Carbon black having a shape-modified aggregate distribution and rubber products using the same

Abstract

Carbon black having a broad aggregate size distribution, unique morphology and shape distribution, and rubber compositions and tires containing such carbon black.

Description

Technical Field

[0001] This disclosure relates to carbon black, and more particularly to carbon black having a distinctive morphology and shape-modified aggregates and aggregate size distributions, and rubber articles comprising such carbon black. Technical Background

[0002] Carbon black is an engineered particulate element of carbon found in countless everyday items. It is a useful component in rubber products, for example, improving their strength, durability, and overall performance. Carbon black is also used as a pigment and as a performance-enhancing component in products such as printing inks, coatings, and plastics.

[0003] The morphology of carbon black has always been an important area of ​​research for developing new types of carbon black, as this property has a significant impact on the properties that carbon black imparts to various composite materials (i.e., rubber products). Typically, in product specifications and literature, carbon black is described by its colloidal properties (i.e., surface area, color, and structure).

[0004] Specifically, variations in the size distribution of carbon black aggregates have been utilized to impart desired properties to rubber compounds. Typically, this is achieved by widening the aggregate size distribution, thereby increasing the average inter-aggregate spacing and reducing the degree of carbon black networking, which is a major contributor to heat generation in rubber compounds. In rubber compounds, lower carbon black networking is traditionally associated with lower hysteresis, a primary source of rolling resistance in tires, and therefore a powerful driver of reduced fuel consumption.

[0005] Therefore, it has become important to design methods to further reduce the networking potential of carbon black, either through surface modification to improve carbon black-elastomer interactions or through carbon black morphology. However, in practice, the ability to broaden the aggregate size distribution has reached its limit. First, from a reactor perspective, the practice of producing carbon black with broad aggregate sizes in a reactor by broadening the conversion oil spray has its own limitations, even considering a wide range of reactor technologies. Furthermore, when the aggregate size is broadened, it usually leads to a broadening of the particle size distribution; therefore, aggregate size distribution and particle size distribution are coupled. In other words, conventional techniques require the particle size distribution to broaden along with the aggregate size distribution, which has its own drawbacks.

[0006] For conventional tire tread compounds, the use of carbon black with a wide aggregate size typically results in poor abrasion resistance and low electrical conductivity.

[0007] Therefore, there is a need for improved carbon black materials that can facilitate optimized aggregate size distribution by broadening and controlling shape distribution, in order to provide a range and balance of significantly improved viscoelastic properties such as dynamic stiffness, hysteresis, tread wear and durability, while maintaining narrow particle size distribution and compound conductivity.

[0008] The carbon black of the present invention, its production method, and compositions comprising it satisfy this and other needs. Summary of the Invention

[0009] In accordance with the purposes of this invention, as embodied and broadly described herein, this disclosure relates in one aspect to shape-modified carbon black, and more particularly to carbon black having unique shape properties and distribution. In the following description, this carbon black will be referred to as "the carbon black of this invention" or "the carbon black of this invention," and both expressions are synonymous.

[0010] Another aspect of the present invention relates to a rubber compound comprising at least one of the carbon blacks of the present invention.

[0011] Further aspects of the invention will be set forth in part in the description which follows, and in part will be apparent from the description, or may be learned by practice of the invention. Advantages of the invention will be realized and obtained by means of the elements and combinations particularly pointed out in the appended claims. It should be understood that the foregoing general description and the following detailed description are merely exemplary and explanatory, and do not limit the claimed invention. Attached Figure Description

[0012] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate several aspects and, together with the specification, serve to explain the principles of the invention.

[0013] Figure 1 An exemplary carbon black reactor according to various aspects of this disclosure is shown.

[0014] Figures 2A to 2D The shape classification of carbon black aggregates according to various aspects of this disclosure is shown, including type 1 spherical ( Figure 2A Type 2 oval ( Figure 2B Type 3 linear () Figure 2C ) and type 4 branching ( Figure 2D ).

[0015] Figure 3A Exemplary carbon black aggregates having a normal aggregate size distribution according to various aspects of this disclosure are shown, along with exemplary diagrams of the aggregate size distribution.

[0016] Figure 3BExemplary carbon black aggregates of the present disclosure according to various aspects thereof are shown, having different distributions of large, high-structure aggregates and small, low-structure aggregates, and exemplary graphs illustrating the aggregate size distribution of modified aggregates.

[0017] Figure 4 The aggregate size distributions corresponding to the normal ASD (solid line) of ASTM type carbon black according to various aspects of this disclosure and the normal ASD (dashed line) of the carbon black of the present invention are shown, and morphological descriptors from typical disk centrifugal optical deposition measurements are also shown.

[0018] Figures 5A to 5E Examples of ASDs of various comparative carbon blacks with similar surface areas and structures to the carbon black of the present invention are shown.

[0019] Figure 6A and Figure 6B Transmission electron micrographs of aggregates of comparative carbon black A and carbon black 1 of the present invention, according to various aspects of this disclosure, are shown.

[0020] Figure 7A and Figure 7B Low-magnification and high-magnification transmission electron micrographs of very large, high-structure aggregates composed of numerous particles of the carbon black of this invention are shown.

[0021] manual

[0022] The invention can be more readily understood by referring to the following detailed description and examples thereof.

[0023] Before disclosing and describing the compounds, compositions, articles, systems, devices, and / or methods of the present invention, it should be understood that, unless otherwise stated, they are not limited to specific synthetic methods, or, unless otherwise stated, they are not limited to specific reagents, as these can certainly vary. It should also be understood that the terminology used herein is for descriptive purposes only and is not intended to be limiting. Although any methods and materials similar to or equivalent to those described herein may be used in the practice or testing of the invention, exemplary methods and materials are now described.

[0024] All disclosures mentioned herein are incorporated herein by reference to disclose and describe the methods and / or materials relating to the listed disclosures.

[0025] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Although any methods and materials similar to or equivalent to those described herein may be used in the practice or testing of this invention, exemplary methods and materials are described hereafter.

[0026] As used herein, unless explicitly stated otherwise, the singular forms “a,” “an,” and “the” include plural indicators, unless the context clearly indicates otherwise. Thus, for example, references to “filler” or “solvent” respectively include mixtures of two or more fillers or solvents.

[0027] "Conventional carbon black" refers to carbon black materials not manufactured using the methods described herein, such as ASTM grade carbon black as described in ASTM D-1765-19, which has historically been used in the tire and rubber industries and exhibits a balance of colloidal properties as described in ASTM D-1765-19.

[0028] As used herein, unless otherwise explicitly stated, the term "heterogeneity index" or "HI" is intended to refer to a ratio that provides a normalized measure of distribution width or polydispersity. Specifically, the term "HI" ASD "HI" refers to the aggregate size heterogeneity index, and the term "HI" is used to describe the heterogeneity of aggregate size. PSD "" refers to the particle size heterogeneity index, both of which are defined as in ASTM D3849-14a ("Determination of morphological characteristics of carbon black using electron microscopy - Method A"). The aggregate size heterogeneity index HI ASD Weight-average aggregate size (“WM”) agg ) divided by the average aggregate size ("M") agg ")Sure,

[0029] HI ASD = WM / agg / M agg (1)

[0030] Among them, the weight average aggregate size WM agg Determined by the following formula:

[0031] WM agg (nm) = ∑ D 4 agg / ∑ D 3 agg (2);

[0032] In equations 2, 3, 5, 6, 9, and 11, Σ represents the summation over all measured aggregates;

[0033] Where the average aggregate size M agg Determined by the following formula:

[0034] M agg (nm) = ∑ D agg / Nt (3);

[0035] Where D agg It is the area equivalent aggregate diameter (nm), expressed as (4A / π). ½ A is the aggregate area (nm) of a two-dimensional projection measured by transmission electron microscopy. 2 ); and N t It is the total number of aggregates measured.

[0036] Particle size heterogeneity index HI PSD Weight average particle size (“WM”) pt ) divided by the average particle size ("M") pt ")Sure:

[0037] HI PSD = WM pt / M pt (4)

[0038] Among them, the weight average particle size WM pt Determined by the following formula:

[0039] WM pt (nm) = [∑ (n * d p 4 )] / [∑ (n * d p 3 )](5),

[0040] Where the average particle size M pt Determined by the following formula:

[0041] M pt (nm) = [∑ (n * d p )] / n t (6),

[0042] Where n t It is ∑n for all measured aggregates or the total number of all particles; n is the total number of particles in the aggregate, denoted as V. A / V P V A It is the aggregate volume, expressed in nm. 3 Represented as (8 / 3)A 2 / P;V P It is the particle volume, expressed in nm. 3 Represented as πd p 3 / 6; A is the aggregate area (nm) 2 P is the aggregate perimeter (nm); d pα is the average particle size of a single aggregate, expressed in nm as απA / P; and α is the aggregation factor, expressed as 13.092(P). 2 / A) -0.92 However, if the calculated value is less than 0.4, then α is 0.4.

[0043] As used herein, unless otherwise explicitly stated, the term "divergence ratio" is intended to refer to the aggregate size distribution heterogeneity index HI determined by TEM / AIA according to ASTM D3849-14A (Method A) (as described above). ASD The particle size distribution heterogeneity index HI, determined by TEM / AIA according to ASTM D3849-14A (Method A) (as described above), is used. PSD The ratio:

[0044] Divergence ratio = HI ASD / HI PSD (7)

[0045] The divergence ratio can be an indicator of the decoupling between aggregate size distribution (ASD) and particle size distribution (PSD). A low divergence ratio, such as a value less than, for example, about 1.5–1.7, can indicate a wide ASD and a wide PSD, or a narrow ASD and a narrow PSD, such that the ASD and PSD are coupled and change synchronously. A higher divergence ratio, such as a value greater than, for example, about 1.5–1.7, can indicate decoupling between the ASD and PSD, such as when the ASD widens at a faster rate than the PSD. This higher divergence ratio can indicate a carbon black grade with a wide ASD and a normal or narrow PSD.

[0046] As used herein, the term "shape distribution" can refer to a method of classifying carbon black into four aggregate shape categories (i.e., spherical (type 1), elliptical (type 2), linear (type 3), and branched (type 4)), respectively, as follows: Figure 2A , Figure 2B , Figure 2C and Figure 2DThe results, as shown and described in "Morphology of Carbon-Black aggregates: Fractalversus Euclidian Geometry" (Herd et al., Rubber Chemistry and Technology, 65th edition, pp. 107-129), provide direct information on the balance between shape-modified carbon black grades and shape types of normally or conventionally manufactured carbon black. Aggregate shape distribution is determined using skeletonization techniques combined with basic image analysis parameters, based on the methods described in "The Use of Skeletonization for the Shape Classification of Carbon-Black Aggregates" (Herd et al., Rubber Chemistry and Technology, 66th edition, pp. 491-509). The term "shape-specific heterogeneity index of type Z" or "SSHI of type Z" refers to the ratio of the weight percentage of a specific aggregate shape class Z present in the carbon black material to the percentage of that aggregate shape class Z in quantity. For example, Type 4 SSHI (or SSHI of branched aggregates or SSHI Type 4) refers to the ratio of the weight percentage of the branched shape category of aggregates present in the carbon black material to the percentage of the number of that branched shape category (SSHI Type 4 = weight% of Type 4 / number% of Type 4). For each type of aggregate shape category, the percentage basis (number%) is simply determined as follows:

[0047] Quantity %t Z = N tZ / N t (8)

[0048] Where N tZ N represents the total number of aggregates in a given shape category Z (1, 2, 3, or 4), and N t This represents the total number of aggregates across all shape categories (1, 2, 3, and 4).

[0049] For each aggregate shape category, the weight percentage baseline (weight%) is simply determined as follows:

[0050] weight %t Z = Σ ((1.8*(8 / 3)*A 2 ) / P) tZ / Σ((1.8*(8 / 3)*A 2 ) / P) t (9)

[0051] Where Σ((1.8*(8 / 3)A 2 ) / P) tZ Represents the total weight of aggregates in a given shape category Z (1, 2, 3, or 4), Σ((1.86*(8 / 3)A 2 ) / P)t represents the total weight of aggregates of all shape categories (1, 2, 3, and 4).

[0052] As used herein, unless otherwise expressly stated, the term "TEM" is intended to refer to transmission electron microscopy.

[0053] As used herein, unless otherwise expressly stated, the term "void volume" is intended to refer to the relative amount of the containment volume of a single aggregate relative to its volume, expressed as void volume = V' / V A ,

[0054] Where V' is the encapsulation volume of the aggregate, and V A The aggregate volume, obtained from TEM measurements, is expressed as:

[0055] V' = V es – V A (10),

[0056] Where V es The volume of the sphere is expressed as 4 / 3πr. 3 The equivalent diameter of a single aggregate is taken as the average Freette diameter (F). av (i.e., the average distance between two parallel lines rotating around a two-dimensional object) and the average diameter of the area equivalent aggregate; V A The aggregate volume is calculated using two-dimensional image analysis parameters of area and perimeter, in nm. 3 It is represented as (4A / π). 1 / 2 A is the aggregate area obtained by two-dimensional TEM projection of the aggregate. For more information on these terms and their relevance to carbon black materials, see ASTM D-3849-14a. When referring to carbon black, the void volume can be further described in the Journal of Colloid and Interface Science, 32, No. 1, January 1970, pp. 115-131 and in ASTM Method D7854-21, which are incorporated herein by reference in their entirety for the purpose of describing the void volume of carbon black and its application in media absorption and release expansion in filled elastomeric compounds.

[0057] For carbon black material measurements performed via TEM / AIA (which represents the aggregate size and shape distribution of the material and comprises multiple aggregates, each with an individual void volume), the apparent void volume of the carbon black material can be calculated by summing the individual void volume of each individual aggregate relative to its proportion in the total measured volume representing the aggregate size distribution. A higher apparent void volume V' / V A The value can indicate a higher degree of branching or the complexity of the aggregate. For example, V' / V A The value of 2 means that carbon black materials can absorb up to twice their own volume.

[0058] V' / V of carbon black materials A The calculation can be performed as follows:

[0059] V' / V A = ΣV' / ΣV A (11),

[0060] This parameter is summed over all aggregates, where V' and V A As previously defined.

[0061] Disc centrifugal optical sedimentation can also be used to determine different aggregate size properties or parameters related to their distribution properties. This technique utilizes a modified version of Stoke's Law for centrifugal sedimentation to determine the Stokes diameter of carbon black aggregates and their aggregate size distribution characteristics. These different aggregate size distribution (ASD) parameters, such as... Figure 4 As shown, it can include the mean, mode, and D. 10 D 50 D 90 And ΔD50 or full width at half height (FWHM). 10 The aggregate diameter represents the volume distribution of 10% located at D. 10 The diameter of aggregates below a certain value, D 50 The aggregate diameter indicates that 50% of the volume distribution is located at D. 50 The D90 aggregate diameter represents the aggregate diameter below a certain value, while the D90 aggregate diameter indicates that 90% of the volume distribution is located within the D90 range. 90 The diameter of aggregates below a certain value. These parameters can also be used to calculate a term known as "span," which is calculated as (D... 90 – D 10 ) / D 50 It can also be used as an indicator of ASD width. Other parameters include ΔD. 50 ΔD is the full width at half maximum (FWHM) of an ASD peak. For unimodal ASD, it can be used as an indicator of the ASD's width, but for multimodal ASD, it may be less useful or even useless, depending on the relative amplitude of one of the modes in the multimodal ASD. Typically, ΔD...50 Divide by the mode (ΔD) 50 The mode is normalized and made comparable across carbon black materials because ΔD 50 These values ​​are directly influenced by particle size, aggregate size, and aggregate structure. Unless otherwise specified, these values ​​can be determined by disc centrifugal optical sedimentation according to standard ISO 15825:2017.

[0062] When the weight parts of a specific element or component in a composition or article are mentioned in the specification and concluding claims, it indicates the weight relationship between that element or component and any other element or component in the composition or article, expressed as parts by weight. Therefore, in a composition containing 2 parts by weight of component X and 5 parts by weight of component Y, X and Y exist in a weight ratio of 2:5, and this ratio applies regardless of whether the composition contains other components.

[0063] The phr of a specific element or component in the composition or article mentioned in the specification and appended claims indicates the number of parts of the specific element or component per 100 units of rubber by mass.

[0064] A range may be expressed herein as from “about” one particular value and / or to “about” another particular value. When expressing such a range, the other side includes from one particular value and / or to another particular value. Similarly, when a value is expressed as an approximation using the antecedent “about”, it should be understood that the particular value forms the other side. It should be further understood that the endpoints of each range are significant relative to and independent of the other endpoint. It should also be understood that many values ​​are disclosed herein, and each value is also disclosed herein as “about” to that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. It should also be understood that each unit between two particular units is also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.

[0065] As used herein, the terms “optional” or “optionally” mean that the event or situation described below may or may not occur, and the description includes both the scenario in which the event or situation occurs and the scenario in which the event or situation does not occur.

[0066] The components used to prepare the compositions of the present invention and the compositions themselves used within the methods disclosed herein are disclosed. These and other materials are disclosed herein, and it should be understood that while specific references to every different individual and collective combination and arrangement of these compounds are not explicitly disclosed when combinations, subsets, interactions, groups, etc., of these materials are disclosed, each is specifically considered and described herein. For example, if a particular compound is disclosed and discussed, and numerous modifications that can be made to the plurality of molecules comprising that compound are discussed, then each combination and arrangement of that compound and possible modifications are specifically considered unless specifically indicated to the contrary. Thus, if a class of molecules A, B, and C and a class of molecules D, E, and F are disclosed, and an example of the combination molecule AD is disclosed, then each combination is considered individually and collectively, even if each combination is not described separately, thereby implying that combinations AE, AF, BD, BE, BF, CD, CE, and CF are disclosed. Similarly, any subsets or combinations of these are also disclosed. Thus, for example, subgroups AE, BF, and CE are considered to be disclosed. This concept applies to all aspects of this application, including but not limited to steps in methods of manufacturing and using the compositions of the present invention. Therefore, if various additional steps are available, it should be understood that each of these additional steps may be performed in conjunction with any specific embodiment or combination of embodiments of the method of the present invention.

[0067] Each conventional carbon black material (or the comparative carbon black described in the examples) along with its manufacturing method is commercially available and / or its production method is known to those skilled in the art. These conventional carbon blacks are available from suppliers such as BirlaCarbon, Cabot Corporation, Orion, etc.

[0068] It should be understood that the compositions disclosed herein have certain functions. This document discloses certain structural requirements for performing the disclosed functions, and it should be understood that multiple structures exist that can perform the same function associated with the disclosed structures, and these structures will generally achieve the same result.

[0069] Carbon black used in rubber applications is typically identified by a four-character "N" or "S" number, such as NXXX or SXXX. The category (grade) is determined according to ASTM D1765-19. The first character of the category gives some indication of the carbon black's effect on the curing rate of a typical rubber formulation containing it, with "N" for normally curing carbon black and "S" for slowly curing carbon black. The second character provides information about the average surface area of ​​the carbon black. Therefore, carbon blacks with the same second character are grouped into series ending in "00," such as the N200 series. The last two characters are arbitrarily assigned.

[0070] The morphological characteristics of carbon black (such as particle size, aggregate size, and aggregate structure) can affect various processing characteristics and performance properties of a variety of end products (such as tires and mechanical rubber products), such as tread wear, rolling resistance, heat generation, hardness, modulus, and tear resistance. Therefore, different grades of carbon black are used in different polymer formulations depending on the specific application requirements of tires and rubber products. For example, different grades of carbon black can also be used in different parts of tires; N100, N200, and N300 series carbon blacks are commonly used in the tread (i.e., tread-grade carbon black), while N300, N500, N600, and N700 series carbon blacks are commonly found in the sidewall and carcass compounds (i.e., carcass-grade carbon black). In one aspect, the carbon black of the present invention may comprise furnace-processed carbon black. In another aspect, the carbon black of the present invention may include shape-modified ASTM grade carbon black, such as, for example, N100, N200, N300, N400, N500, N600, N700, N800, or N900 carbon black. In another aspect, the carbon black of the present invention may include tread grade carbon black suitable for bus tire tread compounds, truck tire tread compounds, and mining tires. In another aspect, the carbon black of the present invention may include carcass grade carbon black. In yet another aspect, the carbon black of the present invention may include carbon black suitable for non-tread or carcass compounds of tires (such as, for example, sidewalls, veneer layers, undertread layers, or tread compounds).

[0071] The morphological characteristics of carbon black include, for example, particle size / fineness, surface area, aggregate size / structure, aggregate size distribution, and aggregate shape. Particle size is a measurement of the diameter of primary carbon black particles. These generally spherical carbon black particles have an average diameter in the nanometer range. Particle size can be measured directly by electron microscopy or indirectly by surface area measurement. Average particle size is an important factor determining the dispersibility, tensile strength, tear resistance, hysteresis, and abrasion resistance of rubber products, and in liquid and plastic systems, average particle size can strongly affect relative color intensity, ultraviolet (UV) stability, and electrical conductivity of composites. Under the same structure, smaller particle size confers higher tensile strength, tear resistance, hysteresis, and abrasion resistance, stronger color, UV resistance, and increased dispersibility.

[0072] The surface area of ​​carbon black is a function of particle size and porosity. Surface area is measured by gas-phase and liquid-phase adsorption techniques and depends on the amount of adsorbent required to form a surface monolayer. Iodine adsorption value, sometimes called iodine number or simply iodine (iodine adsorption number; ASTM D1510-2017), has historically been the primary indicator used to define different grades of surface area. Nitrogen surface area, or NSA (ASTM D6556-2017), and statistical thickness surface area, or STSA (ASTM D6556-2017), are now used more frequently for surface area measurements. NSA and STSA measure true surface area better than iodine because they are less affected by the chemical composition of the carbon black surface. These tests use liquid nitrogen and are based on the original Brunauer, Emmett, and Teller (BET) method. In end applications, surface area, especially STSA, reflects the area accessible to rubber molecules per unit weight of carbon black. High surface area is associated with a high level of reinforcement in rubber compounds, but at the cost of greater difficulty in dispersion, processing, and increased hysteresis.

[0073] Carbon black particles aggregate to form larger clusters or aggregates, which are the main dispersible units of carbon black. The aggregate structure can be measured by electron microscopy or oil absorption, particularly the oil absorption value OAN (ASTM D2414-2018). Another measurement of structure is the compression oil absorption value, or COAN (ASTM D3493-2018), in which the carbon black sample is mechanically compressed before the oil absorption measurement. The difference between OAN and COAN values ​​can serve as an indicator of the structural stability of carbon black. Carbon black with relatively large aggregates and a large number of primary particles can be considered high-structure carbon black with aggregates, which have more porosity and high oil absorption. High-structure carbon black can increase the viscosity, modulus, and conductivity of rubber compounds. High structure can also reduce demolding swell, loading capacity, and improve dispersibility. Lower-structure carbon black can reduce the viscosity and modulus of rubber compounds, increase elongation, demolding swell, and loading capacity, but may also reduce dispersibility. If all other characteristics of carbon black remain constant, a narrow aggregate size distribution increases the difficulty of carbon black dispersion and increases hysteresis and reduces resilience.

[0074] Carbon black aggregates can also have different shapes and can be classified into one of four traditional shape categories, as shown in Figure 2, and as described in Herd et al., Rubber Chemistry and Technology, Vol. 65, pp. 107-129, “Morphology of Carbon-Black aggregates: Fractal versus Euclidian Geometry,” including spherical (Type 1). Figure 2A ), oval (type 2, Figure 2B), linear (type 3, Figure 2C ) and branching (type 4, Figure 2D It should be understood that shape and aggregate size are distributional properties, and for any given carbon black production sample, a series of individual aggregates with different shapes and / or sizes may exist. Image analysis techniques for skeletonization can be performed using transmission electron microscopy with automated image analysis (TEM / AIA), combined with other aggregate shape parameters (e.g., shape factor, roundness, sphericity, aspect ratio, density, number of particles per aggregate, aggregate absorption index, number of skeleton endpoints, and number of skeleton branches) to validate shape descriptors and classify different aggregate shape types that initially visually separate into ideal instances of each shape type. Then, aggregate parameters can be used in discriminant analysis programs (e.g., Statistica) to develop and define regression equations to classify aggregates into various shape categories, as described in Herd et al., Rubber Chemistry and Technology, Vol. 65, pp. 107-129, “Morphology of Carbon-Black Aggregates: Fractal versus Euclidian geometry” and Herd et al., Rubber Chemistry and Technology, Vol. 66, pp. 491-509, “The Use of Skeletonization for the Shape Classification of Carbon-Black Aggregates”.

[0075] Manufacturing of conventional carbon black materials

[0076] The basic methods used to produce carbon black are well known. Typically, carbon black is produced by the partial oxidation or thermal decomposition of a hydrocarbon gas or liquid, in which a hydrocarbon feedstock (hereinafter referred to as "feed hydrocarbon") is injected into a hot gas stream, where the feed hydrocarbon is pyrolyzed and converted into fumes before being quenched by water mist. The hot gas is produced by burning fuel in a combustion section. The hot gas flows from the combustion section into a reaction section in open communication with the combustion section. As the hot gas flows through the reaction section, feed hydrocarbons are introduced into the hot gas, thereby forming a reaction mixture containing particles / aggregates that form carbon black. The reaction mixture flows from the reactor into a cooling section in open communication with the reaction section. At some point in the cooling section, one or more quenching sprays, such as water, are introduced into the flowing reaction mixture, thereby reducing the temperature of the reaction mixture below the temperature required for carbon black formation. The carbon black aggregates are then separated from the hot gas stream. Various types of carbon black can be produced by controlling the operation of the reactor conditions.

[0077] Many carbon black reactors typically include a cylindrical combustion section axially connected to one end of a cylindrical or truncated conical reaction section. A reaction throat is typically axially connected to the other end of the reaction section. The reaction throat has a diameter substantially smaller than the diameter of the reaction section and connects the reaction section to a cooling section. The cooling section is typically cylindrical and has a diameter substantially larger than the diameter of the reaction throat.

[0078] refer to Figure 1 The diagram shows a carbon black reactor 100 including a combustion section 102. The combustion section 102 includes a cylindrical inlet 108 at its upstream end for introducing fuel (such as natural gas or fuel oil), and a second opening 110 in the peripheral wall of the combustion section for introducing oxygen-containing gas (such as air). In the combustion section, the fuel and oxygen-containing gas are combusted.

[0079] The reactor also includes a reaction section 104 aligned axially with the combustion section. The hot gases generated in the combustion section flow substantially axially through the reactor, i.e., substantially parallel to the longitudinal axis of the reactor. The reaction section includes a tapered section 112 extending forward from the downstream end of the combustion section. The reaction section is in open communication with the combustion section via an open downstream end. The reaction section has an inner diameter that gradually decreases as it contracts toward the reaction throat 114. The reaction throat extends forward from the contracted end of the reaction section and is in open communication with the reaction section via an opening in the contracted end.

[0080] When fuel is used to generate hot gases, feedstock hydrocarbons are converted into soot via an incomplete combustion process. Feedstock hydrocarbons or conversion oils can contain a variety of hydrocarbon materials, such as fluidized bed catalytic cracker (FCC) residues, fuel oil, or coal tar. Feedstock hydrocarbons can also be renewable feedstocks. One or more hydrocarbon injection nozzles 116 are positioned along the length of the reaction section and / or reaction throat. Figure 1 In the diagram, the locations of exemplary injection nozzles are indicated by the letters A, B, C, and D. The feed hydrocarbon injection nozzles can extend through the outer walls of the reaction section and reaction throat and into the interior of the carbon black reactor. It should be noted that any number of injection nozzles can be used in the reactor, and the locations of any one or more nozzles can vary depending on the specific reactor design and the desired properties of the resulting carbon black.

[0081] As the hot combustion gas flows axially through the contraction reaction section and then axially through the reaction throat, the feed hydrocarbon is injected into the hot combustion gas stream through the hydrocarbon injection nozzle. When the feed hydrocarbon enters the hot oxygen-containing gas stream, the hot oxygen-containing combustion gas pyrolyzes the feed hydrocarbon, thereby forming a flowing reaction mixture containing hot gas and carbon black particles.

[0082] The flowing reaction mixture axially passes through the reaction throat to reach the cooling section. A cylindrical cooling section 106, with an inner diameter significantly larger than that of the reaction throat, is installed to the downstream portion of the reaction throat. The cooling section includes an annular upstream wall surrounding the reaction throat and a cylindrical outer shell extending forward from the annular upstream wall toward a downstream opening. One or more quenching nozzles 118 may extend from the outer wall of the cooling section into the inner portion of the cooling section.

[0083] As the flowing reaction mixture enters the cooling section, it is carried by a hot gas stream to one or more quenching sprays. The quenching sprays (typically water) lower the temperature of the hot gas stream below the temperature required for carbon black formation, thus stopping or "quenching" the carbon formation process. The cooled gas and the resulting carbon black particles / aggregates then flow from the cooling section to the carbon black recovery system.

[0084] Carbon black recovery systems are well known to those skilled in the art and therefore will not be discussed in detail here. Additives, such as potassium-containing structure control additives, may optionally be mixed with and / or injected separately into one or more feed hydrocarbon injection nozzles.

[0085] although Figure 1 The carbon black reactor shown is illustrated with a cylindrical cross-section; however, it should be understood that carbon black reactors with non-cylindrical cross-sections can also be used to practice this invention. Therefore, this invention is not limited to any particular carbon black reactor design, and those skilled in the art, upon mastering this disclosure, can readily determine how to utilize the invention in a given reactor system. It should also be understood that a combustion section that produces a tangential flow opposite to the axial flow can be used with this invention.

[0086] Routine control of carbon black aggregates, size, and distribution

[0087] As is well known, carbon black exists as an aggregate of alveolar aggregates, encompassing a wide range of particle sizes, surface areas, and aggregate sizes and structures. The average particle size and particle size distribution of carbon black directly determine its specific surface area, and as previously mentioned, a smaller average particle size increases the specific surface area, and vice versa. Aggregate size is determined by the average particle size, the number of particles per aggregate, and their spatial arrangement, or the degree of branching and complexity that defines the aggregate structure.

[0088] Aggregate structure and absorption capacity are reflected in their influence on the viscosity and modulus development of rubber compounds, with higher structure driving higher viscosity and modulus. More fundamentally, from a morphological perspective, structure is reflected in aggregate size and complexity; lower-structure aggregates have a more compact structure, while higher-structure aggregates have more branched and open structures, capable of blocking large amounts of oil or polymer.

[0089] Historically, changes in carbon black structure have been achieved by adding potassium-based compounds to the carbon black reactor. The introduction of these potassium-based compounds directly affects the structure buildup: adding less potassium produces higher-structure carbon black, while adding more produces lower-structure carbon black. While not wishing to be bound by theory, this method is believed to work by imparting a positive charge to the nascent carbon black particles. When a lower-structure carbon black is desired, this positive charge significantly reduces the probability of adhesion between nascent primary particles during collisions and aggregate formation in the reactor, leading to reduced or prevented significant growth and branching of aggregates, thus reducing their structural or aggregate complexity. Conversely, to produce high-structure aggregates, removing the potassium-based additive eliminates the charged particles, causing nascent primary particles to collide and adhere to each other, leading to aggregate growth and branching, thereby increasing their structural or aggregate complexity.

[0090] For various applications, such as tires and mechanical rubber products, the morphological properties of carbon black can significantly influence the viscoelastic properties (such as hardness, modulus, and compression set) of rubber compounds containing carbon black. ASTM-grade carbon black, as well as recently developed grades with narrow or wide aggregate size distributions, have reached significant limits in terms of performance and morphological distribution width. Therefore, methods for controlling the morphological properties of individual aggregates are becoming necessary as a means of producing unique carbon blacks with more controlled and specific dimensions and more controlled and optimized aggregate size distributions.

[0091] In a sense, the morphological properties of carbon black have historically been controlled in a holistic manner, where all aggregates in a given production run are typically modified in the same way. For decades, low, medium, and high-structure grades of carbon black have proliferated for a wide range of applications, from inks, coatings, and plastics to rubber compounds for tires and mechanical rubber products. For ASTM grades in commercial production, the methods used to control structure have been rather coarse, as potassium-based additives are added as uniformly as possible. This approach has been successful in producing materials that provide the generally expected average structure level that meets ASTM D1765-19 target values, providing tire and rubber product manufacturers with the viscoelastic / rheological properties they may require for a wide variety of rubber, liquid, or plastic composites.

[0092] Regarding the size distribution of carbon black aggregates, researchers and carbon black manufacturers have used a variety of techniques to make the aggregate size narrower or wider, depending on the target application and the desired properties of the final compound.

[0093] For narrow aggregate size distributions, the carbon black reactor is typically a single reactor as described in this patent, with a small throat size typically less than 6 inches (152.4 mm) and a conical outlet to prevent the recycling of carbon black and the generation of larger aggregates that may widen the ASD. Such a reactor and process are described in US10,829,613 B2, issued November 10, 2020.

[0094] For carbon black with a wide aggregate size distribution, in almost all methods used to produce such materials, it is clear that the broadening of the carbon black aggregate size distribution is mainly achieved through direct physical blending or by blending carbon blacks of different particle sizes or surface areas by controlling the relative regions of particle and aggregate formation in the reactor (primarily to produce carbon blacks with unique and significantly different average particle sizes or surface areas). The influence of structure on aggregate size distribution at the same surface area has been proposed in the literature, but such processes have not been actually implemented or described in actual production as described in the patent, nor has any description been provided that would allow a person skilled in the art to understand and reproduce such processes.

[0095] Janzen and Kroaus reported several early papers on broad aggregate size distributions in the Proceedings of the International Rubber Conference, Brighton, UK, 1972; Stacy, Johnson, and Kraus, Rubber Chemistry and Technology, 1975, 48, 538; and Hess and Klamp, Rubber Chemistry and Technology, 1983, 56, 390 (full references attached). These papers investigated blends of two or more carbon blacks with different surface areas and average particle sizes, noting that such blends typically resulted in poor tread wear because the tail or larger end of the ASD was primarily composed of carbon black with a larger average particle size. In Janzen and Kraus's 1972 report, blends of carbon blacks with similar average particle sizes but different structures were reported as another method for broadening aggregate particle size distributions. Low and moderate tread wear were found to be unaffected by ASD, but high-severity tread wear was negatively affected by approximately 10%. All of these studies were conducted using laboratory-based physical blends and did not teach anything about carbon black processes to achieve these morphological properties.

[0096] Japanese Patent Application No. S57-159661, filed by Tokai Carbon Company on September 16, 1982, and published on March 21, 1984 (Publication No. S59-49267), describes a "Y"-shaped reactor with two separate reactors, each consisting of its own blower, flame, and conversion oil injection zone, for the initial formation of carbon black particles and aggregates. These particles and aggregates collide at an angle of 30° to 90° in a single reaction and aggregate formation zone further downstream. Slightly downstream of this single formation zone is an annular space that can be opened or closed to varying degrees. The reactor design aims to modify the balance of aggregate structure and improve the COAN for a given OAN level.

[0097] U.S. Patent 4,786,677, also granted by Tokai Carbon Company on November 22, 1988, discloses the use of the same type of "Y" reactor for a rubber composition containing carbon black, wherein the two peak diameters of the carbon black satisfy the relationship 20. < L < 110 - 0.3*(NSA, m) 2 / g), where L is the distance between the two peak diameters determined by DCP (in nanometers, nm). Carbon black is produced in a “Y”-shaped reactor with two separate reactor lines, each with its own flame, blower, and conversion oil inlet, arranged such that forming and already formed particle nuclei and carbon black aggregates collide at angles of 30° to 60° in one region. According to the literature, each production zone produces material corresponding to aggregates equivalent to each of the two peak diameters in a Stokes diameter distribution, which is achieved by controlling the structure and NSA of each reactor leg in the “Y”-shaped reactor. No instructions are given on how to control the structure, but it is noted that the NSA also varies between the two reactors forming the “Y”-shaped structure by controlling the formation time of the particles / aggregates before quenching. Based on the information taught in the patent, the description of the process appears to indicate that, in addition to any contribution from the structure, differences in average particle size and surface area (or wide particle size distribution) are also used to broaden the ASD, without any instructions in the patent on methods of control and variation, nor any absolute values.

[0098] U.S. Patent 5,254,325, granted on October 19, 1993, discloses a method for controlling and broadly altering particle size and its distribution, as well as widening the aggregate size distribution. This is achieved by injecting additional material hydrocarbon streams at different distances along the flow path in the carbon black formation zone of the reactor to produce different particle sizes and distributions and thus widen the ASD.

[0099] US Patent 8,258,207 B2, granted September 4, 2012, reports the preparation and rubber-like properties of physical blends of carbon black, which are prepared in a laboratory and are essentially unimodal, possibly with shoulder peaks. The STSA (or ΔSTSA) of the blend components in these prepared broad ASD materials varies considerably, ranging from 58 m... 2 / g to 182 m 2 / g, indicating that a wide to very wide particle size distribution also primarily serves to alter the ASD. Furthermore, data on the carbon black used in the blends show that, apart from using large STSA variations to broaden the ASD, the structural differences in the blend components remain constant to vary up to 32 ml / 100g compressed OAN (ΔCOAN). It is noted and stated that such blends also exhibit a slightly lower OAN than predicted for the blend components. Note that the combination of PSD differences and OAN or COAN differences enables the production of wide ASD carbon black on a laboratory scale.

[0100] Chinese Patent CN105647242BB, granted on August 22, 2017, discloses a carbon black with an ultra-wide aggregate size distribution, also prepared by a "Y" reactor. In this case, based on the operating conditions of each "Y" reactor described in the patent, a person skilled in the art can determine that the NSA (non-stressed aggregate size distribution) of each reactor in the "Y" produces carbon black with very different STSA (stressed aggregate size distribution). Therefore, the wide aggregate size distribution is primarily driven by the wide particle size distribution. No information regarding variations in aggregate structure is disclosed or stated.

[0101] Even with these overall changes in aggregate properties as described above, there is still a need for modified carbon blacks with altered morphological properties, which can, for example, exhibit an optimized aggregate size distribution, broadened and controlled by controlling the aggregate shape distribution, having a narrow to normal particle size distribution, while maintaining electrical conductivity and optionally maintaining or improving the tread wear properties of the resulting tire compound. The shape-modified carbon black of the present invention can impart such improved performance properties to elastomeric compounds.

[0102] Shape-modified carbon black materials and their manufacturing methods

[0103] As briefly described above, in one aspect, the present invention provides a method for modifying the shape and / or shape distribution of carbon black aggregates. In each aspect, the quantity and / or weight percentage of carbon black aggregates of any one or more shape categories can be increased or decreased. In another aspect, the method of changing the shape distribution of carbon black has little or no effect on the aggregate size distribution and / or particle size distribution of the carbon black. In yet another aspect, such techniques can modify the aggregate size distribution of carbon black by, for example, broadening the aggregate size distribution. In yet another aspect, the aggregate size of carbon black can be broadened without broadening the particle size distribution. In yet another aspect, the aggregate size distribution can be broadened to a greater extent than any broadening of the particle size distribution. In one aspect, the aggregate size distribution can be broadened by expanding the larger size range of the distribution. In another aspect, the aggregate size distribution can be broadened by expanding the smaller size range of the distribution. In yet another aspect, the aggregate size distribution can be broadened by expanding both the smaller and larger size ranges of the distribution. Still in yet another aspect, this disclosure provides a method for preparing an aggregate size distribution that may be broader than conventionally possible.

[0104] For example, the carbon black of the present invention can provide faster carbon black incorporation and improved carbon black dispersion in polymer (e.g., rubber) matrices. In various aspects, modification of the shape and shape distribution of carbon black aggregates when incorporated into elastomers can provide benefits such as, for example, improved hysteresis reduction while maintaining electrical conductivity. In another aspect, carbon black materials using such shape-modified carbon black can provide improved hysteresis while maintaining dynamic stiffness, electrical conductivity, and / or failure properties.

[0105] The carbon black material of the present invention can be prepared using innovative variations of conventional carbon black manufacturing methods. Various methods for preparing the carbon black of the present invention are described below and in examples. Those skilled in the art can identify variations of these methods. In one aspect, the carbon black of the present invention can be produced by modifying a carbon black tread reactor, such as the carbon black reactor generally described in U.S. Patent Nos. 4,927,607 and 5,256,388, the disclosure of which is incorporated herein by reference in its entirety. Other carbon black reactors can be used, and those skilled in the art can determine suitable reactors for specific applications. Raw materials, combustion feed, and quenching materials are well known in the field of carbon black. The selection of these feeds is not critical for the carbon black of the present invention. Those skilled in the art can determine appropriate feeds for specific applications. The amounts of raw materials, combustion feed, and quenching materials can also be determined by those skilled in the art to be suitable for specific applications. Raw materials can be renewable raw materials, such as plant-based raw materials, preferably based on inedible plants, or waste raw materials. Plant-based feedstocks can include wood, grasses, cellulose, hemicellulose, lignin, tall oil, rubber seed oil, tobacco seed oil, castor oil, tall oil, Indian tannin oil, mustard seed oil, neem oil, rice bran oil, etc. Waste feedstocks can include edible oils, distillation residues from biodiesel plants, pyrolysis oils, and waste containing natural or synthetic rubber from tires, cable sheaths, pipes, conveyor belts, shoe soles, hoses, etc. Feedstocks can be mixtures or renewable carbon black feedstocks and hydrocarbon feedstocks. Hydrocarbon feedstocks can be aliphatic or aromatic, saturated or unsaturated hydrocarbons or mixtures thereof, coal tar fractions, residue oil produced during the catalytic cracking of petroleum fractions, and residue oil produced during the cracking of naphtha or gas oil, natural gas, or mixtures or combinations thereof to produce olefins.

[0106] The carbon black of the present invention has an optimized aggregate size distribution (generally wider and optimized by controlling the aggregate shape distribution) and a narrow or normal particle size distribution. The carbon black of the present invention can reduce the tendency of carbon black network formation and reduce hysteresis in the resulting rubber compound, while the particle size distribution, together with the optimized aggregate shape distribution, can provide a better foundation for tread wear properties and electrical conductivity.

[0107] As mentioned above, these methods have reached the practical limits of general reactor technology, but greater flexibility is needed in manipulating and controlling the size distribution of aggregates. Therefore, carbon black with controlled shape distribution has been invented to provide materials with advanced and unique morphological properties.

[0108] In one aspect of the invention, the carbon black of the invention can be produced by non-uniformly injecting structure-controlling additives (such as potassium-containing compounds) into different reactor zones in an effort to control the aggregate structure in each zone, as well as the subsequent aggregate shape and final size distribution. Typically, a wider aggregate size distribution is produced when a shape-modification process is implemented. This aggregate shape control method provides a way beyond the limitations of normal reactors and provides a unique carbon black that imparts beneficial properties to rubber compounds, particularly in reducing network and lowering heat generation, while still maintaining a good balance of durability.

[0109] In one aspect, the carbon black of the present invention can be produced in a single reactor by controlling the additives via a non-uniform injection structure. In another aspect, the carbon black of the present invention can be produced using two or more reactors.

[0110] In one aspect, the methods of this disclosure provide the carbon black of the present invention with a modified and / or controllable aggregate shape distribution. In this aspect, the carbon black of the present invention can have different aggregate distributions ranging from low-structure to medium-structure to high-structure compared to conventional carbon black. In a specific aspect, based on quantity or weight, the amount of each of the low-structure and high-structure aggregates can be greater, or one category can be higher and the other category (higher or lower structure aggregates) lower, and in each case, a different shape distribution relative to conventional carbon black. In another aspect, the modified shape distribution can result in a wider aggregate size distribution (hereinafter referred to as "ASD") of the carbon black without increasing the particle size distribution (i.e., the size of the individual primary particles constituting the aggregates, hereinafter referred to as "PSD"). In yet another aspect, the present invention can provide multi-peak ASD carbon black. In a specific aspect, the present invention can provide bi-peak or even uni-peak ASD carbon black, wherein a greater number of low-structure aggregates and a greater number of high-structure aggregates are produced compared to conventional carbon black. The technology of the present invention provides an improved method for precisely controlling different size portions of ASD at a given particle size, and also results in control over the shape distribution of the resulting carbon black material as well as control over the mode, mean and weight average of ASD.

[0111] In another aspect of the invention, the shape modification method provides a novel approach for controlling the overall average structure level, or OAN, of carbon black materials. Typically, as previously described, this control is achieved by adding more or less potassium-based structure control additives to the oil, which are uniformly distributed between one or more conversion oil spray planes, or in a separate water spray, introduced into all compartments of the reactor after its inlet point. In the shape modification process of the present invention, OAN control can be achieved by varying the oil-to-oil ratio in each of two or more conversion oil spray planes, maintaining the flow rate and concentration of the potassium-based additive at zero or parts per million (ppm) levels in one or more planes, preferably in the plane located behind the spray plane closest to the throat outlet. By varying the oil and potassium flow rates in these planes, the amount of very low, medium, or very high structure aggregates can be manipulated, and the OAN can be controlled very precisely to meet production targets.

[0112] In another aspect of the invention, the shape-modified carbon black of the invention can be prepared using two reactors connected in a common manifold. One reactor produces carbon black with a given surface area but very low to low structure (OAN > 0 ml / 100 g but < 70 ml / 100 g), while a second reactor produces carbon black with very high structure (OAN > 120 ml / 100 g) and a surface area similar to that produced in the first reactor. The method is not limited to two reactors, nor to three, four, or more reactors. However, this method may not be cost-effective because, depending on the blending ratios of various aggregate shapes (low, medium, and / or high structure), one or more reactors may have reduced productivity, thus increasing costs.

[0113] In another aspect of the invention, shape-modified carbon black can also be prepared by physically blending two or more types of carbon black after a reactor in a carbon black production plant, in a separate blending facility, or even in a customer's blending facility. This would require producing separate blend components, packaging them, and then metering and blending them using dedicated blending equipment and processes. This is generally not cost-effective and can reduce bead quality and produce fine powder, negatively impacting dispersion.

[0114] Figure 3A Exemplary aggregates from conventional ASTM grade carbon black are shown, exhibiting narrow / normal ASD and narrow / normal PSD. Figure 3B Exemplary aggregates of carbon black from this invention are shown, exhibiting a very wide ASD and a narrow PSD. Figure 3B In the middle, large high-structure aggregates (shown as gray particles) and many smaller low-structure aggregates are formed.

[0115] In one aspect, the production of carbon black according to the present invention can be achieved by utilizing hydrocarbon injection nozzles located in two or more axial planes (i.e., distances from the throat outlet) within the reactor section and / or throat of the reactor. In various aspects, the planes in which the hydrocarbon injection nozzles are located may depend on the specific reactor design, but may range, for example, from about 1 inch to about 50 inches (2.54 cm to 127 cm) or greater from the throat outlet. In one aspect, hydrocarbon injection nozzles with two planes may be used. In another aspect, hydrocarbon injection nozzles with three planes may be used. In yet another aspect, hydrocarbon injection nozzles with four, five, or more planes may be used. In one aspect, each plane in the multiple hydrocarbon injection nozzle planes can be equidistantly spaced, for example, approximately 2 inches (5.08 cm), 4 inches (10.16 cm), 6 inches (15.24 cm), 8 inches (20.32 cm), 10 inches (25.40 cm), 12 inches (30.48 cm), 14 inches (35.56 cm), 16 inches (40.64 cm), 18 inches (45.72 cm), 20 inches (50.80 cm), 24 inches (60.96 cm), 26 inches (66.04 cm), 28 inches (71.12 cm), 30 inches (76.20 cm), 32 inches (81.28 cm), 34 inches (86.36 cm), 36 inches (91.44 cm), 38 inches (96.52 cm), 40 inches (101.60 cm), 42 inches (106.68 cm), 44 inches (111.76 cm), etc. 46 inches (116.84 cm), 48 inches (121.92 cm), or 50 inches (127.00 cm) or larger. In a specific respect, at least two planes of the hydrocarbon injection nozzle are positioned at least 8 inches (20.32 cm) apart. In other respects, at least two planes of the hydrocarbon injection nozzle are positioned at intervals of at least 10 inches (25.4 cm), 12 inches (30.48 cm), 14 inches (35.56 cm), 15 inches (38.1 cm), 16 inches (40.64 cm), 18 inches (45.72 cm), 20 inches (50.8 cm), 24 inches (60.96 cm), 26 inches (66.04 cm), 28 inches (71.12 cm), 30 inches (76.20 cm), 32 inches (81.28 cm), 34 inches (86.36 cm), 36 inches (91.44 cm), 38 inches (96.52 cm), 40 inches (101.60 cm), 42 inches (106.68 cm), 44 inches (117.76 cm), 46 inches (116.84 cm), and 48 inches (116.84 cm). 50 inches (127.00 cm) or more.

[0116] In another aspect, each of the multiple hydrocarbon injection nozzle planes can be spaced apart from the other planes at irregular distances. In yet another aspect, each plane can include two or more individual hydrocarbon injection nozzles, which are spaced, for example, uniformly around the perimeter of the reactor. If such individual nozzles are uniformly spaced around the perimeter of the reactor, the angle between the individual nozzles can be described as 360° / the number of individual nozzles.

[0117] In one respect, the number of individual hydrocarbon injection nozzles located at each plane can be the same. In another respect, the number of individual hydrocarbon injection nozzles located at each plane can vary. In a related respect, the position and / or arrangement of the individual hydrocarbon injection nozzles can vary from one plane to another. In yet another respect, the amount and / or type of feedstock hydrocarbons injected at any given plane or through any individual hydrocarbon injection nozzle can be the same as or different from any other plane or individual hydrocarbon injection nozzle.

[0118] In one aspect, this disclosure provides a method for manufacturing carbon black, wherein each of a plurality of feedstock hydrocarbon injection nozzles is located in a plane within a carbon black reactor, and wherein these planes are positioned at distances from each other of at least 8 inches (20.32 cm), 10 inches (25.40 cm), 12 inches (30.48 cm), 14 inches (35.56 cm), 16 inches (40.64 cm), 20 inches (50.80 cm), 22 inches (55.88 cm), 24 inches (60.96 cm), 26 inches (66.04 cm), 28 inches (71.12 cm), 30 inches (76.20 cm), 32 inches (81.28 cm), 34 inches (86.36 cm), 36 inches (91.44 cm), 38 inches (96.52 cm), 40 inches (101.60 cm), 42 inches (106.68 cm), and 44 inches (117.76 cm). 46 inches (116.84 cm), 48 inches (116.84 cm), 50 inches (127.00 cm), or longer. In another aspect, the carbon black of the present invention can be manufactured in a reactor configured such that any one or more of a plurality of feed hydrocarbon injection nozzles are located at locations far apart from each other, as measured from the end of a reactor throat, and wherein the feed hydrocarbons are injected into the reactor in a non-uniform manner. In another aspect, the carbon black can be manufactured in a reactor configured such that any one or more of a plurality of feed hydrocarbon injection nozzles are located at locations far apart from each other, as measured from the end of a reactor throat, and wherein structure control additives (such as potassium-containing compounds) are injected into the reactor in a non-uniform manner, either alone or together with the feed hydrocarbons. In one aspect, the feed hydrocarbons can be injected into the reactor via an injection sprayer, wherein potassium-containing compounds can be introduced to a plurality of spray locations, for example, positioned along a throat, and wherein the amount or rate of potassium compound addition can vary between each spray location. In various aspects, the structure control additives can be added in a non-uniform manner. In one aspect, non-uniform structure-controlled addition may involve the addition of all or part of the structure-controlled additive, either alone or in combination with feedstock hydrocarbons, at locations not typically used in carbon black manufacturing. In another aspect, non-uniform structure-controlled addition may involve the addition of all or part of the structure-controlled additive at multiple locations, wherein the amount and / or rate of structure-controlled addition at each of the multiple locations may be the same or may vary. In each aspect, all or part of the structure-controlled additive may be mixed with the feedstock hydrocarbons and added through a single injection nozzle. In another aspect, more structure-controlled additive may be added through a single injection nozzle or multiple injection nozzles in a plane compared to other injection nozzles.

[0119] Properties of the Shape-Modified Carbon Black of the Present Invention

[0120] It should be noted that the carbon black of the present invention may include any grade of carbon black. In one aspect, the carbon black of the present invention may include furnace black. In another aspect, the carbon black of the present invention may have colloidal properties, such as, for example, iodine value, nitrogen surface area, statistical thickness surface area, oil absorption value, or compression oil absorption value, as described for ASTM grade carbon black (ASTM 1765-2019), such as, for example, N134, N121, N115, N110, N220, N234, N299, N330, N339, N550, N539, N660, N762, N772, or N990. Various properties and ranges are listed below. Any combination of such listed ranges is part of the invention. With respect to any range and / or value listed herein, it should be understood that the carbon black of the present invention may also have values ​​higher or lower than any specifically listed range, and this disclosure is not intended to be limited to the specifically listed ranges and / or values.

[0121] In one aspect, the carbon black of the present invention may have approximately 135 μm as measured according to ASTM standard D6556-2017. 2 / g to approximately 145 m 2 / g, approximately 135 m 2 / g to approximately 140 m 2 / g or approximately 130 m 2 / g to approximately 140 m 2 / g, for example, approximately 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144 or 145 m 2 The nitrogen surface area (NSA) is approximately 110 m² / g. In another aspect, the carbon black of the present invention can have an NSA of approximately 110 m² / g. 2 / g to approximately 130 m 2 / g, or approximately 115 m 2 / g to approximately 125 m 2 / g, for example, approximately 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, or 130 m 2 The nitrogen surface area is approximately 95 m² / g. In another aspect, the carbon black of the present invention can have approximately 95 m² / g of nitrogen surface area. 2 / g to approximately 110m 2 / g, or approximately 80 m 2 / g to approximately 145 m 2 / g, for example, approximately 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 102, 104, 106, 108, 110, 112, 114, 116, 118, 120, 122, 124, 126, 128, 130, 132, 134, 136, 138, 140, 142, 144, or 145 m 2 The nitrogen surface area is approximately 75 m² / g. In another aspect, the carbon black of the present invention can have approximately 75 m² / g of nitrogen surface area. 2 / g to approximately 85 m 2 / g, approximately 80 m 2 / g to approximately 90 m 2 / g, or approximately 80 m 2 / g to approximately 85 m 2 / g, for example, approximately 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, or 85 m 2 The nitrogen surface area is approximately 85 m² / g. In another aspect, the carbon black of the present invention can have approximately 85 m² / g of nitrogen surface area. 2 / g to approximately 95 m 2 / g, approximately 80 m 2 / g to approximately 95 m 2 / g, or approximately 90 m 2 / g to approximately 95 m 2 / g, for example, approximately 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, or 95 m 2 / g nitrogen surface area. In another aspect, the carbon black of the present invention can have approximately 60 m² / g nitrogen surface area. 2 / g to approximately 70 m 2 / g, or approximately 65 m 2 / g to approximately 75 m 2 / g, for example, approximately 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, or 75 m 2 The nitrogen surface area is approximately 50 m² / g. In another aspect, the carbon black of the present invention can have approximately 50 m² / g of nitrogen surface area. 2 / g to approximately 60 m 2 / g, or approximately 40 m 2 / g to approximately 75 m 2 / g, for example, approximately 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, 60, 62, 64, 66, 68, 70, 72, 74, or 75 m 2 The nitrogen surface area is 0.5 m² / g. In another aspect, the carbon black of the present invention can have a nitrogen surface area greater than about 0.5 m² / g. 2 / g to approximately 60 m2 / g, or about 1 m 2 / g to approximately 50 m 2 / g, for example, about 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48 or 50 m 2 / g nitrogen surface area. In another aspect, the carbon black of the present invention may have a nitrogen surface area comparable to that of N100 series carbon black. In another aspect, the carbon black of the present invention may have a nitrogen surface area comparable to that of N200 series carbon black. In another aspect, the carbon black of the present invention may have a nitrogen surface area comparable to that of N300 series carbon black. In other aspects, the carbon black of the present invention may have a nitrogen surface area comparable to that of N400 series, N500 series, N600 series, N700 series, N800 series or N900 series carbon black. In other aspects, the carbon black of the present invention may have a nitrogen surface area of ​​about 40 m. 2 / g to approximately 250 m 2 / g, for example, approximately 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, or 250 mg. 2 / g nitrogen surface area.

[0122] In one aspect, the carbon black of the present invention may have approximately 135 μm as measured according to ASTM standard 6556-2017. 2 / g to approximately 145 m 2 / g, approximately 135 m 2 / g to approximately 140 m 2 / g, approximately 130 m 2 / g to approximately 140 m 2 / g, approximately 125 m 2 / g to approximately 135 m 2 / g, for example, approximately 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, or 145 m 2 The statistical thickness surface area (STSA) is approximately 105 m² / g. In another aspect, the carbon black of the present invention can have approximately 105 m² / g. 2 / g to approximately 115 m 2 / g, approximately 110 m 2 / g to approximately 120 m 2 / g, or approximately 110 m 2 / g to approximately 115 m 2 / g, for example, approximately 10⁵, 10⁶, 10⁷, 10⁸, 10⁹, 110, 111, 112, 113, 114, or 115 m 2 / g statistical thickness surface area. In yet another aspect, the carbon black of the present invention can have approximately 70 m². 2 / g to approximately 80 m 2 / g, approximately 65 m 2 / g to approximately 80 m 2 / g, approximately 70 m 2 / g to approximately 85 m 2 / g, approximately 60 m 2 / g to approximately 70 m 2 / g, approximately 80 m 2 / g to approximately 85 m 2 / g, approximately 80 m 2 / g to approximately 90 m 2 / g or approximately 72 m 2 / g to approximately 78 m 2 / g, for example, approximately 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, or 90 m 2 The statistical thickness surface area is / g. In yet another aspect, the carbon black of the present invention can have approximately 120 μm... 2 / g to approximately 125 m 2 / g, or approximately 110 m 2 / g to approximately 140 m 2 / g, for example, approximately 110, 112, 114, 116, 118, 120, 121, 122, 123, 124, 125, 126, 128, 130, 132, 134, 136, 138, or 140 m 2 The statistical thickness surface area is 1 / g. In another aspect, the carbon black of the present invention can have a surface area greater than about 120 μm. 2 / g, for example, approximately 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, or 150 m 2The statistical thickness surface area is 1 / g. In another aspect, the carbon black of the present invention can have a thickness of about 140 to about 200 μm. 2 / g, for example, approximately 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, or 200 m 2 The statistical thickness surface area is / g. In other respects, the carbon black of the present invention can have approximately 1 m². 2 / g to approximately 15 m 2 / g, approximately 5 m 2 / g to approximately 10 m 2 / g, approximately 25 m 2 / g to approximately 40 m 2 / g, approximately 40 m 2 / g to approximately 65 m 2 / g, approximately 65m 2 / g to approximately 95 m 2 / g, approximately 95 m 2 / g to approximately 105 m 2 / g, approximately 95 m 2 / g to approximately 120 m 2 / g, approximately 100 m 2 / g to approximately 130m 2 / g, or about 110 to about 160 m 2 The statistical thickness surface area is / g. In other aspects, the carbon black of the present invention may have a statistical thickness surface area comparable to that of the N100, N200, N300, N400, N500, N600, N700, N800 or N900 series carbon blacks.

[0123] In one aspect, the carbon black of the present invention may have a content of about 115 ml / 100g to about 135 ml / 100g, about 115 ml / 100g to about 125 ml / 100g, about 120 ml / 100g to about 125 ml / 100g, about 120 ml / 100g to about 130 ml / 100g, about 105 ml / 100g to about 125 ml / 100g, about 110 ml / 100g to about 125 ml / 100g, or about 125 ml / 100g to about 135 ml / 100g, as measured according to ASTM standard D2414-2018. Oil absorption value (OAN) of approximately 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, or 135 ml / 100g. In another aspect, the carbon black of the present invention may have an oil absorption value (OAN) of about 65 ml / 100g to about 75 ml / 100g, about 70 ml / 100g to about 80 ml / 100g, or about 70 ml / 100g to about 75 ml / 100g, for example about 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, or 80 ml / 100g. In another aspect, the carbon black of the present invention may have an oil absorption value (OAN) of about 90 ml / 100g to about 105 ml / 100g, about 95 ml / 100g to about 105 ml / 100g, about 100 ml / 100g to about 110 ml / 100g, or about 100 ml / 100g to about 105 ml / 100g, for example about 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, or 110 ml / 100g. In another aspect, the carbon black of the present invention may have an oil absorption value (OAN) of about 80 ml / 100g to about 90 ml / 100g, or about 65 ml / 100g to about 110 ml / 100g, for example about 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, or 110 ml / 100g.In another aspect, the carbon black of the present invention may have an oil absorption value (OAN) of about 80 ml / 100g to about 200 ml / 100g, for example, about 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, or 200 ml / 100g. In another aspect, the carbon black of the present invention may have an oil absorption value (OAN) of less than about 170 ml / 100g, less than about 150 ml / 100g, less than about 130 ml / 100g, or less than about 125 ml / 100g. In other aspects, the carbon black of the present invention may have an oil absorption value comparable to that of N100, N200, N300, N400, N500, N600, N700, N800, or N900 series carbon blacks.

[0124] In one aspect, the carbon black of the present invention may have a compression absorbance value (COAN) of about 60 ml / 100g to about 70 ml / 100g, about 65 ml / 100g to about 75 ml / 100g, or about 65 ml / 100g to about 70 ml / 100g, as measured according to ASTM standard D3493-2018, for example about 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, or 75 ml / 100g. In another aspect, the carbon black of the present invention may have a compression absorbance value (COAN) of about 80 ml / 100g to about 95 ml / 100g, about 85 ml / 100g to about 95 ml / 100g, or about 85 ml / 100g to about 90 ml / 100g, for example about 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, or 95 ml / 100g. In another aspect, the carbon black of the present invention may have a compression absorbance value (COAN) of about 90 ml / 100g to about 105 ml / 100g, about 90 ml / 100g to about 100 ml / 100g, 95 ml / 100g to about 105 ml / 100g, or about 100 ml / 100g to about 110 ml / 100g, for example about 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, or 110 ml / 100g. In another aspect, the carbon black of the present invention may have a compression absorbance value (COAN) of about 75 ml / 100g to about 80 ml / 100g, or about 65 ml / 100g to about 125 ml / 100g, for example about 65, 67, 69, 71, 73, 75, 77, 79, 81, 83, 85, 87, 89, 91, 93, 95, 97, 99, 101, 103, 105, 107, 109, 111, 113, 115, 117, 119, 121, 123, or 125 ml / 100g.In another aspect, the carbon black of the present invention may have a content of about 105 ml / 100g to about 150 ml / 100g, about 105 ml / 100g, about 145 ml / 100g, about 105 ml / 100g to about 140 ml / 100g, about 105 ml / 100g to about 135 ml / 100g, about 105 ml / 100g to about 130 ml / 100g, about 105 ml / 100g to about 125 ml / 100g, about 110 ml / 100g to about 125 ml / 100g, about 110 ml / 100g to about 120 ml / 100g, or about 115 ml / 100g to about 125 ml / 100g. Compression absorbance value (COAN) of approximately 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, or 150 ml / 100g. In other respects, the carbon black of the present invention may have a compression oil absorption value comparable to that of N100, N200, N300, N400, N500, N600, N700, N800 or N900 series carbon blacks.

[0125] In one aspect, as described herein, the carbon black of the present invention may have an aggregate size heterogeneity index (HI) of at least about 2.0. ASD In one aspect, as described herein, the carbon black of the present invention may have an aggregate size heterogeneity index (HI) of at least about 2.2. ASD In one aspect, as described herein, the carbon black of the present invention may have an aggregate size heterogeneity index (HI) of at least about 2.5. ASD In one aspect, as described herein, the carbon black of the present invention may have an aggregate size heterogeneity index (HI) of at least about 2.8. ASD In one aspect, as described herein, the carbon black of the present invention may have an aggregate size heterogeneity index (HI) of at least about 2.7, at least about 2.8, or at least about 2.9. ASD In one aspect, as described herein, the carbon black of the present invention may have an aggregate size heterogeneity index (HI) of at least about 3.0. ASD In one aspect, as described herein, the carbon black of the present invention may have an aggregate size heterogeneity index (HI) of at least about 3.5. ASDIn another aspect, the carbon black of the present invention may have an aggregate size heterogeneity index (HI) of about 2.0 to about 4.0, about 2.2 to about 3.8, about 2.5 to about 4.0, about 2.5 to about 5, or about 2.5 to about 3.5, for example, about 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, or 5.0. ASD In another aspect, the carbon black of the present invention may have an aggregate heterogeneity index (HI) of about 2 to about 10, about 2.2 to about 7.0, about 2.5 to about 3, about 3 to about 6.0, about 2.8 to about 9, or about 4 to about 9, for example, about 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0 or greater. ASD ).

[0126] In one aspect, as described herein, the carbon black of the present invention may have a particle size heterogeneity index (HI) of less than about 1.80. PSD In another aspect, the carbon black of the present invention may have an HI of less than about 1.75, less than about 1.70, less than about 1.68, or less than about 1.65. PSD In another aspect, as described herein, the carbon black of the present invention may have a carbon content of about 1.30 to about 1.80, about 1.35 to about 1.80, about 1.45 to about 1.70, about 1.45 to about 1.50, about 1.45 to about 1.55, about 1.50 to about 1.65, about 1.50 to about 1.60, about 1.50 to about 1.70, about 1.50 to about 1.70, about 1.55 to about 1.70, about 1.55 to about 1.70, or about 1.55 to about 1.55. Particle size heterogeneity index (HI) of approximately 1.60, or approximately 1.65 to approximately 1.70, such as approximately 1.30, 1.35, 1.40, 1.45, 1.46, 1.48, 1.50, 1.52, 1.54, 1.56, 1.58, 1.60, 1.62, 1.64, 1.66, 1.68, 1.69, or 1.70, 1.72, 1.74, 1.76, 1.78, or 1.80. PSD ).

[0127] In one aspect, as described herein, the carbon black of the present invention may have a dispersion ratio of at least about 1.50, at least about 1.60, at least about 1.70, at least about 1.80, at least about 1.90, at least about 2.00, at least about 2.10, at least about 2.20, or at least about 2.30. In another aspect, the carbon black of the present invention may have a dispersion ratio of about 1.50 to about 3.00, about 1.50 to about 2.70, about 1.60 to about 2.70, about 1.70 to about 2.50, about 1.80 to about 2.50, about 1.80 to about 2.70, about 1.70 to about 3.00, or about 1.70 to about 2.70, for example about 1.50, 1.60, 1.70, 1.80, 1.90, 2.00, 2.10, 2.20, 2.30, 2.40, 2.50, 2.60, 2.70, 2.80, 2.90, or 3.00. In another aspect, the carbon black of the present invention may have a dispersion ratio of about 2.00 to about 4.00, about 2.00 to about 6.00, about 2.50 to about 5.00, about 3.00 to about 7.00, or about 3.50 to about 9.00, for example, about 2.00, 2.50, 3.00, 3.50, 4.00, 4.50, 5.00, 5.50, 6.00, 6.50, 7.00, 7.50, 8.00, 8.50, or 9.00.

[0128] In another aspect, as described herein, the carbon black of the present invention has a shape-specific heterogeneity index (SSHI) of at least 2.1, at least 2.2, at least 2.3, at least 2.4, at least 2.5, at least 2.6, at least 2.7, at least 2.8, at least 2.9, at least 3.0, at least 3.1, at least 3.2, at least 3.3, at least 3.4, at least 3.5, or at least 3.6 for type 4 branched aggregates. In another aspect, as described herein, the carbon black of the present invention has an SSHI of about 2.1 to about 4.0, about 2.1 to about 2.5, about 2.3 to about 3.8, about 2.2 to about 2.5, about 2.3 to about 2.5, about 2.5 to about 4.0, about 2.7 to about 3.3, about 2.8 to about 3.2, about 2.7 to about 3.8, about 2.8 to about 3.8, about 2.7 to about 3, about 2.8 to about 3.0 ... The shape-specific heterogeneity index (SSHI) ranges from 3.0 to 4.0, from 3.2 to 3.8, from 3.3 to 3.8, from 3.5 to 3.7, or from 3.5 to 4.0, for example, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, or 4.0.

[0129] In one aspect, the carbon black of the present invention may have a thickness of about 132 μm. 2 / g to approximately 142 m2 / g, approximately 134 m 2 / g to approximately 140m 2 / g, or approximately 137 m 2 / g NSA; approximately 128 m 2 / g to approximately 138 m 2 / g, approximately 130 m 2 / g to approximately 136 m 2 / g, or approximately 133m 2 STSA at approximately 116 ml / 100g to approximately 126 ml / 100g, approximately 118 ml / 100g to approximately 124 ml / 100g, or approximately 121 ml / 100g; COAN at approximately 94 ml / 100g to approximately 104 ml / 100g, approximately 96 ml / 100g to approximately 102 ml / 100g, or approximately 99 ml / 100g; HI at approximately 3.2 to approximately 4.2, approximately 3.4 to approximately 4.0, or approximately 3.7. ASD ; HI of approximately 1.53 to approximately 1.63, approximately 1.56 to approximately 1.60, or approximately 1.58 PSD The carbon black of the present invention may have an SSHI (type 4) of about 1.84 to about 2.84, about 2.04 to about 2.64, or about 2.34; and an SSHI (type 4) of about 3.10 to about 4.10, about 3.30 to about 3.90, or about 3.60. In another aspect, the carbon black of the present invention may have an SSHI (type 4) of about 3.10 to about 4.10, and any one or more other properties listed in this paragraph.

[0130] In one aspect, the carbon black of the present invention may have a density of about 134 μm. 2 / g to approximately 144 m 2 / g, approximately 136 m 2 / g to approximately 142m 2 / g, or approximately 139 m 2 / g NSA; approximately 128 m 2 / g to approximately 138 m 2 / g, approximately 130 m 2 / g to approximately 136 m 2 / g, or approximately 133m 2 / g STSA; about 137 ml / 100g to about 147 ml / 100g, about 139 ml / 100g to about 145 ml / 100g, or about 142 ml / 100g OAN; about 100 ml / 100g to about 110 ml / 100g, about 102 ml / 100g to about 108 ml / 100g, or about 105 ml / 100g COAN; about 3.7 to about 4.8, about 3.9 to about 4.6, or about 4.3 HIASD ; HI of approximately 1.47 to approximately 1.57, approximately 1.49 to approximately 1.55, or approximately 1.52 PSD The carbon black of the present invention may have an SSHI (type 4) of about 2.36 to about 3.36, about 2.56 to about 3.16, or about 2.86; and an SSHI (type 4) of about 3.01 to about 4.01, about 3.26 to about 3.86, or about 3.51. In another aspect, the carbon black of the present invention may have an SSHI (type 4) of about 3.01 to about 4.01, and any one or more other properties listed in this paragraph.

[0131] In one aspect, the carbon black of the present invention may have a thickness of about 135 μm. 2 / g to approximately 145 m 2 / g, approximately 137 m 2 / g to approximately 143m 2 / g, or approximately 140 m 2 / g NSA; approximately 125 m 2 / g to approximately 135 m 2 / g, approximately 127 m 2 / g to approximately 133 m 2 / g, or approximately 130m 2 STSA at approximately 148 ml / 100g to approximately 158 ml / 100g, approximately 150 ml / 100g to approximately 156 ml / 100g, or approximately 153 ml / 100g; OAN at approximately 112 ml / 100g to approximately 122 ml / 100g, approximately 114 ml / 100g to approximately 120 ml / 100g, or approximately 117 ml / 100g; HI at approximately 3.5 to approximately 4.5, approximately 3.7 to approximately 4.3, or approximately 4.0. ASD ; HI of approximately 1.68 to approximately 1.79, approximately 1.69 to approximately 1.76, or approximately 1.74 PSD The carbon black of the present invention may have an SSHI (type 4) of about 1.80 to about 2.80, about 2.00 to about 2.50, or about 2.30; and an SSHI (type 4) of about 2.91 to about 3.91, about 3.11 to about 3.71, or about 3.41. In another aspect, the carbon black of the present invention may have an SSHI (type 4) of about 2.91 to about 3.91, and any one or more other properties listed in this paragraph.

[0132] In one aspect, the carbon black of the present invention may have a thickness of about 130 μm. 2 / g to approximately 140 m 2 / g, approximately 132 m 2 / g to approximately 138m 2 / g, or approximately 135 m 2 / g NSA; approximately 129 m 2 / g to approximately 139 m 2 / g, approximately 131 m 2 / g to approximately 137 m 2 / g, or approximately 134m 2 STSA at approximately 93 ml / 100g to approximately 103 ml / 100g, approximately 95 ml / 100g to approximately 101 ml / 100g, or approximately 99 ml / 100g OAN; COAN at approximately 76 ml / 100g to approximately 86 ml / 100g, approximately 78 ml / 100g to approximately 84 ml / 100g, or approximately 81 ml / 100g; HI at approximately 4.1 to approximately 5.1, approximately 4.3 to approximately 4.9, or approximately 4.6 ASD ; HI of approximately 1.56 to approximately 1.66, approximately 1.58 to approximately 1.64, or approximately 1.61 PSD The carbon black of the present invention may have an SSHI (type 4) of about 2.35 to about 3.35, about 2.55 to about 3.15, or about 2.85; and an SSHI (type 4) of about 3.52 to about 4.22, about 3.72 to about 4.02, or about 3.82. In another aspect, the carbon black of the present invention may have an SSHI (type 4) of about 3.52 to about 4.22, and any one or more other properties listed in this paragraph.

[0133] In one aspect, the carbon black of the present invention may have a thickness of about 130 μm. 2 / g to approximately 140 m 2 / g, approximately 132 m 2 / g to approximately 138m 2 / g, or approximately 135 m 2 / g NSA; approximately 123 m 2 / g to approximately 133 m 2 / g, approximately 125 m 2 / g to approximately 131 m 2 / g, or approximately 128m 2 STSA at approximately 179 ml / 100g to approximately 189 ml / 100g, approximately 181 ml / 100g to approximately 187 ml / 100g, or approximately 184 ml / 100g; OAN at approximately 119 ml / 100g to approximately 129 ml / 100g, approximately 121 ml / 100g to approximately 127 ml / 100g, or approximately 124 ml / 100g; HI at approximately 3.3 to approximately 4.3, approximately 3.5 to approximately 4.1, or approximately 3.8. ASD ; HI of approximately 1.55 to approximately 1.65, approximately 1.57 to approximately 1.63, or approximately 1.60 PSDThe carbon black of the present invention may have an SSHI (type 4) of about 1.87 to about 2.87, about 2.07 to about 2.67, or about 2.37; and an SSHI (type 4) of about 2.39 to about 3.39, about 2.59 to about 3.19, or about 2.89. In another aspect, the carbon black of the present invention may have an SSHI (type 4) of about 2.39 to about 3.39, and any one or more other properties listed in this paragraph.

[0134] In one aspect, the carbon black of the present invention may have a density of about 71 μm. 2 / g to approximately 81 m 2 / g, approximately 73 m 2 / g to approximately 79 m 2 / g, or approximately 76 m 2 / g NSA; approximately 71 m 2 / g to approximately 81 m 2 / g, approximately 73 m 2 / g to approximately 79 m 2 / g, or approximately 76 m 2 / g STSA; about 117 ml / 100g to about 127 ml / 100g, about 119 ml / 100g to about 125 ml / 100g, or about 122 ml / 100g OAN; about 97 ml / 100g to about 107 ml / 100g, about 99 ml / 100g to about 105 ml / 100g, or about 102 ml / 100g COAN; about 3.0 to about 4.0, about 3.2 to about 3.8, or about 3.5 HI ASD ; HI of approximately 1.41 to approximately 1.51, approximately 1.43 to approximately 1.49, or approximately 1.46 PSD The carbon black of the present invention may have an SSHI (type 4) of about 1.89 to about 2.89, about 2.09 to about 2.69, or about 2.39; and an SSHI (type 4) of about 3.69 to about 4.69, about 3.89 to about 4.49, or about 4.19. In another aspect, the carbon black of the present invention may have an SSHI (type 4) of about 3.69 to about 4.49, and any one or more other properties listed in this paragraph.

[0135] In one aspect, the carbon black of the present invention may have a density of about 76 μm. 2 / g to approximately 86 m 2 / g, approximately 78 m 2 / g to approximately 84 m 2 / g, or approximately 81 m 2 / g NSA; approximately 75 m 2 / g to approximately 85 m 2 / g, approximately 77 m 2 / g to approximately 83 m 2 / g, or approximately 80 m2 / g STSA; about 128 ml / 100g to about 138 ml / 100g, about 130 ml / 100g to about 136 ml / 100g, or about 133 ml / 100g OAN; about 105 ml / 100g to about 115 ml / 100g, about 107 ml / 100g to about 113 ml / 100g, or about 110 ml / 100g COAN; about 2.5 to about 3.5, about 2.7 to about 3.3, or about 3.0 HI ASD ; HI of approximately 1.56 to approximately 1.66, approximately 1.58 to approximately 1.64, or approximately 1.61 PSD The carbon black of the present invention may have an SSHI (type 4) of about 1.60 to about 2.39, about 1.70 to about 2.19, or about 1.89; and an SSHI (type 4) of about 2.59 to about 3.59, about 2.79 to about 3.39, or about 3.09. In another aspect, the carbon black of the present invention may have an SSHI (type 4) of about 2.59 to about 3.59, and any one or more other properties listed in this paragraph.

[0136] In one aspect, the carbon black of the present invention may have a density of about 73 μm. 2 / g to approximately 83 m 2 / g, approximately 75 m 2 / g to approximately 81 m 2 / g, or approximately 78 m 2 / g NSA; approximately 73 m 2 / g to approximately 83 m 2 / g, approximately 75 m 2 / g to approximately 81 m 2 / g, or approximately 78 m 2 STSA at approximately 126 ml / 100g to approximately 136 ml / 100g, approximately 128 ml / 100g to approximately 134 ml / 100g, or approximately 131 ml / 100g OAN; COAN at approximately 96 ml / 100g to approximately 106 ml / 100g, approximately 98 ml / 100g to approximately 104 ml / 100g, or approximately 101 ml / 100g; HI at approximately 2.9 to approximately 3.9, approximately 3.1 to approximately 3.7, or approximately 3.4. ASD ; HI of approximately 1.45 to approximately 1.55, approximately 1.47 to approximately 1.53, or approximately 1.50 PSDThe carbon black of the present invention may have an SSHI (type 4) of about 1.91 to about 2.91, about 2.11 to about 2.71, or about 2.41; and an SSHI (type 4) of about 4.00 to about 5.00, about 4.20 to about 4.80, or about 4.50. In another aspect, the carbon black of the present invention may have an SSHI (type 4) of about 4.00 to about 5.00, and any one or more other properties listed in this paragraph.

[0137] In one aspect, the carbon black of the present invention may have a density of about 75 μm. 2 / g to approximately 85 m 2 / g, approximately 77 m 2 / g to approximately 83 m 2 / g, or approximately 80 m 2 / g NSA; approximately 75 m 2 / g to approximately 85 m 2 / g, approximately 77 m 2 / g to approximately 83 m 2 / g, or approximately 80 m 2 / g STSA; about 92 ml / 100g to about 102 ml / 100g, about 94 ml / 100g to about 100 ml / 100g, or about 97 ml / 100g OAN; about 82 ml / 100g to about 92 ml / 100g, about 84 ml / 100g to about 90 ml / 100g, or about 87 ml / 100g COAN; about 3.2 to about 4.2, about 3.4 to about 4.0, or about 3.7 HI ASD ; HI of approximately 1.35 to approximately 1.45, approximately 1.37 to approximately 1.43, or approximately 1.40 PSD The carbon black of the present invention may have an SSHI (type 4) of about 2.13 to about 3.13, about 2.33 to about 3.03, or about 2.63; and an SSHI (type 4) of about 4.57 to about 5.57, about 4.77 to about 5.37, or about 5.07. In another aspect, the carbon black of the present invention may have an SSHI (type 4) of about 4.57 to about 5.57, and any one or more other properties listed in this paragraph.

[0138] In one aspect, the carbon black of the present invention may have a density of about 78 μm. 2 / g to approximately 88 m 2 / g, approximately 80 m 2 / g to approximately 86 m 2 / g, or approximately 83 m 2 / g NSA; approximately 78 m 2 / g to approximately 88 m 2 / g, approximately 80 m 2 / g to approximately 86 m 2 / g, or approximately 83 m2 / g STSA; about 106 ml / 100g to about 116 ml / 100g, about 108 ml / 100g to about 114 ml / 100g, or about 111 ml / 100g OAN; about 87 ml / 100g to about 97 ml / 100g, about 89 ml / 100g to about 95 ml / 100g, or about 92 ml / 100g COAN; about 2.9 to about 3.9, about 3.1 to about 3.7, or about 3.4 HI ASD ; HI of approximately 1.47 to approximately 1.57, approximately 1.49 to approximately 1.55, or approximately 1.52 PSD The carbon black of the present invention may have an SSHI (type 4) of about 1.74 to about 2.74, about 1.94 to about 2.54, or about 2.24; and an SSHI (type 4) of about 3.50 to about 4.50, about 3.70 to about 4.30, or about 4.00. In another aspect, the carbon black of the present invention may have an SSHI (type 4) of about 3.50 to about 4.50, and any one or more other properties listed in this paragraph.

[0139] In one aspect, the carbon black of the present invention has a multi-peak aggregate size distribution. In another aspect, the carbon black of the present invention has a bi-peak aggregate size distribution.

[0140] In one aspect, the carbon black of the present invention has a dispersion ratio greater than 1.5, a particle size heterogeneity index less than about 1.7, an oil absorption value less than about 170 ml / 100g, and a particle size distribution greater than about 120 m 2 / g STSA. In another aspect, the carbon black of the present invention has a dispersion ratio greater than 1.5, a particle size heterogeneity index less than about 1.7, an oil absorption value less than about 125 ml / 100g, and a density greater than about 120 m 2 / g STSA. In another aspect, the carbon black of the present invention has a dispersion ratio greater than 1.5, a particle size heterogeneity index less than about 1.7, an oil absorption value less than about 200 ml / 100g, and a density greater than about 120 m 2 / g STSA. In another aspect, the carbon black of the present invention has a dispersion ratio greater than 1.5, a particle size heterogeneity index less than about 1.7, an oil absorption value less than about 170 ml / 100g, and about 70 m 2 / g to approximately 90 m 2 / g STSA. In another aspect, the carbon black of the present invention has a dispersion ratio greater than about 2.0. In yet another aspect, the carbon black of the present invention has a dispersion ratio greater than about 1.7 and an aggregate size heterogeneity index greater than about 2.8. In yet another aspect, the carbon black of the present invention has a shape-specific heterogeneity index of at least 2.0 or at least 2.1 for type 4 (branched) aggregates. In yet another aspect, compared with corresponding ASTM grade carbon black having the same or similar colloidal properties, the carbon black of the present invention has a significantly higher percentage of low-structure spherical and elliptical aggregates and a lower number of high-structure, branched aggregates.

[0141] In one aspect, the carbon black of the present invention has a shape-specific heterogeneity index of at least 2.1, more preferably at least 2.5, for branched aggregates. In another aspect, the carbon black of the present invention has a shape-specific heterogeneity index of less than 6.0, more preferably less than 5.5, for branched aggregates. In yet another aspect, the carbon black of the present invention has a shape-specific heterogeneity index in the range of 2.6 to 5.3, preferably in the range of 2.8 to 5.1, and even more preferably in the range of 3.4 to 4.6, for branched aggregates. The shape-specific heterogeneity index for branched aggregates is measured as described above.

[0142] In one aspect, the carbon black of the present invention has a shape-specific heterogeneity index of at least 2.1 and a divergence ratio of at least 1.5 for branched aggregates. In another aspect, the carbon black of the present invention has a shape-specific heterogeneity index of at least 2.5 and a divergence ratio of at least 1.6 for branched aggregates. In another aspect, the carbon black of the present invention has a shape-specific heterogeneity index of less than 6.0 and a divergence ratio of less than 4.0 for branched aggregates. In another aspect, the carbon black of the present invention has a shape-specific heterogeneity index of less than 5.5 and a divergence ratio of less than 3.5 for branched aggregates. The divergence ratio is measured as described above.

[0143] In one aspect, the carbon black of the present invention has a shape-specific heterogeneity index in the range of 2.6 to 5.3 and a dispersion ratio in the range of 1.7 to 3.0 for branched aggregates. In another aspect, the carbon black of the present invention has a shape-specific heterogeneity index in the range of 2.8 to 5.1 and a dispersion ratio in the range of 1.8 to 2.9 for branched aggregates. In yet another aspect, the carbon black of the present invention has a shape-specific heterogeneity index in the range of 3.5 to 4.6 and a dispersion ratio in the range of 2.2 to 2.6 for branched aggregates.

[0144] In one aspect, the carbon black of the present invention has a shape-specific heterogeneity index in the range of 2.6 to 5.3 for branched aggregates and has a COAN in the range of 60 to 130 ml / 100g, more preferably 65 to 125 ml / 100g. The COAN is measured according to ASTM D3493-2018.

[0145] In one aspect, the carbon black of the present invention has a shape-specific heterogeneity index in the range of 2.6 to 5.3 for branched aggregates and has a density of 30 to 150 μm. 2 Within the range of / g, more preferably 60 to 145 m 2 STSA within the range of / g. STSA was measured according to D6556-2017.

[0146] In one aspect, the carbon black of the present invention has a shape-specific heterogeneity index in the range of 2.6 to 5.3 for branched aggregates and has a density of 30 to 160 μm. 2 Within the range of / g, more preferably 40 to 150 m 2 NSA within the range of / g; NSA measured according to ASTM D6556-2017.

[0147] In one aspect, the carbon black of the present invention has a shape-specific heterogeneity index in the range of 2.6 to 5.3, a COAN in the range of 80 to 130 ml / 100g, and a m... 2 STSA in the range of / g. More preferably, the carbon black of the present invention has a shape-specific heterogeneity index in the range of 2.6 to 5.3, a COAN in the range of 85 to 120 ml / 100g, and a concentration of 100 to 130 m 2 STSA within the range of / g.

[0148] In one aspect, the carbon black of the present invention has a shape-specific heterogeneity index in the range of 2.6 to 5.3, a COAN in the range of 55 to 120 ml / 100g, and a pH of 60 to 100 m for branched aggregates. 2 STSA in the range of / g. More preferably, the carbon black of the present invention has a shape-specific heterogeneity index in the range of 2.6 to 5.3 for branched aggregates, a COAN in the range of 60 to 110 ml / 100g, and a concentration of 60 to 95 m 2 STSA within the range of / g.

[0149] In one aspect, the carbon black of the present invention has a shape-specific heterogeneity index in the range of 2.6 to 5.3, a divergence ratio in the range of 1.7 to 3.0, a COAN in the range of 55 to 120 ml / 100g, and a concentration of 60 to 100 mg / g for branched aggregates. 2 STSA in the range of / g. More preferably, the carbon black of the present invention has a shape-specific heterogeneity index in the range of 2.8 to 5.1, a divergence ratio in the range of 1.80 to 2.9, a COAN in the range of 60 to 110 ml / 100g, and a concentration of 60 to 95 m 2 STSA within the range of / g.

[0150] In one aspect, the carbon black of the present invention has a shape-specific heterogeneity index in the range of 2.6 to 5.3, a divergence ratio in the range of 1.70 to 3.0, a COAN in the range of 80 to 130 ml / 100g, and a m... 2 STSA in the range of / g. More preferably, the carbon black of the present invention has a shape-specific heterogeneity index in the range of 2.8 to 5.1, a divergence ratio in the range of 1.8 to 2.9, a COAN in the range of 85 to 120 ml / 100g, and a concentration of 100 to 130 m 2 STSA within the range of / g.

[0151] In one aspect, the carbon black of the present invention has a shape-specific heterogeneity index in the range of 3.5 to 4.6, a divergence ratio in the range of 2.2 to 2.6, a COAN in the range of 80 to 130 ml / 100g, and a m... 2 STSA in the range of / g. More preferably, the carbon black of the present invention has a shape-specific heterogeneity index in the range of 3.4 to 4.6, a divergence ratio in the range of 2.2 to 2.6, a COAN in the range of 85 to 120 ml / 100g, and a concentration of 100 to 130 m 2 STSA within the range of / g.

[0152] In one aspect, the carbon black of the present invention has a shape-specific heterogeneity index in the range of 3.5 to 4.6, a divergence ratio in the range of 2.2 to 2.6, a COAN in the range of 55 to 120 ml / 100g, and a concentration of 60 to 110 m 2 STSA in the range of / g. More preferably, the carbon black of the present invention has a shape-specific heterogeneity index in the range of 3.5 to 4.6, a divergence ratio in the range of 2.2 to 2.6, a COAN in the range of 60 to 110 ml / 100g, and a concentration of 60 to 90 m 2 STSA within the range of / g.

[0153] Rubber compositions containing the carbon black of the present invention

[0154] In various aspects, rubber samples containing the carbon black of the present invention may exhibit a reduction in tanΔ value of at least about 5%, 7%, 9%, 11%, 13%, 15%, 17%, 19%, 21%, 23%, 25%, or more compared to rubber samples containing equivalent ASTM grade carbon black. In another aspect, rubber samples containing the carbon black of the present invention may exhibit a reduction in tanΔ value of about 5% to about 15%, about 10% to about 25%, about 10% to about 20%, about 15% to about 30%, or about 15% to about 25% compared to samples containing equivalent ASTM grade carbon black. In yet another aspect, the reduction in tanΔ may vary with the carbon black loading in a given rubber sample. In various aspects, the reduction in tanΔ may be greatest when the carbon black loading is about 40 phr to about 70 phr, about 45 phr to about 65 phr, or about 50 phr to about 60 phr. In still other aspects, the reduction in tanΔ may be greatest when the carbon black loading is less than or greater than any of the specific values ​​listed herein.

[0155] In another aspect, the use of the carbon black of the present invention in rubber can improve the balance between hysteresis and tearing, essentially maintaining or improving the tear properties of the rubber compound, but with a significant reduction in hysteresis. Tear strength, such as Vieth tear strength, is expressed as the median load value divided by the sample thickness. The nodal tear index is the difference between the median tear load and the median load at which the tear stops propagating along a specified path. In one aspect, rubber compounds containing the carbon black of the present invention can exhibit an improvement in the ratio of resilience to Vieth tear strength of at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, or more compared to rubber compounds containing ASTM grade carbon black with similar OAN and surface area. In another aspect, compared to rubber compounds containing ASTM grade carbon black, rubber compounds containing the carbon black of the present invention can exhibit an improvement in the ratio of resilience to Vieth tear strength of about 5% to about 25%, about 5% to about 35%, about 10% to about 35%, about 10% to about 25%, about 10% to about 15%, about 15% to about 25%, about 15% to about 20%, or about 20% to about 35%. Similarly, compared to rubber compounds containing ASTM grade carbon black, rubber compounds containing the carbon black of the present invention can exhibit an improvement in the knot tear index of at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 85%, at least about 90%, or more. In another aspect, compared with rubber compounds containing ASTM grade carbon black, rubber compounds containing the carbon black of the present invention can exhibit an improvement in the knot tear index of about 5% to about 40%, about 10% to about 90%, about 20% to about 90%, about 30% to about 90%, about 40% to about 90%, about 50% to about 90%, about 60% to about 90%, about 70% to about 90%, about 25% to about 100%, about 30% to about 100%, or about 40% to about 100%.

[0156] Mechanical rubber products or MRG products (all rubber products for non-tire components) are typically composed of carbon black-reinforced polymer systems based on natural rubber (NR) or blends of NR with synthetic polymers such as butadiene rubber (BR), ethylene-propylene-diene monomer (EPDM), nitrile rubber and its variants, and fluorinated elastomers. Among the polymers (e.g., rubbers) suitable for use in this invention are any natural rubber, synthetic rubber, and blends of natural and synthetic rubbers. These include, for example, NR, BR, styrene-butadiene rubber (SBR), emulsion styrene-butadiene rubber (ESBR), solution polymerized styrene-butadiene rubber (SSBR), ethylene-propylene-diene monomer rubber (EPDM), butyl rubber, halogenated butyl rubber, or mixtures thereof. The choice and amount of polymer can be determined by those skilled in the art based on those suitable for the desired application.

[0157] In other aspects, the present invention provides elastomeric compounds, for example, comprising one or more natural and / or synthetic rubber compounds that can be used in, for example, tire compounds, wherein the compound comprises one or more of the carbon blacks of the present invention as described herein. In another aspect, this disclosure provides a polymer comprising shape-modified carbon black as described herein. In yet another aspect, the present invention includes a tire tread compound comprising shape-modified carbon black as described herein. In yet another aspect, the present invention includes a passenger car tire tread compound comprising shape-modified carbon black as described herein. In yet another aspect, this disclosure includes a truck tire tread compound comprising shape-modified carbon black as described herein. In yet another aspect, the present invention provides a tire carcass compound comprising shape-modified carbon black as described herein. Still another aspect, the present invention provides a tire, such as, for example, a passenger car tire, a truck tire, or a bus tire, comprising one or more shape-modified carbon blacks as described herein. In yet another aspect, the rubber compound may comprise the same or similar compositions as described in ASTM D3191, or compositions similar to tire compounds known in the art. Those skilled in the art will be able to readily prepare tire compounds using shape-modified carbon black as described herein.

[0158] Another object of the present invention relates to a rubber composition based on at least one diene elastomer, at least one reinforcing filler, and at least one crosslinking system, wherein the reinforcing filler comprises at least one carbon black having a shape-specific heterogeneity index of at least 2.1, more preferably at least 2.5, for branched aggregates. More preferably, the carbon black of the rubber composition has a shape-specific heterogeneity index of less than 6.0, preferably less than 5.5, for branched aggregates. More preferably, the rubber composition is based on at least one diene elastomer, at least one reinforcing filler, and at least one crosslinking system, wherein the reinforcing filler comprises at least one carbon black having a shape-specific heterogeneity index in the range of 2.6 to 5.3, preferably in the range of 2.8 to 5.1, and even more preferably in the range of 3.4 to 4.6, for branched aggregates. The shape-specific heterogeneity index for branched aggregates is measured as described above.

[0159] As described above, the present invention includes compositions comprising a polymer (e.g., an elastomer, plastic, resin) and the carbon black of the present invention. The expression “composition based on” should be understood to mean a composition comprising a mixture of various ingredients used and / or reaction products, some of which are capable of or intended to react with each other at least partially during various stages of the production of the composition, particularly during its crosslinking or vulcanization.

[0160] In the context of this invention, the carbon-containing compounds mentioned in the specification may be of fossil or biological origin. In the latter case, they may be produced partially or entirely from biomass or obtained from renewable starting materials derived from biomass. In particular, polymers, plasticizers, fillers, etc., are involved.

[0161] The rubber composition according to the present invention comprises at least one elastomer, i.e., one elastomer or a mixture of several elastomers. Elastomers are polymers well known to those skilled in the art.

[0162] Preferably, the elastomer is a diene elastomer.

[0163] It should be recalled here that "diene" type elastomers (or "rubber," the two terms being considered synonymous) should be understood in a known manner as meaning one or more elastomers that are at least partially (i.e., homopolymers or copolymers) produced from diene monomers (i.e., monomers with two conjugated or non-conjugated carbon-carbon double bonds).

[0164] Diene elastomers can be classified into two categories: "substantially unsaturated" or "substantially saturated." "Substantially unsaturated" generally refers to diene elastomers that are at least partially derived from conjugated diene monomers having a molar content of more than 15% (mol%) of diene-derived (conjugated diene) units; therefore, diene elastomers (such as butyl rubber or EPDM-type copolymers of dienes and α-olefins) do not fall within the aforementioned definition and can be specifically referred to as "substantially saturated" diene elastomers (low or very low molar content of diene-derived units, always less than 15% (mol%)). Within the category of "substantially unsaturated" diene elastomers, "highly unsaturated" diene elastomers specifically refer to diene elastomers having a molar content of more than 50% (mol%) of diene-derived (conjugated diene) units.

[0165] These definitions give rise to the term "dien elastomer capable of being used in rubber compositions according to the invention," which more specifically means:

[0166] (a) Any homopolymer obtained by polymerization of conjugated diene monomers having 4 to 12 carbon atoms;

[0167] (b) Any copolymer obtained by copolymerizing one or more conjugated dienes with each other or with one or more vinyl aromatic compounds having 8 to 20 carbon atoms;

[0168] (c) Terpolymers obtained by copolymerizing ethylene and α-olefins having 3 to 6 carbon atoms with non-conjugated diene monomers having 6 to 12 carbon atoms, such as elastomers obtained by copolymerizing ethylene and propylene with non-conjugated diene monomers of the above type (in particular, such as 1,4-hexadiene, ethylidene norbornene or dicyclopentadiene).

[0169] (d) Copolymers of isobutylene and isoprene (butyl rubber) and halogenated forms of this type of copolymer, particularly chlorinated or brominated forms.

[0170] Although it is applicable to any type of elastomer, especially diene elastomers, those skilled in the art will understand that the present invention preferably uses substantially unsaturated diene elastomers, particularly diene elastomers of the types (a) or (b) described above.

[0171] In the case of copolymer (b), the latter may contain 20% to 99% diene units and 1% to 80% vinyl aromatic units.

[0172] As conjugated dienes, particularly suitable are: 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di(C1-C5 alkyl)-1,3-butadiene, such as 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl-1,3-butadiene, aryl-1,3-butadiene, 1,3-pentadiene, or 2,4-hexadiene.

[0173] For example, the following are suitable as vinyl aromatic compounds: styrene, o-methylstyrene, m-methylstyrene or p-methylstyrene, "vinyltoluene" commercial mixtures, p-(tert-butyl)styrene, methoxystyrene, chlorostyrene, vinyltrimethylbenzene, divinylbenzene or vinylnaphthalene.

[0174] Preferably, the diene elastomer of the composition according to the invention can be selected from the group consisting of: polybutadiene (BR), synthetic polyisoprene (IR), natural rubber (NR), butadiene copolymers, isoprene copolymers, and mixtures of these elastomers. Such copolymers are more preferably selected from the group consisting of: butadiene / styrene copolymers (SBR), whether the latter is prepared by emulsion polymerization (ESBR) or solution polymerization (SSBR), isoprene / butadiene copolymers (BIR), isoprene / styrene copolymers (SIR), and isoprene / butadiene / styrene copolymers (SBIR). Preferably, the diene elastomer is selected from the group consisting of: polybutadiene (BR), butadiene / styrene copolymers (SBR), isoprene / butadiene copolymers (BIR), isoprene / styrene copolymers (SIR), isoprene / butadiene / styrene copolymers (SBIR), ethylene / butadiene copolymers (EBR), and mixtures of these copolymers.

[0175] Among diene elastomers, the following are suitable: polybutadiene, especially those with a 1,2-unit content (mol%) between 4% and 80%, or cis-1,4-unit content (mol%) greater than 80%; polyisoprene; butadiene / styrene copolymers, especially those with a glass transition temperature (Tg, according to ASTM D3418, ... (Measured in 1999) Copolymers with a styrene content between 5% by weight and 60% by weight, more particularly between 20% by weight and 50% by weight, in the butadiene portion having a 1,2-bond content (mol%) between 4% and 75% and a trans-1,4-bond content (mol%) between 10% and 80%; butadiene / isoprene copolymers, especially those with an isoprene content between 5% by weight and 90% by weight and a Tg in the range of -40°C to -80°C; or isoprene / styrene copolymers, especially those with a styrene content between 5% by weight and 50% by weight and a Tg in the range of -5°C to -50°C. For butadiene / styrene / isoprene copolymers, those with styrene content between 5% and 50% by weight, more particularly between 10% and 40% by weight, isoprene content between 15% and 60% by weight, more particularly between 20% and 50% by weight, butadiene content between 5% and 50% by weight, more particularly between 20% and 40% by weight, 1,2-unit content (mol%) in the butadiene moiety between 4% and 85%, trans-1,4-unit content (mol%) in the butadiene moiety between 6% and 80%, 1,2-plus-3,4-unit content (mol%) in the isoprene moiety between 5% and 70%, and trans-1,4-unit content (mol%) in the isoprene moiety between 10% and 50%, and more generally, any butadiene / styrene / isoprene copolymer with a Tg between -5°C and -70°C, are particularly suitable.

[0176] According to specific embodiments, the diene elastomer is primarily (i.e., more than 50 phr) SBR, whether it is SBR prepared in an emulsion (“ESBR”) or SBR prepared in solution (“SSBR”), or SBR / BR, SBR / NR (or SBR / IR), BR / NR (or BR / IR) or SBR / BR / NR (or SBR / BR / IR) blends (mixtures). In the case of SBR (ESBR or SSBR) elastomers, SBRs with a medium styrene content (e.g., between 20 wt% and 35 wt%) or a high styrene content (e.g., between 35 wt% and 45 wt%), a vinyl bond content (mol%) of the butadiene moiety between 15% and 70%, a trans-1,4-bond content (mol%) between 15% and 75%, and a Tg between -10°C and -55°C are particularly used; such SBRs can be advantageously used as mixtures with BRs preferably having more than 90% (mol%) cis-1,4-bonds.

[0177] According to another specific embodiment of the present invention, the diene elastomer of the composition according to the present invention comprises a blend (mixture) of BR (as a low Tg elastomer) with a cis-1,4-bond content (mol%) greater than 90% and one or more S-SBR or E-SBR (as a high Tg elastomer).

[0178] Elastomers can have any microstructure, depending on the polymerization conditions used, and especially on the presence or absence of modifiers and / or atactic agents and the amount of modifiers and / or atactic agents used. These elastomers can be, for example, block elastomers, atactic elastomers, sequential elastomers, or microsequential elastomers and are prepared in dispersions or solutions; they can be coupled and / or star-branched or functionalized with coupling agents and / or star-branching agents or functionalizing agents.

[0179] The carbon black of the present invention used in the rubber compositions of the present invention may have the following characteristics. In one aspect, the carbon black of the present invention used in the rubber compositions has a shape-specific heterogeneity index of at least 2.1 for branched aggregates and a dispersion ratio of at least 1.5. In another aspect, the carbon black of the present invention used in the rubber compositions has a shape-specific heterogeneity index of at least 2.5 for branched aggregates and a dispersion ratio of at least 1.6. In another aspect, the carbon black of the present invention used in the rubber compositions has a shape-specific heterogeneity index of less than 6.0 for branched aggregates and a dispersion ratio of less than 4.0. In another aspect, the carbon black of the present invention used in the rubber compositions has a shape-specific heterogeneity index of less than 5.5 for branched aggregates and a dispersion ratio of less than 3.5. The dispersion ratio is measured as described above.

[0180] In one aspect, the carbon black of the present invention used in the rubber composition has a shape-specific heterogeneity index in the range of 2.6 to 5.3 for branched aggregates and a dispersion ratio of 1.7 to 3.0. In another aspect, the carbon black of the present invention used in the rubber composition has a shape-specific heterogeneity index in the range of 2.8 to 5.1 for branched aggregates and a dispersion ratio of 1.8 to 2.9. In yet another aspect, the carbon black of the present invention used in the rubber composition has a shape-specific heterogeneity index in the range of 3.5 to 4.6 for branched aggregates and a dispersion ratio of 2.2 to 2.6.

[0181] In one aspect, the carbon black of the present invention used in rubber compositions has a shape-specific heterogeneity index in the range of 2.6 to 5.3 for branched aggregates and a COAN in the range of 60 to 130 ml / 100g, more preferably 65 to 125 ml / 100g. The COAN is measured according to ASTM D3493-2018.

[0182] In one aspect, the carbon black of the present invention used in rubber compositions has a shape-specific heterogeneity index in the range of 2.6 to 5.3 for branched aggregates and has a density of 30 to 150 μm. 2 Within the range of / g, more preferably 60 to 145 m 2 STSA within the range of / g. STSA was measured according to D6556-2017.

[0183] In one aspect, the carbon black of the present invention used in rubber compositions has a shape-specific heterogeneity index in the range of 2.6 to 5.3 for branched aggregates and has a density of 30 to 160 μm. 2 Within the range of / g, more preferably 40 to 150 m 2 NSA within the range of / g; NSA measured according to ASTM D6556-2017.

[0184] In one aspect, the carbon black of the present invention used in rubber compositions has a shape-specific heterogeneity index in the range of 2.6 to 5.3, a COAN in the range of 80 to 130 ml / 100g, and a m... 2 STSA in the range of / g. More preferably, the carbon black of the present invention used in the rubber composition has a shape-specific heterogeneity index in the range of 2.6 to 5.3 for branched aggregates, a COAN in the range of 85 to 120 ml / 100g, and a concentration of 100 to 130 m 2 STSA within the range of / g.

[0185] In one aspect, the carbon black of the present invention used in rubber compositions has a shape-specific heterogeneity index in the range of 2.6 to 5.3, a COAN in the range of 55 to 120 ml / 100 g, and a COAN in the range of 60 to 100 m 2 STSA in the range of / g. More preferably, the carbon black of the present invention used in the rubber composition has a shape-specific heterogeneity index in the range of 2.6 to 5.3 for branched aggregates, a COAN in the range of 60 to 110 ml / 100g, and a concentration of 60 to 95 m 2 STSA within the range of / g.

[0186] In one aspect, the carbon black of the present invention used in rubber compositions has a shape-specific heterogeneity index in the range of 2.6 to 5.3, a divergence ratio in the range of 1.7 to 3.0, a COAN in the range of 55 to 120 ml / 100 g, and a m... 2 STSA in the range of / g. More preferably, the carbon black of the present invention used in the rubber composition has a shape-specific heterogeneity index in the range of 2.8 to 5.1, a divergence ratio in the range of 1.80 to 2.9, a COAN in the range of 60 to 110 ml / 100g, and a concentration of 60 to 95 m 2 STSA within the range of / g.

[0187] In one aspect, the carbon black of the present invention used in rubber compositions has a shape-specific heterogeneity index in the range of 2.6 to 5.3, a divergence ratio in the range of 1.70 to 3.0, a COAN in the range of 80 to 130 ml / 100g, and a m... 2 STSA in the range of / g. More preferably, the carbon black of the present invention used in the rubber composition has a shape-specific heterogeneity index in the range of 2.8 to 5.1, a divergence ratio in the range of 1.8 to 2.9, a COAN in the range of 85 to 120 ml / 100g, and a concentration of 100 to 130 m 2 STSA within the range of / g.

[0188] In one aspect, the carbon black of the present invention used in rubber compositions has a shape-specific heterogeneity index in the range of 3.5 to 4.6, a divergence ratio in the range of 2.2 to 2.6, a COAN in the range of 80 to 130 ml / 100g, and a m... 2STSA in the range of / g. More preferably, the carbon black of the present invention used in the rubber composition has a shape-specific heterogeneity index in the range of 3.4 to 4.6, a divergence ratio in the range of 2.2 to 2.6, a COAN in the range of 85 to 120 ml / 100g, and a concentration of 100 to 130 m 2 STSA within the range of / g.

[0189] In one aspect, the carbon black of the present invention used in rubber compositions has a shape-specific heterogeneity index in the range of 3.5 to 4.6, a divergence ratio in the range of 2.2 to 2.6, a COAN in the range of 55 to 120 ml / 100g, and a m... 2 STSA in the range of / g. More preferably, the carbon black of the present invention used in the rubber composition has a shape-specific heterogeneity index in the range of 3.5 to 4.6, a divergence ratio in the range of 2.2 to 2.6, a COAN in the range of 60 to 110 ml / 100g, and a concentration of 60 to 90 m 2 STSA within the range of / g.

[0190] The amount of carbon black of the present invention in the rubber composition of the present invention can be determined by those skilled in the art, for example, 10 to 110 parts per hundred parts of rubber (phr), preferably 20 to 100 phr, more preferably 40 to 80 phr. Those skilled in the art can determine the appropriate amount of carbon black to be used in a particular application and the appropriate ratio relative to other components.

[0191] In addition to the carbon black of the present invention used in rubber compositions, reinforcing fillers may also include at least one reinforcing inorganic filler. "Reinforcing inorganic filler" should be understood herein to mean, in a known manner, any inorganic or mineral filler, regardless of its color and origin (natural or synthetic), also referred to as "white filler," "transparent filler," or "non-black filler," which, unlike carbon black, is capable of reinforcing rubber compositions by itself without the need for intermediate coupling agents, particularly for the manufacture of tire semi-finished products or tires. In other words, it can replace tire-grade carbon black in the reinforcing action, and is particularly suitable for the manufacture of tire semi-finished products or tires. Such fillers are typically characterized by the presence of functional groups on their surface, particularly hydroxyl (-OH) functional groups, which necessitates the use of coupling agents or systems designed to provide stable chemical bonds between the elastomer and the filler.

[0192] As reinforcing inorganic fillers, siliceous fillers (such as silica) or aluminous, silica-alumina or titanium dioxide fillers can be mentioned.

[0193] The silica used can be any reinforced silica known to those skilled in the art, especially with both BET surface area and CTAB specific surface area less than 450 m². 2 / g, preferably 30 to 400 m 2 / g, especially 60 and 300 m 2 Any precipitated or fumed silica between / g. Highly dispersed precipitated silica (“HDS”) will be referred to as, for example, Ultrasil 7000 and Ultrasil 7005 silica from Degussa, Zeosil 1165MP, Zeosil 1135MP, Zeosil 1115MP and Zeosil Premium 200 MP silica from Rhodia, Hi-SilEZ150G silica from PPG, Zeopol 8715, 8745 and 8755 silica from Huber, and silica with a high specific surface area as described in application WO 03 / 016387. The CTAB specific surface area is determined according to French Standard NF T 45-007 (Method B) of November 1987.

[0194] To couple reinforcing inorganic fillers (especially silica) to diene elastomers, at least a bifunctional coupling agent (or binder) is used in a known manner. This binder is designed to provide sufficient chemical and / or physical properties for bonding between the inorganic filler (the surface of its particles) and the diene elastomer, particularly bifunctional organosilanes or polyorganosiloxanes. Silane polysulfides are used in particular, which are referred to as “symmetric” or “asymmetric” depending on their specific structure, for example, as described in applications WO03 / 002648 (or US 2005 / 016651) and WO 03 / 002649 (or US 2005 / 016650).

[0195] The reinforcing filler may also include another carbon black different from the carbon black used in the rubber compositions of the present invention. The other carbon black may be selected from the group consisting of HAF, ISAF, or SAF carbon black types. In another aspect, the carbon black may be selected from the group including HAF, ISAF, or SAF carbon black types. More specifically, reinforcing carbon blacks of the 100, 200, or 300 series (ASTM grades) will be mentioned.

[0196] In one aspect, the carbon black of the present invention used in the rubber composition of the present invention constitutes at least 30% by weight of the total weight of the reinforcing filler, preferably at least 60% by weight, and in fact even at least 80% by weight.

[0197] Optionally, the polymer composition may contain additional components. For example, the composition may contain curing agents, oils, antioxidants, fillers, or mixtures thereof. The selection of additional components and the amount of each can be determined by those skilled in the art based on those suitable for the desired application.

[0198] The rubber composition according to the invention may also contain all or part of conventional additives typically used in elastomer compositions intended for use in the manufacture of tires, particularly treads, such as, for example, plasticizers or extended oils (whether the latter are aromatic or non-aromatic in nature), pigments, protective agents such as anti-ozone waxes, chemical anti-ozone agents or antioxidants, anti-fatigue agents, reinforcing resins, methylene acceptors (e.g., phenolic varnish resins) or methylene donors (e.g., HMT or H3M), for example, as described in application WO 02 / 10269 (or US2003-0212185), sulfur-based or sulfur-donating and / or peroxide-based and / or bismaleimide-based crosslinking systems, vulcanization accelerators or vulcanization activators, excluding zinc-based activators, of course.

[0199] Preferably, these compositions comprise at least one compound selected from the group consisting of: naphthenic oils, paraffin oils, MES oils, TDAE oils, glycerides (especially trioleates), plasticizing hydrocarbon resins having a high Tg preferably greater than 30°C, and mixtures of such compounds.

[0200] Among the aforementioned plasticizing hydrocarbon resins (it should be noted that the term "resin" is used by definition for solid compounds), resins formed from homopolymers or copolymers of α-pinene, β-pinene, dipentene or polylimonene, C5 fraction, such as those formed from C5 fraction / styrene copolymers, will be mentioned in particular, which can be used alone or in combination with plasticizing oils (such as MES or TDAE oils).

[0201] The rubber composition according to the invention comprises a chemical crosslinking system. Any type of crosslinking system known to those skilled in the art for use in rubber compositions can be used.

[0202] The crosslinking system is preferably a vulcanization system, i.e., a system based on sulfur (or based on a sulfur donor) and a primary vulcanization accelerator. Various known auxiliary vulcanization accelerators or vulcanization activators, such as zinc oxide, stearic acid or equivalent compounds, or guanidine derivatives (especially diphenylguanidine), can be added to this basic vulcanization system, incorporated during the first non-production stage and / or the production stage, as described below.

[0203] When using sulfur, it is preferred to use at concentrations between 0.5 and 12 phr, especially between 1 and 10 phr. The primary vulcanization accelerator is preferred to use at concentrations between 0.5 and 10 phr, with even greater preference between 0.5 and 5.0 phr.

[0204] The vulcanization system of the compositions according to the invention may further comprise one or more additional accelerators, such as thiuram compounds, zinc dithiocarbamate derivatives, sulfenamides, guanidines, or thiophosphates. In particular, any compound capable of acting as a vulcanization accelerator for diene elastomers in the presence of sulfur can be used, especially thiazole accelerators and their derivatives, thiuram accelerators, and zinc dithiocarbamate.

[0205] The method for preparing the polymer composition of the present invention comprising the carbon black of the present invention can utilize techniques generally known in the field of polymer (e.g., rubber) compounding. Variations of these methods can be identified by those skilled in the art. Carbon black can be added to the polymer and the composition can be mixed until the carbon black is dispersed to the desired extent. Additional steps and components can be added, as determined by those skilled in the art.

[0206] The rubber composition, as an embodiment of the present invention, can be produced in a suitable mixer (such as an internal mixer) in a manner known to those skilled in the art. Typically, there are two consecutive preparation stages: a first stage of thermomechanical processing at a high temperature, followed by a second stage of mechanical processing at a lower temperature, in which a crosslinking agent is added.

[0207] The first stage of thermomechanical processing (sometimes referred to as the “non-productive stage”) aims to thoroughly mix the various components of the composition, except for the vulcanization system, by kneading. It is carried out in a suitable kneading device, such as an internal mixer or extruder, until the maximum temperature, typically between 130°C and 200°C, and more narrowly between 145°C and 185°C, is reached under the action of machining and high shear applied to the mixture.

[0208] In one embodiment, the carbon black of the present invention may, for example, have been incorporated into diene elastomers, particularly natural rubber, in the form of a masterbatch (see, for example, patent applications WO 97 / 36724, WO 99 / 16600, WO2017103518 and WO 2019 / 129999, which are incorporated herein by reference). More specifically, the masterbatch containing the carbon black of the present invention is obtained by a continuous method comprising the following steps:

[0209] - A fluid comprising an aqueous dispersion of the carbon black particles of the present invention is prepared by dispersing the carbon black particles of the present invention in water using one or more mills, and the aqueous dispersion of the filler is further passed through a homogenizer to obtain the narrowest possible particle size distribution of the carbon black of the present invention.

[0210] A continuous flow of a first fluid, consisting of elastomer latex, particularly natural rubber, is introduced into the mixing zone of the coagulation reactor. A second continuous flow of a second fluid, consisting of an aqueous dispersion of the carbon black of the present invention obtained under pressure, is incorporated into the mixing zone to form a mixture with the elastomer latex. The mixing of these two fluids has sufficient energy to allow the elastomer latex and the carbon black of the present invention to coagulate almost completely before the outlet orifice of the coagulation reactor.

[0211] - The agglomerate is passed through a dryer (dehydrating extruder) and then dried through a drying extruder (FCM) to obtain a dried masterbatch. During these drying steps, the mixture may be in strip form. The dried masterbatch has a moisture content of less than 2% by weight.

[0212] The masterbatch is then added to the internal mixer along with other components of the rubber composition, such as plasticizers, except for the vulcanization system.

[0213] After the mixture cools, a second stage of machining is carried out at a lower temperature. Sometimes referred to as the “productive” stage, this final refining stage involves incorporating the vulcanization (or crosslinking) system (sulfur, accelerator, activator) by mixing it in a suitable apparatus (e.g., an open mill), although some or all of the accelerator and activator may be mixed in the non-productive stage. It is carried out at a sufficiently low temperature below the vulcanization temperature of the mixture for an appropriate time (typically between 1 and 30 minutes, e.g., between 2 and 10 minutes) to prevent premature vulcanization.

[0214] This rubber composition can be formed into useful articles, including treads for vehicle tires. Treads can be formed as tread strips and then made into part of a tire, or they can be formed directly onto the tire carcass, for example, by extrusion and then cured in a mold. Thus, tread strips can be cured before being placed onto the tire carcass, or they can be cured after being placed onto the tire carcass. Typically, tire treads are cured in a mold in a known manner, which molds tread elements into a tread shape, including, for example, darts molded into tread blocks or ribs.

[0215] Specific embodiments of the present invention include tire treads, tire tread base layers, belt layer wedge rubber, carcass ply and bead filler rubber, and tires having such components, as well as other useful articles made at least in part with the rubber compositions disclosed herein. It has been found that when tires are made from such rubber compositions, improved rolling resistance and improved electrical conductivity can be achieved while maintaining tire durability. The carbon black of the present invention, with or without additional reinforcing fillers as described above, surprisingly provides enhanced physical properties to the finished rubber products.

[0216] As is generally known, the tire tread is the road contact portion of a vehicle tire that extends circumferentially around the tire. It is designed to provide the handling characteristics required by the vehicle; for example, traction, dry braking, wet braking, cornering, etc.—all of which are preferably provided with minimal noise and low rolling resistance.

[0217] Bead filler, also known as "bead triangle rubber," is the rubber layer above the tire bead. Typically, bead filler has a triangular cross-section and is positioned on the outside of the carcass ply, or between the carcass ply and the portion of the carcass ply that encloses the bead. Bead filler provides additional stiffness and support to the lower sidewall.

[0218] Example

[0219] The following examples are provided to provide those skilled in the art with a complete disclosure and description of how to prepare and evaluate the compounds, compositions, articles, apparatuses, and / or methods described and claimed herein, and are intended to be purely exemplary and not to limit the scope of what the inventors consider to be their invention. Efforts have been made to ensure the accuracy of figures (e.g., quantities, temperatures, etc.), but some errors and deviations should be accounted for. Unless otherwise stated, parts are by weight, temperatures are in °C or at ambient temperature (23 °C, 1 atm.), and pressures are at or near atmospheric pressure. Unless otherwise stated, references to injection locations are intended to refer to the distance upstream of the throat outlet. Unless otherwise stated, the composition of fuel oil and carbon black feedstock of a given grade is identical. Only reasonable and routine experiments will be required to optimize such process conditions.

[0220] Example 1 - Comparison of the production of carbon black A

[0221] Comparative N134 reference carbon black was prepared in a standard carbon black tread reactor. This reactor was an 8-inch (20.3 cm) throat diameter tread reactor, similar to the Columbia Axial Tread (CAT) reactor (as generally taught in U.S. Patent Nos. 4,927,607 (e.g., column 4, lines 59 through 6, lines 60) and 5,256,388 (e.g., column 4, lines 61 through 6, lines 62)). The reactor operated at 9,780 Nm. 3Operating at a total air load of / hr, with a fuel flow rate of 466 kg / hr and an inlet air temperature of 850°C, conventional fluidized bed catalytic cracker residue or FCC carbon black feedstock fuel is preheated to approximately 238°C and radially injected via four Monarch model F-94, M30, 80°C injectors (available from Monarch Mfg Works, 7249-B Browning Road, Pennsauken, NJ 08109 USA). The injectors are located -8 inches (20.3 cm) upstream of the throat outlet and operate at a rate of 15 kg / cm³. 2 Pressure operation. Material structure was controlled by adding 0.2 wt% potassium formate aqueous solution at approximately 29 kg / hr and mixing with the feedstock before injection into the reactor. The carbon black formation reaction was quenched by injecting water at a location 70 inches (177.8 cm) downstream of the throat outlet.

[0222] The resulting material was dried and collected, namely Comparative Carbon Black A (“Comp.CB A”), which is ASTM N134 type carbon black.

[0223] Example 2 - Production of carbon black sample 1 of the present invention with shape modification

[0224] The carbon black 1 of this invention is prepared in a standard carbon black tread reactor. This reactor is an 8-inch (20.3 cm) throat diameter tread-grade reactor, similar to the Columbia axial tread (CAT) reactor (as generally taught in U.S. Patent Nos. 4,927,607 and 5,256,388 cited in Example 1). The reactor is operated under an air load of 9,840 Nm. 3 / hr, fuel flow rate is 469Nm 3 The operation is carried out under conditions of / hr and an inlet air temperature of 850°C. Conventional FCC carbon black feedstock oil is preheated to approximately 221°C and radially injected using a Monarch F-94, M30, 80°C sprayer (also available from Monarch Mfg Works). The oil is sprayed in equal volume at a conversion oil spray plane located -5 inches (-12.7 cm) and -28 inches (-71.1 cm) upstream of the throat outlet, at approximately 25 kg / cm³. 2 The process was carried out under pressure. A 24% by weight potassium formate aqueous solution was used to control the material structure at a flow rate of approximately 14 kg / hr and was mixed with the feedstock before injection into the reactor. For carbon black 1 of the present invention, the potassium formate aqueous solution was injected only at a -5 inch (-12.7 cm) spray position to induce shape modification of the carbon black aggregates. The carbon black formation reaction was quenched by injecting water at a position 60 inches (152.4 cm) downstream of the throat outlet.

[0225] The resulting material is dried and collected, which is the carbon black 1 of the present invention (“Inv.CB 1”).

[0226] Example 3 - Production of carbon black samples 2 to 5 of the present invention with shape modification

[0227] The carbon black of this invention in Example 3 was prepared in a standard carbon black tread reactor. This reactor was an 8-inch (20.3 cm) throat diameter tread-grade reactor, similar to the Columbia axial tread (CAT) reactor (as generally taught in U.S. Patent Nos. 4,927,607 and 5,256,388 cited in Example 1). The reactor was operated under an air load of approximately 10,900 Nm. 3 / hr, fuel flow rate is approximately 519 Nm 3 Operating at 850°C / hr and an inlet air temperature of 850°C. Conventional FCC carbon black feedstock oil is preheated to a range of 194°C to 212°C and radially injected using a Monarch F-94, 80°C, M30 spray (also available from Monarch MfgWorks). This spray is positioned as shown in Table 1 below, injected at different proportions into the conversion oil spray plane located -5 inches (-12.7 cm) and -28 inches upstream of the throat outlet, with an operating pressure of approximately 21 kg / cm². 2 (For example, 19 to 23.7 kg / cm) 2 The material structure was controlled using a 40% by weight potassium formate aqueous solution at a flow rate ranging from approximately 2.5 to 37 kg / hr, as detailed in Table 1 below, and was mixed with the feedstock only before being injected into the reactor at a -5 inch (-12.7 cm) level of the conversion oil spray plane. The carbon black formation reaction was quenched by injecting water at a location 60 inches (152.4 cm) downstream of the throat outlet.

[0228] The resulting material is dried and collected, namely the carbon black 2 to 5 of the present invention (“Inv.CB 2, Inv.CB3, Inv.CB 4 and Inv.CB 5”).

[0229] Table 1. Process parameters for manufacturing carbon blacks 2 to 5 of the present invention

[0230]

[0231] Example 4 - Comparison of Carbon Black B Production

[0232] Comparative N347 reference carbon black was prepared in a standard carbon black tread reactor. This reactor was a 9-inch (22.9 cm) throat diameter tread reactor, similar to the Columbia Axial Tread (CAT) reactor (as generally taught in U.S. Patent Nos. 4,927,607 and 5,256,388 cited in Example 1). The reactor was operated at a total air load of 6,500 Nm.3 Operating at 900°C / hr and an inlet air temperature of 900°C. The standard FCC carbon black feedstock is preheated to 300°C and radially injected via a Monarch F-94, 60°C, M60 spray (also available from Monarch Mfg Works), located 8 inches (20.3 cm) upstream of the throat outlet, at an operating pressure of 15 kg / cm². 2 The carbon black formation reaction was quenched by injecting water 120 inches (304.8 cm) downstream of the throat outlet. The material structure was controlled using a 3% by weight potassium formate aqueous solution injected with the feedstock at approximately 2.4 kg / hr.

[0233] The resulting material was dried and collected, namely Comparative Carbon Black B (“Comp.CB B”), which is N347 type carbon black.

[0234] Example 5 - Other Comparative Carbon Blacks

[0235] Compare carbon black C (“Comp.CB C”) to Propel E7. TM It was purchased from Cabot Corporation.

[0236] Comparative Carbon Black D (“Comp.CB D”) is an N330 ASTM type carbon black, purchased from Birla Carbon.

[0237] Example 6 - Production of carbon black samples 6 to 10 of the present invention with shape modification

[0238] The carbon black of this invention in Example 6 was prepared in a standard carbon black tread reactor. This reactor is a 12-inch (30.5 cm) throat diameter tread-grade reactor, similar to the Columbia axial tread (CAT) reactor (as generally taught in U.S. Patent Nos. 4,927,607 and 5,256,388 cited in Example 1). The reactor operates at approximately 11,500 Nm. 3 Operating at a total air load of approximately 650 Nm³ / hr, the natural gas fuel flow rate is approximately 650 Nm³ / hr. 3 / hr (e.g., 616 Nm) 3 / hr to 661 Nm 3The inlet air temperature is approximately 850°C (e.g., 813°C to 846°C). Conventional FCC carbon black feedstock oil is preheated and radially injected via a Monarch sprayer (also available from Monarch Mfg Works), as detailed in Table 2 below, at a pressure of approximately 9.3 bar to approximately 11.6 bar. The carbon black formation reaction is quenched by injecting water at a location 300 cm, 118.1 inches downstream of the throat outlet. A 46% by weight potassium formate aqueous solution injected with the feedstock is used to control the material structure at approximately 5.6 to 30.1 kg / hr. For carbon blacks 6 to 10 of the present invention, the aqueous solution of the potassium formate-based compound is injected only at the -8-inch (-20.3 cm) conversion oil injection plane, and the oil split ratio between the -8-inch (-20.3 cm) and -40-inch (-101.6 cm) injection planes is varied as listed in Table 2 to achieve the desired COAN.

[0239] The resulting material, namely the carbon black 6 to 10 of the present invention, is dried and collected, as detailed in Table 2 below.

[0240] Table 2. Process parameters for manufacturing carbon black 6 to 10 of the present invention

[0241]

[0242] Comparison of the colloidal properties of carbon black and the carbon black of this invention

[0243] The comparative carbon black produced in Examples 1 to 6 and the carbon black of the present invention were subjected to routine colloidal tests, and the test results are detailed in Tables 3 to 5 below.

[0244] As can be seen, the comparative carbon black in Examples 1 to 6 of Table 3 and the carbon black of this invention are N100 series materials, which ASTM D1765 defines as having an NSA value of 121 to 150 μm. 2 Carbon blacks within the range of / g. Therefore, these carbon blacks 1 to 5 of the present invention are compared with comparative carbon black A, which is N134 type carbon black.

[0245] Essentially, the shape-modified carbon blacks of the present invention, 1 to 5, are STSA at approximately 130 μm. 2 The volume / g remained constant, but the overall average structural level, as measured by COAN, varied between approximately 80 ml / 100 g and 125 ml / 100 g. This was done to demonstrate the applicability of the shape modification method and the materials derived therefrom to a wide range of structures or COANs, offering broader applicability of these materials to a range of compounds and applications, as those skilled in the art of compounding polymer compositions may recognize.

[0246] Additionally, Table 4 shows examples of shape-modified carbon blacks of the present invention within the N300 series surface area range, with NSA values ​​ranging from 76 to 83 μm. 2 Within the range of / g. ASTM D1765 defines NSA values ​​as 70 to 99 m 2 N300 series carbon black in the range of / g. Comparison CB B is N347 type carbon black, and the comparisons CB C and D listed in Table 5 are from Propel, Cabot Corporation. TM E7 and N330.

[0247] It should also be noted that, similar to the shape-modified N100 series carbon blacks 1 to 5 of the present invention, the N300 series shape-modified carbon blacks 6 to 10 of the present invention are also produced in a wide COAN range of about 87 ml / 100g to 110 ml / 100g, further demonstrating the practicality of the shape modification process and its materials. These examples serve to emphasize that the shape modification process can be extended to a wide range of surface areas and structures.

[0248] Table 3. Colloidal properties of carbon black

[0249]

[0250] Table 4. Colloidal properties of carbon black

[0251]

[0252] Table 5. Comparison of the colloidal properties of carbon blacks C and D

[0253]

[0254] The size and distribution of carbon black aggregates were analyzed by disc centrifugal optical sedimentation (DCP).

[0255] According to ISO 15825:2017 (ISO 15825:2004 / Cor.1:2006(E)), the morphological properties of the carbon black materials produced in Examples 1 to 6 were studied using the disc centrifugal optical sedimentation method (DCP) of Brookhaven DCP.

[0256] For DCP analysis, prepare a 1-liter water / ethanol (80% / 20% v / v) dispersion containing 0.05% of a nonionic surfactant, such as Triton X-100. Adjust the pH of the dispersion to approximately 9 to 10 using sodium hydroxide (NaOH). Prepare a 1-liter spinning solution consisting of softened water containing 0.05% of a nonionic surfactant (such as Triton X-100). Adjust the pH of the spinning solution to approximately 9 to 10 using sodium hydroxide (NaOH). Disperse carbon black at 25 to 50 mg by weight in 50 ml of the dispersion, and then sonicate for 10 minutes at 70% amplitude using a probe-type ultrasonic generator, such as a Microson XL-2000 (up to 100W) with a 1 / 4-inch to 1 / 8-inch (0.635 to 0.3175 cm) probe, at a power setting of 750 watts.

[0257] Use SRB B5 or IRB No. 7 reference standards to ensure the instrument is calibrated and functioning correctly. The average aggregate diameter of the obtained standards should be 113 nm ± 5 nm. First, warm the disk and instrument by injecting 15 ml of water and run the analysis at the selected speed for 30 minutes to ensure the temperature panel reading is 25 ± 3 °C. Remove the disk and clean, dry, and reinstall it. Inject 0.2 ml of ethanol and start the centrifuge by pressing the MOTOR button on the instrument. Inject 15 ml of spinning buffer, placing it below the ethanol, then inject 0.1 ml of dodecane on top of the gradient layer to reduce evaporative cooling and let it stand for 3 minutes. Click the “Start” menu in the computer window to prepare the instrument. Inject 0.25 ml of the prepared sample into the spinning disk and immediately press Start to acquire data. Surface area is between 10 and 50 m². 2 Carcass or soft carbon black in the range of / g was analyzed at a disk speed of 5,000 rpm for 30 minutes; surface area was between 50 and 125 m². 2 Tread-grade or hard-grade carbon black (N400 to N200 series grades) within the range of / g were analyzed at a disk speed of 9,000 rpm for 60 minutes; and the surface area was >125 m². 2 / g of carbon black (N100 series grade and surface area >125m²) 2 The other carbon black (g) was analyzed at a disk speed of 11,000 rpm for 60 minutes.

[0258] Tables 6 through 9 below detail the aggregate size distribution properties (ASD properties) determined by DCP. The basic terms used to describe these ASDs are mean, mode, and span. The mean is defined as (see ISO 15825:2017(en)) the average diameter calculated from the differential mass distribution curve of the ASD; and the mode is defined as the most common diameter in the ASD, representing the peak value in the ASD, and there can be more than one mode; the span is an indicator of the width of the ASD. This parameter is calculated as follows: Span = (D 90 -D 10 ) / D 50 The value of Dx represents the diameter, where the percentage of X by weight present in the aggregate population is less than this diameter. For example, D... 10 It is the diameter, and 10% of the mass present in the aggregate group is smaller than this diameter. (D) 10 D 50 and D 90 It can be derived from the cumulative aggregate size distribution curve.

[0259] These various morphological parameters from the DCP ASD plot are in Figure 4 The diagram is presented graphically, highlighting the term D in the DCPASD diagram. 10 D 50 D 90 ΔD 50 Mean, left mode, right mode, and anti-mode.

[0260] The span (1 to 10) of these shape-modified carbon blacks of the present invention is larger and wider than their comparative ASTM references, and reflects the broad ASD properties of these carbon blacks of the present invention due to the effects of the shape-modification process.

[0261] Figures 5A to 5E The DCP aggregate size distribution (ASD) is shown as the differential volume distribution of carbon black aggregates relative to their diameter.

[0262] These differences in ASD between carbon black A and carbon black 1 of the present invention are achieved through shape modification of the carbon black aggregates. For example, in carbon black 1 of the present invention, relative to comparative carbon black A, the volume fractions of smaller-sized, lower-structure, less complex-shaped aggregates and larger-sized, higher-structure, more complex-shaped aggregates in its DCP ASD diagram are expanded to smaller and larger diameters, respectively. Figure 6A and Figure 6BTEM micrographs of comparative carbon black A, N134 type, and shape-modified carbon black 1 of the present invention are shown. Clearly, compared to comparative carbon black A, shape-modified carbon black 1 of the present invention exhibits a different aggregate size distribution, wherein the ASD is broadened by widening the range of smaller, lower-structure, less complex aggregates and larger, higher-structure, more complex aggregates. Note that both carbon blacks, namely comparative carbon black A and carbon black 1 of the present invention, have similar STSA, COAN, average particle size, and particle size distribution.

[0263] Therefore, overall, as can be seen in the ASD graph of the carbon black of the present invention with shape modification and the comparative carbon black (ASTM type material), the ASD is wider and bimodal in characteristics, with a higher proportion of smaller and larger aggregates. This is a direct result of the shape modification process, since the smaller aggregates are lower structure, spherical and elliptical aggregates, while the larger aggregates are higher structure, linear and branched aggregates.

[0264] Table 6. DCP ASD Properties

[0265]

[0266] Table 7. DCP ASD Properties

[0267]

[0268] Table 8. DCP ASD Properties

[0269]

[0270] The ASD plots of the carbon black of this invention and its ASTM counterpart reveal the ability of shape-modified carbon black to exhibit ASD. Typically, the shape-modified carbon black of this invention can display a bimodal distribution due to shape modification, and as... Figure 4As shown, the relative peak heights of the left and right peaks can be controlled via shape modification processes to optimize carbon black for a given process or formulation. In these examples of the invention, if we take the ratio of the left to right peaks as an indicator of the ASD range and shape control of carbon black aggregates, we can see in Table 9 below that the ratio ranges from ASDs where the left and right peak heights are approximately equal to those of the right peak to ASDs where the left peak height is significantly lower, such as the ratio of 0.67:1.00 in Inv.CB 7, to ASDs where the left peak height is significantly higher than the right peak height, such as the ratio of 1.00:0.62 in Inv.CB 4. Therefore, shape modification allows for significant control and manipulation of the ASD of carbon black materials, including the ratio of peaks in a bimodal distribution, as well as peak separation and resolution, all achieved at a constant average particle size or surface area, or within a very wide range of average particle size, surface area, and OAN, as indicated by the ASTM N series nomenclature, from tread to carcass.

[0271] Table 9: DCP ASD Properties

[0272]

[0273] The carbon black and the carbon black of this invention were compared by TEM / AIA analysis.

[0274] The particle size distribution (PSD), aggregate size distribution (ASD), and shape distribution properties of the carbon black produced in Examples 1 through 6 were also determined using TEM / AIA according to ASTM D3849-14A (Method A) and as described above. The particle size distribution properties were determined by decomposing the primary structure of cellulose acetate butyrate (CAB) fragments based on the mean chord model used for PSD characterization. The PSD and ASD properties were determined based on various image analysis properties, such as those measured on a two-dimensional projection of the aggregates, including area, perimeter, Freret diameter, and various skeletalization parameters (e.g., ends and branches).

[0275] Tables 10 to 12 below describe in detail the particle size distribution properties (PSD) determined by TEM / AIA. Particle size distribution data comparing Carbon Black A and shape-modified Carbon Blacks 1 to 6 of the present invention (N100 series grades) are shown in Table 10. The average particle size ranges from 16 nm to 21 nm, and the weight-average particle size ranges from 25 nm to 31 nm. The electron microscopy surface area (EMSA) of these materials ranges from 119 m². 2 / g to 140 m 2 / g.

[0276] The particle size distribution data comparing carbon black B and the shape-modified carbon blacks of the present invention, grades 6 to 10 (N300 series), are shown in Table 11, with an average particle size ranging from 31 nm to 36 nm and a weight-average particle size ranging from 45 nm to 53 nm. EMSA values ​​range from 70 nm. 2 / g to 80 m 2 / g.

[0277] In addition, the TEM / AIA term known as the heterogeneity index (weight average / mean) or HI is used as an indicator of the polydispersity or width of PSD or ASD, showing the similarity of ASTM-compared carbon blacks A, B, C, and D, with PSD HI or HI. PSD The values ​​are 1.40 to 1.48, and can be described as narrow to normal for typical ASTM materials. On the other hand, the shape-modified carbon black materials 1 to 10 of the present invention, whether they are N100 or N300 series materials, also have a relatively normal, only slightly wider HI. PSD HI PSD The value ranges from 1.40 to 1.61, and only one material, namely the carbon black 4 of the present invention, has a wide PSD HI of 1.74.

[0278] These PSD results demonstrate that the shape-modified carbon black of the present invention has a narrow to normal PSD but a very wide ASD (as demonstrated by DCP), which is a unique property that essentially decouples the PSD and ASD, where the PSD can be maintained at a narrow to normal distribution width, while the ASD can be manipulated by aggregate shape modification to make the aggregate size distribution width wide and very wide.

[0279] Figure 7A and Figure 7B A high-magnification TEM micrograph of the carbon black 1 of the present invention with intentional shape modification is shown, wherein the overall aggregate size and structure are shown at a lower magnification (e.g., Figure 6A (in the middle), while one of the larger aggregates of higher structures is imaged at a relatively high magnification (e.g. Figure 7B (in Chinese). It is obvious that... Figure 7B The aggregates in the DCP are composed of many small particles, similar in size to smaller, lower-structure aggregates. Therefore, the combination of DCP aggregate size data and TEM / AIA PSD data shows that the ASD and PSD are decoupled, as the ASD of the carbon black of this invention is very wide while the PSD is normal to narrow.

[0280] Table 10. Properties of PSD

[0281]

[0282] Table 11. Properties of PSD

[0283]

[0284] Table 12. PSD Properties

[0285]

[0286] The aggregate size distribution properties of the comparative carbon black and the carbon black of the present invention were also determined using TEM / AIA morphology analysis according to ASTM D3849-14A (Method A). The ASD results are shown in Tables 13 to 15 below.

[0287] Table 13. Properties of ASD

[0288]

[0289] Table 14. Properties of ASD

[0290]

[0291] Table 15. Properties of ASD

[0292]

[0293] With a larger pitch between feedstock hydrocarbon injection nozzles and the implementation of shape modification processes, the average aggregate size decreases significantly, while the weight-average aggregate size increases. This indicates the production of both smaller and larger aggregates, while the particle size distribution remains relatively narrow to slightly wide. The shape-modified carbon black 4 of the present invention has the smallest average size and the largest weight-average size, indicating the production of a greater number of smaller, lower-structure (i.e., spherical and elliptical) aggregates and a smaller number of larger, more complex (i.e., linear and branched) aggregates, which is consistent with DCP ASD. Figure 1 For the N100 and N300 series materials, this variation in the average and weight-average aggregate size was observed for all shape-modified carbon blacks of the present invention compared to comparative carbon blacks shown in Tables 13 to 15, based on TEM / AIA data.

[0294] Due to this change in ASD (resulting in smaller average and larger average weight due to the shape modification process), the aggregate size distribution becomes wider, such as the aggregate size HI. ASD The values ​​are shown in Tables 13 to 15. It can be seen that all shape-modified samples of the present invention (1 to 10) exhibit high HI values. ASD The values ​​range from 3.0 to 4.6, while ASTM comparisons of carbon blacks A, B, C, and D all have an aggregate HI of approximately 2.0. ADS value.

[0295] As previously mentioned, the term "divergence ratio" is an indicator of the breakpoint of the classical coupling between the ASD and PSD of widely distributed carbon blacks, and can be used to demonstrate the unique ASD and PSD balance of the carbon blacks of the present invention with these shape modifications. The divergence ratio is calculated as the ratio of ASD HI / PSD HI.

[0296] The shape-modified carbon blacks 1 to 10 of the present invention exhibit significantly higher dispersion ratios than other analyzed carbon blacks, with dispersion ratios ranging from 1.89 to 2.85, compared to approximately 1.4 for all comparable ASTM carbon blacks. The higher dispersion ratios of the carbon blacks 1 to 10 of the present invention indicate that they possess very wide ASDs and narrow to normal PSDs, suggesting that the carbon blacks of the present invention can provide a very unique balance of properties, such as low hysteresis and similar durability, compared to comparable ASTM carbon blacks. Furthermore, the dispersion ratio values ​​demonstrate that the wide ASD of the carbon blacks of the present invention does not necessarily originate from a wide particle size distribution, but rather occurs primarily due to the shape modification of individual carbon black aggregates and thus the shape distribution of the carbon black aggregates.

[0297] Shape distribution analysis

[0298] As described above, shape classification of carbon black aggregates via TEM / AIA can be performed using discriminant analysis techniques based on a set of shape descriptors that include aggregate shapes from multiple grades of carbon black. These techniques were used to determine the shape distribution properties of the carbon black of the present invention, comparing it with shape-modified carbon black, and the results are shown in Tables 16 to 18 below. Shape distribution properties are provided as a percentage of quantity (or frequency) and based on weight percentage. Decomposing the shape distribution data into a quantity and weight percentage basis allows for differentiation of the relative volume or weight contribution of each shape category, which can be very useful when considering its impact on ASD, the uniqueness of the shape distribution, and the subsequent properties of the polymer composite.

[0299] Table 16. Properties of Aggregate Shape Distribution

[0300]

[0301] As detailed in Tables 16 to 18, compared with the comparative carbon black reference, the percentage of type 1 (spherical) and type 2 (elliptical) aggregates in the shape-modified carbon black of the present invention increases; while compared with the comparative carbon black, the percentage of type 3 (linear) and type 4 (branched) aggregates decreases.

[0302] As an example, Table 16 compares comparative carbon black A and shape-modified carbon black 1 of the present invention. It can be seen that the percentage of type 1 and 2 aggregates in shape-modified carbon black 1 increases from 20.9% to 51.9% from comparative CBA, while the percentage of type 3 and 4 aggregates in shape-modified carbon black 1 decreases from 79.1% to 48.1%. When comparing shape categories based on weight percentage, the percentage of type 1 and 2 aggregates in shape-modified carbon black 1 increases from 8.2% to 23.3% from comparative CBA, while the percentage of type 3 and 4 aggregates in shape-modified carbon black 1 decreases from 91.8% to 76.7%. The decreasing trend in the content of type 3 and 4 aggregates in shape-modified carbon black by weight percentage is not always observed as in the percentage of type 3 and 4 aggregates by number, and in many cases, the weight percentage values ​​of type 3 and 4 in these shape categories may be similar to or higher than those of the comparative carbon black. This surprising finding reveals one of the most unique variations in shape distribution when examining the weight and number percentages of type 4 aggregates. In this case, the weight percentage of type 4 aggregates remains similar to or greater than that of the comparative example, while the number percentage of type 4 aggregates in the shape-modified carbon black is much smaller than that of the comparative example. This means that, due to its shape modification, these type 4 aggregates in the carbon black of the present invention are significantly larger than those in the comparative carbon black. Therefore, the ratio of type 4 weight percentage to number percentage has been identified as a key indicator of shape modification and is described as the Shape Modification Heterogeneity Index, or SSHI. The magnitude of the SSHI can vary among various shape-modified carbon blacks or the carbon black of the present invention, depending on the necessary level of overall structure of a given rubber compound for use in tires or rubber products, or the required level of shape modification for OAN and COAN.

[0303] Tables 17 and 18 below show additional shape classification data for comparing carbon blacks A, B, C, and D, as well as the remaining portions of carbon blacks 2 to 10 of the present invention. For comparing carbon blacks B, C, and D, and the other shape-modified carbon blacks 2 to 10 of the present invention, the same trend as seen with comparing carbon black A and carbon black 1 of the present invention is observed. Clearly, for all the shape-modified carbon blacks of the present invention, the resulting type 4 aggregates have an SSHI > 3. This data indicates that this trend is unique and is a key differentiating factor in predicting the aggregate size and shape distribution that achieves shape modification.

[0304] Table 17: Properties of Aggregate Shape Distribution

[0305]

[0306] Table 18: Properties of Aggregate Shape Distribution

[0307]

[0308] Example 7: Comparison of carbon black and the carbon black of the present invention in various rubber compositions

[0309] This example aims to demonstrate the improved electrical conductivity, stiffness, and rolling resistance (hysteresis) properties achieved by various rubber compositions according to the invention (such as tread tire rubber compositions, carcass ply rubber compositions, and bead filler rubber compositions) used in different locations in a tire, compared to rubber compositions containing prior art carbon black as described below. The rubber compositions of the present invention contain the carbon black of the present invention as described above.

[0310] Dynamic properties

[0311] Dynamic properties G* and tan(δ) 最大 Viscosity measurements were performed using a Metravib VA4000 viscometer according to standard ASTM D 5992-96. Record the results for a vulcanized composition sample (4 mm thickness, 400 mm cross-section). 2 The cylindrical test specimen was subjected to a harmonic alternating sinusoidal shear stress at a frequency of 10 Hz under the temperature conditions determined according to standard ASTM D 1349-14 (2019). Peak-to-peak strain amplitude scans were performed from 0.1% to 100% (outward cycle) and then from 100% to 0.1% (backward cycle). For the backward cycle, the observed maximum tan(δ) value is indicated (tan(δ) maximum). The maximum tan(δ) values ​​given below were measured at 60°C. Stiffness G* was measured at the same temperature at 50% strain during the backward cycle.

[0312] Surface rigidity index:

[0313] Having a high total interfacial area (i.e., the total surface area of ​​carbon black exposed to the polymer, which can be approximated as the carbon black surface area (in m²)) 2 The product of surface area x stiffness (in g) and filler load (in phr) and the rigidity of the compound are beneficial to tire tread wear resistance. When attempting to improve the balance between tire wear performance and rolling resistance, it is therefore desirable to maintain a high surface area x stiffness product while reducing compound hysteresis. The surface area x stiffness index is calculated as STSA (carbon black surface area in m²) as measured according to ASTM D6556-2017. 2 The product of the filler load (in phr) and the rigidity of the compound (in g / g): Surface area x rigidity index = STSA x CB load x G*. G* is measured as described above.

[0314] electrical conductivity

[0315] Volume resistivity ρ (ohm·cm) is expressed in logarithmic form.10 ρ represents the value measured at 23°C and 50% relative humidity as described in ASTM D4496-2021. For each rubber composition, six samples were prepared and measured after a 30-second equilibration time, and log10 ρ was calculated. av The average value of conductivity. The conductivity value is defined as log... 10 ρ av The reciprocal of the value. Therefore, a sample with a conductivity value of 110 means that the reciprocal of the value is... 10 Based on this, its conductivity is 10% higher than that of the reference composition.

[0316] Preparation of rubber composition

[0317] The following rubber composition is prepared as follows: diene elastomer, reinforcing filler, then kneaded for one to two minutes, followed by the introduction of all other components except the vulcanization system into an internal mixer with a 70% fill rate and an initial container temperature of approximately 90°C. Then, thermomechanical processing (non-productive stage) is performed in a single step (total kneading time equal to approximately 5 minutes) until a maximum "drop" temperature of approximately 165°C is reached. The resulting mixture is recovered and cooled, and then the vulcanization system (sulfur and sulfenamide accelerator) is added to an external mixer (homogenizer) at 70°C, where all materials are mixed (productive stage) for approximately 5 to 6 minutes.

[0318] The resulting composition is then calendered into rubber sheets (2 mm to 3 mm thick) to measure its physical or mechanical properties.

[0319] Example 8a: Tire tread rubber composition

[0320] The test aims to demonstrate the performance trade-off improvement achieved by the tire tread rubber composition according to the present invention compared to tire tread rubber compositions containing prior art carbon black.

[0321] For this purpose, four compositions were prepared according to the above process, and they differ from each other mainly in the following technical features:

[0322] T1 is based on natural rubber (100 phr) and contains STSA with a specific surface area of ​​approximately 130 m². 2 Comparison of / g carbon black rubber compositions

[0323] T2 is a comparative rubber, identical to composition T1 except for the properties of its carbon black: T2's carbon black has the same COAN as T1's carbon black, but has a different STSA specific surface area (STSA is approximately 80 m²). 2 / g),

[0324] T3 is a comparative rubber, identical to composition T1 except for the properties of its carbon black: the carbon black in T3 has different coan and stsa compared to that in T1.

[0325] C1 is a composition according to the present invention, which is the same as composition T1 except for the properties of carbon black, and is the carbon black 1 of the present invention described above.

[0326] Tables 19 and 20 below show the formulations of different compositions (Table 19, the content of different components, expressed in phr or parts by weight per hundred parts of elastomer) and the dynamic properties of compositions T1 to T3 and C1 after curing at 130°C for 60 minutes (Table 20).

[0327] Table 19: Formulations of polymer compositions containing comparative carbon black and the carbon black of the present invention

[0328]

[0329] (1) Diene elastomers: natural rubber,

[0330] (2) Comparison of Carbon A in Example 1

[0331] (3) Comparison of Carbon B in Example 4

[0332] (4) Comparative carbon C in Example 5,

[0333] (5) The carbon black of the present invention: the shape-modified carbon black 1 (Inv CB 1) according to the present invention obtained by the process described in the paragraph of Example 2.

[0334] (6) Antioxidant: N-(1,3-dimethylbutyl)-N-phenyl-p-phenylenediamine, sold by Flexsys under the trade name Santoflex 6-PPD.

[0335] (7) Accelerator: N-cyclohexyl-2-benzothiazole sulfenamide, sold by Flexsys under the trade name Santocure CBS.

[0336] Table 20: Properties of polymer compositions containing comparative carbon black and the carbon black of the present invention

[0337]

[0338] Considering Table 20, it is observed that, with respect to comparative rubber composition T1 used as a reference, comparative composition T2 has improved hysteresis properties but lower surface stiffness index and lower electrical conductivity. Compared to control composition T1, control composition T3 has improved hysteresis properties and electrical conductivity, but no improved surface stiffness index.

[0339] Conversely, an improvement in hysteresis characteristics was observed in composition C1 of the present invention. Furthermore, composition C1 of the present invention provides unexpected results related to surface rigidity index and electrical conductivity. In fact, compared to T2 and T3, it is the only composition that simultaneously exhibits improved electrical conductivity and a better surface rigidity index.

[0340] Example 8b: Tire tread rubber composition

[0341] The test aims to demonstrate the performance trade-off improvement achieved by the tire tread rubber composition according to the present invention compared to tire tread rubber compositions containing prior art carbon black.

[0342] For this purpose, four compositions were prepared according to the above process, and they differ from each other mainly in the following technical features:

[0343] T4 is based on natural rubber (100 phr) and contains STSA with a specific surface area of ​​approximately 130 m². 2 Comparison of / g carbon black rubber compositions

[0344] T5 is a comparative rubber, identical to composition T1 except for the properties of its carbon black: T2's carbon black has the same COAN as T1's carbon black, but has a different STSA specific surface area (STSA is approximately 80 m²). 2 / g),

[0345] T6 is a comparative rubber, identical to composition T1 except for the properties of its carbon black: T3 and T6 use the same carbon black, but have different coan and stsa compared to T1.

[0346] C2 is a composition according to the present invention, which is the same as composition T1 except for the properties of carbon black, and is the carbon black 1 of the present invention described above.

[0347] Tables 21 and 22 below show the formulations of different compositions (Table 21, the content of different components, expressed in phr or parts by weight per hundred parts of elastomer) and the dynamic properties of compositions T4 to T6 and C2 after curing at 130°C for 60 minutes (Table 22).

[0348] Table 21: Formulations of polymer compositions containing comparative carbon black and the carbon black of the present invention

[0349]

[0350] Compounds (1) through (7) are the same as those in Table 19.

[0351] (8) Diene elastomer: Buna® Nd 24 EZ, polybutadiene rubber with a cis-1-4 content of greater than 96% and a Tg of -105°C as measured according to standard ASTM D3418 (2008).

[0352] (9) Diene elastomer: styrene-butadiene copolymer having 15.5% by weight of styrene monomer relative to the total weight of the copolymer, for the butadiene portion; having 24% by weight of 1,2-units and 30% by weight of 1,4-cis-units, with a Tg of -65°C as measured according to standard ASTM D3418 (2008).

[0353] Table 22: Properties of polymer compositions containing comparative carbon black and the carbon black of the present invention

[0354]

[0355] Similarly, considering Table 20, it is observed that, with respect to comparative rubber composition T4 as a reference, comparative compositions T5 and T6 have improved hysteresis properties but lower electrical conductivity.

[0356] Conversely, an improvement in hysteresis characteristics was observed in composition C2 of the present invention. Furthermore, composition C2 of the present invention provides unexpected results related to surface x-stiffness index and electrical conductivity. In fact, compared to T5 and T6, it is the only composition that exhibits the optimal surface x-stiffness index without compromising electrical conductivity properties.

[0357] Example 8c: Tire ply rubber composition

[0358] This test aims to demonstrate the improved property trade-offs achieved by the tire carcass ply rubber composition according to the present invention compared to carcass ply rubber compositions containing prior art carbon black. Crucially, the rubber composition used for the carcass ply exhibits a good trade-off in properties such as stiffness, hysteresis, and electrical conductivity. Wear properties are not the primary property sought in the carcass ply rubber composition because, unlike the composition used for the tread, the carcass ply rubber composition does not contact the ground when the tire is in motion.

[0359] Tables 23 and 24 below show the formulations of different compositions (Table 23, the content of different components, expressed in phr or parts by weight per hundred parts of elastomer) and the dynamic properties of compositions T7, C3 and C4 after curing at 130°C for 60 minutes (Table 24).

[0360] Table 23: Formulations of polymer compositions containing comparative carbon black and the carbon black of the present invention

[0361]

[0362] Compounds (1), (2) and (10) are the same as those disclosed in Table 19.

[0363] (10) Cobalt salt: Cobalt naphthenate: Product No. 60830 from Sigma-Aldrich

[0364] (11) DCBS N,N'-Dicyclohexyl-2-benzothiazole-sulfenamide, sold by Flexsys under the name "SantocureDCBS"

[0365] (12) Carbon black of the present invention: Shape-modified carbon black 8 (Inv CB8) according to the present invention obtained by the process described in the paragraph of Example 8.

[0366] (13) Carbon black of the present invention: Shape-modified carbon black 6 (Inv CB6) according to the present invention obtained by the process described in the paragraph of Example 6.

[0367] Table 24: Properties of polymer compositions containing comparative carbon black and the carbon black of the present invention

[0368]

[0369] Considering Table 24, it is surprising to observe that, with respect to the control rubber composition T7, the compositions C3 and C4 of the present invention exhibit reduced hysteresis, while stiffness is reduced slightly or not at all. An improved hysteresis-stiffness trade-off is observed for the compositions C3 and C4 of the present invention, while no such improvement is observed for the control composition T7.

[0370] In addition, the composition of the present invention has the best electrical conductivity compared to T7.

[0371] Example 8d: Tire ply rubber composition

[0372] The test aims to demonstrate the performance trade-off improvement achieved by the rubber composition for tire carcass ply tires according to the present invention compared to carcass ply rubber compositions containing prior art carbon black.

[0373] Tables 25 and 26 below show the formulations of different compositions (Table 25, the content of different components, expressed in phr or parts by weight per hundred parts of elastomer) and the dynamic properties of compositions T8 and C5 after curing at 130°C for 60 minutes (Table 26).

[0374] Table 25: Formulations of polymer compositions comprising comparative carbon black and the carbon black of the present invention

[0375]

[0376] Compounds (1) and (6) are identical to the compounds disclosed in Table 19. Compounds (10) and (11) are identical to the compounds disclosed in Table 23.

[0377] (14) Carbon black of the present invention: Shape-modified carbon black 10 (Inv CB10) according to the present invention obtained by the process described in the paragraph of Example 6.

[0378] Table 26: Properties of polymer compositions containing comparative carbon black and the carbon black of the present invention

[0379]

[0380] Considering Table 26, it is surprising to observe that, with respect to the control rubber composition T8, the composition C5 of the present invention exhibits reduced hysteresis, while stiffness is reduced slightly or not at all. An improved hysteresis-stiffness trade-off is observed for the composition C5 of the present invention, while no such improvement is observed for the control composition T8.

[0381] In addition, the composition of the present invention has the best electrical conductivity compared to T8.

[0382] Example 8e: Tire Bead Rubber Composition

[0383] The test aims to demonstrate the performance trade-off improvement achieved by the bead rubber composition according to the present invention compared to bead rubber compositions containing prior art carbon black.

[0384] Tables 27 and 28 below show the formulations of different compositions (Table 27, the content of different components, expressed in phr or parts by weight per hundred parts of elastomer) and the dynamic properties of compositions T9 and C7 after curing at 130°C for 60 minutes (Table 27).

[0385] Table 27

[0386]

[0387] Compounds (1), (6), and (7) are identical to those disclosed in Table 19. Compound (12) is identical to those disclosed in Table 23.

[0388] Table 28

[0389]

[0390] Considering Table 28, it is surprising to observe that, with respect to the control rubber composition T9, the composition C7 of the present invention exhibits reduced hysteresis without any modification to its stiffness properties. An improved hysteresis-stiffness trade-off is observed for the composition C7 of the present invention without any degradation to its electrical conductivity properties.

[0391] This invention includes aspects / embodiments / features in any order and / or any combination of the following:

[0392] 1. A carbon black having a shape-specific heterogeneity index of at least 2.1, preferably at least 2.5, for branched aggregates.

[0393] 2. The carbon black according to any of the foregoing aspects / examples / features, wherein the shape-specific heterogeneity index for the branched aggregate is less than 6.0; preferably less than 5.5.

[0394] 3. The carbon black according to any of the foregoing aspects / examples / features, wherein the shape-specific heterogeneity index for the branched aggregate is in the range of 2.6 to 5.3; preferably in the range of 2.8 to 5.1; and even more preferably in the range of 3.4 to 4.6.

[0395] 4. The carbon black according to any of the foregoing aspects / examples / features, wherein the carbon black has a dispersion ratio of at least 1.5; preferably at least 1.6.

[0396] 5. The carbon black according to any of the foregoing aspects / examples / features, wherein the dispersion ratio is less than 4.0, preferably less than 3.5.

[0397] 6. The carbon black according to any of the foregoing aspects / examples / features, wherein the dispersion ratio is in the range of 1.7 to 3.0, preferably in the range of 1.8 to 2.9, or more preferably in the range of 2.2 to 2.6.

[0398] 7. The carbon black according to any of the foregoing aspects / examples / features, wherein the aggregate size heterogeneity index HI of the carbon black is... ASD Greater than or equal to 2.2.

[0399] 8. The carbon black according to any of the foregoing aspects / examples / features, wherein the aggregate size heterogeneity index HI ASD The range is from 2.2 to 5.5, preferably from 2.4 to 4.8.

[0400] 9. The carbon black according to any of the foregoing aspects / examples / features, wherein the aggregate size heterogeneity index HI ASD In the range of 2.9 to 5.5 or 2.9 to 4.8.

[0401] 10. The carbon black according to any of the foregoing aspects / examples / features, wherein the particle size heterogeneity index HI of the carbon black is... PSD Greater than or equal to 1.2.

[0402] 11. The carbon black according to any of the foregoing aspects / examples / features, wherein the particle size heterogeneity index HI PSDWithin the range of 1.3 to 2.0; preferably 1.3 to 1.9.

[0403] 12. The carbon black according to any of the foregoing aspects / examples / features, wherein the particle size heterogeneity index HI PSD It is in the range of 1.3 to 1.7.

[0404] 13. The carbon black according to any of the foregoing aspects / examples / characteristics, wherein the carbon black has a 30 μm content measured according to ASTM D6556-2017. 2 / g to 200 m 2 Within the range of / g; preferably 30 m 2 / g to 150 m 2 / g; more preferably 60 m 2 / g to 145 m 2 Statistical thickness surface area (STSA) / g.

[0405] 14. The carbon black according to any of the foregoing aspects / examples / characteristics, wherein the carbon black has a 90 μm content measured according to ASTM D6556-2017. 2 / g to 145 m 2 Within the range of / g; preferably 100 m 2 / g to 130 m 2 Statistical thickness surface area (STSA) within the range of / g.

[0406] 15. The carbon black according to any of the foregoing aspects / exemplary / features 1 to 13, wherein the carbon black has a 60 μm content measured according to ASTM D6556-2017. 2 / g to 110 m 2 Within the range of / g; preferably 65 m 2 / g to 95 m 2 Statistical thickness surface area (STSA) within the range of / g.

[0407] 16. The carbon black according to any of the foregoing aspects / examples / characteristics, wherein the carbon black has a compression absorbance value (COAN) in the range of 60 to 150 ml / 100g, preferably 60 to 140 ml / 100g, more preferably 60 to 130 ml / 100g, or even more preferably 65 to 125 ml / 100g, as measured according to ASTM D3493-2018.

[0408] 17. The carbon black according to any of the foregoing aspects / examples / characteristics, wherein the carbon black has a compression oil absorption value (COAN) in the range of 80 to 130 ml / 100g, preferably in the range of 85 to 120 ml / 100g, as measured according to ASTM D3493-2018.

[0409] 18. The carbon black according to any of the foregoing aspects / examples / features 1 to 16, wherein the carbon black has a compression oil absorption value (COAN) in the range of 55 to 120 ml / 100g, preferably in the range of 60 to 120 ml / 100g, as measured according to ASTM D3493-2018.

[0410] 19. The carbon black according to any of the foregoing aspects / examples / characteristics, wherein the carbon black has a content of 40 to 160 μm as measured according to ASTM D6556-2017. 2 Within the range of / g, preferably 50 to 150 m 2 Nitrogen surface area (NSA) within the range of / g.

[0411] 20. The carbon black according to any of the foregoing aspects / examples / characteristics, wherein the carbon black may have a content of 100 to 150 μm as measured according to ASTM D6556-17. 2 Within the range of / g, preferably 115 to 140 m 2 Nitrogen surface area (NSA) within the range of / g.

[0412] 21. The carbon black according to any of the foregoing aspects / examples / features 1 to 19, wherein the carbon black may have a content of 60 to 100 μm as measured according to ASTM D6556-17. 2 Within the range of / g, preferably 70 to 95 m 2 Nitrogen surface area (NSA) within the range of / g.

[0413] 22. A rubber composition comprising at least one diene elastomer, a reinforcing filler, and a crosslinking system, characterized in that the reinforcing filler comprises carbon black according to any one of the foregoing aspects / examples / features 1 to 21.

[0414] 23. The rubber composition according to any of the foregoing aspects / examples / features 22, wherein the carbon black in the rubber composition accounts for more than 60% by weight of the total weight of the reinforcing filler in the rubber composition.

[0415] 24. The rubber composition according to any of the foregoing aspects / examples / features 22 to 23, wherein the carbon black in the rubber composition accounts for more than 90% by weight of the total weight of the reinforcing filler.

[0416] 25. The rubber composition according to any of the foregoing aspects / examples / features 22 to 24, wherein the carbon black in the rubber composition is the sole reinforcing filler of the composition.

[0417] 26. The rubber composition according to any of the foregoing aspects / examples / features 22 to 25, wherein the rubber composition further comprises an inorganic reinforcing filler.

[0418] 27. The rubber composition according to any of the foregoing aspects / examples / features 22 to 26, wherein the inorganic reinforcing filler is silica.

[0419] 28. The rubber composition according to any of the foregoing aspects / examples / features 22 to 27, wherein the diene elastomer is selected from the group consisting of: polybutadiene, synthetic polyisoprene, natural rubber, butadiene copolymers, isoprene copolymers, and mixtures of these elastomers.

[0420] 29. The rubber composition according to any of the foregoing aspects / examples / features 22 to 28, wherein the total content of reinforcing filler is in the range of 10 to 110 phr, preferably 20 to 100 phr.

[0421] 30. The rubber composition according to any of the foregoing aspects / examples / features 22 to 29, wherein the rubber composition is a tire rubber composition.

[0422] 31. A tire tread comprising a rubber composition according to any of the foregoing aspects / examples / features 22 to 29.

[0423] 32. A ply carcass comprising a rubber composition according to any of the foregoing aspects / examples / features 22 to 29.

[0424] 33. A bead filler comprising a rubber composition according to any of the foregoing aspects / examples / features 22 to 29.

[0425] 34. A tire comprising carbon black according to any of the foregoing aspects / examples / features 1 to 21 or at least one rubber composition according to any of the foregoing aspects / examples / features 22 to 29.

[0426] 35. A method for manufacturing carbon black, the method comprising providing a carbon black reactor and injecting a material into the carbon black reactor in a non-uniform manner, wherein the material comprises at least one of a hydrocarbon oil or a structure control additive.

[0427] 36. The method according to any of the foregoing aspects / exemplary features 35, wherein the material comprises hydrocarbon oil.

[0428] 37. The method according to any of the foregoing aspects / executives / features 36, wherein the material comprises a structure control additive.

[0429] 38. The method according to any of the foregoing aspects / exemplary features 37, wherein the material comprises a potassium-containing compound.

[0430] 39. The method according to any of the foregoing aspects / embodiments / features 35 to 38, wherein injecting the material in a non-uniform manner comprises injecting a first portion of the material into a first axial plane of the carbon black reactor and injecting a second portion of the material into a second axial plane of the carbon black reactor, wherein the injection rates in the first axial plane and the injection rates in the second axial plane are not equal.

[0431] 40. The method according to any of the foregoing aspects / embodiments / features 35 to 38, wherein injecting the material in a non-uniform manner comprises injecting a first portion of the material into a first axial plane of the carbon black reactor and injecting a second portion of the material into a second axial plane of the carbon black reactor, wherein the concentrations of the first portion and the second portion are not equal.

[0432] 41. The method according to any of the foregoing aspects / embodiments / features 39 or 40, wherein the first axial plane and the second axial plane are located in the throat section of the carbon black reactor, the combustion section of the carbon black reactor, or a combination thereof.

[0433] 42. The method according to any of the foregoing aspects / exemplary / feature 39, wherein a third portion of the material is injected into a third axial plane of the carbon black reactor.

[0434] 43. The method according to any of the foregoing aspects / exemplary features 42, wherein a fourth portion of the material is injected into a fourth axial plane of the carbon black reactor.

[0435] 44. The method according to any of the foregoing aspects / exemplary / feature 40, wherein a third portion of the material is injected into a third axial plane of the carbon black reactor.

[0436] 45. The method according to any of the foregoing aspects / exemplary / feature 44, wherein a fourth portion of the material is injected into a fourth axial plane of the carbon black reactor.

[0437] 46. ​​The method according to any of the foregoing aspects / exemplary / feature 35, wherein a first portion of the hydrocarbon oil material is injected into a first axial plane of the carbon black reactor, a second portion of the hydrocarbon oil material is injected into a second axial plane of the carbon black reactor, a first portion of the structure control additive is injected into a third axial plane of the carbon black reactor, and a second portion of the structure control additive is injected into a fourth axial plane of the carbon black reactor, wherein each of the hydrocarbon oil and the structure control additive is injected in a non-uniform manner.

[0438] 47. The method according to any of the foregoing aspects / examples / features 35, wherein the carbon black reactor has a single combustion section.

[0439] 48. The method according to any of the foregoing aspects / examples / features 35, wherein the carbon black reactor has two or more combustion sections.

[0440] 49. A carbon black reactor comprising a plurality of hydrocarbon injection ports disposed in two or more axial planes of a throat section, a combustion section, or a combination thereof.

[0441] 50. A carbon black reactor comprising a plurality of structure control additive injection ports disposed in two or more axial planes of a throat section, a combustion section, or a combination thereof.

Claims

1. A carbon black having a shape-specific heterogeneity index of at least 2.1 for type 4 aggregates.

2. A carbon black having a shape-specific heterogeneity index of about 2.1 to about 6.0 for type 4 (branched) aggregates.

3. The carbon black according to claim 1 or claim 2, wherein the carbon black has a dispersion ratio greater than 1.

6.

4. The carbon black according to claim 1 or claim 2, wherein the carbon black has a dispersion ratio greater than about 1.

8.

5. The carbon black according to claim 1 or claim 2, wherein the carbon black has a dispersion ratio greater than about 1.

9.

6. The carbon black according to claim 1 or claim 2, wherein the carbon black has a dispersion ratio greater than about 2.

7. The carbon black according to claim 1 or claim 2, wherein the carbon black has a particle size heterogeneity index (HI) of less than about 1.

7. PDS .

8. The carbon black according to claim 1 or claim 2, wherein the carbon black has a particle size heterogeneity index (HI) of less than about 1.

6. PDS .

9. The carbon black according to claim 1 or claim 2, wherein the carbon black has a particle size heterogeneity index HI of less than about 1.

5. PDS .

10. The carbon black according to claim 1 or claim 2, wherein the carbon black has an aggregate size heterogeneity index HI greater than about 2.

5. ADS .

11. The carbon black according to claim 1 or claim 2, wherein the carbon black has an aggregate size heterogeneity index (HI) greater than about 2.

8. ADS .

12. The carbon black according to claim 1 or claim 2, wherein the carbon black has an aggregate size heterogeneity index HI greater than about 2.

9. ADS .

13. The carbon black according to claim 1 or claim 2, wherein the carbon black has an aggregate size heterogeneity index HI greater than about 3. ADS .

14. The carbon black according to claim 1 or claim 2, wherein the carbon black has an aggregate size heterogeneity index HI greater than about 3.

5. ADS .

15. The carbon black according to claim 1 or claim 2, wherein the carbon black has one or more colloidal properties of ASTM N100 series carbon blacks.

16. The carbon black according to claim 1 or claim 2, wherein the carbon black has one or more colloidal properties of ASTM N300 series carbon black.

17. The carbon black according to claim 1 or claim 2, wherein the carbon black has an oil absorption value of less than about 200.

18. The carbon black according to claim 1 or claim 2, wherein the carbon black has an oil absorption value of less than about 170.

19. The carbon black according to claim 1 or claim 2, wherein the carbon black has an oil absorption value of less than about 140.

20. The carbon black according to claim 1 or claim 2, wherein the carbon black is furnace-processed carbon black.

21. The carbon black according to claim 1 or claim 2, wherein the carbon black is tread grade carbon black.

22. The carbon black according to claim 1 or claim 2, wherein the carbon black is a matrix-grade carbon black.

23. The carbon black according to claim 1 or claim 2, wherein the carbon black has an oil absorption value of less than about 110.

24. The carbon black according to claim 1 or claim 2, wherein the carbon black has an oil absorption value of less than about 90.

25. The carbon black according to claim 1 or claim 2, wherein the carbon black has an oil absorption value of at least about 80.

26. The carbon black according to claim 1 or claim 2, wherein the carbon black has an oil absorption value of about 80 to about 200.

27. A carbon black having a dispersion ratio greater than 1.6 and one or more of the following: a particle size heterogeneity index less than about 1.7, an aggregate size heterogeneity index greater than about 2.0, an oil absorption value less than about 200; and an STSA greater than about 120.

28. The carbon black according to claim 27, wherein the carbon black has an oil absorption value of less than about 125.

29. The carbon black according to claim 27, wherein the carbon black has a dispersion ratio greater than about 1.7 and an aggregate size heterogeneity index greater than about 2.

8.

30. A polymer composition comprising carbon black according to any of the preceding claims.

31. The polymer composition of claim 30, wherein the polymer composition comprises one or more of NR, BR, SBR, EPDM and butyl rubber.

32. The rubber composition of claim 30, wherein the rubber composition comprises about 35 phr to about 65 phr of the carbon black.

33. A tire comprising a polymer composition comprising carbon black according to any of the preceding claims.

34. A method for manufacturing carbon black, the method comprising providing a carbon black reactor and injecting material into the carbon black reactor in a non-uniform manner, wherein the material comprises at least one of a hydrocarbon oil or a structure control additive.

35. The method of claim 34, wherein the material comprises hydrocarbon oil.

36. The method of claim 34, wherein the material comprises a structure control additive.

37. The method of claim 34, wherein the material comprises a potassium-containing compound.

38. The method according to any one of claims 34 to 37, wherein injecting the material in a non-uniform manner comprises injecting a first portion of the material into a first axial plane of the carbon black reactor and injecting a second portion of the material into a second axial plane of the carbon black reactor, wherein the injection rates in the first axial plane and the injection rates in the second axial plane are not equal.

39. The method according to any one of claims 34 to 37, wherein injecting the material in a non-uniform manner comprises injecting a first portion of the material into a first axial plane of the carbon black reactor and injecting a second portion of the material into a second axial plane of the carbon black reactor, wherein the concentrations of the first portion and the second portion are not equal.

40. The method of claim 38, wherein the first axial plane and the second axial plane are located in the throat section of the carbon black reactor, the combustion section of the carbon black reactor, or a combination thereof.

41. The method of claim 39, wherein the first axial plane and the second axial plane are located in the throat section of the carbon black reactor, the combustion section of the carbon black reactor, or a combination thereof.

42. The method of claim 38, wherein a third portion of the material is injected into a third axial plane of the carbon black reactor.

43. The method of claim 42, wherein a fourth portion of the material is injected into a fourth axial plane of the carbon black reactor.

44. The method of claim 39, wherein a third portion of the material is injected into a third axial plane of the carbon black reactor.

45. The method of claim 44, wherein a fourth portion of the material is injected into a fourth axial plane of the carbon black reactor.

46. ​​The method of claim 34, wherein a first portion of the hydrocarbon oil material is injected into a first axial plane of the carbon black reactor, a second portion of the hydrocarbon oil material is injected into a second axial plane of the carbon black reactor, a first portion of the structure control additive is injected into a third axial plane of the carbon black reactor, and a second portion of the structure control additive is injected into a fourth axial plane of the carbon black reactor, wherein each of the hydrocarbon oil and the structure control additive is injected in a non-uniform manner.

47. The method of claim 34, wherein the carbon black reactor has a single combustion section.

48. The method of claim 34, wherein the carbon black reactor comprises two or more combustion sections.

49. A carbon black reactor comprising a plurality of hydrocarbon injection ports disposed in two or more axial planes of a throat section of the carbon black reactor, a combustion section of the carbon black reactor, or a combination thereof.

50. A carbon black reactor comprising a plurality of structure control additive injection ports disposed in two or more axial planes of a throat section, a combustion section, or a combination thereof.

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