WO2002024790A2 - Dispersions and latexes of polar group modified polymers - Google Patents
Dispersions and latexes of polar group modified polymers Download PDFInfo
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- WO2002024790A2 WO2002024790A2 PCT/US2001/026223 US0126223W WO0224790A2 WO 2002024790 A2 WO2002024790 A2 WO 2002024790A2 US 0126223 W US0126223 W US 0126223W WO 0224790 A2 WO0224790 A2 WO 0224790A2
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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
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/126—Polyphenylene oxides modified by chemical after-treatment
-
- 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
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
-
- 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
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
Definitions
- This invention relates to dispersions and artificial latexes derived from polar group modified polymers. More particularly, the present invention relates to stable dispersions or latexes of such a polymer in a non-oleophilic continuous phase, especially an aqueous, continuous phase. The resulting dispersions and latexes are usefully employed as coatings and paints. In a particularly preferred embodiment, a thin coating of the polar group modified polymer may be applied to a solid material in order to improve its compatibility with additional components of a resin blend containing such material. For example, U.S. Patent No.
- 5,391,603 discloses reinforced blends of syndiotactic vinylaromatic polymers containing fibrous reinforcing agents that bear a surface coating of a maleic anhydride- or fumaric acid- grafted polyphenylene ether.
- the coating could be suitably applied from either a solution or an emulsion.
- Stable dispersions contain an internal or dispersed phase in the form of finely divided liquid or solid regions and an external or continuous phase.
- the two phases are incompatible. Ifboth phases are liquids, the dispersion is known as an emulsion.
- a solid internal phase dispersed in a liquid continuous phase is referred to as a latex. So long as the continuous phase remains in the form of a thin liquid film that separates adjacent internal phase domains, the internal phase will not normally agglomerate or coalesce. Often, the dispersion can only be formed and stabilized against agglomeration or coalescence by use of a surfactant that promotes compatibility between the continuous phase and the surface of the internal phase domains.
- the dispersed phase is represented by an arrangement of spheres of equal radii, the theoretical maximum volume attributable thereto is 0.74, which is the volume fraction of the most compact arrangement of spheres of equal radii. Generally, however, the dispersed phase forms non- spheroidal shapes or contains a range of particle sizes. The internal phase volume fraction for such dispersions may exceed 0.74. Very high internal phase volume fraction dispersions may have dispersed phase volume fractions as high as 0.99. These dispersions are known as high internal phase ratio (fflPR) dispersions. Techniques for forming HIPR dispersions have been disclosed in U.S. Patent No.'s 5,539,021, 5,688,842, 4,018,426 and elsewhere.
- Dispersions of solid polymers in an aqueous liquid external phase are well known in the art. They occur naturally or may be prepared from synthetic polymers using one of several techniques. In one method, a polymer is dissolved in an organic liquid solvent, a water-in-oil or oil- in-water emulsion is formed therefrom, and thereafter the organic solvent is removed. Continuous methods for forming latexes from a HIPR emulsion are disclosed in the foregoing U.S. Patent No.'s
- a dispersion having a dispersed phase with a mean, volume average particle size of 2 ⁇ m or less was produced.
- the dispersion exhibited some separation upon sitting for one week at room temperature, thereby indicating inadequate stability of the dispersion.
- dispersions having small internal phase domain size especially dispersions having an internal phase particle size of less than 2.0 ⁇ m, from polar group modified polymers has proven to be difficult.
- Dispersions, especially latexes, having smaller mean, volume average particle size internal phases generally show improved stability.
- aqueous dispersions especially latexes, of polar group modified polymers having a mean, volume average particle size dispersed phase of less than 2.0 ⁇ m, preferably 1.25 ⁇ m or less, more preferably 1.1 ⁇ m or less, highly preferably 1.0 ⁇ m or less, and most preferably 0.8 ⁇ m or less, or even 0.5 ⁇ m or less.
- a dispersion of a polar group modified polyphenylene ether or a polar group modified block copolymer of a vinyl aromatic monomer and a conjugated diene said dispersion having a mean, volume average particle size dispersed phase of less than 2.0 ⁇ m, preferably 1.25 ⁇ m or less, more preferably 1.1 ⁇ m or less, highly preferably 1.0 ⁇ m or less, most preferably, 0.8 ⁇ m or less, and most highly preferably, 0.5 ⁇ m or less.
- a latex of a polar group modified polyphenylene or a polar group modified block copolymer of a vinyl aromatic monomer and a conjugated diene said latex having a mean, volume average particle size dispersed phase of less than 2.0 ⁇ m, preferably 1.25 ⁇ m or less, more preferably 1.1 ⁇ m or less, highly preferably 1.0 ⁇ m or less, most preferably, 0.8 ⁇ m or less, and most highly preferably, 0.5 ⁇ m or less.
- a high internal phase volume dispersion of a polar group modified polyphenylene ether or a polar group modified block copolymer of a vinyl aromatic monomer and a conjugated diene said dispersion having a mean, volume average particle size dispersed phase of less than 2.0 ⁇ m, preferably 1.25 ⁇ m or less, more preferably 1.1 ⁇ m or less, highly preferably 1.0 ⁇ m or less, most preferably, 0.8 ⁇ m or less, and most highly preferably, 0.5 ⁇ m or less.
- a high internal phase volume latex of a polar group modified polyphenylene ether or a polar group modified block copolymer of a vinyl aromatic monomer and a conjugated diene said latex having a mean, volume average particle size dispersed phase of less than 2.0 ⁇ m, preferably 1.25 ⁇ m or less, more preferably 1.1 ⁇ m or less, highly preferably 1.0 ⁇ m or less, most preferably, 0.8 ⁇ m or less, and most highly preferably, 0.5 ⁇ m or less.
- an inorganic filler for use in a thermoplastic composite having a polar functionalized polyphenylene ether or a polar group modified block copolymer of a vinyl aromatic monomer and a conjugated diene coated on the surface thereof is prepared by contacting an inorganic filler, preferably a fibrous reinforcing agent, optionally having one or more sizing or compatibilizing compounds deposited on the surface thereof, with a latex of a polar group modified polyphenylene ether, or a polar group modified block copolymer of a vinyl aromatic monomer and a conjugated diene, and thereafter drying the latex.
- a composition comprising: 1) a thermoplastic resin and
- an inorganic filler characterized in that the filler initially comprises a coating on the surface thereof formed from the above latexes.
- a surfactant is desirably employed to form the dispersion or latex.
- This surfactant is a monovalent salt of an alkaryloxypolyalkyleneoxysulfate.
- Polar group modified polymers for use herein especially include derivatives of polyphenylene ethers or block copolymers of a vinyl aromatic monomer and a conjugated diene that have been modified by one or more chemical processes to include therein at least 0.1 to 10 mole percent of a polar functional group, preferably a carboxylic acid.
- Preferred polar group modified polymers for use herein are the foregoing polymers that have been grafted with an ethylenically unsaturated dicarboxylic acid or an anhydride thereof, especially maleic anhydride or fumaric acid.
- Suitable polyphenylene ethers and processes for their preparation are well known and have been described in many publications, for example U.S. Patent Nos. 3,306,874, 3,306,875, 3,639,656, 3,642,699, 3,219,625, 3,378,505 and 3,661,848.
- the processes most frequently used for the preparation of polyphenylene ethers comprise autocondensation of monohydric phenols in a solvent in the presence of oxygen and a catalyst.
- Preferred catalysts are metal-amine complexes, in particular copper-amine complexes.
- Preferred solvents are aromatic hydrocarbons.
- Preferred polyphenylene ethers comprise a chain of alkyl-substituted benzene rings, preferably linked in the para-position via an oxygen atom. More preferred polyphenylene ethers are formed by oxidative coupling of a 2,6-dialkylphenol, including 2,6-dimethylphenol, 2,6- diethylphenol, 2-methyl-6-ethylphenol, 2-methyl-6-propylphenol, 2,6-dibutylphenol, 2,3,6- trimethylphenol, and mixtures thereof. Most preferred polyphenylene ethers are poly(2,6- dialkylphenols), especially poly(2,6-dimethylphenol).
- Suitable polymers are those having number average molecular weights (Mn) of from 10,000 to 90,000, preferably from 20,000 to 80,000. A suitable technique for measuring such polymer molecular weights is taught in Macromolecular Synthesis. 1 (1978), 83.
- Suitable vinylaromatic/ conjugated diene block copolymers include styrene/conjugated diene/styrene block copolymers comprising at least one polymeric block which comprises predominantly styrene monomer units and at least one polymeric block which comprises predominantly butadiene or isoprene monomer units.
- the block copolymer may be linear, branched, or radial, and the blocks may be prepared by sequential addition of monomers or by coupling.
- Linear block copolymers include those described in U.S. Patent Nos. 3,231,635; 3,265,765 and 3,322,856.
- Coupled and radial block copolymers include polymers of the type described in U.S. Patent Nos. 4,033,888; 4,077,893; 4,141,847; 4,391,949 and 4,444,953.
- Hydrogenated or partially hydrogenated derivatives of the foregoing polymers are included as well.
- the proportion of vinylaromatic polymer blocks in the block copolymer is preferably between about 2 and about 65 percent by weight, and more preferably between about 5 and about 40 percent by weight.
- the vinylaromatic polymer blocks preferably have weight average molecular weights from 1 ,000 to 125,000, preferably from 2,000 to 60,000 and most preferably from 4,000 to 25,000.
- the conjugated diene blocks preferably have weight average molecular weights of 10,000 to about 450,000, preferably 15,000 to 150,000 and most preferably 20,000 to 100,000. The foregoing molecular weights are suitably measured using gel permeation chromatography and/or low angle light scattering techniques.
- Hydrogenated derivatives of any of the foregoing block copolymers include all such polymers having ethylenic unsaturation, aromatic unsaturation or both ethylenic and aromatic unsaturation hydrogenated or partially hydrogenated. Hydrogenation preferably reduces the ethylenic unsaturation of the block copolymer to less than 10 percent of the original ethylenic unsaturation, more preferably to less than 2 percent. Aromatic unsaturation may remain or be reduced from that of the original polymer.
- Essentially fully hydrogenated block copolymers are those block copolymers wherein the aromatic unsaturation is reduced to less than 10 percent of the original aromatic unsaturation, more preferably reduced to less than 5 percent.
- the aromatic unsaturation is preferably reduced by less than 10 percent of the original aromatic unsaturation by the selective hydrogenation thereof, and is more preferably reduced by less than 5 percent.
- Suitable techniques for the hydrogenation of block copolymers are known in the art, having been disclosed in U.S. Patent Nos. 3,494,942; 3,634,594; 3,670,054; 3,700,633, 5,688,842 and Re 27,145, and elsewhere.
- the polymer used in this invention must comprise polar functionality.
- the polar functionality is grafted to the polymer after initial formation of the ungrafted polymer.
- Preferred polar functional groups include carboxylic acids, salts or anhydrides of carboxylic acids, sulfonic acids, salts or anhydrides of sulfonic acids, esters, alcohols, amines, epoxides and ketones. Carboxylic acids and their anhydrides are most preferred.
- Graft functionalization of the polymer with a source of the desired polar functional group involves heating the polymer and source of the polar functional group, optionally in the presence of an initiator, such as an organic peroxide compound.
- Preferred sources of the polar functional group include unsaturated carboxylic acids or carboxylic acid derivatives, which may be monofunctional acids such as acrylic, methacrylic, cinnamic, crotonic, isocrotonic, mesaconic, or alpha - methylmesaconic acid and the like, or polyfunctional acids, such as maleic, fumaric, itaconic, citraconic acids and the like.
- the corresponding anhydride derivative of a difunctional carboxylic acid especially maleic anhydride is employed.
- the reaction may be performed in a molten state, such as in an extruder, or in a solution.
- Suitable graft functionalization techniques for use with respect to the foregoing polymers are taught in U.S. Patent Nos. 3,375,228, 4,292,414, 4,308,353, 4,578,429, 4,771,096, 4,654,405, and 5,346,963.
- Polar group functionalized polymers useful in this invention preferably contain from 0.1 to
- Suitable alkaryloxypolyalkyleneoxysulfate surfactants for use herein correspond to the formula:
- R 1 is a linear or branched, C 5-2 alkyl group
- Ar is a C 6- ⁇ 2 aryl group, or a mono- or poly- C ⁇ alkyl substituted aryl group;
- R 2 independently each occurrence is a C 2-4 alkylene group, n is a number from 1 to 5 indicating the average number of OR 2 groups;
- X* is monovalent cation, preferably Na + , K + or NH + .
- a preferred alkaryloxypolyalkyleneoxysulfate surfactant is ammonium nonylphenoxytetra(ethoxy)sulfate NH ), where n is four.
- This surfactant is sold commercially under the tradename Rhodapex ® CO-436 by Rhodia Inc.
- Rhodapex ® CO-436 sold commercially under the tradename Rhodapex ® CO-436 by Rhodia Inc.
- the viscosity of the resulting dispersion or latex may be adjusted by addition of a thickener or by dilution with additional quantities of water if desired.
- the particular thickener utilized is not critical and a wide variety may be utilized.
- Thickeners may be simple viscosity modifiers or may also function as thixotropic agents.
- Thixotropic agents are incorporated in suspension or emulsion compositions to raise low-shear viscosities while retaining a low, high-shear viscosity. Thixotropic agents permit stirring, mixing, and application of the dispersion to substrates but reduce running and dripping of the dispersion after application to substrates.
- the amount of thickening agent required depends somewhat on the effectiveness of the particular thickening agent utilized, but generally about 0.1 to 30 weight percent based on total formulation weight may be employed.
- Acceptable classes of thickening agents include soap gels, lipophilic fatty acid esters, polysaccharide gums, water soluble cellulose derivatives, clays and alumina gels. Useful thickeners which also function as thixotropic agents include organo clays.
- Organo clays are clays treated with quaternary ammonium compounds. Specific examples include dimethyl di(hydrogenated tallow) ammonium chlorides, dimethyl(hydrogenated tallow) benzylammonium chloride and methyl di(hydrogenated tallow) benzylammonium chloride.
- Commercial organo clay products which are usefully employed herein include Cyanamer TM P-250, available from American Cyanamid Co., and Acrysol TM ASE and Acrysol TM RM-5, available from Rohm and Haas Company.
- the dispersion or latex may contain other known additives, such as fillers, pigments, antioxidants and crosslinking agents.
- additives such as fillers, pigments, antioxidants and crosslinking agents.
- thickeners, thixotropic agents and other components may be either in the aqueous phase, the dispersed phase, in a phase separate from both the dispersed phase or the water phase, or in a combination of the foregoing.
- the aqueous phase is preferably present in an amount between about 50 and about 900 parts by weight based on 100 parts by weight of polymer. More preferably, the amount of water is between about 100 and about 300 parts by weight based on 100 parts by weight of functionalized polymer. With less water, the dispersion or latex has a relatively high viscosity. Larger amounts of water are generally not preferred due to the increased volume of material to be processed.
- the polar group functionalized polymer is dissolved or prepared in a suitable solvent that is not miscible with the aqueous phase, such as an oleophilic liquid solvent.
- a suitable solvent such as an oleophilic liquid solvent. Examples include toluene, alkanes and chlorinated aliphatic hydrocarbons.
- the dispersion may be prepared directly without first isolating the polymer, if desired. This solution is combined with the remaining components of the dispersion and processed under high shear conditions at a temperature from about 10 to 250°C for a time sufficient to form the dispersion. In this embodiment of the invention, it may be desirable to first remove interfering components from the reaction mixture.
- unreacted functionalizing agents such as maleic anhydride or fumaric acid or initiator residue
- the resulting dispersion is treated in order to remove the solvent, thereby leaving the polymer in a dispersed solid form in the aqueous continuous phase.
- a preferred method of removing the solvent is heating, optionally under reduced pressure.
- the latex may be formed directly from the polymer if it is first cryogenically ground to a fine particle size, such as 60 mesh (250 ⁇ m volume average particle size or less), and added to the aqueous medium under conditions of high shear, preferably at a temperature above the glass transition temperature of the polymer.
- a fine particle size such as 60 mesh (250 ⁇ m volume average particle size or less)
- a number of high shear mixing devices and techniques may be utilized to form the dispersion.
- suitable dispersers include, but are not restricted to, a rotating shaft within a sleeve-type disperser, as described by Warner et al. in U.S. Patent No. 4,123,403; a high-shear stator rotor; an extruder, a submerged jet, or a centrifugal pump-head.
- One particularly suitable disperser is a Model Ml lOET Microfluidizer, available from Microfluidics Corp., Newton, Mass.
- This device heats a polymer slurry to above 200°C under a high pressure, passes the slurry through two interaction chambers in series, and then rapidly cools the dispersion to near ambient temperature.
- the chambers contain channels that provide a focused interaction zone of intense turbulence causing a release of energy amid both cavitation and shear forces. Velocities in excess of 1500 feet per second (460 m/s) are achieved and a pressure of 16,000 psi (110 Mpa) is utilized.
- the slurry may be repeatedly passed through the disperser until a dispersion of the desired properties is obtained. The dispersion is rapidly cooled in order to prevent reagglomeration of the dispersed phase.
- the dispersion or latex may have a multimodal distribution of particles or a monomodal distribution of particles. Preparation of monomodal, high internal phase volume dispersions and latexes are desirable to enable formation of uniform sized, small particle volume dispersions. Such dispersions are particularly desired in order to prepare uniform coatings of the polar group functionalized polymer on the surface of extremely small particle sized inorganic particles.
- the dispersions and latexes of the present invention can be used for applications normally associated with dispersions or latexes.
- coatings, paints, adhesives, sealants, caulks, carpet backing, and solid film articles such as gloves and condoms may be prepared therefrom, using standard methods well known to the skilled artisan.
- use of a latex according to the present invention, especially a latex of a polar group modified polyphenylene ether, rather than an emulsion or coating thereof beneficially reduces the quantity of volatile components, such as organic solvent, emitted during the coating and drying process.
- the resulting coated fibers retain the beneficial properties obtainable by the use of organic coatings of the same polymer, such as adhesion to thermoplastic resins, and compatibility with sizing agents or compatibilizing agents, while achieving reduced hydrocarbon emissions due to use of a latex rather than an emulsion.
- Ammonium nonylphenoxytetra(ethoxy)sulfate (108g, Rhodapex ® CO-436 available from Rhodia Inc.), was added to the polymer solution and the polymer solution was dispersed in water at room temperature using the continuous process described in United States Patent No. 5,124,073.
- the resulting product was a smooth, oil-in-water type emulsion.
- Toluene was stripped from the product in a rotary evaporator at 80 to 85°C.
- the final solvent-free dispersion (latex) contained 40 weight percent solids and had a mean volume average particle diameter of 1.0-1.1 ⁇ m as measured by use of a LS 130 Particle Size Analyzer, available from Coulter, Inc.
- Example 2 30 grams of fumaric acid modified poly(2,6-dimethylphenol) polymer pellets (prepared as in
- Example 1 were dissolved in 70 grams of toluene.
- the polymer solution and 2.1 grams of ammonium nonylphenoxytetra(ethoxy)sulfate, sold commercially under the tradename Rhodapex ® CO-436 by Rhodia Inc. were added to a 16-oz (470 ml) glass jar.
- the jar was placed in a water bath set at 65°C and the contents were mixed for about 1 minute using a Caframo brand mixer with a 20- inch (50 cm) Cowles blade at a speed of 3000 rpm. Water at 25°C was added slowly in 10 ml aliquots every 30 to 60 seconds while continuously mixing.
- the emulsion began as a water-in-oil emulsion but flipped to an oil in water emulsion when 20 to 25 ml of water had been added. After a total of 100 ml of water was added, the jar was removed from the water bath and allowed to cool to room temperature. The final emulsion was smooth and creamy and remained stable at room temperature for several weeks after formation.
- BlendexTM BHPP820 polyphenylene ether available from General Electric Chemicals
- maleic anhydride at 5 parts per 100 parts polyphenylene ether
- the radical initiator, l,l-bis(t-butylperoxy)- 3,3,5-trimethylcyclohexane was added at 5 parts per 100 parts polyphenylene ether and the solution was agitated at 90°C for 4 hours to form a solution of maleic anhydride grafted polyphenylene ether with about 0.8 percent functionalization.
- the emulsion began as a water-in-oil emulsion but flipped to an oil in water emulsion when about 20 ml of water had been added. After a total of 70 ml of water were added, the jar was removed from the water bath and allowed to cool to about 25°C. Chlorobenzene was stripped in a rotary evaporator at 70°C. The resulting latex had a mean volume particle diameter of 1.25 ⁇ m as measured by a particle size analyzer (model LS 130TM available commercially from Coulter, Inc).
- Example 1 The latex of Example 1 was included in the sizing formulation coated onto chopped fibers of E-glass having average diameter of 10 ⁇ m (PPG 3540, available from PPG Corporation) to provide varying amounts of FAPPO on the surface of the glass.
- the amount of FAPPO was determined by pyrolysis/gas chromatography/mass spectroscopic analysis (pyrolysis/GS/MS).
- SPS syndiotactic polystyrene
- Comparative resins made without FAPPO coated glass, and without FAPPO coated glass but with FAPPO added to the blend were produced as well. Results are contained in Table 1.
- the properties of the composition are essentially comparable to those of the control containing 2 weight percent FAPPO added to the composite during compounding. Therefor, less modifier is required to obtain equivalent performance if the modifier is coated onto the filler material from an emulsion rather than blending the modifier resin into the composite matrix during compounding.
Abstract
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AU2001285195A AU2001285195A1 (en) | 2000-09-22 | 2001-08-22 | Dispersions and latexes of polar group modified polymers |
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US23471300P | 2000-09-22 | 2000-09-22 | |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2007003568A1 (en) * | 2005-06-30 | 2007-01-11 | Basf Aktiengesellschaft | Aqueous formulations containing polyaromatic compounds with acid groups |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5141986A (en) * | 1990-09-28 | 1992-08-25 | Shell Oil Company | Block copolymer dispersions and process to prepare block copolymer dispersions |
US5391603A (en) * | 1992-03-09 | 1995-02-21 | The Dow Chemical Company | Impact modified syndiotactic vinyl aromatic polymers |
US5539021A (en) * | 1995-06-05 | 1996-07-23 | The Dow Chemical Company | Process for preparing high internal phase ratio emulsions and latexes derived thereof |
-
2001
- 2001-08-22 WO PCT/US2001/026223 patent/WO2002024790A2/en active Application Filing
- 2001-08-22 AU AU2001285195A patent/AU2001285195A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5141986A (en) * | 1990-09-28 | 1992-08-25 | Shell Oil Company | Block copolymer dispersions and process to prepare block copolymer dispersions |
US5391603A (en) * | 1992-03-09 | 1995-02-21 | The Dow Chemical Company | Impact modified syndiotactic vinyl aromatic polymers |
US5539021A (en) * | 1995-06-05 | 1996-07-23 | The Dow Chemical Company | Process for preparing high internal phase ratio emulsions and latexes derived thereof |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007003568A1 (en) * | 2005-06-30 | 2007-01-11 | Basf Aktiengesellschaft | Aqueous formulations containing polyaromatic compounds with acid groups |
US7776957B2 (en) | 2005-06-30 | 2010-08-17 | Basf Aktiengesellschaft | Aqueous formulations containing polyaromatic compounds with acid groups |
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AU2001285195A1 (en) | 2002-04-02 |
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