HK1158675A - Carbon black, method for the production thereof, and use thereof - Google Patents

Description

Carbon black, method for the production thereof and use thereof

The present invention relates to carbon black, a process for its preparation, and its use.

The structure of Carbon Black is known to have a considerable influence on the reinforcing properties of Carbon Black in rubber mixtures, assuming that the polymer has good adhesion to the Carbon Black (Donnet J. -B., Bansal R.C., WangM.J. (ed.), Gersbacher M: Carbon Black, Marcel Dekker Inc., New York, (1993), 2 nd edition, p.386). Another well-known fact is that as the specific surface area increases, the hysteresis increases, whereby the energy loss increases under cyclic stress-strain conditions. The wear resistance increases with increasing specific surface area. The compression set increases with increasing specific surface area, which is particularly disadvantageous for the gasket, since the pressure exerted by the gasket decreases therewith. Thus, low surface area carbon blacks are particularly useful in process rubber products because their abrasion resistance is not particularly important. These carbon blacks may also be used in the area of tire carcass (Reinfenunterbaus). The smaller specific surface area of carbon black thus results in a reduction in hysteresis and thus also in rolling resistance. As mentioned above, the structure has a decisive influence on the reinforcing effect. The increase in rolling resistance caused by the tire frame leads to an increase in fuel consumption and thus an increase in carbon dioxide emission. This is undesirable for economic and environmental reasons.

It is also known that Carbon blacks achieve good dispersion in polymers if their structure (COAN, OAN) has sufficient values (Donnet, Bansal, Wang (ed.), Funt j.m., Sifleet w.l., tommy m.: Carbon Black, Marcel Dekker inc., New York, (1993), 2 nd edition, p.390).

Therefore, it is desirable to use a low specific surface area carbon black to reduce the rolling resistance of the tire carcass for economic and environmental reasons. In addition, it is also desirable to reduce the weight of the part by reducing the filler content and part density by improving the reinforcing effect. For economic and processing-technical reasons, it is desirable to use improved reinforcement of fillers, so that oil can be used instead of the polymer component in rubber formulations. Another key factor in the effectiveness of the filler is the degree of dispersion, and it is therefore desirable to use a filler that is readily dispersible.

U.S. Pat. No. 3, 2008/0110552, 1 discloses carbon blacks whose COAN is greater than 90ml/(100g) but less than 150ml/(100g) and whose BET is greater than 50m²A ratio of the total of the carbon atoms to the carbon atoms of less than 69m²(ii) in terms of/g. Distribution index DI (D)_wRatio D_modeThe ratio) is greater than 1.15. These carbon blacks, because of their high specific surface area, produce undesirable levels of hysteresis in the rubber mixtures.

U.S. Pat. No. 3, 2003/0013797, 1 discloses carbon blacks having an STSA of 10 to 200m in polymer conductive applications²The iodine value is 15-250mg/g, the chroma value is up to 130%, DBPA is 20-450ml/(100g), CDBP is 20-400ml/(100g), the ratio of iodine value to STSA is 0.4-2.5, the average grain diameter is 14-250nm, and the content of volatile components is less than 1%.

Furthermore, US 005236992a discloses furnace blacks which are characterized by: CTAB specific surface area is 45-55m²The specific iodine number (specific iodine number) is 48-58mg/g, the chroma value is 65-75%, the CDBP is 90-100ml/(100g), and the DBP is 122-. The carbon blacks are prepared by adding oil radially and axially within the constriction of a furnace carbon black reactor. The disadvantages of these carbon blacks are low OAN levels and small differences between OAN and COAN. Moreover, the specific surface area of this carbon black is still high, with the attendant disadvantages.

Furthermore, JP11-302557A discloses carbon blacks which have a CTAB surface area of 25 to 60m²(iv)/g, and DBP/(ml/100g) > 0.6 CTAB/(m)²G) + 120. In addition, for the mode, it is required to conform to D_st/nm＜6000m²Stokes diameter of/g/CTAB + 60. As a result of this situation, the carbon black produced in JP11-302557A contains smaller aggregates. These conditions lead to undesirable properties of the carbon black.

JP07-268148 discloses carbon blacks which have a DBP of greater than 140ml/(100 g). The particle diameter is represented by d_p38nm or 42 nm.

JP04-18438 discloses carbon blacks having an STSA < 60m²(ii)/g and DBP ≤ 100ml/(100 g).

JP01-272645 preferably uses carbon black having an iodine value of 10-40ml/g and a DBP of 100-500ml/(100 g).

EP 1783178 discloses a furnace carbon black process in which the feedstock for the carbon black is added in a first stage and mixed with a hot gas stream in order to form a precursor consisting essentially of the carbon black in the reaction gas stream, and then further amounts of the feedstock for the carbon black are added to the precursor in order thereby to partially quench (abzuschrecken) the reaction gas stream and then to quench the entire reaction gas stream completely. The hot gas stream may be produced as combustion gas from the reaction of a fuel and an oxidant (e.g., air), and the ratio of air to fuel may vary from 1: 1 (stoichiometric) to an infinite ratio.

The object of the present invention is to provide carbon blacks which exhibit very high reinforcing action and low hysteresis in rubber mixtures and have good dispersion.

The present invention provides a carbon black characterized in that it has a CTAB surface area of 20 to 49m²A/g, preferably from 30 to 48m²Per g, particularly preferably from 35 to 47m²Per g, very particularly preferably from 38 to 46m²A COAN of greater than 90ml/(100g), preferably greater than 95ml/(100g), particularly preferably greater than 98ml/(100g), particularly preferablyPreferably greater than 100ml/(100g) and the sum of OAN and COAN is greater than 235ml/(100g), preferably greater than 250ml/(100g), particularly preferably greater than 260ml/(100g), particularly preferably greater than 270ml/(100 g).

The Quartile-Ratio (Quartile-Ratio) may be greater than 1.60, preferably 1.65 to 2.50, particularly preferably 1.70 to 2.50, very particularly preferably 1.75 to 2.50, particularly preferably 1.80 to 2.50, and very particularly preferably 1.85 to 2.45.

Mode D of aggregate particle size distribution of carbon black of the present invention_StCan be more than 6000m²nm/g/CTAB+60nm。

The carbon black of the present invention can be prepared into pellets. The carbon black can particularly preferably be wet granulated.

The ratio of the Δ D-50 value to the mode of the aggregate size distribution of the carbon black of the invention may be greater than 0.95, preferably greater than 1.0, very particularly preferably greater than or equal to 1.05.

Aggregate particle size distribution D of carbon black of the present invention_WThe value (mass average particle diameter) may be greater than 200 nm.

The carbon blacks of the present invention may have a chroma value of less than 120, preferably less than 105, particularly preferably less than 90, very particularly preferably less than 75.

For the carbon black of the present invention, the ratio of its number average diameter to the mode of the aggregate particle size distribution may be greater than 1.35, preferably greater than 1.4.

The carbon black of the present invention may be a gas black, channel black, lamp black or furnace black, preferably a furnace black.

The carbon blacks of the invention may have an OAN > 100ml/(100g), preferably > 130ml/(100g), particularly preferably > 160ml/(100 g).

The carbon black of the present invention may have an average primary particle diameter of more than 42nm, preferably 43nm to less than 160nm, particularly preferably 43nm to 90 nm.

The carbon blacks of the present invention may be carbon blacks that have not been surface modified and have not been post-treated.

The carbon blacks of the present invention may have a pH > 5.

CTAB value was measured according to ASTM D3765-04.

BET specific surface area and STSA surface area were determined according to ASTM D6556-04, according to parameters relating to relative pressure, as described in section 10.4.4.

The COAN values were determined according to ASTM D3493-06, and the following parameters were used: oil: paraffin wax; method for determining an endpoint: and B, step B.

OAN was measured according to ASTM D2414-00.

The colorimetric values were determined according to ASTM D3265-06, using the following parameters: HooverMuller paste, Erichsen colorimeter-film draw down.

The pH was measured according to ASTM D1512-00.

Primary particle size is measured according to ASTM D3849-07.

The quartile ratio is calculated from the aggregate size distribution.

The aggregate size distribution is determined here in accordance with ISO 15825 standard, 1 st edition, 2004-11-01, with the following changes:

supplement to ISO 15825 standard, section 4.6.3: to the mode of the mass distribution curve.

Supplement to section 5.1 of the ISO 15825 standard: the equipment used included a BI-DCP particle Sizer and was equipped with dcplw32 calculation software, version 3.81, all available from Brookhaven instruments Corporation, 750 Blue Point Rd., Holtsville, NY, 11742.

Supplement to ISO 15825 standard, section 5.2: the equipment used comprised a GM2200 ultrasound control unit, a UW2200 acoustic transducer and a DH13G ultrasound generator (sonotrode). The ultrasonic control unit, acoustic transducer and ultrasonic generator are available from Bandelin electronic GmbH & co. kg, heinrichlasse 3-4, D-12207 Berlin. In the present invention, the ultrasonic control unit sets values as follows: power% 50 and cycle 8. This corresponds to a nominal power level set at 100 watts and a pulse level set at 80%.

Supplement to ISO 15825 standard, section 5.2.1: the ultrasonic time was set to 4.5 minutes.

The definition given in section 6.3 of the ISO 15825 standard was changed, the "surfactant" was defined as follows: "surfactant" is Nonidet P40 Substite, an anionic surfactant from Fluka available from Sigma-Aldrich Chemie GmbH, Industriestrass 25, CH-9471Buchs SG, Switzerland.

The spin-on fluid (spin fluid) definition given in section 6.5 of the ISO 15825 standard was varied as follows: the spin-on fluid was formulated by taking 0.25g of Nonidet P40 Substite surfactant from Fluka (section 6.3) and bringing to 1000ml with deionized water (section 6.1). The pH of the spin-on fluid solution was then adjusted to 9-10 by using 0.1mol/l NaOH solution. The spin-on fluid must be used up to 1 week after it is formulated.

The definition of the dispersion fluid given in section 6.6 of the ISO 15825 standard was changed as follows: the dispersion fluid was prepared by taking 200ml of ethanol (section 6.2) and 0.5g of Nonidet P40 Substite surfactant from Fluka (section 6.3) and bringing to 1000ml with deionised water (section 6.1). Then, the pH of the dispersion fluid solution was adjusted to 9-10 by using 0.1mol/l NaOH solution. The dispersion fluid must be used up to 1 week after it is formulated.

Supplement to ISO 15825 standard, section 7: the materials used were all carbon black granulated.

The instructions in sections 8.1, 8.2 and 8.3 of the ISO 15825 standard are all replaced by the following instructions: slowing granulation of carbon black in an agate mortarSlowly grind. Then, in a 30ml crimped bottle: () (diameter 28mm, height 75mm, wall thickness 1.0mm) 20ml of the dispersion solution (section 6.6) was mixed with 20mg of carbon black and treated with ultrasonic waves (section 5.2) in a cooling bath (16 ℃ C. +/-1 ℃ C.) for 4.5 minutes (section 5.2.1), whereby the carbon black was suspended in the dispersion solution. After sonication, the samples were assayed in a centrifuge within 5 minutes.

Supplement to section 9 of the ISO 15825 standard: the density value of the carbon black to be fed was 1.86g/cm³. The temperature to be input is measured according to section 10.11. For spin-on fluid types, the "aqueous" option is chosen. This gave a spin-on fluid density value of 0.997(g/cc), and a spin-on fluid viscosity value of 0.917 (cP). By using selectable options in dcplw32 software: file ═ carbon. Mie correction for light scattering.

Supplement to section 10.1 of the ISO 15825 standard: the speed of the centrifuge was set to 11000 r/min.

Supplement to section 10.2 of the ISO 15825 standard: inject 0.85cm³Ethanol (section 6.2) instead of injecting 0.2cm³Ethanol (section 6.2).

Supplement to section 10.3 of the ISO 15825 standard: inject exactly 15cm³Spin coating fluid (section 6.5). Then 0.15cm was injected³Ethanol (section 6.2).

The description of the operation in section 10.4 of the ISO 15825 standard is omitted entirely.

Supplement to ISO 15825 standard, section 10.7: using 0.1cm immediately after starting to record data³Dodecane covers the spin-on fluid in the centrifuge (section 6.4).

Supplement to ISO 15825 standard, section 10.10: if the measurement curve does not return to baseline within 1 hour, the assay is terminated after just 1 hour of measurement time, rather than being restarted with a different centrifuge-spin speed.

Supplement to ISO 15825 standard, section 10.11: instead of using the method described in the operational description for determining the measured temperature, the measured temperature T to be input to the computer program is determined as follows:

T＝2/3(Te-Ta)+Ta，

where Ta is the temperature of the measurement chamber before measurement and Te is the temperature of the measurement chamber after measurement. The temperature difference should not exceed 4 DEG K.

The Δ D-50 values and modes were likewise obtained from the aggregate size distribution according to the ISO 15825 standard mentioned above.

The invention also provides a process for the preparation of the carbon blacks of the invention in a furnace carbon black reactor, comprising, along the reactor axis, a combustion zone, a reaction zone and a termination zone, generating a hot exhaust gas stream by combustion of a fuel in an oxygen-containing gas in the combustion zone, and the exhaust gas passing from the combustion zone without passing through a constriction and then into the termination zone, mixing with the feedstock for the carbon black into the hot exhaust gas in the reaction zone, and terminating the formation of the carbon black in the termination zone by water injection, characterized in that in the first third of the reaction zone, from 20% to 58% by weight, preferably from 30% to 50% by weight, of the feedstock for the carbon black is added radially through a nozzle, and the remaining amount of the feedstock for the carbon black is added to the reactor through a nozzle at least one other point upstream.

The reaction zone is charged first with the feedstock for carbon black and is terminated with a quench.

The oxygen-containing gas may be air that is not enriched in oxygen.

The size of the reactor may become large after the second refueling. This can be achieved in multiple stages or in one stage. Preferably only one stage is used.

The ratio of the cross-sectional area of the reactor cross-section at the second oil addition to the cross-sectional area of the reactor cross-section downstream of the reaction space can be less than 1.0, preferably less than 0.5, particularly preferably less than 0.1, and very particularly preferably less than 0.05.

The fuel may be liquid, liquid to some extent and gaseous to some extent, or gaseous.

The fuel atomizers used may comprise atomizers which operate purely with pressure (single-fluid atomizers) or two-fluid atomizers which utilize internal or external mixing. The fuel can be introduced by using an atomizer which operates purely with pressure (single-fluid atomizer), or by using a two-fluid atomizer equipped with internal or external mixing. If the fuel is a liquid, the conditions may be chosen to balance the following factors: the droplet size achieved during atomization, the residence time of these droplets before contacting the feedstock for the carbon black, and the reaction temperature, such that greater than 80% of the mass flow rate of the fuel used in contact with the feedstock for carbon black is gaseous. In particular, the use of a two-fluid atomizer and a liquid fuel enables the droplet size to be controlled within a wide range regardless of throughput, thereby enabling it to be balanced with the residence time of the fuel and the reaction temperature prior to contacting the feedstock for the carbon black.

The droplet size distribution can be determined by means of optical methods. Various commercially available nozzle manufacturers provide these measurement services, for example, Dusen-Schlick GmbH, D-96253Untersiemau/Coburg, Germany. The residence time of the droplets and the reaction temperature during the process can be determined from computer-aided rheological simulation calculations. For example, "Fluent", version 6.3, from Fluent (Fluent deutschland gmbh, 64295 Darmstadt) is a commercial software that can simulate a furnace reactor in use, and after all incoming process flow data (including measured droplet size distributions) are entered, its underlying chemical model can be used to calculate residence time and evaporation rate of the fuel droplets, as well as reaction temperature.

The feedstock for the carbon black can be introduced through a nozzle using a star nozzle (radiallanzen). The number of star nozzles used may be 2 to 32, preferably 3 to 16, particularly preferably 3 to 8.

The feedstock for the carbon black may be supplied axially at the beginning of the reaction zone (initial addition of feedstock for carbon black).

The feedstock for the carbon black may be liquid or gaseous, or liquid to some extent and gaseous to some extent.

The liquid feedstock for the carbon black may be atomized by pressure, by a gas stream, by a gas such as compressed air, or by a gaseous feedstock.

The liquid feedstocks which can be used for the carbon black are liquid aliphatic or aromatic, saturated or unsaturated hydrocarbons, hydrocarbon-containing mixtures, such as liquid biomass, or renewable feedstocks, or mixtures thereof, or coal tar, distillates, or residues produced in the catalytic cracking of petroleum fractions or in the cracking of naphtha or diesel to olefins.

The gaseous feedstock for the carbon black may be a gaseous aliphatic, saturated or unsaturated hydrocarbon, mixtures thereof, or natural gas.

The "K coefficient" is often used as a variable to characterize excess air. The K-factor is the ratio between the amount of air required for stoichiometric combustion of the fuel and the actual amount of air introduced during combustion. Thus, a K factor of 1 refers to stoichiometric combustion. If excess air is present, the K factor is less than 1. The K factor in the process of the invention may be from 0.2 to 1.0. The K factor may preferably be from 0.3 to 0.9, particularly preferably from 0.3 to 0.8.

The process is not limited to any particular reactor geometry and may be adapted to a variety of reactor types and reactor sizes.

The atomizer of the feedstock for carbon black can be an atomizer operating solely with pressure (single fluid atomizer), or a two-fluid atomizer with internal or external mixing. The atomizing medium for the liquid feedstock of carbon black may be a gaseous feedstock, or a vapor or gas such as air.

A two-fluid atomizer may be used to atomize the liquid feedstock for carbon black. In the case of a single fluid atomizer, the change in throughput can also result in a change in droplet size, but in the case of a two fluid atomizer, the droplet size can be controlled substantially independently of throughput.

If the feedstock for the carbon black contains both a liquid feedstock and a gaseous feedstock, such as methane, the gaseous feedstock may be separately injected from the feedstock into the hot exhaust stream through a dedicated gas injection head.

The carbon black of the present invention may be used as reinforcing or other fillers, UV stabilizers, conductive carbon black or pigments. The carbon blacks of the present invention can be used in rubber, plastics, printing inks, inkjet inks, other inks, toners, lacquers, coatings, paper, pastes (Pasten), batteries, and in cosmetics, as well as in asphalt, concrete, flame-retardant materials and other building materials. The carbon black of the present invention can be used as a reducing agent for metallurgy.

The carbon blacks of the present invention can be used as reinforcing carbon blacks in rubber mixtures.

The invention also provides rubber mixtures which are characterized in that they comprise at least one rubber, preferably at least one diene rubber, particularly preferably at least natural rubber and at least one carbon black according to the invention.

The carbon blacks of the invention can be used in an amount of from 10 to 250phr (parts per 100 parts of rubber), preferably from 20 to 200phr, particularly preferably from 30 to 170phr and very particularly preferably from 30 to 150phr, relative to the amount of rubber used.

The rubber mixtures according to the invention may comprise silica, preferably precipitated silica. The rubber mixtures according to the invention may comprise organosilanes, such as bis (triethoxysilylpropyl) polysulfide or (mercaptoorganyl) -alkoxysilanes.

The rubber mixtures according to the invention may comprise rubber auxiliaries.

Suitable materials for preparing the rubber mixtures according to the invention include not only natural rubber but also synthetic rubber. Preferred synthetic rubbers are described, for example, in W.Hofmann, Kautschuktechnology [ Rubbert technology ], Genter Verlag, Stuttgart 1980. They include, in addition to these

-a polybutadiene (BR),

-polyisoprene (IR),

styrene/butadiene copolymers, such as Emulsion SBR (ESBR) or Solution SBR (SSBR), preferably with a styrene content of from 1% to 60% by weight, particularly preferably from 2% to 50% by weight, relative to the total polymer,

-Chloroprene (CR),

-isobutene/isoprene copolymers (IIR),

-butadiene/acrylonitrile copolymers, preferably having an acrylonitrile content of from 5% to 60% by weight, preferably from 10% to 50% by weight, relative to the total amount of the polymer (NBR),

-partially or fully hydrogenated NBR rubber (HNBR),

ethylene/propylene/diene copolymers (EPDM),

ethylene/propylene copolymers (EPM), or

The abovementioned rubbers additionally having further functional groups, such as carboxyl, silanol OR epoxy groups, for example epoxidized NR, carboxyl-functional NBR, OR silanol (-SiOH) -functional OR siloxy-functional SBR,

and mixtures of these rubbers.

The production of truck tire carcasses may preferably use natural rubber, or mixtures thereof with diene rubbers.

SBR, or a mixture thereof with diene rubber, may preferably be used for the production of automobile tire frames.

The rubber mixtures of the invention may comprise further rubber auxiliaries, for example reaction accelerators, antioxidants, heat stabilizers, light stabilizers, antiozonants, processing aids, plasticizers, tackifiers, blowing agents, dyes, pigments, waxes, extenders, organic acids, retarders, metal oxides, and activators, for example diphenylguanidine, triethanolamine, polyethylene glycol, alkoxy-terminated polyethylene glycol, or hexanetriol, which are known in the rubber industry.

The amount of rubber auxiliaries can be conventional and, moreover, depends on the desired use. Exemplary conventional amounts may range from 0.1 to 50phr, relative to the rubber.

Crosslinking agents that can be used are sulfur, organic sulfur donors, or radiation, or free radical initiators. The rubber mixtures according to the invention may also comprise vulcanization accelerators.

Examples of suitable vulcanization accelerators may be mercaptobenzothiazoles, sulfenamides, guanidines, thiurams, dithiocarbamates, thioureas, and thiocarbonates.

The vulcanization accelerators and crosslinking agents can be used in amounts of 0.1 to 10phr, preferably 0.1 to 5phr, based on the rubber.

The mixing of the rubber with the filler, if appropriate also with the rubber auxiliary and, if appropriate, with the organosilane can be carried out in or on conventional mixing elements, such as rolls, internal mixers and mixing extruders. Such rubber mixtures can generally be prepared in an internal mixer, starting from one or more successive thermomechanical mixing stages, in which the following are added: the rubber, the carbon black of the invention, if appropriate silica, and if appropriate organosilanes, and the rubber auxiliaries, are carried out at 100 ℃ and 170 ℃. The order of addition and the timing of addition of the individual components have a decisive influence on the properties of the mixture obtained. The crosslinking chemical may then be mixed with the resulting rubber mixture in an internal mixer or on a roller system at 40-130 ℃, preferably 50-120 ℃, and this mixture is then processed to give a so-called raw mixture for subsequent processing steps, such as shaping and vulcanization steps.

The vulcanization of the rubber mixtures according to the invention can take place at temperatures of from 80 to 200 ℃ and preferably at from 130 to 180 ℃ and, where appropriate, at pressures of from 10 to 200 bar.

The rubber mixtures according to the invention are suitable for producing mouldings () For example for the production of pneumatic or other tyres, tyre carcasses, cable sheaths, hoses, drive belts, conveyor belts, roller coverings, shoe soles, sealing rings, profiles (Profilen) and damping elements.

The carbon blacks of the present invention have the advantage of very high shear modulus and low loss modulus in rubber mixtures. Another feature of the carbon black is that it significantly inhibits die swell (die swell) of the polymer. The carbon blacks of the present invention have very good dispersibility in polymers.

Examples

Example 1 (preparation of carbon black):

the carbon blacks of the present invention are prepared in a carbon black reactor as shown in FIG. 1.

Fig. 1 shows a longitudinal section through the furnace reactor. The carbon black reactor has a combustion chamber 5 in which the hot process gas for the pyrolysis of carbon black oil is produced by the super-stoichiometric combustion of a fuel. Gaseous or liquid fuels may be used to prepare the carbon blacks of the present invention.

The combustion air is introduced through a plurality of holes 2 concentrically distributed with respect to the fuel supply. The fuel is added through a burner disposed at the end of the combustion chamber.

There is also an oil lance 1 leading into the combustion chamber, through which the feedstock for the carbon black is introduced into the reactor. The oil jets may be moved axially to best practice the method of the present invention. The combustion chamber narrows conically to the area defining the cross-section 6. The raw material for the carbon black is introduced into the interior or front of the constriction by means of a star nozzle 3 via a nozzle. After passing through the constriction, the reaction gas mixture flows into the reaction chamber 7.

L3 and L5 show the various locations where carbon black oil is injected into the hot process gas using oil jets 1 and 3. A suitable spray nozzle has been fitted at the front end of the oil spray head. At each injection site there are at least 4 injectors distributed around the circumference of the reactor.

In the termination zone, water is sprayed into the system via the quench-water spray headers 4.

FIG. 1 uses Roman numerals I-III to characterize the combustion zone, reaction zone, and termination zone. The exact axial dimensions of these zones depend on the respective arrangement of the burner tip, the oil tip and the quench-water tip. The reaction zone started at the first addition of the feedstock for the carbon black and ended at the addition of water at L4.

The dimensions of the reactors used can be found in the following table:

I

maximum diameter of combustion chamber D1: 930mm

Length of combustion chamber to narrowest section L1: 1670mm

Length L2 of tapered portion of combustion chamber: 1300mm

Diameter of constriction D2: 114mm

Length of constricted portion L6: 80mm

Diameter of reaction chamber D3: 875mm

Position L540 mm of oil spray head

L3 1300mm

Maximum position of quench-water nozzle L48290 mm

To prepare the carbon black of the present invention, natural gas may be used as a fuel, and the raw material for the carbon black may contain carbon black oil having a carbon content of 91% by weight and a hydrogen content of 6% by weight.

Comparative carbon blacks used were available from Evonik Degussa GmbHN550 andN660。

the reactor parameters used to prepare the carbon blacks of the present invention are listed in table 1.

The carbon blacks obtained are treated by the conventional wet granulation method and then characterized and incorporated into rubber mixtures.

Table 1:

table 2 lists the analytical data for the carbon blacks produced:

table 2:

¹⁾mass ratio of carbon black having aggregate particle size of more than 150nm (derived from aggregate particle size distribution)

Example 2 (vulcanization test in natural rubber):

the following table 3 gives the formulations for the natural rubber mixtures. The unit phr here denotes the parts by weight relative to 100 parts of crude rubber used.

General methods for the preparation of rubber mixtures and vulcanizates thereof are described in the book: "Rubber technology handbook", W.Hofmann, Hanser Verlag 1994.

Table 3:

SMR10 natural rubber, ML4 ═ 60-70, is SMR10, pulverized by a common method on a roll mill, and then subjected to a blending and mixing treatment, after which the intermediate is stored at room temperature for at least 24 hours but at most 1 week. This pulverized SMR10 had an ML 1+4(100 ℃) value of 60-70. The ML 1+4 values are determined in accordance with DIN 53523/3. Natural rubber is available from Lanxess.

4020 is the antioxidant 6PPD from Rhein Chemie GmbH.

Is the antioxidant TMQ from Lanxess AG.Is an antiozonant wax from Paramelt b.v.Is a TBBS-type vulcanization accelerator from Bayer AG, containing 80% active ingredient.

Stearic acid is EDENOR ST1 from Caldic Deutschland GmbH.

ZnO is ZnO RS RAL 844C from Arnsperger Chemikalien GmbH, 50858 Cologne, Germany.

The sulfur vulcanizing agent was 80/90KMS ground sulfur (ground sulfur) from Laborchemie Handdelsgesellschaft Sangkt Augustin, Germany.

The carbon black used was comparative carbon black 1Or the carbon black "carbon black 1" of the present invention. Comparative carbon black 1 is available from Evonik Degussa GmbH.

The rubber mixtures were prepared in an internal mixer according to the mixing instructions in table 4.

TABLE 4

Homogenizing:

the material was cut and folded 3 times to the left and 3 times to the right, followed by rolling the material 3 times with a narrow nip (3mm) and 3 times with a wide nip (6mm), and taking out the rolled sheet

Table 5 compares the methods used for rubber testing. These also apply to the following embodiments.

TABLE 5

The preparation method of the sample for resistance measurement is as follows:

by using circular blades (82mm) samples were cut from a vulcanized sheet having a thickness of 2mm and degreased with isopropanol. Using calipers (30mm) the thickness of the test specimen was measured to the nearest 0.01mm at various positions. The volume resistance was calculated using the average thickness of the sample.

A circular template and silver marker pen were used to mark the area to be covered by the conductive silver 200 coating. The conductive silver paint was applied and after 1 hour of drying, the test sample was ready. The volume resistance and surface resistance were measured using a Milli-TO3 instrument from Fischer Elektronik.

Using a feed fromThe apparent viscosity at a temperature of 100 ℃ was determined by Rheograph 6000 high pressure capillary rheometer from D-74711 Buchen.

Dynamic shear was applied using an RPA 2000 apparatus from Alpha Technologies UK, 74078Heilbronn to determine torque components S' and S ".

Table 6 gives the results of the vulcanization test. The vulcanization time of the mixture at 150 ℃ was 15 minutes.

TABLE 6

DIN abrasion (mm)³) The higher the value, the poorer the abrasion resistance of the rubber mixture. Thus, for each carbon black of each carbon black group, the abrasion resistance index calculation is performed as follows:

abrasion resistance index (DIN abrasion/DIN abrasion with reference to carbon black) 100.

Thus, an abrasion resistance index of > 100 indicates improved abrasion resistance and an abrasion resistance index value of < 100 indicates reduced abrasion resistance relative to the respective reference carbon black.

The higher the needle temperature (. degree.C.) value, the higher the exothermic level and therefore the higher the hysteresis in the rubber mixture against dynamic stresses and therefore the poorer the expected rolling resistance.

Rolling resistance index (refer to needle temperature/needle temperature of carbon black) 100.

Thus, a rolling resistance index of > 100 indicates an improvement, i.e. a reduction in rolling resistance, relative to the respective reference carbon black, and a rolling resistance index value of < 100 indicates a deterioration in rolling resistance.

The results in table 6 show that when the carbon blacks of the present invention are compared to the comparative carbon blacks, they show higher stiffness in both shear and elongation tests due to the higher structural value. This enables the density of the mixture to be reduced by reducing the carbon black content and provides a level of reinforcement over that of the carbon black. Furthermore, the higher the structure value, the larger the aggregates are produced for the same primary particle size. This ultimately results in a lower tan (δ) value. A corresponding reduction in carbon content to give comparable hardness levels to the comparative carbon blacks will further reduce the tan (delta) value.

Example 3 (vulcanization test in EPDM):

the formulation for the EPDM mixture is given in table 7 below.

Table 7:

LipOXOL 4000 is a polyethylene glycol from Brenntag GmbH with a molar mass of 4000 g/mol.

BUNA EPG 5455 is EPDM rubber from Rhein Chemie GmbH, Germany.

SUNPAR 150 is a paraffin oil from Schill & Seilacher GmbH.

PERKANIT TBZTD PDR D is a TBZTD vulcanization accelerator from Weber & Schaer.

Stearic acid is EDENOR ST1 from Caldic Deutschland GmbH.

The vulcanization acceleratorMerkapto C is 2-mercaptobenzothiazole from Rhein Chemie GmbH.

Rhenocure TP/S is a vulcanization accelerator from Rhein Chemie GmbH.

ZnO is ZnO RS RAL 844C from Arnsperger Chemikalien GmbH, 50858 Cologne, Germany.

The sulfur vulcanizing agent was 80/90KMS ground sulfur from Laborchemie Handdelsgesellschaft Sangkt Augustin, Germany.

The carbon black used was comparative carbon black 1Or the carbon black "carbon black 1" of the present invention. Comparative carbon black 1 was obtained from Evonik Degussa GmbH.

The rubber mixtures were prepared in an internal mixer according to the mixing instructions in table 8.

TABLE 8

Rolling for 6 times, and taking out the rolled sheet

The batch temperature is 100 ℃ and 120 DEG C

Table 9 gives the results of the vulcanization test. The vulcanization time of the mixture at 170 ℃ was 16 minutes.

TABLE 9

The results in table 9 show that the carbon blacks of the present invention exhibit high hardness, lower tan (δ), higher ball rebound, lower compression set, and higher 300 modulus, higher S' value, and significantly better dispersion. With the addition of SUNPAR oil, the properties (eignenschaftsprofil) were reduced. When 60phr to 70phr of oil are added, the properties obtained are similar to those of the reference mixture. However, good dispersibility is maintained even at high oil contents. The viscosity of the uncrosslinked mixture (50phr of SUNPAR oil) was comparable to that of the reference mixture. As the oil content increases, the viscosity of the mixture decreases as expected, which is accompanied by better processability.

Example 4 (vulcanization test in NR/SBR):

the formulation for the NR/SBR blend is given in Table 10 below.

Table 10:

krynol 1712 is SBR from Rhein Chemie.

Vulcanization acceleratorDM/MG-C is MBTS from Rhein Chemie.

NR RSS 1 is a natural rubber available from Krahn Chemie.

Vulkanox HS/LG is TMQ from Rhein Chemie.

Antioxidant agent4020/LG is 6PPD from Lanxess AG.

Stearic acid is EDENOR ST1 from Caldic Deutschland GmbH.

Vulcanization acceleratorCZ/EG-C is CBS from Lanxess AG.

The ZnO is ZnO RS RAL 844C from Arnsperger Chemikalien GmbH, 50858 Cologne, Germany.

The vulcanizing agent sulfur was 100% ground sulfur from Kali Chemie AG, Hanover, Germany.

The carbon black used was comparative carbon black 1Comparative carbon Black 2Or the carbon black "carbon black 1" of the present invention. Comparative carbon BlackAndavailable from Evonik Degussa GmbH.

The rubber mixtures were prepared in an internal mixer according to the mixing instructions in table 11. The vulcanization time of the mixture at 150 ℃ was 20 minutes.

TABLE 11

Table 12 gives the results of the vulcanization test.

TABLE 12

The results in table 12 show that the carbon black of the invention (carbon black 1) gives higher hardness in the NR/ESBR blend (blend 8) than in the comparative blend 7, lower tan (δ) values at 60 ℃, higher ball rebound, higher 300 modulus, and higher complex modulus E.

The content of carbon black according to the invention was reduced to 44phr (mixture 10), the hardness and complex modulus E obtained were similar to those of mixture 7. In contrast, the tan (δ) at 60 ℃ is significantly reduced with respect to the comparative mixture 7, which, if used in a tire support, for example, results in a lower rolling resistance.N660 also had a low tan (delta) value (60 ℃ C.) (mixture 7 and mixture 11) due to its lower specific surface area, and if this was used as a control, a higher tan (delta) value (60 ℃ C.) was obtained when compared to the mixture made with the carbon black of the present invention (mixture 10) for the same hardness and the same complex modulus (mixture 12))。

Claims (11)

1. Carbon black characterized in that it has a CTAB surface area of 20 to 49m²(ii)/g, its COAN is greater than 90ml/(100g), and its sum of OAN and COAN is greater than 235ml/(100 g).

2. The carbon black 1 according to claim, wherein D is the mode_St＞6000m²nm/g/CTAB+60nm。

3. Carbon black according to claims 1-2, characterized in that the sum of OAN and COAN is greater than 250ml/(100 g).

4. The carbon black according to claims 1 to3, characterized in that its mass-average particle diameter is greater than 200 nm.

5. Carbon black according to claims 1 to 4, characterized in that its quartile ratio is greater than 1.60.

6. A process for the production of the carbon black of claim 1 in a furnace carbon black reactor, the process comprising, along a reactor axis, a combustion zone, a reaction zone and a termination zone, generating a hot exhaust stream by combustion in an oxygen-containing gas by a fuel in the combustion zone, and the exhaust passing from the combustion zone without passing through a constriction and then into the termination zone, mixing with the feedstock for the carbon black into the hot exhaust in the reaction zone, and terminating the formation of the carbon black in the termination zone by water injection, characterized in that in the first third of the reaction zone, from 20% to 58% by weight of the feedstock for the carbon black is added radially through a nozzle, and the remaining amount of the feedstock for the carbon black is added to the reactor through the nozzle at least one other point upstream.

7. Use of the carbon black according to claim 1 as reinforcing or other filler, UV stabilizer, conductive carbon black or pigment.

8. Use of the carbon black according to claim 1 in rubber, plastics, printing inks, inkjet inks, other inks, toners, lacquers, coatings, paper, pastes, batteries, and in cosmetics, and in asphalt, concrete, flame retardant materials and other building materials.

9. Rubber mixture, characterized in that it comprises at least one rubber and at least one carbon black according to claim 1.

10. A rubber mixture according to claim 9, characterized in that the rubber is a diene rubber.

11. Rubber mixture according to claim 10, characterized in that the diene rubber is a natural rubber, an EPDM rubber or an SPR rubber.