WO1998027143A1 - New targetable solids for polymer blends and methods of manufacturing the solids and blends containing the same - Google Patents
New targetable solids for polymer blends and methods of manufacturing the solids and blends containing the same Download PDFInfo
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- WO1998027143A1 WO1998027143A1 PCT/US1997/022504 US9722504W WO9827143A1 WO 1998027143 A1 WO1998027143 A1 WO 1998027143A1 US 9722504 W US9722504 W US 9722504W WO 9827143 A1 WO9827143 A1 WO 9827143A1
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- polymer
- solid
- blend
- filler
- polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
Definitions
- This invention relates to new, modified solids, e.g. fillers and curatives, for polymers, elastomers, polyolefins, rubbers, and blends thereof and methods of preparing the modified solids and blends containing the same.
- the invention relates to targetable solids for addition to polymer blends, i.e., solids which may be custom designed to locate themselves in specific polymer components of the blend.
- solids have been utilized and/or incorporated into general purpose rubber (GPR), polymers, elastomers, polyolefins, and/or mixtures of the above.
- GPR general purpose rubber
- numerous solid fillers have been proposed for rubber and polymer blends in order to enhance the properties of tires, for example, to decrease the rolling resistance of tires by modifying the rubber compositions used for the treads of tires.
- Reinforcing white fillers such as silica, bentonite, clay, titanium oxide, talc, etc., have been proposed for use in tire treads which tend to decrease the resistance to travel of the tires having a tread comprising such fillers.
- Various fillers and processes for blending the same into rubber compositions have been proposed. For example, Rauline, in U.S.
- Patent No. 5,227,425 describes the use of a copolymer of a conjugated diene with an aromatic vinyl compound prepared in solution with a special silica, known per se, to obtain dispersion of the silica in the elastomeric matrix.
- a preferred embodiment comprises a rubber component comprising 20 to 60 weight percent styrene/butadiene rubber, 20 to 60 weight percent butadiene rubber, and 10 to 30 weight percent of a halogenated rubber, a silica filler, and an organosilane cross-linking agent. It is disclosed that in a preferred embodiment, the rubber compositions comprise 10 to 30 parts per 100 parts rubber of untreated, precipitated silica employed with an effective amount of organosilane coupling agent, for example, 1 to 8 parts per hundred rubber.
- the filler reinforces all phases, i.e., the polymeric phase of a blend, and curing can be controlled for each polymer phase component of the blend.
- the filler migrates from one polymer phase component to the other polymer phase component during processing. Consequently, these effects greatly limit the enhancement of properties that can be achieved with fillers, and the curing and cure state of articles made therefrom.
- polymer blends e.g., those used to produce tires
- crosslinked e.g., those used to produce tires
- the physical properties, performance characteristics, and durability of vulcanized rubber compounds are directly related to the number (crosslink density) and type of crosslinks formed during the vulcanization reaction. (See, e.g., The
- polymer blends may be crosslinked by adding curative molecules, for example sulfur, zinc, metals, radical initiators, etc. followed by heating. This method may be accelerated and is often used for the vulcanization of elastomer blends.
- curative molecules for example sulfur, zinc, metals, radical initiators, etc.
- the mechanism for accelerated vulcanization of natural rubber involves complex interactions between the curative, accelerator, activators and polymers. Ideally, all of the available curative is consumed in the formation of effective crosslinks which join together two polymer chains and enhance the overall strength of the polymer matrix.
- curatives include, but are not limited to, the following: zinc oxide, stearic acid, tetramethylthiuram disulfide (TMTD), 4,4'-dithiodimorpholine (DTDM), tetrabutylthiuram disulfide (TBTD), benzothiazyl disulfide (MBTS), hexamethylene- 1,6-bisthiosulfate disodium salt dihydrate (ERP 390),
- the invention is directed toward a method for the preparation of a targetable solid, i.e., a filler for addition to a rubber composition or a blend of at least two polymeric components.
- the method comprises contacting or treating the filler with the polymer component of the blend having the least affinity for said filler as compared to the other polymer blend components, and thereafter contacting said first polymer treated filler with a second polymer component having a greater affinity for the filler.
- the filler contacted with the polymer components is further subjected to thermal curing under nitrogen atmosphere.
- the invention is also directed to methods wherein the filler is contacted with a polymer or polymers which is/are not the same as either of the polymers of the blend but are compatible, i.e., generally miscible, with one or both of the polymers of the blend.
- the invention is also directed to a filler produced according to the above-described methods.
- the invention is directed toward a method for the preparation of a filled blend comprising polymer treated filler and polymer(s) blend components to produce a blend.
- the polymer blend comprises two or more polymer components with the treated filler dispersed throughout.
- the method comprises contacting or treating the filler with a minor amount of a polymer, which may, e.g., be the first component of the polymer blend.
- the first polymer has the least aflSnity for the filler as compared to other polymer for treatment of the filler.
- the filler, including said first polymer is subsequently contacted with a minor amount of a second polymer having a greater affinity for said filler than said first polymer . Thereafter, the coated filler is mixed with the polymer(s) for forming the blend.
- the invention is also directed to a filled blend produced according to the above-described methods.
- the invention is directed to a filler, e.g., a particle, for addition to a polymer comprising a first polymer and/or a blend of a first polymer with a second polymer.
- the filler has a coating thereon comprised of at least one polymer compatible with at least one of the blend polymer(s) or, e.g., at least one of the first or second polymer blend components.
- the invention is directed to a filled blend comprising a polymer blend comprising at least two polymers and a filler, said filler having at least one polymer compatible with at least one of the polymer blend components coated thereon.
- the invention is directed to methods for crosslinking polymer blends comprising at least two polymers.
- the method generally comprises pretreating the solid with a curative, mixing the pretreated solid with the two polymers of the blend to form a curable polymer mixture, and subjecting the blend to curing conditions, such as sufficiently heating the mixture to obtain crosslinking and/or curing.
- the method of forming a solid comprising curative may, according to an embodiment, be accomplished by precipitation of a polymer from a solution comprising curative molecules, wherein the curative is the sole solid.
- the method of forming a solid comprising curative comprises adsorption of curative molecules onto an inert solid, isolation of the solid, and adsorption of a polymer onto the curative treated solid.
- the method of forming a solid comprising curative may comprise adsorption of a polymer coating onto curative particles.
- the method of forming a solid comprising curative may comprise mixing curative with a solid to form a mixture, and adsorbing a polymer onto the mixture.
- the present invention is also directed to polymer blends produced according to the above-described methods.
- the present invention is further directed to curative precursors used in crosslinking polymer blends, said precursors produced from: (1) the precipitation of a polymer from a solution comprising dissolved or suspended curative molecules; (2) adsorbing curative molecules onto a solid, and adsorbing a polymer onto the solid; (3) adsorbing a polymer onto curative particles; or (4) mixing or grinding curative molecules together with an inert solid to form a mixture, and adsorbing a polymer onto the mixture.
- the invention is also directed to methods for making curative molecules.
- the present invention provides a composition based on a mixture or blend of rubbers, elastomers, polyolefins, polymers, etc. comprising a polymer blend or mixture and a solid.
- the solid may, for example, be a filler, such as silica, wherein the filler has coated thereon or has adsorbed on its surface one or more of the components of the polymer phase.
- the solid may be pretreated with a curative .
- Rubbers, polymers (thermoplastic, thermoset and mixtures thereof), elastomers, and polyolefins and products produced therefrom useful in the practice of the invention include, but are not limited to, brominated butyl rubber (commonly called bromobutyl and as used herein, the term “butyl rubber” means a copolymer of isobutylene and a diene such as isoprene); chlorinated butyl rubber (commonly called chlorobutyl where isoprene is the diene copolymerized with isobutylene); star-branched polyisobutylene comprising branched or star-shaped polyisobutylene subunits, such as star-branched bromobutyl; isobutylene-bromomethylstyrene copolymers such as isobutylene ⁇ para- bromomethylstyrene, isobutylene/chloromethylstyrene copolymers such as isobut
- Patent No. 5,162,445 which is hereby incorporated by reference; isoprene and halogenated isobutylene copolymers (chlorinated or brominated); polychloroprene (neoprene); and the like, and mixtures thereof
- the invention is also preferably directed to blends comprising halogenated isobutylene rubbers including halogenated terpolymers comprising isobutylene such as halogenated isobutylene/styrene/dienes, for example, isobutylene/styrene isoprene, and halogenated isobutylene/methylstyrene/dienes, for example, isobutylene/methylstyrene/isoprene; isobutylene/halomethylstyrene/diene terpolymers including isobutylene/bromomethylstyrene ⁇ soprene; isobutylene/haloisobutylene/die
- elastomers useful in the invention include: polybutadiene, BR; styrene- butadiene rubber, SBR; nitrile-butadiene rubber, NBR; natural rubber, NR; polyisoprene, IR; and ethylene-alphaolefin elastomers like ethylene-propylene rubber,
- Thermoplastics useful in this invention include polyethylene, polypropylene, polystyrene, polycarbonate, and nylon.
- Fillers which can be utilized in the practice of the present invention include, but are not limited to, silica, pumice, bentonite, clay, titanium oxide, talc, calcium carbonate, high styrene resins, coumarone-indene resin, phenolic resin, lignin, modified melamine resins, and petroleum resins.
- the fillers of the present invention may be any size and typically range, e.g., in the tire industry, from about 0.0001 to about 100 microns.
- silica is meant to refer to any type or particle size silica or another silicic acid derivative, or silicic acid, processed by solution, pyrogenic or the like methods and having a surface area, including untreated, precipitated silica, crystalline silica, colloidal silica, aluminum or calcium silicates, fumed silica, and the like.
- the curatives useful in the practice of the present invention generally include curatives used in the rubber industry, e.g., sulfur compounds, zinc compounds, metal compounds, radical initiators, etc. and include, but are not limited to, zinc oxide, stearic acid, tetramethylthiuram disulfide (TMTD), 4,4'-dithiodimo holine (DTDM), tetrabutylthiuram disulfide (TBTD), benzothiazyl disulfide (MBTS), hexamethylene- 1,6-bisthiosulfate disodium salt dihydrate (ERP 390), 2-(mo ⁇ holinothio) benzothiazole (MBS or MOR), blends comprising 90% MOR and 10% MBTS (MOR 90), N- oxydiethylene thiocarbamyl-N-oxydiethylene sulfonamide (OTOS) zinc 2-ethyl hexanoate (ZEH); and MC sulfur.
- TMTD tetra
- compositions produced in accordance with the present invention may also contain other components and additives customarily used in rubber mixes, such as plasticizers, pigments, anti-oxidants, vulcanization accelerators, napthenic or aromatic extender oils if the presence of an extension oil is desired, and silane coupling agents, etc.
- the polymer blend is comprised of a blend of two components, for example, polybutadiene and a brominated copolymer of isobutene and 4-methylstyrene or polymers compatible with polybutadiene and brominated copolymer of isobutene and 4-methylstyrene.
- the filler utilized in the above-described preferred embodiment is silica having co-adsorbed thereon minor amounts of polybutadiene and brominated copolymer of isobutene and 4-methylstyrene.
- a method for the preparation of filler for addition to a blend of at least two polymer components selected from the group consisting of elastomers, rubbers, polyolefins, polymers and mixtures thereof.
- the filler before blending the filler with the polymer blend component(s), the filler is contacted with a minor amount of the polymer component which has the least affinity for the filler as compared to the other polymer components to form a stable surface saturated layer.
- the thickness of the layer may be varied by varying adsorption conditions. Depending upon the filler and the polymer(s), the adsorption time may range from about one second to several hours.
- solvents may be utilized including, but not limited to, aliphatic and aromatic solvents like pentane, hexane, and toluene.
- the adsorption may be conducted at low temperatures, e.g., -40° C where the amount of polymer to be adsorbed is large, to high temperatures, e.g., up to 200°0 C when the amount of polymer to be adsorbed is small.
- the filler e.g., silica
- the filler is preferably first contacted with a minor amount of the brominated copolymer of isobutene and 4-methylstyrene.
- This copolymer has less affinity for said filler as compared to the polybutadiene.
- the term "minor amount” means in an amount sufficient to provide a stable surface saturated layer on the filler.
- the filler After contacting the filler with the brominated copolymer of isobutene and 4-methylstyrene, preferably forming a layer by the adso ⁇ tion of the same onto the filler surface, the filler is contacted with a minor amount of the second component of the polymer blend and/or the polybutadiene. In this manner, a filler is provided which will not completely migrate from the brominated copolymer of isobutene and 4- methylstyrene during the blending of the two components of the polymer phase.
- the contacted filler is subjected to curing conditions such as to heat or thermal curing under a nitrogen atmosphere at temperatures ranging from about 60° C to about 120° C.
- the exchange was performed from both directions, that is, adsorbing from solution the brominated copolymer of isobutene and 4-methylstyrene (hereinafter "brominated copolymer”) first and then placing the brominated copolymer-loaded silica filler into a solution of polybutadiene and vice versa.
- the polymer-loaded filler sample remained wet with solvent, e.g., one weight percent solution of pentane, during the transfer to a solution, e.g., one weight percent solution, of the second polymer. After exposure to the solution of the second polymer for a time interval, a sample of the polymer-loaded filler was removed and washed in an excess of solvent.
- composition of the resulting solvent was monitored by solid state H MAS-NMR which was used to measure the ratio of one polymer to another. This quantity can be measured precisely without any other standards.
- the total polymer composition was determined by carbon elemental analysis, and polymers in the same molecular weight were used.
- E EXXPRO ® 90-10 (Brominated Copolymer of Isobutene and 4- methylstyrene)
- B Budene 1207 (Polybutadiene)
- Budene 1207 polybutadiene
- HiSil sica
- EXXPRO ® 90-10 brominated copolymer of isobutene and 4-methylstyrene
- Example I is the control in which EXXPRO ® 90-10 (30 phr), Budene 1207 (70 phr) and conventional HiSil 233 (30 phr) are blended by milling together.
- the dispersion of the silica filler can be detected by scanning electron microscopy. The scanning electron microscopy showed that the conventional silica filler was not found to be present in the EXXPRO ® phase of the blend.
- Coated silica used in this example was prepared by stirring for 30 minutes a suspension of 100 g. HiSil 233 in a 0.5 wt% polymer in cyclohexane solution. The coated filler was removed and washed with cyclohexane three times.
- Example II Modified silica filler was prepared by adso ⁇ tion of poly(isoprene) from dilute solution 0.5% polymer in cyclohexane, with vigorous stirring at about 22° C for approximately 1 hour. The coated silica was washed three times in cyclohexane. The weight percent carbon of the product was 6.18%.
- the above-described product was then subjected to heat or thermal curing under a nitrogen atmosphere at temperatures ranging from 60° C to 120° C for 60 minutes.
- the polyisoprene layer was extensively crosslinked because polyisoprene signals of the adsorbed polyisoprene layer were no longer observed in the solid state NMR spectrum.
- Crosslinked coatings formed in this example are stable to exchange by other polymers including polar polymers with a high affinity for the filler like NBR. These coated fillers will be primarily found in the polyisoprene regions when used in blends of polyisoprene and
- the present invention also relates and generally applies, e.g., to various curing or vulcanization systems including, but not limited to, conventional systems (polysulfidic crosslinks produced by sulfur system); conventional systems with post vulcanization stabilizers, e.g., dihydrate of the sodium salt of hexamethylene-1, 6- bisthiosulfate-s-ester; EV systems (low concentration of sulfur and high concentration of an organic accelerator); sulfurless or sulfur donor systems (using, for example, TMTD); Semi-EV (intermediate system between conventional and EV systems); Soluble EV and Soluble Semi-EV systems; and the EV System of Hofmann (combination of sulfur donors, like TMTD and DTDM, in conjunction with sulfenamide (OTOS).
- conventional systems polysulfidic crosslinks produced by sulfur system
- conventional systems with post vulcanization stabilizers e.g., dihydrate of the sodium salt of hexamethylene-1, 6- bisthiosulfate
- the curative precursors of the present invention are generally comprised of a solid containing or comprising curative.
- the curative precursor of the present invention may be formed by, e.g., the following methods: (1) precipitation of a polymer from a solution containing dissolved or suspended curativ ); (2) adso ⁇ tion of curative(s) onto an inert solid, e.g., alumina or silica, followed by isolation of the curative-loaded solid, and adso ⁇ tion of a polymer coating to the surface of the loaded solid; (3) adso ⁇ tion of a polymer coating to the surface of curative particles; or (4) mixing and/or grinding together curativ ⁇ ) with an inert solid, followed by adso ⁇ tion of a polymer coating to the surface of the resulting solid curative mixture.
- the polymers useful in the preparation of the curative precursors of the present invention may be comprised of the same polymers of the blend and/or polymers compatible with one or more polymers of the blend.
- compatible as used herein means generally considered
- a method for the preparation of curative precursors for addition to a blend of at least two polymers selected from the group consisting of, for example, but not limited to elastomers, rubbers, polyolefins, polymers and mixtures thereof.
- a curative loaded solid or solid curative is, according to one embodiment, contacted with one of the polymers of the blend and/or a polymer compatible with one or both of the polymers of the blend and the polymer is adsorbed onto the surface of the curative loaded solid or solid curative.
- the solid curative precursor is contacted with a minor amount of the polymer of the blend which has the "least affinity" for the curative solid as compared to the other polymer(s) of the blend to form a stable surface saturated layer, e.g., which preferably is not removed by any subsequent solvent extractions.
- the thickness of the layer may be varied by varying adso ⁇ tion conditions.
- the adso ⁇ tion time may range from about one second to several hours. It should be noted that depending upon the polymer, different solvents may be utilized including, but not limited to, aliphatic and aromatic solvents like pentane, hexane, and toluene.
- the adso ⁇ tion may be conducted at low temperatures, e.g., -40° C where the amount of polymer to be adsorbed is large, to high temperatures, e.g., up to 200° C when the amount of polymer to be adsorbed is small.
- the curative loaded silica solid is preferably first contacted with a minor amount of the brominated copolymer of isobutene and 4- methylstyrene. This copolymer has the "least affinity" for said loaded solid as compared to the polybutadiene.
- the term "minor amount” means in an amount sufficient to provide a stable surface saturated layer on the filler.
- the curative precursor is subjected to heat or thermal curing under a nitrogen atmosphere at temperatures ranging from about 60° C to about 120° C.
- heat or thermal curing under a nitrogen atmosphere at temperatures ranging from about 60° C to about 120° C.
- the following test is performed which may be modified, if needed, for other polymer systems.
- the exchange of elastomers on a solid precursor may be measured using a practical and rapid method comprising solid state H MAS-NMR. This method allows the possibility to monitor and rank polymer interactions with solids by measuring the exchange.
- the curative- loaded, first polymer-coated solid of the precursor is kept wet with solvent, e.g., one weight percent solution of pentane, during transfer to a solution, e.g., one weight percent solution, of the second polymer.
- solvent e.g., one weight percent solution of pentane
- a sample of the polymer-coated precursor should be removed and washed in an excess of solvent.
- the composition of the resulting solvent may be monitored by solid state H MAS-NMR which can measure the ratio of one polymer to another. This quantity can be measured precisely without any other standards.
- the total polymer composition may be determined by carbon elemental analysis.
- thermomechanical work can include only a single step of suitable duration, temperature and intensity, or it can include several steps which can, if desired, be separated by at least a cooling step.
- the final heating step of the method of the present invention is generally carried out using typical procedures known to one of ordinary skill in the art for crosslinking and curing polymer blends.
- the blend is heated sufficiently to obtain crosslinking, i.e., cure of the blend.
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Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL97333930A PL333930A1 (en) | 1996-12-17 | 1997-11-24 | Novel orientable solid ingredients of polymeric mixes and method of obtaining such solid ingredients and mixes containing them |
BR9713077-0A BR9713077A (en) | 1996-12-17 | 1997-11-24 | Target solids for polymer mixtures and methods of manufacturing the solids and mixtures that contain them. |
JP52778798A JP2001506306A (en) | 1996-12-17 | 1997-11-24 | New potential solids for polymer blends, and methods of making the solids and blends containing the solids |
EP97948623A EP0946627A1 (en) | 1996-12-17 | 1997-11-24 | New targetable solids for polymer blends and methods of manufacturing the solids and blends containing the same |
EA199900514A EA199900514A1 (en) | 1996-12-17 | 1997-11-24 | NEW SPECIAL HARD SUBSTANCES FOR POLYMERIC MIXTURES, METHODS OF PREPARATION OF THESE SOLID SUBSTANCES AND CONTAINING THEIR MIXTURES |
CA002271128A CA2271128A1 (en) | 1996-12-17 | 1997-11-24 | New targetable solids for polymer blends and methods of manufacturing the solids and blends containing the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US3302696P | 1996-12-17 | 1996-12-17 | |
US60/033,026 | 1996-12-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998027143A1 true WO1998027143A1 (en) | 1998-06-25 |
Family
ID=21868160
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1997/022504 WO1998027143A1 (en) | 1996-12-17 | 1997-11-24 | New targetable solids for polymer blends and methods of manufacturing the solids and blends containing the same |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP0946627A1 (en) |
JP (1) | JP2001506306A (en) |
KR (1) | KR20000057591A (en) |
BR (1) | BR9713077A (en) |
CA (1) | CA2271128A1 (en) |
EA (1) | EA199900514A1 (en) |
HU (1) | HUP9904187A3 (en) |
PL (1) | PL333930A1 (en) |
TW (1) | TW400352B (en) |
WO (1) | WO1998027143A1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20000063679A (en) * | 2000-07-28 | 2000-11-06 | 최재영 | The elastic fillers and compositions |
US6214924B1 (en) | 1997-02-28 | 2001-04-10 | The Dow Chemical Company | Filled polyethylene compositions |
US6472042B1 (en) | 1994-02-10 | 2002-10-29 | Dow Global Technologies Inc. | Highly filled thermoplastic compositions |
US7485677B2 (en) | 2001-06-08 | 2009-02-03 | Exxonmobil Chemical Patents Inc. | Low permeability nanocomposites |
US9051683B2 (en) | 1997-02-28 | 2015-06-09 | Columbia Insurance Company | Carpet, carpet backings and methods |
US9376769B2 (en) | 1997-02-28 | 2016-06-28 | Columbia Insurance Company | Homogeneously branched ethylene polymer carpet backsizing compositions |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5018664B2 (en) * | 2008-06-17 | 2012-09-05 | 横浜ゴム株式会社 | Method for producing elastomer composition and pneumatic tire using the same |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1090972A (en) * | 1964-02-12 | 1967-11-15 | Dunlop Rubber Co | Improvements in or relating to polymeric compositions |
DE1806118A1 (en) * | 1968-10-30 | 1970-05-21 | Amicon Corp | Polymeric substance reinforced by fillers |
US4480057A (en) * | 1981-12-15 | 1984-10-30 | Mitsubishi Petrochemical Co., Ltd. | Impact-resistant poly(phenylene oxide) compositions comprising encapsulated filler material |
US5135971A (en) * | 1989-02-18 | 1992-08-04 | Basf Aktiengesellschaft | Flameproofed thermoplastic molding compositions based on phlegmatized red phosphorus |
-
1997
- 1997-11-24 WO PCT/US1997/022504 patent/WO1998027143A1/en not_active Application Discontinuation
- 1997-11-24 CA CA002271128A patent/CA2271128A1/en not_active Abandoned
- 1997-11-24 EP EP97948623A patent/EP0946627A1/en not_active Withdrawn
- 1997-11-24 JP JP52778798A patent/JP2001506306A/en active Pending
- 1997-11-24 EA EA199900514A patent/EA199900514A1/en unknown
- 1997-11-24 PL PL97333930A patent/PL333930A1/en unknown
- 1997-11-24 HU HU9904187A patent/HUP9904187A3/en unknown
- 1997-11-24 KR KR1019990705365A patent/KR20000057591A/en not_active Application Discontinuation
- 1997-11-24 BR BR9713077-0A patent/BR9713077A/en not_active Application Discontinuation
- 1997-12-10 TW TW086118617A patent/TW400352B/en active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1090972A (en) * | 1964-02-12 | 1967-11-15 | Dunlop Rubber Co | Improvements in or relating to polymeric compositions |
DE1806118A1 (en) * | 1968-10-30 | 1970-05-21 | Amicon Corp | Polymeric substance reinforced by fillers |
US4480057A (en) * | 1981-12-15 | 1984-10-30 | Mitsubishi Petrochemical Co., Ltd. | Impact-resistant poly(phenylene oxide) compositions comprising encapsulated filler material |
US5135971A (en) * | 1989-02-18 | 1992-08-04 | Basf Aktiengesellschaft | Flameproofed thermoplastic molding compositions based on phlegmatized red phosphorus |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6472042B1 (en) | 1994-02-10 | 2002-10-29 | Dow Global Technologies Inc. | Highly filled thermoplastic compositions |
US6214924B1 (en) | 1997-02-28 | 2001-04-10 | The Dow Chemical Company | Filled polyethylene compositions |
US9051683B2 (en) | 1997-02-28 | 2015-06-09 | Columbia Insurance Company | Carpet, carpet backings and methods |
US9376769B2 (en) | 1997-02-28 | 2016-06-28 | Columbia Insurance Company | Homogeneously branched ethylene polymer carpet backsizing compositions |
KR20000063679A (en) * | 2000-07-28 | 2000-11-06 | 최재영 | The elastic fillers and compositions |
US7485677B2 (en) | 2001-06-08 | 2009-02-03 | Exxonmobil Chemical Patents Inc. | Low permeability nanocomposites |
Also Published As
Publication number | Publication date |
---|---|
CA2271128A1 (en) | 1998-06-25 |
BR9713077A (en) | 2000-04-11 |
HUP9904187A3 (en) | 2000-05-29 |
TW400352B (en) | 2000-08-01 |
EA199900514A1 (en) | 2000-02-28 |
EP0946627A1 (en) | 1999-10-06 |
HUP9904187A2 (en) | 2000-04-28 |
KR20000057591A (en) | 2000-09-25 |
PL333930A1 (en) | 2000-01-31 |
JP2001506306A (en) | 2001-05-15 |
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