CZ9903435A3 - Elastomeric compositions, with built in carbon black treated with metal - Google Patents

Abstract

The elastomeric composition comprises an elastomer, e.g., natural rubber, polybutadiene, and metal treated carbon black having a phase containing carbon black and a phase containing metal, and optionally binding agent. In a process for preparing metal treated carbon black, it is introduced at least one metal containing compound to the reactor together with a feedstock for producing carbon black at a temperature sufficient for decomposing the metal compound to form the metal treated carbon black. A method of making elastomeric compounds comprises kneading and mixing the metal-treated carbon black with the elastomer and optionally a binding agent to form the parent rubber composition, which further comprises a vulcanizing agent and optionally a binding agent to form the elastomeric compound.

Description

Technical field

The invention relates to novel aggregates and elastomeric compounds. In particular, the invention relates to metal-containing carbon blacks and elastomeric compounds in which such metal-containing carbon blacks, for example aluminum or zinc-treated carbon blacks, are incorporated and products made therefrom.

BACKGROUND OF THE INVENTION

Carbon black is widely used as pigments, fillers and reinforcing agents in the manufacture of rubber and other elastomeric compounds. Carbon blacks are particularly useful as reinforcing agents in the manufacture of elastomeric compounds for the manufacture of tires.

Carbon black is generally produced in a furnace reactor by pyrolysis of the hydrocarbon feedstock by hot off-gases to produce combustion products containing soot particles.

Carbon black exists in the form of aggregates. Aggregates, on the other hand, consist of soot particles. However, carbon black particles generally do not exist separately on the aggregate. Carbon blacks are typically characterized by analytical properties which include, but are not limited to, particle size and specific surface area; size, shape and distribution of aggregates; and chemical and physical surface properties. The properties of the carbon black are determined analytically using v

01-2319-99 Tests known in the art. For example, the nitrogen adsorbent surface area (measured according to ASTM Test Method D3037 - Method A) and the cetyltrimethylammonium bromide (CTAB) adsorption value (measured according to ASTM Test Method D3765 [09.01]) are specific surface area values. Absorption of dibutyl phthalate by ground carbon black (CDBP) (measured according to ASTM test procedure D3493-86) and unground carbon black (DBP) (measured according to ASTM test procedure D2414-93) are in turn values related to the aggregate structure. The bonded rubber value in turn refers to the surface activity of the carbon black. The properties of the carbon blacks depend on the process conditions and can be modified, for example, by changing the temperature, pressure, feedstock, reactor time, quenching temperature, production capacity, or other parameters.

In the manufacture of tires, it is generally desirable to use carbon black containing compounds for the manufacture of treads and other tire parts. A suitable tread compound is, for example, an elastomeric compound which imparts high abrasion resistance and a good hysteresis balance at various temperatures to the final tire. A tire that exhibits high abrasion resistance is desirable because abrasion resistance is directly proportional to its service life. In the case of tread compounds, the physical properties of the carbon black directly affect the abrasion resistance and hysteresis. Carbon blacks with a high surface area and small particle size will generally impart high abrasion resistance and high hysteresis to compounds intended for tread production. The concentration of the carbon black in the elastomeric compounds also affects the abrasion resistance of the elastomeric compounds. Abrasion resistance increases to a certain concentration with increasing concentration, while beyond this optimum concentration, abrasion resistance decreases.

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Hysteresis of an elastomeric compound refers to the energy consumed by cyclic deformation. In other words, the hysteresis of the elastomeric composition corresponds to the difference between the energy applied to the deformation of the elastomeric composition and the energy released upon regeneration of the elastomeric composition to its original, non-deformed state. Hysteresis is characterized by a loss tangent tan δ, which is the ratio of the loss module to the storage module (ie viscous module to elastic module). Tires made from a compound having a low hysteresis measured at higher temperatures, such as 40 ° C or higher, will have a reduced rolling resistance, which in turn will result in reduced fuel consumption for the vehicle that uses the tire. At the same time, tire treads with a higher hysteresis value, measured at low temperatures, for example 0 ° C or less, will have high shear resistance on wet roads, which will increase driving safety, so that a tread compound that exhibits low hysteresis at high temperatures and high hysteresis at low temperatures may be considered to have a good hysteresis balance.

There are a number of other applications where the carbon black is used to provide an elastomer that exhibits a good hysteresis balance but where abrasion resistance is not an important factor. Such applications include, but are not limited to, use in the manufacture of individual tire components, such as treads, sidewalls, carcasses, crowns, beads, cord fabric compositions; engine mounts; and drive and self-supporting belts.

Silica is also used as a reinforcing agent (or filler) for the elastomers. However, by using silica alone • · · ··········· · · · · · · · ·

01-2319-99 As a reinforcing agent for elastomer, poor performance is achieved compared to the results obtained using carbon black alone as a reinforcing agent. It is theoretically proven that a strong filler-filler interaction and a weak filler-elastomer interaction are due to poor silica performance. The silica-elastomer interaction can be enhanced by chemically coupling the two components with a chemical coupling agent, for example bis (3-triethoxysilylpropyl) tetrasulfane, which is commercially available as Si-69 from Degussa AG, Germany. Binding agents such as Si-69 form a chemical bond between the elastomer and the silica, thereby binding the silica to the elastomer.

In the case of chemical binding of silica to the elastomer, certain performance characteristics of the resulting elastomer composition of the composition are increased. When incorporated into tires, these elastomeric compounds provide an increased hysteresis balance, however, elastomeric compounds that contain silica as a basic reinforcing agent exhibit low thermal conductivity, high electrical resistance, high density, and poor processability.

When carbon black alone is used as a reinforcing agent in elastomeric compositions, it will not chemically bond to the elastomer, but the carbon black surface will provide many sites for interaction with the elastomer. Although the use of a binder for carbon black can provide some improvement in the performance of the elastomer composition, this improvement is not comparable to that achieved with the binder for silica.

It has been found that the hysteresis of the filled compounds is largely influenced by the filler network formed in the polymer matrix, which causes high hysteresis at high temperature, and

01-2319-99 Low hysteresis at low temperature, which is undesirable in tire production. A major factor in controlling filler network formation is the filler-filler interaction.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide compounds which can be incorporated as a filler into elastomeric compounds. In particular, it is an object of the invention to provide an elastomeric composition in which a metal treated carbon black, for example an aluminum or zinc treated carbon black, is incorporated. Another object of the invention is to provide an elastomeric compound in which metal treated carbon blacks are incorporated that can be effectively coupled to the elastomer by a coupling agent. Such carbon blacks may be used, for example, in compounds intended for the manufacture of tires, industrial rubber products and other rubber goods. Another object of the invention is to provide formulations comprising an elastomer selected from a variety of elastomers that are useful for various applications and metal treated carbon black.

Other features and advantages of the invention will become apparent from the following description. The invention may be practiced using the elements and combinations specifically described in the specification and the appended claims.

As already mentioned, the invention relates to metal-treated carbon blacks in the form of aggregates comprising at least one carbon black phase and one metal-containing species phase. The invention also relates to an elastomeric composition comprising an elastomer and a metal treated carbon black and optionally a binding agent. To the extent

The invention encompasses a variety of elastomers and formulations employing these elastomers. The invention also includes elastomeric compositions comprising an elastomer and a metal treated carbon black. The invention also relates to methods for making metal-treated elastomeric compounds and products made thereof.

Brief description of the pictures

Giant. 1 schematically illustrates a portion of one type of carbon black reactor that can be used to produce metal treated carbon blacks of the invention; and

Giant. 2 is a graph demonstrating hysteresis values at various stresses at 70 ° C for the elastomeric compositions of the invention.

The invention relates to metal treated carbon blacks. These metal-treated carbon blacks can be incorporated into elastomeric compounds for a variety of applications, such as tire manufacturing. The metal-treated carbon black is in the form of aggregates comprising at least the carbon black and the metal-containing phase. This metal-containing species includes compounds containing aluminum, zinc, magnesium, calcium, titanium, vanadium, cobalt, nickel, zirconium, tin, antimony, chromium, neodymium, lead, tellurium, barium, cesium, iron and molybdenum. Preferably, the metal-containing species phase is an aluminum or zinc-containing species phase. Metal containing species include, but are not limited to, metal oxides. The phase of the metal-containing species can be distributed to at least part of the aggregate and is an integral part of the aggregate. The metal treated carbon black according to the invention can be incorporated.

01-2319-99 for elastomeric compounds to which they can impart desirable properties.

Metal treated carbon black aggregates are not a mixture of discrete carbon black and metal containing discrete aggregates. The metal-treated carbon black aggregates of the invention include at least one metal-containing region concentrated on or near the aggregate surface (but which is an integral part of the aggregate) or within the aggregate so that, as mentioned, the metal-treated carbon black aggregates can be described as aggregates containing a carbon black phase and a metal containing phase. Thus, the aggregates comprise at least two phases, one of which is carbon black and the other is a metal containing species. The phase of the metal-containing species that is part of the aggregate is not bound to the carbon black aggregate as a silane coupling agent, but is a true part of that aggregate, as is the carbon black phase. Also encompassed by the invention are metal-treated carbon black aggregates comprising more than one type of metal-containing species phase, for example, a silicon-containing species phase and / or a boron-containing species phase. For example, the metal-treated carbon black may be part of an aggregate comprising a carbon black phase, an aluminum-containing species phase, and a zinc-containing species phase. It follows from the above that the metal treated carbon blacks of the invention may have two or more different types of metal-containing species phases and / or other non-metallic species phases.

As indicated above, the aggregate of the invention may further comprise a phase of a silicon-containing species, see US patent applications 08 / 446,141; US 08 / 446,142; US 08 / 528,895; and US 08 / 750,017 and published PCT application WO 96/37547, which are incorporated herein by reference.

01-2319-99 »· · φ φ φ · · · · · · · · · · · ·

Metal treated carbon black can be obtained by producing carbon black in the presence of volatile or decomposable metal containing compounds. Such carbon black is preferably produced in the modular or "stepped furnace carbon black reactor" shown in FIG. A furnace soot reactor has a combustion zone 11 with a tapered diameter zone 2, a zone 3 for injecting a reduced diameter feedstock, and a reaction zone 4.

In the production of the carbon black in the reactor described above, hot combustion gases are generated in the combustion zone 1 by contacting a liquid or gaseous fuel with a stream of a suitable oxidizing agent, for example air, oxygen or a mixture of air and oxygen. Fuels which are suitable for contacting the oxidant stream in the combustion zone 1 and thus for generating hot off-gases include streams of easily combustible gases, vapors or liquids such as natural gas, hydrogen, methane, acetylene, alcohols or kerosene. However, it is generally preferred to use fuels having a high content of carbon-containing components, and in particular the use of hydrocarbons. The air to fuel ratio varies with the type of fuel used. When natural gas is used to produce the carbon black of the present invention, the air to fuel ratio may range from about 10: 1 to 1000: 1. Preheating of the oxidant stream facilitates the production of hot off-gases.

The hot off-gas stream flows from zones 1 and 2 to zones 3 and 4. The flow direction of the hot off-gases is shown in FIG. 1 is shown by an arrow. The carbon black feedstock 6 is introduced into the feedstock injection zone 3 at point 7. The feedstock is injected into the gas stream through nozzles that are designed to optimally

01-2319-99 Distributed oil to the gas stream by 9 Φ «φ φ φ φ» »» »» »» »» »» »» »» » These nozzles can be either single or double-fluid. Dual-fluid nozzles may use steam or air to atomize the fuel. In the case of single-fluid nozzles, the feedstock is atomized under pressure or may be injected directly into the gas stream. In the latter case, the spraying provides a gas stream.

Carbon black can be produced by pyrolysis or incomplete combustion of any liquid or gaseous hydrocarbon. Preferred carbon black feedstocks include petroleum refinery sources, for example, decanted oils from catalytic cracking processes, as well as by-products from coking and olefin production.

The mixture of the carbon black yielding feedstock and the hot off-gases flows through zones 3 and 4. In the reactor reaction zone, the feedstock is pyrolyzed to carbon black. The reaction is maintained in the quench zone of the reactor. The quenching zone 8 is the next part of the reaction zone in which the quenching liquid, typically water, is sprayed into the stream of newly formed carbon black portions. Quenching serves to cool the carbon black particles, reduce the temperature of the gaseous stream, and reduce the reaction rate. Q is the distance from the beginning of the reaction zone 8 to the quenching point 8 and varies with the location of the quenching zone. The quenching may optionally be stepwise or may be carried out at several points in the reactor. After the soot has been quenched, the cooled gases and soot will pass to any conventional coolant and release agent where the soot is recovered. Conventional means, such as a cyclone separator, bag filter or other means known in the art, are used to separate the carbon black from the gas stream. After separating the carbon black from the gas stream, the carbon black is optionally processed into pellets.

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The metal-treated carbon black according to the invention can be produced by introducing a volatile compound containing the carbon black. metal to the carbon black reactor at a point upstream of the quench zone. Useful volatile compounds (i.e., metal containing compounds) include any compound that is volatile at the operating temperature of the carbon black reactor. Examples include volatile or decomposition compounds that include aluminum, zinc, magnesium, calcium, titanium, vanadium, cobalt, nickel, zirconium, tin, antimony, chromium, neodymium, lead, tellurium, barium, cesium, iron, and molybdenum. Specific examples include but are not limited to butoxides, for example, aluminum n-butoxide and aluminum s-butoxide, and propoxides, for example, aluminum isopropoxide. Examples of suitable zinc-containing compounds include, but are not limited to, zinc naphthenate octoate. Other examples include calcium, zinc and non-limiting magnesium, magnesium, titanium isopropoxide isopropoxide, cobalt naphthenate, tin diethyloxide, neodynoxalate, and the like by way of method. The percentage by weight of elemental metal (e.g. elemental aluminum or zinc) in the treated carbon black is generally from about 0.1 to 25% by weight. but may be set at any desired level, for example up to 50 wt%, more than 50 wt%. or up to 99 wt. aggregate.

The volatile compound may be premixed with the carbon black feedstock and introduced into the reaction zone together with the carbon black feedstock. Alternatively, the volatile compound can be introduced into the reaction zone separately. The point of introduction of the compound may be upstream or downstream of the injection point for the feedstock, provided that the point of introduction of the volatile compound is upstream of the quench zone.

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For example, the volatile compound can be introduced into zone Q at point 12 or at any other reaction point in the zone, see FIG. 1. After evaporation and exposure to high temperatures in the reactor, this compound decomposes and reacts with other species in the reaction zone so that the metal or metal-containing species becomes an integral part of the carbon black and gives the metal treated carbon black.

In addition to volatile compounds, metal-containing compounds which are decomposed but not necessarily volatile can also be used to obtain the metal-treated carbon black.

As will be discussed in more detail below, if the volatile compound is introduced into the reactor substantially simultaneously with the feedstock, then the metal-treated areas are dispersed in at least a portion of the carbon black aggregate.

In the second embodiment of the invention, the volatile compound is introduced into the reaction zone after the formation of the carbon black, but before the reaction stream is cooled. In this embodiment metal-treated carbon black aggregates are obtained in which the phase of the metal-containing species is concentrated predominantly on or near the surface of the aggregate.

It has been found that elastomeric compounds in which metal treated carbon black is incorporated can be further combined with one or more binders to further improve the properties of the elastomeric compound. Binding agents as used herein include, but are not limited to, compounds that are capable of binding fillers such as carbon black or silica to an elastomer. Binding agents useful for binding silica or carbon black are expected to be useful for metal treated carbon blacks. Useful coupling agents include, but are not limited to, silane coupling agents, for example bis (3-triethoxy01-2319-99 Ce).

• t · 44 4 · 4 » 4 «4 4 ♦ 4 4 4 * Φ 4 9 44 4 4 9 4 4 4 4 4 9 9 • 4 4 • • 4 4 444 94 • · 4 444 • · 4 4

silylpropyl) tetrasulfan (Si-69), 3-thiocyanatopropyltriethoxysilane (Si-264, Degussa AG, Germany), g-mercaptopropyltrimethoxysilane (A189, Union Carbide Corp., Danbury, Connecticut); zirconate binding agents, for example zirconium dialkanolatodi (3-mercapto) propionate-0 (NZ 66A, Kenrich Petrochemicals, Inc., Bayonne, New Jersey); titanate binders; nitro-coupling agents such as N, N'-bis (2-methyl-2-nitropropyl) -1,6-diaminohexane (Sumifine 1162, Sumitomo Chemical Co., Japan); and mixtures thereof. A binder may be a mixture of a binder with a suitable carrier, for example X50-S, which is a mixture of Si-69 and N330 carbon black from Degussa AG.

The metal treated carbon black may also be modified to contain at least one organic group. Thus, alternatively or additionally, a mixture of metal-treated carbon black and modified carbon black having at least one organic group attached thereto may be used. The invention also encompasses the use of a mixture of two or more types of metal-treated carbon black in the elastomeric compositions of the invention.

Methods for attaching organic groups to carbon black and further discussion of the types of organic groups that can be attached to carbon black can be found in U.S. Patent Applications 08 / 356,660; US 08 / 572,525; and US 08 / 356,459, current US Patent 5,559,169; and PCT published applications WO 96/18688 and WO 96/18696, which are incorporated herein by reference.

One method of attaching an organic group to a carbon black comprises reacting at least one diazonium salt with a carbon black in the absence of an externally applied stream sufficient to reduce the diazonium salt. In other words, the reaction between the diazonium salt and the carbon black takes place without an external source

01-2319-99 Če

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an electron sufficient to reduce the diazonium salt. Mixtures of different diazonium salts may be used in the process of the invention. This process can be carried out under a variety of reaction conditions and in any type of reaction medium including protic and aprotic solvent systems or suspensions.

In another method, a diazonium salt is reacted with a carbon black in a protic reaction medium; the diazonium salts of the present invention may be used. This process can also be used for various reaction conditions.

at least one when making mixtures of different perform in

Preferably, in both methods described, the diazonium salt is formed in situ. If desired, in both methods the carbon black product can be isolated and dried by means known in the art. In addition, the final carbon black product can be treated by known techniques to remove all impurities. Various preferred embodiments of these methods are described below.

These methods can be performed under a variety of conditions and are generally not limited to a particular condition. The reaction conditions must be such that the diazonium salt in question is sufficiently stable to react with the carbon black. Thus, these processes can be carried out under reaction conditions that allow a short lifetime of the diazonium salt. The reaction between the diazonium salt and the carbon black takes place, for example, over a wide range of pH values and temperatures. The methods can be carried out in both acidic and neutral and basic environments. Preferably, the pH is from about 1 to 9. The reaction temperature may preferably be from 0 ° C to 100 ° C.

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Diazonium salts known in the art can be prepared, for example, by reaction of primary amines with aqueous nitric acid solutions. A general discussion of diazonium salts and methods for their preparation can be found in Morrison and Boyd, Organic Chemistry, 5th Edition, p. 973983, (Allyn and Bacon Inc., 1987) and in March, Advanced Organic Chemistry: Reactions, Mechanisms, _and Structures,

4th edition, (Wiley, 1992). According to the invention, the diazonium salt is an organic compound having at least one diazonium group.

The diazonium salt may be prepared prior to reaction with the carbon black, or more preferably, may be generated in situ using known techniques. In situ generation also allows the use of unstable diazonium salts, for example alkyl diazonium salts, and eliminates unnecessary manipulation of the diazonium salt. In particularly preferred methods, both nitrous acid and diazonium salt are generated in situ.

The diazonium salt known in the art can be prepared by reacting the primary amine with nitrite and acid. The nitrite may be any metal nitrite, preferably lithium nitrite, sodium nitrite, potassium nitrite or zinc nitrite, or any organic nitrite, for example isoamyl nitrite or ethyl nitrite. The acid may be any acid, organic or inorganic, which is effective in the preparation of the diazonium salt. Preferably, the acids include nitric acid (HNO ₃ ), hydrochloric acid (HCl) and sulfuric acid (H 2 SO 4).

The diazonium salt can also be prepared by reacting the primary amine with an aqueous solution of nitrogen dioxide. Aqueous solution of nitrogen dioxide (NO ₂ / H ₂ O)

AND

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01-2319-99 provides nitrous acid, which is needed to generate the diazonium salt.

The preparation of the diazonium salt in the presence of excess hydrochloric acid may be less advantageous than the other alternatives because hydrochloric acid corrodes stainless steel. Another advantage of the preparation of the diazonium salt by means of an aqueous solution of nitrogen dioxide is its low corrosive effect on stainless steel and other metals commonly used in the production of reaction vessels. Preparation using sulfuric acid and sodium nitrite or nitric acid and sodium nitrite is also relatively non-corrosive.

Generally, the preparation of the diazonium salt from the primary amine, nitrite and acid requires two equivalents of acid based on the amount of amine used. In an in situ process, the diazonium salt can be generated using one equivalent of acid. If the primary amine contains a strong acid group, the addition of a separate acid is not necessary. The acid group or groups of the primary amine may supply one or both of the necessary acid equivalents. If the primary amine contains a strong acid group, then preferably no further acid is added to the process of the invention to generate the diazonium salt in situ, or no more than one equivalent of the additionally added acid is added. The additionally added acid can be used in a slight excess. An example of a useful primary amine is paraaminobenzenesulfonic acid (sulfanilic acid).

Diazonium salts are generally thermally unstable. They are generally prepared in solution at low temperatures, for example 0 ° C to 5 ° C and used without isolation of the salt. Heating of a solution of some diazonium salts may occur

01-2319-99 Če

99 99 99 99

9 9 9 9 9

98 9 9 9 9 9 9 9

9 9 9 9 9 9

9 9 9 9 9 9 9 9 • 99 99 99 9999 99 99 to release nitrogen and either to generate the corresponding alcohols in the acid medium or to produce organic free radicals in the basic medium.

However, in the case of diazonium salts, it is only necessary that they are sufficiently stable and able to react with the carbon black, so that the processes can be performed using some diazonium salts, which may otherwise be considered unstable and subject to decomposition. Some degradation processes may compete with the reaction between the carbon black and the diazonium salt and may reduce the total number of organic groups bound to the carbon black. In addition, the reaction could be carried out at elevated temperatures at which many diazonium salts tend to decompose. Elevated temperatures may also advantageously increase the solubility of the diazonium salt in the reaction medium and improve its processability during the process. However, elevated temperatures may lead to some losses of the diazonium salt, which may cause further decomposition processes.

The reagents used to prepare the diazonium salt in situ may be added to the carbon black slurry in the reaction medium, for example in water, so that the carbon black slurry to be used may already contain one or more diazonium salt reagents and the process may be completed by adding the remaining reagents.

The reactions used to prepare the diazonium salt are compatible with a wide variety of functional groups commonly found in organic compounds. Thus, the process of the invention will only limit the availability of the diazonium salt for reaction with the carbon black.

The methods of the invention can be carried out in any reaction medium that allows the reaction to proceed between

01-2319-99 English • ·· fefe fefe fefe fefe • fefe fefefe ···· • fefefe fefe · ···· • fefe fefe · · fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe fefe soot. A preferred reaction medium is a solvent-based system. The solvent may be a protic solvent, an aprotic solvent or a mixture of solvents. Protic solvents are solvents, for example water or methanol, which contain hydrogen bonded to oxygen or nitrogen and which are therefore sufficiently acidic to form hydrogen bonds. Aprotic solvents are solvents that do not contain acidic hydrogen as defined above. Aprotic solvents include, for example, solvents such as hexanes, tetrahydrofuran (THF), acetonitrile, and benzonitrile. A discussion of protic and aprotic solvents can be found in Morrison and Boyd, Organic Chemistry, 5th Edition, pp. 228-231, (Allyn and Bacon, Inc., 1987).

The methods are preferably carried out in a protic reaction medium, i. in a protic solvent alone or in a solvent mixture comprising at least one protic solvent. Preferred protic media include, but are not limited to, water, aqueous media containing water and other solvents, alcohols, and any alcohol containing media, or mixtures thereof.

The reaction between the diazonium salt and the carbon black may be carried out using any type of carbon black, for example, in a fluffy or pelletized form. In one embodiment, which aims to reduce manufacturing costs, the reaction can be performed during the production of the carbon black pellets. For example, the carbon black product of the present invention can be produced in a dry drum by spraying a solution or suspension of a diazonium salt onto carbon black. Alternatively, the carbon black product may be prepared by pelletizing the carbon black in the presence of a solvent system such as water containing a diazonium salt or reagents to generate a carbon black product.

01-2319-99 Če

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Z ΦΦ ΦΦ ΦΦΦΦ ΦΦ ΦΦ diazonium salts in situ. Aqueous solvent systems are preferred. Thus, another embodiment of the present invention provides a method for producing a carbon black product in the form of pellets comprising: introducing a carbon black and an aqueous suspension or solution of a diazonium salt into a pelletizer, reacting the diazonium salt with the carbon blacks to bind the organic group to the carbon black; bound organic group. The pelletized carbon black product can then be dried using conventional techniques.

These processes generally produce inorganic by-products, for example salts. Some end users, such as those described below, consider these by-products undesirable. There are several possible methods for producing the carbon black product without the undesirable inorganic by-products or salts that follow.

First, the diazonium salt can be purified prior to use by removing the undesirable inorganic by-product using means known in the art. Secondly, the diazonium salt can be generated using an organic nitrite as the diazotizing agent to yield the corresponding alcohol rather than an inorganic salt, and thirdly, the diazonium salt can be prepared from an amine having an acid group and an aqueous solution of nitrogen dioxide which also does not form. no inorganic salts. It will be understood that other methods will be apparent to those skilled in the art.

In addition to inorganic by-products, the process can also produce organic by-products that can be removed, for example, by extraction with organic solvents. Other ways of obtaining products without undesirable organic

Fcfc · fcfc fcfc · fcfc fcfc · fcfc fcfc fcfc fcfc fcfc fcfc fcfc fcfc · fcfc fcfc · fcfc The byc products are known to those skilled in the art and include reverse osmosis elution or ion removal.

The reaction between the diazonium salt and the carbon black produces a carbon black product in which organic groups are attached to the carbon black. The diazonium salt may contain an organic group to be attached to the carbon black. It is possible to produce the carbon black products of the invention by other means known in the art.

The organic group may be an aliphatic group, a cyclic organic group, or an organic group having an aliphatic moiety and a cyclic moiety. As discussed above, the diazonium salt useful in the process of the present invention can be derived from a primary amine having one of these groups and capable of forming a transiently diazonium salt. The organic group may be substituted or unsubstituted and branched or unbranched. Aliphatic groups include, for example, groups derived from alkanes, alkenes, alcohols, ethers, aldehydes, ketones, carboxylic acids, and sugars. Cyclic organic groups include, but are not limited to, alicyclic hydrocarbon groups (e.g., cycloalkyl and cycloalkenyl groups), heterocyclic hydrocarbon groups (e.g., pyrrolidinyl, pyrrolinyl, piperidinyl, morpholinyl, and the like), aryl groups (e.g., phenyl, naphthyl, anthracenyl) and the like) and heteroaryl groups (imidazolyl, pyrazolyl, pyridinyl, thienyl, thiazolyl, furyl, indolyl, etc.). With increasing spherical inhibition substituted organic

01-2319-99 English • 9 99 «9 4 • 9 9 Λ

The 9999 group reduces the number of organic groups attached to the carbon black by reaction between the diazonium salt and the carbon black.

If the organic group is substituted, it may contain any functional group compatible with the formation of the diazonium salt. Preferred functional groups include, but are not limited to, R, OR, COR, COOR, OCOR, carboxylate salts such as COOL 1, COONa, COOK, COO-NR ₄ ⁺ , halogen, cyano, NR 2, sulfite, sulfonate salts such as lithium sulfonate, sodium sulfonate, potassium sulfonate, SO3 ⁺ NR4 ⁺ , sulfates and salts of sulfuric acid, NR (COR), C0NR2, nitro, phosphonic acid, phosphonate salts such as sodium hydrogen phosphonate and sodium phosphonate, phosphate salts such as sodium hydrogen phosphate and sodium phosphate , N = NR, NR ₃ ⁺ X ', PR3 ⁺ X, SkR, SSO ₃ H, SS0 ₃ salts, SO ₂ NRR', SO ₂ SR, SNRR ', SNQ, SO ₂ NQ, CO ₂ NQ, S- ( 1,4-piperazinediyl) -SR, 2- (1,3-dithianyl), 2- (1,3-dithiolanyl),

SOR and SO ₂ R. R and R ', which may be the same or different, are independently hydrogen, branched or unbranched, substituted or unsubstituted, saturated or unsaturated hydrocarbon having 1 to 20 carbon atoms, for example alkyl, alkenyl, alkynyl a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkylaryl group, or a substituted or unsubstituted arylalkyl group. The subscript k is an integer from 1 to 8 and preferably from 2 to 4. Anion X 'is a halide group or an acid-derived anion. The substituent Q is (CH ₂ ) _x NR (CH ₂ ) z or (CH ₂ ) _X S (CH ₂ ) _z , in which the subscript w is an integer from 2 to 6 and the subscripts x and z are integers from 1 to 6 .

mineral organic (CH ₂ ) _w , (CH ₂ ) _x 0 (CH ₂ ) _z ,

01-2319-99 Če

• 99 99 «· 99 ·· 99 9 9 • • · • 9 • · • 999 9 • 9 • · • · 9 9 9 • • 9 • · • 9 999 99 ·· 9990 ·· 99

A preferred organic group is an aromatic group of formula A _y Ar -, which corresponds to the primary amine of formula A _y ArNH ₂ . In the general formula, the individual variables have the following meanings: Ar represents an aromatic radical such as an aryl or heteroaryl group. Preferably, Ar is selected from the group consisting of phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, pyridinyl, benzothiadiazolyl and benzothiazolyl. A represents a substituent on an aromatic radical independently selected from the preferred functional groups described above or A represents a linear, branched or cyclic hydrocarbon radical (preferably containing 1 to 20 carbon atoms) which is unsubstituted or substituted by at least one of the functional groups, and lower the index y represents an integer from 1 to the total number of -CH radicals in the aromatic radical. For example, if Ar is a phenyl group, then subscript y is an integer from 1 to 5, if Ar is naphthyl, then subscript y is 1 to 7, when Ar is anthracenyl, phenanthrenyl, or biphenyl, then subscript y is 1-9 and when Ar is pyridinyl group, the subscript y is 1 to 4. In the general formula above are specific examples of R and R 'are NH ₂ -C ₆ H ₄ -, CH ₂ CH ₂ C _s H ₄ -NH ₂ , CH ₂ -C ₆ H ₄ -NH ₂ and C ₆ H ₅ .

Another preferred set of organic groups that can be attached to the carbon black are organic groups substituted with an ionic or ionizable group that form a functional group. An ionizable group is a group which is capable of forming an ionic group in the medium used. Ionic

01-2319-99 Če

9 99 99 99 99 99 • 9 • • • 9 9 9 «9 • 999 • • • 9 9 9 9 9 9 9 9 • • • 9 9 9 99 99 99 ···· 9 · 99

the group may be an anionic group or a cationic group and the ionizable group may form an anion or a cation.

Ionizable functional groups forming anions include, for example, acid groups or salts of acid groups. Organic groups thus include groups derived from organic acids. Preferably, it comprises an ionizable anion forming group, for example an organic group having a) an aromatic group and b) at least one acid group having a pKa of less than 11 or at least one salt of the acid group having a pKa of less than 11 or a mixture of at least one acid group with pKa less than 11 and at least one acid group salt with a pKa of less than 11. The pKa of the acid group refers to the pKa of the organic group as a whole, and not only the acid substituent. More preferably, the pK a is less than 10 and most preferably less than 9. Preferably, the aromatic group of the organic group is directly attached to the carbon black. The aromatic group may be unsubstituted or may be further substituted, for example by alkyl groups. More preferably, the organic group is a phenyl group or a naphthyl group and the acid group is a sulfonic acid group, a sulfinic acid group, a phosphonic acid group or a carboxylic acid group. Examples of these acid groups and their salts are discussed above. Most preferably, the organic group is a substituted or unsubstituted sulfophenyl group or a salt thereof;

substituted or unsubstituted (polysulfo) phenyl or a salt thereof; substituted or unsubstituted sulfonaphthyl or a salt thereof; or a substituted or unsubstituted (polysulfo) naphthyl group or a salt thereof. Preferred substituted

The sulfophenyl group is a hydroxysulfophenyl group or a salt thereof.

Specific organic groups having an ionizable anion-forming functional group (and their corresponding primary amines) are p-sulfophenyl (p-sulfanilic acid), 4-hydroxy-3-sulfophenyl (2-hydroxy-5-aminobenzenesulfonic acid) and 2-sulfoethyl ( 2-aminoethanesulfonic acid). Other organic groups having ionizable anionic functional groups may also be used.

Amines represent examples of ionizable functional groups that form cationic groups. For example, amines can be protonated to form ammonium groups in acidic media. Preferably, the organic group having an amine substituent pKb is less than 5. Quaternary ammonium groups (- NR ₃ ⁺ ) and quaternary phosphonium groups (-PR ³⁺ ) also represent examples of cationic groups. The organic group preferably contains an aromatic group such as a phenyl or naphthyl group and a quaternary ammonium or quaternary phosphonium group. The aromatic group is preferably attached directly to the carbon black. Quaternized cyclic amines as well as quaternized aromatic amines can also be used as an organic group. Thus, N-substituted pyridinium compounds such as N-methylpyridyl may be used in this regard. Examples of organic groups include, without limitation, (C 5 H ₄ N) C ₂ H ₅ ^+, C6H4 (NC5H5) ⁺ CSH ₄ COCH ₂ N _{(CH3) ^3+,} C6H4COCH2 (NC5H5) ^+, (C 5 H ₄ N) CH ₃ ^+, and C _S H ₄ CH ₂ N (CH _{3) 3} ^+.

The advantage of carbon black products having an attached organic group substituted by an ionic or ionizable group is that the carbon black product can

01-2319-99 How to increase the water dispersibility compared to the corresponding untreated carbon black. The aqueous dispersibility of the carbon black product increases along with the number of carbon black groups attached to the carbon black having at least one ionizable group bound to the organic group, so increasing the number of ionizable groups associated with the carbon black product should increase the aqueous dispersibility of the carbon black product. required level. It should be noted that the aqueous dispersibility of the carbon black product containing an amine bound as an organic group can be increased by acidifying the aqueous medium.

Since the aqueous dispersibility of the carbon black products depends to some extent on charge stabilization, it is preferred that the ionic strength of the aqueous medium be less than 0.1 molar. More preferably, the ionic strength is less than 0.01 molar.

When such a water dispersible carbon black product is prepared, it is preferred that the ionic or ionizable group be ionized in the reaction medium. The resulting product solution or suspension may be used as such or may be diluted prior to use. Alternatively, the carbon black product may be dried using techniques used for conventional carbon black. These techniques include, but are not limited to, kiln or rotary kiln drying. However, over-drying may result in the loss of some degree of water dispersibility.

In addition to their aqueous dispersibility, carbon black products having an organic group substituted with an ionic or ionizable group may also be dispersible in polar organic solvents, for example dimethylsulfoxide (DMSO) and formamide. Dispersibility of carbon black products having an organic group containing

01-2319-99 The use of complexing agents such as crown ethers can increase the acid group of a metal salt in alcohols, such as ethanol or methanol.

Aromatic sulfides form another group of preferred organic groups. Carbon black products having aromatic sulfide groups are particularly useful in rubber compositions. These aromatic compounds represented by the general formulas may be sulfides

Ar (CH ₂ ) _q S _k (CH ₂ ) _r Ar 'or

Ar (CH ₂ ) _q S _k (CH ₂ ) _r Ar 'in which Ar

Ar 'is independently substituted or unsubstituted arylene or heteroarylene groups, Ar' is aryl or heteroaryl, the subscript k is 1 to 8 and the subscripts q and r are 0 to 4. Substituted aryl groups would include substituted alkylaryl groups. Preferred arylene groups include phenylene groups and especially p-phenylene groups or benzothiazolylene groups. Preferred aryl groups include phenyl, naphthyl and benzothiazolyl. The number of sulfur atoms present, defined by the subscript k, is preferably in the range from 2 to 4. Preferred carbon black products are those having an aromatic sulfide organic group of the formula (C ₅ H ₄ ) -S _k - (C ₆ H) ₄ ) -, wherein the subscript k is an integer from 1 to 8 and more preferably from 2 to 4. Particularly preferred aromatic sulfide groups are bis-para- (C ₆ H ₄ ) -S ₂ (C ₆ H ₄ ) - and para- (C ₆ H ₄ ) -S ₂ - (C ₆ H ₅ ). Diazonium salts of these aromatic sulfide groups can be conveniently prepared from the corresponding primary amines H ₂ N-Ar-S _to -Ar'-NH ₂ or H ₂ NAr-Sk-Ar ''. Preferred groups include dithiodi-4,1-phenylene, tetrathiodi-4,1-phenylene, phenyldithiophenylene, dithiodi-4,1 (3-chlorophenylene), - (4- _{δ δ} Η ₄ ) -SS- (2-C ₇ H) ₄ NS), - (4-C ₆ H ₄₎ -S-S01-2319-99 Ce (4-C ₆ H ₄₎ -OH, -6- (2-C7H3NS) -SH, - _(4-C H ₄ ) -CH ₂ CH ₂ -SS-CH ₂ CH ₂ - (4C ₆ H ₄ ) -, - (4-C _with H ₄ ) -CH ₂ CH ₂ -SSS-CH ₂ CH ₂ - (4-C _with H ₄ ) -, - (2-C ₆ H ₄ ) -SS- (2-C ₆ H ₄ ) -, - (3-C ₆ H ₄ ) -SS- (3-C _with H ₄ ) -, -6- (C ₆ H ₃ N ₂ S) -6- (2C7H3NS) -S-NRR 'groups where RR' is _{-CH2 CH2 OCH2 CH2} -, - (4C ₆ H ₄₎ -SSSS - (4-C _with H ₄ ) -, - (4-C _with H ₄ ) -CH = CH ₂ , - (4-C _with H ₄ ) -S-SO 3 H,

- (4-C ₆ H ₄ ) -SO ₂ NH- (4-C ₆ H ₄ ) -SS- (4-C ₆ H ₄ ) -NHSO ₂ - (4-C ₆ H ₄ ) -, -6- (2C7H3NS) -SS-2- (6-C7H3NS) -, - (4C ₆ H ₄₎ -S-CH ₂ - (4C _s H ₄₎ -, - (4C ₆ H ₄₎ -SO ₂ S- (4-C ₆ H ₄₎ - (4-C ₆ H ₄₎ -CH ₂ -S-CH ₂ - (4-C ₆ H ₄₎ -, - (3-C ₆ H ₄₎ CH ₂ -S-CH ₂ - (3-C ₆ H ₄ ) -, - (4-C _with H ₄ ) -CH ₂ -SS-CH ₂ - (4-C ₆ H ₄ ) -, - (3C _with H ₄ ) -CH ₂ -SS-CH ₂ - (3-C _with H ₄ ) -, - (4-C ₆ H ₄ ) -S-NRR ', wherein RR' is CH ₂ CH ₂ OCH ₂ CH ₂ - , - (4-C ₆ H ₄ ) -SO ₂ NH-CH ₂ CH ₂ -SS-CH ₂ CH ₂ NHSO ₂ - (4-C ₆ H ₄ ) -, - (4-C ₆ H ₄ ) -2 - (1, 3-dithianyl), and - (4-C ₆ H ₄₎ -S (1,4-piperizindiyl) -S- (4-C _e H ₄₎

Another preferred set of organic groups that can be attached to the carbon black are organic groups having an aminophenyl group, for example (C ₅ H ₄ ) -NH ₂ , (C ₆ H ₄ ) -CH ₂ (C ₅ H ₄ ) -NH ₂ (C _s H ₄₎ -SO ₂ - (C _s H ₄₎ -NH _second Preferred organic groups also include aromatic sulfides of the formula Ar-S _n -Ar 'or Ar-S _n -Ar'', in which Ar and Ar' are independently an arylene group, Ar '' is an aryl group and the subscript n is 1 to 1 Methods for attaching these organic groups to carbon black are discussed in U.S. Patent Applications 08 / 356,660, 08 / 572,525 and 08 / 356,459, which are incorporated herein by reference.

The invention furthermore relates to the use of a mixture of silica and metal treated with carbon black. Any combination of other metal-treated carbon black components may also be used. Such combinations are, for example, the following combinations:

01-2319-99 Če

(a) organic-bonded metal-treated carbon black, optionally treated with a silane coupling agent;

b) silica;

c) modified silica, for example with an attached organic group; or

(d) other inorganic fillers and their chemically modified derivatives;

(e) carbon black; or

(f) modified carbon black with an attached organic group;

(g) silicon-treated carbon black, where appropriate with attached organic groups.

Examples of silica include, but are not limited to, silica, precipitated silica, amorphous silica, quartz glass, fused silica, silicates (e.g. aluminosilicates) and other silicon-containing fillers such as clay, talc, wollastonite, etc. Silicas are commonly available from sources such as Cabot Corporation (under the trade names Cab-O-Sil), PPG 'Industries (under the trade names Hi-Sil and Ceptane), Rhone-Poulenc (under the trade names Zeosil) and Degussa AG (under the trade names Ultrašil and Coupsil).

The elastomeric compounds of the invention can be prepared from the treated carbon black by combining it with any of the elastomers that include elastomers useful for coupling with the carbon black.

01-2319-99 Če

Any suitable elastomer can be combined with the metal treated carbon black to prepare the elastomeric compound of the invention. Such elastomers include, but are not limited to, rubbers, homopolymers or copolymers of 1,3-butadiene, styrene, isoprene, isobutylene, 2,3-dimethyl-1,3-butadiene, acrylonitrile, ethylene, and propylene. The glass transition temperature (Tg) of the elastomers is preferably in the range of about -120 ° C to 0 ° C, as measured by differential scanning calorimetry (DSC). Examples of elastomers include, but are not limited to, styrene-butadiene rubber (SBR), natural rubber, polybutadiene, polyisoprene, and oil-based derivatives thereof. Mixtures of any of the above-mentioned elastomers may also be used.

The rubbers suitable for use in the present invention include natural rubber and its derivatives, for example chlorinated rubber. The metal-treated carbon black products of the invention can also be used as an additive in synthetic rubbers such as: copolymers of about 10 wt. % to 70 wt. % styrene and about 30 wt. % to 90 wt. butadiene, for example a copolymer of 19 parts styrene and 81 parts butadiene, a copolymer 30 parts styrene and 70 parts butadiene, a copolymer 43 parts styrene and 57 parts butadiene, and a copolymer 50 parts styrene and 50 parts butadiene; polymers and copolymers of conjugated dienes, for example polybutadiene, polyisoprene, polychloroprene and the like, and copolymers of these conjugated dienes with a copolymerizable ethylene group-containing monomer, for example styrene, methylstyrene, chlorostyrene, acrylonitrile, 2-vinylpyridine, 5-methyl-2-vinylpyridine ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine, alkyl-substituted acrylates, vinyl ketone, methylisopropenyl01-2319-99 ketone, methyl vinyl ether, α-methylenecarboxylic acids and their esters and amides, such as acrylic acid and dialkylacrylic acid amide; and copolymers of ethylene and other higher α-olefins, such as propylene, 1-butene and 1-pentene, are also suitable for use in the present invention.

Accordingly, the rubber compositions of the invention may comprise elastomer, vulcanizing agents, reinforcing filler, binding agent and optionally various processing aids, oil extenders and antidegradants. In addition to the above examples, the elastomer may be, for example, polymers (e.g., homopolymers, copolymers and terpolymers) made of 1,3-butadiene, styrene, isoprene, isobutylene, 2,3-dimethyl-1,3-butadiene, acrylonitrile, ethylene, propylene, and the like. It is preferred that the glass transition temperature (Tg) of these elastomers be between -120 ° C and 0 ° C as measured by DSC. Examples of such elastomers are poles (butadiene), styrene-butadiene copolymer and poles (isoprene).

Elastomeric compounds also include vulcanized compositions (VR), thermoplastic vulcanizates (TPV), thermoplastic elastomers (TPE), and thermoplastic polyolefins (TPO). Furthermore, TPV, TPE and TPO materials are characterized by their extrudability and multiple formability without loss of performance characteristics.

One or more vulcanizing agents, such as sulfur, sulfur donors, activators, accelerators, peroxides, and other systems used to vulcanize the elastomeric composition may be used in the manufacture of the elastomeric compositions.

· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

01-2319-99 Če

Formulation of the metal-treated carbon blacks of the present invention with elastomers provides advantages that do not occur when formulating elastomers with conventional carbon blacks.

The following examples are illustrative only, and are not intended to limit the scope of the invention as set forth in the appended claims.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

Using a pilot plant reactor as generally described in the specification, shown in FIG. 1, aluminum treated carbon black according to the invention was prepared. The reactor used had the following dimensions: D ₁ = 10 cm, D ₂ = 5 cm, D ₃ = 12.5 cm, Li = 10 cm, L ₂ = 12.5 cm, L ₃ = 17.5 cm, L ₄ = 30 , 48 cm and Q = 137.25 cm.

These conditions led to the production of carbon black designated by ASTM as N234. A commercially available example of N234 is Vulcan 7H from Cabot Corporation, Boston, Mass. In the production of the aluminum treated carbon blacks of the present invention, these conditions were changed by adding an aluminum-containing volatile compound to the reactor. The flow rate of the volatile compound was adjusted to affect the weight percent of aluminum in the aluminum-treated carbon black. The weight percent of aluminum in the treated carbon black was determined by ashing according to ASTM test procedure D-1506.

One such new aluminum-treated carbon black was produced by introducing a solution containing 70% of aluminum s-butoxide and% s-butanol into the hydrocarbon feedstock. This ·· ·· · · ··

01-2319-99 Če

31 compound is acquired from Gelest Inc., Tullytown, BYE. Resulting aluminum treated carbon black j sou marked as Al-CB1, Al- -CB2 and A1CB4. Introducing volatile

the aluminum-containing compounds to the reactor at point L4. different aluminum treated carbon black (A1-CB3) was prepared.

Since it is known that changes in the reaction temperature affect the surface area of the carbon black and that the reaction temperature is very sensitive to variation in the feedstock flow rate in the injection zone (zone 3 in Fig. 1), the feedstock flow rate has been reduced to approximately compensate for the volatile compound feed. containing aluminum, so that the reactor temperature remained constant. This resulted in a substantially constant outer surface area (measured as t area) of the carbon black produced. All other conditions were maintained at the values required for the production of carbon black N234. In the manufacture of sample CB3-A1, in which the volatile aluminum-containing compound fed to the reactor at point L _4, no such adjustment is needed. In order to maintain the specific structure of the carbon black N234, a structure control additive (potassium acetate solution) was injected into the feedstock. The flow rate of this additive was kept constant during the production of the aluminum-treated carbon black described in all the following examples.

The outer surface area (t-area) was measured according to ASTM D3037 - Method A for the nitrogen surface area. For this measurement, the nitrogen adsorption isotherm expanded to a maximum of 0.55 relative pressure. The relative pressure is the pressure (P) divided by the saturation pressure (P _o ) (the pressure at which nitrogen condenses). The thickness of the adsorption layer (ti) was then calculated using the following formula:

01-2319-99 Če

13.99 ¹ 7 ^ 034 - 1ο _§ (Ρ / Ρ _θ )

The values of the adsorbed nitrogen volume (V) were then plotted against the ti values. A line was drawn between the t1 points of 0.39 and 0.62 nm. Using the following formula, the t-area was obtained from the slope of this line:

t-area, m ² / gm = 15-47 x slope

TABLE. 1

A1-CB1 A1-CB2 A1-CB3 A1-CB4 Conditions Airflow, 1 / h 362.4 362.4 362.4 362.4 Gas flow rate, 1 / h 29, 251 29,138 29,110 29, 336 Starting material flow kg / h 58.06 6 6.68 74.39 64.41 Al compound flow rate kg / h 14,515 3, 629 3, 629 7,257

The surface area and aluminum content of the obtained carbon blacks were analyzed. These values are summarized in Table 2 below.

TABLE 2

t-Surface DBP CDBP % wt. Al N234 119 125, 8 101 0.03 A1-CB1 116 136 104 2.9 A1-CB2 128 123 98 0.9 A1-CB3 122 121 100 ALIGN! 0.8 A1-CB4 115 116 95 2.3

01-2319-99 Če

Example 2

A ZnO-treated carbon black and a ZnO-treated carbon black according to the invention were prepared using a pilot plant reactor. The reaction conditions defined in Table 3 below were used to produce the carbon black.

These conditions led to the formation of carbon black, which corresponds to ASTM designation N234. A commercially available example of N234 is Vulcan 7H from Cabot Corporation, Boston, Mass. In order to obtain zinc-treated carbon black and combinations of zinc-treated compounds and silicon-treated compounds for producing zinc-silicon-treated carbon blacks, these conditions were changed by adding a zinc-containing volatile compound to the reactor. The flow rate of the volatile compounds was adjusted to affect the weight percent of zinc and silicon in the treated carbon black. The weight percent of zinc and silicon in the treated carbon black was determined by ashing according to ASTM test procedure D-1506.

One such new carbon black was produced by introducing zinc octoate (C ₁₆ H ₃₀ O ₄ ) into the hydrocarbon feedstock. The resulting zinc-treated carbon black was designated herein as Zn-CB1 and Zn-CB2. Carbon black treated with a combination of zinc and silicon (Zn-Si-CB) was prepared by introducing a zinc-containing volatile compound (zinc octoate) and a silicon-containing volatile compound (octamethyltetrasiloxane) into the hydrocarbon feedstock.

Since changes in the reaction temperature are known to affect the surface area of the carbon black and the reaction temperature is very sensitive to variation in the feedstock flow rate in the injection zone (zone 3 in Fig. 1), the feedstock flow has been reduced to approximately compensate for the volatile feed.

01-2319-99 φ φ φ · · · φ φ φ φ • • • φ φ φ φ φ φ · · · φ φ · φ φ φ φ takže takže obsahující obsahující obsahující obsahující reactor remained constant. This resulted in a substantially constant outer surface area (measured as t area) of the carbon black produced. In order to maintain the specific structure of the carbon black N234, a structure control additive (potassium acetate solution) was injected into the feedstock. The flow rate of this additive was kept constant during the production of the zinc and silica treated carbon blacks described in all the following examples.

TABLE 3

Zn-CBl Zn-CB2 Zn-Si-CB Conditions Airflow, 1 / h 362.4 339, 7 362, 4 Gas flow rate, 1 / h 26, 90 26.98 26, 90 Starting material flow kg / h 63.73 47.53 61.55 Zn compound flow rate kg / h 5, 08 11.11 5.89 Si-compound flow rate, kg / h 0 0 2.90

The surface area and the content of silicon and zinc were analyzed for the final carbon black. These values are summarized in Table 4 below.

TABLE 4

t area DBP CDBP % wt. Zn % wt. Si N234 116.8 123.3 96 Zn-CBl 117.2 124.5 91.2 2.85 Zn-CB2 116 112.8 90.8 8 Zn-Si-CB 119.9 134.4 104.9 2.95 3.01

01-2319-99 Če

0 0 0 0 · 0 ·· · 0 · · 000 · 00 ··

0 * 0 ·· · 0 »·· 0 · 0 0 · 00 00 0 · 00 00 0 0 0 0000

00 00 00 00 00 00 00

Example 3 - Preparation of Elastomeric Compositions

The carbon black and multiphase aggregates of the previous examples were used to make elastomeric compositions. Elastomeric compositions in which the aluminum-treated carbon black, zinc-treated carbon black, and silicon-treated carbon black discussed above were incorporated using the following elastomers: SBR solution (Duradene 715 from the companies

Firestone Synthetic Rubber & Latex Co., Akron, Ohio, and NS 116 from Nippon Zeon Co., Japan), BR (polybutadiene, Taktene 1203 from Bayer Inc, Akron, Ohio). The elastomeric compositions had the following composition:

TABLE 5

N234 N234 (B) Al-CB Zn-CB Zn-Si-CB SBR solution 75 75 75 75 75 BR 25 25 25 25 25 N234 75 80 - - - Al-CB - - 75 - - Zn-CB - - - 80 - Zn-Si-CB - - - - 80 Si 69 (/ h) - - 4,5 - - Sundex 8125 25 32.5 25 32.5 32.5 Zinc oxide 3.5 3.5 3,5- 3, 5 3, 5 Stearic acid 2 2 2 2 2 Fexzone 7P 1.5 2 1.5 1.5 1.5 Sunproof Imp. 1.5 2.5 1.5 1.5 1.5 Durax 1.5 1.35 1, 5 1.5 1.5 Vanax DPG - - 1— “ O 0.5 0, 5 TMTD 0.4 - 0.4 - - Sulfur 1.4 1.4 1.4 1.4 1.4 Benzyl Tuex - - - 0.25 0.25

• ·

01-2319-99 Jun «« · · · ··· «··· ♦» «· ·······

Si 69 = bis (3-triethoxysilylpropyl) tetrasulfide, coupling agent from Deggusa AG, Germany;

Sundex 8125 = a high aromatic oil from R. E. Carrroll, Trenton, NJ;

Flexzone 7P = N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, an antioxidant from Uniroyal Chemical Co., Middlebury, CT;

Sunproof improved = a mixture of waxy materials from Uniroyal Chemical Co., Middlebury, CT;

Durax = N-cyclohexane-2-benzothiazolesulfenamide, an accelerator from R.T. Vanderbilt Co., Norwalk, CT .;

Vanax DPG = diphenyl guanidine, an accelerator from R.T. Vanderbilt Co., Norwalk, CT .;

Benzyl Teux = tetrabenzylthiuram disulfide, an accelerator from Uniroyal Chemical Co., Middleburg, CT;

TMTD = tetramethylthiuram disulfide, an accelerator from R. E. Carrroll, Trenton, NJ; and

Sulfur = crosslinking agent from R.E.Carroll,

Trenton, NJ.

Compounds were prepared using either a two-stage or three-stage mixing procedure. An Plasti-Corder EPL-V internal mixer (from CW Brabender, South Hackensack, New Jersey) equipped with a cam-type mixing head (600 ml capacity) was used to prepare the compounds. In the first step, the mixer is set at 80 ° C and rotor speed 60 min ^-1. In the case of the three-stage mixing, after the mixer was conditioned to 100 ° C by heating the training chamber, an elastomer was introduced into the chamber, which was kneaded for 1 minute. Then, the carbon black premixed with the binder (Si 69) was added. After further stirring for 2.5 minutes or when the temperature reached

0 0 0 0 0 0000 0 00 * 00 «0000 0 000 0 · 00 00 0

01-2319-99 Če 37 0 0 0 0 0 000 00 0 · 0 0 0 0 0 0000 00 00 approximately 160 ° C, oil was added. Seven minutes total time the mother rubber mixture ready in the first degree removed from the blender. This mixture then three times

passed through an open mill and stored at room temperature for two hours. In the second stage, the temperature of the mixing chamber set at 80 ° C and rotor speed 60 min ^-1. After the mixer was conditioned to 100 ° C by heating the training chamber, the first stage mother liquor was introduced into the mixer chamber, which was kneaded for 1 minute, after which time zinc oxide and stearic acid were added to the chamber. After another one minute, Flexzone 7P and Sunroof Improved were added. In the last step, the mixing chamber temperature was set to 80 ° C and a rotor speed of 35 min ^-1. The mother blend from the second stage was introduced into the conditioned mixer and stirred for one minute. Then, curing additives (including sulfur and accelerators) were added. After two minutes, the material was removed from the mixer and passed through an open mill three times.

The carbon black of the previous example was used for batches of compounds. Conventional carbon black N234 was used as a control. After mixing, each of the elastomeric compositions was vulcanized at 145 ° C to an optimum cure state, as determined by Monsanto ODR Rheometer.

Example 4 - Dynamic Hysteresis and Abrasion Resistance

For the elastomeric compositions prepared according to Example 3 above, the values of dynamic hysteresis and abrasion resistance were measured.

01-2319-99 Če

Φ · · φ φ φ »» »» »» »· · · · · · φ φ φ φ φ φ φ φ φ φ φ φ φ φ

Abrasion resistance was determined using the Lambourn type abrasion testing machine described in U.S. Pat. No. 4,995,197, which is incorporated herein by reference. The tests were performed at 14% shear. The percent shear was determined based on the relative velocities of the sample wheel and the grinding wheel. The abrasion index was calculated from the mass loss of the elastomer compound. Dynamic properties were determined using a direct deflection Rheometerics Dynamic Spectrometer II (RDS II, Rheometrics, Inc., N.J.). The measurements were performed at 0 ° C and 70 ° C, in the range of two direct amplitudes (DSA) of 0.2 to 120%. The maximum tan δ values on the direct deflection curves were read to compare the hysteresis of the individual elastomeric compounds.

TABLE 6

Tan δ at Low: 14 ° C Tan δ at 70 ° C Abrasion index at 14% shear Duradene 715 BR N234 0.451 0, 225 100 ALIGN! A1-CB1 0, 369 0.139 85, 0 A1-CB2 0, 407 0, 184 93, 2 A1-CB3 0, 399 0.173. 99, 3 A1-CB4 0, 393 0, 160 88, 4 NS116 / BR N234 0, 448 0, 241 100 ALIGN! A1-CB1 0, 410 0.129 83, 4 A1-CB2 0.451 0.177 101.0 A1-CB3 0.447 0, 157 93, 9 A1-CB4 0, 431 0.154 89, 5

01-2319-99 Če · · -23 -23 -23 -23 -23 -23 -23 -23 -23 -23 -23 -23 -23 -23 -23 -23 -23 -23 -23 -23 -23 -23 -23 · · * »· · · · · Pokračování pokračování ♦ pokračování pokračování pokračování pokračování pokračování

Tan δ at Low: 14 ° C Tan δ at 70 ° C Abrasion index at 14% shear Duradene 715 BR N234 (B) 0.492 0, 31 100 ALIGN! Zn-CBl 0.465 0, 268 81 Zn-CB2 0.455 0, 226 104 Zn-Si-CB 0.466 0.23 98

As can be seen from Table 4 and FIG. 2, tan δ values measured at 70 ° C decreased by 18.2 to 38.2% for Duradene 715 / BR and 26.6 to 46.5% for NS116 / BR polymer system, while tan δ, measured at 0 ° C, decreased by 11.0 to 18.2% for the Duradene 715 / BR and 0.7% to 8.4% for the NS116 / BR. In the case of abrasion resistance compared to that of N234, the maximum reduction was noted for A1-CB1-treated aluminum soot, which was 15% for Duradene 715 / BR and NS116 / BR

16.6%. The carbon black A1-CB2 and A1-CB3 showed abrasion resistance comparable to traditional carbon black. Zinc treated carbon black and zinc and silicon treated carbon black showed similar improvements in endpoints.

Shear resistance on a wet substrate was measured using an improved British Portable Skid Tester (BPST) and using the procedure described by Ouyang et al. (GB Ouyang, N. Tokita, CH Sheih; “Carbon Black Effects on Friction Properties of Tread Compound - Using a Modified ASTM-E303 Pendulum Skid Tester and Presented at the Rubber Division, ACS, Denver, Colorado, 18-21 May 1993). Friction coefficients are

01-2319-99 English 99 ti 49 44 4 9 9 4

443 4 9 · 4 4 4 4

4 4 4 4 4 · · · 4 4 9 • 4 4 4 4 4 4 4 4

444 94 44 4449 94 49 based on the compound loaded with N234 (100%). The higher the number, the higher the shear resistance on a wet substrate.

TABLE 7

Shear resistance on damp substrates% N234 100 ALIGN! Zn-CBl 102 Zn-CB2 104 Zn-Si-CB 106

All patents, patent applications, test methods, and publications mentioned herein are incorporated by reference.

Claims (70)

PATENT CLAIMS An elastomeric composition comprising an elastomer and an aggregate comprising a carbon black and a metal containing species. 2. The elastomeric compound of claim 1, wherein the metal-containing species comprises a magnesium-containing species phase, a calcium-containing species phase, a titanium-containing species phase, a vanadium-containing species phase, a cobalt-containing species phase, a nickel-containing species phase, a zirconium-containing species phase , tin-containing phase, antimony-containing phase, chromium-containing phase, neodymium-containing phase, lead-containing species phase, tellurium-containing phase, barium-containing phase, cesium-containing phase, iron-containing phase, molybdenum-containing phase or mixtures thereof. 3. The elastomeric compound of claim 1 wherein the metal-containing species phase comprises an aluminum-containing species phase. 01-2319-99 Če 0 · · «···· 4. The elastomeric compound of claim 1 wherein the metal-containing species phase comprises a zinc-containing species phase. 5. The elastomeric compound of claim 1, further comprising a binding agent. 6. The elastomeric compound of claim 1 wherein the phase of the metal containing species is predominantly on the surface of the aggregate. 7. The elastomeric compound of claim 1, wherein the metal-containing species phase is distributed throughout the aggregate. 8. The elastomeric compound of claim 1 wherein the elastomer comprises SBR solution, natural rubber, SBR functional solution, SBR emulsion, polybutadiene, polyisoprene, or mixtures thereof. 9. The elastomeric compound of claim 1, further comprising a filler. • · · 01-2319-99 Če 10. Elastomeric compound according to Claim 1 v y - marked by team oxidized. that stage kinds containing metal is e 11. Elastomeric compound according to Claim 1 you - marked by those m, further containing carbon black, silica, carbon blacks having an organic group bound thereto, silicon-treated carbon blacks, or combinations thereof. 12. The elastomeric compound of claim 1 wherein at least a portion of said aggregate has an organic group attached thereto and is optionally treated with a silane coupling agent. 13. The elastomeric compound of claim 1, further comprising carbon black having an organic group attached thereto. 14. The elastomeric compound of claim 1, further comprising carbon black. 15. The elastomeric compound of claim 1, wherein a portion of said aggregate has an organic group attached thereto, and the elastomeric compound further comprises a carbon black having an organic group attached thereto, silica, carbon black, or mixtures thereof. 01-2319-99 English · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · (>) · · · · · fefe · 16. The elastomeric compound of claim 1, wherein the phase of the metal containing species comprises about 0.1 wt. % to 25 wt. elemental metal, based on the weight of the aggregate. 17. The elastomeric compound of claim 16 wherein the metal-containing species phase comprises about 0.5 wt. % to 10 wt. elemental metal, based on the weight of the aggregate. 18. The elastomeric compound of claim 17, wherein the phase of the metal containing species comprises about 2 wt. % to 6 wt. elemental metal, based on the weight of the aggregate. 19. The elastomeric compound of claim 5, wherein the binding agent comprises a silane binding agent, a zirconate binding agent, a titanate binding agent, a nitro compound-based binding agent, or a mixture thereof. 20. The elastomeric compound of claim 5, wherein the binding agent comprises bis (3-triethoxysilylpropyl) tetrasulfan, 3-thiocyanatopropyltriethoxysilane, .gamma.-mercaptopropyltrimethoxysilane, zirconium dineoalkanolatodium (3-mercapto) propionate-O, .beta.-2-β, 2-β, 2-ε, nitropropyl) -1,6-diaminohexane or mixtures thereof. 01-2319-99 Če 21. The elastomeric compound of claim 5, wherein the binding agent comprises about 0.1-15 parts per hundred parts of elastomers. 22. An elastomeric compound comprising an elastomer and an aggregate comprising a carbon black and a metal containing phase, characterized in that the elastomer comprises ethylene propylene diene monomeric rubber, polychloroprene, natural rubber, hydrogenated nitrile butadiene rubber, nitrile butadiene rubber, chlorinated polyethylene, styrene butadiene rubber, polyepichlorohydrin, ethylene vinyl acetate or mixtures thereof. 23. The elastomeric compound of claim 22, wherein the aggregate comprises about 10 to 300 parts per hundred parts of elastomers. 24. The elastomeric compound of claim 23, wherein the aggregate comprises about 100 to 200 parts per hundred parts of elastomers. 25. The elastomeric compound of claim 24, wherein the aggregate comprises about 10 to 150 parts per hundred parts of elastomers. 01-2319-99 Če 26. The elastomeric compound of claim 25, wherein the aggregate comprises about 20 to 80 parts per hundred parts of elastomers. An article made from the elastomeric compound of claim 22. 28. A process for preparing a carbon black-containing aggregate and at least one metal-containing species phase comprising introducing at least one decomposed or volatile metal-containing compound into a reactor together with a carbon black feedstock or during carbon black formation at a temperature sufficient to decompose or evaporate said compound, and to form an aggregate comprising a carbon black phase and at least one phase of a metal containing species. 29. The method of claim 28, wherein the metal-containing species comprises a magnesium-containing species phase, a calcium-containing species phase, a titanium-containing species phase, a vanadium-containing species phase, a cobalt-containing species phase, a nickel-containing species phase, a zirconium-containing species phase. the tin-containing phase, the antimony-containing species phase, the chromium-containing species phase, the neodymium-containing phase, the lead-containing species phase, the tellurium-containing species phase, the barium-containing species phase, the cesium-containing species phase, the iron-containing species phase, the molybdenum-containing species phase; mixtures thereof. 01-2319-99 Če 47 ··· · · · · · · · ♦ ··· · · · ♦ · • · · ··· ··· • ·· ·· ·· ···· ·· ·· 30. The method of claim 28, v marked by kind containing metal includes phase species containing aluminum. 31. Method according to claim 28, v marked that species containing metal includes phase species containing zinc. 32. The method of Claim 28 in marked by the phase kind containing metal is mainly located on the aggregate surface. 33. The method of Claim 28 in marked in that the phase of the metal-containing species is distributed throughout the aggregate. 34. The method of claim 28, wherein the phase of the metal-containing species is oxidized. 35. The method of claim 28, wherein the metal-containing species phase comprises about 0.1 wt. % to 25 wt. elemental metal, based on the weight of the aggregate. • · · · · · · · · · · · · 01-2319-99 English • · 36. The method of claim 35, wherein the phase of the metal-containing species comprises about 0.5 wt. % to 10 wt. elemental metal, based on the weight of the aggregate. 37. The method of claim 36, wherein the phase of the metal-containing species comprises about 2 wt. % to 6 wt. elemental metal, based on the weight of the aggregate. 38. A process for preparing an elastomeric compound, comprising kneading and mixing the aggregate containing the carbon black and the metal containing species and the elastomers and optionally the binder in a mixer for a time sufficient to form a parent rubber composition; grinding said parent rubber composition; cooling the parent rubber composition which facilitates the addition of the vulcanizing additive and prevents substantial premature crosslinking; and kneading and mixing the composition comprising the parent rubber composition and the vulcanizing additive and optionally the binding agent in the mixer for a sufficient time at a temperature sufficient to form the elastomeric compound. 39. The method of claim 38, wherein the metal-containing species phase is predominantly on the aggregate surface. 9 · 999 01-2319-99 Che, J. · .. * 40. The method of claim 38, wherein the metal-containing species phase is distributed throughout the aggregate. 41. The method of claim 38, wherein the metal-containing species phase is oxidized. 42. The method of claim 38, wherein the elastomer comprises SBR solution, natural rubber, SBR functional solution, SBR emulsion, polybutadiene, polyisoprene, or a mixture thereof. 43. The method of claim 38, wherein the metal-containing species phase comprises about 0.1 wt. % to 25 wt. elemental metal, based on the weight of the aggregate. 44. The method of claim 43, wherein the phase of the metal-containing species comprises about 0.5 wt. % to 10 wt. elemental metal, based on the weight of the aggregate. 45. The method of claim 44, wherein the phase of the metal containing species comprises about 2 wt. % to 6 wt. elemental metal, based on the weight of the aggregate. 01-2319-99 Če 46. The method of claim 38, wherein the binder comprises a silane binder, a zirconate binder, a titanate binder, a nitro-based binder, or a mixture thereof. 47. The method of claim 38, wherein the binding agent comprises bis (3-triethoxysilylpropyl) tetrasulfan, 3-thiocyanatopropyltriethoxysilane, [gamma] -mercaptopropyltrimethoxysilane, zirconium dineoalkanolate, di- (3-mercapto) propionate-O, 2-, N ' -bis. methyl-2-nitropropyl) -1,6-diaminohexane or mixtures thereof. 48. The method of claim 47, wherein the binding agent comprises about 0.1-15 parts per hundred parts of the elastomer. 49. The elastomeric compound of claim 5, wherein the binding agent comprises about 0.1 to 6 parts per hundred parts of the elastomer. 50. The elastomeric compound of claim 1, wherein the elastomer comprises a homopolymer, copolymer or terpolymer. 01-2319-99 • Če Β · · ΒΒΒ Β Β ΒΒΒΒ ΒΒΒΒ Β Β Β Β Β Β Β ΒΒ ΒΒΒ ΒΒΒΒ ΒΒ ΒΒ ΒΒ ΒΒΒΒ ΒΒ ΒΒ 51. The elastomeric composition of claim 1, wherein the elastomer has a glass transition temperature measured by DSC of less than 20 ° C. 52. The elastomeric composition of claim 51, wherein the elastomer has a glass transition temperature, measured by DSC, of between -120 [deg.] C and 0 [deg.] C. 53. An aggregate comprising a carbon black phase and at least one phase of a metal containing species. 54. The aggregate of claim 53, wherein the metal-containing species comprises a magnesium-containing species phase, a calcium-containing species phase, a titanium-containing species phase, a vanadium-containing species phase, a cobalt-containing species phase, a nickel-containing species phase, a zirconium-containing species phase. the tin-containing phase, the antimony-containing species phase, the chromium-containing species phase, the neodymium-containing phase, the lead-containing species phase, the tellurium-containing species phase, the barium-containing species phase, the cesium-containing species phase, the iron-containing species phase, the molybdenum-containing species phase; mixtures thereof. 55. The aggregate of claim 53, wherein the metal-containing species comprises a phase of the aluminum-containing species. 01-2319-99 «« Če · ft ft ft ft ft ft ft ft ft -23 -23 -23 -23 -23 -23 -23 -23 -23 -23 -23 -23 -23 -23 · 56. The aggregate of claim 53, wherein the metal-containing species comprises a phase of the zinc-containing species. 57. The aggregate of claim 53, wherein the phase of the metal containing species is predominantly on the surface of the aggregate. 58. The aggregate of claim 53, wherein the metal-containing species phase is distributed throughout the aggregate. 59. The aggregate of claim 53, wherein the metal-containing species phase is oxidized. 60. The aggregate of claim 53, wherein the metal-containing species phase comprises about 0.1 wt. % to 25 wt. elemental metal, based on the weight of the aggregate. 61. The aggregate of claim 60, wherein the metal-containing species phase comprises about 0.5 wt. % to 10 wt. elemental metal, based on the weight of the aggregate. 0 »» 0 · 1 ·· 0 0 «· 0 ·» 0 0 0 0 0 0 0 0 0 000 000 0 0 0 0 0 0 0 0 00 0000 00 0 » 01-2319-99 Če 0 ·· 62. The aggregate of claim 61, wherein the phase of the metal-containing species comprises about 2 wt. % to 6 wt. elemental metal, based on the weight of the aggregate. 63. The aggregate of claim 53, further comprising a phase of a silicon-containing species. 64. The elastomeric compound of claim 1, wherein the aggregate further comprises a phase of a silicon-containing species. 65. The elastomeric compound of claim 1, wherein the aggregate comprises at least two different phases of the metal-containing species. 66. The elastomeric compound of claim 1, wherein the aggregate further comprises a phase of the boron-containing species. 67. The aggregate of claim 53, comprising at least two phases of a metal-containing species. 01-2319-99 • · *.............. 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 i 99 99 99 99 99 68. The aggregate of claim 53, further comprising a phase of the boron-containing species. 69. A process for producing an elastomeric compound comprising introducing at least one volatile or decomposable metal-containing compound into a reactor together with a feedstock for carbon black production or during carbon black formation at a temperature sufficient to decompose or evaporate said compound and form an aggregate comprising a carbon black phase and at least one phase of a metal-containing species; and mixing the prepared aggregate with an elastomer and a binding agent to form an elastomeric compound. 70. The method of claim 69, wherein the volatile or decomposable compound comprises:. the metal calcium, titanium, includes a compound containing magnesium, vanadium, cobalt, nickel, zirconium, tin, antimony, chromium, neodymium, lead, tellurium, barium, cesium, iron or molybdenum, or mixtures thereof. 71. The method of claim 69 wherein the volatile or decomposable metal-containing compound comprises an aluminum-containing compound. 01-2319-99 Če 72. The method of claim 69 wherein the volatile or decomposable metal-containing compound comprises a zinc-containing compound. 73. A method of improving hysteresis of an elastomeric compound, comprising introducing the aggregate of claim 53 into the elastomeric compound. 74. A method of improving the abrasion resistance of an elastomeric compound, comprising introducing the aggregate of claim 53 into the elastomeric compound. 75. A method of improving shear resistance on a wet substrate or adhesion of an elastomeric compound to comprising comprising an elastomeric wet substrate, comprising introducing the aggregate of claim 53 into the compound. 76. A method for improving the adhesion of a compound, comprising introducing the aggregate of claim 53 into an elastomeric compound comprising elastomeric compounds. Represented by: 01-2319-99 Če 1/2 PV wq- 3U3S · »» U U U U · Giant. 01-2319-99 2/2 PV ww -SAZS00 000 · e 0 <0 · 0 0 · 0 0 0 • 0 ·· «· CM • 0 ·· 0 «0 · 0 0 0 · 0 »0 · 0 0