Title of Invention	A MODIFIED PARTICLE HAVING AN ATTACHED HALIDE GROUP AND METHODS OF MAKING THE SAME
Abstract	The present invention relates to a modified particle such as herein described comprising a particle having attached a group having the formula: wherein R1 an alkyl or alkylene group or an aryl or arylene group; R1and R1which can be the same or different, represent hydrogen, an alkyl group, an aryl group, -OR1-NHR1- NR^R1or -SR1wherein R1which is the same or different, represents an alkyl group or an aryl group; and Q represents a labile halide containing species.

Title of Invention

A MODIFIED PARTICLE HAVING AN ATTACHED HALIDE GROUP AND METHODS OF MAKING THE SAME

Abstract

The present invention relates to a modified particle such as herein described comprising a particle having attached a group having the formula: wherein R1 an alkyl or alkylene group or an aryl or arylene group; R1and R1which can be the same or different, represent hydrogen, an alkyl group, an aryl group, -OR1-NHR1- NR^R1or -SR1wherein R1which is the same or different, represents an alkyl group or an aryl group; and Q represents a labile halide containing species.

Full Text	A PARTICLE HAVING AN ATTACHED HALIDE GROUP AND METHODS OF MAKING THE SAME BACKGROUND OF THE INVENTION The present invention relates to particles, such as carbon black, having an attached halide containing radical which permits the formation of modified panicles having blocked radical sources. The present invention further relates to methods of preparing and using such modified particles. The role of carbon black as a thermal stabilizer in polymeric systems is discussed by W. L. Hawkins, R. H. Hansen, W. Matreyek, F. H. Winslow; 7. Applied Polymer Science, vol. 1. pages 37-42, 1959; J. T. Cmver, K. W. Rollmaim: J. Applied Polymer Science, vol. 8. pages 1169-83, 1964, and by G. Ivan, M. Giurgina: Revue Roumaine de Chemie, vol. 29, number 8, pages 639-646, 1984. In each discussion the mechanism is through phenolic and quinone oxygen groups on the carbon black surface behaving either as radical traps or peroxide decomposers. One skilled in the art, however, would consider these sites unavailable as initiating sites for polymerization processes. Belmont et al. (J. A. Belmont, J. M. Funt; International Rubber Conference, Essen, Germany, June 24-27 1991) identified the presence of peroxide groups, typically in the range 0.1 to 0.4 micromoles/sq meter, on the carbon black surface. However, the majority (greater than 80%) of the peroxide groups are thermally stable to heat treatment at 200°C and hence cannot be considered to be potential initiating sites for radical polymerization. Tsubokawa et al, (K. Fujiki, N. Tsubokawa, Y. Sone: Polymer J., vol. 22, number 8, pages 661-70, 1990, and N. Tsubokawa: Prog. Polymer Science, vol. 17, pages 417-70, 1992) discuss growing polymers from an activated carbon black surface by first attaching a reacdve group via the oxygen groups on the carbon black surface. Typical examples include the use of glycidyl methacrylate where the glycidyl group reacts with phenolic hydroxyl groups on the carbon black surface providing a vinyl functionality; the reaction of 4,4* azo bis-{4-cyanovaieric acid) whereby the isocyanate group reacts with phenolic hydroxyl groups and subsequent heating decomposes the azo group to generate an alkyl radical; and the reaction of the phenolic hydroxyl groups with butyl lithium which can then be used as an initiation site for anionic polymerization. All of these approaches require the presence of oxygen groups on the carbon black surface. Since the level of reactive hydroxyl and carboxylic acid groups, relative to the above approaches, present on a typical furnace or thermal carbon black is typically 0.01 to 0.1 micromoles/sq meter, the number of potential initiation sites is quite low. Further, subsequent polymerization from these activated sites will most likely occur in the normal manner for free radical polymerization with the chains being irreversible terminated by chain combination reactions, combination with unreacted oxygen groups on the carbon black surface, and/or the addition of chain stoppers. In all cases the polymerization cannot be reiniuated. Accordingly, there is a need to provide modified particles which overcome the above-described limitations. SUMMARY OF THE INVENTION In accordance with the purpose of the present invention, as embodied and broadly described herein, the present invention relates to a modified particle which includes a particle having an attached group having the formula: wherein A represents an aromatic group or an alky! group; R' represents a bond, an arylene group, an alkylene group, wherein R1is an alkyl or alkylene group or an aryl or arylene group; R1and R\ which can be the same or different, represent hydrogen, an alkyl group, an aryl group, -0R1-NHR\ -NRR1or -SR1wherein R1which can be the same or different, represents hydrogen, an alkyl group or an aryl group; and Q represents a labile halide containing radical. The present invention further relates to a modified particle or aggregate wherein the particle or aggregate is a carbon-metal multiphase aggregate, a carbon-silicon containing species multiphase aggregate, a metal oxide, or a metal hydroxide. Attached to the particle or wherein Coup A represents a Si-containing group, a Ti-containing group, a Cr-containing group, or a Zr-containing group; R1and R1which can be the same or different, represent hydrogen, an alkyl group, an aryl group, -0R'°, -NHR'1-NR'°R'1or -SR'1wherein R'°, which can be the same or different, represents hydrogen, an alkyl group or an aryl group; Q represents a labile halide containing radical, and n is an integer of from 1 to 3. The present invention further relates to a modified panicle with an attached polymer or blocked radial sources, wherein the modified particle has an attached group having the formula: wherein X represents blocked radial sources or a polymer formed from at least one polymerizable vinyl or diene based monomer, A represents an aromatic group or an aJkyl group; R1represents a bond, an arylene group, an alkylene group, wherein R1is an alkyl or alkylene group or an aryl or arylene group; R" and R\ which can be the same or different, represent hydrogen, an alkyl group, an aryl group, -0R1-NHR\ -NR1R1or -SR1, wherein R1which can be the same or different, represents an alkyl group or an aryl group; and Q represents a labile halide containing radical. The present invention also relates to another modified particle having an attached polymer. The particle is a carbon-metal multiphase aggregate, a carbon-silicon containing species multiphase aggregate, a metal oxide, or a metal hydroxide. Attached to the particle is a wherein CoupA represents a Si-containing group, a Ti-coniaining group, a Cr-containing group, or a Zr-coniaining group; R and R , which can be the same or different, represent hydrogen, an alkyl group, an aryl group, -0R'°, -NHR'°, -NR'°R1or -SR'1, wherein R'1which can be the same or different, represents an alkyl group or an aryl group; Q represents a labile halide containing radical, X is blocked radical sources or a polymer formed from at least one polymerizable monomer, and n is an integer of from 1 to 3. The present invention, in addition, relates to a method for preparing and using these various modified particles. In making the modified particle of formula (I), the particle can have the aromatic or alkyl group and the -R'-CR1R* attached in any fashion either in a single step or multiple steps. -Q can then be attached using sufficient temperature and acid. In making the modified particle with the attached polymer, the method includes reacting a particle having an attached aromatic group substimted with R'-CR1R1-Q with a transition metal halide, a complexing ligand, and a polymerizable monomer. The present invenuon, in addition, relates to a method for preparing and using these various modified panicles. For instance, in making the modified panicle of formula (I), the particle can have the aromatic or alkyl group and the -R'-CR1-R1attached in any fashion eidier in a single step or multiple steps, -Q can then be attached using an esterification technique, such as acid catalyzed esterification. In making the modified panicle witii the attached polymer, the method includes reacting a panicle having an attached aromatic or alkyl group substimted with R'-CR1R1-Q with a transition metal halide. a complexing ligand, and a polymerizable monomer. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the present invention, as claimed. DETAILED DESCRIPTION OF THE PRESENT INVENTION In one embodiment, the present invention relates to a modified panicle comprising a particle having attached a group having the formula: wherein R1is an alkyl or alkylene group or an aiyl or arylene group; R1and R\ which can be the same or different, represent hydrogen, an alkyl group, an aryl group. -0R1-NHR1-NR1\ or SR\ wherein R1which can be the same or different, represents an alkyl group or an aryl group; and Q represents a labile halide containing radical. The particle, to be modified, can be any particle capable of having a group represented by any one of the formulas described herein attached thereto, such as formula (IHIV). Preferably, the particle has a carbon reactive site (C-), since in a preferred embodiment for the groups of formula (I) and (III). -Q and -X-Q are preferably attached through a carbon bond on the particle. The particle, for instance, can be carbon products, colored pigments other than carbon products, metal oxides (e.g.. silica), metal hydroxides, multiphase aggregates comprising a carbon phase and a silicon-containing species phase, multi-phase aggregates comprising a carbon phase and a metal-containing species phase, and the like. The carbon may be of the crystalline and/or amorphous type. Examples of carbon products include, but are not limited to. graphite, carbon black, vitreous carbon, activated charcoal, activated carbon, carbon fiber, and mixmres thereof. Finely divided forms of the above are preferred. Most preferably, the particle is a carbon product, and most preferably carbon black. The multi-phase aggregate containing the carbon phase and the silicon-containing species phase can also be considered a silicon-treated carbon black aggregate and the multiphase aggregate containing a carbon phase and a metal-containing species phase can be considered to be a metal-treated carbon black aggregate as long as one realizes that in either case, the silicon-containing species and/or metal-containing species are a phase of the aggregate just like the carbon phase. The multi-phase aggregates do not represent a niixture of discrete carbon black aggregates and discrete silica or metal aggregates and is not a silica coated carbon black. Rather, the multi-phase aggregates used in the present invention include at least one silicon-containing or metal- The aggregate, thus contains at least two phases, one of which is carbon and the other of which is a silicon-containing species, a metal-containing species, or both. The silicon-containing species that can be a pan of the aggregate is not attached to a carbon black aggregate like a silica coupling agent, but actually is pan of the same aggregate as the carbon phase. For instance, when die multi-phase aggregate having a carbon phase and a silicon-containing species phase is examined under STEM-EDX, the silicon signal corresponding to the silicon-containing species is found to be present in individual carbon black aggregates. By comparison, for example, in a physical mixture of silica and carbon black, STEM-EDX examination reveals distincdy separate silica and carbon black aggregates. The metal-treated carbon blacks are aggregates containing at least a carbon phase and a metal-containing species phase. The metal-containing species include 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. The metal-containing species phase can be distributed through at least a portion of the aggregate and is an inu-insic part of the aggregate. Further, it is widiin the bounds of the present invention to have a metal-treated carbon black containing more than one type of metal-containing species phase or the metal-treated carbon black can also contain a silicon-containing species phase and/or a boron-containing species phase. For example, the metal-treated carbon black of the present invention can have an aggregate comprising a carbon phase, an aluminum-containing species phase, and a zinc-containing species phase. Accordingly, the multi-phase aggregates used in the present invention can have two or more different types of metal-containing species phases and/or additional non-metal species phases. Preferably, for purposes of the present invention, the amount of elemental silicon and/or elemental metal present in the multi-phase aggregate is from about 0.1 to about 25 wt. %, more preferably, from about 0.5 wt. % to about 10 wt. %, and most preferably from about 0.2 wt. % to about 5.4 wt. %, by weight of the aggregate. The details of making the multi-phase aggregates are explained in U.S. Patent Nos.-5,904J62; 5.877,238; 5,869,550; and 5,830,930; PCT Publication No. WO 96/37547, U.S. Patent Application No, 08/828,785, filed March 27, 1997; U.S. Patent Application No. 08/837,493, filed April 18, 1997; and U.S. Patent Application No. 09/061,871 filed April 17, 1998. All are hereby incorporated in their entireties herein by reference. A silica-coated carbon product can also be used as the particle, which is described in PCT Application No, WO 96/37547, published November 28, 1996, and is hereby incorporated in its entirety herein by reference. The colored pigment is any pigment which can be modified with the attachment of an aromatic group or an alky I group. The colored pigments other than carbon products include, but are not limited to, black, white, blue, brown, cyan, green, violet, magenta, red, yellow, as well as mixtures thereof. Suitable classes of colored pigments include, but are not limited to, anthraquinones, phthalocyanine blues, phthalocyanine greens, diazos, monoazos, pyranthrones, perylenes, heterocyclic yellows, quinacridones, and (thio)indigoids. Specific examples and further information concerning the colored pigments and methods of making colored pigments with attached aromatic groups or alkyl groups are described in PCT Publication No. WO 97/47699, incorporated in its entirety by reference herein. Particles useful for the present invention may, for example, have primary panicles sizes in the general range of from about 10 nm to about 500 nm, and preferably from about 10 nm to about 250 nm, and primary aggregate sizes in the genera! range of from about 50 nm to about 100 microns, preferably from about 50 nm to about 10 microns, still more preferably from about 75 nm to about 1 micron. The BET surface area of these particles can be any suitable surface area and preferably ranges from about 10 mVg to about 2000 mVg and more preferably, from about 10 mVg to about 1,000 mVg, and still more preferably from about 50 mVg to about 500 mVg; and the particle structure preferably ranges from about 10 cc/lOOg to about 1000 cc/g, more preferably, from about 50 cc/lOOg to about 200cc/100g. The number of Q groups attached to the particle prior to polymerization can be any amount. For instance, the number of -Q groups may range from about 0.01 mmole/g (of particle) to about 10 mmole/g, preferably from about 0.1 mmole/g to about 4 mmole/g, and still more preferably from about 0.5 mmole/g to about 3 mmole/g. When the particle is a multi-phase aggregate, like a carbon phase and a silicon-containing species phase, preferably the group of formula (I) or (III) is attached at least, if not .exclusively, on the carbon phase. With regard to the aromatic group, any aromatic group may be used. Unlike the polymerizable monomer discussed later, the aromatic group is not a polymer and is not polymerized. Examples include, but are not limited to, arylene groups. Preferred aryiene groups include, but are not limited to, phenylene and naphthalene groups. The aromatic group includes, but is not limited to, unsaturated cyclic hydrocarbons containing one or more rings. The aromatic group may be substituted or unsubstituted. Aromatic groups include aryl group (for example, phenyl, naphthyl, anthracenyl, and the like), and heteroaryi groups (for example, imidazolyl, pyrazolyl, pyridinyl, thienyl, thiazolyl, fiiryl, triazinyl, indolyl, and the like). The alkyl group is preferably a C1-CI2 alkyl group, and may be branched or unbranched, and is preferably ethyl. With respect to R. preferred arylene groups include, but are not limited to, benzene ring containing groups. Preferred alkylene groups include, but are not limited to, Ci - C's aikylene-containing groups. These groups can be linear, branched, or unsaturated. These examples of arylene and alkylene groups can also be considered examples of R1. Preferred alkyl groups for R1are CJ-C20 alkyl groups, more preferably Ci-D alkyl groups and preferred aryl groups are phenyl, biphenyl. and naphthyl. With respect to R1and R1which can be the same or different, exanqjles of alkyl groups (e.g. C1-C20 alkyl group) include, but are not limited to, methyl, ethyl, propyl.1-butyl, and the like. Preferably, the alkyl group is a Ci-O alkyl group. Examples of aryl groups include, but are not limited to, phenyl, biphenyl, and naphthyl. The alkyl and aryl groups mentioned here as well as the arylene and alkylene groups mentioned throughout can be unsubstituted or substituted for purposes of the present invention. R1can be the same type of alkyl and aryl groups mentioned above with respect to R1and RThe labile halide containing group which is substituted or attached to the aromatic group as shown in formula (I) above, is a halide containing group wherein the labile halide {e.g., fluorine, bromine, iodine, chlorine) in the group is capable of forming an oxidized species with a transition metal halide. Preferably, the labile halide has a weak halide bond between the halide and the atom capable of forming the free radical. The labile halide is capable of undergoing chemical reaction resulting in the formation of the radical group which previously contained the labile halide. The group containing the labile halide in turn forms a radical which comprises a carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, boron atom, and/or silicon atom. Other organic species or groups can be a part of the group containing the labile halide such as alkyl, aryl, and the like. Specific examples of the labile halide containing group include, but are not limited to, aryl halides, aryl alkyl halides, alkyl haiides, benzyl halides, arenesufonyl halides, phosphorous halides, haloallcyl esters, sulfur halides, silicon halides, arenecarbonyl halides, and other labile halide containing groups. A more specific example of a labile haiide containing group a bromo-or chloro-alkyl, such as bromoethyl, bromomethyl, bromo propyl and bromododecyl as well as the chloro versions of these groups which can form radicals. Another embodiment of the present invention relates to a modified panicle or aggregate having a group of formula (II) attached thereto. The panicle can be a metal oxide, a metal hydroxide, an aggregate comprising at least one carbon phase and a metal-containing species phase, or an aggregate comprising at least one carbon phase and at least one silicon-containing species phase. Attached to this particle or aggregate is a group having the formula: wherein CoupA represents a Si-containing group, a Ti-containing group, a Cr-containing group, or a Zr-containing group; R and R1which can be the same or different, represent hydrogen, an alkyl group, an aryl group. -0R'1-NHR°. -NR'1'1or -SR'°, wherein R'° represents an alkyl group or an aryl group; Q represents a labile halide containing radical, and where n is an integer of from 1 to 3. Preferably, CoupA is attached to the particle or aggregate, especially in the case of a Si-containing group, via an oxygen radical which can form a pan of a CoupA. Examples of Si-containing groups include, but are not limited to, dimethylsilylmethyU dialkoxysiiylmethyU and the like. Examples of Ti-containing groups include, but are not limited to, alpha substituted ai-acetyl titanate and the like. Examples of Zr-containing groups include, but are not limited to, dialpha methoxy neopentylzirconate, aluminum zirconates and the like. Examples of die substituents R1and R' can be the same as the subsuments R1and R1mentioned above. Likewise, examples of the substiment R'** can be the same as the substituent R1discussed above. Also, the Q is the same as discussed above. The modified particles having the attached group of the formulas, such as formula (I), can be made in the following manner. A particle, such as carbon black, can first have a substituted or non-substituted aromatic or alkyl group attached to the panicle, wherein ttie aromatic or alkyl group is directly attached to the panicle. This attachment can be accomplished by the methods described in PCT International Application No. WO 96/18688 and U.S. Patent Nos. 5,851,280; 5,630,868; 5,559,169; 5,571,311; and 5,559.169 as well as U.S. Patent Application No. 08/572,525, all of which are hereby incorporated in iheir entireties by reference herein. The panicle having the attached aromatic or aikyl group can then react with -R'-CR1R1and then a labile halide containing radical source for a sufficient time and at a sufficient temperarure to form the modified particle having the attached group, like that of formula I. The labile halide containing radical source is present in amounts sufficient to react with -A-R'-CR1R1present on the particle. Preferably, the amount of the labile halide containing radical source is from about 0.01 mmoles/g (of particle) to about 10 mmoles/g and more preferably from about 0.01 to about 5 mmoles/g. Alternatively, the labile halogenating containing species can be formed by halogenation of a C-0 bond with a halogenating agent such as phosphorous tri-bromide. Alternatively, the modified particles of the present invention can be made by first forming the groups of the formulas described above, such as formula (I), Preferably, the labile haiide containing radical group is attached in the meta or para position of the aromatic group, if present. This group is then attached to the particle by a diazonium treatment in the manner described in the above referenced patents and patent applications, where a diazonium salt will first be formed containing a group of one of the formulas described above in the manner described in the above-referenced patents. The groups of the formulas can be then subsequently attached to the particle. In a less preferred way, the formulas of the present invention can be attached to the particle through a hydroxyl or carbonyl group present on the particle. Also, the modified panicle of the present invention can be formed by attaching a labile halide containing group containing at least one aikoxy silyl, aikoxy titanyl, or alkoxy zirconyl group to the particle which, in this particular process is preferably a metal oxide or metal hydroxide, or a carbon surface. This particular embodiment would attach a group of formula (ID or (IV) to a particle. In another process, the modified particle can be formed by first taking an aromatic or alkyl group and reacting it with R'CR1R1containing compound to form the groups of the formulas described above except for the presence of the -Q group. In other words, a group having the formula A-R'-CR"R1would first be formed and then the -Q group would be attached to this group to form a group of formula (I) of the present invention which can then be attached to the particle. In this process, R1and R1are preferably hydrogen. Alternatively, the process of making the modified particles of the present invention can be a three step process where A is first attached to the particle and then the group having the formula R1-C-R1R1can be attached to the aromatic or alkyl group. Then in a third step, the -Q can be attached to the R'-C-R1R1group. The modified particles of formula (II) can be made in the following manner. The aggregate comprising at least one carbon phase and at least one metal-containing species phase can be made as described in U.S. Patent Application No. 08/828,725. hereby incorporated herein by reference. The aggregate comprising at least one carbon phase and at least one metal containing species phase can be made as described in U.S. Patent No. 5,904,762 and 5,877,238. The aggregate or particle can then be reacted with a coupling agent by adding the coupling agent to the aggregate in a medium and mixing. Then, the aggregate or particle having the attached coupling group can be reacted with a labile halide containing radical source as described above. For purposes of the above-described reactions, the reaction should occur for a time and temperature sufficient to form the attached group onto the particle or aggregate. Generally, this time is from about 3 minutes to about 96 hours and more preferably from about 1 hour to about 24 hours- With the modified particles described above, polymers can be attached onto these attached groups by reacting these modified particles or aggregates with a polymerizable monomer such as a vinyl or diene containing monomer. Specific examples of such monomers include, but are not limited to, styene, isoprene, butadiene, chloromethylstyrene, methyl methacrylate, and butyl mcthacrylate, as well as acrylic acid and esters of acrylic acid and methacrylic acid and esters of methacrylic acid. More specific monomer examples include, but are not limited to, hydroxyalkyl (meth)acrylates, such as hydroxyethyl (meth)acrylaie, hydrox>proyl (meth)acrylate; alkyl (meth)acrylates such as methyl acrylate or butyl acrylate; glycidyl (meth)acrylate; dimethylaminoethylacrylate; 2-acryl trimethyl ethylammonium chloride; aminoethyl acerylate; acrylonitirle; vinyl acetrate, and the like. Mixtures of two or more monomers can be also used or polymerized sequentially. If polymeric gels are described, then the monomer or ponion thereof is preferably a halide containing vinyl monomer or diene containing monomer (e.g., chloromethyl styrene or vinyl chloride). The polymerization reaction is conducted under conditions which permits the poiymerizadon of the monomer so that it forms a part of the attached group onto the panicle or aggregate. These conditions include ambient temperatures and can include preferably heating modified particles with a monomer above 80°C, preferably from about 120°C to about ISO'1'C, in the presence of a solvent, a transition metal halide, and a complexing ligand. The reaction can be ended by lowering the temperature. The sequence of addition is not important and the particle (for instance Formula (I) or (III) complexing ligand, and transition metal halide can be added in any order. A preformed transition metal halide complex can alternatively be used in lieu of the separate components. In addition, complexing ligand and transition metaJ halide can first be reacted to form a complex or the reaction can occur in situ. The polymer-modified particle can then be subjected to distillation, steam stripping, or precipitation or other known methods in order to remove residual monomers and solvents. Examples of transition metal halides include, but are not limited to, copper (I) halides, and transition metal halides wherein the metal is copper, rhodium, iron, nickel, cobalt, palladium, and ruthenium. A specific and preferred example of the transition metal halide is copper (I) chloride. The complexing ligand can be any compound capable of complexing with the transition metal halide in order to be an efficient halide atom transfer promoter. Examples of the complexing ligand include, but are not limited to, 2,2'-bipyridine and derivatives thereof (e.g., alkyl substituted bipyridines), derivatives of uriphenyl phosphines, and muitidentate amines were the nitrogen atoms are preferably separated by ethylene or propylene units. The polymerization reaction thus can produce any length of polymer on the modified particle or aggregate. For example, polymers having average molecular weights, preferably ranging from about 500 to about 1,000,000 can be made. Other ranges of average molecular weights include, but are not limited to, from about 500 to about 3,000, and from about 500 to about 2,000, and firom about 500 to about 500,000, and from about 1,000 to about 250,000. The polymers can be any type, such as homopolymers, co-polymers, ter-polymers. or higher chain polymers. The polymers can also be block, graft, or random-type polymers. The polymers can be branched or unbranched. Polymers, such as comb polymers, can be formed or located off of the main polymer chain, and these polymers can be any type of polymer. Specific examples include, but are not limited to, polyamines. such as poiyethyleneimine or polyalkylene oxides, grafted onto the main polymer chain. The polymers that are formed can be ionic (e.g., canonic or anionic) or non-ionic polymers. Specific examples of polymers include, but are not limited to, polyamides, polyacrylics, polyvinylacetates, polyvinylalcohols. polyvinylpyridines, polyvinylpyrrilodones, polyvinylimidazoles, and acrylamides and derivatives thereof as well as combinations thereof Once the polymerizauon occurs, the modified particle will have a group attached having the formula: wherein the substituents are the same as described earlier for formula (I) and X is a polymer formed from at least one polymerizable monomer. Similarly, when the modified particle or aggregate having a group of formula (II) is polymerized by the introduction of one or more monomers, the group attached to the particle or aggregate will have the formula: wherein the substituents are the same as described in formula (II) and X is a polymer formed from at least one polymerizable monomer. Within the above-described groups containing the labile halide group, the modified particle or aggregate containing the labile halide group can be terminated by means known to those skUled in the art in view of the present application. In particular, the halide group can be replaced with a proton, subjected to disproportionation, or replaced with a chemical group dirough group transfer and the like. For instance, the halide group can be replaced with a hydroxy group. This termination or removing the halide group and replacing it or terminating it with another group can be accomplished, for instance, by methods described at Advanced Organic Chemistry, J. March, Wiley, 4"* Ed., (1992), for instance at page 370, which is incorporated in their enurety by reference herein. The modified particles of the present invention can form part of a polymeric composition and be present with other ingredients commonly used and found in polymeric composidons. A particle, as described herein, can also be modified as described herein and can also be modified as described in U.S. Patent Application Nos. 08/962,244 and 08/968,299. and the Application entitled "Methods of Making a Particle Having an Attached Stable Free Radical" filed June 3, 1998. all of which are incorporated in their entirety herein by reference. In more detail, a particle can be dual or multi-modified to have a group of formulae (I) - (IV)) attached thereto and also have a group having a labile halide containing radical attached as well, such as a group having the formulae (I) - (IV) as described in the above-referenced applications. The polymerization of the monomers on the multiple groups attached onto the particle can be accomplished in any sequence or simultaneously. The modified particle of the present invention can be used in a variety of applications. For instance, it can be used in coating formulations or compositions, or ink formulations or compositions, or toner formulations or compositions, such as printing inks and ink jet inks, toners, automobile coatings, and the like. Also, the modified particles can be used as reinforces for compositions, such as polymeric compositions and can also serve as impact modifiers, or as agents used to increase compatibility of a polymeric composition. In more detail, reinforcement of elastomeric compositions include tire, hose, profile extrusion, seals, gaskets, and vibration isolation units, as well as the specific reinforcement of a single elastomer phase in a multiphase elastomer blend composition; reinforcement of thermoplastic compositions such as polyolefmes, styrenic, acrylics, polyesters, and polyamides. and thermoplastic elastomers and thermoplastic polyoiefines; reinforcement of thermoset compositions, elg., acrylics; impact modification of thermoplastic compositions, coatings, thermoplastic elastomers, and crosslinked compositions; as a synthetic support for solid phase organic synthesis; as a support or medium for effluent extraction processes - both organic and inorganic components; as a catalyst support; and/or as a superadsorbant for either aqueous of hydrocarbon materials e.g., use in sanitary wear, growing medium for plants. The modified particles of the present invention can be incorporated in and form a part of elastomeric compositions. Other conventional ingredients for elastomeric con:5)Osirions can also be present, such as coupling agents and the like. Coupling agents, as used herein, include, but are not limited to. compounds that are capable of coiq)ling fillers such as carbon black or silica to an elastomer having one functionality which will attach to the panicle and another functionality which will attach to the elastomer. Coupling agents useful for coupling silica or carbon black to an elastomer, are ejq)ected to be useful with the silicon-treated carbon blacks. Useful coupling agents include, but are not limited to, silane coupling agents such as bis(3)triethoxysilylpropyl)tetrasulfane (Si-69). 3-thiocyanatopropyl-niethoxy silane (Si-264, from Degussa AG, Germany), Y-mercaptopropyl-trimethoxy silane (A189. from Union Carbide Corp., Danbury, Connecticut); zirconate coupling agents, such as zirconium dineoalkanolatiodi(3-mercapto) propionato-0 (NZ 66A, from Kenrich Peu-ochemicals,Inc., of Bayonne, New Jersey); titianate coupling agents; niao coupling agents such as N,N'-bis(2-methyl-2-nitropropyl)-1.6-diaminohexane (Sumifine 1162, from Sumitomo Chemical Co., Japan); polyalkoxysiloxane (e.g., Zeruma from the Yokahama Rubber Co. Ltd.. Japan) and mixtures of any of the foregoing. The coupling agents can be provided as a mixture with a suitable carrier1for example X50-S which is a mixture of Si-69 and N330 carbon black, available from Degussa AG. The elastomeric compounds of the present invention may be prepared from the modified particles of the present invention by compounding with any elastomer including those useful for compounding a carbon black. Any suitable elastomer may be compounded with the modified particles to provide the elastomeric compounds of the present invention. Such elastomers include, but are not limited to. homo- or co-polymers of 1,3 butadiene, styrene, isoprene, isobutylene, 2,3-dimethyH,3-butadiene, acrylonitrile, ethylene, and propylene. Preferably, the elastomer has a glass transition temperamre (Tg) as measured by differential scanning colorimeter (DSC) rangii1from about -120'C to about 0C. Examples include, but are not limited to, styrene-butadiene rubber (SBR), natural rubber, polybutadiene, polyisoprene, and their oil-extended derivatives. Blends of any of the foregoing may also be used. Among the rubbers suitable for use with the present invention are natural rubber and its derivatives, such as chlorinated rubber and epoxidized rubber. TTie modified particles of the present invention may also be used with synthetic rubbers such as: copolymers of from about 10 to about 70 percent by weight of styrene and from about 90 to about 30 percent by weight of butadiene such as copolymer of 19 parts styrene and 81 parts butadiene, a copolymer of 30 parts styrene and 70 parts butadiene, a copolymer of 43 parts styrene and 57 parts butadiene and a copolymer of 50 parts styrene and 50 parts butadiene; polymers and copolymers of conjugated dienes such as polybutadiene, polyisoprene, polychloroprene, and the like, and copolymers of such conjugated dienes with an ethylenic group-containing monomer copolymerizable therewith such as styrene, methyl styrene, chlororaethylscyrene, acrylonitrile, 2-vinyl-pyridine, 5-methyl 2-vinylpryidine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine. alkyl-substimted acrylates or mediacrylates, vinyl ketone, methyl isopropenyl ketone, methyl vinyl ether, alpha-methylene carboxylic acids and the esters and amides thereof such as acrylic acid, mediacrylic acid, and dialkylacrylic acid amide; also suitable for use herein are copolymers of ediylene and other high alpha olefins such as propylene, butane, pentane, hexane, and octane. Other monomers that could be used include norborene and hex-l,5-diene, and the like. The rubber compositions of the present invention can therefore contain one or more elastomers, curing agents, reinforcing fillers, coupling .agents, and, opuonally, various processing aids, oil extenders, and anti-degradents. In addition to the examples mentioned •' 'above, the elastomer can be, but is not limited to, polymers (e.g., homopolymers, copolymers. and terpolymers) manufactured from 1,3 butadiene, scyrene, isoprene, isobutylene, 2,3-dimethyl-l,3-butadiene, acrylonitrile, ethylene, propylene, and the like. It is preferred that" these elastomers have a glass transidon point (Tg), as measured by DSC, between -IIQ'1C and O1C, Examples of such elastomers include poly(butadiene). poly(styrene-co-butadiene), and poly(isoprene). Elastomeric compositions disclosed in the present invention include, but are not limited to, vulcanized compositions (VR), thermoplastic vulcanizates (TPV). thermoplastic elastomers (TPE). and thermoplastic polyolefins (TPO), TPV, TPE, and TPO materials are further classified by their ability to be extruded and molded several times without loss of performance characteristics. The elastomeric compositions may include one or more curing agents such as. for example, sulfur, sulfur donors, activators, accelerators, peroxides, and other system used to effect vulcanization of the elastomer composition. The resultant elastomeric compounds containing the aggregates of the present invention and optionally containing one or more coupling agents may be used for various elastomeric products such as a tread compound, undertread compound, sidewall compound, wire skim compound, inner liner con1und. bead, apex, any compound used in carcass and other components for vehicle tires, industrial rubber products, seals, timing belts, power transmission belting, and odier rubber goods. In an embodiment of the present invention, the elastomeric compositions of the present invention, which contain at least one modified particle of the present invention, can have a total residue after nin-ogen pyrolysis at 6501C of from about 1 % to about 60% by weight. For purposes of the present invention, the ink includes at least one type of polymerized-terminated modified particle, and at least one ink vehicle. The inkjct ink formulation includes at least one type of polymerized terminated modified particle, and at least one inkjet ink vehicle. Generally, the formulations described in WO 97/47699 with respect to coatings and inks can be used herein, however, incorporating the modified particles of the present invention. The coating formulations contain at least one type of polymerized-terminated modified particle and at least one suitable solvent. Other conventional additives may be incorporated into Ac coating formulations, such as a binder. Each of these fonnulations can contain additional conventional colorant and other optional, conventional ingredients or additives, for instance, ad described in U.S. Patent Nos. 5,571,311; 5,672,198; 5,266.361; 5.707,432 such as a humectant, binders, dyes, biocides, surfactants, penetrants. All of these patents are incorporated herein in their entirety by reference herein. I The toner can contain at least one polymcrized-ierminaied modified particle and resin panicies. The conventional and standard ingredients or addiuves for toner formulations, such as those described in U.S. Parent Nos. 5,278,018; 5,275,900; 5.695.899, and 5,116.712, can be used in the present invenuon, and are incorporated in their entirety by reference herein. The toner can be a posiuveiy or negadvely charged toner composiuon. In the various products incorporating the modified particles of the present invention, one or more types of other panicles can also be present, such as a carbon product (e.g., carbon black), metal oxide (e.g., silica, zinc oxide, andaluminiim oxide), metal silicate (e.g., clay, aluminum, calcium, magnesium silicates), modified silica, modified carbon products having an anacbed organic group, an aggregate comprising at least one carbon phase and at least one silicon-containing species phase optionally having an attached organic group, carbon black at least partially coated with silica, or any combioauon thereof, in any product mendoned herein, more than one type of modified panicle of the present invention can be present in the various products described above. The present invendon will be further clarified by the following examples, which are intended to be purely exeirqplaiy of the invenuon. KXAIVtPLES Example 1 Bromo Modiikd Carbon JBlack 4 To a soiuuon of benzoic acid Vulcan* 7H modified carbon black 5 (50 g, 0.02 mol) in toiuene (250 mL) was added bromodocecanol (10.6 g, 0.04 mol) and ;?-ioluene sulfonic acid (3.8 g, 0.02 mol). The mixrure was heaied at reflux under niurogen for 18h in the presence of a Dean & Stark trap. The raixiure was filiered and washed wich toluene (3 x 100 mL) and dried in a vacuum oven at 70°C for 12h. PoIy(acryla£e) Modified Carbon Black 6 To a solution of the modified carbon black (5 g, 0.002 mol) in toluene (25 mL) was added copper (I) chloride (0.05 g), 2,2'-bipyridyI (0.16 g) and (2-dimeihyianiino) eihyl mediacrylate (4 mL). The raixmre was heated at 130°C for 72h under niurogen, then filtered and washed with methanol. The residue was further exiracied with hot methanol in a soxhlet extractor for 72h, followed by soxhlec extracdon with toluene for 72h. Siiazie Modified Silica 7 Silica (lOOg) was suspended in a 10:1 acetone water mixture and adjusted to pH 8 with sodium hydroxide. Chloropropyltrimethoxsilane (7.9 g. 0.04 mol) was added and the soiuuon hf3T1f) at 50*C under nicrogen for 4h. The mixture was filtered and washed with water (4 x 200 mL) and acetone (4 x 200 mL). Scyreoe Modified Silka 8 To a solution of silica (5 g, 3.75 ramol) in toluene (25 mL) was added copper (I) chloride (20 mg, 0.19 mmol), 2,2'-bipyridyl (60 mg, 0.38 mmol) and scyrene (8.6 mL, 75 mmol). The mixoire was heaied at 130'C for 7212 under niurogen and filtered. The residue was washed widi medianol (3 x 200 raL) and soxhlet exuracted with toluene for 72h. Styrene Modified SiUcon-Trealed Carbon Black (Silica Phase) 10 A soiuiion of the halogenaied TEMPO adduct 9 of silicon-creared carbon black (5 g. 1,25 mmol) in styrene (20 mL) was added copper (I) chloride (60 mg, 0.6 mmol) and 2,2'-bipyridyl (200 mg, 1.27 mmol). The solution was heated at 90°C for 72h under nitrogen, dissolved in methylene chloride, precipitated into methanol and vacuum oven dried overnight. Styrene Modified (Carbon Phase) 11 A solution of the halogenated TEMPO adduct 9 of silicon-treated carbon black (5 g, 1.25 mmol) in styrene (20 mL), was heated at 130°C for 72h under nitrogen, dissolved in methylene chloride, precipitated into methanol and vacuum oven dried overnight. Hybrid TEMPO/SUane Modified Carbon Black 9 The carbon phase of dual phase silica/carbon black particles were modified with a TEMPO moiety by the method detailed in US patent application 08/968.299, incorporated herein by reference. These particles (25g) were suspended in a acetone/water (10:1, ISOmL) solution and the pH adjusted to 8.0 with potassium hydroxide. Chloropropyl trimeihoxysilane (4mL, excess) was then added dropwise and the solution and heated at 5010 for 4 hours under nitrogen. Upon cooling the suspension was filtered and washed with acetone (3 x lOOmL) and water (3 x lOOmL) and dried overnight in a vacuum oven at 40°C. To a chilled (0°C) solution of benzyl alcohol Vulcan 7H® modified carbon black (5g, 2mmoI) in dry hexane (50mL) was dropwise added phosphorus tribromide (0.4 mL. 4mmol). The solution was stirred for 5 minutes, before the removal of the ice bath and stirring for a further 30 minutes. Methanol (0.5mL) was added slowly, followed by slow addidon of sodium hydrogencarbonate (satd. aq., 2mL) and brine (satd. aq., 2mL). The suspension was filtered and washed with water (3 x lOOmL), methanol (3 x lOOmL), and acetone (3 x lOOmL) before the resulting solid was dried overnight in a vacuum oven at 40°C. Example: Isoprene (300mL) was added to TEMPO modified V7H (20g. 0.35 mmol/g) in a Parr pressure reactor. The reactor was sealed, degassed, and pressurized with Argon. The mixture was heated to MS1C for 18h. The resuhing black suspension was precipitated into rapidly agitating methanol and isolated by filtration. The black solid was dried at 70®C. Analysis: 48.32wt% Isoprene (TGA) T» (onset) =-59.25C Other embodunents of the present invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims. WHAT IS CLAIMED IS: 1. A modified panicle comprising a particle having attached a group having the formula: wherein R* is an alkyl or alkylene group or an aryl or arylene group; R1 and R1 which can be the same or different, represent hydrogen, an alkyl group, an aryl group, -0R1 -NHR\ -NRHR1 or •SR\ wherein R1 which is the same or different, represents an alkyl group or an aryl group; and Q represents a labile'halide containing species. 2. The modified particle of claim 1, wherein said Q is an aryl halide, alkyl halide, arenesulfonyl halide, or arenecarbonyl halide, phosphorous halide, sulfur halide, haioalkyl ester, or silicon halide. 3. The modified particle of claim 1, wherein Q comprises a labile halide and a carbon atom, a nitrogen atom, a sulfur atom, a phosphorous atom, a boron atom or a silicon atom. 4. The modified particle of claim 1, wherein said particle is a carbon product, a colored pigment other than a carbon product, a metal oxide, a metal hydroxide, or mixtures thereof. 5. The modified particle of claim 1, wherein said particle is graphite, vitreous carbon, activated charcoal, carbon fiber, activated carbon, or mixtures thereof. 6. The modified panicle of claim U wherein said panicle is carbon black. 7. The modified panicle of claim 1, wherein said panicle is an aggregate comprising at least one silicon-containing species phase and at least one carbon phase. 8. The modified particle of claim 1, wherein said panicle is an aggregate comprising at least one metal-containing species phase and at least one carbon phase. 9. The modified panicle of claim I, wherein said Q is a bromoalkyl radical, a chloroalkyl radical, or a silyl propyl chloride radical. 10. A modified panicle or aggregate comprising a) an aggregate comprising at least one carbon phase and at least one metal-containing species phase, an aggregate comprising at least one carbon phase and at least one silicon-containing species phase, a metal oxide» or a metal hydroxide and b) attached to said panicle or aggregate, a group having the formula: wherein CoupA represents a Si-based group, a Ti-based group, a Cr-based group, or a Zr-based group; R* and R1. which can be the same or different, represent hydrogen, an alkyl group, an aryl group. -0R'°. -NHR'1 -NR'°R'1 or -SR'°. wherein R11 which is the same or different, represents an alkyl group or an aryl group; Q represents a labile halide containing radical; and or is an integer of from I to 3. 11. The modified panicle or aggregate of claim 10, wherein said metal-containing species phase comprises an aluminum containing species phase, a zinc containing species phase, 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, a tin-containing species phase, an antimony-containing species phase, a chromium-containing species phase, a neodymium-containing species phase, a lead-containing species phase, a tellurium-containing species phase, a barium-containing species phase, a cesium-containing species phase, an iron-containing species phase, a molybdenum-containing species phase, or mixtures thereof. 12. The modified particle or aggregate of claim 10, wherein said metal-containing species phase comprises an aluminum-containing species phase. 13. The modified particle or aggregate of claim 10, wherein said metal-containing species phase comprises a zinc-containing species phase. 14. The modified panicle or aggregate of claim 10, wherein said Q comprises a labile halide and a carbon atom, a nitrogen atom, a sulfur atom, a phosphorous atom, a boron atom or a silicon atom. 15. The modified particle or aggregate of claim 10, wherein said-particle or aggregate is an aggregate comprising at least one carbon phase and at least one metal-containing species phase or an aggregate comprising at least one carbon phase and at least one silicon- containing species phase, 16. A modified particle comprising a particle having attached a group having the formula: wherein R** is an alkyl or alkyiene group or an aryl or arylene group; R1 and R\ which can be the same or different, represent hydrogen, an alkyl group, an aryl group, -0R\ -NHR1 -NR1R1 or -SR1 wherein R\ which is the same or different, represents an alkyl group or an aryl group; Q represents a labile halide containing species and X represents a polymer formed from at least one polymerizable monomer. 17. The modified particle of claim 16, wherein said polymerizable monomer is a vinyl or diene containing monomer. 18. The modified particle of claim 16, wherein said particle is a carbon product, a colored pigment other than a carbon product, a metal oxide, a metal hydroxide, or mixtures thereof 19. The modified particle of claim 16, wherein said particle is graphite, carbon black, vitreous carbon, activated charcoal, carbon fiber, activated carbon, or mixtures thereof 20. The modified particle of claim 16, wherein said panicle is an aggregate comprising at least one silicon-containing species phase and at least one carbon phase. 21. The modified panicle of claim 16, wherein said particle is an aggregate comprising a metal-containing species phase and a carbon phase. 22. The modified panicle of claim 16, wherein said particle is carbon black. 23. The modified panicle of claim 16, wherein said Q comprises a labile halide and a carbon atom, a nitrogen atom, a sulfur atom, a phosphorous atom, a boron atom or a silicon atom. 24. A modified panicle or aggregate comprising a) an aggregate comprising at least one carbon phase and at least one metai-containing species phase, an aggregate comprising at least one carbon phase and at least one silicon-containing species phase, a metal oxide, or a metal hydroxide and b) attached to said particle or aggregate a group having the formula: wherein CoupA represents a Si-based group, a Ti-based group, a Cr-based group, or a Zr-based group; R' and R1, which can be the same or different, represent hydrogen, an alkyl group, an aryl group, -0R'°, 'NHR'°, -NR'1'1 or -SR'°, wherein R'1 which is the same or different, represents an alky! group or an aryl group; Q represents a labile halide containing radical; X represents a polymer formed from at least one polymerizabie monomer; and n is an integer of from 1 to 3. 25. The modified particle or aggregate of claim 24, wherein said metai-containing species phase comprises an aluminum containing species phase, a zinc containing species phase, a magnesium-containing species phase, a calcium containing species phase, a vanadium-containing species phase, a cobalt-containing species phase, a nickel-containing species phase, a zirconium-containing species phase, a tin-containing species phase, an antimony-containing species phase, a chromium-containing species phase, a neodymium-containing species phase, a lead-containing species phase, a tellurium-containing species phase, a barium-containing species phase, a cesium-containing species phase, an iron- containing species phase, a molybdenum-containing species phase, or mixtures thereof, 26. The modified particle or aggregate of claim 24, wherein said metal-containing species phase comprises an aluminum-containing species phase. 27. The modified panicle or aggregate of claim 24, wherein said metal-containing species phase comprises a zinc-containing species phase. 28. The modified panicle or aggregate of claim 24, wherein said particle or aggregate is an aggregate comprising at least one carbon phase and at least one metal-containing species phase or an aggregate comprising at least one carbon phase and at least one silicon-containing species phase. 29. The modified carbon-metal aggregate of claim 24, wherein said Q comprises a labile halide and a carbon atom, a nitrogen atom, a sulfur atom, a phosphorous atom, a boron atom or a silicon atom. 30. The modified carbon-metal aggregate of claim 24, wherein said polymerizable monomer is a vinyl or diene containing monomer. 3L A modified for preparing the modified particle of claim 1, comprising reacting a particle having an attached -A-R1CR2R3 with a labile halide containing species 32. A method of preparing the modified particle of claim 16, comprising reacting the modified panicle of claim 1 with a) a polymerizable monomer, and b) a transition metal halide, and a complexing ligand or a preformed transition metal halide complex. 33. The method of claim 32, wherein the transition metal in the transition metal is copper, rhodium, iron, nickel, cobalt, palladium, or ruthenium. 34. The method of claim 32, wherein said transition metal halide is copper (I) halide. 35. The method of claim 32, wherein said complexing ligand is 2,2'bipyridine. 36. The method of claim 32, wherein said polymerizable monomer comprises styrenic, acrylic esters, methacrylic esters, or combinations thereof. 37. A polymeric composition comprising the modified particle of claim 16. 38. A polymeric composition comprising the modified particle or aggregate of claim 24. 39. A coating or ink composition comprising an aqueous or non-aqueous solvent, and the modified panicle of claim 1. 40. A coating or ink composition comprising an aqueous or non-aqueous solvent, and the modified panicle of claim 16. 41. A coating or ink composition comprising an aqueous or non-aqueous solvent, and the modified particle of claim 24. 42. An eiastomeric composition comprising at least one elastomer and the modified panicles of claim 1 and optionally a coupling agent. 43. The eiastomeric composition of claim 42, wherein said elastomer comprises natural rubber, polyisoprene, poly butadiene, emulsion SBR, solution SBR, functionalized SBR, NBR, butyl rubber, EPDM, EPM, or homo- or co-polymers based on or containing 1,3-butadiene, acrylonitrile, ethylene, propylene, or derivatives thereof. 44. The elastomeric composition of claim 42, further comprising a crosslinking agent, reinforcing filler, a coupling agent, processing aids, oil extenders, antidegradents, or combinations thereof. 45. The elastomeric composition of claim 42, further comprising silica, carbon black, or mixnires thereof. 46. The elastomeric composition of claim 42, further comprising silica, carbon black, modified carbon black having an attached organic group, modified silica, carbon black at least partially coated with silica, an aggregate comprising at least one carbon phase and at least one silicon-containing species phase, an aggregate containing at least one carbon phase and at least one metal-containing species phase, or combinations thereof. 47. The elastomeric composition of claim 42, wherein said elastomeric composition has low hystersis at high temperature, wherein said high temperature is from 20 to liX)°C. 48. A tire or compound thereof comprising the elastomeric composition of claim 42. 49. An article comprising at least one component made form the elastomeric composition of claim 42. 50. The article of claim 49, wherein said article is a tire component, a timing belt, or a power transmission belt. 51. A toner composition comprising resin particles and the modified particles of claim 1. 52. A toner composition comprising resin particles and the modified panicles of claim 16. 53. A toner composition comprising resin particles and the modified panicles of claim 24. 54. An ink composition comprising an ink vehicle and the modified particles of claim 1. 55. An ink composition comprising an ink vehicle and the modified particles of claim 16. 56. An Inkjet ink composition comprising an Inkjet ink vehicle and the modified particles of claim 1. 57. An Inkjet ink composition comprising an inkjet ink vehicle and the modified particles of claim 16. 58. An elastomeric composition comprising at least one elastomer and one or more modified particles or aggregate of claim 10. 1SQ. An elastomeric composition comprising at least one elastomer and one or more modified particles of claim 16. 60. An elastomeric composition comprising at least one elastomer and one or more modified panicles of claim 24.

Full Text

A PARTICLE HAVING AN ATTACHED HALIDE GROUP AND METHODS OF MAKING THE SAME
BACKGROUND OF THE INVENTION
The present invention relates to particles, such as carbon black, having an attached halide containing radical which permits the formation of modified panicles having blocked radical sources. The present invention further relates to methods of preparing and using such modified particles.
The role of carbon black as a thermal stabilizer in polymeric systems is discussed by W. L. Hawkins, R. H. Hansen, W. Matreyek, F. H. Winslow; 7. Applied Polymer Science, vol. 1. pages 37-42, 1959; J. T. Cmver, K. W. Rollmaim: J. Applied Polymer Science, vol. 8. pages 1169-83, 1964, and by G. Ivan, M. Giurgina: Revue Roumaine de Chemie, vol. 29, number 8, pages 639-646, 1984. In each discussion the mechanism is through phenolic and quinone oxygen groups on the carbon black surface behaving either as radical traps or peroxide decomposers. One skilled in the art, however, would consider these sites unavailable as initiating sites for polymerization processes.
Belmont et al. (J. A. Belmont, J. M. Funt; International Rubber Conference, Essen, Germany, June 24-27 1991) identified the presence of peroxide groups, typically in the range 0.1 to 0.4 micromoles/sq meter, on the carbon black surface. However, the majority (greater than 80%) of the peroxide groups are thermally stable to heat treatment at 200°C and hence cannot be considered to be potential initiating sites for radical polymerization.
Tsubokawa et al, (K. Fujiki, N. Tsubokawa, Y. Sone: Polymer J., vol. 22, number 8, pages 661-70, 1990, and N. Tsubokawa: Prog. Polymer Science, vol. 17, pages 417-70, 1992) discuss growing polymers from an activated carbon black surface by first attaching a reacdve group via the oxygen groups on the carbon black surface. Typical examples include the use of glycidyl methacrylate where the glycidyl group reacts with phenolic hydroxyl groups on the carbon black surface providing a vinyl functionality; the reaction of 4,4* azo bis-{4-cyanovaieric acid) whereby the isocyanate group reacts with phenolic hydroxyl groups and subsequent heating decomposes the azo group to generate an alkyl radical; and the reaction of the phenolic hydroxyl groups with butyl lithium which can then be used as an initiation site for anionic polymerization.
All of these approaches require the presence of oxygen groups on the carbon black surface. Since the level of reactive hydroxyl and carboxylic acid groups, relative to the above approaches, present on a typical furnace or thermal carbon black is typically 0.01 to 0.1

micromoles/sq meter, the number of potential initiation sites is quite low.
Further, subsequent polymerization from these activated sites will most likely occur in the normal manner for free radical polymerization with the chains being irreversible terminated by chain combination reactions, combination with unreacted oxygen groups on the carbon black surface, and/or the addition of chain stoppers. In all cases the polymerization cannot be reiniuated. Accordingly, there is a need to provide modified particles which overcome the above-described limitations.
SUMMARY OF THE INVENTION
In accordance with the purpose of the present invention, as embodied and broadly described herein, the present invention relates to a modified particle which includes a particle having an attached group having the formula:

wherein A represents an aromatic group or an alky! group; R' represents a bond, an arylene group, an alkylene group,

wherein R1is an alkyl or alkylene group or an aryl or arylene group; R1and R\ which can be the same or different, represent hydrogen, an alkyl group, an aryl group, -0R1-NHR\ -NR*R1or -SR1wherein R1which can be the same or different, represents hydrogen, an alkyl group or an aryl group; and Q represents a labile halide containing radical.
The present invention further relates to a modified particle or aggregate wherein the particle or aggregate is a carbon-metal multiphase aggregate, a carbon-silicon containing species multiphase aggregate, a metal oxide, or a metal hydroxide. Attached to the particle or

wherein Coup A represents a Si-containing group, a Ti-containing group, a Cr-containing group, or a Zr-containing group; R1and R1which can be the same or different, represent hydrogen, an alkyl group, an aryl group, -0R'°, -NHR'1-NR'°R'1or -SR'1wherein R'°, which can be the same or different, represents hydrogen, an alkyl group or an aryl group; Q represents a labile halide containing radical, and n is an integer of from 1 to 3.
The present invention further relates to a modified panicle with an attached polymer or blocked radial sources, wherein the modified particle has an attached group having the formula:

wherein X represents blocked radial sources or a polymer formed from at least one polymerizable vinyl or diene based monomer, A represents an aromatic group or an aJkyl group; R1represents a bond, an arylene group, an alkylene group,

wherein R1is an alkyl or alkylene group or an aryl or arylene group; R" and R\ which can be the same or different, represent hydrogen, an alkyl group, an aryl group, -0R1-NHR\ -NR1R1or -SR1, wherein R1which can be the same or different, represents an alkyl group or an aryl group; and Q represents a labile halide containing radical.
The present invention also relates to another modified particle having an attached polymer. The particle is a carbon-metal multiphase aggregate, a carbon-silicon containing species multiphase aggregate, a metal oxide, or a metal hydroxide. Attached to the particle is a

wherein CoupA represents a Si-containing group, a Ti-coniaining group, a Cr-containing group, or a Zr-coniaining group; R and R , which can be the same or different, represent hydrogen, an alkyl group, an aryl group, -0R'°, -NHR'°, -NR'°R1or -SR'1, wherein R'1which can be the same or different, represents an alkyl group or an aryl group; Q represents a labile halide containing radical, X is blocked radical sources or a polymer formed from at least one polymerizable monomer, and n is an integer of from 1 to 3.
The present invention, in addition, relates to a method for preparing and using these various modified particles. In making the modified particle of formula (I), the particle can have the aromatic or alkyl group and the -R'-CR1R** attached in any fashion either in a single step or multiple steps. -Q can then be attached using sufficient temperature and acid. In making the modified particle with the attached polymer, the method includes reacting a particle having an attached aromatic group substimted with R'-CR1R1-Q with a transition metal halide, a complexing ligand, and a polymerizable monomer.
The present invenuon, in addition, relates to a method for preparing and using these various modified panicles. For instance, in making the modified panicle of formula (I), the particle can have the aromatic or alkyl group and the -R'-CR1-R1attached in any fashion eidier in a single step or multiple steps, -Q can then be attached using an esterification technique, such as acid catalyzed esterification. In making the modified panicle witii the attached polymer, the method includes reacting a panicle having an attached aromatic or alkyl group substimted with R'-CR1R1-Q with a transition metal halide. a complexing ligand, and a polymerizable monomer.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the present invention, as claimed.
DETAILED DESCRIPTION OF THE PRESENT INVENTION
In one embodiment, the present invention relates to a modified panicle comprising a particle having attached a group having the formula:

wherein R1is an alkyl or alkylene group or an aiyl or arylene group; R1and R\ which can be the same or different, represent hydrogen, an alkyl group, an aryl group. -0R1-NHR1-NR1\ or SR\ wherein R1which can be the same or different, represents an alkyl group or an aryl group; and Q represents a labile halide containing radical.
The particle, to be modified, can be any particle capable of having a group represented by any one of the formulas described herein attached thereto, such as formula (IHIV). Preferably, the particle has a carbon reactive site (C-), since in a preferred embodiment for the groups of formula (I) and (III). -Q and -X-Q are preferably attached through a carbon bond on the particle. The particle, for instance, can be carbon products, colored pigments other than carbon products, metal oxides (e.g.. silica), metal hydroxides, multiphase aggregates comprising a carbon phase and a silicon-containing species phase, multi-phase aggregates comprising a carbon phase and a metal-containing species phase, and the like. The carbon may be of the crystalline and/or amorphous type. Examples of carbon products include, but are not limited to. graphite, carbon black, vitreous carbon, activated charcoal, activated carbon, carbon fiber, and mixmres thereof. Finely divided forms of the above are preferred. Most preferably, the particle is a carbon product, and most preferably carbon black.
The multi-phase aggregate containing the carbon phase and the silicon-containing species phase can also be considered a silicon-treated carbon black aggregate and the multiphase aggregate containing a carbon phase and a metal-containing species phase can be considered to be a metal-treated carbon black aggregate as long as one realizes that in either case, the silicon-containing species and/or metal-containing species are a phase of the aggregate

just like the carbon phase. The multi-phase aggregates do not represent a niixture of discrete carbon black aggregates and discrete silica or metal aggregates and is not a silica coated carbon black. Rather, the multi-phase aggregates used in the present invention include at least one silicon-containing or metal- The aggregate, thus contains at least two phases, one of which is carbon and the other of which is a silicon-containing species, a metal-containing species, or both. The silicon-containing species that can be a pan of the aggregate is not attached to a carbon black aggregate like a silica coupling agent, but actually is pan of the same aggregate as the carbon phase. For instance, when die multi-phase aggregate having a carbon phase and a silicon-containing species phase is examined under STEM-EDX, the silicon signal corresponding to the silicon-containing species is found to be present in individual carbon black aggregates. By comparison, for example, in a physical mixture of silica and carbon black, STEM-EDX examination reveals distincdy separate silica and carbon black aggregates.
The metal-treated carbon blacks are aggregates containing at least a carbon phase and a metal-containing species phase. The metal-containing species include 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. The metal-containing species phase can be distributed through at least a portion of the aggregate and is an inu-insic part of the aggregate.
Further, it is widiin the bounds of the present invention to have a metal-treated carbon black containing more than one type of metal-containing species phase or the metal-treated carbon black can also contain a silicon-containing species phase and/or a boron-containing species phase. For example, the metal-treated carbon black of the present invention can have an aggregate comprising a carbon phase, an aluminum-containing species phase, and a zinc-containing species phase. Accordingly, the multi-phase aggregates used in the present invention can have two or more different types of metal-containing species phases and/or additional non-metal species phases.
Preferably, for purposes of the present invention, the amount of elemental silicon and/or elemental metal present in the multi-phase aggregate is from about 0.1 to about 25 wt. %, more preferably, from about 0.5 wt. % to about 10 wt. %, and most preferably from about 0.2 wt. % to about 5.4 wt. %, by weight of the aggregate.

The details of making the multi-phase aggregates are explained in U.S. Patent Nos.-5,904J62; 5.877,238; 5,869,550; and 5,830,930; PCT Publication No. WO 96/37547, U.S. Patent Application No, 08/828,785, filed March 27, 1997; U.S. Patent Application No. 08/837,493, filed April 18, 1997; and U.S. Patent Application No. 09/061,871 filed April 17, 1998. All are hereby incorporated in their entireties herein by reference.
A silica-coated carbon product can also be used as the particle, which is described in PCT Application No, WO 96/37547, published November 28, 1996, and is hereby incorporated in its entirety herein by reference.
The colored pigment is any pigment which can be modified with the attachment of an aromatic group or an alky I group. The colored pigments other than carbon products include, but are not limited to, black, white, blue, brown, cyan, green, violet, magenta, red, yellow, as well as mixtures thereof. Suitable classes of colored pigments include, but are not limited to, anthraquinones, phthalocyanine blues, phthalocyanine greens, diazos, monoazos, pyranthrones, perylenes, heterocyclic yellows, quinacridones, and (thio)indigoids. Specific examples and further information concerning the colored pigments and methods of making colored pigments with attached aromatic groups or alkyl groups are described in PCT Publication No. WO 97/47699, incorporated in its entirety by reference herein.
Particles useful for the present invention may, for example, have primary panicles sizes in the general range of from about 10 nm to about 500 nm, and preferably from about 10 nm to about 250 nm, and primary aggregate sizes in the genera! range of from about 50 nm to about 100 microns, preferably from about 50 nm to about 10 microns, still more preferably from about 75 nm to about 1 micron. The BET surface area of these particles can be any suitable surface area and preferably ranges from about 10 mVg to about 2000 mVg and more preferably, from about 10 mVg to about 1,000 mVg, and still more preferably from about 50 mVg to about 500 mVg; and the particle structure preferably ranges from about 10 cc/lOOg to about 1000 cc/g, more preferably, from about 50 cc/lOOg to about 200cc/100g.
The number of Q groups attached to the particle prior to polymerization can be any amount. For instance, the number of -Q groups may range from about 0.01 mmole/g (of particle) to about 10 mmole/g, preferably from about 0.1 mmole/g to about 4 mmole/g, and still more preferably from about 0.5 mmole/g to about 3 mmole/g.
When the particle is a multi-phase aggregate, like a carbon phase and a silicon-containing species phase, preferably the group of formula (I) or (III) is attached at least, if not .exclusively, on the carbon phase.

With regard to the aromatic group, any aromatic group may be used. Unlike the polymerizable monomer discussed later, the aromatic group is not a polymer and is not polymerized. Examples include, but are not limited to, arylene groups. Preferred aryiene groups include, but are not limited to, phenylene and naphthalene groups. The aromatic group includes, but is not limited to, unsaturated cyclic hydrocarbons containing one or more rings. The aromatic group may be substituted or unsubstituted. Aromatic groups include aryl group (for example, phenyl, naphthyl, anthracenyl, and the like), and heteroaryi groups (for example, imidazolyl, pyrazolyl, pyridinyl, thienyl, thiazolyl, fiiryl, triazinyl, indolyl, and the like). The alkyl group is preferably a C1-CI2 alkyl group, and may be branched or unbranched, and is preferably ethyl.
With respect to R*. preferred arylene groups include, but are not limited to, benzene ring containing groups. Preferred alkylene groups include, but are not limited to, Ci - C's aikylene-containing groups. These groups can be linear, branched, or unsaturated. These examples of arylene and alkylene groups can also be considered examples of R1. Preferred alkyl groups for R1are CJ-C20 alkyl groups, more preferably Ci-D alkyl groups and preferred aryl groups are phenyl, biphenyl. and naphthyl.
With respect to R1and R1which can be the same or different, exanqjles of alkyl groups (e.g. C1-C20 alkyl group) include, but are not limited to, methyl, ethyl, propyl.1-butyl, and the like. Preferably, the alkyl group is a Ci-O alkyl group. Examples of aryl groups include, but are not limited to, phenyl, biphenyl, and naphthyl. The alkyl and aryl groups mentioned here as well as the arylene and alkylene groups mentioned throughout can be unsubstituted or substituted for purposes of the present invention. R1can be the same type of alkyl and aryl groups mentioned above with respect to R1and RThe labile halide containing group which is substituted or attached to the aromatic group as shown in formula (I) above, is a halide containing group wherein the labile halide {e.g., fluorine, bromine, iodine, chlorine) in the group is capable of forming an oxidized species with a transition metal halide. Preferably, the labile halide has a weak halide bond between the halide and the atom capable of forming the free radical. The labile halide is capable of undergoing chemical reaction resulting in the formation of the radical group which previously contained the labile halide. The group containing the labile halide in turn forms a radical which comprises a carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, boron atom, and/or silicon atom. Other organic species or groups can be a part of the group containing the labile halide such as alkyl, aryl, and the like. Specific examples of the labile halide containing group include, but are not limited to, aryl halides, aryl alkyl halides, alkyl haiides, benzyl halides,

arenesufonyl halides, phosphorous halides, haloallcyl esters, sulfur halides, silicon halides, arenecarbonyl halides, and other labile halide containing groups. A more specific example of a labile haiide containing group a bromo-or chloro-alkyl, such as bromoethyl, bromomethyl, bromo propyl and bromododecyl as well as the chloro versions of these groups which can form radicals. Another embodiment of the present invention relates to a modified panicle or aggregate having a group of formula (II) attached thereto. The panicle can be a metal oxide, a metal hydroxide, an aggregate comprising at least one carbon phase and a metal-containing species phase, or an aggregate comprising at least one carbon phase and at least one silicon-containing species phase. Attached to this particle or aggregate is a group having the formula:

wherein CoupA represents a Si-containing group, a Ti-containing group, a Cr-containing group, or a Zr-containing group; R* and R1which can be the same or different, represent hydrogen, an alkyl group, an aryl group. -0R'1-NHR*°. -NR*'1'1or -SR'°, wherein R'° represents an alkyl group or an aryl group; Q represents a labile halide containing radical, and where n is an integer of from 1 to 3. Preferably, CoupA is attached to the particle or aggregate, especially in the case of a Si-containing group, via an oxygen radical which can form a pan of a CoupA.
Examples of Si-containing groups include, but are not limited to, dimethylsilylmethyU dialkoxysiiylmethyU and the like. Examples of Ti-containing groups include, but are not limited to, alpha substituted ai-acetyl titanate and the like. Examples of Zr-containing groups include, but are not limited to, dialpha methoxy neopentylzirconate, aluminum zirconates and the like.
Examples of die substituents R1and R' can be the same as the subsuments R1and R1mentioned above. Likewise, examples of the substiment R'** can be the same as the substituent R1discussed above. Also, the Q is the same as discussed above.
The modified particles having the attached group of the formulas, such as formula (I), can be made in the following manner. A particle, such as carbon black, can first have a substituted or non-substituted aromatic or alkyl group attached to the panicle, wherein ttie aromatic or alkyl group is directly attached to the panicle. This attachment can be accomplished by the methods described in PCT International Application No. WO 96/18688 and U.S. Patent Nos. 5,851,280; 5,630,868; 5,559,169; 5,571,311; and 5,559.169 as well as

U.S. Patent Application No. 08/572,525, all of which are hereby incorporated in iheir entireties by reference herein.
The panicle having the attached aromatic or aikyl group can then react with -R'-CR1R1and then a labile halide containing radical source for a sufficient time and at a sufficient temperarure to form the modified particle having the attached group, like that of formula I. The labile halide containing radical source is present in amounts sufficient to react with -A-R'-CR1R1present on the particle. Preferably, the amount of the labile halide containing radical source is from about 0.01 mmoles/g (of particle) to about 10 mmoles/g and more preferably from about 0.01 to about 5 mmoles/g. Alternatively, the labile halogenating containing species can be formed by halogenation of a C-0 bond with a halogenating agent such as phosphorous tri-bromide.
Alternatively, the modified particles of the present invention can be made by first forming the groups of the formulas described above, such as formula (I), Preferably, the labile haiide containing radical group is attached in the meta or para position of the aromatic group, if present. This group is then attached to the particle by a diazonium treatment in the manner described in the above referenced patents and patent applications, where a diazonium salt will first be formed containing a group of one of the formulas described above in the manner described in the above-referenced patents. The groups of the formulas can be then subsequently attached to the particle. In a less preferred way, the formulas of the present invention can be attached to the particle through a hydroxyl or carbonyl group present on the particle.
Also, the modified panicle of the present invention can be formed by attaching a labile halide containing group containing at least one aikoxy silyl, aikoxy titanyl, or alkoxy zirconyl group to the particle which, in this particular process is preferably a metal oxide or metal hydroxide, or a carbon surface. This particular embodiment would attach a group of formula (ID or (IV) to a particle.
In another process, the modified particle can be formed by first taking an aromatic or alkyl group and reacting it with R'CR1R1containing compound to form the groups of the formulas described above except for the presence of the -Q group. In other words, a group having the formula A-R'-CR"R1would first be formed and then the -Q group would be attached to this group to form a group of formula (I) of the present invention which can then be attached to the particle. In this process, R1and R1are preferably hydrogen.
Alternatively, the process of making the modified particles of the present invention can

be a three step process where A is first attached to the particle and then the group having the formula R1-C-R1R1can be attached to the aromatic or alkyl group. Then in a third step, the -Q can be attached to the R'-C-R1R1group.
The modified particles of formula (II) can be made in the following manner. The aggregate comprising at least one carbon phase and at least one metal-containing species phase can be made as described in U.S. Patent Application No. 08/828,725. hereby incorporated herein by reference. The aggregate comprising at least one carbon phase and at least one metal containing species phase can be made as described in U.S. Patent No. 5,904,762 and 5,877,238. The aggregate or particle can then be reacted with a coupling agent by adding the coupling agent to the aggregate in a medium and mixing. Then, the aggregate or particle having the attached coupling group can be reacted with a labile halide containing radical source as described above.
For purposes of the above-described reactions, the reaction should occur for a time and temperature sufficient to form the attached group onto the particle or aggregate. Generally, this time is from about 3 minutes to about 96 hours and more preferably from about 1 hour to about 24 hours-
With the modified particles described above, polymers can be attached onto these attached groups by reacting these modified particles or aggregates with a polymerizable monomer such as a vinyl or diene containing monomer. Specific examples of such monomers include, but are not limited to, styene, isoprene, butadiene, chloromethylstyrene, methyl methacrylate, and butyl mcthacrylate, as well as acrylic acid and esters of acrylic acid and methacrylic acid and esters of methacrylic acid. More specific monomer examples include, but are not limited to, hydroxyalkyl (meth)acrylates, such as hydroxyethyl (meth)acrylaie, hydrox>proyl (meth)acrylate; alkyl (meth)acrylates such as methyl acrylate or butyl acrylate; glycidyl (meth)acrylate; dimethylaminoethylacrylate; 2-acryl trimethyl ethylammonium chloride; aminoethyl acerylate; acrylonitirle; vinyl acetrate, and the like. Mixtures of two or more monomers can be also used or polymerized sequentially. If polymeric gels are described, then the monomer or ponion thereof is preferably a halide containing vinyl monomer or diene containing monomer (e.g., chloromethyl styrene or vinyl chloride).
The polymerization reaction is conducted under conditions which permits the poiymerizadon of the monomer so that it forms a part of the attached group onto the panicle or aggregate. These conditions include ambient temperatures and can include preferably heating modified particles with a monomer above 80°C, preferably from about 120°C to about ISO'1'C, in the presence of a solvent, a transition metal halide, and a complexing ligand. The reaction

can be ended by lowering the temperature. The sequence of addition is not important and the particle (for instance Formula (I) or (III) complexing ligand, and transition metal halide can be added in any order. A preformed transition metal halide complex can alternatively be used in lieu of the separate components. In addition, complexing ligand and transition metaJ halide can first be reacted to form a complex or the reaction can occur in situ. The polymer-modified particle can then be subjected to distillation, steam stripping, or precipitation or other known methods in order to remove residual monomers and solvents. Examples of transition metal halides include, but are not limited to, copper (I) halides, and transition metal halides wherein the metal is copper, rhodium, iron, nickel, cobalt, palladium, and ruthenium. A specific and preferred example of the transition metal halide is copper (I) chloride. The complexing ligand can be any compound capable of complexing with the transition metal halide in order to be an efficient halide atom transfer promoter. Examples of the complexing ligand include, but are not limited to, 2,2'-bipyridine and derivatives thereof (e.g., alkyl substituted bipyridines), derivatives of uriphenyl phosphines, and muitidentate amines were the nitrogen atoms are preferably separated by ethylene or propylene units.
The polymerization reaction thus can produce any length of polymer on the modified particle or aggregate. For example, polymers having average molecular weights, preferably ranging from about 500 to about 1,000,000 can be made. Other ranges of average molecular weights include, but are not limited to, from about 500 to about 3,000, and from about 500 to about 2,000, and firom about 500 to about 500,000, and from about 1,000 to about 250,000. The polymers can be any type, such as homopolymers, co-polymers, ter-polymers. or higher chain polymers. The polymers can also be block, graft, or random-type polymers. The polymers can be branched or unbranched. Polymers, such as comb polymers, can be formed or located off of the main polymer chain, and these polymers can be any type of polymer. Specific examples include, but are not limited to, polyamines. such as poiyethyleneimine or polyalkylene oxides, grafted onto the main polymer chain. The polymers that are formed can be ionic (e.g., canonic or anionic) or non-ionic polymers. Specific examples of polymers include, but are not limited to, polyamides, polyacrylics, polyvinylacetates, polyvinylalcohols. polyvinylpyridines, polyvinylpyrrilodones, polyvinylimidazoles, and acrylamides and derivatives thereof as well as combinations thereof
Once the polymerizauon occurs, the modified particle will have a group attached
having the formula:

wherein the substituents are the same as described earlier for formula (I) and X is a polymer formed from at least one polymerizable monomer.
Similarly, when the modified particle or aggregate having a group of formula (II) is polymerized by the introduction of one or more monomers, the group attached to the particle or aggregate will have the formula:
wherein the substituents are the same as described in formula (II) and X is a polymer formed from at least one polymerizable monomer.
Within the above-described groups containing the labile halide group, the modified particle or aggregate containing the labile halide group can be terminated by means known to those skUled in the art in view of the present application. In particular, the halide group can be replaced with a proton, subjected to disproportionation, or replaced with a chemical group dirough group transfer and the like. For instance, the halide group can be replaced with a hydroxy group. This termination or removing the halide group and replacing it or terminating it with another group can be accomplished, for instance, by methods described at Advanced Organic Chemistry, J. March, Wiley, 4"* Ed., (1992), for instance at page 370, which is incorporated in their enurety by reference herein.
The modified particles of the present invention can form part of a polymeric composition and be present with other ingredients commonly used and found in polymeric composidons.
A particle, as described herein, can also be modified as described herein and can also be modified as described in U.S. Patent Application Nos. 08/962,244 and 08/968,299. and the Application entitled "Methods of Making a Particle Having an Attached Stable Free Radical" filed June 3, 1998. all of which are incorporated in their entirety herein by reference. In more detail, a particle can be dual or multi-modified to have a group of formulae (I) - (IV)) attached thereto and also have a group having a labile halide containing radical attached as well, such as a group having the formulae (I) - (IV) as described in the above-referenced applications. The

polymerization of the monomers on the multiple groups attached onto the particle can be accomplished in any sequence or simultaneously.
The modified particle of the present invention can be used in a variety of applications. For instance, it can be used in coating formulations or compositions, or ink formulations or compositions, or toner formulations or compositions, such as printing inks and ink jet inks, toners, automobile coatings, and the like. Also, the modified particles can be used as reinforces for compositions, such as polymeric compositions and can also serve as impact modifiers, or as agents used to increase compatibility of a polymeric composition.
In more detail, reinforcement of elastomeric compositions include tire, hose, profile extrusion, seals, gaskets, and vibration isolation units, as well as the specific reinforcement of a single elastomer phase in a multiphase elastomer blend composition; reinforcement of thermoplastic compositions such as polyolefmes, styrenic, acrylics, polyesters, and polyamides. and thermoplastic elastomers and thermoplastic polyoiefines; reinforcement of thermoset compositions, elg., acrylics; impact modification of thermoplastic compositions, coatings, thermoplastic elastomers, and crosslinked compositions; as a synthetic support for solid phase organic synthesis; as a support or medium for effluent extraction processes - both organic and inorganic components; as a catalyst support; and/or as a superadsorbant for either aqueous of hydrocarbon materials e.g., use in sanitary wear, growing medium for plants.
The modified particles of the present invention can be incorporated in and form a part of elastomeric compositions. Other conventional ingredients for elastomeric con:5)Osirions can also be present, such as coupling agents and the like.
Coupling agents, as used herein, include, but are not limited to. compounds that are capable of coiq)ling fillers such as carbon black or silica to an elastomer having one functionality which will attach to the panicle and another functionality which will attach to the elastomer. Coupling agents useful for coupling silica or carbon black to an elastomer, are ejq)ected to be useful with the silicon-treated carbon blacks. Useful coupling agents include, but are not limited to, silane coupling agents such as bis(3)triethoxysilylpropyl)tetrasulfane (Si-69). 3-thiocyanatopropyl-niethoxy silane (Si-264, from Degussa AG, Germany), Y-mercaptopropyl-trimethoxy silane (A189. from Union Carbide Corp., Danbury, Connecticut); zirconate coupling agents, such as zirconium dineoalkanolatiodi(3-mercapto) propionato-0 (NZ 66A, from Kenrich Peu-ochemicals,Inc., of Bayonne, New Jersey); titianate coupling agents; niao coupling agents such as N,N'-bis(2-methyl-2-nitropropyl)-1.6-diaminohexane (Sumifine 1162, from Sumitomo Chemical Co., Japan); polyalkoxysiloxane (e.g., Zeruma from the Yokahama Rubber Co. Ltd.. Japan) and mixtures of any of the foregoing. The coupling agents

can be provided as a mixture with a suitable carrier1for example X50-S which is a mixture of Si-69 and N330 carbon black, available from Degussa AG.
The elastomeric compounds of the present invention may be prepared from the modified particles of the present invention by compounding with any elastomer including those useful for compounding a carbon black.
Any suitable elastomer may be compounded with the modified particles to provide the elastomeric compounds of the present invention. Such elastomers include, but are not limited to. homo- or co-polymers of 1,3 butadiene, styrene, isoprene, isobutylene, 2,3-dimethyH,3-butadiene, acrylonitrile, ethylene, and propylene. Preferably, the elastomer has a glass transition temperamre (Tg) as measured by differential scanning colorimeter (DSC) rangii1from about -120'*C to about 0**C. Examples include, but are not limited to, styrene-butadiene rubber (SBR), natural rubber, polybutadiene, polyisoprene, and their oil-extended derivatives. Blends of any of the foregoing may also be used.
Among the rubbers suitable for use with the present invention are natural rubber and its derivatives, such as chlorinated rubber and epoxidized rubber. TTie modified particles of the present invention may also be used with synthetic rubbers such as: copolymers of from about 10 to about 70 percent by weight of styrene and from about 90 to about 30 percent by weight of butadiene such as copolymer of 19 parts styrene and 81 parts butadiene, a copolymer of 30 parts styrene and 70 parts butadiene, a copolymer of 43 parts styrene and 57 parts butadiene and a copolymer of 50 parts styrene and 50 parts butadiene; polymers and copolymers of conjugated dienes such as polybutadiene, polyisoprene, polychloroprene, and the like, and copolymers of such conjugated dienes with an ethylenic group-containing monomer copolymerizable therewith such as styrene, methyl styrene, chlororaethylscyrene, acrylonitrile, 2-vinyl-pyridine, 5-methyl 2-vinylpryidine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine. alkyl-substimted acrylates or mediacrylates, vinyl ketone, methyl isopropenyl ketone, methyl vinyl ether, alpha-methylene carboxylic acids and the esters and amides thereof such as acrylic acid, mediacrylic acid, and dialkylacrylic acid amide; also suitable for use herein are copolymers of ediylene and other high alpha olefins such as propylene, butane, pentane, hexane, and octane. Other monomers that could be used include norborene and hex-l,5-diene, and the like.
The rubber compositions of the present invention can therefore contain one or more
elastomers, curing agents, reinforcing fillers, coupling .agents, and, opuonally, various
processing aids, oil extenders, and anti-degradents. In addition to the examples mentioned
•' 'above, the elastomer can be, but is not limited to, polymers (e.g., homopolymers, copolymers.

and terpolymers) manufactured from 1,3 butadiene, scyrene, isoprene, isobutylene, 2,3-dimethyl-l,3-butadiene, acrylonitrile, ethylene, propylene, and the like. It is preferred that*" these elastomers have a glass transidon point (Tg), as measured by DSC, between -IIQ'1C and O1C, Examples of such elastomers include poly(butadiene). poly(styrene-co-butadiene), and poly(isoprene).
Elastomeric compositions disclosed in the present invention include, but are not limited to, vulcanized compositions (VR), thermoplastic vulcanizates (TPV). thermoplastic elastomers (TPE). and thermoplastic polyolefins (TPO), TPV, TPE, and TPO materials are further classified by their ability to be extruded and molded several times without loss of performance characteristics. The elastomeric compositions may include one or more curing agents such as. for example, sulfur, sulfur donors, activators, accelerators, peroxides, and other system used to effect vulcanization of the elastomer composition.
The resultant elastomeric compounds containing the aggregates of the present invention and optionally containing one or more coupling agents may be used for various elastomeric products such as a tread compound, undertread compound, sidewall compound, wire skim compound, inner liner con1und. bead, apex, any compound used in carcass and other components for vehicle tires, industrial rubber products, seals, timing belts, power transmission belting, and odier rubber goods.
In an embodiment of the present invention, the elastomeric compositions of the present invention, which contain at least one modified particle of the present invention, can have a total residue after nin-ogen pyrolysis at 6501C of from about 1 % to about 60% by weight.
For purposes of the present invention, the ink includes at least one type of polymerized-terminated modified particle, and at least one ink vehicle. The inkjct ink formulation includes at least one type of polymerized terminated modified particle, and at least one inkjet ink vehicle. Generally, the formulations described in WO 97/47699 with respect to coatings and inks can be used herein, however, incorporating the modified particles of the present invention. The coating formulations contain at least one type of polymerized-terminated modified particle and at least one suitable solvent. Other conventional additives may be incorporated into Ac coating formulations, such as a binder.
Each of these fonnulations can contain additional conventional colorant and other optional, conventional ingredients or additives, for instance, ad described in U.S. Patent Nos. 5,571,311; 5,672,198; 5,266.361; 5.707,432 such as a humectant, binders, dyes, biocides, surfactants, penetrants. All of these patents are incorporated herein in their entirety by reference herein.

I
The toner can contain at least one polymcrized-ierminaied modified particle and resin panicies.
The conventional and standard ingredients or addiuves for toner formulations, such as those described in U.S. Parent Nos. 5,278,018; 5,275,900; 5.695.899, and 5,116.712, can be used in the present invenuon, and are incorporated in their entirety by reference herein. The toner can be a posiuveiy or negadvely charged toner composiuon.
In the various products incorporating the modified particles of the present invention, one or more types of other panicles can also be present, such as a carbon product (e.g., carbon black), metal oxide (e.g., silica, zinc oxide, andaluminiim oxide), metal silicate (e.g., clay, aluminum, calcium, magnesium silicates), modified silica, modified carbon products having an anacbed organic group, an aggregate comprising at least one carbon phase and at least one silicon-containing species phase optionally having an attached organic group, carbon black at least partially coated with silica, or any combioauon thereof, in any product mendoned herein, more than one type of modified panicle of the present invention can be present in the various products described above.
The present invendon will be further clarified by the following examples, which are intended to be purely exeirqplaiy of the invenuon.
KXAIVtPLES
Example 1

Bromo Modiikd Carbon JBlack 4
To a soiuuon of benzoic acid Vulcan* 7H modified carbon black 5 (50 g, 0.02 mol) in toiuene (250 mL) was added bromodocecanol (10.6 g, 0.04 mol) and ;?-ioluene sulfonic acid (3.8 g, 0.02 mol). The mixrure was heaied at reflux under niurogen for 18h in the presence of a Dean & Stark trap. The raixiure was filiered and washed wich toluene (3 x 100 mL) and dried in a vacuum oven at 70°C for 12h.
PoIy(acryla£e) Modified Carbon Black 6
To a solution of the modified carbon black (5 g, 0.002 mol) in toluene (25 mL) was added copper (I) chloride (0.05 g), 2,2'-bipyridyI (0.16 g) and (2-dimeihyianiino) eihyl mediacrylate (4 mL). The raixmre was heated at 130°C for 72h under niurogen, then filtered and washed with methanol. The residue was further exiracied with hot methanol in a soxhlet extractor for 72h, followed by soxhlec extracdon with toluene for 72h.

Siiazie Modified Silica 7
Silica (lOOg) was suspended in a 10:1 acetone water mixture and adjusted to pH 8 with sodium hydroxide. Chloropropyltrimethoxsilane (7.9 g. 0.04 mol) was added and the soiuuon hf3T1f) at 50**C under nicrogen for 4h. The mixture was filtered and washed with water (4 x 200 mL) and acetone (4 x 200 mL).

Scyreoe Modified Silka 8
To a solution of silica (5 g, 3.75 ramol) in toluene (25 mL) was added copper (I) chloride (20 mg, 0.19 mmol), 2,2'-bipyridyl (60 mg, 0.38 mmol) and scyrene (8.6 mL, 75 mmol). The mixoire was heaied at 130'C for 7212 under niurogen and filtered. The residue was washed widi medianol (3 x 200 raL) and soxhlet exuracted with toluene for 72h.

Styrene Modified SiUcon-Trealed Carbon Black (Silica Phase) 10
A soiuiion of the halogenaied TEMPO adduct 9 of silicon-creared carbon black (5 g. 1,25 mmol) in styrene (20 mL) was added copper (I) chloride (60 mg, 0.6 mmol) and 2,2'-bipyridyl (200 mg, 1.27 mmol). The solution was heated at 90°C for 72h under nitrogen, dissolved in methylene chloride, precipitated into methanol and vacuum oven dried overnight.

Styrene Modified (Carbon Phase) 11
A solution of the halogenated TEMPO adduct 9 of silicon-treated carbon black (5 g, 1.25 mmol) in styrene (20 mL), was heated at 130°C for 72h under nitrogen, dissolved in methylene chloride, precipitated into methanol and vacuum oven dried overnight.
Hybrid TEMPO/SUane Modified Carbon Black 9
The carbon phase of dual phase silica/carbon black particles were modified with a TEMPO moiety by the method detailed in US patent application 08/968.299, incorporated herein by reference. These particles (25g) were suspended in a acetone/water (10:1, ISOmL) solution and the pH adjusted to 8.0 with potassium hydroxide. Chloropropyl trimeihoxysilane (4mL, excess) was then added dropwise and the solution and heated at 50*10 for 4 hours under nitrogen. Upon cooling the suspension was filtered and washed with acetone (3 x lOOmL) and water (3 x lOOmL) and dried overnight in a vacuum oven at 40°C.

To a chilled (0°C) solution of benzyl alcohol Vulcan 7H® modified carbon black (5g, 2mmoI) in dry hexane (50mL) was dropwise added phosphorus tribromide (0.4 mL. 4mmol). The solution was stirred for 5 minutes, before the removal of the ice bath and stirring for a further 30 minutes. Methanol (0.5mL) was added slowly, followed by slow addidon of sodium hydrogencarbonate (satd. aq., 2mL) and brine (satd. aq., 2mL). The suspension was filtered and washed with water (3 x lOOmL), methanol (3 x lOOmL), and acetone (3 x lOOmL) before the resulting solid was dried overnight in a vacuum oven at 40°C.

Example:
Isoprene (300mL) was added to TEMPO modified V7H (20g. 0.35 mmol/g) in a Parr pressure reactor. The reactor was sealed, degassed, and pressurized with Argon. The mixture was heated to MS1C for 18h. The resuhing black suspension was precipitated into rapidly agitating methanol and isolated by filtration. The black solid was dried at 70®C.
Analysis:
48.32wt% Isoprene (TGA) T» (onset) =-59.25C
Other embodunents of the present invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.

WHAT IS CLAIMED IS:
1. A modified panicle comprising a particle having attached a group having the
formula:

wherein R* is an alkyl or alkylene group or an aryl or arylene group; R1 and R1 which can be the same or different, represent hydrogen, an alkyl group, an aryl group, -0R1 -NHR\ -NRHR1 or
•SR\ wherein R1 which is the same or different, represents an alkyl group or an aryl group; and Q represents a labile'halide containing species.
2. The modified particle of claim 1, wherein said Q is an aryl halide, alkyl halide, arenesulfonyl halide, or arenecarbonyl halide, phosphorous halide, sulfur halide, haioalkyl ester, or silicon halide.
3. The modified particle of claim 1, wherein Q comprises a labile halide and a carbon atom, a nitrogen atom, a sulfur atom, a phosphorous atom, a boron atom or a silicon atom.
4. The modified particle of claim 1, wherein said particle is a carbon product, a
colored pigment other than a carbon product, a metal oxide, a metal hydroxide, or mixtures
thereof.
5. The modified particle of claim 1, wherein said particle is graphite, vitreous
carbon, activated charcoal, carbon fiber, activated carbon, or mixtures thereof.

6. The modified panicle of claim U wherein said panicle is carbon black.
7. The modified panicle of claim 1, wherein said panicle is an aggregate comprising at least one silicon-containing species phase and at least one carbon phase.
8. The modified particle of claim 1, wherein said panicle is an aggregate comprising at least one metal-containing species phase and at least one carbon phase.
9. The modified panicle of claim I, wherein said Q is a bromoalkyl radical, a chloroalkyl radical, or a silyl propyl chloride radical.
10. A modified panicle or aggregate comprising a) an aggregate comprising at least one carbon phase and at least one metal-containing species phase, an aggregate comprising at least one carbon phase and at least one silicon-containing species phase, a metal oxide» or a metal hydroxide and b) attached to said panicle or aggregate, a group having the formula:

wherein CoupA represents a Si-based group, a Ti-based group, a Cr-based group, or a Zr-based group; R* and R1. which can be the same or different, represent hydrogen, an alkyl group, an aryl group. -0R'°. -NHR'1 -NR'°R'1 or -SR'°. wherein R11 which is the same or different, represents an alkyl group or an aryl group; Q represents a labile halide containing radical; and or is an integer of from I to 3.
11. The modified panicle or aggregate of claim 10, wherein said metal-containing species phase comprises an aluminum containing species phase, a zinc containing species phase, 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, a tin-containing species phase, an antimony-containing species phase, a chromium-containing species phase, a neodymium-containing species phase, a lead-containing species phase, a tellurium-containing species phase, a barium-containing species phase, a cesium-containing species phase, an iron-containing species phase, a molybdenum-containing species phase, or mixtures thereof.
12. The modified particle or aggregate of claim 10, wherein said metal-containing species phase comprises an aluminum-containing species phase.
13. The modified particle or aggregate of claim 10, wherein said metal-containing species phase comprises a zinc-containing species phase.
14. The modified panicle or aggregate of claim 10, wherein said Q comprises a labile halide and a carbon atom, a nitrogen atom, a sulfur atom, a phosphorous atom, a boron

atom or a silicon atom.
15. The modified particle or aggregate of claim 10, wherein said-particle or
aggregate is an aggregate comprising at least one carbon phase and at least one metal-containing
species phase or an aggregate comprising at least one carbon phase and at least one silicon-
containing species phase,
16. A modified particle comprising a particle having attached a group having the
formula:

wherein R** is an alkyl or alkyiene group or an aryl or arylene group; R1 and R\ which can be the same or different, represent hydrogen, an alkyl group, an aryl group, -0R\ -NHR1 -NR1R1 or -SR1 wherein R\ which is the same or different, represents an alkyl group or an aryl group; Q represents a labile halide containing species and X represents a polymer formed from at least one polymerizable monomer.
17. The modified particle of claim 16, wherein said polymerizable monomer is a
vinyl or diene containing monomer.
18. The modified particle of claim 16, wherein said particle is a carbon product, a
colored pigment other than a carbon product, a metal oxide, a metal hydroxide, or mixtures
thereof
19. The modified particle of claim 16, wherein said particle is graphite, carbon
black, vitreous carbon, activated charcoal, carbon fiber, activated carbon, or mixtures thereof
20. The modified particle of claim 16, wherein said panicle is an aggregate
comprising at least one silicon-containing species phase and at least one carbon phase.

21. The modified panicle of claim 16, wherein said particle is an aggregate comprising a metal-containing species phase and a carbon phase.
22. The modified panicle of claim 16, wherein said particle is carbon black.
23. The modified panicle of claim 16, wherein said Q comprises a labile halide and a carbon atom, a nitrogen atom, a sulfur atom, a phosphorous atom, a boron atom or a silicon atom.
24. A modified panicle or aggregate comprising a) an aggregate comprising at least
one carbon phase and at least one metai-containing species phase, an aggregate comprising at
least one carbon phase and at least one silicon-containing species phase, a metal oxide, or a
metal hydroxide and b) attached to said particle or aggregate a group having the formula:

wherein CoupA represents a Si-based group, a Ti-based group, a Cr-based group, or a Zr-based group; R' and R1, which can be the same or different, represent hydrogen, an alkyl group, an aryl group, -0R'°, 'NHR'°, -NR'1'1 or -SR'°, wherein R'1 which is the same or different, represents an alky! group or an aryl group; Q represents a labile halide containing radical; X represents a polymer formed from at least one polymerizabie monomer; and n is an integer of from 1 to 3.
25. The modified particle or aggregate of claim 24, wherein said metai-containing
species phase comprises an aluminum containing species phase, a zinc containing species phase,
a magnesium-containing species phase, a calcium containing species phase, a vanadium-containing species phase, a cobalt-containing species
phase, a nickel-containing species phase, a zirconium-containing species phase, a tin-containing
species phase, an antimony-containing species phase, a chromium-containing species phase, a
neodymium-containing species phase, a lead-containing species phase, a tellurium-containing
species phase, a barium-containing species phase, a cesium-containing species phase, an iron-
containing species phase, a molybdenum-containing species phase, or mixtures thereof,
26. The modified particle or aggregate of claim 24, wherein said metal-containing
species phase comprises an aluminum-containing species phase.
27. The modified panicle or aggregate of claim 24, wherein said metal-containing
species phase comprises a zinc-containing species phase.
28. The modified panicle or aggregate of claim 24, wherein said particle or
aggregate is an aggregate comprising at least one carbon phase and at least one metal-containing

species phase or an aggregate comprising at least one carbon phase and at least one silicon-containing species phase.
29. The modified carbon-metal aggregate of claim 24, wherein said Q comprises a labile halide and a carbon atom, a nitrogen atom, a sulfur atom, a phosphorous atom, a boron atom or a silicon atom.
30. The modified carbon-metal aggregate of claim 24, wherein said polymerizable monomer is a vinyl or diene containing monomer.
3L A modified for preparing the modified particle of claim 1, comprising reacting a particle having an attached -A-R1CR2R3 with a labile halide containing species
32. A method of preparing the modified particle of claim 16, comprising reacting the modified panicle of claim 1 with a) a polymerizable monomer, and b) a transition metal halide, and a complexing ligand or a preformed transition metal halide complex.
33. The method of claim 32, wherein the transition metal in the transition metal is copper, rhodium, iron, nickel, cobalt, palladium, or ruthenium.
34. The method of claim 32, wherein said transition metal halide is copper (I) halide.
35. The method of claim 32, wherein said complexing ligand is 2,2'bipyridine.
36. The method of claim 32, wherein said polymerizable monomer comprises styrenic, acrylic esters, methacrylic esters, or combinations thereof.
37. A polymeric composition comprising the modified particle of claim 16.
38. A polymeric composition comprising the modified particle or aggregate of claim 24.
39. A coating or ink composition comprising an aqueous or non-aqueous solvent, and the modified panicle of claim 1.
40. A coating or ink composition comprising an aqueous or non-aqueous solvent, and the modified panicle of claim 16.
41. A coating or ink composition comprising an aqueous or non-aqueous solvent, and the modified particle of claim 24.
42. An eiastomeric composition comprising at least one elastomer and the modified panicles of claim 1 and optionally a coupling agent.
43. The eiastomeric composition of claim 42, wherein said elastomer comprises natural rubber, polyisoprene, poly butadiene, emulsion SBR, solution SBR, functionalized SBR, NBR, butyl rubber, EPDM, EPM, or homo- or co-polymers based on or containing 1,3-butadiene, acrylonitrile, ethylene, propylene, or derivatives thereof.

44. The elastomeric composition of claim 42, further comprising a crosslinking agent, reinforcing filler, a coupling agent, processing aids, oil extenders, antidegradents, or combinations thereof.
45. The elastomeric composition of claim 42, further comprising silica, carbon black, or mixnires thereof.
46. The elastomeric composition of claim 42, further comprising silica, carbon black, modified carbon black having an attached organic group, modified silica, carbon black at least partially coated with silica, an aggregate comprising at least one carbon phase and at least one silicon-containing species phase, an aggregate containing at least one carbon phase and at least one metal-containing species phase, or combinations thereof.
47. The elastomeric composition of claim 42, wherein said elastomeric composition has low hystersis at high temperature, wherein said high temperature is from 20 to liX)°C.
48. A tire or compound thereof comprising the elastomeric composition of claim 42.
49. An article comprising at least one component made form the elastomeric composition of claim 42.
50. The article of claim 49, wherein said article is a tire component, a timing belt, or a power transmission belt.
51. A toner composition comprising resin particles and the modified particles of
claim 1.
52. A toner composition comprising resin particles and the modified panicles of
claim 16.
53. A toner composition comprising resin particles and the modified panicles of
claim 24.
54. An ink composition comprising an ink vehicle and the modified particles of claim 1.
55. An ink composition comprising an ink vehicle and the modified particles of claim 16.
56. An Inkjet ink composition comprising an Inkjet ink vehicle and the modified particles of claim 1.
57. An Inkjet ink composition comprising an inkjet ink vehicle and the modified particles of claim 16.
58. An elastomeric composition comprising at least one elastomer and one or more modified particles or aggregate of claim 10.

1SQ. An elastomeric composition comprising at least one elastomer and one or more modified particles of claim 16.
60. An elastomeric composition comprising at least one elastomer and one or more modified panicles of claim 24.

Documents:

abs-in-pct-2000-754-che.jpg

in-pct-2000-754-che-abstract.pdf

in-pct-2000-754-che-assignment.pdf

in-pct-2000-754-che-claims filed.pdf

in-pct-2000-754-che-claims granted.pdf

in-pct-2000-754-che-correspondence others.pdf

in-pct-2000-754-che-correspondence po.pdf

in-pct-2000-754-che-description complete filed.pdf

in-pct-2000-754-che-description complete granted.pdf

in-pct-2000-754-che-form 1.pdf

in-pct-2000-754-che-form 26.pdf

in-pct-2000-754-che-form 3.pdf

in-pct-2000-754-che-form 5.pdf

in-pct-2000-754-che-other documents.pdf

in-pct-2000-754-che-pct.pdf

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Patent Number

202345

Indian Patent Application Number

IN/PCT/2000/754/CHE

PG Journal Number

05/2007

Publication Date

02-Feb-2007

Grant Date

04-Oct-2006

Date of Filing

01-Dec-2000

Name of Patentee

CABOT CORPORATION

Applicant Address

75 STATE STREET BOSTON, MASSACHUSETTS 02109-1806

Inventors:

#	Inventor's Name	Inventor's Address
1	DEVONPORT, WAYNE	246 LANCASTER DRIVE TEWKSBURY MASSACHUSETTS 01876

PCT International Classification Number

C09C1/56

PCT International Application Number

PCT/US99/12283

PCT International Filing date

1999-06-02

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	09/089,263	1998-06-03	U.S.A.