wherein the conductive rubber composition, when cured or uncured, has an electrical resistance at 23 ℃ of about 5 Ω to about 10M Ω when formed into a wire of about 10 inches (254 millimeters) length and diameter of 2 millimeters.

Aspect 74 the conductive rubber composition of any one of the preceding aspects, wherein the conductive rubber composition, when cured or uncured, has an electrical resistance at 23 ℃ of about 5 Ω to about 100 k Ω when formed into a wire that is about 10 inches (254 millimeters) long and 2 millimeters in diameter.

Aspect 75. The conductive rubber composition of any of the preceding aspects, wherein the conductive rubber composition has a T25 of about 1 minute to about 30 minutes when measured at 150 ℃ for 60 minutes using a spinless rheometer standard test.

Aspect 76. The conductive rubber composition of any of the preceding aspects, wherein the conductive rubber composition has a T90 of about 5 minutes to about 60 minutes when measured at 150 ℃ for 60 minutes using a spinless rheometer standard test.

Aspect 77. The conductive rubber composition of any of the preceding aspects, wherein the conductive rubber composition has a Zwick rebound at 23 ℃ of about 30 to about 60.

Aspect 78 the conductive rubber composition of any one of the preceding aspects, wherein the conductive rubber composition has a Zwick rebound at 100 ℃ of from about 45 to about 75.

Aspect 79 the conductive rubber composition of any one of the preceding aspects, wherein the conductive rubber composition has a final torque of about 10 dN ∈m to about 45 dN ∈m when measured at 150 ℃ for 60 minutes.

Aspect 80. The conductive rubber composition of any one of the preceding aspects, wherein the conductive rubber composition exhibits a reversion time of 2 pt of from about 0.1 minutes to about 40 minutes when measured at 150 ℃ for 60 minutes.

Aspect 81. An article comprising the conductive rubber composition of any of aspects 1-77.

The article of aspect 82, aspect 81, wherein the article comprises a tire, a tire stack, a wire, a sensor, a hose, an electromagnetic interference shielding gasket, a weatherable seal, an adhesive article, or any combination thereof.

Examples

The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how to make and evaluate the compounds, compositions, articles, devices, and/or methods claimed herein, and are intended to be purely exemplary of the disclosure and are not intended to limit the scope of what the inventors regard as their disclosure. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless otherwise indicated, parts are parts by weight, temperature is in degrees celsius or at ambient temperature, and pressure is at or near atmospheric pressure.

Example 1: property analysis and characterization procedure

Mooney viscosity ML (for large rotors) or MS (for small rotors) was determined at 100℃using standard test method ASTM D1646.

A Rubber Processing Analyzer (RPA) was used to determine the following: an uncured storage modulus G' at 15% strain, 100 ℃ and 0.83 Hz; t25; t90; storage modulus G' (1%, 10% and 50%) at 100 ℃ and 11 Hz; and Tan delta (10%) at 100 ℃ and 1 Hz.

Maximum and minimum torque, delta torque, final torque, 1 pt rise time, T25, T90 and 2 pt reversion were measured using a rotor-less rheometer (MDR) standard test method for rubber properties based on standard test methods ASTM D5289 and ISO 6502 (vulcanization using a rotor-less curing meter). The test was carried out at 150℃for 60 minutes.

The 10%, 50%, 100%, 200% and 300% moduli, tensile strength and elongation at break were measured using a tensile test (die C) at 23 ℃ based on standard test method ASTM D412.

The external surface area (STSA) based on the statistical thickness method was measured according to standard test method ASTM D6556.

The resistance of the uncured rubber wire was measured at 23℃using a Fluke 117 true effective multimeter. Typical wires used in this test were 10 inches (254 mm) long and 2 mm in diameter. In this test, the result of "OL" indicates an open circuit (open line) where resistance cannot be measured.

Zwick rebound at 23 ℃ and 100 ℃ was measured using standard test methods DIN 53512, ISO 4662 (for rubber) and/or BS 903 for elastomers and rubbers.

Example 2: exemplary compositions and Properties thereof

Exemplary conductive rubber compositions using carbon black as the conductive carbon compound are provided in table 1.

^a All amounts are provided in parts per hundred rubber (phr).

^b TSR20 natural rubber consists essentially of cis-1, 4-polyisoprene and has a T of-70 ℃ _g And 20% of the maximum impurity.

^c The RSS natural rubber is #2 ribbed smoke film (# 2RSS) natural rubber with T at-70deg.C _g 。

^d Natsyn2200 is a synthetic cis-1, 4-polyisoprene with T at-64 DEG C _g 。

^e PLF1502 is an emulsion polymerized styrene-butadiene rubber with a T of about 23.5% styrene, 12% vinyl, 55% trans, 10% cis, and-55℃ _g 。

^f Exp SBR is a trial Li-solution SBR having a T of-26 ℃ _g 。

^g Carbon black A is an N299 ASTM grade carbon black.

^h Carbon black C is commercially available as PRINTEX XE2B from Orion Engineered Carbons.

ⁱ The oil is a standard rubber processing oil.

^j The fatty acid is a mixture of stearic acid, palmitic acid and oleic acid.

^k The accelerator is a sulfenamide sulfur curing accelerator.

Properties of the compositions using carbon black as the conductive carbon compound are provided in table 2.

^a OL (open circuit) indicates that the measurement cannot be completed.

Exemplary compositions using a combination of carbon black and short carbon fibers as conductive carbon compounds are provided in table 3.

^a All amounts are provided in parts per hundred rubber (phr).

^b See table 1 for further information regarding the components.

^c Carbon black B was commercially available as propeller X22 from Cabot Corporation.

^d The short carbon fibers have a diameter of 150-600 nm and a length of greater than 1 μm.

The properties of the compositions using a combination of carbon black and short carbon fibers are provided in table 4.

^a OL (open circuit) indicates that the measurement cannot be completed.

It should be emphasized that the above-described embodiments of the present disclosure are merely possible examples of implementations set forth for a clear understanding of the principles of the disclosure. Many variations and modifications may be made to the above-described embodiment(s) without departing substantially from the spirit and principles of the disclosure. All such modifications and variations are intended to be included herein within the scope of this disclosure and protected by the following claims.

Claims

3. The conductive rubber composition of claim 1, wherein the conductive rubber composition comprises a blend of two or more rubber components.

4. The conductive rubber composition of claim 1, wherein the rubber component comprises about 5 x 10 ⁴ Da to about 3X 10 ⁷ Molecular weight of Da (M _w ）。

5. The conductive rubber composition of claim 1, wherein the rubber component comprises a mooney viscosity UML of about 0.01 to about 150 or a mooney viscosity UMS of about 2 to about 150.

6. The conductive rubber composition of claim 1, wherein the rubber component comprises a glass transition temperature of about-110 ℃ to about 30 ℃.

7.The conductive rubber composition of claim 1, wherein the rubber component comprises a molecular weight distribution (M _w /M _n ）。

8. The conductive rubber composition of claim 1, wherein the one or more conductive carbon components comprise carbon black, short carbon fibers, graphite powder, graphene powder, or any combination thereof.

9. The conductive rubber composition of claim 1, wherein the one or more conductive carbon components are present in an amount of about 20 phr to about 150 phr.

10. The conductive rubber composition of claim 1, wherein the one or more conductive carbon components comprise a polymer having an average particle size of about 5 nm to about 100 nm and about 20 m ² /g to about 1700 m ² Carbon black with BET surface area per gram.