WO1998034960A1 - The use of modified carbon black in gas-phase polymerizations - Google Patents
The use of modified carbon black in gas-phase polymerizations Download PDFInfo
- Publication number
- WO1998034960A1 WO1998034960A1 PCT/US1998/002518 US9802518W WO9834960A1 WO 1998034960 A1 WO1998034960 A1 WO 1998034960A1 US 9802518 W US9802518 W US 9802518W WO 9834960 A1 WO9834960 A1 WO 9834960A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbon black
- polymer
- groups
- silicon
- product
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Definitions
- the present invention relates to gas phase polymerization using modified carbon black and further relates to the products made from gas phase polymerization using modified carbon black.
- Gas phase polymerization has been described as a means of polymerizing polymers such as ethylene/propylene diene monomer (EPDM) and diene-type polymers such as butadiene rubber, without the use of solvents.
- EPDM ethylene/propylene diene monomer
- diene-type polymers such as butadiene rubber
- One advantage of this approach is the lower cost of the resulting polymer because there is no need to recover and recycle solvents.
- Another advantage is the granular form of the polymer which facilitates mixing of the polymer, e.g., elastomer, with the other ingredients in a formulation.
- One problem encountered in gas-phase polymerization which must be overcome is the tendency of the polymer particles formed in the gas phase to stick together in the reactor, thereby giving undesirably large lumps of polymer.
- One feature of the present invention is to provide a gas-phase polymerization method which uses modified carbon blacks as fillers to function as partitioning agents to keep the polymeric particles separated.
- An additional feature of the present invention is to use particular modified carbon blacks to further enhance the properties of the polymeric particles resulting from the gas-phase polymerization. It is an additional feature of the present invention to provide polymeric or resin particles which incorporate the particular modified carbon blacks and which are made by the gas-phase polymerization method.
- the present invention relates to a process for the production of polymers using gas-phase polymerization.
- This process comprises conducting polymerization in a fluidized bed reactor in the presence of a catalyst and in the presence of a modified carbon black as that term is understood herein.
- the present invention additionally relates to the polymer resulting from the above-described process which comprises a polymer and a modified carbon black.
- One type of particles resulting from the above-described process of the present invention is a particle having a polymer mass as its core and a shell comprising a mixture of polymer and modified carbon black.
- FIG. 1 is a schematic view of a portion of one type of carbon black reactor which may be used to produce the treated carbon blacks of the present invention.
- Fig. 2 is a graph demonstrating the results of a bound rubber test carried out on elastomeric compositions of the present invention.
- Figs. 3a, 3b and 3c are graphs demonstrating hysteresis values measured at different temperatures and strains on elastomeric compositions of the present invention.
- Figs. 4a - 4d are photomicrographs comparing carbon blacks useful in the present invention and prior art carbon blacks.
- polymers are made using gas-phase polymerization.
- polymerization occurs in a fluidized bed reactor or a reactor for gas-phase production of polymers.
- the polymerization occurs in the presence of a catalyst and in the presence of a modified carbon black, as that term is to be defined herein.
- the details of the type of fluidized bed reactor or reactors for the gas-phase production of polymers which can be used for purposes of the process of the present invention are described in U.S. Patents Nos. 4,558,790, 5, 1 62,463, 5,200,477, and 5,304,588, all incorporated in their entirety herein by reference.
- the process set forth in PCT International Publication No. WO 88/02379, published April 1 988, can also be used for purposes of the present invention.
- the polymers produced by the process of the present invention can involve a process for producing polymers wherein the polymerization reaction temperature is in excess of the softening temperature of the resulting polymer or polymerization temperatures can be used which are not in excess of the softening temperatures of the produced polymers.
- polymers which can be produced by the present invention include, but are not limited to, ethylene/propylene/diene monomer and diene-type elastomers such as polybutadiene polymers or copolymers.
- Other examples of polymers which can be produced by the process of the present invention include ethylene/propylene rubbers, polybutadiene rubbers, high ethylene content propylene/ethylene block copolymers, poiyd -butene), very low density polyethylenes, ethylene/propylene/ethylidenenorbornene, and ethylene/propylene hexadiene terpolymers of low density. Additional types of polymers that can be made using the process of the present invention are further described in U.S.
- modified carbon black can be used in the process of the present invention.
- the mean particle size of the modified carbon black is from about 0.01 to about 1 0 mm.
- modified carbon black means a) a silicon-treated carbon black (i.e., a particulate comprising carbon black and a silicon-containing species and the silicon-containing species are dispersed within the particulate, wherein the particulate is not a physical mixture of silica and carbon black) .
- An alternative way to describe the silicon-treated carbon black is an aggregate comprising a carbon phase and a silicon compound containing phase.
- the aggregate can comprise one or more primary particles, wherein the primary particle comprises a carbon phase and a silicon-compound containing phase.
- silica-treated carbon black For purposes of convenience, the term "silicon-treated carbon black" will be used hereinafter; b) a silica-coated carbon black; c) a carbon black having an attached organic group(s); d) a silicon-treated carbon black having an attached organic group(s); e) a silica-coated carbon black having an attached organic group(s); or f) a mixture of one or more of the above a)-e) .
- a silicon-containing species including but not limited to, oxides and carbides of silicon, may be distributed through at least a portion of the aggregate comprising a carbon phase and is an intrinsic part of the aggregate.
- the aggregates used in the present invention do not represent a mixture of discrete carbon black aggregates and discrete silica aggregates. Rather, the aggregates of the present invention include a carbon phase and at least one silicon-containing region either at the surface of or within the aggregate. In other words, the aggregate comprises a carbon phase and a silicon compound containing phase.
- the silicon compound containing phase can be inorganic or organic silicon compound.
- the silicon signal corresponding to the silicon-containing species is found to be present in the individual aggregates.
- STEM-EDX examination reveals distinctly separate silica and carbon black aggregates.
- the silicon-treated carbon blacks may be obtained by manufacturing the carbon black in the presence of volatizable silicon-containing compounds.
- Such carbon blacks are preferably produced in a modular or "staged,” furnace carbon black reactor as depicted in Figure 1 .
- the furnace carbon black reactor has a combustion zone 1 , with a zone of converging diameter 2; a feedstock injection zone with restricted diameter 3; and a reaction zone 4.
- hot combustion gases are generated in combustion zone 1 by contacting a liquid or gaseous fuel with a suitable oxidant stream such as air, oxygen, or mixtures of air and oxygen.
- a suitable oxidant stream such as air, oxygen, or mixtures of air and oxygen.
- the fuels suitable for use in contacting the oxidant stream in combustion zone 1 are included any readily combustible gas, vapor or liquid streams such as natural gas, hydrogen, methane, acetylene, alcohols, or kerosene. It is generally preferred, however, to use fuels having a high content of carbon-containing components and in particular, hydrocarbons.
- the ratio of air to fuel varies with the type of fuel utilized. When natural gas is used to produce the carbon blacks of the present invention, the ratio of air to fuel may be from about 10:1 to about 1000:1 .
- the oxidant stream may be pre-heated.
- the hot combustion gas stream flows downstream from zones 1 and 2 into zones 3 and 4.
- the direction of the flow of hot combustion gases is shown in Figure 1 by the arrow.
- Carbon black feedstock 6 is introduced at point 7 into the feedstock injection zone 3.
- the feedstock is injected into the gas stream through nozzles designed for optimal distribution of the oil in the gas stream.
- nozzles may be either single or bi-fluid.
- Bi-fluid nozzles may use steam or air to atomize the fuel.
- Single-fluid nozzles may be pressure atomized or the feedstock can be directly injected into the gas- stream. In the latter instance, atomization occurs by the force of the gas- stream.
- Carbon blacks can be produced by the pyrolysis or partial combustion of any liquid or gaseous hydrocarbon.
- Preferred carbon black feedstocks include petroleum refinery sources such as decanted oils from catalytic cracking operations, as well as the by-products from coking operations and olefin manufacturing operations.
- the mixture of carbon black-yielding feedstock and hot combustion gases flows downstream through zone 3 and 4.
- the feedstock is pyrolyzed to carbon black.
- the reaction is arrested in the quench zone of the reactor.
- Quench 8 is located downstream of the reaction zone and sprays a quenching fluid, generally water, into the stream of newly formed carbon black particles.
- the quench serves to cool the carbon black particles and to reduce the temperature of the gaseous stream and decrease the reaction rate.
- Q is the distance from the beginning of reaction zone 4 to quench point 8, and will vary according to the position of the quench.
- quenching may be staged, or take place at several points in the reactor.
- the cooled gases and carbon black pass downstream into any conventional cooling and separating means whereby the carbon black is recovered.
- the separation of the carbon black from the gas stream is readily accomplished by conventional means such as a precipitator, cyclone separator, bag filter or other means known to those skilled in the art.
- the carbon black After the carbon black has been separated from the gas stream, it is optionally subjected to a pelletization step.
- the silicon treated carbon blacks of the present invention may be made by introducing a volatilizable silicon containing compound into the carbon black reactor at a point upstream of the quench zone.
- Useful volatilizable compounds include any compound, which is volatilizable at carbon black reactor temperatures. Examples include, but are not limited to, silicates such as tetraethoxy orthosilicate (TEOS) and tetramethoxy orthosilicate, silanes such as, tetrachloro silane, and trichloro methylsilane; and volatile silicone polymers such as octamethylcyclotetrasiloxane (OMTS) .
- TEOS tetraethoxy orthosilicate
- OMTS octamethylcyclotetrasiloxane
- the flow rate of the volatilizable compound will determine the weight percent of silicon in the treated carbon black.
- the weight percent of silicon in the treated carbon black can range from about 0.1 % to about 99.9%, preferably from about 0.1 % to 25%, and more preferably about 0.5% to about 10%, and most preferably about 2% to about 6%. It has been found that injecting silicon containing compound into the carbon black reactor results in an increase in the structure (e.g., CDBP) of the product. This is desirable in many applications of carbon black and would provide additional advantages in the partitioning characteristics of the modified carbon black.
- CDBP structure
- the volatilizable compound may be premixed with the carbon black- forming feedstock and introduced with the feedstock into the reaction zone.
- the volatilizable compound may be introduced to the reaction zone separately from the feedstock injection point. Such introduction may be upstream or downstream from the feedstock injection point, provided the volatilizable compound is introduced upstream from the quench zone.
- the volatilizable compound may be introduced to zone Q at point 1 2 or any other point in the zone.
- the compound Upon volatilization and exposure to high temperatures in the reactor, the compound decomposes, and reacts with other species in the reaction zone, yielding silicon treated carbon black, such that the silicon, or silicon containing species, becomes an intrinsic part of the aggregate also comprising the carbon phase.
- silicon-containing species is silica.
- decomposable compounds which are not necessarily volatilizable can also be used to yield the silicon-treated carbon black.
- the silicon- treated regions are distributed throughout at least a portion of the aggregate of the present invention which also comprises the carbon phase.
- the volatilizable compound can alternatively be introduced to the reaction zone at a point after carbon black formation has commenced but before the reaction stream has been subjected to the quench.
- the silicon-treated carbon black is obtained in which a silicon containing species is present primarily at or near the surface of the aggregate. Further details of the silicon-treated carbon black can be found in U.S. Patent Applications Serial Nos. 08/446, 141 ; 08/528,895; and 08/750,01 7, all incorporated in their entirety by reference herein.
- the silica coated carbon blacks may be obtained by coating a silicon oxide compound onto at least a portion of the carbon black aggregate. Any carbon black may be used.
- the carbon black may be fully or partially coated with a silicon oxide compound by a number of different methods. One such method is taught in Japanese (Kokai) patent application No. HEI 5(1 993)-1 78604.
- an organo-silicate such as tetraethylorthosilicate, or a silane such as tetraethoxysilane
- a solvent such as methanol
- Another solution is made by adding 5-20% of a 28% aqueous ammonia solution to ethanol.
- a carbon black is then slowly added to the ammonia solution, while continuously stirring the mixture. Simultaneously, the silicon compound solution is added dropwise to the ammonia solution. After up to several hours of this operation, the silica coated carbon black is extracted, filtered and dried.
- a carbon black coated with silica, thus made, is expected to impart advantages over carbon black, silica, or mixtures thereof in an elastomer. Without being bound by theory, it is believed that such a silica coated carbon black would have more functional groups, specifically silanols, on its surface, allowing for greater interaction with a coupling agent, thereby improving hysteresis when compounded with an elastomer compared to uncoated carbon black. The silica coated carbon black is also expected to impart significant advantages over silica in an elastomer.
- the partially coated carbon blacks which can be used in the present invention may further have an organic groups attached, such as the groups described below. Further details of the silicon coated carbon black can be found in U.S. Patent Applications Serial Nos. 08/446, 140;
- One process for attaching an organic group to the carbon black involves the reaction of at least one diazonium salt with a carbon black in the absence of an externally applied current sufficient to reduce the diazonium salt. That is, the reaction between the diazonium salt and the carbon black proceeds without an external source of electrons 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 both protic and aprotic solvent systems or slurries.
- At least one diazonium salt reacts with a carbon black in a protic reaction medium.
- Mixtures of different diazonium salts may be used in this process of the invention. This process can also be carried out under a variety of reaction conditions.
- the diazonium salt is formed in situ.
- the carbon black product can be isolated and dried by means known in the art.
- the resultant carbon black product can be treated to remove impurities by known techniques. The various preferred embodiments of these processes are discussed below.
- the processes can be carried out under a wide variety of conditions and in general are not limited by any particular condition.
- the reaction conditions must be such that the particular diazonium salt is sufficiently stable to allow it to react with the carbon black.
- the processes can be carried out under reaction conditions where the diazonium salt is short lived.
- the reaction between the diazonium salt and the carbon black occurs, for example, over a wide range of pH and temperature.
- the processes can be carried out at acidic, neutral, and basic pH.
- the pH ranges from about 1 to 9.
- the reaction temperature may preferably range from 0 ° C to 1 00 ° C.
- Diazonium salts may be formed for example by the reaction of primary amines with aqueous solutions of nitrous acid.
- a general discussion of diazonium salts and methods for their preparation is found in Morrison and Boyd, Organic Chemistry. 5th Ed., pp. 973-983, (Allyn and Bacon, Inc. 1 987) and March, Advanced Organic Chemistry: Reactions. Mechanisms, and Structures, 4th Ed., (Wiley, 1 992) .
- a diazonium salt is an organic compound having one or more diazonium groups.
- the diazonium salt may be prepared prior to reaction with the carbon black or, more preferably, generated in situ using techniques known in the art. In situ generation also allows the use of unstable diazonium salts such as alkyl diazonium salts and avoids unnecessary handling or manipulation of the diazonium salt. In particularly preferred processes, both the nitrous acid and the diazonium salt are generated in situ.
- a diazonium salt may be generated by reacting a primary amine, a nitrite and an acid.
- the nitrite may be any metal nitrite, preferably lithium nitrite, sodium nitrite, potassium nitrite, or zinc nitrite, or any organic nitrite such as for example isoamylnitrite or ethylnitrite.
- the acid may be any acid, inorganic or organic, which is effective in the generation of the diazonium salt.
- Preferred acids include nitric acid, HN0 3 , hydrochloric acid, HCI, and sulfuric acid, H 2 S0 4 .
- the diazonium salt may also be generated by reacting the primary amine with an aqueous solution of nitrogen dioxide.
- the aqueous solution of nitrogen dioxide, N0 2 /H 2 O, provides the nitrous acid needed to generate the diazonium salt.
- Generating the diazonium salt in the presence of excess HCI may be less preferred than other alternatives because HCI is corrosive to stainless steel.
- Generation of the diazonium salt with N0 2 /H 2 0 has the additional advantage of being less corrosive to stainless steel or other metals commonly used for reaction vessels.
- Generation using H 2 S0 4 /NaNO 2 or HNO 3 /NaNO 2 are also relatively non-corrosive.
- generating a diazonium salt from a primary amine, a nitrite, and an acid requires two equivalents of acid based on the amount of amine used.
- the diazonium salt can be generated using one equivalent of the acid.
- adding a separate acid may not be necessary.
- the acid group or groups of the primary amine can supply one or both of the needed equivalents of acid.
- the primary amine contains a strong acid group, preferably either no additional acid or up to one equivalent of additional acid is added to a process of the invention to generate the diazonium salt in situ. A slight excess of additional acid may be used.
- One example of such a primary amine is paraaminobenzenesulfonic acid (sulfanilic acid) .
- diazonium salts are thermally unstable. They are typically prepared in solution at low temperatures, such as 0-5 ° C, and used without isolation of the salt. Heating solutions of some diazonium salts may liberate nitrogen and form either the corresponding alcohols in acidic media or the organic free radicals in basic media.
- the diazonium salt need only be sufficiently stable to allow reaction with the carbon black.
- the processes can be carried out with some diazonium salts otherwise considered to be unstable and subject to decomposition.
- Some decomposition processes may compete with the reaction between the carbon black and the diazonium salt and may reduce the total number of organic groups attached to the carbon black.
- the reaction may be carried out at elevated temperatures where many diazonium salts may be susceptible to decomposition. Elevated temperatures may also advantageously increase the solubility of the diazonium salt in the reaction medium and improve its handling during the process. However, elevated temperatures may result in some loss of the diazonium salt due to other decomposition processes.
- Reagents can be added to form the diazonium salt in situ, to a suspension of carbon black in the reaction medium, for example, water.
- a carbon black suspension to be used may already contain one or more reagents to generate the diazonium salt and the process accomplished by adding the remaining reagents.
- 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, like water or methanol, containing a hydrogen attached to an oxygen or nitrogen and thus are sufficiently acidic to form hydrogen bonds.
- Aprotic solvents are solvents which do not contain an acidic hydrogen as defined above.
- Aprotic solvents include, for example, solvents such as hexanes, tetrahydrofuran (THF), acetonitrile, and benzonitrile.
- solvents such as hexanes, tetrahydrofuran (THF), acetonitrile, and benzonitrile.
- the processes are preferably carried out in a protic reaction medium, that is, in a protic solvent alone or a mixture of solvents which contains 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 media containing an alcohol, or mixtures of such media.
- a carbon black product of the invention can be prepared in a dry drum by spraying a solution or slurry of a diazonium salt onto a carbon black.
- the carbon black product can be prepared by pelletizing a carbon black in the presence of a solvent system, such as water, containing the diazonium salt or the reagents to generate the diazonium salt in situ.
- a solvent system such as water
- another embodiment provides a process for forming a pelletized carbon black comprising the steps of: introducing a carbon black and an aqueous slurry or solution of a diazonium salt into a pelletizer, reacting the diazonium salt with the carbon black to attach an organic group to the carbon black, and pelletizing the resulting carbon black having an attached organic group.
- the pelletized carbon black product may then be dried using conventional techniques.
- the processes produce inorganic by-products, such as salts. In some end uses, such as those discussed below, these by-products may be undesirable.
- the diazonium salt can be purified before use by removing the unwanted inorganic by-product using means known in the art.
- the diazonium salt can be generated with the use of an organic nitrite as the diazotization agent yielding the corresponding alcohol rather than an inorganic salt.
- the diazonium salt is generated from an amine having an acid group and aqueous NO 2 , no inorganic salts are formed.
- a process may also produce organic by-products. They can be removed, for example, by extraction with organic solvents. Other ways of obtaining products without unwanted organic by-products may be known to those of skill in the art and include washing or removal of ions by reverse osmosis.
- the reaction between a diazonium salt and a carbon black forms a carbon black product having an organic group attached to the carbon black.
- the diazonium salt may contain the organic group to be attached to the carbon black. It may be possible to produce the carbon black products of this invention by other means known to those skilled in the art.
- the organic group may be an aliphatic group, a cyclic organic group, or an organic compound having an aliphatic portion and a cyclic portion.
- the diazonium salt employed in the processes can be derived from a primary amine having one of these groups and being capable of forming, even transiently, a diazonium salt.
- the organic group may be substituted or unsubstituted, branched or unbranched.
- Aliphatic groups include, for example, groups derived from alkanes, alkenes, alcohols, ethers, aldehydes, ketones, carboxylic acids, and carbohydrates.
- Cyclic organic groups include, but are not limited to, alicyclic hydrocarbon groups
- heterocyclic hydrocarbon groups for example, pyrrolidinyl, pyrrolinyl, piperidinyl, morpholinyl, and the like
- aryl groups for example, phenyl, naphthyl, anthracenyl, and the like
- heteroaryl groups imidazolyl, pyrazolyl, pyridinyl, thienyl, thiazolyl, furyl, indolyl, and the like.
- organic group When the organic group is substituted, it may contain any functional group compatible with the formation of a diazonium salt.
- Preferred functional groups include, but are not limited to, R, OR, COR, COOR, OCOR, carboxylate salts such as COOLi, COONa, COOK, COO " NR 4 + , halogen, CN, NR 2 , S0 3 H, sulfonate salts such as SO 3 Li, S0 3 Na, S0 3 K,
- R and R' which can be the same or different, are independently hydrogen, branched or unbranched C C 20 substituted or unsubstituted, saturated or unsaturated hydrocarbon, e.g., alkyl, alkenyl, alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkylaryl, or substituted or unsubstituted arylalkyl.
- the integer k ranges from 1 -8 and preferably from 2-4.
- the anion X " is a halide or an anion derived from a mineral or organic acid.
- Q is (CH 2 ) W , (CH 2 ) x O(CH 2 ) z , (CH 2 ) X NR(CH 2 ) Z , or (CH 2 ) X S(CH 2 ) 2 , where w is an integer from 2 to 6 and x and z are integers from 1 to 6.
- a preferred organic group is an aromatic group of the formula A y Ar-, which corresponds to a primary amine of the formula A y ArNH 2 .
- Ar is an aromatic radical such as an aryl or heteroaryl group.
- Ar is selected from the group consisting of phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, pyridinyl, benzothiadiazolyl, and benzothiazolyl;
- A is a substituent on the aromatic radical independently selected from a preferred functional group described above or A is a linear, branched or cyclic hydrocarbon radical (preferably containing 1 to 20 carbon atoms), unsubstituted or substituted with one or more of those functional groups; and y is an integer from 1 to the total number of -CH radicals in the aromatic radical.
- y is an integer from 1 to 5 when Ar is phenyl, 1 to 7 when Ar is naphthyl, 1 to 9 when Ar is anthracenyl, phenanthrenyl, or biphenyl, or 1 to 4 when Ar is pyridinyl.
- R and R' are NH 2 -C 6 H 4 -, CH 2 CH 2 -C 6 H 4 -NH 2 , CH 2 -C 6 H 4 -NH 2 , and C 6 H 5 .
- organic groups which may be attached to the carbon black are organic groups substituted with an ionic or an ionizable group as a functional group.
- An ionizable group is one which is capable of forming an ionic group in the medium of use.
- the ionic 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, acidic groups or salts of acidic groups.
- the organic groups therefore, include groups derived from organic acids.
- an ionizable group forming an anion such an organic group has a) an aromatic group and b) at least one acidic group having a pKa of less than 1 1 , or at least one salt of an acidic group having a pKa of less than 1 1 , or a mixture of at least one acidic group having a pKa of less than 1 1 and at least one salt of an acidic group having a pKa of less than 1 1 .
- the pKa of the acidic group refers to the pKa of the organic group as a whole, not just the acidic substituent. More preferably, the pKa is less than 10 and most preferably less than 9.
- the aromatic group of the organic group is directly attached to the carbon black. The aromatic group may be further substituted or unsubstituted, for example, with alkyl groups. More preferably, the organic group is a phenyl or a naphthyl group and the acidic group is a sulfonic acid group, a sulfinic acid group, a phosphonic acid group, or a carboxylic acid group. Examples of these acidic groups and their salts are discussed above.
- the organic group is a substituted or unsubstituted sulfophenyl group or a salt thereof; a substituted or unsubstituted (polysulfo)phenyl group or a salt thereof; a substituted or unsubstituted sulfonaphthyl group or a salt thereof; or a substituted or unsubstituted (polysulfo)naphthyl group or a salt thereof.
- a preferred substituted sulfophenyl group is hydroxysulfophenyl group or a salt thereof.
- organic groups having an ionizable functional group forming an anion are p-sulfophenyl (p- sulfanilic acid), 4-hydroxy-3-sulfophenyl (2-hydroxy-5-amino- benzenesulfonic acid), and 2-sulfoethyl (2-aminoethanesulfonic acid) .
- Other organic groups having ionizable functional groups forming anions can also be used.
- Amines represent examples of ionizable functional groups that form cationic groups.
- amines may be protonated to form ammonium groups in acidic media.
- an organic group having an amine substituent has a pKb of less than 5.
- Quaternary ammonium groups (-NR 3 + ) and quaternary phosphonium groups (-PR 3 + ) also represent examples of cationic groups.
- the organic group contains an aromatic group such as a phenyl or a naphthyl group and a quaternary ammonium or a quaternary phosphonium group. The aromatic group is preferably directly attached to the carbon black.
- Quaternized cyclic amines, and even quaternized aromatic amines, can also be used as the organic group.
- N-substituted pyridinium compounds such as N-methyl- pyridyl
- organic groups include, but are not limited to, (C 5 H 4 N)C 2 H 5 + , C 6 H 4 (NC 5 H 5 ) + , C 6 H 4 COCH 2 N(CH 3 ) 3 + , C 6 H 4 COCH 2 (NC 5 H 5 ) + , (C 5 H 4 N)CH 3 + , and C 6 H 4 CH 2 N(CH 3 ) 3 + .
- An advantage of the carbon black products having an attached organic group substituted with an ionic or an ionizable group is that the carbon black product may have increased water dispersability relative to the corresponding untreated carbon black.
- Water dispersibility of a carbon black product increases with the number of organic groups attached to the carbon black having an ionizable group or the number of ionizable groups attached to a given organic group.
- increasing the number of ionizable groups associated with the carbon black product should increase its water dispersibility and permits control of the water dispersibility to a desired level.
- the water dispersibility of a carbon black product containing an amine as the organic group attached to the carbon black may be increased by acidifying the aqueous medium.
- the ionic strength of the aqueous medium be less than 0.1 molar. More preferably, the ionic strength is less than 0.01 molar.
- the ionic or ionizable groups be ionized in the reaction medium.
- the resulting product solution or slurry may be used as is or diluted prior to use.
- the carbon black product may be dried by techniques used for conventional carbon blacks. These techniques include, but are not limited to, drying in ovens and rotary kilns.
- carbon black products having an organic group substituted with an ionic or an ionizable group may also be dispersible in polar organic solvents such as dimethylsulfoxide (DMSO), and formamide.
- polar organic solvents such as dimethylsulfoxide (DMSO), and formamide.
- DMSO dimethylsulfoxide
- use of complexing agents such as crown ethers increases the dispersibility of carbon black products having an organic group containing a metal salt of an acidic group.
- Aromatic sulfides encompass another group of preferred organic groups. Carbon black products having aromatic sulfide groups are particularly useful in rubber compositions. These aromatic sulfides can be represented by the formulas Ar(CH 2 ) utilizatS k (CH 2 ) r Ar' or A-(CH 2 ) q S ⁇ (CH 2 ) r Ar" wherein Ar and Ar' are independently substituted or unsubstituted arylene or heteroarylene groups, Ar” is an aryl or heteroaryl group, k is 1 to 8 and q and r are 0-4. Substituted aryl groups would include substituted alkylaryl groups.
- Preferred arylene groups include phenylene groups, particularly p- phenylene groups, or benzothiazolylene groups.
- Preferred aryl groups include phenyl, naphthyl and benzothiazolyl.
- the number of sulfurs present, defined by k preferably ranges from 2 to 4.
- Preferred carbon black products are those having an attached aromatic sulfide organic group of the formula -(C 6 H 4 )-S k -(C 6 H 4 )-, where k is an integer from 1 to 8, and more preferably where k ranges from 2 to 4.
- 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 ) .
- the diazonium salts of these aromatic sulfide groups may be conveniently prepared from their corresponding primary amines, H 2 N-Ar-S k -Ar'-NH 2 or H 2 N-Ar-S k -Ar".
- Preferred groups include dithiodi-4, 1 -phenylene, tetrathiodi- 4, 1 -phenylene, phenyldithiophenylene, dithiodi-4, 1 -(3-chlorophenylene), -(4-
- Preferred organic groups also include aromatic sulfides, represented by the formulas Ar-S n -Ar' or Ar-S n -Ar", wherein Ar and Ar" are independently arylene groups, Ar” is an aryl and n is 1 to 8.
- the silicon-treated carbon black may also be modified to have at least one organic group attached to the silicon-treated carbon black.
- a mixture of silicon-treated carbon black and a modified carbon black having at least one attached organic group may be used.
- any combination of additional components with the modified carbon black may be used such as one or more of the following: a) silicon-treated carbon black with an attached organic group optionally treated with silane coupling agents; b) clay; c) silica; d) modified silica, for example, having an attached organic group, and/or e) carbon black.
- silica examples include, but are not limited to, silica, precipitated silica, amorphous silica, vitreous silica, fumed silica, fused silica, silicates (e.g., alumino silicates) and other Si containing fillers such as clay, talc, wollastonite, etc.
- Silicas are commercially available from such sources as Cabot Corporation under the Cab-O-Sil ® tradename; PPG Industries under the Hi-Sil and Ceptane tradenames; Rhone-Poulenc under the Zeosil tradename; and Degussa AG under the Ultrasil and Coupsil tradenames.
- the particles resulting from the process of the present invention comprise polymer and modified carbon black.
- One type of particle resulting from the process of the present invention is a particle having a polymer mass as its core and a shell comprising a mixture of polymer and modified carbon black. Generally, this type of particle occurs when a sticky polymer is made such as EPDM.
- the use of the modified carbon black as part of the present invention has significantly different surface properties than the fillers typically used in gas-phase polymerization which are conventional silica or carbon black. These differences in surface chemistry can favorably influence the performance of the modified carbon black in the gas-phase polymerization.
- EPDM which is made from gas-phase polymerization is used in radiator hoses. It is expected that the modified carbon blacks when used in the process of the present invention will produce an EPDM product containing the modified carbon black and provide a hose compound having reduced electrical conductivity which in turn reduces the tendency for electrochemical degradation which is a recognized problem in the automotive industry.
- using the modified carbon blacks in the process of the present invention is expected to lead to improved tear resistance, for instance, of the EPDM compound. This provides an additional advantage for the EPDM made by gas-phase polymerization in such industries as the roofing market.
- the introduction of the modified carbon blacks in a gas-phase polymerization of such polymers as polybutadiene polymers or copolymers can be advantageous for tire manufacturers since the product can be mixed more easily in the form that is produced by gas-phase polymerization.
- Using the modified carbon blacks in the gas-phase polymerization will produce a product which, when used in tires, provides a desirable balance of rolling resistance, handling, and wear as described in U.S. Patent Applications Nos. 08/446, 140 and 08/446, 141 .
- modified carbon blacks used in the gas-phase polymerization described in this invention are particulates comprising silicon-containing species such as silica and carbon black, it is expected that the use of the modified carbon blacks of this type will provide the advantages offered by silica and carbon black at the same time.
- N234 Vulcan ® 7H from Cabot Corporation, Boston, Mass.
- N234 Vulcan ® 7H from Cabot Corporation, Boston, Mass.
- the flow rate of the volatilizable compound was adjusted to alter the weight percent of silicon in the treated carbon black.
- the weight percent of silicon in the treated carbon black was determined by the ashing test, conducted according to
- OMTS organo-silicon compound
- D4 octamethyl-cyclotetrasiloxane
- TEOS-CB silicon-treated carbon black
- the external surface area (t-area) was measured following the sample preparation and measurement procedure described in ASTM D3037 - Method A for Nitrogen surface area. For this measurement, the nitrogen adsorption isotherm was extended up to 0.55 relative pressure. The relative pressure is the pressure (P) divided by the saturation pressure (P 0 ) (the pressure at which the nitrogen condenses) . The adsorption layer thickness (t.) was then calculated using the relation:
- V volume (V) of nitrogen adsorbed was then plotted against t A straight line was then fitted through the data points for t, values between 3.9 and 6.2 Angstroms. The t-area was then obtained from the slope of this line as follows:
- CDBP CDBP
- cc/100g 101 .5 104.1 103.5 t-Area m 2 /g 1 1 7.0 1 21 .0 1 21 .0
- STEM system may be used to examine an individual aggregate of carbon black for elemental composition.
- a physical mixture of carbon black and silica will result in the identification of silica aggregates which show mostly silicon signal and little or background carbon signal.
- some of the aggregates will show a high Si/C signal ratio, corresponding to aggregates of silica.
- the grid was scanned for potential silica aggregates at low magnification (less than 200,000X) . This was done by searching for aggregates that had a Si/C count ratio greater than unity. After this initial scan, typically thirty aggregates were selected for detailed analysis at higher magnification (from between 200,000X and 2,000,000X) . The selected aggregates included all of the aggregates which contained Si/C count ratios greater than unity, as identified by the initial scan. The highest ratios of Si/C counts thus determined are set forth in Table 3 for N234,
- OMTS-CB OMTS-CB and a mixture of N234 and silica.
- Hydrofluoric acid is able to dissolve silicon compounds but does not react with carbon.
- a conventional (untreated) carbon black or a mixture of silica and carbon black is treated with HF, the surface and surface area of the carbon black will remain unchanged, because it is unaffected by the dissolution of the silicon compounds removed from the mixture.
- silicon containing species are distributed throughout at least a portion, including the surface, of the carbon black aggregate, the surface area will markedly increase as micropores are formed as the silicon compound is dissolved out of the carbon black structure.
- Another silicon-treated carbon black was made by injecting TEOS into the reaction zone of the reactor immediately (one foot) downstream from the hydrocarbon feedstock injection plane, as indicated at injection point 1 2 in Figure 1 . All other reaction conditions were maintained as required for manufacturing N234 black, as described in Example 1 .
- the TEOS flow rate was adjusted to 1 7.6 lbs per hour.
- the resultant black was analyzed for silicon content and surface area, before and after HF extraction as described in Example 3. The results are described in Table 4A.
- This example illustrates the preparation of a carbon black product of the present invention.
- a pelleted carbon black with a surface area of 230 m 2 /g and a DBPA of 64 ml/1 00g was used.
- An aqueous solution of 4- bromobenzenediazonium chloride was prepared from 0.688 g of 4- bromoaniline, 0.300 g of sodium nitrite, 1 .38 g of concentrated HCI and 2.90 g of water at ⁇ 5°C. This solution was added to a suspension of 10 g of the pelleted carbon black in 60 g of water at room temperature. Bubbles were released.
- the resulting carbon black product was removed by filtration, washed with water and subjected to Soxhlet extraction with tetrahydrofuran (THF) overnight. Analysis of the carbon black product after extraction showed that it contained 2.49% bromine, compared to ⁇ 0.01 % for the untreated pelleted carbon black prior to use in this example. This corresponds to 78% of the bromophenyl groups being attached to the carbon black product. Therefore, the carbon black product has 0.31 mmol/g of attached bromophenyl groups.
- Example 5 The pelleted carbon black used in Example 5 was used in Examples 6-8.
- An aqueous solution of 4- bromobenzenediazonium chloride was prepared from 0.688 g of 4- bromoaniline, 0.300 g of sodium nitrite, 1 .38 g of concentrated HCI and 2.90 g of water at ⁇ 5° C. This solution was added to a suspension of 10 g of the pelleted carbon black in 60.5 g of a 0.826% NaOH solution at the temperature indicated. Bubbles were released. After stirring for the time indicated in the following table, the resulting carbon black product was removed by filtration, washed with water and subjected to Soxhlet extraction with THF overnight. Bromine analysis of the product after extraction showed that a substantial fraction of the bromophenyl groups had been attached to the carbon black product. This shows that the preparation of carbon black products according to the invention can be carried our at different times, temperatures and pHs.
- This example further illustrates the preparation of a carbon black product of the present invention.
- a fluffy carbon black with a surface area of 560 m2/g, a DBPA of 90 ml/100 g and a volatile content of 9.5% was used.
- Fifty grams of the fluffy carbon black were added to a solution of 8.83 g of sulfanilic acid dissolved in 420 g of water.
- the resulting suspension was cooled to room temperature.
- Nitrogen dioxide (5.1 6 g) was dissolved in 30 g of ice cold water, and then added to the fluffy carbon black suspension over a period of several minutes and stirred rapidly, to produce 4-sulfobenzenediazonium inner salt in situ, which reacts with the fluffy carbon black.
- the resulting dispersion was dried in an oven at 1 25°C, leaving only the carbon black product.
- the carbon black product contained 1 .94% sulfur after Soxhlet extraction with ethanol overnight, compared to 0.24% sulfur for the untreated carbon black. This corresponds to attaching 52% of the p-C6H4S03- groups to the carbon black product. Therefore, the carbon black product had 0.53 mmol/g of attached p-C 6 H 4 S0 3 - groups.
- Example 10 Preparation of a carbon black product
- This example illustrates another method for the preparation of a carbon black product of the present invention.
- Sulfanilic acid 2.1 3 g
- Ten grams of a carbon black with a CTAB surface area of 350 m2/g and a DBPA of 1 20 ml/100g were added.
- the mixture was cooled to room temperature and isobutyl nitrite (1 .27g) was added. Bubbles were released.
- 4-Sulfobenzene diazonium hydroxide inner salt was generated in situ and it reacted with the carbon black.
- the mixture was stirred for 30 minutes, and dried in an oven at 1 25°C.
- Example 1 Preparation of a carbon black product in an aprotic solvent
- This example illustrates the preparation of a treated carbon black product of the present invention in an aprotic solvent.
- a 0.1 M solution of tetrabutylammonium hexafluorophosphate in anhydrous acetonitrile was prepared and allowed to stand overnight over 3A molecular sieves.
- a 5.4% solution of chlorobenzenediazonium hexafluorophosphate in anhydrous acetonitrile was prepared and allowed to stand overnight over 3A molecular sieves.
- a carbon black with a surface area of 230 m2/g and a DBPA of 70 ml/100g was dried at 1 50°C under nitrogen for 4 hours.
- the carbon black (1 0 g) was stirred into 80 mL of the tetrabutylammonium hexafluorophosphate solution.
- the diazonium solution (21 g) was added, and the mixture was stirred for four hours.
- the carbon black product was recovered by filtration and was washed with anhydrous acetonitrile. All operations up to this point were carried out in a dry box under an argon atmosphere.
- a sample of the carbon black product that was subjected to Soxhlet extraction overnight with THF and dried had a chlorine content of 0.76%, compared to 0.02% for the untreated carbon black. Therefore, the carbon black product had 0.21 mmol/g of attached chlorophenyl groups.
- This example illustrates the preparation of a treated carbon black product of the present invention in an aprotic solvent.
- This example illustrates another method for the preparation of a carbon black product of the present invention.
- a fluffy carbon black with a surface area of 560 m2/g, a DBPA of 90 ml/1 00 g and a volatile content of 9.5% was used.
- Fifty grams of the fluffy carbon black were added to a solution of 8.83 g of sulfanilic acid dissolved in 420 g of water.
- the resulting suspension was cooled to 30°C and 4.6 g of concentrated nitric acid was added.
- An aqueous solution containing 3.51 g of sodium nitrite was then added gradually with stirring, forming 4-sulfobenzenediazonium hydroxide inner salt in situ, which reacts with the fluffy carbon black.
- the resulting product was dried in an oven at 1 25°C, leaving the carbon black product.
- the carbon black product contained 1 .97% sulfur after Soxhlet extraction with ethanol overnight, compared to 0.24% sulfur for the untreated fluffy carbon black. This corresponds to attaching 53% of the p- C 6 H 4 S0 3 - groups to the carbon black product. Therefore, the carbon black product had 0.54 mmol/g of attached p-C 6 H 4 S0 3 - groups.
- This example shows another method for the preparation of a carbon black product of the present invention.
- a fluffy carbon black with a surface area of 230 m2/g and a DBPA of 70 ml/100 g was used. Twenty grams of this black were added to a solution of 4.9 g of 2- aminoethanesulfonic acid in 1 80 g of water. Concentrated nitric acid (4.32 g) was added. A solution of 3.33 g of sodium nitrite in 1 5 g of water was added slowly with stirring, forming 2-sulfoethanediazonium nitrate in situ, which reacted with the fluffy carbon black. A large quantity of bubbles evolved. The product was dried in an oven at 1 35°C, leaving a carbon black product.
- the resulting carbon black product contained 1 .68% sulfur after Soxhlet extraction with ethanol overnight, compared to 0.4% for the untreated fluffy carbon black. This corresponds to attaching 20% of the C 2 H 4 S0 3 - groups to the carbon black product. Therefore, the carbon black product had 0.40 mmol/g of attached C 2 H 4 S0 3 - groups.
- Example 1 5 Preparation of a carbon black product with a benzyldiazonium salt
- This example shows another method for the preparation of a carbon black product of the present invention.
- a suspension of 0.676 g of 4- bromobenzyl amine, 0.60 g of concentrated HCI, 30 g of water and 1 0.22 g of the untreated carbon black used in Example 7 was prepared in an ice bath.
- An aqueous solution containing 0.269 g of sodium nitrite was added and the resulting suspension was stirred for 1 5 minutes, forming 4- bromophenylmethanediazonium chloride in situ, which reacted with the untreated carbon black.
- the product was filtered off, and was subjected to Soxhlet extraction with THF overnight.
- the resulting carbon black product contained 0.26% bromine, compared to ⁇ 0.01 % for the untreated carbon black product. This shows that 9% of the bromobenzyl groups used in the example became attached to the carbon black product. Therefore, the carbon black product had 0.031 mmol/g of attached bromobenzyl groups.
- This example illustrates the preparation of a carbon black product of the present invention.
- Ten grams of a carbon black with a surface area of 230 m2/g and a DBPA of 70 ml/100g was added to a stirring solution of 0.8 g 4-bromobenzamide and 90 ml of acetone in 90 g of water.
- Concentrated HCI (0.87 g) was added followed by 0.33g of NaN0 2 .
- This example shows another method for the preparation of a carbon black product of the present invention.
- a pin pelletizer was charged with 400 g of a fluffy carbon black with a surface area of 80 m2/g and a DBPA of 85 ml/100 g.
- a cold suspension of 4-sulfobenzenediazonium hydroxide inner salt prepared from 27.1 g of the sodium salt of sulfanilic acid, 1 0.32 g of sodium nitrite, 29.0 g of concentrated HCI and 293.5 g of water and was added to the pelletizer. After pelletizing for 2 minutes, the sample was removed and dried at 1 1 5 °C to constant weight.
- Soxhlet extraction with ethanol overnight gave a carbon black product containing 1 .1 % sulfur, compared against 0.8% for the untreated carbon black. This shows that 27% of the p-C 6 H 4 S0 3 - groups were attached to the carbon black product.
- the carbon black product had 0.09 mmol/g of attached p- C 6 H 4 S0 3 - groups.
- Example 1 8 Preparation of a carbon black product in a pin pelletizer with a diazonium salt generated in situ
- This example illustrates another method for preparing a carbon black product of the present invention.
- a pin pelletizer was charged with 200 g of a carbon black with a CTAB surface area of 350 m2/g and a DBPA of
- the carbon black product had 0.88 mmol/g of attached p- C 6 H 4 S0 3 - groups.
- Example 1 9 Preparation of a carbon black product in a pin pelletizer with a diazonium salt generated in situ
- This example further illustrates the preparation of a carbon black product of the present invention.
- a pin pelletizer was charged with 200 g of a carbon black product with a surface area of 560 m2/g, a DBPA of 90 ml/100 g and a volatile content of 9.5%.
- Water (60 g), concentrated nitric acid (25.2 g), sulfanilic acid (40.4 g) and a solution of 1 9.7 g of sodium nitrite in 35 g of water were added successively; the pelletizer was run for one minute after each addition.
- 4-Sulfobenzenediazonium hydroxide inner salt was generated in situ, and it reacted with the carbon black. After standing for five minutes, the resulting carbon black product was dried at 1 25°C.
- This example illustrates another method for the preparation of a carbon black product of the present invention.
- a carbon black (200 g) with a CTAB surface area of 350 m2/g and a DBPA of 1 20 ml/1 OOg and 42.4 g sulfanilic acid were placed in a pin pelletizer. After mixing for 40 seconds, a solution of 20.7 NaN0 2 in 1 50 g of water was then added. 4- sulfobenzene diazonium hydroxide inner salt was formed in situ, which reacted with the carbon black. After mixing for 45 seconds, the resulting carbon black product was dried in an oven at 1 20°C.
- This example illustrates another method for preparing a carbon black product of the present invention.
- a carbon black with a CTAB surface area of 1 33 m2/g and a fluffy DBPA of 1 90 ml/100 g is introduced into a continuously operating pin pelletizer at a rate of 100 parts by weight per hour.
- a 30% solution of sodium nitrite in water and a suspension containing 5.43% concentrated nitric acid, 8.72 % sulfanilic acid and 85.9% water are introduced into the pelletizer.
- the sodium nitrite solution is introduced at 1 6 parts by weight per hour and the suspension is added at 1 1 2 parts by weight per hour.
- This example shows another method for preparing a carbon black product of the present invention.
- the acid for the diazotization reaction comes from the amine forming the diazonium salt, sulfanilic acid.
- Sulfanilic acid (2.1 2 g) was dissolved in 90 g water at 70°C. The solution was added to 10 g of a carbon black with a CTAB surface area of 350 m2/g and a DBPA of 120 ml/100 g, and cooled to room temperature. A solution of 1 .04 g NaN0 2 in 10 g water was added with stirring.
- This example illustrates another method for the preparation of a carbon black product of the present invention.
- the acid for the diazotization reaction comes from the amine forming the diazonium salt, sulfanilic acid.
- a carbon black (10 g) with a CTAB surface area of 350 m2/g and a DBPA of 120 ml/100 g was added to a boiling solution of 2.1 2 g sulfanilic acid in 90 g of water.
- a solution of 1 .04 g of NaN0 2 in 10 g water was added cautiously.
- 4- Sulfobenzene diazonium hydroxide inner salt was formed in situ, which reacted with the carbon black.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU61533/98A AU6153398A (en) | 1997-02-11 | 1998-02-09 | The use of modified carbon black in gas-phase polymerizations |
DE69813512T DE69813512T2 (en) | 1997-02-11 | 1998-02-09 | THE USE OF MODIFIED SOOT IN GAS PHASE POLYMERIZATIONS |
EP98906265A EP0960136B1 (en) | 1997-02-11 | 1998-02-09 | The use of modified carbon black in gas-phase polymerizations |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/798,224 US5919855A (en) | 1997-02-11 | 1997-02-11 | Use of modified carbon black in gas-phase polymerizations |
US08/798,224 | 1997-02-11 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998034960A1 true WO1998034960A1 (en) | 1998-08-13 |
Family
ID=25172846
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1998/002518 WO1998034960A1 (en) | 1997-02-11 | 1998-02-09 | The use of modified carbon black in gas-phase polymerizations |
Country Status (6)
Country | Link |
---|---|
US (1) | US5919855A (en) |
EP (1) | EP0960136B1 (en) |
AU (1) | AU6153398A (en) |
DE (1) | DE69813512T2 (en) |
ES (1) | ES2195318T3 (en) |
WO (1) | WO1998034960A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1065220A1 (en) * | 1999-06-29 | 2001-01-03 | Union Carbide Chemicals And Plastics Company, Inc. | Process for the production of a sticky polymer in the presence of a treated carbon black |
US6180738B1 (en) | 1999-06-29 | 2001-01-30 | Union Carbide Chemicals & Plastics Technology Corporation | Production of a sticky polymer using an improved carbon black |
EP1900766A1 (en) | 1999-01-20 | 2008-03-19 | Cabot Corporation | Aggregates having attached polymer groups and polymer foams |
EP2316874A1 (en) | 1999-01-20 | 2011-05-04 | Cabot Corporation | Aggregates having attached polymer groups and polymer foams |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5904762A (en) | 1997-04-18 | 1999-05-18 | Cabot Corporation | Method of making a multi-phase aggregate using a multi-stage process |
US6458458B1 (en) | 1998-10-13 | 2002-10-01 | Cabot Corporation | Polymer coated carbon products and other pigments and methods of making same by aqueous media polymerizations or solvent coating methods |
US6479571B1 (en) * | 2000-01-25 | 2002-11-12 | Cabot Corporation | Elastomeric compositions containing polymer coated carbon products and other pigments |
EP1338611A1 (en) * | 2002-02-22 | 2003-08-27 | Tim Dr. Bast | Additive component for the improvement of the performance of olefin polymerisation catalysts |
US7087187B2 (en) * | 2002-06-06 | 2006-08-08 | Grumbine Steven K | Meta oxide coated carbon black for CMP |
US7446039B2 (en) * | 2006-01-25 | 2008-11-04 | Chartered Semiconductor Manufacturing Ltd. | Integrated circuit system with dummy region |
US8163075B2 (en) | 2006-10-31 | 2012-04-24 | Sensient Colors Llc | Inks comprising modified pigments and methods for making and using the same |
EP3483222A3 (en) | 2007-08-23 | 2019-08-07 | Sensient Colors LLC | Self-dispersed pigments and methods for making and using the same |
CA2757928A1 (en) | 2009-04-07 | 2010-10-14 | Sensient Colors Inc. | Self-dispersing particles and methods for making and using the same |
US8263524B1 (en) * | 2009-05-11 | 2012-09-11 | Nei, Corp. | Environmentally benign sorbents for removing mercury from flue gas |
US8263525B1 (en) * | 2009-05-27 | 2012-09-11 | Nei Corporation | Nanoparticle sorbent for efficient mercury remediation from contaminated water |
WO2016016869A1 (en) * | 2014-08-01 | 2016-02-04 | Bridgestone Corporation | Rubber mixture comprising pyrolysis carbon black, a method to prepare the mixure and use of said mixture |
CN116382032B (en) * | 2023-02-07 | 2023-09-22 | 万思得新材料科技(中山)有限公司 | High-stability black nano dispersion liquid suitable for LCD photoresist |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1054620A (en) * | 1964-12-11 | |||
US5162463A (en) * | 1990-12-10 | 1992-11-10 | Union Carbide Chemicals & Plastics Technology Corporation | Method for producing sticky polymers |
US5200477A (en) * | 1991-02-22 | 1993-04-06 | Union Carbide Chemicals & Plastics Technology Corporation | Process for producing sticky polymers |
EP0570966A1 (en) * | 1992-05-21 | 1993-11-24 | Union Carbide Chemicals & Plastics Technology Corporation | Process for producing a particle which has an inner core of sticky polymer and an outer shell of particulate material |
US5397807A (en) * | 1993-10-14 | 1995-03-14 | The Dow Chemical Company | Compatibilized carbon black and a process and a method for using |
WO1996037546A1 (en) * | 1995-05-22 | 1996-11-28 | Cabot Corporation | Elastomeric compounds incorporating partially coated carbon blacks |
Family Cites Families (188)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1999573A (en) * | 1930-08-29 | 1935-04-30 | William W Odell | Special carbon black |
US2121535A (en) * | 1934-09-22 | 1938-06-21 | Cabot Godfrey L Inc | Granular product and method of preparing the same |
US2156591A (en) * | 1936-06-29 | 1939-05-02 | Sealco By Products Company | Manufacture of carburized silica |
US2375795A (en) * | 1941-12-22 | 1945-05-15 | Phillips Petroleum Co | Carbon black process |
US2502254A (en) * | 1945-12-07 | 1950-03-28 | Ici Ltd | Manufacture of pigments |
US2564700A (en) * | 1947-04-25 | 1951-08-21 | Phillips Petroleum Co | Production of carbon black |
US2514236A (en) * | 1948-03-12 | 1950-07-04 | Ici Ltd | Manufacture of pigments |
US2632713A (en) * | 1948-10-29 | 1953-03-24 | Phillips Petroleum Co | Carbon black process |
DE957755C (en) * | 1949-06-08 | 1957-01-17 | W. R. Grace a Co., New York, N. Y. (V. St. A.) | Process for the production of a silica gel suitable as a matting agent for paints or the like |
US2793100A (en) * | 1952-10-16 | 1957-05-21 | Degussa | Process of modifying carbon black |
US2833736A (en) * | 1953-07-20 | 1958-05-06 | Western Union Telegraph Co | Aqueous graphite-polyvinyl alcohol ink composition |
US3011902A (en) * | 1954-05-27 | 1961-12-05 | Cabot Corp | Process of manufacturing carbon black pellets for inks |
US2867540A (en) * | 1955-12-30 | 1959-01-06 | Monsanto Chemicals | Modified carbon black product and process |
US2891595A (en) * | 1956-07-31 | 1959-06-23 | Exxon Research Engineering Co | Chlorinated rubbery copolymers |
GB862018A (en) | 1957-01-16 | 1961-03-01 | Etude Des Ind Du Petrole Au Po | Water-dispersible carbon black and production thereof |
FR1164786A (en) | 1957-01-16 | 1958-10-14 | Etude Des Ind Du Petrole Au Po | Water soluble carbon black and its preparation |
US3094428A (en) * | 1957-06-07 | 1963-06-18 | Monsanto Chemicals | Composition of metal oxides and carbon black |
GB910309A (en) * | 1958-07-22 | 1962-11-14 | Dunlop Rubber Co | Rubber compositions |
US3043708A (en) * | 1958-07-22 | 1962-07-10 | Dunlop Rubber Co | Modified carbon black |
FR1215895A (en) | 1958-11-21 | 1960-04-21 | Etude Des Ind Du Petrole Au Po | Modified carbon black, its preparation and applications |
FR1224131A (en) | 1959-01-16 | 1960-06-22 | Etude Des Ind Du Petrole Au Po | Modified soluble carbon blacks, their preparation and applications |
BE626217A (en) * | 1961-12-18 | 1900-01-01 | ||
FR1331889A (en) | 1962-08-24 | 1963-07-05 | Bayer Ag | Manufacture of carbon black preparations |
US3317458A (en) * | 1963-10-07 | 1967-05-02 | Degussa | Mixture of carbon black and light filler aqueous suspension added to rubber latex |
US3335020A (en) * | 1964-03-02 | 1967-08-08 | Huber Corp J M | Modified carbon blacks |
US3674670A (en) * | 1964-12-04 | 1972-07-04 | Ppg Industries Inc | Coating method |
US3390006A (en) * | 1965-08-30 | 1968-06-25 | Huber Corp J M | Method of making carbon black/silica pigment |
US3479300A (en) * | 1965-10-22 | 1969-11-18 | Cabot Corp | Carbonaceous products |
CH487232A (en) | 1966-06-24 | 1970-03-15 | Degussa | Process for the production of a gray pigment |
GB1191872A (en) | 1966-08-18 | 1970-05-13 | Japan Gas Chemical Co | Process for Preparing a Carbon Black-Synthetic Resin Composition |
UST860001I4 (en) * | 1966-12-22 | 1969-03-18 | Defensive publication | |
US3528840A (en) * | 1967-11-15 | 1970-09-15 | Huber Corp J M | Sulfonated carbon black |
GB1213186A (en) | 1968-04-08 | 1970-11-18 | Huber Corp J M | Method of making carbon black/silica pigment |
DE1792148A1 (en) * | 1968-07-27 | 1971-10-21 | Degussa | Improved pre-wetted pigment preparations |
US3622650A (en) * | 1969-02-04 | 1971-11-23 | Cabot Corp | Rubber reinforcing compositions |
US3607813A (en) * | 1969-09-05 | 1971-09-21 | Union Carbide Corp | Printing ink compositions |
DE1948443C3 (en) * | 1969-09-25 | 1981-02-19 | Degussa Ag, 6000 Frankfurt | Process for the production of highly dispersed, homogeneous mixtures consisting of or containing silicon dioxide and carbon black |
US3686111A (en) * | 1970-06-22 | 1972-08-22 | Ppg Industries Inc | Non-aqueous polymeric pseudo-dispersion |
US3876603A (en) * | 1970-06-22 | 1975-04-08 | Ppg Industries Inc | Method of encapsulating pigments in organic dispersions of polymers |
US4014844A (en) * | 1970-06-26 | 1977-03-29 | Agence Nationale De Valorisation De La Recherche (Anvar) | Process for grafting polymers on carbon black through free radical mechanism |
US3689452A (en) * | 1970-07-16 | 1972-09-05 | Burke Oliver W Jun | Elastomer-silica pigment masterbatches and production processes relating thereto |
US3716513A (en) * | 1970-07-16 | 1973-02-13 | O Burke | Silica pigments and elastomer-silica pigment masterbatches and production processes relating thereto |
GB1363428A (en) | 1970-11-12 | 1974-08-14 | Electricity Council | Concrete |
US3846141A (en) * | 1970-12-07 | 1974-11-05 | Dick Co Ab | Jet printing ink composition |
US3873489A (en) * | 1971-08-17 | 1975-03-25 | Degussa | Rubber compositions containing silica and an organosilane |
US3997356A (en) * | 1971-08-17 | 1976-12-14 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Reinforcing additive |
GB1506464A (en) * | 1974-05-29 | 1978-04-05 | Degussa | Aqueous carbon black preparation |
US4003751A (en) * | 1974-09-05 | 1977-01-18 | Union Carbide Corporation | Coating and ink compositions |
US4074035A (en) * | 1975-04-22 | 1978-02-14 | Exxon Research & Engineering Co. | Halomethylated aromatic interpolymers |
JPS51137506A (en) * | 1975-05-22 | 1976-11-27 | Konishiroku Photo Ind | Composition of ink for ink jet recording |
DE2536674C3 (en) * | 1975-08-18 | 1979-09-27 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Crosslinkable mixtures based on rubber, organosilanes and silicate fillers |
US4014833A (en) * | 1975-11-28 | 1977-03-29 | Owens-Illinois, Inc. | Aqueous printing ink with polyethylene oxide |
US4061830A (en) * | 1975-12-23 | 1977-12-06 | Ppg Industries, Inc. | Selective solar energy receiver and method for its production |
US4071496A (en) * | 1976-04-30 | 1978-01-31 | Phillips Petroleum Company | Carbon black for low-hysteresis rubber compositions |
US4108679A (en) * | 1976-11-22 | 1978-08-22 | Ebonex Corporation | Pigment composition containing elemental carbon and process of making the same |
US4204871A (en) * | 1978-04-04 | 1980-05-27 | Sun Chemical Corporation | Printing inks containing nucleated organic pigments |
US4204876A (en) * | 1978-07-17 | 1980-05-27 | M. Hamburger & Sons, Inc. | Cement coloring composition and method of producing same |
DE2910991C3 (en) | 1979-03-21 | 1982-01-21 | Degussa Ag, 6000 Frankfurt | Process for the production of mixed granules from carbon black, water and light filler and its use |
US4211578A (en) * | 1979-06-08 | 1980-07-08 | J. M. Huber Corporation | Method of producing a carbon black silica pigment |
DE2933346C2 (en) * | 1979-08-17 | 1982-07-01 | Degussa Ag, 6000 Frankfurt | Silane / filler preparations, processes for their production and application of the same |
JPS5682859A (en) * | 1979-12-11 | 1981-07-06 | Sakura Color Prod Corp | Ink composition |
US4290072A (en) * | 1980-01-28 | 1981-09-15 | American Can Company | Opaque jet ink printing method and composition |
JPS592451B2 (en) * | 1980-01-30 | 1984-01-18 | 株式会社ブリヂストン | rubber composition |
JPS56128362A (en) | 1980-03-05 | 1981-10-07 | Toho Beslon Co | Production of carbon fiber |
US4293394A (en) * | 1980-03-31 | 1981-10-06 | Ppg Industries, Inc. | Electrolytically producing chlorine using a solid polymer electrolyte-cathode unit |
DE3115532A1 (en) * | 1980-04-17 | 1982-01-28 | Canon K.K., Tokyo | INK-JET RECORDING METHOD AND RECORDING INK FOR RECORDING ON AN IMAGE RECEIVER |
US4478905A (en) * | 1980-04-21 | 1984-10-23 | Ppg Industries, Inc. | Spandrel product with silicate coating |
US4476270A (en) * | 1980-06-06 | 1984-10-09 | E. I. Du Pont De Nemours And Company | Process for making high solids acrylic dispersion lacquer |
US4328041A (en) * | 1980-06-09 | 1982-05-04 | Milliken Research Corporation | Comminuted inorganic materials |
DE3039527C2 (en) | 1980-10-20 | 1984-02-02 | Chemische Werke Brockhues AG, 6229 Walluf | Colorants for cementitious objects |
JPS5821434A (en) * | 1981-07-31 | 1983-02-08 | Japan Synthetic Rubber Co Ltd | Polybutadiene rubber composition |
EP0098338B1 (en) * | 1982-07-09 | 1988-04-20 | Battelle Memorial Institute | Low viscosity stable aqueous dispersion of graft carbon black |
DE3228723A1 (en) * | 1982-07-31 | 1984-02-02 | Basf Farben + Fasern Ag, 2000 Hamburg | STORAGE-STABLE, HEAT-CURABLE MATERIAL MIXTURES MADE OF POLYISOCYANATE AND COMPOUNDS WITH REACTIVE COMPOSITIONS, METHOD FOR THE PRODUCTION AND USE THEREOF |
US4713427A (en) * | 1982-08-09 | 1987-12-15 | E. I. Du Pont De Nemours And Company | High solids coating compositions |
EP0114819B1 (en) * | 1982-08-09 | 1986-12-03 | Ford Motor Company Limited | Glycidyl-hydroxy-acrylic high solids coating compositions |
US4451597A (en) * | 1982-11-15 | 1984-05-29 | E. I. Du Pont De Nemours And Company | High solids color coat containing alcohol soluble cellulose acetate butyrate |
US4442256A (en) * | 1982-12-16 | 1984-04-10 | E. I. Du Pont De Nemours And Company | Additive for alkyd resin coating compositions |
US4605596A (en) * | 1982-12-20 | 1986-08-12 | E. I. Du Pont De Nemours And Company | Additive for coating compositions |
DE3311513A1 (en) * | 1983-03-30 | 1984-10-04 | Basf Farben + Fasern Ag, 2000 Hamburg | HEAT-CURABLE COATING AGENTS AND THEIR USE |
DE3319251C1 (en) * | 1983-05-27 | 1984-04-19 | Degussa Ag, 6000 Frankfurt | Vulcanizable halogen rubber compounds and methods for vulcanizing or crosslinking |
US4680204A (en) * | 1983-09-06 | 1987-07-14 | Ppg Industries, Inc. | Color plus clear coating system utilizing inorganic microparticles |
US4503174A (en) * | 1983-09-06 | 1985-03-05 | E. I. Du Pont De Nemours And Company | Low temperature curing coating composition |
US4525521A (en) * | 1983-10-14 | 1985-06-25 | E. I. Du Pont De Nemours And Company | Coating composition of an acrylic polymer having amino ester groups and a glycidyl acrylic polymer |
US4556427A (en) * | 1983-12-12 | 1985-12-03 | Union Camp Corporation | Use of humates in printing inks |
US4503175A (en) * | 1983-12-19 | 1985-03-05 | E. I. Du Pont De Nemours And Company | Acrylic polyurethane coating composition |
US4555535A (en) * | 1984-03-07 | 1985-11-26 | E. I. Du Pont De Nemours And Company | Acrylic polyurethane coating composition |
US4620994A (en) * | 1984-03-30 | 1986-11-04 | Ppg Industries, Inc. | Color plus clear coating system utilizing organo-modified clay |
US4620993A (en) * | 1984-03-30 | 1986-11-04 | Ppg Industries, Inc. | Color plus clear coating system utilizing organo-modified clay in combination with organic polymer microparticles |
FR2562534B1 (en) * | 1984-04-06 | 1986-06-27 | Rhone Poulenc Chim Base | NOVEL PRECIPITATED SILICA WITH IMPROVED MORPHOLOGICAL CHARACTERS, PROCESS FOR OBTAINING THE SAME AND APPLICATION THEREOF, IN PARTICULAR AS FILLER |
FR2564489B1 (en) | 1984-05-18 | 1986-10-10 | Onera (Off Nat Aerospatiale) | ELECTROCHEMICAL PROCESS FOR THE SURFACE TREATMENT OF CARBON FIBERS, FIBER TREATED BY THIS PROCESS AND COMPOSITE MATERIAL COMPRISING SUCH FIBERS |
JPS60260499A (en) * | 1984-06-07 | 1985-12-23 | Idemitsu Kosan Co Ltd | Preparation of sic whisker |
US4665128A (en) * | 1984-09-17 | 1987-05-12 | E. I. Du Pont De Nemours And Company | Flexible coating compositions |
US4719132A (en) * | 1984-09-21 | 1988-01-12 | Ppg Industries, Inc. | Process for the preparation of multi-layered coatings and coated articles derived therefrom |
US4692481A (en) * | 1984-09-27 | 1987-09-08 | E. I. Du Pont De Nemours And Company | Process for matching color of paint to a colored surface |
US4741780A (en) * | 1985-02-11 | 1988-05-03 | Atkinson George K | Treatment of titanium dioxide and other pigments to improve dispersibility |
JPS61203145A (en) * | 1985-03-05 | 1986-09-09 | Bridgestone Corp | Rubber composition for tire tread |
US5026755A (en) | 1985-03-13 | 1991-06-25 | Sun Chemical Corporation | Water-based printing ink prepared from polyamide/acrylic graft copolymers |
US5008335A (en) | 1985-08-07 | 1991-04-16 | Ppg Industries, Inc. | Powder coating compositions of polyepoxides, acrylic copolymers and aliphatic or polyester dibasic acids |
US4681811A (en) * | 1985-08-19 | 1987-07-21 | Ppg Industries, Inc. | Color plus clear coatings employing polyepoxides and polyacid curing agents in the clear coat |
US4650718A (en) * | 1985-08-19 | 1987-03-17 | Ppg Industries, Inc. | Color plus clear coatings employing polyepoxides and polyacid curing agents |
US4883838A (en) | 1985-09-30 | 1989-11-28 | Basf Lacke & Farben Ag | Soluble acrylate copolymer containing carboxyl groups, processes for its preparation and coating agents based on the acrylate copolymer |
DE3545618A1 (en) | 1985-12-21 | 1987-06-25 | Basf Lacke & Farben | WATER-DISCOVERABLE COATING AGENT FOR PRODUCING THE BASE LAYER OF A MULTILAYER COATING |
US4659770A (en) * | 1986-02-03 | 1987-04-21 | E.I. Du Pont De Nemours And Company | Coating composition of an amine polymer and a blocked polyisocyanate |
US4670059A (en) * | 1986-02-11 | 1987-06-02 | Hewlett Packard Company | Increased solubility of carbon black |
US4764430A (en) * | 1986-03-07 | 1988-08-16 | Ppg Industries, Inc. | Crosslinkable compositions containing polyepoxides and polyacid curing agents |
US4727100A (en) * | 1986-08-15 | 1988-02-23 | E. I. Du Pont De Nemours And Company | Coating composition containing a reactive urethane component an acrylic fatty acid drying oil resin and a metallic alkylate |
DE3629470A1 (en) | 1986-08-29 | 1988-03-10 | Basf Lacke & Farben | CARBOXYL GROUPS AND TERTIAL AMINO GROUPS CONTAINING POLYCONDENSATION AND / OR ADDITION PRODUCT, COATING AGENTS BASED ON THE SAME AND THEIR USE |
US5319044A (en) | 1986-09-10 | 1994-06-07 | Basf Lacke + Farben Ag | Branched polymer containing silyl groups, a process for the preparation thereof, coating agents based on the polymer, and the use thereof |
DE3636726C1 (en) * | 1986-10-29 | 1988-03-17 | Pelikan Ag | Aqueous writing fluids and a process for their preparation |
US4752532A (en) * | 1986-10-31 | 1988-06-21 | E. I. Du Pont De Nemours And Company | Polyester primer composition |
FR2607528B1 (en) | 1986-12-02 | 1989-03-17 | Onera (Off Nat Aerospatiale) | ELECTROCHEMICAL PROCESS FOR CARBON SURFACE TREATMENT; CARBON, ESPECIALLY CARBON FIBERS, TREATED BY THIS PROCESS AND COMPOSITE MATERIAL COMPRISING SUCH FIBERS |
US4880857A (en) | 1986-12-17 | 1989-11-14 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Carbon black-graft polymer, method for production thereof, and use thereof |
JPS63156841A (en) * | 1986-12-22 | 1988-06-29 | Yokohama Rubber Co Ltd:The | Pneumatic radial tire |
JPH0832804B2 (en) * | 1987-02-24 | 1996-03-29 | 横浜ゴム株式会社 | Rubber composition |
JPH068366B2 (en) * | 1987-04-23 | 1994-02-02 | 株式会社ブリヂストン | Rubber composition for tires |
US4808656A (en) * | 1987-05-04 | 1989-02-28 | Ppg Industries, Inc. | High solids coating compositions |
US4840674A (en) * | 1987-06-01 | 1989-06-20 | Xerox Corporation | Ink compositions |
US4789400A (en) * | 1987-07-10 | 1988-12-06 | Xerox Corporation | Waterfast ink jet compositions and process |
US4927868A (en) | 1987-08-19 | 1990-05-22 | Ppg Industries, Inc. | High solids coating compositions containing a polyepoxide and a copolymer of an alpha-olefin and an olefinically unsaturated monoanhydride |
US4798746A (en) * | 1987-08-24 | 1989-01-17 | Ppg Industries, Inc. | Basecoat/clearcoat method of coating utilizing an anhydride additive in the thermoplastic polymer-containing basecoat for improved repairability |
US4798745A (en) * | 1987-08-24 | 1989-01-17 | Ppg Industries, Inc. | Non-yellowing coating composition based on a hydroxy component and an anhydride component and utilization in a process of coating |
US4853037A (en) * | 1987-10-30 | 1989-08-01 | Hewlett-Packard Company | Low glycol inks for plain paper printing |
ZA891937B (en) | 1988-04-04 | 1990-11-28 | Ppg Industries Inc | Pigment grinding vehicles containing quaternary ammonium and ternary sulfonium groups |
US4975474A (en) | 1988-06-27 | 1990-12-04 | E. I. Du Pont De Nemours And Company | Multi-component coating composition comprising an anhydride containing polymer, a glycidyl component and a self-stabilized dispersion resin |
US5093391A (en) | 1988-06-27 | 1992-03-03 | E. I. Du Pont De Nemours And Company | Multi-component coating composition comprising an anhydride containing polymer, a glycidyl component and an acid functional component |
US4908397A (en) | 1988-06-27 | 1990-03-13 | E. I. Du Pont De Nemours And Company | Multi-component coating composition comprising an anhydride containing polymer, a glycidyl component and a self-stabilized dispersion resin |
US5017435A (en) | 1988-06-27 | 1991-05-21 | E. I. Du Pont De Nemours And Company | Multi-component coating composition comprising an anhydride containing polymer, a glycidyl component and a monomeric or oligomeric anhydride component |
US4894420A (en) | 1988-09-14 | 1990-01-16 | The Goodyear Tire & Rubber Company | Tire with tread of selective rubber blend |
DE3834738A1 (en) | 1988-10-12 | 1990-04-19 | Basf Lacke & Farben | METHOD FOR PRODUCING A MULTI-LAYER COATING, AQUEOUS COATING COMPOSITION, WATER-DISCOVERABLE POLYACRYLATE RESINS AND METHOD FOR PRODUCING WATER-DISCOVERABLE POLYACRYLATE RESINS |
DE3906818C2 (en) | 1989-03-03 | 1994-01-13 | Degussa | Gray-black inclusion pigments and process for their preparation |
US5204404A (en) | 1989-03-21 | 1993-04-20 | E. I. Du Pont De Nemours And Company | Waterbased acrylic silane and polyurethane containing coating composition |
US5066733A (en) | 1989-04-03 | 1991-11-19 | Ppg Industries, Inc. | Chip resistant coatings and methods of application |
US5242751A (en) | 1989-04-27 | 1993-09-07 | Ppg Industries, Inc. | Paint composites |
US5264521A (en) | 1989-04-28 | 1993-11-23 | Bridgestone Corporation | Rubber compositions |
DE69006788T2 (en) | 1989-07-24 | 1994-07-07 | Sumitomo Chemical Co | Rubber compound with excellent dynamic properties. |
DE3924618A1 (en) | 1989-07-26 | 1991-01-31 | Basf Lacke & Farben | COATING AGENTS BASED ON CARBOXYL GROUP-CONTAINING POLYMERS AND EPOXY GROUP GROUPING NETWORKS, METHOD FOR PRODUCING THE COATING AGENT AND ITS USE |
US5051464A (en) | 1989-09-01 | 1991-09-24 | E. I. Du Pont De Nemours And Company | Waterborne acrylourethane pigment dispersant polymer |
JP2889326B2 (en) | 1989-09-14 | 1999-05-10 | 昭和キャボット株式会社 | Carbon black and rubber composition |
US5168106A (en) | 1989-09-14 | 1992-12-01 | Cabot Corporation | Carbon blacks |
US5064719A (en) | 1989-09-26 | 1991-11-12 | E. I. Du Pont De Nemours And Company | Coating composition of acrylic polymers containing reactive groups and an epoxy organosilane |
EP0429828B1 (en) | 1989-10-19 | 1994-03-16 | Canon Kabushiki Kaisha | Ink and ink jet recording method, ink cartridge, ink jet device and ink jet recording apparatus using the same |
DE59009466D1 (en) | 1989-10-26 | 1995-09-07 | Ciba Geigy Ag | Aqueous printing inks for inkjet printing. |
US5076843A (en) | 1989-10-27 | 1991-12-31 | Lexmark, International, Inc. | Nonaqueous thermaljet ink compositions |
US5266406A (en) | 1989-11-08 | 1993-11-30 | E. I. Du Pont De Nemours And Company | Waterbased methylol (meth)acrylamide acrylic polymer and an acrylic hydrosol coating composition |
WO1991007470A1 (en) | 1989-11-21 | 1991-05-30 | Seiko Epson Corporation | Ink for use in ink jet recording |
DE59004417D1 (en) | 1989-12-11 | 1994-03-10 | Ciba Geigy | Process for dyeing leather. |
US5122552A (en) | 1989-12-12 | 1992-06-16 | E. I. Du Pont De Nemours And Company | Coating composition of polyesterurethane and multifunctional epoxy compound |
EP0509018B1 (en) | 1990-01-08 | 1996-04-10 | Cabot Corporation | Carbon blacks imparting superior treadwear/hysteresis performance and process for producing carbon blacks |
US5200164A (en) | 1990-04-04 | 1993-04-06 | Cabot Corporation | Easily dispersible carbon blacks |
US5182355A (en) | 1990-04-05 | 1993-01-26 | Ppg Industries, Inc. | Polyurethane polyanhydride oligomers and method of preparation |
DE4021126C2 (en) | 1990-07-03 | 1998-01-29 | Basf Lacke & Farben | Paints and use of the paints for painting car bodies |
DE4023537A1 (en) | 1990-07-25 | 1992-01-30 | Degussa | CHEMICALLY MODIFIED ROUGS WITH ORGANOSILICIUM COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
US5281261A (en) | 1990-08-31 | 1994-01-25 | Xerox Corporation | Ink compositions containing modified pigment particles |
US5100470A (en) | 1990-10-25 | 1992-03-31 | Hewlett-Packard Company | Waterfast ink formulations for thermal ink-jet using organic amines |
DE4038000A1 (en) | 1990-11-29 | 1992-06-04 | Bayer Ag | RUBBER VOLCANISATES WITH IMPROVED HYSTERESIS BEHAVIOR |
US5314945A (en) | 1990-12-03 | 1994-05-24 | E. I. Du Pont De Nemours And Company | Waterbased coating compositions of methylol(meth)acrylamide acrylic polymer, polyurethane and melamine crosslinking agent |
US5290848A (en) | 1990-12-18 | 1994-03-01 | E. I. Du Pont De Nemours And Company | Coating composition of a glycidyl acrylic polymer, an aminoester acrylic polymer and a polyester or a polyesterurethane |
US5221581A (en) | 1990-12-18 | 1993-06-22 | E. I. Du Pont De Nemours And Company | Coating composition of a glycidyl acrylic polymer, an aminoester acrylic polymer and a polyester or a polyesterurethane |
US5206295A (en) | 1991-02-25 | 1993-04-27 | E. I. Du Pont De Nemours And Company | Coating composition comprising an anhydride-containing polymer and a structured epoxy-containing polymer |
FR2673187B1 (en) | 1991-02-25 | 1994-07-01 | Michelin & Cie | RUBBER COMPOSITION AND TIRE COVERS BASED ON SAID COMPOSITION. |
US5286286A (en) | 1991-05-16 | 1994-02-15 | Xerox Corporation | Colorless fast-drying ink compositions for printing concealed images detectable by fluorescence |
US5141556A (en) | 1991-06-13 | 1992-08-25 | E. I. Du Pont De Nemours And Company | Penetrants for aqueous ink jet inks |
DE4119959A1 (en) | 1991-06-18 | 1992-12-24 | Degussa | METHOD FOR PRODUCING VULCANIZABLE, RUSSELED PLASTIC AND RUBBER MIXTURES |
US5162409B1 (en) | 1991-08-02 | 1997-08-26 | Pirelli Armstrong Tire Corp | Tire tread rubber composition |
US5114477A (en) | 1991-09-03 | 1992-05-19 | Xerox Corporation | Liquid ink compositions |
US5314953A (en) | 1991-10-21 | 1994-05-24 | E. I. Du Pont De Nemours And Company | Clear coating composition for clear coat/color coat finish |
US5229452A (en) | 1991-11-13 | 1993-07-20 | Cabot Corporation | Carbon blacks |
US5173111A (en) | 1991-11-18 | 1992-12-22 | Sun Chemical Corporation | Abrasion resistant printing inks |
US5236992A (en) | 1991-11-18 | 1993-08-17 | Cabot Corporation | Carbon blacks and their use in rubber applications |
US5232974A (en) | 1991-11-25 | 1993-08-03 | Cabot Corporation | Low rolling resistance/high treadwear resistance carbon blacks |
DE4222372A1 (en) | 1992-07-08 | 1994-01-13 | Merck Patent Gmbh | Carbon black pigments |
US5310778A (en) | 1992-08-25 | 1994-05-10 | E. I. Du Pont De Nemours And Company | Process for preparing ink jet inks having improved properties |
US5356973A (en) | 1992-08-31 | 1994-10-18 | Ppg Industries, Inc. | Aqueous based coating compositions having improved metallic pigment orientation |
US5334650A (en) | 1992-09-29 | 1994-08-02 | Basf Corporation | Polyurethane coating composition derived from long-chain aliphatic polyol |
US5324790A (en) | 1992-09-29 | 1994-06-28 | E. I. Du Pont De Nemours And Company | Esterification of carboxylate containing polymers |
US5272189A (en) | 1992-10-19 | 1993-12-21 | Ppg Industries, Inc. | Reduced yellowing electrodepositable coating composition |
US5294253A (en) | 1992-11-06 | 1994-03-15 | Hydril Company | Carbon black system and improved rubber stock |
US5430087A (en) | 1993-09-02 | 1995-07-04 | Hydril Company | Carbon black pair with different particle size and improved rubber stock |
US5352289A (en) | 1992-12-18 | 1994-10-04 | Cabot Corporation | Low ash carbon blacks |
US5302197A (en) | 1992-12-30 | 1994-04-12 | E. I. Du Pont De Nemours And Company | Ink jet inks |
US5401313A (en) | 1993-02-10 | 1995-03-28 | Harcros Pigments, Inc. | Surface modified particles and method of making the same |
CA2104537A1 (en) | 1993-06-18 | 1994-12-19 | Paul Harry Sandstrom | Silica reinforced rubber composition |
CA2104529A1 (en) | 1993-06-18 | 1994-12-19 | Paul Harry Sandstrom | Tire with silica reinforced tread |
US5366828A (en) | 1993-11-08 | 1994-11-22 | Struthers Ralph C | Metal alloy laded carbon aerogel hydrogen hydride battery |
US5575845A (en) | 1994-12-15 | 1996-11-19 | Cabot Corporation | Carbon black products for coloring mineral binders |
US5554739A (en) | 1994-12-15 | 1996-09-10 | Cabot Corporation | Process for preparing carbon materials with diazonium salts and resultant carbon products |
US5571311A (en) | 1994-12-15 | 1996-11-05 | Cabot Corporation | Ink jet ink formulations containing carbon black products |
US5559169A (en) | 1994-12-15 | 1996-09-24 | Cabot Corporation | EPDM, HNBR and Butyl rubber compositions containing carbon black products |
-
1997
- 1997-02-11 US US08/798,224 patent/US5919855A/en not_active Expired - Fee Related
-
1998
- 1998-02-09 WO PCT/US1998/002518 patent/WO1998034960A1/en active IP Right Grant
- 1998-02-09 AU AU61533/98A patent/AU6153398A/en not_active Abandoned
- 1998-02-09 EP EP98906265A patent/EP0960136B1/en not_active Expired - Lifetime
- 1998-02-09 DE DE69813512T patent/DE69813512T2/en not_active Expired - Fee Related
- 1998-02-09 ES ES98906265T patent/ES2195318T3/en not_active Expired - Lifetime
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1054620A (en) * | 1964-12-11 | |||
US5304588A (en) * | 1989-09-28 | 1994-04-19 | Union Carbide Chemicals & Plastics Technology Corporation | Core-shell resin particle |
US5162463A (en) * | 1990-12-10 | 1992-11-10 | Union Carbide Chemicals & Plastics Technology Corporation | Method for producing sticky polymers |
US5200477A (en) * | 1991-02-22 | 1993-04-06 | Union Carbide Chemicals & Plastics Technology Corporation | Process for producing sticky polymers |
EP0570966A1 (en) * | 1992-05-21 | 1993-11-24 | Union Carbide Chemicals & Plastics Technology Corporation | Process for producing a particle which has an inner core of sticky polymer and an outer shell of particulate material |
US5397807A (en) * | 1993-10-14 | 1995-03-14 | The Dow Chemical Company | Compatibilized carbon black and a process and a method for using |
WO1996037546A1 (en) * | 1995-05-22 | 1996-11-28 | Cabot Corporation | Elastomeric compounds incorporating partially coated carbon blacks |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1900766A1 (en) | 1999-01-20 | 2008-03-19 | Cabot Corporation | Aggregates having attached polymer groups and polymer foams |
EP2316873A1 (en) | 1999-01-20 | 2011-05-04 | Cabot Corporation | Aggregates having attached polymer groups and polymer foams |
EP2316874A1 (en) | 1999-01-20 | 2011-05-04 | Cabot Corporation | Aggregates having attached polymer groups and polymer foams |
EP2316875A1 (en) | 1999-01-20 | 2011-05-04 | Cabot Corporation | Aggregates having attached polymer groups and polymer foams |
EP1065220A1 (en) * | 1999-06-29 | 2001-01-03 | Union Carbide Chemicals And Plastics Company, Inc. | Process for the production of a sticky polymer in the presence of a treated carbon black |
US6180738B1 (en) | 1999-06-29 | 2001-01-30 | Union Carbide Chemicals & Plastics Technology Corporation | Production of a sticky polymer using an improved carbon black |
US6255412B1 (en) | 1999-06-29 | 2001-07-03 | Union Carbide Chemicals & Plastics Technology Corporation | Polymerization of a sticky polymer in the presence of a treated carbon black |
Also Published As
Publication number | Publication date |
---|---|
DE69813512T2 (en) | 2003-11-13 |
EP0960136B1 (en) | 2003-04-16 |
ES2195318T3 (en) | 2003-12-01 |
DE69813512D1 (en) | 2003-05-22 |
AU6153398A (en) | 1998-08-26 |
EP0960136A1 (en) | 1999-12-01 |
US5919855A (en) | 1999-07-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0975699B8 (en) | Multi-phase aggregate comprising carbon and its preparation | |
US5869550A (en) | Method to improve traction using silicon-treated carbon blacks | |
AU749800B2 (en) | Elastomeric compositions incorporating metal-treated carbon blacks | |
EP0828789B1 (en) | Elastomeric compounds incorporating silicon-treated carbon blacks | |
US5977213A (en) | Pre-coupled silicon-treated carbon blacks | |
US6028137A (en) | Elastomeric compounds incorporating silicon-treated carbon blacks | |
US6323273B1 (en) | Elastomeric compounds incorporating silicon-treated carbon blacks | |
EP0960136B1 (en) | The use of modified carbon black in gas-phase polymerizations | |
CZ282899A3 (en) | Use of modified carbon black when conducting polymerization processes in gaseous phase |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CZ DE DK EE ES FI GB GE GH GM GW HU ID IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG UZ VN YU ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW SD SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: PV1999-2828 Country of ref document: CZ |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1998906265 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1998906265 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
NENP | Non-entry into the national phase |
Ref country code: JP Ref document number: 1998534997 Format of ref document f/p: F |
|
WWP | Wipo information: published in national office |
Ref document number: PV1999-2828 Country of ref document: CZ |
|
WWG | Wipo information: grant in national office |
Ref document number: 1998906265 Country of ref document: EP |