WO1999009070A1 - High internal phase emulsions and porous materials prepared therefrom - Google Patents
High internal phase emulsions and porous materials prepared therefrom Download PDFInfo
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- WO1999009070A1 WO1999009070A1 PCT/US1998/016596 US9816596W WO9909070A1 WO 1999009070 A1 WO1999009070 A1 WO 1999009070A1 US 9816596 W US9816596 W US 9816596W WO 9909070 A1 WO9909070 A1 WO 9909070A1
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
- C08J9/283—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum a discontinuous liquid phase emulsified in a continuous macromolecular phase
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/245—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it being a foam layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/32—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed at least two layers being foamed and next to each other
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/32—Polymerisation in water-in-oil emulsions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2266/00—Composition of foam
- B32B2266/06—Open cell foam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/02—Cellular or porous
- B32B2305/022—Foam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/02—Cellular or porous
- B32B2305/026—Porous
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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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/028—Foaming by preparing of a high internal phase emulsion
Definitions
- Emulsions are dispersions of discontinuous or discrete particles commonly referred to as the "internal" phase in a continuous or “external” phase.
- Emulsions can be either oil-in-water (o/w), having an oil internal phase and an aqueous external phase, or water-in-oil (w/o), having an aqueous internal phase and an oil external phase.
- Emulsions can contain as much as and more than 70 volume percent internal phase. These are often referred to as high internal phase emulsions (HIPEs).
- HIPEs high internal phase emulsions
- the volume fraction of the internal phase in such emulsions can be as high as 90 percent and frequently is as high as 95 percent with some HIPEs being reported as high as 98 percent aqueous phase.
- HIPEs high internal phase emulsions
- U.S. Patent 3,974,1 16 The high static viscosity of HIPEs prevents particles from settling.
- HIPEs have been used as transport fluids for particulates through pipelines. See for example U.S. Patent 3,617,095. Again, the high static viscosity of the emulsion prevents the solid particles from settling, yet the decreased viscosity while under shear allows the emulsion to be pumped efficiently through a pipeline.
- the use of high internal phase emulsions (HIPEs) in forming porous polymeric materials is also well known and is described, for example, in U.S. Patents 5,210,104 5,200,433; 4,536,521 ; 4,788,225; 5,147,345; 5,331 ,015; 5,260,345; 5,268,224 and 5,318,554.
- the external oil phase typically comprises a vinyl polymerizable monomer, such as 2-ethylhexyl acrylate and styrene, and a cross-linking monomer such as divinylbenzene.
- the internal aqueous phase typically comprises water, a radical initiator (if not in the oil phase) and an electrolyte.
- emulsion stabilizing surfactants include, for example, nonionic surfactants, such as sorbitan esters (for example, sorbitan monooleate and sorbitan monolaurate).
- sorbitan esters for example, sorbitan monooleate and sorbitan monolaurate
- stabilizing surfactants include certain polyglycerol aliphatic esters such as those described in U.S.
- Patent No. 5,500,451 Porous polymeric materials prepared from HIPEs have been shown useful in many applications. For instance, U.S. Patents 5,260,345; 5,268,224; 5,331 ,015 teach the use of HIPE foams as absorbent materials for use in diaper-type articles.
- An attractive feature of HIPE foams for such an application is that their high void volume and low density provides a high capacity for liquid.
- a 98 weight percent internal phase HIPE can produce a foam with approximately a 49 gram capacity for water per gram of foam (g/g capacity), assuming a polymer density of 1 g/cc.
- the g/g capacity of a foam can be increased either by increasing the void volume of the foam or by decreasing the density.
- Void volume is typically dictated by the internal phase ratio of the emulsion, the higher the internal phase ratio the higher the final void volume of the foam.
- Another method of increasing void volume in a HIPE foam is by including an inert oil in the external phase. After polymerization, the oil is removed, leaving voids in the polymer walls and struts. Collection and disposal of the inert oil, however, must be considered after the polymerization process. Furthermore, increasing the void volume tends to produce thinner struts in the foam walls thereby resulting in a weaker foam structure.
- HIPE foams are combustible because they are organic.
- this invention is a high internal phase emulsion having an emulsion stabilizing surfactant, an insoluble filler, at least 70 volume percent of an internal phase and less than 30 volume percent of an external phase containing one or more vinyl polymerizable monomers.
- the present invention is a process for preparing the high internal phase emulsion of the first aspect which comprises preparing an external phase, preparing an internal phase, adding an insoluble filler to one or both phases, and then mixing the internal phase with the external phase under conditions sufficient to form an emulsion.
- the present invention is a process for preparing the high internal phase emulsion of the first aspect which comprises preparing an external phase and an internal phase, mixing the aqueous phase with the oil phase under conditions sufficient to form an emulsion and then adding an insoluble filler to the emulsion.
- this invention is an open-cell porous polymeric material prepared by polymerizing the high internal phase emulsion of the first aspect.
- this invention is an open-cell porous polymeric material having insoluble fillers incorporated into its polymeric backbone.
- HIPEs high internal phase emulsions
- insoluble fillers can not only be prepared with insoluble fillers, but can also be polymerized into foams containing insoluble filler in the polymeric backbone.
- HIPEs with selected insoluble fillers have been known, we have been able to prepare HIPEs with a broader spectrum of insoluble fillers including montmorillonite clays which are reported to break HIPEs (see reference above) and to incorporate them into a HIPE with vinyl polymerizable monomers.
- montmorillonite clays which are reported to break HIPEs (see reference above) and to incorporate them into a HIPE with vinyl polymerizable monomers.
- the fact that the HIPE can be polymerized into an open-celled foam and still retain the insoluble filler is surprising.
- HIPEs In order to form open-celled structures, HIPEs must break to a certain extent during polymerization in order to create openings in the cell walls, but not break so much as to result in phase separation. Insoluble particulates, as noted above, have been known to break emulsions. Therefore, polymerizing a HIPE containing an insoluble particulate to an open-celled structure without resulting in phase separation is surprising.
- the HIPEs of the present invention are useful in preparing polymeric foam materials with either increased or decreased densities without increasing or decreasing the internal phase ratio of the HIPE.
- the polymeric foams of the present invention are also useful as thermal insulating materials and sound abatement materials as well as for fluid absorption.
- Figurel is a comparison of sound attenuation spectra for the foams prepared in Example 6 and Comparative Example B.
- the high internal phase emulsion (HIPE) of the present invention has greater than about 70 volume percent, more preferably, greater than about 90 volume percent and, most preferably, greater than about 95 volume percent of an internal phase; less than about 30 volume percent, more preferably, less than about 10 volume percent and, most preferably, less than about 5 volume percent of an external phase; and an insoluble filler.
- the HIPE is a water-in-oil emulsion comprising an aqueous internal phase and an oil external phase. HIPEs of as much as 98 volume percent or more of internal aqueous phase can be made by the present invention.
- the external phase comprises one or more vinyl polymerizable monomer.
- the external phase also contains a cross-linking monomer.
- the internal phase comprises water.
- a water-soluble radical initiator is added to the aqueous phase. If an oil-soluble initiator is employed, it is added to the oil phase.
- the HIPE comprises a surfactant and an insoluble filler.
- Vinyl polymerizable monomers which can be employed in the practice of the present invention are any polymerizable monomers having an ethylenic unsaturation.
- the HIPEs are advantageously prepared from either or both (i) at least one monomer that tends to impart glass-like properties (glassy monomers) to the resulting porous polymeric material and (ii) at least one monomer that tends to impart rubber-like properties (rubbery monomers) to the resulting porous polymeric materials.
- the glassy monomers are, for the purposes of the present invention, defined as monomeric materials which would produce homopolymers having a glass transition temperature above about 40°C.
- Preferred glassy monomers include methacrylate-based monomers, such as, for example, methyl methacrylate, and styrene-based monomers, such as, for example, various monovinylidene aromatics such as styrene, o-methylstyrene, chloromethylstyrene, vinylethylbenzene and vinyl toluene. More preferred glassy monomers include styrene, o-methylstyrene, and chloromethylstyrene. The most preferred glassy monomer is styrene.
- the rubbery monomers are, for the purposes of the present invention, defined as monomeric materials which would produce homopolymers having a glass transition temperature of about 40°C or lower.
- Preferred rubbery monomers include alkyl esters of ethylenically unsaturated acids ("acrylate esters” or “methacrylate” esters), such as 2-ethylhexyl acrylate, butyl acrylate, hexyl acrylate, butyl methacrylate, lauryl methacrylate, isodecyl methacrylate and mixtures thereof; vinyl aliphatic and alicyclic hydrocarbons such as butadiene; isoprene; and combinations of these comonomers.
- acrylate esters alkyl esters of ethylenically unsaturated acids
- More preferred rubbery monomers include butyl acrylate, 2-ethylhexyl acrylate, butadiene, isoprene and combinations of these comonomers.
- the most preferred rubbery monomer is 2-ethylhexyl acrylate.
- the HIPE emulsion includes at least one glassy monomer and at least one rubbery monomer.
- the rubbery monomer provides the foams with flexibility and is used in an amount sufficient to allow compression, bending and twisting during processing, packaging, shipping, storing and use of articles containing such foams.
- the glassy monomer provides the foams with structural integrity and is used in an amount sufficient to minimize the incidence of foam tearing or fragmenting encountered when such foams are subjected to both dynamic and static forces.
- the ratio of the glassy monomer to the rubbery monomer generally ranges from 1 :25 to 1.5:1 , more preferably from 1 :9 to 1.5:1.
- the amount of the vinyl polymerizable monomers most advantageously employed depends on a variety of factors, such as the specific monomers, in general, the vinyl polymerizable monomer is used in an amount of from 50 to 100 weight percent, preferably from 80 to 95 weight percent, and most preferably from 85 to 93 weight percent, based on the total external phase.
- Insoluble fillers which can be employed in the practice of the present invention for preparing the HIPE include both inert and reactive fillers.
- the inert fillers are those which do not become copolymerized with the monomers used in preparation of HIPE foams.
- the reactive fillers are those which become chemically attached to the molecular chains during polymerization.
- Inert fillers for use in this invention include for example, carbon black; graphite; metal hydroxides, such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, zirconium hydroxide, manganese hydroxide and iron hydroxide; metal powders such as iron powder; and hollow ceramic microspheres.
- An example of reactive fillers is cross-linked polymeric materials with acrylate surface functionalities.
- the term "insoluble" means at least a finite amount of the material introduced into the system does not dissolve in either the external oil phase or the internal aqueous phase of the HIPE. Preferably at least 50 percent, more preferably at least 80 percent and most preferably 100 percent of the filler loading does not dissolve in either the external oil phase or the internal aqueous phase.
- Hollow fillers such as ceramic or glass microspheres can be used in the practice of the present invention.
- Hollow fillers can be prepared having a density below 1 g/cc. By incorporating such low density fillers into a HIPE foam, one may decrease the density (while simultaneously increasing the g/g capacity) without increasing the internal phase ratio of the HIPE precursor and without using inert oils in the external oil phase.
- Examples of hollow fillers include the various PQ Hollow Spheres available from The PQ Corporation (Valley Forge, PA) which range in density down to 0.13 g/cc.
- Infrared blocking fillers such as carbon black and graphite powder can be used in the practice of the present invention and can reduce the infrared radiation transmitted through the final HIPE foam, increasing the effective thermal insulating value of the foam.
- Organic and inorganic compounds containing phosphorus, antimony, boron, bismuth and halogens are known as fillers for increasing flame retardancy (see, for example, G.T. Gmitter, et al. Flexible Polyurethane Foams. In Plastic Foams: Part I; Frisch, K.C., Saunders, J.H., Eds.; Marcel Dekker, Inc.: New York, 1972; page 142) and can be used as fillers in the practice of the present invention.
- Other inorganic compounds useful as fire retardants in this invention include alumina trihydrate (also known as ATH, aluminum hydroxide, AI(OH)3) (see, for example, Hawley's Condensed Chemical Dictionary, 12 th
- Ferromagnetic materials such as iron and nickel, can be incorporated to render magnetic properties to the final foam.
- a foam containing ferromagnetic materials can be useful, for example, in thermal and acoustical insulation on metal ceilings.
- a foam for example, can be prepared with the ferromagnetic materials dispersed in a thin layer on one side of a foam. The ferromagnetic materials can either be magnetized before or after introduction into the foam. The foam composition can then be easily attached to a ceiling containing ferromagnetic materials without nails or glue. Alternatively, the ferromagnetic materials in the foam may remain unmagnetized and the foam then would be attracted to magnetized materials.
- Water and/or oil swellable fillers such as cross-linked sodium polyacrylate can also be used in the practice of the present invention as long as a HIPE can be made, preferably as long as the HIPE with the filler can be polymerized into a foam.
- Metal oxide and metal carbonate can also be used as fillers in the practice of the present invention.
- Such materials include calcium oxide, magnesium oxide, zirconium oxide, titanium oxide, manganese oxide, iron oxide, aluminum oxide, calcium carbonate, magnesium carbonate, manganese carbonate, iron carbonate and zirconium carbonate.
- Metal nitride, metal carbide and metal boride materials such as aluminum nitride, silicon nitride, iron nitride, silicon carbide, manganese carbide, iron carbide, iron boride, aluminum boride, manganese boride or other materials used in the preparation of ceramic materials may also be used in the practice of the present invention for preparing the HIPE. Mixtures of one or more such materials may also be employed.
- Naturally occurring members of the clay mineral family or synthetic members of the clay mineral family can also be employed as fillers in the practice of the present invention.
- Such fillers include talc, mica and additional members of the clay mineral family such as montmorillonite, hectorite, kaolinite, dickite, nacrite, halloysite, saponite, nontronite, beidellite, volhonskoite, sauconite, magadiite, medmontite, kenyaite, vermiculite, serpentines, chlorites, palygorskite, kulkeite, aliettite, sepiolite, allophane and imogolite can also be employed. Mixtures of one or more such materials may also be employed.
- the multilayered inorganic material which may be used in the practice of the invention can be any swellable layered inorganic material.
- the layered inorganic material is comprised of layers having two opposing faces which may be relatively flat or slightly curved. Such materials are described in U.S. Patent 4,889,885.
- swellable layered inorganic materials include members of the clay mineral family such as those described previously.
- Other representative examples of such swellable layered inorganic materials include illite minerals such as ledikite; the layered double hydroxides or mixed metal hydroxides such as Mg 6 AI 3 .4(OH)-
- Ni(CN) 2 Ni(CN) 2 ; and oxides such as H 2 Si2 ⁇ 5 , V 5 O 13 , HTiNbO 5 , Cro.5Vo.5S2, W0.2 2.8O7. Cr3 ⁇ s, Mo ⁇ 3(OH)2, VOPO4-2H2O, CaPO4CH 3 -H 2 O, MnHAs ⁇ 4-H 2 O and Ag 6 Mo- ⁇ o ⁇ 33. Mixtures of one or more such materials may also be employed.
- the preferred insoluble fillers are carbon black, graphite, metal powders, metal hydroxides, hollow fillers such as glass or ceramic microspheres, natural or synthetic clays, nanofillers, powders of metals, flame retardant fillers such as those containing phosphorus, antimony, boron, bismuth and/or halogens, copolymerizable fillers such as acrylate functionalized polymeric powders, oil swellable fillers such as lightly cross-linked polymeric powders, and aqueous swellable materials such as cross-linked sodium polyacrylate.
- the more preferred insoluble fillers are carbon black, graphite powder, metal powders, metal hydroxides, hollow ceramic microspheres, nanofillers, and powders of metals.
- the most preferred insoluble fillers are carbon black, graphite, aluminum trihydroxide, magnesium hydroxide, hollow ceramic microspheres, Clayton APA Montmorillonite silicate clay, and iron powder.
- Insoluble fillers can modify many characteristics of a HIPE foam including density, modulus, tensile strength, thermal conductivity, flame retardancy, and magnetic property. Typically, more than one property is modified upon incorporation of a single insoluble filler. For example, incorporation of a large volume of iron powder will simultaneously increase the density of a foam and increase its ferromagnetic property. Often, large amounts of insoluble filler will tend to decrease the tensile strength of the foam. This tensile strength loss is suspected to arise from weak adhesion between the polymer and the filler. A reduction in tensile strength can be countered by using a filler which chemically or mechanically binds into the polymeric network.
- One example is to modify the surfaces of the filler with a coupling agent, many of which are well known in the art.
- Known coupling agents include organofunctional silicon compounds such as vinyl trimethoxy silane and ⁇ -methacryloxypropyl trimethoxy silane, and titanium compounds such as and isopropyl triisostearoyl titanate and isopropyl trimethacryl titanate.
- the methacrylate functional coupling agent could be especially effective as the methacryl groups take part in the polymerization reaction.
- Another example is to use an acrylate functionalized filler which will copolymerize with the monomers during polymerization. Fillers which are swellable in the organic monomer can become strongly bound mechanically as monomer polymerized through the swollen filler particle.
- the amount of insoluble filler most advantageously employed depends on a number of factors including the desired application of the HIPE or polymerized HIPE foam and the type of filler used. As previously described, often more than one property of a foam is modified when a filler is incorporated. Thus, the amount of filler employed must be adjusted to achieve the desired property. For example, if one desires a dense foam with ferromagnetic properties they could prepare a HIPE with large amounts of iron powder. However, if a person wants ferromagnetic properties but does not desire high density they could use much less iron powder, or prepare a layered structure with iron powder in a thin layer and hollow, low density filler in another layer. Some fillers require a higher concentration than others to reach a desired effect.
- carbon black can significantly effect the thermal conductivity of a foam at a loading of less than 15 weight percent while approximately 30 weight percent or more ATH must be used to notice a significant increase in flame retardancy. Therefore, the application and type of filler used plays a role in determining optimal filler concentrations.
- the insoluble filler can be employed in an amount up to and exceeding 100 volume percent relative to the continuous phase.
- a broader domain of insoluble fillers can be employed up to 100 volume percent relative to the continuous phase; an even broader domain of insoluble fillers can be employed up to 50 volume percent relative to the continuous phase; a still broader domain of insoluble fillers can be employed up to 10 volume percent relative to the continuous phase; and the broadest domain of insoluble fillers can be employed up to 1 volume percent relative to the continuous phase.
- Cross-linking monomers which can be employed in the practice of the present invention for preparing the HIPE include any multifunctional unsaturated monomers capable of reacting with the vinyl monomers.
- Multifunctional unsaturated cross-linking monomers include, for example, divinyibenzene, ethylene glycol dimethacrylate, 3-butylene dimethacrylate, trimethylolpropane triacrylate and allyl methacrylate. While the amount of cross-linking monomers most advantageously employed depends on a variety of factors, such as the desired polymer modulus, in general, the cross-linking monomer is used in an amount of from 0 to 50 weight percent, preferably from 5 to 20 weight percent, and most preferably from 7 to 15 weight percent, based on the total external phase.
- Radical initiators which can be employed in the practice of the present invention for preparing the HIPE include the water-soluble initiators such as, for example, potassium or sodium persulfate and various redox systems such as ammonium persulfate together with sodium metabisulfite and oil-soluble initiators, such as, for example, azobisisobutyronitrile (AIBN), benzoyl peroxide, methyl ethyl ketone peroxide and di-2-ethyl- hexyl-peroxydicarbonate and lauroyl peroxide.
- AIBN azobisisobutyronitrile
- benzoyl peroxide methyl ethyl ketone peroxide and di-2-ethyl- hexyl-peroxydicarbonate and lauroyl peroxide.
- the initiator can be added to the aqueous phase or to the oil phase, depending on whether the initiator is water-soluble or oil-soluble.
- the initiator should be present in an effective amount to polymerize the monomers. Typically, the initiator can be present in an amount of from 0.005 to 20 weight percent, preferably from 0.1 to 10 weight percent and most preferably from 0.1 to 5 weight percent, based on total monomers.
- the aqueous phase can include a water-soluble electrolyte for aiding the surfactant in forming a stable emulsion, controlling porosity of the foam and/or enhancing the hydrophilicity of the resulting polymeric foam material if left as a residual component of the foam material.
- Water-soluble electrolytes which can be employed in the practice of the present invention include inorganic salts (monovalent, divalent, trivalent or mixtures thereof), for example, alkali metal salts, alkaline earth metal salts and heavy metal salts such as halides, sulfates, carbonates, phosphates and mixtures thereof.
- Such electrolytes include, for example, sodium chloride, sodium sulfate, potassium chloride, potassium sulfate, lithium chloride, magnesium chloride, calcium chloride, magnesium sulfate, aluminum chloride and mixtures thereof.
- Mono- or divalent salts with monovalent anions, such as halides are preferred.
- the electrolytes can be employed up to 20, more preferably up to 5 and most preferably up to about 1 weight percent, based on the total aqueous mixture.
- the aqueous phase can additionally comprise a non-electrolyte component, such as, for example, glycerin, as long as a HIPE can still be prepared and polymerized into a foam.
- Surfactants which can be employed in the practice of the present invention for preparing water-in-oil high internal phase emulsions include nonionic surfactants, such as, for example, sorbitan esters, including sorbitan monooleate and sorbitan monolaurate; glycerol esters, such as glycerol monooleate; PEG 200 dioleate, partial fatty acid esters of polyglycerol; cationic surfactants, such as ammonium salts; and anionic surfactants, such as certain organic sulfate and sulfonate compounds. Also suitable are polymerizable surfactants such as those described in copending Application Serial No. 558,333, filed November 15, 1995.
- Such surfactants include surfactants having polymerizable vinyl groups and surfactants capable of undergoing a graft reaction (graftable surfactants) at the conditions of polymerization. Also suitable are the poly(butylene oxide/ethylene oxide) sulfate-based surfactants described in copending Provisional Application Serial No. 60,046,910 filed May 16, 1997.
- the amount of surfactant used must be such that a high internal phase emulsion will form. Generally, the amount of surfactant needed varies with the specific surfactant and the type of formulation used. As little as about 0.125 weight percent, or less, based on continuous phase can be used. More generally, as little as about 0.25 weight percent based on continuous phase can be used. Generally, up to about 25 weight percent or more, based on the continuous phase, can be used, if desired.
- water-in-oil HIPE can be prepared in batches.
- the water phase is gradually added to a mixture of oil phase and surfactant while the mixture is being agitated. Agitation can be accomplished any number of ways including impeller-type agitation.
- water-in-oil HIPEs can be prepared in a continuous flow manner. Methods for continuous flow HIPE preparation are also well established in the literature. See, for example, U.S. Patents 4,018,426 and 5,198,472.
- insoluble fillers into the HIPE can be done prior to or after emulsification. If incorporated prior to emulsification, the insoluble filler can typically be added to the oil phase or aqueous phase or to both phases. The insoluble filler can be added as a separate phase during the emulsification process, particularly in a continuous flow procedure. Alternatively, the filler can be mixed into the emulsion after the emulsion has been formed. The preferred method of incorporating the filler depends on a number of factors including the emulsification procedure used and the type and amount of filler used.
- an insoluble filler which does not disperse into an aqueous phase would not be optimally incorporated into the emulsion by adding it to the aqueous phase prior to emulsification.
- Such a filler would be better incorporated into the emulsion by either adding it to the oil phase, adding it as a separate phase, or adding it after polymerization.
- Layered foam compositions can be prepared from the HIPE of the present invention in accordance with the process described in copending Provisional Application Serial No. 60/055,852 filed August 15, 1997.
- a layered foam composition can be prepared comprising two or more layers with differing amounts or types of fillers.
- One application where layered filled foams are useful is in sound abatement.
- Layered compositions with iron sponge powder in one layer and hollow ceramic microspheres in another have demonstrated enhanced sound attenuation properties over similar foams prepared without fillers, with only the iron or only the microspheres, or with a homogeneous mix of iron powder and ceramic microspheres.
- Clayton APA Montmorillonites Silicate Clay (a montmorillonite silicate clay available from Southern Clay Products, Inc.) was mixed to a 2-weight percent concentration into a monomer mix comprising 64 weight percent 2-ethylhexyl acrylate, 14 weight percent styrene, and 22 weight percent divinylbenzene (55 percent active).
- Into 4.6 grams of the monomer/clay mix was dissolved 1.1 grams SPANTM 80 (sorbitan monooleate) and 0.35 g SPANTM 85 (sorbitan trioleate).
- a separate aqueous phase was prepared comprising 114 g water, 1.1 g calcium chloride dihydrate and 0.3 g potassium persulfate.
- the aqueous phase was added dropwise to the monomer/clay/surfactant mix while stirring at 300 RPM using a three-paddle mixer.
- a thick white HIPE was produced.
- the HIPE was polymerized at 60 9 C for 16 hours in a PYREX® dish covered with Saran WrapTM (Trademark of The Dow Chemical Company).
- the sample was soaked in 2-propanol until it can be compressed free of the internal aqueous phase. Three rinses were done in the 2-propanol, three rinses in water, and a final rinse again in 2-propanol. The sample was squeezed between paper towels and allowed to dry at room temperature. The final foam was expanded, compressible and resilient.
- An oil phase was prepared by mixing 6.75 g 2-ethylhexyl acrylate, 4.62 g styrene, 1.13 g divinylbenzene (55 percent active), 2.50 g SPAN 80 (sorbitan monooleate), and 0.10 g lauroyl peroxide.
- An aqueous phase was prepared by mixing 133.65 g water, 1.35 g calcium chloride dihydrate, and 0.70 g potassium persulfate.
- a HIPE was prepared by adding the aqueous phase dropwise to the oil phase while mixing at 300 RPM with a three-paddle mixer. The HIPE was mixed an additional 2 minutes after forming to ensure homogeneity.
- ANCOR B iron sponge powder Hoeganaes, Inc.; Valley Forge, PA
- the resulting gray emulsion was polymerized at 65 9 C for 20.5 hours in a PYREX dish covered with Saran WrapTM.
- the resulting foam was squeezed free of aqueous phase and rinsed three times in 2-propanol, three times in water, and a final time in 2-propanol.
- the cleaned foam was squeezed free of alcohol and allowed to air-dry.
- the resulting foam has iron powder incorporated in its polymer matrix and was attracted to a magnet.
- Example 3 - HIPE foam with Hollow Ceramic Microspheres An oil phase was prepared by mixing 17.9 g 2-ethylhexyl acrylate, 12.25 g styrene, 3.00 g divinylbenzene (55 percent active), 6.63 g SPAN 80 (sorbitan monooleate), and 0.27 g lauroyl peroxide.
- An aqueous phase was prepared by mixing 354.51 g water, 3.58 g calcium chloride dihydrate, and 1.86 g potassium persulfate.
- a HIPE was prepared by adding the aqueous phase dropwise to the oil phase while mixing at 300 RPM with a three-paddle mixer. The HIPE was mixed an additional 2 minutes after forming to ensure homogeneity.
- HIPE hollow ceramic microspheres
- the HIPE was polymerized at 65 9 C for 18 hours in a PYREX dish covered with Saran WrapTM.
- the resulting foam was squeezed free of aqueous phase and rinsed three times in 2- propnaol, three times in water, and a final time in 2-propanol.
- the cleaned foam was squeezed free of alcohol and allowed to air-dry.
- An oil phase was prepared by mixing 17.90 g 2-ethylhexyl acrylate, 12.25 g styrene, 3.00 g divinylbenzene (55 percent active), 0.27 g lauroyl peroxide and 6.63 g SPAN 80 (sorbitan monooleate).
- An Aqueous phase was prepared by mixing 354.51 g water, 3.58 g calcium chloride dihydrate, and 1.86 g potassium persulfate. The aqueous phase was added dropwise while mixing the oil phase at 300 RPM with a three-paddle mixer. Once the aqueous phase was completely added and while continuing mixing, 4.48 g ceramic microspheres and 14.38 g iron sponge powder was mixed into the emulsion.
- the resulting HIPE was mixed an additional 2 minutes to insure homogeneity.
- the emulsion was put into a PYREX dish, covered with SaranTM Wrap and polymerized in a forced-air oven at 65°C overnight.
- the resulting foam was squeezed free of aqueous phase and rinsed three times in 2-propanol, three times in water, and again in 2-propanol.
- the rinsed foam was squeezed free of most of the 2-popanol and allowed to air-dry to an expanded foam.
- An oil phase was prepared by mixing 8.67 g 2-ethylhexyl acrylate, 1.90 g styrene, 2.98 g divinylbenzene (55 percent active), 1.45 g SPANTM 80 (sorbitan monooleate), and 0.06 g lauroyl peroxide.
- a water phase was prepared by mixing 132.96 g water, 1.34 g calcium chloride dihydrate, and 0.64 g potassium persulfate. The aqueous phase was added dropwise to the oil phase while mixing at 300 RPM using a three- paddle mixer. The emulsion was mixed an additional 5 minutes after all of the aqueous phase was added to ensure homogeneity.
- the emulsion was put into PYREX dishes, covered SaranTM wrap, and polymerized in a forced-air oven at 65°C for 16 hours.
- the resulting foam was rinsed 3 times in 2-propanol (I PA), 3 times in water, and again in I PA.
- the final foam was squeezed free of most of the I PA and then dried in a vacuum oven at 80°C for several hours. The expanded foam was then allowed to set at room temperature for 2 days.
- An oil phase was prepared by mixing 4.65 g 2-ethylhexyl acrylate, 1.02 g styrene, 1.60 g divinylbenzene (55 percent active), 1.45 g SPAN 80 (sorbitan monooleate), and 0.06 g lauroyl peroxide.
- Into this oil phase was mixed 6.30 g aluminum trihydroxide.
- An aqueous phase was prepared by mixing 132.96 g water, 1.34 g calcium chloride dihydrate, and 0.64 g potassium persulfate. The aqueous phase was added dropwise to the oil phase while mixing with a three-paddle mixer at 300 RPM in a polypropylene beaker.
- the emulsion was mixed an additional 5 minutes to insure homogeneity.
- the emulsion was poured into PYREX dishes, covered with Saran WrapTM and placed in a forced-air oven at 65°C for 16 hours.
- the resulting foam was compressed free of most of the aqueous phase.
- the foam was rinsed and dried as described in Comparative Example A, producing an expanded foam.
- the foam was easily ignited and burned down the entire 7 cm in 17 seconds, with near complete incineration in about 35 seconds.
- Example 7 Foam - ATH Filled Foam The foam was difficult to ignite. Once ignited, the flame self-extinguished in 1 minute and 16 seconds having only burned the top 2 cm of the foam strip.
- An oil phase was prepared by mixing 17.90 g 2-ethylhexyl acrylate, 12.25 g styrene, 3.00 g divinylbenzene (55 percent active), 0.27 g lauroyl peroxide and 6.63 g SPAN 80 (sorbitan monooleate).
- An Aqueous phase was prepared by mixing 354.51 g water, 3.58 g calcium chloride dihydrate, and 1.86 g potassium persulfate. The aqueous phase was added dropwise while mixing the oil phase at 300 RPM with a three-paddle mixer. The resulting HIPE was mixed an additional 2 minutes to insure homogeneity.
- the emulsion was put into a PYREX dish, covered with SaranTM Wrap and polymerized in a forced-air oven at 65°C overnight.
- the resulting foam was squeezed free of aqueous phase and rinsed three times in 2-propanol, three times in water, and again in 2-propanol.
- the rinsed foam was squeezed free of most of the 2-popanol and allowed to air-dry to an expanded foam.
- Two HIPEs were prepared, layered, and then polymerized.
- the bottom layer was prepared similar to that in Comparative Example C except 28.76 g ANCOR grade B iron sponge powder was mixed into the emulsion once it was formed.
- This bottom layer HIPE was placed into a PYREX dish. On top of the bottom layer was placed a thin sheet of polypropylene non-woven material.
- a second HIPE was prepared as described in Example 3. The second HIPE was carefully deposited over the polypropylene non-woven covering the bottom layer and the composition was polymerized in a forced-air oven at 65°C overnight.
- the final foam structure was carefully squeezed free of aqueous internal phase and rinsed three times with 2-propanol, three times with water, and again with 2-propanol.
- the rinsed foam was squeezed free of 2-propanol and allowed to dry to an expanded layered structure.
- the sound attenuation was determined for the foams prepared in Comparative Example B and Example 6 using a laboratory sound attenuation apparatus.
- the apparatus basically comprises a source chamber, a receiver chamber, and a test sample fixture between the source and receiver chamber. A 3-inch diameter aperture was provided in the fixture.
- the source chamber was equipped with speakers and a microphone.
- the receiver chamber was equipped with a microphone that records the sound intensity in that chamber. Noise was produced in the source chamber and the sound intensity spectrum collected at the microphone in the receiver chamber with and without a sample blocking the aperture.
- the sound attenuation was defined as:
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Abstract
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU86991/98A AU8699198A (en) | 1997-08-15 | 1998-08-10 | High internal phase emulsions and porous materials prepared therefrom |
BR9811303-8A BR9811303A (en) | 1997-08-15 | 1998-08-10 | High internal phase emulsions and porous materials prepared from them |
KR1020007001539A KR20010022934A (en) | 1997-08-15 | 1998-08-10 | High internal phase emulsions and porous materials prepared therefrom |
JP2000509747A JP2001515104A (en) | 1997-08-15 | 1998-08-10 | High internal phase emulsions and porous materials made therefrom |
EP98938468A EP1003788A1 (en) | 1997-08-15 | 1998-08-10 | High internal phase emulsions and porous materials prepared therefrom |
CA002296347A CA2296347A1 (en) | 1997-08-15 | 1998-08-10 | High internal phase emulsions and porous materials prepared therefrom |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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US5585297P | 1997-08-15 | 1997-08-15 | |
US9825998A | 1998-06-16 | 1998-06-16 | |
US60/055,852 | 1998-06-16 | ||
US09/098,259 | 1998-06-16 |
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WO1999009070A1 true WO1999009070A1 (en) | 1999-02-25 |
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PCT/US1998/016596 WO1999009070A1 (en) | 1997-08-15 | 1998-08-10 | High internal phase emulsions and porous materials prepared therefrom |
Country Status (8)
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EP (1) | EP1003788A1 (en) |
JP (1) | JP2001515104A (en) |
KR (1) | KR20010022934A (en) |
CN (1) | CN1265678A (en) |
AU (1) | AU8699198A (en) |
BR (1) | BR9811303A (en) |
CA (1) | CA2296347A1 (en) |
WO (1) | WO1999009070A1 (en) |
Cited By (14)
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US6353037B1 (en) | 2000-07-12 | 2002-03-05 | 3M Innovative Properties Company | Foams containing functionalized metal oxide nanoparticles and methods of making same |
US6750261B1 (en) | 2003-04-08 | 2004-06-15 | 3M Innovative Properties Company | High internal phase emulsion foams containing polyelectrolytes |
EP1568715A1 (en) * | 2002-12-06 | 2005-08-31 | SOKEN CHEMICAL & ENGINEERING CO. LTD., | Process for microchannel production of colored spherical grain and microchannel production apparatus for use therein |
EP1918320A1 (en) | 2002-12-20 | 2008-05-07 | Huntsman Advanced Materials (Switzerland) GmbH | Flame retardant polymer compositions |
EP2185598A1 (en) * | 2007-08-23 | 2010-05-19 | Agency for Science, Technology And Research | Polymerization on particle surface with reverse micelle |
CN102199242A (en) * | 2011-03-26 | 2011-09-28 | 鲁东大学 | Preparation method of porous high-oil-absorbing resin |
US8916240B2 (en) | 2012-11-28 | 2014-12-23 | Eastman Kodak Company | Porous organic polymeric films and preparation |
US9217094B2 (en) | 2011-07-28 | 2015-12-22 | The Board Of Trustees Of The University Of Illinois | Superhydrophobic compositions |
US9364859B2 (en) | 2011-07-28 | 2016-06-14 | Kimberly-Clark Worldwide, Inc. | Superhydrophobic surfaces |
US9440255B2 (en) | 2012-11-28 | 2016-09-13 | Eastman Kodak Company | Preparation of porous organic polymeric films |
US9803100B2 (en) | 2013-04-30 | 2017-10-31 | Kimberly-Clark Worldwide, Inc. | Non-fluorinated water-based superhydrophobic surfaces |
US10005917B2 (en) | 2013-04-30 | 2018-06-26 | Kimberly-Clark Worldwide, Inc. | Non-fluorinated water-based superhydrophobic compositions |
US10533096B2 (en) | 2015-02-27 | 2020-01-14 | Kimberly-Clark Worldwide, Inc. | Non-fluorinated water-based superhydrophobic compositions |
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- 1998-08-10 CN CN98807899A patent/CN1265678A/en active Pending
- 1998-08-10 WO PCT/US1998/016596 patent/WO1999009070A1/en not_active Application Discontinuation
- 1998-08-10 JP JP2000509747A patent/JP2001515104A/en active Pending
- 1998-08-10 EP EP98938468A patent/EP1003788A1/en not_active Withdrawn
- 1998-08-10 CA CA002296347A patent/CA2296347A1/en not_active Abandoned
- 1998-08-10 AU AU86991/98A patent/AU8699198A/en not_active Abandoned
- 1998-08-10 KR KR1020007001539A patent/KR20010022934A/en not_active Application Discontinuation
- 1998-08-10 BR BR9811303-8A patent/BR9811303A/en not_active Application Discontinuation
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US6462100B1 (en) | 2000-07-12 | 2002-10-08 | 3M Innovative Properties Company | Foams containing functionalized metal oxide nanoparticles and methods of making same |
US6353037B1 (en) | 2000-07-12 | 2002-03-05 | 3M Innovative Properties Company | Foams containing functionalized metal oxide nanoparticles and methods of making same |
EP1568715A1 (en) * | 2002-12-06 | 2005-08-31 | SOKEN CHEMICAL & ENGINEERING CO. LTD., | Process for microchannel production of colored spherical grain and microchannel production apparatus for use therein |
EP1568715A4 (en) * | 2002-12-06 | 2008-06-18 | Soken Kagaku Kk | Process for microchannel production of colored spherical grain and microchannel production apparatus for use therein |
US8372899B2 (en) | 2002-12-20 | 2013-02-12 | Huntsman Advanced Materials Americas Llc | Flame retardant polymer compositions |
EP1918320A1 (en) | 2002-12-20 | 2008-05-07 | Huntsman Advanced Materials (Switzerland) GmbH | Flame retardant polymer compositions |
US7635728B2 (en) | 2002-12-20 | 2009-12-22 | Huntsman Advanced Materials Americas Llc | Flame retardant polymer compositions |
US6750261B1 (en) | 2003-04-08 | 2004-06-15 | 3M Innovative Properties Company | High internal phase emulsion foams containing polyelectrolytes |
US6890963B2 (en) | 2003-04-08 | 2005-05-10 | 3M Innovative Properties Company | High internal phase emulsion foams containing polyelectrolytes |
EP2185598A1 (en) * | 2007-08-23 | 2010-05-19 | Agency for Science, Technology And Research | Polymerization on particle surface with reverse micelle |
EP2185598A4 (en) * | 2007-08-23 | 2011-02-09 | Agency Science Tech & Res | Polymerization on particle surface with reverse micelle |
CN102199242A (en) * | 2011-03-26 | 2011-09-28 | 鲁东大学 | Preparation method of porous high-oil-absorbing resin |
CN102199242B (en) * | 2011-03-26 | 2013-05-08 | 鲁东大学 | Preparation method of porous high-oil-absorbing resin |
US9217094B2 (en) | 2011-07-28 | 2015-12-22 | The Board Of Trustees Of The University Of Illinois | Superhydrophobic compositions |
US9364859B2 (en) | 2011-07-28 | 2016-06-14 | Kimberly-Clark Worldwide, Inc. | Superhydrophobic surfaces |
US8916240B2 (en) | 2012-11-28 | 2014-12-23 | Eastman Kodak Company | Porous organic polymeric films and preparation |
US9284429B2 (en) | 2012-11-28 | 2016-03-15 | Eastman Kodak Company | Porous organic polymeric films and preparation |
US9440255B2 (en) | 2012-11-28 | 2016-09-13 | Eastman Kodak Company | Preparation of porous organic polymeric films |
US9803100B2 (en) | 2013-04-30 | 2017-10-31 | Kimberly-Clark Worldwide, Inc. | Non-fluorinated water-based superhydrophobic surfaces |
US10005917B2 (en) | 2013-04-30 | 2018-06-26 | Kimberly-Clark Worldwide, Inc. | Non-fluorinated water-based superhydrophobic compositions |
US11180364B2 (en) * | 2014-09-03 | 2021-11-23 | Snaptrack, Inc. | Covering for a component and method for producing a covering for a component |
US10533096B2 (en) | 2015-02-27 | 2020-01-14 | Kimberly-Clark Worldwide, Inc. | Non-fluorinated water-based superhydrophobic compositions |
Also Published As
Publication number | Publication date |
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KR20010022934A (en) | 2001-03-26 |
EP1003788A1 (en) | 2000-05-31 |
CA2296347A1 (en) | 1999-02-25 |
CN1265678A (en) | 2000-09-06 |
AU8699198A (en) | 1999-03-08 |
BR9811303A (en) | 2000-08-29 |
JP2001515104A (en) | 2001-09-18 |
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