阅读说明：本技术 具有80-150m2/g的stsa、至少180ml/100g的oan和至少110ml/100g的coan的炭黑以及混有该炭黑的橡胶配混料 (Carbon black having an STSA of 80-150M2/G, an OAN of at least 180ML/100G and a COAN of at least 110ML/100G and rubber compounds incorporating the same ) 是由 J.崔 T.F.克拉克 D.多施 于 2018-04-27 设计创作，主要内容包括：描述了炭黑,例如,具有高结构的补强级炭黑。该炭黑可具有以下性质：80m<Sup>2</Sup>/g～150m<Sup>2</Sup>/g的统计厚度表面积(STSA)、至少180mL/100g的吸油值(OAN)、以及至少110mL/100g的挤压吸油值(COAN)。还描述了混有该炭黑的橡胶配混料。(Carbon blacks, for example, reinforcement-grade carbon blacks having high structures are described. The carbon black may have the following properties: 80m 2 /g～150m 2 A statistical thickness surface area per gram (STSA), an Oil Absorption Number (OAN) of at least 180mL/100g, and a Crush Oil Absorption Number (COAN) of at least 110mL/100 g. Rubber compounds incorporating the carbon black are also described.)

1. Carbon black having the following properties:

80m²/g～150m²STSA per gram;

at least 180mL/100g of OAN;

at least 110mL/100g of COAN.

2. The carbon black of claim 1, having the following properties:

90m²/g～150m²the STSA in/g;

at least 180mL/100g of the OAN;

at least 120mL/100g of said COAN.

3. The carbon black of claim 1, having the following properties:

100m²/g～150m²the STSA in/g;

at least 200mL/100g of the OAN;

at least 120mL/100g of said COAN.

4. The carbon black of claim 1, wherein the carbon black has an iodine adsorption/STSA ratio of 0.9 to 1.5.

5. The carbon black of claim 4, wherein the iodine adsorption/STSA ratio is from 1 to 1.3.

6. The carbon black of claim 4, wherein the iodine adsorption value is from 90mg/g to 220 mg/g.

7. The carbon black of claim 1, wherein the OAN is at least 200mL/100 g.

8. The carbon black of claim 1, wherein the OAN is at least 220mL/100 g.

9. The carbon black of claim 1, wherein the OAN is from 200mL/100g to 310mL/100 g.

10. The carbon black of claim 1, wherein the COAN is at least 130mL/100 g.

11. The carbon black of claim 1, wherein the COAN is 120mL/100g to 150mL/100 g.

12. The carbon black of claim 1, wherein the carbon black has a thickness of 70m²/g～200m²BET surface area in g.

13. The carbon black of claim 1, wherein the carbon black has a particle size of 90m²/g～200m²BET surface area in g.

14. The carbon black of claim 1, wherein the carbon black has a thickness of 70m²/g～130m²BET surface area in g.

15. The carbon black of claim 1, wherein the carbon black has a Δ D of 75nm or less₅₀。

16. The carbon black of claim 1, wherein the carbon black further comprises 133.33 × (Δ D)₅₀/D_{Mode number})/COAN<1 in the formula (I).

17. The carbon black of claim 1, wherein the carbon black has

18. The carbon black of claim 1, wherein the carbon black has a primary particle size of 24nm or less.

19. The carbon black of claim 1, wherein the carbon black has an average primary particle size of from about 12nm to 24 nm.

20. The carbon black of claim 1, wherein the carbon black has about 1mJ/m²About 15mJ/m²The surface energy of (1).

21. The carbon black of claim 1, wherein the carbon black has a color strength of 110% to 140%.

22. A modified carbon black comprising the carbon black of claim 1 modified by at least one of: at least one coupling agent attached to a surface thereof, at least one chemical group adsorbed on a surface thereof, a surface coating, a surface oxidation, or any combination thereof.

23. The modified carbon black of claim 22, wherein said at least one chemical group is at least one organic group.

24. A rubber compound comprising at least one polymer and the carbon black of claim 1.

25. A vulcanized rubber compound comprising at least one polymer and the carbon black of claim 1.

Background

The present invention relates to carbon black and to rubber compounds incorporating the same.

Carbon blacks have been used to adjust the mechanical, electrical and optical properties of compositions. Carbon black and other fillers have been used as pigments, fillers, and/or reinforcing agents in the compounding and preparation of compositions used in rubber, plastic, paper, or fabric applications. The nature of the carbon black or other filler is an important factor in determining various performance characteristics of these compositions. An important use of elastomeric compositions relates to the manufacture of tires, and, often, other ingredients are added to impart specific properties to the final article or its components (components). Carbon blacks have been used to adjust the functional properties, electrical conductivity, rheology, surface properties, viscosity, appearance, and other properties of elastomeric compositions, as well as other types of compositions.

As previously mentioned, carbon black and other fillers can provide reinforcement benefits to a variety of materials including elastomeric-based compositions. In addition to conventional filler attributes, it is also desirable to provide a filler that is capable of improving one or more elastomeric properties (e.g., hysteresis, abrasion resistance, or stiffness). However, in the past, for some elastomeric compositions that use carbon black or other fillers, the filler typically was able to improve one property, but impaired another. Therefore, there is a continuing need to provide fillers for elastomeric compositions that are preferably capable of enhancing elastomeric properties without causing damage to another property.

Disclosure of Invention

It is a feature of the present invention to provide novel carbon blacks having a unique combination of carbon black properties.

An additional feature of the present invention is to provide carbon blacks, when present, that promote one or more beneficial properties of rubber or other elastomeric compositions without causing any significant impairment to other properties of the rubber or other elastomeric compositions.

It is a further feature of the present invention to provide such carbon blacks, when present, can impart a beneficial balance of properties to the rubber composition.

An additional feature of the present invention is to provide carbon black having a high structure, which when present, may have the ability to improve hysteresis while maintaining the stiffness of the rubber composition.

It is a further feature of the present invention to provide carbon blacks having high structures that can be used in energy storage devices as well as other electrical (electrical) or electrochemical components and devices, for example, electrodes (such as the positive electrode of lithium ion batteries) and capacitors (such as electrochemical capacitors).

An additional feature of the present invention is to provide a rubber compound modified with said carbon black.

Additional features and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the present invention will be realized and attained by means of the elements and combinations particularly pointed out in the description and appended claims.

To achieve these and other advantages and in accordance with the purpose of the present invention, as embodied and broadly described herein, the present invention relates to a carbon black having: 80-150m²A statistical thickness surface area per gram (STSA), an Oil Absorption Number (OAN) of at least 180mL/100g, and a Crush Oil Absorption Number (COAN) of at least 110mL/100 g.

The invention further relates to a rubber compound comprising at least one polymer and said carbon black. The rubber compound may be a vulcanized rubber composition, a rubber composition capable of being vulcanized, or an uncured rubber composition.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the present invention, as claimed.

The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate some of the features of the present invention and together with the description, serve to explain the principles of the invention.

Drawings

FIG. 1 is a cross-sectional view of a carbon black reactor that may be used to make carbon blacks according to examples of the present application.

FIG. 2 is a cross-sectional view of another related carbon black reactor that may be used to manufacture carbon black according to an example of the present application.

Detailed Description

The present invention relates to carbon black and a rubber composition containing the same. The carbon black of the present invention may be a reinforcing grade carbon black. The carbon blacks of the present invention having analytical properties within the specified ranges can impart improved reinforcement properties and low hysteresis to rubber compositions while maintaining stiffness and conductivity, thereby avoiding or reducing adverse compromises in overall properties. The hysteresis of the compound refers to the difference between the energy applied to deform the rubber compound and the energy released when the rubber compound returns to its original, undeformed state. For example, a tire with a lower hysteresis value may have reduced rolling resistance and, thus, may reduce fuel consumption of a vehicle using the tire. For the components of the tire (e.g., the carcass), sufficient stiffness must be maintained for physical structure and performance. The carbon blacks of the present invention can be used at lower loadings for components of non-tread tires while maintaining stiffness relative to standard carbon blacks used in the present application (e.g., N300, N500, or other "N" series carbon blacks that have been used in the carcass or sidewall materials of tires).

There is significant regulatory and environmental pressure to make vehicles improve their fuel economy. Tires play an important role in determining fuel consumption of passenger, light and heavy truck vehicles. The function of the remaining carcass or other non-tread components is different, and therefore, the choice of filler material also tends to be different, as compared to the tread providing friction and grip performance. The carbon blacks of the present invention may be used in tire components (e.g., carcasses or other non-tread components) in place of the N300, N500 or other N series carbon blacks that have been used in such components. As stated, the carbon blacks of the present invention are capable of providing the ability to: in reinforced tire components or other rubber components, carbon black is used to reduce hysteresis, but still maintain stiffness and conductivity. Unusually high structure carbon blacks can be provided in the present invention, which can break (avoid)Or reduced) loss of stiffness and improvement (reduction) in hysteresis. As shown by the results from the experimental studies disclosed in the examples herein, for which tan δ (delta) can be used_{Maximum of}The carbon blacks of the present invention are capable of providing rubber compounds modified therewith with such stiffness and hysteresis as to provide a measure of the rolling resistance contribution to rubber compounds containing commercially available carbon blacks that have been comparatively tested (e.g.,

m carbon black,

6 carbon black or

E6 carbon black,

10H carbon black,

7H carbon black, or other carbon blacks, such as N100, N200, or N300 series carbon blacks or other ASTM carbon blacks) with a stiffness G' (10%) (MPa) and a hysteresis tan delta_{Maximum of}The ratio is at least about 5% higher, or at least about 10% higher, or at least about 15% higher, or at least about 20% higher, or at least 25% higher, or other values greater.

In view of these improved effects, the carbon blacks of the present invention can be advantageously used in rubber compounds. Rubber compounds benefiting from the carbon black of the present invention may include extruded, molded or cast rubber articles. The rubber article may be, for example, a tire, tire component, hose, tube, belt, seal, liner, or other rubber article. Tire components that may be reinforced with the carbon blacks of the present invention include a carcass, sidewalls, bead encapsulation (tires), belts, treads, or other tire components. Alternatively, the carbon blacks of the present invention may be used to modify non-tread components such as tire carcasses, sidewalls, bead wraps, or other tire components.

Structure is a measure of the complexity of the carbon black aggregate particles. For the purposes of the present invention, the structure of carbon black is characterized by oil absorption (oil absorption) and squeeze oil absorption properties measured for the material. The structure characterized by oil absorption is determined as Oil Absorption Number (OAN) as determined by ASTM D2414-13a, wherein the OAN value is expressed as milliliters of oil relative to 100 grams of carbon black. The value of OAN is also known as the dibutylphthalate absorption number (DBP). Crush Oan (COAN) measurements are used to determine the COAN value of carbon black. The COAN value is the OAN value of carbon black determined after controlled compression, expressed in milliliters of oil relative to 100 grams of compressed carbon black. The COAN value is also known as the extruded dibutyl phthalate absorption value (CDBP, 24M4 DBP). As used herein, the COAN value is based on an altered form of ASTM standard D3493-13a, unless otherwise specified. For purposes herein, the procedure of ASTM test method D3493-13a is used for the COAN measurement disclosed herein, with the changes being: in the compression cylinder (compression cylinder) described in the procedure of the test method, 15g of carbon black are pressed and then 10g of these pressed 15g of carbon black are tested in an absorptometer for determining the oil absorption value according to the procedure of the ASTM test method, after which the results are scaled (scale) to 100g of mass. The OAN and COAN values determined according to the ASTM standards also apply to values determined according to JIS standards corresponding thereto (e.g., JIS K6221).

For the purposes of this application, the surface area of the carbon black is defined and determined according to ASTM standard D6556-10. As explained in ASTM Standard D6556-10, this test method covers the determination of the nitrogen surface area by multiple points and the external surface area based on statistical thickness surface area method (STSA) by Brunauer, Emmett and Teller (Brunauer, Stephen; Emmett, P.H.; Teller, Edward (1938); "Adsorption of gases in Multimolecular Layers". Journal of the American Chemical society.60(2): 309-. The total surface measurement (NSA measurement) is based on b.e.t. theory and includes inclusion of pores with diameters less than 2nm

The total surface area including micropores, whereas the external surface area based on the statistical thickness surface area method (STSA) is defined as the specific surface area accessible to the rubber.

As stated, the carbon blacks of the present invention are characterized by a combination of properties defined by an external surface area (STSA) value, and OAN and COAN values determined for the same material.

One option of the present invention provides a carbon black having the following properties:

a)80m²/g～150m²(ii) the STSA in terms of/g,

b) OAN ≥ 180mL/100g, and

c)COAN≥110mL/100g。

another option provides a carbon black having the following properties:

a)90m²/g～150m²(ii) the STSA in terms of/g,

b) OAN ≥ 180mL/100g, and c) COAN ≥ 120mL/100 g.

Another option provides a carbon black having the following properties:

100m²/g～150m²the STSA in/g;

at least 200mL/100g of the OAN; and

at least 120mL/100g of said COAN.

Alternatively, STSA (i.e., property a)) may be 80m²/g～150m²A ratio of/g or 90m²/g～150m²A ratio of/g or 100m²/g～150m²A ratio of/g or 90m²/g～145m²A value of/g, or 95m²/g～145m²A ratio of/g or 100m²/g～145m²A ratio of/g or 90m²/g～140m²A value of/g, or 95m²/g～140m²A ratio of/g or 100m²/g～140m²A value of/g or 105m²/g～135m²A value of/g, or 110m²/g～130m²A value of/g, or 115m²/g～125m²G, or other values.

Alternatively, the OAN (i.e., property b)) may be at least 180mL/100g, or at least 190mL/100g, at least 200mL/100g, or at least 210mL/100g, or at least 220mL/100g, or at least 230mL/100g, or 180mL/100g to 320mL/g, or 190mL/100g to 320mL/g, or 200mL/100g to 320mL/g, or 210mL/100g to 320mL/g, or 180mL/100g to 310mL/g, or 190mL/100g to 310mL/g, or 200mL/100g to 310mL/100g, or 210mL/100g to 310mL/g, or 180mL/100g to 300mL/g, or 190mL/100g to 300mL/g, or 200mL/100g to 300mL/g, Or 210mL/100g to 300mL/g, or 220mL/100g to 290mL/100g, or 230mL/100g to 280mL/g, or other values.

Alternatively, the COAN (i.e., property c)) can be at least 110mL/100g, or at least 120mL/100g, or at least 130mL/100g, or at least 140mL/100g, or 110mL/100g to 160mL/g, or 115mL/100g to 160mL/g, or 120mL/100g to 160mL/g, or 110mL/100g to 155mL/g, or 115mL/100g to 155mL/100g, or 115mL/100g to 155mL/g, or 110mL/100g to 150mL/g, or 115mL/100g to 150mL/g, or 120mL/100g to 150mL/g, or 110mL/100g to 145mL/g, or 115mL/100g to 145mL/g, or 120mL/100g to 145mL/g, Or 125mL/100g to 145mL/100g, or 130mL/100g to 140mL/g, or other values.

The carbon blacks of the present invention may have any combination of any of the indicated values for STSA, OAN, and COAN (i.e., properties a), b), and c)) in any manner.

In addition to the indicated properties of STSA, OAN, and COAN (i.e., properties a), b), and c)), other properties can be present with respect to the carbon blacks of the present invention, which can include, but are not limited to, one or more of the following additional properties:

d) an iodine adsorption value (ASTM-D1510-13) of 85mg/g to 220mg/g, or 90mg/g to 220mg/g, or 100mg/g to 210mg/g, or 85mg/g to 210mg/g, or 90mg/g to 210mg/g, or 100mg/g to 210mg/g, or 85mg/g to 200mg/g, or 90mg/g to 200mg/g, or 100mg/g to 200mg/g, or 110mg/g to 200mg/g, or 115mg/g to 190mg/g, or 120mg/g to 180mg/g, or other values;

e) the ratio of iodine adsorption value/STSA is 0.9 to 1.5, or 0.95 to 1.5, or 1 to 1.5, or 0.9 to 1.45, or 0.95 to 1.45, or 1 to 1.45, or 0.9 to 1.4, or 0.95 to 1.4, or 1 to 1.4, or 0.9 to 1.35, or 0.95 to 1.35, or 1 to 1.35, or 0.9 to 1.3, or 0.95 to 1.3, or 1.0 to 1.3, or 1.05 to 1.25, or 1.10 to 1.20, or others. The iodine adsorption/STSA ratio distinguishes unetched carbon black from etched carbon black, e.g., etched carbon black will have a greater iodine adsorption/STSA ratio;

f) BET surface area of 70m²/g～200m²A ratio of/g or 90m²/g～200m²A ratio of/g or 80m²/g～170m²A ratio of/g or 70m²/g～135m²A ratio of/g or 50m²/g～140m²A value of/g or 105m²/g～135m²A value of/g, or 110m²/g～130m²A value of/g, or 115m²/g～125m²(iv)/g, or other values;

g)ΔD₅₀(ii) it is 75nm or less, or 70nm or less, or 65nm or less, or 60nm or less, or 55nm or less, or 50nm or less, or 40nm to 75nm, or 45nm to 70nm, or 50nm to 65nm, or 55nm to 60nm, or other values;

h) crystallite size (L)_a) Which is a

Or smaller, or

Or smaller, or

Or smaller, or

Or smaller,

Or smaller, orOr smaller, or

Or smaller, or

Or smaller, or

Or smaller, or

Or smaller, or is

Or isOr is

Or is

Or other values;

i) an average primary particle size of from about 8nm to about 50nm, or from about 12nm to about 24nm, or from about 13nm to about 23nm, or from about 14nm to about 22nm, or from about 15nm to about 21nm, or from about 16nm to about 20nm, or other values;

j) surface energy of about 1mJ/m²About 15mJ/m²Or about 2mJ/m²About 13mJ/m²About 3mJ/m²About 12mJ/m²Or about 4mJ/m²About 11mJ/m²Or about 5mJ/m²About 10mJ/m²Or other values;

k) a tint strength (ASTM-D3265-15a) of 105% to 140%, or 110% to 140%, or 115% to 135%, or 120% to 130%, or having other values.

Alternatively, the carbon blacks of the present invention may have a combination of properties a), b) and c), or alternatively, properties a), b) and c) with additional designationsCombinations of one or more of the properties d) to k) in any combination. For example, in addition to the properties a), b) and c), the carbon black of the invention may have at least one, two, three, four, five, six, seven or all eight of the properties d) to k). The carbon black may have any combination of properties a) to k). The Δ D of property g) can be measured using the Disc center Photosedimentometry method, model BI-DCP, manufactured by Brookhaven Instruments, according to the method ISO 15825₅₀. The average primary particle size of property i) can be determined by ASTM-D3849-14 a. Can be used to determine property h) (i.e., crystallite size L)_a(i.e., the size of ordered domains of microcrystalline carbon black, as determined by raman spectroscopy as disclosed in U.S. patent No.9,287,565)) and j) (i.e., the surface energy) are disclosed in U.S. patent No.9,287,565, which is incorporated herein by reference in its entirety. The other properties a) -f) and k) can be determined as described above or as described in the examples herein.

The rubber compounds of the present invention can be prepared from carbon black by compounding with any elastomer, including those used for carbon black compounding. Any suitable elastomer may be compounded with carbon black to provide the elastomeric-based compounds of the present invention. Such elastomers include, but are not limited to: 1, 3-butadiene, styrene, isoprene, isobutylene, 2, 3-dimethyl-1, 3-butadiene, acrylonitrile, polymers (e.g., homopolymers, copolymers, or terpolymers) of ethylene and propylene, rubber. Preferably, the elastomer has a glass transition temperature (Tg) of about-120 ℃ to about 0 ℃, as measured by Differential Scanning Calorimetry (DSC). Examples include, but are not limited to, styrene-butadiene rubber (SBR), natural rubber, polybutadiene, polyisoprene, and oil-extended derivatives thereof. Blends of any of the foregoing elastomers may also be used, as well as functional derivatives of these polymers.

Alternatively, rubbers suitable for use in the present invention are natural rubbers and derivatives thereof (e.g., chlorinated rubbers). The carbon black of the present invention can be used with synthetic rubbers such as: about 10 to about 70 weight percent of a copolymer of styrene and about 90 to about 30 weight percent of butadiene, for example, a copolymer of 19 parts of styrene and 81 parts of butadiene, a copolymer of 30 parts of styrene and 70 parts of butadiene, a copolymer of 43 parts of styrene and 57 parts of butadiene, and a copolymer of 50 parts of styrene and 50 parts of butadiene; polymers and copolymers of conjugated dienes such as polybutadiene, polyisoprene, polychloroprene, and the like, and copolymers of such conjugated dienes and ethylenic group-containing monomers copolymerizable therewith (e.g., styrene, methylstyrene, chlorostyrene, acrylonitrile, 2-vinyl-pyridine, 5-methyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine, alkyl-substituted acrylates, vinyl ketones, methyl isopropenyl ketone, methyl vinyl ether, alpha-methylene carboxylic acid, and esters and amides thereof (e.g., acrylic acid and dialkylacrylic acid amides)); also suitable for use herein are copolymers of ethylene with other high alpha olefins such as propylene, butene-1 and pentene-1. Other suitable elastomers will be apparent to those skilled in the art, given the benefit of this disclosure.

Alternatively, the rubber compound of the invention may comprise: elastomer(s) and the carbon black of the present invention; and a curing agent, a coupling agent; and, optionally, additional reinforcing fillers other than the carbon black of the present invention, various processing aids, oil fillers, antidegradants, and/or other additives. For example, in the manufacture of rubber compositions, one or more curatives may be used, such as sulfur, sulfur donors, activators, accelerators, peroxides, and other systems used to effect vulcanization of the elastomer composition. The loading level of carbon black in the rubber compound may depend on the intended use of the composition. Alternatively, the amount of carbon black may include 1 to 90, or 5 to 85, or 10 to 80, or 20 to 75, or 25 to 70, or 30 to 65, or 35 to 60 weight percent, or other amounts, based on the total weight of the rubber compound.

The rubber compound with the carbon black and other ingredients may be produced by any suitable method. The methods may include those employing dry blending techniques, wet mixing techniques, multi-stage mixing processes, or other methods for mixing and processing ingredients, such as those disclosed in U.S. Pat. nos. 5,916,956, 6,048,923, 7,582,688, 8,586,651, and 8,536,249, which are incorporated herein by reference in their entirety. As noted, the resulting rubber compounds can be used to produce a variety of elastomeric-type articles, such as vehicle tire components (e.g., carcass, sidewalls, bead rubbers (treads), industrial rubber articles, seals, timing belts, power transmission belts, and the like, as well as other rubber articles.

Alternatively, the carbon black may be channel black, furnace black, and lamp black. The carbon black is preferably furnace carbon black. As a preferred option, the production of carbon black involves the use of multiple stages of carbon black reactors. As used herein, a "multistage reactor" is provided with multiple feedstock injection locations, wherein one or more subsequent injection locations are located downstream of a first injection location. More preferably, the multistage reactor has at least two stages (two, three, four, or more stages), wherein there is generally at least two (e.g., two, three, four, or more) feedstock introduction occurrences.

FIGS. 1 and 2 show illustrative portions of two types of associated carbon black reactors that may be used to produce the carbon blacks of the present invention using a multi-stage furnace process in view of the process conditions described herein.

The process conditions and reactor arrangement for producing the high structure carbon blacks of the present invention in the two reactors shown in fig. 1 and 2 may involve two transition zones (transitions) upstream of the full quench where the carbon black-producing feedstock is introduced (i.e., injected) separated by spaced channels of increased volume spacing, allowing for the option of intermediate injection of quench water and/or the use of water-cooled metal spaced channels between the two transition zones. Carbon blacks may be produced in these reactors wherein a carbon black-yielding feedstock is introduced in a first transition zone (stage) and combined with a hot gas stream to form a precursor and, after a residence time in spaced channels, downstream of the precursor in a second transition zone (stage), a carbon black-yielding second feedstock is subsequently introduced and thereafter the reactant stream is quenched to terminate the reaction.

For reactor 2 in fig. 1, the transition zones are labeled 12 and 22, the spacing channels are labeled 18, and the full quench position is labeled 58. In the reactor 2 shown in fig. 1, the spacing channels 18 are lined with a lining 19, which lining 19 may be a refractory brick. In the reactor 2 shown in fig. 1, an intermediate partial quench can be injected into the spaced channels 18 via an internal injection port 24A, or 24B, or both, for example, by employing an intermediate quench fluid (e.g., water or other quench fluid such as nitrogen).

For reactor 200 in fig. 2, the transition zones are labeled 212 and 220, the spacing channels are labeled 180, and the full quench position is labeled 580. In the reactor 200 shown in fig. 2, the partition passage 180 is formed of water-cooled metal sheets arranged in a cylindrical structure. For example, the spacing channels 180 may be provided as water-cooled, thermally conductive metal wall enclosures, e.g., metal tube structures having an integral water jacket through which cooling water may be continuously passed. In the reactor 200 shown in fig. 2, an intermediate partial quench may be injected into the spaced-apart channels 180 via one or more injection ports 240, for example, by employing an intermediate quench fluid (e.g., water or other quench fluid). Alternatively, the injection port 24A, 24B, or 240 may be a water jacketed pipe that includes a drain passage and a separate passage for cooling water to flow within the water injection probe.

The increased volume provided by the spaced channels between the transition zones (12 and 22 in fig. 1, and 212 and 220 in fig. 2) in these reactors (2, 200) allows for more recirculation, and a longer residence time between planes defined by two separate feedstock-injection locations located at the transition zones of each reactor, both of which enhance the ability of the carbon black to form as much structure as possible during each stage. Furthermore, after the second transition zone (22 in fig. 1, 220 in fig. 2), there may be a sharp expansion (50 in fig. 1, 500 in fig. 2) of the reactor diameter size, which may also help to maximize the structural build in the carbon black. Without wishing to be bound by any particular theory, the two related reactor geometries shown in fig. 1 and 2 may be used to produce a range of unusual highly structured carbon blacks, characterized by OAN and COAN, for example.

With respect to other features of the reactor 2 shown in fig. 1, the reactor 2 includes a combustion chamber 10 into which a combustion gas (liquid or gaseous fuel) 13 is introduced that is mixed with an oxidant 15 (including, for example, oxygen, air) (e.g., introduced into the chamber 10 through an orifice (not shown)) and ignited by any method known in the art. The resulting hot gas flow F flows through the frustoconical region 11 to converge in diameter to a generally cylindrical region comprising a plurality of tubular portions (12, 18 and 22) in series. The carbon black-yielding feedstock introduced in either transition zone (12, 22) may be introduced in any conventional manner, e.g., as a single stream or multiple streams. The introduction of the feedstock can occur at any rate. The rate of each stream may be the same or different for the multiple streams. In fig. 1, the feedstock injection ports 32 and 42 are located within forward and terminal tubular portions that define the first transition zone 12 and the second transition zone 22, respectively, wherein the second transition zone 22 is located downstream of the first transition zone 12. Although fig. 1 illustrates a single feed injection port (32, 42) per transition zone (12, 22), typically more than one feed injection port is circumferentially disposed at each transition zone 12 and 22 to inject multiple feed streams (streams) 30 into the first transition zone 12 and multiple feed streams 40 into the second transition zone 22. Any manner capable of introducing the carbon black-yielding feedstock can be employed. For example, the carbon black-yielding feedstock can be injected into the reactor at the transition zone through multiple streams, entering the interior region of the hot combustion gas stream at transition zone 12, and entering the reactant stream at second transition zone 22 to ensure high rates of mixing and shearing of the carbon black-yielding feedstock with the combustion gases/reactant stream. As shown, the spacing channel 18 is located between the transition regions 12 and 22.

In the configuration of fig. 1, fuel is ignited at the combustion chamber 10 and the resulting stream is directed to a channel-like region comprised of regions 12, 18 and 22 where the fuel contacts a first injection zone of feedstock injection at the first transition zone 12. The subsequent flow into the spacing channel 18 allows for a longer residence time between the feedstock injection locations and the recirculation prior to contact with the second feed of feedstock introduced at the second transition zone 22. As shown in fig. 1, the spacing channel 18 may have a cylindrical portion of constant diameter at its forward end adjacent the first transition zone 12 and a tapered refractory piece at its aft end that tapers in diameter toward the second transition zone 22. As shown, an intermediate partial water quench or other quench fluid may be provided in the spacing channel 18. The gas/carbon black particulate mixture exiting the transition zone 22 then flows into one or more increased diameter reactor zones (50, 52, and 54), which may be lined with a liner 56 (e.g., lining the one or more increased diameter reactor zones with a refractory material), and subsequently quenched. Quenching is typically performed by water jets at a quench location 58, which may vary in distance from the transition zone 22. The reaction of the carbon black-yielding feedstock may be stopped by a quench 58 at point 57 that injects a quench fluid 59. Q is the distance from the downstream end 55 of the transition zone 22 (which may coincide with the beginning of the reactor zone 50) to the point 57, and will vary depending on the location of the quench.

The reactor 200 shown in fig. 2 may generally operate in a manner similar to that of the reactor 2 of fig. 1, except for the illustrated differences in the structure of the spaced channels located between the transition zones. In the configuration of fig. 2, the fuel is ignited at the combustion chamber 110, and the resulting stream is directed to the channel-like region consisting of regions 212, 180, and 220, where the fuel contacts the first injection zone 320 of feedstock injection at the first transition zone 212. The subsequent flow into the spacing channel 180 allows for a longer residence time between the feedstock injection locations and the recirculation prior to contact with the second feed 420 of feedstock introduced at the second transition zone 220. As shown, an intermediate partial water quench or other quench fluid may be provided in the spacing channel 180. The gas/carbon black particulate mixture exiting the transition zone 220 then flows into one or more reactor zones (500) of increased diameter and is then quenched at quench location 580.

For the intermediate quench fluid introduced to the spaced-apart channels 18 of reactor 2 in fig. 1 or the spaced-apart channels 180 of reactor 200 in fig. 2, the weight ratio of the injected fluid (e.g., quench water) to the amount of carbon black-yielding feedstock introduced at the first transition zone (12, 120) may be relatively small compared to the ratio of the feedstock. Alternatively, the weight ratio of the injected fluid (e.g., quench water) to the amount of carbon black-yielding feedstock introduced at the first transition zone (12, 120) may be from 0 to about 1:1, alternatively from about 0.05:1 to about 1:1, alternatively from about 0.1:1 to about 1:1, alternatively from about 0.2:1 to about 0.5:1, alternatively from about 0.3:1 to about 0.7:1, alternatively from about 0.4:1 to about 0.8:1, or other amounts.

In fig. 1 and 2, a plurality of D numbers represent a plurality of inner diameter dimensions of a plurality of sections of the reactor, and a plurality of L numbers represent a plurality of lengths of a plurality of sections of the reactor. As shown, Q is the distance from the end of the second transition zone to the final quench. Examples of these D, L and Q parameters are illustrated in the examples section herein. Other values may be used. The term "diameter" as used herein with respect to any zone or stage of the carbon black reactor is the hydraulic diameter (D)_H) It is calculated by the following formula: 4A/P, wherein A is the cross-sectional area and P is the perimeter length.

With respect to the hot gas stream combined with the carbon black-yielding feedstock, the hot gas stream may also be considered a hot combustion gas that may be produced by contacting a solid, liquid, and/or gaseous fuel with a suitable oxidant stream, such as, but not limited to, air, oxygen, a mixture of air and oxygen, or the like. Alternatively, the preheated oxidant stream may be passed through without the addition of liquid or gaseous fuel. Examples of fuels suitable for contacting with the oxidant stream to produce a hot gas include any combustible gas, vapor, or liquid stream, such as natural gas, hydrogen, carbon monoxide, methane, acetylene, alcohol, or kerosene. In general, it is preferred to use fuels having a high content of carbon-containing components, and in particular hydrocarbons. The ratio of air to fuel used to produce the carbon black of the present invention can be about 0.6:1 to infinity (e.g., 1:1 (stoichiometric ratio) to infinity), or 0.6:1 to 10:1, or 1:1 to 10: 1. As noted, the oxidant stream may be preheated in order to facilitate the production of hot gases. Preferably, the hot gas stream is formed upstream of any location where the carbon black-yielding feedstock is introduced into the reactor.

The carbon black-yielding feedstock can be any conventional carbon black-yielding feedstock that results in the formation of carbon black. For example, any hydrocarbon material may be used. Suitable feedstocks can be any carbon black-yielding hydrocarbon feedstock that can be readily volatilized under reaction conditions. For example, unsaturated hydrocarbons (such as acetylene); olefins (such as ethylene, propylene, butylene); aromatics (such as benzene, toluene, and xylene); certain saturated hydrocarbons; and other hydrocarbons such as kerosene, naphthalene, terpenes, ethylene tar, aromatic cycle stocks, and the like. Preferably, the introduction of the carbon black-yielding feedstock at the second (downstream) transition zone does not completely quench the reaction. The carbon black-yielding feedstock introduced at the second transition zone may be the same type of feedstock as the carbon black-yielding feedstock introduced in the first (upstream) transition zone or a different feedstock therefrom. Further, the application of additional feedstock to the pre-existing carbon black particles may be repeated any number of times until the reaction of the feedstock to the carbon black ceases. The temperature of the entire reaction mixture generally decreases and the particle size of the carbon black increases each time additional feedstock is added. In this way, the additional introduction of feedstock can act as a partial quench for cooling the carbon black.

The total amount of carbon black-yielding feedstock introduced into the reactor (2, 200) may be divided between the first transition zone (12, 120) and the second transition zone (22, 220) based on their feed rates (in weight/time) at about 15:85 to 85:15, or about 20:80 to 80:20, or 30:70 to 70:30, or 60:40 to 40:60, respectively. Alternatively, the carbon black-yielding feedstock introduced at the second transition zone comprises at least 15 wt% of the total amount of carbon black-yielding feedstock used throughout the process. The carbon black-yielding feedstock introduced at the second transition zone may comprise from about 15 wt% to about 80 wt% of the total amount of carbon black-yielding feedstock used throughout the process. Other ranges include from about 25 wt% to about 70 wt% or from about 30 wt% to about 60 wt% of the total amount of carbon black-yielding feedstock used throughout the process.

Alternatively, the first and second transition zones may have respective first and second temperature zones having a temperature difference with respect to each other. In this option, the first temperature zone and the second temperature zone may have a temperature difference of 200 ℃ or more, and preferably a temperature difference of 300 ℃ or more. Suitable ranges for the temperature difference may be, for example, from about 200 ℃ to about 900 ℃ or from about 400 ℃ to about 700 ℃. Other temperature ranges for the temperature difference may be employed. Generally, with respect to this temperature difference, the first temperature zone has a higher temperature and the second temperature zone has a lower temperature, thereby creating a temperature difference, although this is only a preferred embodiment. The difference in temperature can be achieved in many ways, for example, by the action of an intermediate quench as shown in the spacing channel, or by avoiding any further introduction of combustion gases, or by avoiding or minimizing the formation of combustion gases in the second temperature zone, or by any combination of these. Other means for achieving this difference may be employed. For example, a water jacket may be used around the location where the carbon black-yielding feedstock is introduced or after at the second transition zone of the reactor (or portion of the reactor). Alternatively, or in combination, steam may be introduced at this point. Additionally, or alternatively, other quenchants (e.g., nitrogen, water, or other suitable quenchants) may be used to effect the temperature reduction at the point of introduction of the second carbon black-yielding feedstock or thereafter. Preferably, no water jacket or other quenching device or means is present in the first temperature zone of any of the embodiments of the present invention, and preferably any such quenching occurs just prior to, during, or just after the introduction of the carbon black-yielding feedstock at the second transition zone.

After the mixture of hot combustion gases and carbon black-yielding feedstock is fully quenched, the cooled gases may be passed downstream into any conventional cooling and separation device whereby the carbon black is recovered. Separation of the carbon black from the gas stream can be readily accomplished by conventional means (e.g., a precipitator, cyclone separator, or bag filter). With respect to fully quenching the reaction to form the final carbon black, any conventional means for quenching the reaction downstream of the introduction of the carbon black-yielding feedstock at the second transition zone can be employed and are known to those skilled in the art. For example, a quench fluid (which may be water or other suitable fluid for stopping the chemical reaction) may be injected. The carbon black may be used as such or, optionally, may be pelletized or further processed or treated (e.g., surface modified).

Optionally, the production of carbon black may further comprise controlling the introduction of at least one of: the substance is or comprises at least one element (or ion thereof) of group IA or group IIA of the periodic table of the elements. The charge of the metal ions can provide a repulsive force between the individual carbon black particles. The repulsive force may prevent the particles from aggregating, thereby reducing the overall structure of the carbon black. In view of this, the presence of at least one group IA or group IIA element in carbon black may be detrimental to providing carbon black having a very high structure. Alternatively, to provide some limited adjustment in structure, selected small amounts of at least one group IA or IIA element may be tolerated or even introduced in small amounts at one or more stages of the reaction, provided that the resulting carbon product still meets the OAN and COAN requirements specified herein, e.g., the at least one group IA or IIA element is present in an amount of about 10ppm or less, e.g., about 5ppm or less, about 2ppm or less, about 1ppm or less, about 0.5ppm or less, about 0.2ppm or less, or about 0.1ppm or less. Preferably, the at least one group IA or group IIA element is present in an amount of about 0 ppm. The at least one group IA or IIA element or the substance comprising at least one group IA or IIA element may comprise at least one alkali or alkaline earth metal, e.g., lithium, sodium, potassium, rubidium, cesium, francium, calcium, barium, strontium, or radium, or a combination thereof. The substance may be a solid, a solution, a dispersion, a gas, a salt, or any combination thereof. If used, the material may be introduced prior to complete quenching. As indicated, the amount of group IA or IIA metal-containing substance, if used or allowed to be present, can be any amount so long as the carbon black can be formed that still meets the OAN and COAN values specified for the structure.

Alternatively, the carbon black may be modified. For example, the carbon blacks of the present invention may include chemical groups and/or coupling agents attached to the surface, or include chemical groups adsorbed thereon, or have a coating (e.g., a chemical coating such as a silica coating or other coating) on the surface of the carbon black, or have an oxidized surface, or any combination thereof. The carbon blacks of the present invention may have attached chemical groups (e.g., organic groups). A process for attaching a chemical group to a carbon black can involve the reaction of at least one diazonium salt with a carbon black. Other methods of attaching chemical groups to carbon black may be employed. The chemical groups and methods for attaching these groups to carbon black may include those shown in the following U.S. patents and publications: 5,851,280, 5,837,045, 5,803,959, 5,672,198, 5,571,311, 5,630,868, 5,707,432, 5,554,739, 5,689,016, 5,713,988, 8,975,316, 9,388,300, WO96/18688, WO97/47697, and WO97/47699, all of which are incorporated by reference herein in their entirety. The carbon black of the present invention may have chemical groups (e.g., organic groups) adsorbed thereon. The chemical groups and methods for adsorbing these groups to carbon black can include those shown in U.S. Pat. Nos. 8,975,316 and 9,175,150, which are incorporated herein by reference in their entirety.

Alternatively, or in addition, a coupling agent may be used. The coupling agent may be or include one or more silane coupling agents, one or more zirconate coupling agents, one or more titanate coupling agents, one or more nitro coupling agents, or any combination thereof. The coupling agent may be or include bis (3-triethoxysilylpropyl) tetrasulfane (e.g., Si 69 from Evonik Industries, Struktol SCA98 from Struktol Company), bis (3-triethoxysilylpropyl) disulfane (e.g., Si 75 and Si 266 from Evonik Industries, Struktol SCA985 from Struktol Company), 3-thiocyanate (thiocyanato) propyl-triethoxysilane (e.g., Si264 from Evonik Industries), γ -mercaptopropyl-trimethoxysilane (e.g., VP Si163 from Evonik Industries, Struktol SCA989 from Struktol Company), γ -mercaptopropyl-triethoxysilane (e.g., VP Si 263 from Evonik Industries), zirconium di-neoalkanolato di (3-mercapto) propionate (O, N-methyl propyl) -N2 '-bis (3-methyl propyl) -2' -nitro-2, 6-diaminohexane, S- (3- (triethoxysilyl) propyl) octane mercaptide (e.g., NXT coupling agents from Momentive, Friendly, WV), and/or other silica coupling agents known to those of skill in the art.

Alternatively, or in addition, the carbon black particles may be treated with other silica modifiers or hydrophobizing agents. Such agents may be covalently or non-covalently attached to the carbon black particles. Exemplary hydrophobic (hydroalizing) agents include silicone fluids. Non-limiting examples of useful silicone fluids include polydimethylsiloxane, polydiethylsiloxane, phenylmethylsiloxane copolymers, fluoroalkylsiloxane copolymers, diphenylsiloxane-dimethylsiloxane copolymers, phenylmethylsiloxane-diphenylsiloxane copolymers, methylhydrosiloxane-dimethylsiloxane copolymers, polyalkylene oxide-modified silicones, cyclic polysiloxanes of the types D3, D4, and D5, and the like. Modified silicone fluids, for example, hydroxyl terminated siloxanes, can also be used.

Alternatively, or in addition, the silica modifier may comprise a hydrophobic silane. For example, the hydrophobic silane can be a compound of the formula: r³ _4-nSiX_nWherein n is 1 to 3, each R³Independently selected from hydrogen, C₁-C₁₈Alkyl radical, C₃-C₁₈Haloalkyl and C₆-C₁₄An aromatic group, and each X is independently C₁-C₁₈Alkoxy or halogen. Alternatively, or in addition, the silica modifier comprises a silazane. For example, the hydrophobizing agent can be hexamethyldisilazane, octamethyltrisilazane, cyclic silazane, and the like. In certain embodiments, the silica modifier comprises a chargeModifiers, such as one or more of those disclosed in U.S. patent application publication 2010/0009280, the disclosure of which is incorporated herein by reference. Alternatively, or in addition, the dimethylsiloxane copolymers disclosed in U.S. patent application publication 2011/0244382A1, the disclosure of which is incorporated herein by reference, may be used to treat carbon black particles.

The carbon black of the present invention can be modified by depositing a silicon-containing substance (e.g., silica) on at least a part of the surface of the carbon black to cover (coat) the carbon black. The carbon black may be coated with silica. Silica coating materials and methods of coating carbon black with silica can include those shown in U.S. Pat. Nos. 6,197,274 and 6,541,113, which are incorporated herein by reference in their entirety. The silica coating may partially or completely cover the surface of the carbon black.

The carbon black may be oxidized. Suitable oxidizing agents may include, but are not limited to, acids (e.g., nitric acid) and ozone. Coupling agents may be used with the oxidized carbon blacks, for example, the coupling agent shown in U.S. Pat. No.6,057,387 (which is incorporated herein by reference in its entirety), or other coupling agents as described herein.

The invention will be further elucidated by the following examples, which are intended as illustrations of the invention only.