WO2008079276A1 - Fluorescent nanoparticles - Google Patents

Fluorescent nanoparticles Download PDF

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Publication number
WO2008079276A1
WO2008079276A1 PCT/US2007/026031 US2007026031W WO2008079276A1 WO 2008079276 A1 WO2008079276 A1 WO 2008079276A1 US 2007026031 W US2007026031 W US 2007026031W WO 2008079276 A1 WO2008079276 A1 WO 2008079276A1
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fluorescent
nanoparticle
monomer
core
formula
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PCT/US2007/026031
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English (en)
French (fr)
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Christine M. Rademacher
Xiaorong Wang
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Bridgestone Corporation
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/773—Nanoparticle, i.e. structure having three dimensions of 100 nm or less
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2998—Coated including synthetic resin or polymer

Definitions

  • the technology disclosed herein is generally related to fluorescent nanoparticles. More particularly, it relates to a fluorescent nanoparticle comprising a core, an intermediate layer, and a shell. This disclosure also provides a method of making the fluorescent nanoparticles.
  • Fluorescent microparticles may be prepared by several practical methods from a variety of polymerizable monomers, including styrenes, dienes, acrylates and unsaturated chlorides, esters, acetates, amides and alcohols.
  • U.S. Patent 4,326,008 to Rembaum discloses fluorescent microspheres obtained by copolymerizing an acrylic monomer containing a covalent bonding group such as hydroxyl, amine, or carboxyl with a fluorescent co-monomer such as dansyl allyl amine.
  • U.S. Patent 5,194,300 to Cheung and U.S. Patent 4,774,189 to Schwartz disclose fluorescent microspheres that are coated by covalently attaching to their surface one or more fluorescent dyes.
  • U.S. Patent 5,073,498 to Schwartz and U.S. Patent 4,717,655 to Fulwyler disclose fluorescent dyes added during particle polymerization process.
  • U.S. Patent 5,723,218 to Haugland et al. discloses diffusely dyeing microparticles with one or more dipyrrometheneboron difluoride dyes.
  • Fluorescent particles to which biological molecules have been attached have been used for immunoassays, as described, for example, in U.S. Patent 4,808,524 to Snyder et al.; as labels for cell surface antigens, as described, for example, in Jett, Keller, Martin, Nguyen, & Saunders, Ultrasensitive Molecular-Level Flow Cytometry, in FLOW CYTOMETRY AND SORTING, p. 381 , 2 nd ed., Wiley-Liss Inc., N. Y.
  • nanoparticles have also attracted increased attention not only in the technical fields such as catalysis, combinatorial chemistry, protein supports, magnets, and photonics, but also in the manufacture of rubber products such as tires.
  • nanoparticles can modify rubbers by uniformly dispersing throughout a host rubber composition as discrete particles.
  • the physical properties of rubber such as moldability and tenacity can often be improved through such modifications.
  • the nanoparticles described herein are each made up of a group or a collection of several polymer chains that are organized around a center 1.
  • the polymer chains are linked together by a core formed from dialkenylbenzene(s).
  • the polymer chains extend from the core 2 outwardly to form an intermediate layer 3.
  • the intermediate layer 3 includes the portions of the polymers that are not at the outer terminal end of the polymers (i.e., the intermediate layer includes monomer units that are not in the shell 4). It should be understood that the intermediate layer is not limited to a single monomer unit in each polymer chain, but may include several monomer units.
  • the intermediate layer may be separated into sublayers, and the sublayers may include blocks of various homopolymer or copolymer.
  • a sublayer may include a block of randomized styrene-butadiene copolymer or a homopolymer such as polyisoprene or polystyrene.
  • a shell layer or shell 4 is comprised of the monomer units or functionally or non-functionally initiated polymer chain heads at the outer terminal ends of each polymer.
  • the shell layer 4 is the outermost portion of the nanoparticle.
  • the living polymers form micelles due to the aggregation of ionic chain ends and the chemical interactions of the hydrophobic polymer chains in hydrocarbon solvent.
  • the micelles become crosslinked and the stable nanoparticle is formed.
  • a fluorescent nanoparticle comprises (1) a core made from alkenylbenzene; (2) an intermediate layer; (3) a shell layer comprising the outer surface of the nanoparticle; and (4) a fluorescent portion that arises from the addition of a corresponding monomer with a structure represented by the following formula:
  • An example method of preparing such fluorescent nanoparticles includes: (i) preparing a living polymer with a fluorescent portion by a step selected from the group consisting of: (a) copolymerizing a fluorescent monomer with a monomer or monomers; (b) polymerizing a monomer or monomers with a fluorescent initiator; and (c) polymerizing a monomer to produce a living polymer, and subsequently adding a fluorescent monomer to the living polymer to create a fluorescent block; (ii) adding a crosslinking agent; and (iii) quenching the ionic chain ends with a proton source.
  • a fluorescent nanoparticle includes a core, an intermediate layer, and a shell layer.
  • the intermediate and shell layers include ionic chain ends that extend from the intermediate layer into the core.
  • the shell is the outermost layer of the nanoparticle.
  • the core includes alkenylbenzene monomer units that have crosslinked the ionic chain ends of the intermediate layer.
  • the alkenylbenzene monomers may have the same structure or may be a mixture of two or more different structures.
  • a fluorescent portion is located in at least one of the intermediate or shell layers, or at the core.
  • the fluorescent portion includes at least one fluorescent monomer with a structure represented by the following formula:
  • the fluorescent monomer may be located at the core, the intermediate layer, or the shell layer.
  • the fluorescent nanoparticles can be used in rubber compositions.
  • Fig. 1 is an example diagram of a nanoparticle
  • Fig. 2 is a transmission electron microscopy (TEM) photograph of fluorescent nanoparticles.
  • Fig. 3 is the microscopy picture of a film containing the fluorescent nanoparticles.
  • An exemplary fluorescent nanoparticle comprises a core including crosslinked alkenylbenzene monomers, an intermediate layer that includes polymer chains, and an outer shell layer that includes the head of the polymer chains.
  • a fluorescent portion is located along the polymer chain in the intermediate layer, the shell, or at the core.
  • the intermediate layer may have various thicknesses, i.e. the polymers may include one or many monomers.
  • the nanoparticle is less than 200 nm in diameter (expressed as a mean average diameter), more preferably less than about 100 nm, and most preferably less than about 50 nm.
  • the nanoparticles are preferably spherical, though shape defects are acceptable, provided the nanoparticles generally retain their discrete nature with little or no polymerization between particles.
  • the fluorescent nanoparticles can be copolymerized in several ways.
  • one or more monomers are polymerized with an initiator such as butyl lithium.
  • the resulting ionic chain ends self-assemble into micelles around a center to form an aggregate core, while the hydrophobic polymer chains radiate out away from the ionic chain ends.
  • a crosslinking agent such as divinylbenzene (DVB) is then added along with a fluorescent monomer (or optionally the fluorescent monomer can be added in a separate step).
  • Acceptable crosslinking agents include di- or tri-vinyl- substituted aromatic hydrocarbons.
  • Crosslinking agents which are at least bifunctional, wherein the two functional groups are capable of reacting with vinyl- substituted aromatic hydrocarbon monomers are also acceptable.
  • a proton source is used to quench the living polymer chains. Suitable proton sources are well known to those of skill in the art and include, but are not limited to, alcohols such as isopropanol.
  • one or more monomers are polymerized using a fluorescent initiator.
  • the fluorescent initiator can be formed from a fluorescent monomer and an initiator such as butyl lithium.
  • the resulting polymers have a fluorescent portion at one end.
  • a hydrocarbon solvent the ionic chain ends aggregate into a micelle with the fluorescent portion on the outer surface.
  • a crosslinking agent such as DVB, is added to crosslink portions of the ionic chain ends of the micelle, thereby forming and stabilizing the core of the nanoparticle.
  • a proton source is used to quench the living polymer chains.
  • one or more monomers and at least one fluorescent monomer are copolymerized using an initiator such as butyl lithium.
  • the resultant living copolymers have a fluorescent portion within the chains.
  • the ionic chain ends then self-assemble into micelles in a hydrocarbon solvent.
  • a crosslinking agent, such as DVB, is added to crosslink portions of the ionic chain ends of the micelle, thereby forming and stabilizing the core of the nanoparticle.
  • a proton source is used to quench the living polymer chains.
  • one or more monomers are polymerized using an initiator such as butyl lithium to a desired degree of polymerization.
  • the resulting polymers are then copolymerized with one or more fluorescent monomers.
  • the living copolymer chains then self-assemble into micelles in a hydrocarbon solvent.
  • a crosslinking agent, such as DVB, is added to crosslink portions of the ionic chain ends within the micelle, thereby forming and stabilizing the core of the nanoparticle.
  • a proton source is used to quench the living polymer chains.
  • additional monomers can be copolymerized with the monomer, yielding various copolymers.
  • the fluorescent monomer can be added at various stages in the copolymerization so as to control where in the polymer chain the fluorescent monomer is located.
  • Examples of the types of monomers that may be used to prepare the polymer chains of the nanoparticles include: styrene, f-butyl styrene, butadiene, isoprene, copolymers of a combination of these, or derivatives thereof. Mixtures of different polymers and copolymers are also possible in a single nanoparticle.
  • An exemplary fluorescent nanoparticle synthesis method comprises a multi-stage anionic polymerization. Multi-stage anionic polymerizations have been conducted to prepare block-copolymers, for example in U.S. Pat. No. 4,386,125, which is incorporated herein by reference.
  • a liquid hydrocarbon medium can function as the solvent, and may be selected from any suitable aliphatic hydrocarbon, alicyclic hydrocarbon, or mixture thereof, with a proviso that it exists in liquid state during the preparation of the nanoparticles.
  • exemplary aliphatic hydrocarbons include, but are not limited to, pentane, isopentane, 2,2 dimethyl-butane, hexane, heptane, octane, nonane, decane, and the like.
  • Exemplary alicyclic hydrocarbons include, but are not limited to, cyclopentane, methyl cyclopentane, cyclohexane, methyl cyclopentane, cycloheptane, cyclooctane, cyclononane, cyclodecane, and the like.
  • aromatic hydrocarbons and polar solvents are not preferred as the liquid medium.
  • the liquid hydrocarbon medium comprises hexane or cyclohexane.
  • the fluorescent nanoparticles are formed from polymers having a poly(alkyl-substituted styrene) block and a polymer block of fluorescent monomers having a structure represented by the formula shown below:
  • L is a direct bond or any suitable divalent group
  • F is any fluorescent moiety
  • the fluorescent moiety F may be selected from the group consisting of perylene, phenanthrene, anthracene, naphthalene, pyrene, chrysene, naphthacene, and combinations thereof.
  • the -F group has a structure represented by the formula as shown below (pyrene):
  • the -L- group may be just a direct bond or any suitable divalent group, for example, methylene, ethylene, and propylene group.
  • the -L- group has a structure represented by the formula as shown below:
  • X comprises a heteroatom such as O, S, P(R 2 ), Si(R 2 ) 2 , Si(OR 2 ) 2 (where R 2 is as defined below), and N (where N can be substituted such that the -L- group contains a tertiary amino group); and R 1 is a straight or branched C-i-C ⁇ alkylene group.
  • the -L- group has a structure represented by the formula as shown below:
  • the fluorescent monomer may have, for example, a structure represented by the formula as shown below:
  • the fluorescent block may also optionally further comprise other monomers.
  • An example alkyl-substituted styrene block monomer of the example polymer may have a structure represented by the formula shown below:
  • R 2 may be selected from saturated or unsaturated, substituted or unsubstituted, straight or branched, cyclic or acyclic C 3 -C 8 alkyl groups.
  • Another exemplary alkyl-substituted styrene monomer comprises te/f-butyl styrene (TbST) such as f-butyl styrene as shown below:
  • alkyl group in the alkyl-substituted styrene monomer lowers the overall solubility of the resulting living polymer in a selected liquid hydrocarbon medium thereby facilitating micelle self-assembly and nanoparticle formation.
  • the alkyl-substituted styrene monomer may be copolymerized with any suitable fluorescent comonomers; and as a result, the later formed nanoparticles will have a fluorescent intermediate later.
  • Fluorescent comonomers for this purpose include, but are not limited to cinnamyl-O-CH 2 -pyrene.
  • An exemplary polymerization of alkyl-substituted styrene monomers into a poly(alkyl- substituted styrene) block is initiated via addition of anionic initiators that are known in the art.
  • the anionic initiator can be selected from any known organolithium compounds. Suitable organolithium compounds are represented by the formula as shown below:
  • R(Li) x wherein R is a hydrocarbyl group having 1 to x valence(s).
  • R generally contains 1 to 20, preferably 2-8, carbon atoms per R group, and x is an integer of 1-4.
  • x is 1
  • the R group includes aliphatic groups and cycloaliphatic groups, such as alkyl, cycloalkyl, cycloalkylalkyl, alkylcycloalkyl, alkenyl, as well as aryl and alkylaryl groups.
  • R groups include, but are not limited to, alkyls such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, f-butyl, n-amyl, isoamyl, n- hexyl, n-octyl, n-decyl, and the like; cycloalkyls and alkylcycloalkyl such as cyclopentyl, cyclohexyl, 2,2,1-bicycloheptyl, methylcyclopentyl, dimethylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, isopropylcyclohexyl, 4-butylcyclohexyl, and the like; cycloalkylalkyls such as cyclopentyl
  • ⁇ -butyllithium, sec-butyllithium, terf-butyllithium, or a mixture thereof are used to initiate the polymerization of alkyl-substituted styrene monomers into a poly(alkyl-substituted styrene) block.
  • a fluorescent initiator may be used to initiate the polymerization of alkyl-substituted styrene monomers; and as a result, the later formed nanoparticles will have a fluorescent surface.
  • fluorescent initiator examples include, but are not limited to, the following lithium compound:
  • the polymerization of alkyl-substituted styrene monomers into a poly(alkyl- substituted styrene) block may last until a predetermined degree of polymerization is obtained.
  • the degree of polymerization may be selected for particular applications.
  • a predetermined degree of polymerization of the poly(alkyl-substituted styrene) block may be broadly within the range of from about 1 to about 50, preferably within the range of from about 1 to about 25, more preferably within the range of from about 1 to about 10, and most preferably within the range of from about 1 to about 5.
  • the living polymer block that contains one or more fluorescent monomers may be copolymerized or crosslinked with a multiple vinyl-substituted aromatic hydrocarbon to form the desired fluorescent nanoparticles.
  • the fluorescent nanoparticles preferably retain their discrete nature with little or no polymerization between each other.
  • the fluorescent nanoparticles are substantially monodisperse and uniform in shape.
  • a mixture of multiple vinyl-substituted aromatic hydrocarbon and fluorescent monomer may be used to copolymerize with the poly(alkyl-substituted styrene) block, thus producing a crosslinked fluorescent core.
  • An exemplary multiple vinyl-substituted aromatic hydrocarbon has a formula as shown below:
  • p is an integer and 2 ⁇ p ⁇ 6, preferably, p is 2 or 3, more preferably p is 2, i.e. divinylbenzene (DVB).
  • the divinylbenzene may be selected from any one of the following isomers or any combination thereof:
  • the fluorescent nanoparticles are formed from the micelles with a core including crosslinked alkyl-substituted styrene blocks and an intermediate layer including fluorescent blocks.
  • the polymerization reactions used to prepare the fluorescent nanoparticles may be terminated with a terminating agent. Suitable terminating agents are known to those skilled in the art and include, but are not limited to, alcohols such as methanol, ethanol, propanol, and isopropanol.
  • the molecular weight (grams/mole) of the fluorescent nanoparticles may be broadly within the range of from about 50,000 to about 100 million, preferably within the range of from about 100,000 to about 10 million.
  • compositions including the fluorescent nanoparticles discussed herein may be sprayed or coated on a tire sidewalk
  • the fluorescent property of the nanoparticles may function to improve traffic safety at night by increasing the visibility of the tires and the vehicle.
  • Biological applications are also envisioned.
  • Example 1 Preparation of Cinnamyl-O-CH 2 -pyrene Fluorescent Monomer
  • Example 5 Preparation of FNMPs with Butadiene
  • hexane (20 mL
  • butadiene (5 gr, 20% in hexane)
  • oligomeric oxolanyl propane (OOPs) (0.03 mL, 1.6M solution)
  • butyl lithium 0.1 mL, 1.54M
  • the bottle would then be placed into 80 0 C water bath for 10 minutes.
  • a charge of cinnamyl-1- methylpyrene ether (10 mL, 0.14M in cyclohexane) would be added into the bottle.
  • DVB 0.5 mL
  • the reaction would proceed for 1 hour, and then would be terminated by adding isopropanol (0.1 mL).
  • Example 6 Preparation of FNMPs with Styrene Butadiene [0059] To a 10 oz. nitrogen purged bottle, hexane (20 mL), styrene (1 gr, 30% in hexane), butadiene (5 gr, 20% in hexane), oligomeric oxolanyl propane (OOPs) (0.03 mL, 1.6M solution) and butyl lithium (0.1 mL, 1.54M) would be added. The bottle would be placed into 80 0 C water bath for 10 minutes.
  • OOPs oligomeric oxolanyl propane
  • Example 7 Characterization of Fluorescent Nano Micelle Particles (FNMPs) [0060] A 1 mL portion of the Example 3 solution was diluted to about a 1 xiO "4 wt% solution in toluene. A drop of the diluted solution was then coated on a graphed copper micro-screen. After the solvent evaporated, the screen was exposed to RUCM for about 5 minutes, and then examined by TEM. The image (see Figure 2) shows that the FNMPs have a mean size of about 40 nm.
  • Example 8 Characterization of Fluorescent Nano Micelle Particles (FNMPs) [0061] A 5 mL aliquot was taken from the Example 3 reaction and added to an aluminum pan. After the solvent evaporated, a film of about 0.1 mm thickness resulted. The characterization was performed using an Olympus-BH2 microscope equipped with a Polaroid camera. The polymer film was examined under a UV light. The film showed fluorescence under green light ( ⁇ 450 to 510 nm). As shown in Figure 2, the film was entirely glowing as compared to the background. The experiment indicated that the desired nano-sized materials with fluorescent properties were produced.
  • FNMPs Fluorescent Nano Micelle Particles
PCT/US2007/026031 2006-12-19 2007-12-19 Fluorescent nanoparticles WO2008079276A1 (en)

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US9428604B1 (en) 2011-12-30 2016-08-30 Bridgestone Corporation Nanoparticle fillers and methods of mixing into elastomers

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2099645A1 (US20080145660A1-20080619-C00008.png) * 1970-07-28 1972-03-17 Xerox Corp
EP1783168A2 (en) * 2005-11-02 2007-05-09 Fujifilm Corporation Fluorescent polymer fine particle

Family Cites Families (260)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US24011A (en) * 1859-05-17 Improvement in soap
US192408A (en) * 1877-06-26 Improvement in shoes for scaffoldings
US53813A (en) * 1866-04-10 Improvement in steps for spindles
US135579A (en) * 1873-02-04 Improvement in feeding mechanisms for sewing-machines
US173130A (en) * 1876-02-08 Improvement in grain-binders
US173115A (en) * 1876-02-08 Improvement in wood-screws
US215693A (en) * 1879-05-20 Improvement in harness
US122819A (en) * 1872-01-16 Improvement in hemmers for sewing-machines
US7011A (en) * 1850-01-08 Mill foe
US149649A (en) * 1874-04-14 Improvement in log-turners for saw-mills
US161754A (en) * 1875-04-06 Improvement in turpentine-pans
US147714A (en) * 1874-02-17 Improvement in shaft-couplings
US2531396A (en) 1947-03-29 1950-11-28 Nat Lead Co Elastomer reinforced with a modified clay
US3177186A (en) * 1963-06-07 1965-04-06 American Cyanamid Co Crystallizable polymers of t-butyl acrylate and methacrylate
GB1130770A (en) 1965-12-29 1968-10-16 Asahi Chemical Ind Process for producing thermoplastic elastomers
US3598884A (en) 1967-08-04 1971-08-10 Polymer Corp Cross-linking of polymers
SU465010A3 (ru) 1967-12-21 1975-03-25 Асахи Касеи Когио Кабусики Кайша (Фирма) Способ получени термопластичных эластомеров
US3840620A (en) 1970-04-15 1974-10-08 Stauffer Chemical Co Additives for the preparation of clear,impact resistant vinyl chloride polymer compositions
US3793402A (en) 1971-11-05 1974-02-19 F Owens Low haze impact resistant compositions containing a multi-stage,sequentially produced polymer
US3972963A (en) 1973-06-20 1976-08-03 Mobil Oil Corporation Organic reinforcing fillers for rubber
US3927143A (en) 1973-10-12 1975-12-16 Exxon Research Engineering Co Thermoplastic block copolymers
FR2289566A1 (fr) 1974-10-29 1976-05-28 Firestone Tire & Rubber Co Copolymeres greffes du polybutadiene et d'un polyacrylate substitue, et leur obtention
US4326008A (en) 1976-08-27 1982-04-20 California Institute Of Technology Protein specific fluorescent microspheres for labelling a protein
US4247434A (en) 1978-12-29 1981-01-27 Lovelace Alan M Administrator Process for preparation of large-particle-size monodisperse
US4233409A (en) 1979-07-05 1980-11-11 Monsanto Company Polymeric blend
US4248986A (en) * 1979-08-27 1981-02-03 The Goodyear Tire & Rubber Company Selective cyclization of block copolymers
GB2088387A (en) 1980-11-25 1982-06-09 Exxon Research Engineering Co Adhesive sealants for double glazing
DE3260590D1 (en) 1981-02-20 1984-09-27 Asahi Chemical Ind A film, sheet or tube of a block copolymer or a composition containing the same
US4417029A (en) 1981-08-03 1983-11-22 Atlantic Richfield Company Derivatization of star-block copolymers
CA1196139A (en) 1982-02-26 1985-10-29 Hiroshi Furukawa Elastomer composition
US4717655A (en) 1982-08-30 1988-01-05 Becton, Dickinson And Company Method and apparatus for distinguishing multiple subpopulations of cells
JPS59168014A (ja) 1983-03-15 1984-09-21 Kanegafuchi Chem Ind Co Ltd 硬化性弾性組成物
US4602052A (en) 1983-09-21 1986-07-22 Amoco Corporation Rubber composition and method of incorporating carbon black and a quaternary ammonium coupling agent salt into natural rubber containing compositions
US4598105A (en) 1983-09-21 1986-07-01 Amoco Corporation Rubber composition and method
NL8304029A (nl) 1983-11-23 1985-06-17 Dow Chemical Nederland Met rubber versterkte polymeren van monovinylideen-aromatische verbindingen met een zeer goede verhouding tussen glans en sterkteeigenschappen en een werkwijze voor hun bereiding.
US4659790A (en) 1984-06-05 1987-04-21 Japan Synthetic Rubber Co., Ltd. Heat-resistant copolymer of alpha-methylstyrene and acrylonitrile, process for preparing the same, and thermoplastic resin composition containing the same
ZA855083B (en) * 1984-07-05 1987-03-25 Du Pont Acrylic star polymers
EP0169536B1 (en) 1984-07-26 1994-05-18 Kanegafuchi Chemical Industry Co., Ltd. Curable polymer composition
DE3434983C2 (de) 1984-09-24 1993-10-14 Hoechst Ag Gelbildendes organophiles Schichtsilikat, Verfahren zu seiner Herstellung und Verwendung
JPS61141761A (ja) 1984-12-12 1986-06-28 Kanegafuchi Chem Ind Co Ltd 硬化性組成物
US4774189A (en) 1984-12-24 1988-09-27 Flow Cytometry Standards Corp. Fluorescent calibration microbeads simulating stained cells
US5073498A (en) 1984-12-24 1991-12-17 Caribbean Microparticles Corporation Fluorescent alignment microbeads with broad excitation and emission spectra and its use
US5354825A (en) * 1985-04-08 1994-10-11 Klainer Stanley M Surface-bound fluorescent polymers and related methods of synthesis and use
US4764572A (en) 1985-07-23 1988-08-16 Shell Oil Company Anionic polymerization process
FR2585373B1 (fr) * 1985-07-25 1990-05-04 Univ Toulouse Procede de fabrication de corps creux, fermes et continus, corps creux obtenus et installation de mise en oeuvre dans le cas de billes creuses
US4987202A (en) * 1986-04-14 1991-01-22 Zeigler John M Methods for the synthesis of polysilanes
CA1274647C (en) 1986-06-25 1990-09-25 CURING ISOBUTYLENE POLYMER
IT1196987B (it) 1986-07-23 1988-11-25 Enichem Sintesi Copolimeri sililati dell'isobutilene reticolabili in condizioni ambientali e procedimento per la loro preparazione
US4871814A (en) 1986-08-28 1989-10-03 Mobil Oil Corporation High impact, highly transparent linear styrene-diene block copolymers with five or more blocks and their preparations by anionic dispersion polymerization
US4837274A (en) 1986-09-30 1989-06-06 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Curable composition
US4725522A (en) 1986-10-16 1988-02-16 Xerox Corporation Processes for cold pressure fixable encapsulated toner compositions
MX168323B (es) 1986-10-21 1993-05-18 Rohm & Haas Modificadores de impacto de nucleo cubierto para resinas estirenicas
US5183851A (en) * 1986-11-11 1993-02-02 Elf Atochem Italia S.R.L. Low haze transparent compositions and processes for preparing them
JPH0651752B2 (ja) 1987-02-20 1994-07-06 鐘淵化学工業株式会社 官能性末端を有するイソブチレン系ポリマ−の製造法
FR2615279B1 (fr) 1987-05-11 1990-11-02 Commissariat Energie Atomique Capteur de deplacement a fibres optiques decalees
US5194300A (en) 1987-07-15 1993-03-16 Cheung Sau W Methods of making fluorescent microspheres
US4773521A (en) 1987-07-23 1988-09-27 Chen Ming Chin Compact portable conveyor
GB8718036D0 (en) 1987-07-30 1987-09-03 Tioxide Group Plc Polymeric particles
CA1312409C (en) 1987-10-16 1993-01-05 Masayoshi Imanaka Sealant for double-layered glass
GB8724437D0 (en) 1987-10-19 1987-11-25 Shell Int Research Elastomeric compositions
DE3735403A1 (de) 1987-10-20 1989-05-03 Basf Ag Verzweigte copolymerisate und verfahren zu ihrer herstellung
US4942209A (en) 1987-12-18 1990-07-17 Mobil Oil Corporation Anionic polymerization in high viscosity dispersing medium to form microparticles with narrow size distribution
IT1224419B (it) 1987-12-29 1990-10-04 Montedipe Spa Processo per imidizzare copolimeri dell'anidride maleica con monomeri vinil aromatici
US4829135A (en) 1987-12-29 1989-05-09 Mobil Oil Corporation Multi-stage anionic dispersion homopolymerization to form microparticles with narrow size distribution
US4904730A (en) 1988-04-08 1990-02-27 The Dow Chemical Company Rubber-modified resin blends
US5169914A (en) 1988-05-03 1992-12-08 Edison Polymer Innovation Corporation Uniform molecular weight polymers
US4906695A (en) 1988-07-08 1990-03-06 Dow Corning Corporation Pressure-sensitive adhesives containing an alkoxy-functional silicon compound
US5164440A (en) 1988-07-20 1992-11-17 Ube Industries, Ltd. High rigidity and impact resistance resin composition
US5742118A (en) 1988-09-09 1998-04-21 Hitachi, Ltd. Ultrafine particle film, process for producing the same, transparent plate and image display plate
JP2717719B2 (ja) 1989-02-28 1998-02-25 鐘淵化学工業株式会社 有機重合体、その製造方法及びそれを用いた硬化性組成物
US5247021A (en) 1989-06-06 1993-09-21 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Process for preparation of a polymer having reactive terminal group
JPH0798890B2 (ja) 1989-06-23 1995-10-25 日本ゼオン株式会社 粘着剤用ブロック共重合体組成物及び粘着剤組成物
US5594468A (en) * 1989-11-07 1997-01-14 Proxima Corporation Optical system auxiliary input calibration arrangement and method of using same
CA2028410C (en) 1990-01-02 1996-09-17 William J. Trepka Tapered block styrene/butadiene copolymers
US5352743A (en) 1990-01-16 1994-10-04 Mobil Oil Corporation Solid elastomeric block copolymers
US5066729A (en) 1990-04-09 1991-11-19 Bridgestone/Firestone, Inc. Diene polymers and copolymers terminated by reaction with n-alkyl and n-aryl imines
US5290873A (en) 1990-04-16 1994-03-01 Kanegafuchi Chemical Industry Co., Ltd. Isobutylene polymer having unsaturated group and preparation thereof
EP0472344A3 (en) 1990-08-14 1992-09-30 Ube Industries, Ltd. Reinforced elastomer composition and polypropylene composition containing same
US5728791A (en) 1990-11-30 1998-03-17 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Polyvinyl graft-polymers and manufacturing method thereof
US5227419A (en) 1990-12-20 1993-07-13 Phillips Petroleum Company Tapered block styrene/butadiene copolymers
US5256736A (en) 1991-05-08 1993-10-26 Phillips Petroleum Company Tapered block copolymers of conjugated dienes and monovinylarenes
CA2077370C (en) 1991-09-03 1998-12-15 James E. Hall Dispersion copolymers in linear aliphatic solvents
US5241008A (en) 1991-09-03 1993-08-31 Bridgestone/Firestone, Inc. Process for producing continuously tapered polymers and copolymers and products produced thereby
JP3154529B2 (ja) 1991-10-14 2001-04-09 鐘淵化学工業株式会社 官能基を有するイソブチレン系重合体及びその製造法
US5237015A (en) 1991-11-04 1993-08-17 Polysar Rubber Corporation Core-shell polymer for use in tire treads
US5219945A (en) 1992-02-20 1993-06-15 E. I. Du Pont De Nemours And Company ABC triblock methacrylate polymers
US5336712A (en) 1992-05-08 1994-08-09 Shell Oil Company Process for making submicron stable latexes of block copolymers
EP0575809B1 (en) 1992-06-09 1997-02-19 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Polyolefin resin composition, process for the preparation thereof and molded article made thereof
JP2611717B2 (ja) 1992-06-10 1997-05-21 住友化学工業株式会社 ブタジエン系共重合体
DE4220563A1 (de) 1992-06-24 1994-01-13 Bayer Ag Kautschukmischungen enthaltend Polybutadien-Gel
JPH0693134A (ja) 1992-07-31 1994-04-05 Sumitomo Chem Co Ltd 優れたグリップ性能と転動抵抗を有するゴム組成物およびその製造方法
US5329005A (en) 1992-10-02 1994-07-12 Bridgestone Corporation Soluble anionic polymerization initiators and preparation thereof
DE4234601A1 (de) 1992-10-14 1994-04-21 Basf Ag Verfahren zur Herstellung von Blockcopolymeren durch ionische Polymerisation
US5290875A (en) 1992-11-30 1994-03-01 Phillips Petroleum Company Conjugated diene/monovinylarene block copolymers with multiple tapered blocks
DE4241538A1 (de) 1992-12-10 1994-06-16 Leuna Werke Ag Verfahren zur Herstellung von nichtäquimolar aufgebauten alpha-Methylstyrol-MSA-Copolymeren
US5331035A (en) 1992-12-22 1994-07-19 Bridgestone Corporation Process for the preparation of in situ dispersion of copolymers
US5614579A (en) 1992-12-22 1997-03-25 Bridgestone Corporation Process for the preparation of tapered copolymers via in situ dispersion
US5891947A (en) 1992-12-22 1999-04-06 Bridgestone Corporation In-situ anionic continuous dispersion polymerization process
US5487054A (en) * 1993-01-05 1996-01-23 Apple Computer, Inc. Method and apparatus for setting a clock in a computer system
US5296547A (en) * 1993-01-28 1994-03-22 Minnesota Mining And Manufacturing Company Block copolymer having mixed molecular weight endblocks
US5405903A (en) 1993-03-30 1995-04-11 Shell Oil Company Process for the preparation of a block copolymer blend
SG48758A1 (en) 1993-04-27 1998-05-18 Asahi Chemical Ind Expanded foamed bead of a rubber-modified styrene polymer
US5514753A (en) 1993-06-30 1996-05-07 Bridgestone Corporation Process for preparing a block copolymer
JPH0753630A (ja) 1993-06-30 1995-02-28 Shell Internatl Res Maatschappij Bv 末端に水酸基を有する液状スターポリマー
WO1995006090A1 (en) 1993-08-23 1995-03-02 Alliedsignal Inc. Polymer nanocomposites comprising a polymer and an exfoliated particulate material derivatized with organo silanes, organo titanates and organo zirconates dispersed therein and process of preparing same
CA2127919A1 (en) 1993-09-03 1995-03-04 Jessie Alvin Binkley Process for producing ultrafine sized latexes
US5436298A (en) 1993-09-30 1995-07-25 Phillips Petroleum Company Block copolymers of monovinylarenes and conjugated dienes and preparation thereof
US5855972A (en) 1993-11-12 1999-01-05 Kaeding; Konrad H Sealant strip useful in the fabrication of insulated glass and compositions and methods relating thereto
JP2865577B2 (ja) 1993-11-26 1999-03-08 住友ゴム工業株式会社 トレッドゴム組成物
US5747152A (en) * 1993-12-02 1998-05-05 Dai Nippon Printing Co., Ltd. Transparent functional membrane containing functional ultrafine particles, transparent functional film, and process for producing the same
US5399628A (en) 1993-12-02 1995-03-21 Phillips Petroleum Company Block copolymers of monovinylarenes and conjugated dienes containing two interior tapered blocks
JP3393906B2 (ja) 1993-12-14 2003-04-07 鐘淵化学工業株式会社 官能基を含有する重合体の製造方法
BE1008739A3 (fr) 1994-01-12 1996-07-02 Kanegafuchi Chemical Ind Procede de preparation d'un polymere d'isobutylene.
US5462994A (en) 1994-01-27 1995-10-31 The Dow Chemical Company Preparation of conjugated diene-monoalkenyl arene block copolymers having a low polydispersity index
DE69525615D1 (de) 1994-03-18 2002-04-04 Kanegafuchi Chemical Ind Verfahren zur isolation eines isobutylenpolymers
US5438103A (en) 1994-03-23 1995-08-01 Phillips Petroleum Company Block copolymers of monovinylaromatic and conjugated diene monomers
US5421866A (en) 1994-05-16 1995-06-06 Dow Corning Corporation Water repellent compositions
US5688856A (en) 1994-10-27 1997-11-18 Shell Oil Company Process for making submicron stable latexes of hydrogenated block copolymers
GB9424247D0 (en) 1994-12-01 1995-01-18 Dow Corning Sa Silyl group containing organic polymers
US5521309A (en) 1994-12-23 1996-05-28 Bridgestone Corporation Tertiary-amino allyl-or xylyl-lithium initiators and method of preparing same
JPH08253531A (ja) 1995-01-17 1996-10-01 Kanegafuchi Chem Ind Co Ltd イソブチレン系重合体の製造方法及びイソブチレン系重合体
DE19507777A1 (de) 1995-03-06 1996-09-12 Basf Ag Filtrierbare Polystyrol-Dispersionen
US5868966A (en) 1995-03-30 1999-02-09 Drexel University Electroactive inorganic organic hybrid materials
US5530052A (en) 1995-04-03 1996-06-25 General Electric Company Layered minerals and compositions comprising the same
US5674592A (en) 1995-05-04 1997-10-07 Minnesota Mining And Manufacturing Company Functionalized nanostructured films
DE19517452A1 (de) * 1995-05-12 1996-11-14 Henkel Teroson Gmbh Zweikomponenten-Kleb-/Dichtstoff mit hoher Anfangshaftfestigkeit
US5574105A (en) 1995-05-12 1996-11-12 Advanced Elastomer Systems, L.P. Thermoplastic elastomers having improved high temperature performance
HUP0104321A3 (en) 1995-06-23 2003-05-28 Exxon Research Engineering Co Latex, nanocomposite and production of latex containing nanocomposite
US5811501A (en) 1995-06-29 1998-09-22 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Process for producing unsaturated group-terminated isobutylene polymer
DE19528717A1 (de) 1995-08-04 1997-02-06 Basf Ag Polymerteilchen und Verfahren zu deren Herstellung
AU6643196A (en) 1995-08-04 1997-03-05 Fmc Corporation Telechelic polystyrene/polyethylene copolymers and processes for making same
US6096828A (en) 1995-08-29 2000-08-01 Phillips Petroleum Company Conjugated diene/monovinylarene block copolymers, methods for preparing same, and polymer blends
US6835778B2 (en) * 1995-08-29 2004-12-28 Chevron Phillips Chemical Company Lp Conjugated diene/monovinylarene block copolymers blends
DE19533915A1 (de) * 1995-09-13 1997-03-20 Bayer Ag Verfahren zur Herstellung von Poly(diorganosiloxanen) mit Diorganyloxyorganylsilyl- oder Triorganylsilyl-Endgruppen, vernetzbare Mischungen, enthaltend Poly(diorganosiloxane) mit Diorganyloxyorganylsilyl- oder Triorganyloxysilyl-Endgruppen und deren Verwendung
US5534592A (en) 1995-09-22 1996-07-09 The Goodyear Tire & Rubber Company High performance blend for tire treads
EP0864588B1 (en) 1995-11-27 2002-10-09 Kaneka Corporation Processes for producing polymers having functional groups
ES2175061T3 (es) * 1995-11-29 2002-11-16 Vantico Ag Particulas nucleo-cascara (core-shell) y composiciones que contienen estas resinas epoxireticulables.
JP4072833B2 (ja) 1995-11-30 2008-04-09 住友精化株式会社 吸水性樹脂の製造方法および吸水性樹脂
US5773521A (en) 1995-12-19 1998-06-30 Shell Oil Company Coupling to produce inside-out star polymers with expanded cores
EP0934956B1 (en) * 1996-02-21 2011-08-03 Kaneka Corporation Curable composition
US6011116A (en) 1996-05-08 2000-01-04 Kaneka Corporation Thermoplastic resin composition
JP3545532B2 (ja) 1996-05-08 2004-07-21 鐘淵化学工業株式会社 複合ゴム粒子および複合ゴム系グラフト共重合体粒子
CA2205099A1 (en) * 1996-05-24 1997-11-24 Patricia Marie Lesko Fluorescent polymers and coating compositions
WO1997049736A2 (en) * 1996-06-27 1997-12-31 G.D. Searle And Co. Particles comprising amphiphilic copolymers, having a cross-linked shell domain and an interior core domain, useful for pharmaceutical and other applications
EP0839872B1 (en) * 1996-11-01 2003-03-12 Kaneka Corporation Curable polymer having reactive silicon-containing functional groups
CA2221974A1 (en) 1996-11-25 1998-05-25 Kaneka Corporation Curable composition
US20010011109A1 (en) * 1997-09-05 2001-08-02 Donald A. Tomalia Nanocomposites of dendritic polymers
DE19701488A1 (de) 1997-01-17 1998-07-23 Bayer Ag SBR-Kautschukgele enthaltende Kautschukmischungen
JPH10206603A (ja) * 1997-01-20 1998-08-07 Dainippon Printing Co Ltd 反射防止フィルム及びその製造方法
CA2290091A1 (en) * 1997-05-12 1998-11-19 Kgi, Inc. Vapor-liquid contact tray with two-stage downcomer
US6106953A (en) 1997-05-16 2000-08-22 Beiersdorf Ag Using a cleaning cloth impregnated with coupling agent for adhesive films
US5910530A (en) 1997-05-19 1999-06-08 Bridgestone Corporation High damping gel derived from extending grafted elastomers and polypropylene
US6060549A (en) * 1997-05-20 2000-05-09 Exxon Chemical Patents, Inc. Rubber toughened thermoplastic resin nano composites
US5837756A (en) 1997-05-28 1998-11-17 The Goodyear Tire & Rubber Company Polymer for asphalt cement modification
US6087016A (en) 1997-06-09 2000-07-11 Inmat, Llc Barrier coating of an elastomer and a dispersed layered filler in a liquid carrier
WO1999009080A1 (en) 1997-08-13 1999-02-25 The Dow Chemical Company High gloss high impact monovinylidene aromatic polymers
US6117932A (en) 1997-09-18 2000-09-12 Kabushiki Kaisha Toyota Chuo Kenkyusho Resin composite
US6348546B2 (en) * 1997-12-04 2002-02-19 Kaneka Corporation Alkenyl-containing isobutylene group block copolymer and process for producing it
US5955537A (en) 1998-02-13 1999-09-21 The Goodyear Tire & Rubber Company Continuous polymerization process
DE69907162T2 (de) * 1998-02-20 2004-02-19 Vantico Ag Organophile phyllosilikate
US5905116A (en) 1998-05-06 1999-05-18 Bridgestone Corporation Gels derived from extending grafted α-olefin-maleimide centipede polymers and polypropylene
US6204354B1 (en) * 1998-05-06 2001-03-20 Bridgestone Corporation Soft compounds derived from polypropylene grafted disubstituted ethylene- maleimide copolymers
US5994468A (en) 1998-05-06 1999-11-30 Bridgestone Corporation High damping gels derived from nylon grafted polymers
JP2000129133A (ja) 1998-05-28 2000-05-09 Kanegafuchi Chem Ind Co Ltd 硬化性組成物
EP0962789B1 (en) 1998-06-05 2008-02-06 FUJIFILM Corporation Anti-reflection film and display device having the same
US6252014B1 (en) * 1998-08-04 2001-06-26 Colorado School Of Mines Star polymers and polymeric particles in the nanometer-sized range by step growth reactions
US6060559A (en) * 1998-09-04 2000-05-09 Dow Corning Corporation Curable polyolefin compositions containing organosilicon compounds as adhesion additives
US6191217B1 (en) * 1998-11-17 2001-02-20 Bridgestone Corporation Gels derived from polypropylene grafted alkyl vinylether-maleimide copolymers
JP3978961B2 (ja) * 1998-12-25 2007-09-19 特種製紙株式会社 偽造防止用紙に使用する蛍光発色粒子、その製造方法、及び蛍光発色粒子を使用した偽造防止用紙
US6734256B1 (en) 1998-12-29 2004-05-11 3M Innovative Properties Company Block copolymer hot-melt processable adhesives, methods of their preparation, and articles therefrom
US6255372B1 (en) 1999-01-08 2001-07-03 Bridgestone Corporation Tire components having improved tear strength
JP2000239476A (ja) 1999-02-22 2000-09-05 Kanegafuchi Chem Ind Co Ltd 非晶性ポリオレフィン系樹脂組成物
US6248807B1 (en) 1999-03-15 2001-06-19 Fina Technology, Inc. Method for the preparation of core-shell morphologies from polybutadiene-polystyrene graft copolymers
US6649702B1 (en) 1999-05-19 2003-11-18 University Of Utah Research Foundation Stabilization and acoustic activation of polymeric micelles for drug delivery
US6225394B1 (en) * 1999-06-01 2001-05-01 Amcol International Corporation Intercalates formed by co-intercalation of onium ion spacing/coupling agents and monomer, oligomer or polymer ethylene vinyl alcohol (EVOH) intercalants and nanocomposites prepared with the intercalates
WO2000075226A1 (fr) * 1999-06-04 2000-12-14 Kaneka Corporation Composition durcissable et son procede d'utilisation
EP1094340B1 (en) * 1999-09-29 2007-07-18 FUJIFILM Corporation Anti-glare and anti-reflection film, polarizing plate, and image display device
US6506567B2 (en) * 2000-01-31 2003-01-14 Fuji Photo Film Co., Ltd. Water-soluble flourescent intercalator compound
US6379791B1 (en) * 2000-02-08 2002-04-30 3M Innovative Properties Company Compatibilized pressure-sensitive adhesives
US6448353B1 (en) 2000-02-08 2002-09-10 3M Innovative Properties Company Continuous process for the production of controlled architecture materials
JP2001240637A (ja) 2000-02-25 2001-09-04 Nippon Zeon Co Ltd ブロック共重合ゴム、樹脂改質剤および樹脂組成物並びに樹脂組成物の製造方法
JP4666737B2 (ja) 2000-03-08 2011-04-06 株式会社カネカ プライマー組成物および接着方法
EP1149867B1 (en) * 2000-04-27 2010-06-16 JSR Corporation Crosslinked rubber particles and rubber compositions
EP1152030B1 (en) 2000-05-01 2012-12-12 JSR Corporation Rubber mixtures based on crosslinked rubber particles and non-crosslinked rubbers
FR2808691B1 (fr) * 2000-05-12 2005-06-24 Coletica Cyclodextrines substituees preferentiellement sur leur face primaire par des fonctions acide ou amine
US6952666B1 (en) * 2000-07-20 2005-10-04 Microsoft Corporation Ranking parser for a natural language processing system
US6598645B1 (en) 2000-09-27 2003-07-29 The Goodyear Tire & Rubber Company Tire with at least one of rubber/cord laminate, sidewall insert and apex of a rubber composition which contains oriented intercalated and/or exfoliated clay reinforcement
US6268451B1 (en) 2000-10-03 2001-07-31 University Of Massachusetts Lowell Silyl-functional pseudo-telechelic polyisobutylene terpolymers
BR0105083A (pt) * 2000-11-17 2002-06-25 Goodyear Tire & Rubber Composição de borracha leve contendo argila
DE10059236B4 (de) 2000-11-29 2005-12-15 Continental Aktiengesellschaft Verwendung einer Kautschukmischung für Reifenlaufstreifen
RU2184125C1 (ru) 2000-11-30 2002-06-27 Институт катализа им. Г.К.Борескова СО РАН Водная гетерополимерная дисперсия для изготовления покрытий и способ ее получения
KR100405308B1 (ko) 2000-12-18 2003-11-12 주식회사 엘지화학 인조안료 및 그의 제조방법
US6359075B1 (en) * 2001-01-09 2002-03-19 Bridgestone/Firestone, Inc. Means of producing high diblock content thermoplastic elastomers via chain transfer
US6573313B2 (en) 2001-01-16 2003-06-03 The Hong Kong Polytechnic University Amphiphilic core-shell latexes
ES2205961B2 (es) 2001-02-13 2005-03-01 Eads Construcciones Aeronauticas, S.A. Procedimiento de fabricacion de elementos de material compuesto mediante la tecnoclogia del coencolado.
US8137699B2 (en) 2002-03-29 2012-03-20 Trustees Of Princeton University Process and apparatuses for preparing nanoparticle compositions with amphiphilic copolymers and their use
US6774185B2 (en) 2001-04-04 2004-08-10 Bridgestone Corporation Metal hydroxide filled rubber compositions and tire components
US6858665B2 (en) * 2001-07-02 2005-02-22 The Goodyear Tire & Rubber Company Preparation of elastomer with exfoliated clay and article with composition thereof
JP2003095640A (ja) 2001-09-21 2003-04-03 Teijin Ltd 粘土有機複合体
US6956084B2 (en) * 2001-10-04 2005-10-18 Bridgestone Corporation Nano-particle preparation and applications
US6437050B1 (en) * 2001-10-04 2002-08-20 Bridgestone Corporation Nano-particle preparation and applications
US6689469B2 (en) * 2001-12-31 2004-02-10 Bridgestone Corporation Crystalline polymer nano-particles
US6845797B2 (en) 2001-10-12 2005-01-25 Bridgestone Corporation Tire compositions comprising epoxidized natural rubber and a functionalized polyolefin
US6759464B2 (en) 2001-12-21 2004-07-06 The Goodyear Tire & Rubber Company Process for preparing nanocomposite, composition and article thereof
US6861462B2 (en) * 2001-12-21 2005-03-01 The Goodyear Tire & Rubber Company Nanocomposite formed in situ within an elastomer and article having component comprised thereof
US6706823B2 (en) * 2001-12-31 2004-03-16 Bridgestone Corporation Conductive gels
JP4162519B2 (ja) 2002-03-27 2008-10-08 横浜ゴム株式会社 有機化処理された層状粘土鉱物並びにそれを含む有機重合体組成物及びタイヤ用インナーライナー
US20030225190A1 (en) 2002-04-26 2003-12-04 Janos Borbely Polymeric product for film formation
JP4524078B2 (ja) 2002-05-31 2010-08-11 富士フイルム株式会社 磁性粒子およびその製造方法、並びに、磁気記録媒体およびその製造方法
DE10227071A1 (de) * 2002-06-17 2003-12-24 Merck Patent Gmbh Verbundmaterial enthaltend Kern-Mantel-Partikel
US6737486B2 (en) * 2002-07-16 2004-05-18 Eastman Kodak Company Polymerization process
US7939170B2 (en) * 2002-08-15 2011-05-10 The Rockefeller University Water soluble metal and semiconductor nanoparticle complexes
US6780937B2 (en) 2002-08-29 2004-08-24 The Goodyear Tire & Rubber Company Emulsion particles as reinforcing fillers
US7576155B2 (en) 2002-12-18 2009-08-18 Bridgestone Corporation Method for clay exfoliation, compositions therefore, and modified rubber containing same
DE10260065A1 (de) * 2002-12-19 2004-07-01 Röhm GmbH & Co. KG Kern-Schale-Teilchen zur Schlagzähmodifizierung von Poly(meth)acrylat-Formmassen
US6777500B2 (en) 2002-12-31 2004-08-17 The Goodyear Tire & Rubber Company Core-shell polymer particles
US6875818B2 (en) * 2003-01-16 2005-04-05 Bridgestone Corporation Polymer nano-strings
US7193004B2 (en) * 2003-06-30 2007-03-20 The Goodyear Tire & Rubber Company Pneumatic tire having a component containing low PCA oil
DE10344976A1 (de) 2003-09-27 2005-04-21 Rhein Chemie Rheinau Gmbh Mikrogele in vernetzbaren, organischen Medien
US7056840B2 (en) 2003-09-30 2006-06-06 International Business Machines Corp. Direct photo-patterning of nanoporous organosilicates, and method of use
US7037980B2 (en) 2003-11-10 2006-05-02 Chevron Phillips Chemical Company, Lp Monovinylarene/conjugated diene copolymers having lower glass transition temperatures
KR100591759B1 (ko) 2003-12-03 2006-06-22 삼성전자주식회사 반도체 메모리의 전원 공급장치
US7205370B2 (en) 2004-01-12 2007-04-17 Bridgestone Corporation Polymeric nano-particles of flower-like structure and applications
US7718737B2 (en) * 2004-03-02 2010-05-18 Bridgestone Corporation Rubber composition containing functionalized polymer nanoparticles
US7112369B2 (en) * 2004-03-02 2006-09-26 Bridgestone Corporation Nano-sized polymer-metal composites
US7408005B2 (en) 2004-03-12 2008-08-05 The Goodyear Tire & Rubber Company Hairy polymeric nanoparticles
CN1246351C (zh) 2004-03-12 2006-03-22 清华大学 环氧功能型交联核壳结构纳米高分子微球及其制备方法
US20050215693A1 (en) 2004-03-29 2005-09-29 Xiaorong Wang Clay modified rubber composition and a method for manufacturing same
US20050228074A1 (en) * 2004-04-05 2005-10-13 Bridgestone Corporation Amphiphilic polymer micelles and use thereof
US7071246B2 (en) 2004-04-13 2006-07-04 The Goodyear Tire & Rubber Company Rubber composition containing resinous nanopractice
US7347237B2 (en) * 2004-04-13 2008-03-25 The Goodyear Tire & Rubber Company Rubber composition containing resinous nanoparticle
US20050282956A1 (en) 2004-06-21 2005-12-22 Xiaorong Wang Reversible polymer/metal nano-composites and method for manufacturing same
US7244783B2 (en) 2004-06-24 2007-07-17 The Goodyear Tire & Rubber Company Thermoplastic elastomer composition
JP4846224B2 (ja) 2004-08-02 2011-12-28 株式会社ブリヂストン 表示媒体用粒子及びそれを用いた情報表示用パネル、情報表示装置
US20060072283A1 (en) * 2004-09-27 2006-04-06 Thompson James G Uninterruptible power supply with integral applications processor
JP2006106596A (ja) 2004-10-08 2006-04-20 Bridgestone Corp 情報表示用パネルに用いる表示媒体用粒子
US7838112B2 (en) 2004-11-30 2010-11-23 The Goodyear Tire & Rubber Company Modified gel particles and rubber composition
FR2880349B1 (fr) 2004-12-31 2009-03-06 Michelin Soc Tech Nanoparticules de polyvinylaromatique fonctionnalise
FR2880354B1 (fr) 2004-12-31 2007-03-02 Michelin Soc Tech Composition elastomerique renforcee d'une charge de polyvinylaromatique fonctionnalise
US7572855B2 (en) 2005-01-28 2009-08-11 Bridgestone Corporation Nano-composite and compositions manufactured thereof
US7659342B2 (en) * 2005-02-03 2010-02-09 Bridgestone Corporation Polymer nano-particle with polar core and method for manufacturing same
US7348447B2 (en) 2005-10-11 2008-03-25 Xerox Corporation Aromatic disiloxane compositions
FR2894252B1 (fr) 2005-12-07 2013-01-04 Arkema Composition reticulee comprenant un copolymere coeur ecorce, son procede d'obtention et ses utilisations
DE102005059625A1 (de) 2005-12-14 2007-06-21 Lanxess Deutschland Gmbh Mikrogel-enthaltende vulkanisierbare Zusammensetzung auf Basis von hydriertem Nitrilkautschuk
US7538159B2 (en) 2005-12-16 2009-05-26 Bridgestone Corporation Nanoparticles with controlled architecture and method thereof
US9061900B2 (en) 2005-12-16 2015-06-23 Bridgestone Corporation Combined use of liquid polymer and polymeric nanoparticles for rubber applications
US7884160B2 (en) 2005-12-19 2011-02-08 Bridgestone Corporation Non-spherical nanoparticles made from living triblock polymer chains
US8288473B2 (en) * 2005-12-19 2012-10-16 Bridgestone Corporation Disk-like nanoparticles
US8697775B2 (en) 2005-12-20 2014-04-15 Bridgestone Corporation Vulcanizable nanoparticles having a core with a high glass transition temperature
US7560510B2 (en) 2005-12-20 2009-07-14 Bridgestone Corporation Nano-sized inorganic metal particles, preparation thereof, and application thereof in improving rubber properties
US8877250B2 (en) 2005-12-20 2014-11-04 Bridgestone Corporation Hollow nano-particles and method thereof
JP2007304409A (ja) 2006-05-12 2007-11-22 Bridgestone Corp 表示媒体用粒子および情報表示用パネル
US20080001116A1 (en) * 2006-06-12 2008-01-03 Fredrickson Glenn H Method for producing bi-continuous and high internal phase nanostructures
FR2903411B1 (fr) * 2006-07-06 2012-11-02 Soc Tech Michelin Nanoparticules de polymere vinylique fonctionnalise
CN101516779B (zh) * 2006-07-28 2016-05-04 株式会社普利司通 具有界面区域的聚合物核-壳纳米颗粒
US7597959B2 (en) 2006-12-19 2009-10-06 Bridgestone Corporation Core-shell fluorescent nanoparticles
US7649049B2 (en) * 2006-12-20 2010-01-19 Bridgestone Corporation Rubber composition containing a polymer nanoparticle
US7923478B2 (en) 2006-12-28 2011-04-12 Bridgestone Corporation Nanoporous polymeric material and preparation method
US8778575B2 (en) 2007-01-15 2014-07-15 Fujifilm Corporation Curable composition, color filter using the same and manufacturing method therefor, and solid image pickup element
US7829624B2 (en) 2007-06-29 2010-11-09 Bridgestone Corporation One-pot synthesis of nanoparticles and liquid polymer for rubber applications

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2099645A1 (US20080145660A1-20080619-C00008.png) * 1970-07-28 1972-03-17 Xerox Corp
EP1783168A2 (en) * 2005-11-02 2007-05-09 Fujifilm Corporation Fluorescent polymer fine particle

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
O'REILLY RACHEL K ET AL: "Functionalization of micelles and shell cross-linked nanoparticles using click chemistry", CHEM. MATER.; CHEMISTRY OF MATERIALS NOV 29 2005, vol. 17, no. 24, 29 November 2005 (2005-11-29), pages 5976 - 5988, XP002480353 *

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