WO2008079807A1 - Rubber composition containing a polymer nanoparticle - Google Patents
Rubber composition containing a polymer nanoparticle Download PDFInfo
- Publication number
- WO2008079807A1 WO2008079807A1 PCT/US2007/087869 US2007087869W WO2008079807A1 WO 2008079807 A1 WO2008079807 A1 WO 2008079807A1 US 2007087869 W US2007087869 W US 2007087869W WO 2008079807 A1 WO2008079807 A1 WO 2008079807A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mono
- vinyl aromatic
- conjugated diene
- poly
- rubber
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- 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
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- 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
- C08F297/04—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 polymerising vinyl aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/005—Modified block copolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Definitions
- the disclosure provides a rubber composition incorporating nanoparticles comprising a core and a surface layer, wherein the surface layer comprises a poly(mono-vinyl aromatic-conjugated diene) and the core has a glass transition temperature (Tg) between about 150° C and about 600° C.
- Tg glass transition temperature
- a common method of increasing the steering response of the tire is to use a tread rubber with high stiffness.
- High stiffness compounds typically have a high dynamic storage modulus.
- Conventional compounding techniques used to increase the dynamic storage modulus include using a high filler loading, using a filler with a high surface area, using less softener, and using styrene-butadiene polymers with a high styrene content.
- each of these conventional methods has performance tradeoffs.
- the above mentioned conventional techniques can increase the hysteresis of the rubber compound.
- Increasing the hysteresis of the rubber results in more energy lost as heat, and thus increases fuel consumption.
- increasing the filler loading, using a filler with a high surface area, and lowering the softener level can have a negative effect on processing, as they all increase the time it takes to disperse the filler into the rubber.
- a need remains to improve the dynamic modulus of a rubber compound without significantly impacting compound hysteresis or compound processing.
- composition comprising a rubber and a polymer nanoparticle comprising a poly(mono-vinyl aromatic) core and a poly(mono-vinyl aromatic-conjugated diene) surface layer, wherein the core of the polymeric nano- particle has a glass transition temperature (Tg) of between about 150° C and about 600° C.
- Tg glass transition temperature
- compositions comprising at least two (mono-vinyl aromatic-conjugated diene) copolymer rubbers and a polymeric nano-particle comprising a poly(mono-vinyl aromatic) core and a poly(mono-vinyl aromatic- conjugated diene) surface layer; wherein the core of the polymeric nano-particle has a glass transition temperature (Tg) of between about 150° C and about 600° C, and the poly(mono-vinyl aromatic-conjugated diene) surface layer of the polymeric nano- particle comprises a mono-vinyl aromatic content that is between about 50 percent and about 150 percent that of the mono-vinyl content of one of the (mono-vinyl aromatic-conjugated diene) copolymer rubbers.
- Tg glass transition temperature
- a tire comprising a tread.
- the tread comprises a rubber and a polymer nano-particle comprising a poly(mono-vinyl aromatic) core and a poly(mono-vinyl aromatic-conjugated diene) surface layer, wherein the core of the polymeric nano-particle has a glass transition temperature (Tg) of between about 150° C and about 600° C.
- Tg glass transition temperature
- FIGURE 1 is a graphical depiction of Differential Scanning Calorimetry analysis of the nano-particles utilized in example 1.
- Polymer nanoparticles with a surface layer and a core with a Tg between about 150° C and about 600° C may be prepared by:
- step (ii) takes place, a sufficient amount of the copolymers comprising the poly(conjugated diene) block and the aromatic block may assemble to form micelle structures, and typically in the meanwhile, the aromatic blocks may be crosslinked by the multiple-vinyl aromatic monomers.
- the polymer nanoparticles with a surface layer and a core with a Tg between about 150° C and about 600° C are formed through dispersion polymerization, although emulsion polymerization may also be contemplated.
- the polymerization may be accomplished by a multi-stage anionic polymerization. Multistage 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. Other relevant references include U.S. Pat. No. 6,437,050 and U.S. Patent Application 2004/0143064.
- the polymer nanoparticles can be formed from di-block copolymer chains comprising the poly(conjugated diene) block and the aromatic block.
- the aromatic blocks are typically crosslinked due to the presence of multiple-vinyl aromatic monomers, at least partially giving a way of controlling the core Tg.
- the polymer nanoparticles preferably retain their discrete nature with little or no polymerization between each other.
- the nanoparticles are substantially monodisperse and uniform in shape.
- the liquid hydrocarbon medium functions as the dispersion solvent, and may be selected from any suitable aliphatic hydrocarbons, alicyclic hydrocarbons, or mixtures thereof, with a proviso that it exists in liquid state during the nanoparticles' formation procedure.
- 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.
- any suitable conjugated diene or mixture thereof may be used as the monomer(s) to produce the poly(conjugated diene) block.
- the conjugated diene monomers include, but are not limited to, 1 ,3-butadiene, isoprene (2-methyl-1 ,3-butadiene), cis- and frans-piperylene (1 ,3-pentadiene), 2,3-dimethyl- 1 ,3-butadiene, 1 ,3-pentadiene, cis- and frans-1 , 3-hexadiene, cis- and trans-2- methyl-1 ,3-pentadiene, cis- and frans-3-methyl-1 ,3-pentadiene, 4-methyl-1,3- pentadiene, 2,4-dimethyl-1 ,3-pentadiene, and the like, and the mixture thereof.
- isoprene or 1 ,3-butadiene isoprene or
- the polymerizing of conjugated diene monomers into a poly(conjugated diene) 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 radicals and cycloaliphatic radicals, such as alkyl, cycloalkyl, cycloalkylalkyl, alkylcycloalkyl, alkenyl, as well as aryl and alkylaryl radicals.
- R groups include, but are not limited to, alkyls such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-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
- lithium initiators include, but are not limited to, 1 ,4-dilithiobutane, 1 ,5-dilithiopetane, 1 ,10-dilithiodecane, 1 ,20-dilithioeicosane, 1 ,4-dilithiobenzene, 1 ,4-dilithionaphthalene, 1 , 10-dilithioanthracene, 1 ,2-dilithio-1 ,2-diphenylethane, 1 ,3,5-trilithiopentane, 1 ,5,15-trilithioeicosane, 1 ,3,5-trilithiocyclohexane, 1 ,3,5,8- tetralithiodecane, 1 ,5,10,20-tetralithioeicosane, 1 ,2,4,6-tetralithiocyclohexane, 4,4'- dilithiobiphenyl,
- Preferred lithium initiators include n-butyllithium, sec- butyllithium, tert-butyllithium, 1 ,4-dilithiobutane, and mixtures thereof.
- Other lithium initiators which can be employed are lithium dialkyl amines, lithium dialkyl phosphines, lithium alkyl aryl phosphines and lithium diaryl phosphines.
- Functionalized lithium initiators may also be utilized.
- Preferred functional groups include amines, formyl, carboxylic acids, alcohol, tin, silicon, silyl ether and mixtures thereof.
- n-butyllithium, sec-butyllithium, tert-butyllithium, or mixture thereof are used to initiate the polymerization of the conjugated diene monomers into a poly(conjugated diene) block.
- the polymerization of conjugated diene monomers into a poly(conjugated diene) block may last as long as necessary until the desired monomer conversion, degree of polymerization (DP), and block molecular weight are obtained.
- the polymerization reaction of this step may last from about 0.25 hours to about 10 hours, or from about 0.5 hours to about 4 hours, or from about 0.5 hours to about 2 hours.
- the polymerization reaction of this step may be conducted at a temperature of from about 70°F to about 350°F, or from about 74°F to about 250 0 F, or from about 80 0 F to about 200 0 F. In exemplified embodiments, the polymerization lasts about 90 minutes at 65-195 0 F.
- the anionic polymerization of conjugated diene monomers may be conducted in the presence of a modifier or a 1 ,2-microstructure controlling agent, so as to, for example, increase the reaction rate, equalize the reactivity ratio of monomers, and/or control the 1 ,2-microstructure in the conjugated diene monomers.
- Suitable modifiers include, but are not limited to, triethylamine, tri-n- butylamine, hexamethylphosphoric acid triamide, N, N, N', N'-tetramethylethylene diamine, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, 1 ,4- diazabicyclo [2.2.2] octane, diethyl ether, tri-n-butylphosphine, p-dioxane, 1 ,2 dimethoxy ethane, dimethyl ether, methyl ethyl ether, ethyl propyl ether, di-n-propyl ether, di-n-octyl ether, anisole, dibenzyl ether, diphenyl ether, dimethylethylamine, bix-oxalanyl propane, tri-n
- the anionic polymerization can also be conducted in the presence of an amine compound such as triethyl amine, trimethyl amine, tripropyl amine, tri- isopropyl amine, tri-n-butyl amine, and the like, and the mixture thereof.
- an amine compound such as triethyl amine, trimethyl amine, tripropyl amine, tri- isopropyl amine, tri-n-butyl amine, and the like, and the mixture thereof.
- Other modifiers or 1 ,2-microstructure controlling agents may be linear oxolanyl oligomers represented by the structural formula (IV) and cyclic oligomers represented by the structural formula (V), as shown below:
- R 14 and Ri 5 are independently hydrogen or a CrC 8 alkyl group
- R- ⁇ 6i R 17 , R18, and Rig are independently hydrogen or a C- ⁇ -C- 6 alkyl group
- y is an integer of 1 to 5 inclusive
- z is an integer of 3 to 5 inclusive.
- modifiers or 1 ,2-microstructure controlling agents include, but are not limited to, oligomeric oxolanyl propanes (OOPs); 2,2-bis-(4- methyl dioxane); bis(2-oxolanyl) methane; 1 ,1-bis(2-oxolanyl) ethane; bistetrahydrofuryl propane; 2,2-bis(2-oxolanyl) propane; 2,2-bis(5-methyl-2- oxolanyl) propane; 2,2-bis-(3,4,5-trimethyl-2-oxolanyl) propane; 2,5-bis(2-oxolanyl- 2-propyl) oxolane; octamethylperhydrocyclotetrafurfurylene (cyclic tetramer); 2,2- bis(2-oxolanyl) butane; and the like.
- a mixture of two or more modifiers or 1 ,2- microstructure controlling agents also can be used.
- the poly(conjugated diene) block has a randomized structure comprising conjugated diene monomers and mono-vinyl aromatic monomers that are copolymerized using an anionic initiator, optionally in the presence of a modifier.
- Suitable mono-vinyl aromatic monomers include, but are not limited to, styrene, ethylvinylbenzene, ⁇ -methyl-styrene, 1 -vinyl naphthalene, 2-vinyl naphthalene, vinyl toluene, methoxystyrene, t-butoxystyrene, and the like; as well as alkyl, cycloalkyl, aryl, alkaryl, and aralkyl derivatives thereof, in which the total number of carbon atoms in the monomer is generally not greater than about 18; and mixtures thereof.
- the mono-vinyl aromatic monomer comprises styrene or ethylvinylbenzene or mixture thereof. If the poly(conjugated diene) block has a randomized structure comprising conjugated O
- the resulting polymer nanoparticle will have a surface layer, having a copolymer comprising conjugated diene units and mono-vinyl aromatic units.
- a mixture of mono-vinyl aromatic monomers and multiple-vinyl aromatic monomers may then be copolymerized with the living poly(conjugated diene) block.
- the weight ratio between the mono-vinyl aromatic monomers and multiple-vinyl aromatic monomers may broadly range from about 99.9:0.01 to about 0.01 :99.9, preferably from about 99:1 to about 1 :99, and more preferably from about 90:10 to about 10:99.
- any compound that comprises one vinyl group and an aromatic group may be used as the mono-vinyl aromatic monomer.
- Suitable mono-vinyl aromatic monomers include, but are not limited to styrene, ethylvinylbenzene, ⁇ -methyl- styrene, 1 -vinyl naphthalene, 2-vinyl naphthalene, vinyl toluene, methoxystyrene, t- butoxystyrene, and the like; as well as alkyl, cycloalkyl, aryl, alkaryl, and aralkyl derivatives thereof, in which the total number of carbon atoms in the monomer is generally not greater than about 18; and mixtures thereof.
- the mono-vinyl aromatic monomer comprises styrene or ethylvinylbenzene or mixture thereof.
- any compound that comprises two or more vinyl groups and an aromatic group may be used as the multiple-vinyl aromatic monomer.
- Suitable multiple-vinyl aromatic monomers include, but are not limited to compounds with a general 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. di-vinyl-benzene (DVB).
- the DVB may be selected from any one of the following isomers or any combination thereof:
- Additional anionic initiator such as lithium initiator may be added when the mixture of mono-vinyl aromatic monomers and multiple-vinyl aromatic monomers is copolymerized with the living poly(conjugated diene) block.
- Exemplary anionic initiators may be those described above.
- n- butyllithium, sec-butyllithium, tert-butyllithium, or mixture thereof are used.
- the polymerization may last as long as necessary until the desired core Tg, monomer conversion, degree of polymerization (DP), and block molecular weight are obtained.
- the polymerization reaction of this step may last from about 0.5 hours to about 10 hours, or from about 1 hour to about 6 hours, or from about 1 hour to about 4 hours.
- the polymerization reaction of this step may be conducted at a temperature of from about 70 0 F to about 350 0 F, or from about 74 0 F to about 25O 0 F, or form about 80 0 F to about 200 0 F.
- the polymerization step lasts 3 hours at 165 0 F and then 1 hour at 21O 0 F.
- the polymer nanoparticles are formed from the micelle-like structures with a core made from the aromatic blocks, and a surface layer made from the poly(conjugated diene) blocks.
- the polymerization reactions used to prepare the polymer nanoparticles may be terminated with a terminating agent.
- Suitable terminating agents include, but are not limited to, alcohols such as methanol, ethanol, propanol, and isopropanol; amines, MeSiCI 3 , Me 2 SiCI 2 , Me 3 SiCI, SnCI 4 , MeSnCI 3 , Me 2 SnCI 2 , Me 3 SnCI, and etc.
- the polymerization reaction mixture was cooled down and dropped in an isopropanol/acetone solution optionally containing an antioxidant such as butylated hydroxytoluene (BHT).
- BHT butylated hydroxytoluene
- the isopropanol/acetone solution may be prepared, for example, by mixing 1 part by volume of isopropanol and 4 parts by volume of acetone.
- the polymer nanoparticles may be functionalized via one or more mechanisms, including functionalization by a specifically designed initiator; functionalization by a specifically designed terminating agent; functionalization by copolymerization of a functionalized comonomer when generating the surface layer and/or the core; or functionalization by modification of any unsaturated groups such as vinyl groups in the poly(conjugated diene) surface layer.
- exemplary functional groups that may be incorporated into the polymer nano-particles include, but are not limited to, maleimide, hydroxyl, carboxy, formyl, azocarboxy, epoxide, amino, colonids, bromide, and the like, and the mixture thereof.
- polymer nanoparticles are made according to the following process.
- a random poly(conjugated diene) block is prepared through the solution polymerization of conjugated diene monomers and mono-vinyl aromatic monomers in a hexane solvent using a butyl-lithium initiator and in the presence of a randomizing agent, oligomeric oxolanyl propanes (OOPs).
- the conjugated diene monomers may comprise 1 ,3-butadiene and the mono- aromatic monomers may comprise styrene.
- a mixture of mono-vinyl aromatic monomers and multiple-vinyl aromatic monomers is then copolymerized with the living poly(conjugated diene) block, optionally using an additional amount of butyl lithium initiator.
- the mono-vinyl aromatic monomers may comprise styrene and the multiple-vinyl aromatic monomers may comprise divinylbenzene.
- the reaction is terminated with alcohol and then dried and desolventized.
- the product is a star-shaped polymer nanoparticle with a crosslinked core. [0037]
- the polymer nanoparticle may take the shape of nano-spheres.
- the mean diameter of the spheres may be within the range of from about 5nm to about 200nm, or from about 5nm to about 100nm, or from about 10nm to about 80nm, or from about 15nm to about 60nm.
- the molecular weight (Mn, Mw or Mp) of the poly(conjugated diene) block may be controlled within the range of from about 1 ,000 to about 1 ,000,000, within the range of from about 1 ,000 to about 100,000, or within the range of from about 1 ,000 to about 80,000.
- the molecular weight (Mn, Mw or Mp) of the polymer nano-particle may be controlled within the range of from about 100,000 to about 1 ,000,000,000, or from about 1 ,000,000 to about 100,000,000.
- the polydispersity (the ratio of the weight average molecular weight to the number average molecular weight) of the polymer nano-particle may be controlled within the range of from about 1.01 to about 1.3, within the range of from about 1.01 to about 1.2, or within the range of from about 1.01 to about 1.1.
- the nano-particles can be produced in two polymerization steps, rather than three steps, i.e., mono-vinyl aromatic monomers and multiple-vinyl aromatic monomers, as a mixture, are polymerized in one step or simultaneously, rather than mono-vinyl aromatic monomers are polymerized first, and then multiple-vinyl aromatic monomers are copolymerized or summoned for crosslinking.
- This simpler process results in a higher yield of particles than in the three-step process (80-98% vs. 40-85%).
- the process can efficiently yield a high conversion of monomers to high molecular weight nanoparticles (typically > 90% yield of nanoparticles).
- the particles of the invention have a vulcanizable surface layer such as a sulfur curable surface layer.
- the vulcanizable surface layer is a sulfur or peroxide curable surface layer.
- suitable sulfur vulcanizing agents include "rubber maker's" soluble sulfur; elemental sulfur (free sulfur); sulfur donating vulcanizing agents such as organosilane polysulfides, amine disulfides, polymeric polysulfides or sulfur olefin adducts; and insoluble polymeric sulfur.
- the nanoparticles have a core that is sufficiently crosslinked such that the Tg of the nanoparticle core may broadly range from about 150 0 C to about 600 0 C, from about 200 0 C to about 400 0 C, or from about 25O 0 C to about 300 0 C. Glass transition temperature may be determined, for example, by a differential scanning calorimeter at a heating rate of 10 0 C per minute.
- the nano-particles are compounded into a rubber composition, such as a tire rubber tread composition.
- Rubber compositions may be prepared by mixing a rubber and the nano-particles with a reinforcing filler comprising silica, or a carbon black, or a mixture of the two, optionally a processing aid, optionally a coupling agent, optionally a cure agent, other desirable or acceptable tire tread components, and an effective amount of sulfur to achieve a satisfactory cure of the composition.
- exemplary rubbers include conjugated diene polymers, copolymers or terpolymers of conjugated diene monomers and monovinyl aromatic monomers. These can be utilized as 100 parts of the rubber in the tread stock compound i.e. make up the entire rubber component of the compound, or they can be blended with any conventionally employed treadstock rubber which includes natural rubber, synthetic rubber and blends thereof.
- Such rubbers are well known to those skilled in the art and include synthetic polyisoprene rubber, styrene-butadiene rubber (SBR), styrene-isoprene rubber, styrene-isoprene-butadiene rubber, butadiene-isoprene rubber, polybutadiene, butyl rubber, neoprene, acrylonitrile-butadiene rubber (NBR), silicone rubber, the fluoroelastomers, ethylene acrylic rubber, ethylene-propylene rubber, ethylene-propylene terpolymer (EPDM), ethylene vinyl acetate copolymer, epicholrohydrin rubber, chlorinated polyethylene-propylene rubbers, chlorosulfonated polyethylene rubber, hydrogenated nitrile rubber, terafluoroethylene-propylene rubber, and the like.
- SBR styrene-butadiene rubber
- EPDM ethylene-propylene terpol
- Examples of reinforcing silica fillers which can be used in the vulcanizable elastomeric composition include wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), calcium silicate, and the like.
- Other suitable fillers include aluminum silicate, magnesium silicate, and the like.
- precipitated amorphous wet-process, hydrated silicas are preferred.
- Silica can be employed in the amount of about one to about 100 parts per hundred parts of the elastomer (phr), preferably in an amount of about 5 to 80 phr and, more preferably, in an amount of about 30 to about 80 phrs. The useful upper range is limited by the high viscosity imparted by fillers of this type.
- silica examples include, but are not limited to, HiSil® 190, HiSil® 210, HiSil® 215, HiSil® 233, HiSil® 243, and the like, produced by PPG Industries (Pittsburgh, Pa.).
- a number of useful commercial grades of different silicas are also available from DeGussa Corporation (e.g., VN2, VN3), Rhone Poulenc (e.g., Zeosil® 1165MP0, and J. M. Huber Corporation).
- the rubber can be compounded with all forms of carbon black, optionally additionally with silica.
- the carbon black can be present in amounts ranging from about one to about 100 phr.
- the carbon black can include any of the commonly available, commercially-produced carbon blacks, but those having a surface are of at least 20 m 2 /g and, or preferably, at least 35 m 2 /g up to 200 m 2 /g or higher are preferred.
- useful carbon blacks are furnace black, channel blacks, and lamp blacks. A mixture of two or more of the above blacks can be used in preparing the carbon black products of the invention.
- Typical suitable carbon blacks are N-110, N- 220, N-339, N-330, N-352, N-550, N-660, as designated by ASTM D-1765-82a.
- Certain additional fillers can be utilized including mineral fillers, such as clay, talc, aluminum hydrate, aluminum hydroxide and mica. The foregoing additional fillers are optional and can be utilized in the amount of about 0.5 phr to about 40 phr.
- silica-based coupling and compatibilizing agents include silane coupling agents containing polysulfide components, or structures such as, for example, trialkoxyorganosilane polysulfides, containing from about 2 to about 8 sulfur atoms in a polysulfide bridge such as, for example, bis-(3- triethoxysilylpropyl) tetrasulfide (Si69), bis-(3-triethoxysilylpropyl) disulfide (Si75), and those alkyl alkoxysilanes of the such as octyltriethoxy silane, and hexyltrimethoxy silane.
- silane coupling agents containing polysulfide components, or structures such as, for example, trialkoxyorganosilane polysulfides, containing from about 2 to about 8 sulfur atoms in a polysulfide bridge such as, for example, bis-(3- triethoxysilylpropyl) t
- Processing oils can be added to the vulcanizable elastomeric composition. Processing oils may be utilized in the amount of 0 phr to about 70 phr. The processing oil may be added to the composition by itself, or may be added in the form of an oil extended elasatomer. Exemplary processing oils include aromatic, naphthenic, and low PCA oils. Suitable low PCA oils include those having a polycyclic aromatic content of less than 3 percent by weight as determined by the IP346 method. Procedures for the IP346 method may be found in Standard Methods for Analysis & Testing of Petroleum and Related Products and British Standard 2000 Parts, 2003, 62nd edition, published by the Institute of Petroleum, United Kingdom.
- Suitable low PCA oils include mild extraction solvates (MES), treated distillate aromatic extracts (TDAE), and heavy naphthenics.
- MES oils are available commercially as Catenex SNR from Shell, Prorex 15 and Flexon 683 from ExxonMobil, VivaTec 200 from BP, Plaxolene MS from TotalFinaElf, Tudalen 4160/4225 from Dahleke, MES-H from Repsol, MES from Z8, and Olio MES S201 from Agip.
- Suitable TDAE oils are available as Tyrex 20 from ExxonMobil, VivaTec 500, VivaTec 180 and Enerthene 1849 from BP, and Extensoil 1996 from Repsol.
- Suitable heavy naphthenic oils are available as Shellflex 794, Ergon Black Oil, Ergon H2000, Cross C2000, Cross C2400, and San Joaquin 2000L.
- the rubber composition can be compounded by methods generally known in the rubber compounding art, such as mixing the rubber(s) with various commonly used additive materials such as, for example, curing agents, activators, retarders and accelerators processing additives, such as oils, resins, including tackifying resins, plasticizers, pigments, additional fillers, fatty acid, zinc oxide, waxes, antioxidants, anti-ozonants, and peptizing agents.
- additives mentioned above are selected and commonly used in the conventional amounts.
- the nano-particles are added to a tire tread that comprises at least one rubber.
- exemplary rubbers include conjugated diene polymers, copolymers or terpolymers of conjugated diene monomers and mono-vinyl aromatic monomers. These can be utilized as 100 parts of the rubber in the tread stock compound i.e. make up the entire rubber component of the compound, or they can be blended with any conventionally employed treadstock rubber which includes natural rubber, synthetic rubber and blends thereof.
- Such rubbers are well known to those skilled in the art and include synthetic polyisoprene rubber, styrene-butadiene rubber (SBR), styrene-isoprene rubber, styrene-isoprene-butadiene rubber, butadiene-isoprene rubber, polybutadiene, butyl rubber, neoprene, acrylonitrile- butadiene rubber (NBR), silicone rubber, the fluoroelastomers, ethylene acrylic rubber, ethylene-propylene rubber, ethylene-propylene terpolymer (EPDM), ethylene vinyl acetate copolymer, epicholrohydrin rubber, chlorinated polyethylene-propylene rubbers, chlorosulfonated polyethylene rubber, hydrogenated nitrile rubber, terafluoroethylene-propylene rubber, and the like.
- SBR styrene-butadiene rubber
- EPDM ethylene-propylene terpol
- a tire tread comprises at least two rubbers, each of which is comprised of at least one conjugated diene monomer unit and at least one mono-vinyl aromatic monomer unit.
- conjugated diene monomers include , but are not limited to, 1 ,3-butadiene, isoprene (2-methyl-1,3-butadiene), cis- and frans-piperylene (1 ,3-pentadiene), 2,3-dimethyl-1 ,3-butadiene, 1 ,3- pentadiene, cis- and trans- ⁇ , 3-hexadiene, cis- and fraA7S-2-methyl-1 ,3-pentadiene, cis- and frans-3-methyl-1 ,3-pentadiene, 4-methy I- 1 ,3-pentadiene, 2,4-dimethyl-1 ,3- pentadiene, and the like, and the mixture thereof.
- isoprene or 1 ,3-butadiene or mixture thereof is used as the conjugated diene monomer.
- exemplary mono-vinyl aromatic units include, but are not limited to styrene, ethylvinylbenzene, ⁇ -methyl-styrene, 1 -vinyl naphthalene, 2-vinyl naphthalene, vinyl toluene, methoxystyrene, t-butoxystyrene, and the like; as well as alkyl, cycloalkyl, aryl, alkaryl, and aralkyl derivatives thereof, in which the total number of carbon atoms in the monomer is generally not greater than about 18; and mixtures thereof.
- the nano-particles can be used in place of the (mono-vinyl aromatic- conjugated diene) copolymer rubber that has a mono-vinyl aromatic content that most closely matches the mono-vinyl aromatic content of the surface layer of the nano-particles.
- the mono-vinyl aromatic content of the surface layer of the nano- particles can be between about 50 percent and about 150 percent, or between about 75 percent and about 125 percent, or between about 90 percent and 110 percent that of the mono-vinyl aromatic content of one of the (alkenylbenzene- conjugated diene) copolymers. This allows for the incorporation of the nano- particles into the rubber without significantly impacting the overall mono-vinyl aromatic content of the rubber matrix.
- the nano-particles can be added to a rubber composition at a level of less than about 50 phr, less than about 30 phr, or less than about 20 phr.
- the core of the nano-particle acts as a filler dispersed in the rubber. The filler effect is attributed to the relative hardness of the core in comparison to the rubber matrix.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009543130A JP5383503B2 (en) | 2006-12-20 | 2007-12-18 | Rubber composition comprising polymer nanoparticles |
KR1020097014949A KR101506986B1 (en) | 2006-12-20 | 2007-12-18 | Rubber composition containing a polymer nanoparticle |
EP07865780.6A EP2099861B1 (en) | 2006-12-20 | 2007-12-18 | Rubber composition containing a polymer nanoparticle |
BRPI0720393-4A BRPI0720393A2 (en) | 2006-12-20 | 2007-12-18 | RUBBER COMPOSITION CONTAINING A POLYMER NANOParticle |
CN2007800478952A CN101568584B (en) | 2006-12-20 | 2007-12-18 | Rubber composition containing a polymer nanoparticle |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/642,795 US7649049B2 (en) | 2006-12-20 | 2006-12-20 | Rubber composition containing a polymer nanoparticle |
US11/642,795 | 2006-12-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2008079807A1 true WO2008079807A1 (en) | 2008-07-03 |
Family
ID=39271418
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2007/087869 WO2008079807A1 (en) | 2006-12-20 | 2007-12-18 | Rubber composition containing a polymer nanoparticle |
Country Status (8)
Country | Link |
---|---|
US (1) | US7649049B2 (en) |
EP (1) | EP2099861B1 (en) |
JP (1) | JP5383503B2 (en) |
KR (1) | KR101506986B1 (en) |
CN (1) | CN101568584B (en) |
BR (1) | BRPI0720393A2 (en) |
WO (1) | WO2008079807A1 (en) |
ZA (1) | ZA200904457B (en) |
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7649049B2 (en) | 2006-12-20 | 2010-01-19 | Bridgestone Corporation | Rubber composition containing a polymer nanoparticle |
US7659342B2 (en) | 2005-02-03 | 2010-02-09 | Bridgestone Corporation | Polymer nano-particle with polar core and method for manufacturing same |
US7718738B2 (en) | 2001-10-04 | 2010-05-18 | Bridgestone Corporation | Self assembly of molecules to form nano-particles |
US7718737B2 (en) | 2004-03-02 | 2010-05-18 | Bridgestone Corporation | Rubber composition containing functionalized polymer nanoparticles |
US7786236B2 (en) | 2004-01-12 | 2010-08-31 | Bridgestone Corporation | Polymeric nano-particles of flower-like structure and applications |
US7829624B2 (en) | 2007-06-29 | 2010-11-09 | Bridgestone Corporation | One-pot synthesis of nanoparticles and liquid polymer for rubber applications |
US7884160B2 (en) | 2005-12-19 | 2011-02-08 | Bridgestone Corporation | Non-spherical nanoparticles made from living triblock polymer chains |
US7998554B2 (en) | 2004-07-06 | 2011-08-16 | Bridgestone Corporation | Hydrophobic surfaces with nanoparticles |
US8063142B2 (en) | 2004-03-02 | 2011-11-22 | Bridgestone Corporation | Method of making nano-particles of selected size distribution |
US8288473B2 (en) | 2005-12-19 | 2012-10-16 | Bridgestone Corporation | Disk-like nanoparticles |
US8349964B2 (en) | 2004-06-21 | 2013-01-08 | Bridgestone Corporation | Reversible polymer/metal nano-composites and method for manufacturing same |
US8410225B2 (en) | 2006-12-19 | 2013-04-02 | Bridgestone Corporation | Fluorescent nanoparticles |
US8541503B2 (en) | 2006-07-28 | 2013-09-24 | Bridgestone Corporation | Polymeric core-shell nanoparticles with interphase region |
US8697775B2 (en) | 2005-12-20 | 2014-04-15 | Bridgestone Corporation | Vulcanizable nanoparticles having a core with a high glass transition temperature |
US8846819B2 (en) | 2008-12-31 | 2014-09-30 | Bridgestone Corporation | Core-first nanoparticle formation process, nanoparticle, and composition |
US8877250B2 (en) | 2005-12-20 | 2014-11-04 | Bridgestone Corporation | Hollow nano-particles and method thereof |
US9061900B2 (en) | 2005-12-16 | 2015-06-23 | Bridgestone Corporation | Combined use of liquid polymer and polymeric nanoparticles for rubber applications |
US9062144B2 (en) | 2009-04-03 | 2015-06-23 | Bridgestone Corporation | Hairy polymeric nanoparticles with first and second shell block polymer arms |
US9115222B2 (en) | 2009-12-29 | 2015-08-25 | Bridgestone Corporation | Well defined, highly crosslinked nanoparticles and method for making same |
US9428604B1 (en) | 2011-12-30 | 2016-08-30 | Bridgestone Corporation | Nanoparticle fillers and methods of mixing into elastomers |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7538159B2 (en) * | 2005-12-16 | 2009-05-26 | Bridgestone Corporation | Nanoparticles with controlled architecture and method thereof |
WO2008147395A2 (en) * | 2006-11-10 | 2008-12-04 | Grune Guerry L | Anti-microbial compounds used in garments for water based activities |
US7832490B2 (en) * | 2007-05-31 | 2010-11-16 | Baker Hughes Incorporated | Compositions containing shape-conforming materials and nanoparticles to enhance elastic modulus |
US20110172364A1 (en) * | 2009-12-29 | 2011-07-14 | Chen Yaohong | Charged Nanoparticles And Method Of Controlling Charge |
EP2495267B1 (en) * | 2011-03-04 | 2016-10-12 | Trinseo Europe GmbH | High styrene high vinyl styrene-butadiene rubber and methods for preparation thereof |
FR2980205B1 (en) * | 2011-09-19 | 2013-09-27 | Michelin Soc Tech | PNEUMATIC TIRE TREAD OFF THE ROAD |
JP2018021111A (en) * | 2016-08-02 | 2018-02-08 | 株式会社ブリヂストン | Rubber member and tire |
FR3069189A1 (en) * | 2017-07-21 | 2019-01-25 | Compagnie Generale Des Etablissements Michelin | PNEUMATIC HAVING IMPROVED WEAR AND ROLL RESISTANCE PROPERTIES |
CN112135738B (en) * | 2018-04-11 | 2022-09-09 | 埃克森美孚化学专利公司 | Propylene-based polymer additives for improved tire tread performance |
CN114106273A (en) * | 2020-08-25 | 2022-03-01 | 中国石油化工股份有限公司 | Application of 1, 2-dialkoxypropane as polarity regulator for synthesizing high-vinyl aryl ethylene-conjugated diene block copolymer |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003085040A2 (en) * | 2001-10-04 | 2003-10-16 | Bridgestone Corporation | Nano-particle preparation and applications |
US20040127603A1 (en) * | 2002-12-31 | 2004-07-01 | The Goodyear Tire & Rubber Company | Core-shell polymer particles |
US20070196653A1 (en) * | 2005-12-20 | 2007-08-23 | Hall James E | Vulcanizable nanoparticles having a core with a high glass transition temperature |
Family Cites Families (207)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US454403A (en) * | 1891-06-16 | o odkolek | ||
US48390A (en) * | 1865-06-27 | Improvement in puddling-furnaces | ||
US2531396A (en) | 1947-03-29 | 1950-11-28 | Nat Lead Co | Elastomer reinforced with a modified clay |
US3598884A (en) | 1967-08-04 | 1971-08-10 | Polymer Corp | Cross-linking of polymers |
US3840620A (en) | 1970-04-15 | 1974-10-08 | Stauffer Chemical Co | Additives for the preparation of clear,impact resistant vinyl chloride polymer compositions |
BE770501A (en) | 1970-07-28 | 1972-01-26 | Xerox Corp | POLYMERS CONTAINING PYRENE, PREPARED BY ANIONIC POLYMERIZATION |
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 |
FR2289566A1 (en) | 1974-10-29 | 1976-05-28 | Firestone Tire & Rubber Co | COPOLYMER GRAFTS OF POLYBUTADIENE AND A SUBSTITUTE POLYACRYLATE, AND THEIR OBTAINING |
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 |
GB2088387A (en) | 1980-11-25 | 1982-06-09 | Exxon Research Engineering Co | Adhesive sealants for double glazing |
EP0058952B1 (en) | 1981-02-20 | 1984-08-22 | Asahi Kasei Kogyo Kabushiki Kaisha | A film, sheet or tube of a block copolymer or a composition containing the same |
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 (en) | 1983-03-15 | 1984-09-21 | Kanegafuchi Chem Ind Co Ltd | Curable elastomer composition |
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 (en) | 1983-11-23 | 1985-06-17 | Dow Chemical Nederland | RUBBER-REINFORCED POLYMERS OF MONOVINYLIDE AROMATIC COMPOUNDS HAVING A VERY GOOD RATIO BETWEEN GLOSS AND STRENGTH PROPERTIES AND A PROCESS FOR THEIR PREPARATION. |
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 |
EP0169536B1 (en) | 1984-07-26 | 1994-05-18 | Kanegafuchi Chemical Industry Co., Ltd. | Curable polymer composition |
DE3434983C2 (en) | 1984-09-24 | 1993-10-14 | Hoechst Ag | Gel-forming organophilic layered silicate, process for its production and use |
JPS61141761A (en) | 1984-12-12 | 1986-06-28 | Kanegafuchi Chem Ind Co Ltd | Curable composition |
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 |
US4764572A (en) | 1985-07-23 | 1988-08-16 | Shell Oil Company | Anionic polymerization process |
CA1274647C (en) | 1986-06-25 | 1990-09-25 | Curable isobutylene polymer | |
IT1196987B (en) | 1986-07-23 | 1988-11-25 | Enichem Sintesi | SILILATED COPYLIMERS OF ISOBUTYLENE CROSS-LINKED IN ENVIRONMENTAL CONDITIONS AND PROCEDURE FOR THEIR PREPARATION |
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 (en) | 1986-10-21 | 1993-05-18 | Rohm & Haas | COVERED NUCLEUS IMPACT MODIFIERS FOR STYRENE RESINS |
JPH0651752B2 (en) | 1987-02-20 | 1994-07-06 | 鐘淵化学工業株式会社 | Process for producing isobutylene-based polymer having functional end |
FR2615279B1 (en) | 1987-05-11 | 1990-11-02 | Commissariat Energie Atomique | DISPLACEMENT SENSOR WITH OFFSET FIBER OPTICS |
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 |
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 (en) | 1987-12-29 | 1990-10-04 | Montedipe Spa | PROCESS FOR IMIDIZING MALEIC ANHYDRIDE COPOLYMERS WITH AROMATIC VINYL MONOMERS |
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 (en) | 1989-02-28 | 1998-02-25 | 鐘淵化学工業株式会社 | Organic polymer, production method thereof and curable composition using the same |
US5247021A (en) | 1989-06-06 | 1993-09-21 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Process for preparation of a polymer having reactive terminal group |
JPH0798890B2 (en) | 1989-06-23 | 1995-10-25 | 日本ゼオン株式会社 | Block copolymer composition for pressure-sensitive adhesive and pressure-sensitive adhesive composition |
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 |
US5241008A (en) | 1991-09-03 | 1993-08-31 | Bridgestone/Firestone, Inc. | Process for producing continuously tapered polymers and copolymers and products produced thereby |
CA2077370C (en) | 1991-09-03 | 1998-12-15 | James E. Hall | Dispersion copolymers in linear aliphatic solvents |
JP3154529B2 (en) | 1991-10-14 | 2001-04-09 | 鐘淵化学工業株式会社 | Isobutylene polymer having functional group and method for producing the same |
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 (en) | 1992-06-10 | 1997-05-21 | 住友化学工業株式会社 | Butadiene copolymer |
DE4220563A1 (en) | 1992-06-24 | 1994-01-13 | Bayer Ag | Rubber mixtures containing polybutadiene gel |
JPH0693134A (en) | 1992-07-31 | 1994-04-05 | Sumitomo Chem Co Ltd | Rubber composition excellent in grip and rolling resistance and its production |
US5329005A (en) | 1992-10-02 | 1994-07-12 | Bridgestone Corporation | Soluble anionic polymerization initiators and preparation thereof |
DE4234601A1 (en) | 1992-10-14 | 1994-04-21 | Basf Ag | Process for the preparation of block copolymers by ionic polymerization |
US5290875A (en) | 1992-11-30 | 1994-03-01 | Phillips Petroleum Company | Conjugated diene/monovinylarene block copolymers with multiple tapered blocks |
DE4241538A1 (en) | 1992-12-10 | 1994-06-16 | Leuna Werke Ag | Non-equimolar alpha-methylstyrene/maleic anhydride copolymer(s) prodn. - by radical-initiated soln. copolymerisation in presence of organo-bromine cpds., esp. tetra-bromo-methane, or excess alpha-methylstyrene |
US5331035A (en) | 1992-12-22 | 1994-07-19 | Bridgestone Corporation | Process for the preparation of in situ dispersion of copolymers |
US5891947A (en) | 1992-12-22 | 1999-04-06 | Bridgestone Corporation | In-situ anionic continuous dispersion polymerization process |
US5614579A (en) | 1992-12-22 | 1997-03-25 | Bridgestone Corporation | Process for the preparation of tapered copolymers via in situ dispersion |
US5487054A (en) * | 1993-01-05 | 1996-01-23 | Apple Computer, Inc. | Method and apparatus for setting a clock in a computer system |
US5405903A (en) | 1993-03-30 | 1995-04-11 | Shell Oil Company | Process for the preparation of a block copolymer blend |
WO1994025516A1 (en) | 1993-04-27 | 1994-11-10 | Asahi Kasei Kogyo Kabushiki Kaisha | Expanded foamed bead of a rubber-modified styrene polymer |
JPH0753630A (en) | 1993-06-30 | 1995-02-28 | Shell Internatl Res Maatschappij Bv | Liquid star polymer with terminal hydroxyl groups |
US5514753A (en) | 1993-06-30 | 1996-05-07 | Bridgestone Corporation | Process for preparing a block copolymer |
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 (en) | 1993-11-26 | 1999-03-08 | 住友ゴム工業株式会社 | Tread rubber composition |
US5399628A (en) | 1993-12-02 | 1995-03-21 | Phillips Petroleum Company | Block copolymers of monovinylarenes and conjugated dienes containing two interior tapered blocks |
JP3393906B2 (en) | 1993-12-14 | 2003-04-07 | 鐘淵化学工業株式会社 | Method for producing polymer containing functional group |
US5527870A (en) | 1994-01-12 | 1996-06-18 | Kanagafuchi Kagaku Kogyo Kabushiki Kaisha | Process for the preparation of isobutylene polymer |
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 |
WO1995025754A1 (en) | 1994-03-18 | 1995-09-28 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Method of isolating isobutylene polymer |
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 (en) | 1995-01-17 | 1996-10-01 | Kanegafuchi Chem Ind Co Ltd | Production of isobutylene polymer, and isobutylene polymer |
DE19507777A1 (en) | 1995-03-06 | 1996-09-12 | Basf Ag | Filterable polystyrene dispersions |
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 |
DE19517452A1 (en) | 1995-05-12 | 1996-11-14 | Henkel Teroson Gmbh | Two-component adhesive / sealant with high initial adhesion |
US5574105A (en) | 1995-05-12 | 1996-11-12 | Advanced Elastomer Systems, L.P. | Thermoplastic elastomers having improved high temperature performance |
EP0833863A4 (en) | 1995-06-23 | 1999-04-14 | Exxon Research Engineering Co | Polymer nanocomposite formation by emulsion synthesis |
US5811501A (en) | 1995-06-29 | 1998-09-22 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Process for producing unsaturated group-terminated isobutylene polymer |
DE19528717A1 (en) | 1995-08-04 | 1997-02-06 | Basf Ag | Polymer particles and process for their manufacture |
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 |
EP0864588B1 (en) | 1995-11-27 | 2002-10-09 | Kaneka Corporation | Processes for producing polymers having functional groups |
DE59609259D1 (en) | 1995-11-29 | 2002-07-04 | Vantico Ag | Core / Shell particles and curable epoxy resin compositions containing them |
JP4072833B2 (en) | 1995-11-30 | 2008-04-09 | 住友精化株式会社 | Method for producing water absorbent resin and water absorbent resin |
US5773521A (en) | 1995-12-19 | 1998-06-30 | Shell Oil Company | Coupling to produce inside-out star polymers with expanded cores |
US6020446A (en) | 1996-02-21 | 2000-02-01 | Kaneka Corporation | Curable composition |
US6011116A (en) | 1996-05-08 | 2000-01-04 | Kaneka Corporation | Thermoplastic resin composition |
JP3545532B2 (en) | 1996-05-08 | 2004-07-21 | 鐘淵化学工業株式会社 | Composite rubber particles and composite rubber-based graft copolymer particles |
JP2001508762A (en) | 1996-06-27 | 2001-07-03 | ジー.ディー.サール アンド カンパニー | Particles consisting of an amphiphilic copolymer having a cross-linked outer shell region and inner core region, 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 (en) | 1997-01-17 | 1998-07-23 | Bayer Ag | Rubber mixtures containing SBR rubber gels |
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 |
US6441090B1 (en) | 1997-08-13 | 2002-08-27 | 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 |
BR9908120A (en) | 1998-02-20 | 2000-10-24 | Vantico Ag | Organophilic phyllosilicates |
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 |
US5905116A (en) | 1998-05-06 | 1999-05-18 | Bridgestone Corporation | Gels derived from extending grafted α-olefin-maleimide centipede polymers and polypropylene |
JP2000129133A (en) | 1998-05-28 | 2000-05-09 | Kanegafuchi Chem Ind Co Ltd | Curable composition |
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 (en) | 1998-12-25 | 2007-09-19 | 特種製紙株式会社 | Fluorescent coloring particles used for anti-counterfeit paper, manufacturing method thereof, and anti-counterfeit paper using fluorescent coloring particles |
US6255372B1 (en) | 1999-01-08 | 2001-07-03 | Bridgestone Corporation | Tire components having improved tear strength |
JP2000239476A (en) | 1999-02-22 | 2000-09-05 | Kanegafuchi Chem Ind Co Ltd | Amorphous polyolefinic resin composition |
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 |
EP1195405A4 (en) | 1999-06-04 | 2009-07-08 | Kaneka Corp | Curable composition and method of use thereof |
ATE367591T1 (en) | 1999-09-29 | 2007-08-15 | Fujifilm Corp | ANTI-GLARE AND ANTI-REFLECTION LAYER, POLARIZER AND IMAGE DISPLAY DEVICE |
US6448353B1 (en) | 2000-02-08 | 2002-09-10 | 3M Innovative Properties Company | Continuous process for the production of controlled architecture materials |
US6379791B1 (en) | 2000-02-08 | 2002-04-30 | 3M Innovative Properties Company | Compatibilized pressure-sensitive adhesives |
JP2001240637A (en) | 2000-02-25 | 2001-09-04 | Nippon Zeon Co Ltd | Block copolymer rubber, resin modifier, resin composition and method for producing the same resin composition |
JP4666737B2 (en) | 2000-03-08 | 2011-04-06 | 株式会社カネカ | Primer composition and adhesion method |
DE60142379D1 (en) | 2000-04-27 | 2010-07-29 | Jsr Corp | Crosslinked rubber particles and rubber compositions |
US6653404B2 (en) | 2000-05-01 | 2003-11-25 | Jsr Corporation | Rubber compositions |
FR2808691B1 (en) | 2000-05-12 | 2005-06-24 | Coletica | CYCLODEXTRINS SUBSTITUTED PREFERENTIALLY ON THEIR PRIMARY SURFACE BY ACID OR AMINE FUNCTIONS |
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 (en) | 2000-11-17 | 2002-06-25 | Goodyear Tire & Rubber | Light rubber composition containing clay |
DE10059236B4 (en) | 2000-11-29 | 2005-12-15 | Continental Aktiengesellschaft | Use of a rubber compound for tire treads |
KR100405308B1 (en) | 2000-12-18 | 2003-11-12 | 주식회사 엘지화학 | Artificial pigment and method for preparing the same |
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 (en) | 2001-02-13 | 2005-03-01 | Eads Construcciones Aeronauticas, S.A. | PROCEDURE FOR THE MANUFACTURE OF COMPOSITE MATERIAL ELEMENTS THROUGH THE COENCOLATE TECHNOLOGY. |
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 (en) | 2001-09-21 | 2003-04-03 | Teijin Ltd | Clay organic composite |
US6689469B2 (en) | 2001-12-31 | 2004-02-10 | Bridgestone Corporation | Crystalline polymer nano-particles |
US6437050B1 (en) | 2001-10-04 | 2002-08-20 | Bridgestone Corporation | Nano-particle preparation and applications |
US6845797B2 (en) | 2001-10-12 | 2005-01-25 | Bridgestone Corporation | Tire compositions comprising epoxidized natural rubber and a functionalized polyolefin |
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 |
US6759464B2 (en) | 2001-12-21 | 2004-07-06 | The Goodyear Tire & Rubber Company | Process for preparing nanocomposite, composition and article thereof |
US6706823B2 (en) | 2001-12-31 | 2004-03-16 | Bridgestone Corporation | Conductive gels |
JP4162519B2 (en) | 2002-03-27 | 2008-10-08 | 横浜ゴム株式会社 | Organized layered clay mineral, organic polymer composition containing the same and tire inner liner |
US20030225190A1 (en) | 2002-04-26 | 2003-12-04 | Janos Borbely | Polymeric product for film formation |
DE10227071A1 (en) | 2002-06-17 | 2003-12-24 | Merck Patent Gmbh | Composite material containing core-shell particles |
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 |
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 (en) | 2003-09-27 | 2005-04-21 | Rhein Chemie Rheinau Gmbh | Microgels in cross-linkable, organic media |
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 |
US7205370B2 (en) | 2004-01-12 | 2007-04-17 | Bridgestone Corporation | Polymeric nano-particles of flower-like structure and applications |
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 |
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 (en) | 2004-08-02 | 2011-12-28 | 株式会社ブリヂストン | Particles for display medium, information display panel using the same, and information display device |
JP2006106596A (en) | 2004-10-08 | 2006-04-20 | Bridgestone Corp | Particle for display medium used for panel for information display |
FR2880354B1 (en) | 2004-12-31 | 2007-03-02 | Michelin Soc Tech | ELASTOMERIC COMPOSITION REINFORCED WITH A FUNCTIONALIZED POLYVINYLAROMATIC LOAD |
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 |
JP2007146149A (en) | 2005-11-02 | 2007-06-14 | Fujifilm Corp | Fluorescent polymer fine particle, method for producing fluorescent polymer fine particle, fluorescence-detecting kit and method for detecting the fluorescence |
DE102005059625A1 (en) | 2005-12-14 | 2007-06-21 | Lanxess Deutschland Gmbh | Microgel-containing vulcanizable composition based on hydrogenated nitrile rubber |
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 |
US8877250B2 (en) | 2005-12-20 | 2014-11-04 | Bridgestone Corporation | Hollow nano-particles and method thereof |
US7560510B2 (en) | 2005-12-20 | 2009-07-14 | Bridgestone Corporation | Nano-sized inorganic metal particles, preparation thereof, and application thereof in improving rubber properties |
JP2007304409A (en) | 2006-05-12 | 2007-11-22 | Bridgestone Corp | Particle for display medium, and panel for information display |
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 |
US7829624B2 (en) | 2007-06-29 | 2010-11-09 | Bridgestone Corporation | One-pot synthesis of nanoparticles and liquid polymer for rubber applications |
-
2006
- 2006-12-20 US US11/642,795 patent/US7649049B2/en not_active Expired - Fee Related
-
2007
- 2007-12-18 CN CN2007800478952A patent/CN101568584B/en not_active Expired - Fee Related
- 2007-12-18 WO PCT/US2007/087869 patent/WO2008079807A1/en active Application Filing
- 2007-12-18 BR BRPI0720393-4A patent/BRPI0720393A2/en not_active IP Right Cessation
- 2007-12-18 JP JP2009543130A patent/JP5383503B2/en not_active Expired - Fee Related
- 2007-12-18 KR KR1020097014949A patent/KR101506986B1/en not_active IP Right Cessation
- 2007-12-18 EP EP07865780.6A patent/EP2099861B1/en not_active Not-in-force
-
2009
- 2009-06-25 ZA ZA200904457A patent/ZA200904457B/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003085040A2 (en) * | 2001-10-04 | 2003-10-16 | Bridgestone Corporation | Nano-particle preparation and applications |
US20040127603A1 (en) * | 2002-12-31 | 2004-07-01 | The Goodyear Tire & Rubber Company | Core-shell polymer particles |
US20070196653A1 (en) * | 2005-12-20 | 2007-08-23 | Hall James E | Vulcanizable nanoparticles having a core with a high glass transition temperature |
Cited By (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7718738B2 (en) | 2001-10-04 | 2010-05-18 | Bridgestone Corporation | Self assembly of molecules to form nano-particles |
US7795344B2 (en) | 2001-10-04 | 2010-09-14 | Bridgestone Corporation | Nano-particle preparation and applications |
US8057899B2 (en) | 2001-10-04 | 2011-11-15 | Bridgestone Corporation | Nano-particle preparation and applications |
US7786236B2 (en) | 2004-01-12 | 2010-08-31 | Bridgestone Corporation | Polymeric nano-particles of flower-like structure and applications |
US8063142B2 (en) | 2004-03-02 | 2011-11-22 | Bridgestone Corporation | Method of making nano-particles of selected size distribution |
US7718737B2 (en) | 2004-03-02 | 2010-05-18 | Bridgestone Corporation | Rubber composition containing functionalized polymer nanoparticles |
US7897690B2 (en) | 2004-03-02 | 2011-03-01 | Bridgestone Corporation | Rubber composition containing functionalized polymer nanoparticles |
US8349964B2 (en) | 2004-06-21 | 2013-01-08 | Bridgestone Corporation | Reversible polymer/metal nano-composites and method for manufacturing same |
US7998554B2 (en) | 2004-07-06 | 2011-08-16 | Bridgestone Corporation | Hydrophobic surfaces with nanoparticles |
US7659342B2 (en) | 2005-02-03 | 2010-02-09 | Bridgestone Corporation | Polymer nano-particle with polar core and method for manufacturing same |
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 |
US8957154B2 (en) | 2005-12-19 | 2015-02-17 | Bridgestone Corporation | Disk-like nanoparticles |
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 |
US10023713B2 (en) | 2005-12-20 | 2018-07-17 | Bridgestone Corporation | Hollow nano-particles and method thereof |
US8877250B2 (en) | 2005-12-20 | 2014-11-04 | Bridgestone Corporation | Hollow nano-particles and method thereof |
US8541503B2 (en) | 2006-07-28 | 2013-09-24 | Bridgestone Corporation | Polymeric core-shell nanoparticles with interphase region |
US8410225B2 (en) | 2006-12-19 | 2013-04-02 | Bridgestone Corporation | Fluorescent nanoparticles |
US7649049B2 (en) | 2006-12-20 | 2010-01-19 | Bridgestone Corporation | Rubber composition containing a polymer nanoparticle |
US7829624B2 (en) | 2007-06-29 | 2010-11-09 | Bridgestone Corporation | One-pot synthesis of nanoparticles and liquid polymer for rubber applications |
JP2015045000A (en) * | 2008-12-31 | 2015-03-12 | 株式会社ブリヂストン | Nanoparticle formation proces of initially forming core, nanoparticles and composition |
US9631056B2 (en) | 2008-12-31 | 2017-04-25 | Bridgestone Corporation | Core-first nanoparticle formation process, nanoparticle, and composition |
US8846819B2 (en) | 2008-12-31 | 2014-09-30 | Bridgestone Corporation | Core-first nanoparticle formation process, nanoparticle, and composition |
US9062144B2 (en) | 2009-04-03 | 2015-06-23 | Bridgestone Corporation | Hairy polymeric nanoparticles with first and second shell block polymer arms |
US9493601B2 (en) | 2009-04-03 | 2016-11-15 | Bridgestone Corporation | Hairy polymeric nanoparticles with first and second shell block polymer arms |
US9115222B2 (en) | 2009-12-29 | 2015-08-25 | Bridgestone Corporation | Well defined, highly crosslinked nanoparticles and method for making same |
US9428604B1 (en) | 2011-12-30 | 2016-08-30 | Bridgestone Corporation | Nanoparticle fillers and methods of mixing into elastomers |
US10407522B1 (en) | 2011-12-30 | 2019-09-10 | Bridgestone Corporation | Nanoparticle fillers and methods of mixing into elastomers |
US11505635B2 (en) | 2011-12-30 | 2022-11-22 | Bridgestone Corporation | Nanoparticle fillers and methods of mixing into elastomers |
Also Published As
Publication number | Publication date |
---|---|
BRPI0720393A2 (en) | 2014-01-14 |
JP2010514854A (en) | 2010-05-06 |
US7649049B2 (en) | 2010-01-19 |
KR20090104033A (en) | 2009-10-05 |
CN101568584A (en) | 2009-10-28 |
CN101568584B (en) | 2012-05-23 |
EP2099861A1 (en) | 2009-09-16 |
EP2099861B1 (en) | 2018-01-17 |
KR101506986B1 (en) | 2015-04-01 |
US20080149238A1 (en) | 2008-06-26 |
JP5383503B2 (en) | 2014-01-08 |
ZA200904457B (en) | 2010-03-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2099861B1 (en) | Rubber composition containing a polymer nanoparticle | |
US9061900B2 (en) | Combined use of liquid polymer and polymeric nanoparticles for rubber applications | |
US8697775B2 (en) | Vulcanizable nanoparticles having a core with a high glass transition temperature | |
US7884160B2 (en) | Non-spherical nanoparticles made from living triblock polymer chains | |
US7238751B2 (en) | Multi-layer nano-particle preparation and applications | |
US9493601B2 (en) | Hairy polymeric nanoparticles with first and second shell block polymer arms | |
US6875818B2 (en) | Polymer nano-strings | |
US7786236B2 (en) | Polymeric nano-particles of flower-like structure and applications | |
EP1884376B1 (en) | Pneumatic tire | |
US20090054554A1 (en) | Disk-like Nanoparticles | |
WO1997019990A1 (en) | Rubber composition | |
CN112055729A (en) | Rubber composition and pneumatic tire | |
CN109563195B (en) | Process for producing branched modified rubber, rubber composition comprising branched modified rubber prepared by the process, and use thereof | |
JPH1129659A (en) | Rubber composition | |
US11155706B2 (en) | Polymer composition and tire | |
JP2001335663A (en) | Oil extended rubber, rubber composition and pnewmatic tire using it | |
BRPI0720393B1 (en) | RUBBER COMPOSITION CONTAINING A POLYMER NANOParticle |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200780047895.2 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 07865780 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2009543130 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2007865780 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020097014949 Country of ref document: KR |
|
ENP | Entry into the national phase |
Ref document number: PI0720393 Country of ref document: BR Kind code of ref document: A2 Effective date: 20090619 |