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CN1265678A - High internal phase emulsions and porous materials prepared therefrom - Google Patents

High internal phase emulsions and porous materials prepared therefrom Download PDF

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Publication number
CN1265678A
CN1265678A CN98807899A CN98807899A CN1265678A CN 1265678 A CN1265678 A CN 1265678A CN 98807899 A CN98807899 A CN 98807899A CN 98807899 A CN98807899 A CN 98807899A CN 1265678 A CN1265678 A CN 1265678A
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emulsion
internal phase
high internal
phase
filler
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S·W·莫克
J·H·索尔克
C·P·帕克
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Dow Chemical Co
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Dow Chemical Co
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Textile Engineering (AREA)
  • Polymerisation Methods In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Colloid Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

一种高内相乳液,它含有稳定乳液的表面活性剂,一种或多种不可溶填料,体积分数至少为70%的非连续内相;体积分数小于30%的连续外相,连续外相包含一种或多种可聚合的乙烯基单体。使这种油包水高内相乳液聚合,可以制备出一种开孔型多孔聚合物材料,在其聚合物骨架中结合有不可溶填料。A high internal phase emulsion comprising a surfactant to stabilize the emulsion, one or more insoluble fillers, a discontinuous internal phase with a volume fraction of at least 70%; a continuous external phase with a volume fraction of less than 30%, the continuous external phase comprising a One or more polymerizable vinyl monomers. By polymerizing this water-in-oil high internal phase emulsion, an open-cell porous polymer material can be prepared with insoluble fillers incorporated in its polymer backbone.

Description

High Internal Phase Emulsion and porous material prepared therefrom
The present invention relates to High Internal Phase Emulsion and by its prepared porous polymer material.
Emulsion is discontinuous or isolated dispersion of particles body, this discontinuous or isolated particle be commonly referred to as external phase or " outside " " interior " phase in mutually.Emulsion both can be oil-in-water (oil/water) type, and phase and water-based foreign minister in the oiliness are arranged, and can be again water-in-oil (water/oil) type, and phase and oiliness foreign minister in the water-based are arranged.It is interior phase more than 70% or 70% that emulsion can contain volume fraction, and they are commonly referred to as High Internal Phase Emulsion (HIPEs).The volume fraction of phase can be up to 90% in this emulsion, and often reaches 95%, it is reported that some HIPEs water volume fractions can reach 98%.
An early stage application of High Internal Phase Emulsion (HIPEs) is as the solid suspension medium, as U.S. Patent No. 3974116 disclosed examples.The high static viscosity of HIPEs can prevent particle precipitation, and in a similar application, HIPEs is used as and transports the transmitting fluid of particulate by pipeline, as U.S. Patent No. 3617095 disclosed examples.The high static viscosity of emulsion can prevent the solids sedimentation, but under shearing action the viscosity degradation of emulsion, can make the pipeline that passes through of emulsion highly effective by pump pressure.Because the particulate resemble the polynite can be used to breakdown of emulsion, therefore can make the ability of particle suspension in HIPEs seem somewhat wondrous, as K.J, Lissant is in " emulsion and emulsion technology " first part " preparation of emulsion and breakdown of emulsion ", the 122nd～123 page (1974).
The application of High Internal Phase Emulsion (HIPEs) aspect the preparation porous polymer material is also well-known, for example all describes to some extent at U.S. Patent No. 5210104, No.5200433, No.4536521, No.4788225, No.5147345, No.5331015, No.5260345, No.5268224 and No.6318554.In described HIPEs, typical oiliness foreign minister is made of polymerisable vinyl monomer (for example 2-EHA and vinylbenzene) and cross-linking monomer (as Vinylstyrene).Be to constitute mutually in the typical water-based by water, radical initiator (if not at oil phase) and ionogen.In order to form stable emulsion, in oil phase, adding tensio-active agent before the emulsification.Generally being used for the tensio-active agent of stable emulsion for example comprises nonionic surface active agent, as sorbitan ester (for example sorbitan monooleate and sorbitan mono-laurate).Other known stabilization tensio-active agent has Polyglycerine fat family ester, and is disclosed as United States Patent (USP) 5500451.
By the prepared porous polymer material of HIPE in a lot of fields all of great use.For example United States Patent (USP) 5260345,5268224,5331015 discloses the absorbing material that the hipe foam material is used as the diaper based article.The excellent characteristics that the HIPEs foam materials is used as absorbing material is its high void volume rate and low density, and high liquid absorption capacity is provided.If the density of supposition polymkeric substance is 1g/cc, interior is about 49 gram water/gram foam materialss (gram/gram receptivity) for the liquid absorption capacity of the foam materials of the HIPE of 98wt% preparation mutually.Both can also improve the gram/gram receptivity of foam materials by reduction density by improving the abscess rate of foam materials.On history, change one of them factor, then another factor becomes thereupon.That is to say that improving foam materials abscess rate just makes density reduce.The abscess rate is by the decision of the internal-phase ratio of emulsion example, and the internal-phase ratio example is high more, and the final abscess rate of foam materials is high more.Can polymerization how much enter foam materials but can reach many height as for the internal-phase ratio example mutually with interior, this is limited.Another method that improves hipe foam material abscess rate is that inert oil is added the foreign minister, removes inert oil after the polymerization, stays the space in polymer wall and polymer support structure, but the collection and the handling problem of inert oil after must considering polymerization process.And improve the abscess rate thin supporting structure of generation on the foam materials wall easily, so just produce more weak foamy structure.Therefore if do not improve the internal-phase ratio example or do not use inert oil and can improve the gram/gram receptivity of hipe foam material, this will be very desirable.
The Another application of hipe foam material is the barrier material that is used as heat and sound.The application of this respect is for example disclosed in U.S. Patent No. 5633291.As lagging material, stoping heat is very important by insulating material.A kind of mode that heat passes material is radiation, and at this moment infrared wave directly reaches the other side by insulation layer.If add the infrared rays barrier material, the thermal radiation part just can be reduced or eliminate, and the heat-insulating capability of hipe foam material just can be enhanced.Lagging material and soundproof material general requirement are fire retardant materials, but because the hipe foam material is an organic materials, therefore inflammable.
Ideal method is to improve the gram/gram receptivity of hipe foam material and not improve internal-phase ratio routine or do not use inert oil.In addition, and another ideal method provides water-in-oil High Internal Phase Emulsion and porous polymer material prepared therefrom, adds the heat-proof quality that the infrared rays barrier material is strengthened the foam materials product therein.If can provide the hipe foam material that adds fire retardant material then more satisfactory.
First aspect, the present invention is a kind of High Internal Phase Emulsion, contains the tensio-active agent of stable emulsion, soluble filler, volume fraction and is at least 70% interior phase and volume fraction less than 30% foreign minister, the foreign minister is contained one or more polymerisable vinyl monomers.
Second aspect, the present invention is the method for High Internal Phase Emulsion of preparation first aspect, this method comprises preparation foreign minister and Nei mutually, to wherein one mutually or add soluble filler in the two-phase, then under being enough to form the condition of emulsion with the foreign minister with Nei mix mutually.
The third aspect, the present invention is the method for High Internal Phase Emulsion of preparation first aspect, this method comprises preparation foreign minister and Nei mutually, water and oil phase is mixed being enough to form under the condition of emulsion, adds soluble filler then in emulsion.
Fourth aspect, the present invention is a kind of open cell type porous polymer material, makes by the High Internal Phase Emulsion polymerization that makes first aspect.
The 5th aspect, the present invention is a kind of open cell type porous polymer material, mixes soluble filler in its polymer backbone.
We find, High Internal Phase Emulsion (HIPEs) not only can make containing under the situation of soluble filler, and can polymerization enter foam materials, and foam materials contains soluble filler in its polymer backbone.Though it is known to contain the HIPE of specific soluble filler, but we can prepare the HIPE that contains the insoluble filler of wide region more and they can be mixed among the HIPE with the polymerizable vinyl monomer, these fillers comprise the smectites clay, and the smectites clay it is reported and can destroy HIPE (referring to above-mentioned document).And HIPE can aggregate into the open cell type foam materials and still contain soluble filler, and this is beat all.In order to form the open cell type structure, in polymerization process HIPEs must be in to a certain degree breakdown of emulsion so that on cell wall, form perforate.But breakdown of emulsion can not too form and be separated.As mentioned above, known soluble particulate can breakdown of emulsion.Therefore, make the HIPE polymerization that contains soluble particulate form open-celled structure and do not form and be separated, this is beat all.
HIPEs of the present invention is very useful aspect the preparation polymer foams, and this polymer foams both can improve or reduce density, and need not improve or reduce the internal-phase ratio example of HIPE.
Polymer foams of the present invention also can be used for lagging material and sound-absorbing material, also can be used for liquid-absorbent.
Fig. 1 is that the acoustic attenuation spectrogram of embodiment 6 and the prepared foam materials of Comparative Examples B compares.
It is about 70% that the volume fraction of the interior phase of High Internal Phase Emulsion of the present invention (HIPEs) is higher than, more Preferably volume fraction is greater than about 90%, and most preferably volume fraction is greater than about 95%; Its Foreign minister's volume fraction is less than about 30%, and more preferably volume fraction is less than about 10%, optimum What select is that volume fraction is less than about 5%; And contain insoluble filler. Preferred HIPE is the oil bag Aqueous emulsion comprises phase and oiliness foreign minister in the water-based. Contain volume fraction and be 98% or higher water-based The HIPEs of interior phase can make by the present invention. The foreign minister comprises one or more polymerizable second Alkenyl monomer, preferably the foreign minister also comprises cross-linking monomer, the interior water that comprises mutually. Typically, Water-soluble radical initiator adds water. If the use oil-soluble initiator then adds oil Phase. In addition, HIPE also comprises surfactant and soluble filler.
The polymerizable vinyl monomer that the present invention adopts in practice is with ethylenic unsaturated bond Any polymerisable monomer. In general, HIPEs a kind of by in the following monomer advantageously Make or both make jointly: (i) at least a monomer (glassy state monomer), give last The porous polymer material that is synthesized is with the glassy state performance; (ii) at least a monomer (rubbery state monomer) gives the last porous polymer material that is synthesized with the rubber state property Energy.
For the present invention, the glassy state monomer is defined as generating glass transition temperature Degree is at those monomers of about homopolymers more than 40 ℃. Preferred glassy state monomer comprises: first Base acrylic ester monomer, for example methyl methacrylate; And styrene monomer, example Such as various monovinylidene aromatics, such as styrene, o-methyl styrene, chloromethylbenzene Ethene, vinyl ethylbenzene, vinyltoluene. Preferred glassy state monomer comprises: benzene second Alkene, o-methyl styrene and 1-chloro-4-methyl-benzene. Most preferred glassy state monomer is styrene.
For the present invention, the rubbery state monomer is defined as generating glass transition temperature Degree is at those monomers of about 40 ℃ or lower homopolymers. Preferred rubbery state monomer comprises: The Arrcostab of ethylenic unsaturated acid (" acrylate " or " methacrylate "), example As 2-EHA, butyl acrylate, Hexyl 2-propenoate, butyl methacrylate, Lauryl methacrylate, the different certain herbaceous plants with big flowers ester of methacrylic acid and their mixture; And Vinyl fat hydrocarbon and alicyclic, for example butadiene, isoprene; With these comonomers Combination. Preferred rubbery state monomer comprise butyl acrylate, 2-EHA, The combination of butadiene, isoprene and these comonomers. Optimal rubbery state monomer is 2-EHA.
Preferably, the HIPE emulsion contains at least a glassy state monomer and at least a rubber The attitude monomer. Do not want to be limited by theory, the rubbery state monomer is believed to give foamed material Pliability, and should have certain quantity adding to guarantee the goods that contain this foamed material Can bear compression, bending and torsion in worker, packing, shipment, storage and the use procedure. The glassy state monomer is believed to give the globality of foamed material with structure, and should have certain Quantity to guarantee that this foamed material is subjected to dynamic force and static force is done the time spent, can be with foam Minimum is down in tearing with broken damage envelope that material suffers. Generally speaking, glass The ratio of attitude monomer and rubbery state monomer is between 1: 25 to 1.5: 1, preferably at 1: 9 In 1.5: 1.
The best usage quantity of polymerizable vinyl monomer depends on several factors, as concrete Monomeric species. In general, the operating weight scope of polymerizable vinyl monomer be whole outside The 50%-100% of phase weight is more preferably 80%-95%, most preferably is 85%-93%.
The present invention's selected soluble filler when preparation HIPE comprises inert filler and activity Filler. Inert filler refer to can not with that of the monomer generation copolymerization of preparation hipe foam material One class filler. Active filler then in polymerization process with strand generation chemical bond. This The inert filler of bright use for example comprises: carbon black; Graphite; The hydroxide of metal is such as hydrogen Aluminium oxide, magnesium hydroxide, calcium hydroxide, zirconium hydroxide, manganous hydroxide and iron hydroxide; Metal dust is such as iron powder; Ceramic microspheres. An example of active filler is with third The crosslinked polymeric materials of olefin(e) acid ester surface functional group.
In this article, the meaning of " soluble " word is the material in the adding system, extremely Rare some both had been insoluble to the oiliness foreign minister of HIPE, also was insoluble to phase in the water-based. Preferably At least 50% filler, more preferably at least 80%, most preferably 100% filler both had been insoluble to oil The property foreign minister, also be insoluble to phase in the water-based.
Can use hollow packing among the present invention, as pottery or glass microsphere.Can make the hollow packing of density less than 1 gram/cc.By such low density filler is added in the hipe foam material, density (and having improved gram/gram receptivity simultaneously) can be reduced, and the internal-phase ratio example of HIPE precursor need not be improved, also externally use inert oil in the oil phase.The example of hollow packing comprises that (its density range can be low to moderate 0.13 gram/cc for Valley Forge, various PQ hollow spheres PA) from Pq Corp..
Can use infrared rays to completely cut off filler in the present invention's practice, as carbon black and Graphite Powder 99, they can reduce the infrared radiation by final hipe foam material conduction, improve effective thermal resistance coefficient of foam materials.
Known that inorganic the and organic compound that contains phosphorus, antimony, boron, bismuth and halogen can be used as filler and improves fire retardancy and (for example see G.T.Gmitter etc., flexible polyurethane foams, plastic foam (Plastic Foams), first part; Frisch, K.C., Saunders, J.H., Eds.; Marcel Dekker, Inc.: New York, 1972; The 142nd page), it can be used as filler in the present invention.Other mineral compound that can be used as fire retardant in the present invention comprises that hibbsite (also is referred to as ATH, aluminium hydroxide Al (OH) 3) (for example see the compression chemistry dictionary of Hawley, the 12 edition, 1993, Richard J.Lewis compiles, p43), magnesium hydroxide and graphite.These mineral compound can use separately, also can be used in combination with other organic or inorganic fire retardant.
Also can add ferromagnetic substance in the foam materials,, give final foam materials with magnetic property as iron and nickel.The foam materials that for example contains ferromagnetic substance the sound absorption of metal ceiling and heat insulation aspect very useful.For example, ferromagnetic substance is dispersed into thin layer in a side of foam materials, prepares this foam materials.Before both can be in having joined foam materials, also can after ferromagnetic substance is magnetized.The foam materials synthetics just can be easily attached on the top ceiling that contains ferromagnetic substance like this, and does not need nail or tackiness agent.Another selectable method is that the ferromagnetic substance in the foam materials keeps unmagnetized, and foam materials just can be attracted by magnetized material so.
In the present invention, also water can be adopted or/and oily swellable filler as crosslinking sodium polyacrylate, as long as can be prepared into HIPE, can polymerization form foam materials as long as even more preferably contain the HIPE of filler.
The present invention also uses the carbonate of metal oxide and metal as filler, and such material comprises calcium oxide, magnesium oxide, zirconium white, titanium oxide, manganese oxide, ferric oxide, aluminum oxide, lime carbonate, magnesiumcarbonate, manganous carbonate, iron carbonate and zirconium carbonate.
Resemble aluminium nitride, silicon nitride, nitrided iron, silicon carbide, manganess carbide, iron carbide, FeB, aluminum boride, manganese boride such metal nitride, metallic carbide and metal bromide and some other in making stupalith employed raw material, also can be used for preparing HIPE in the practice of the present invention.Also can adopt one or more mixtures of material.
In practice of the present invention, also can adopt in the clay pit system natural or synthesis of clay as filler.Such filler comprises talcum powder, mica and other clay pit composition material, such as talcum between polynite, lithium montmorillonite, kaolin, dickite, nakrite, halloysite, saponite, nontronite, beidellite, volkonskoite, sauconite, magadiite, medmontite, fibrous morphology crystals, vermiculite, serpentine, chlorite, polygorskite, green mud, sliding between saponite, sepiolite, malthacite and imogolite.Also can adopt one or more these mixtures of material.
Other fillers that adopt in practice of the present invention have multilayer inorganic materials (being called " millimicro filler " traditionally).The layered inorganic material that can be used for multilayer inorganic materials of the present invention can be any swellable.Typically, the layered inorganic material is made up of each layer that has two apparent surfaces, and the surface is should be relatively flat or bending arranged slightly, as U.S. Patent No. 4889885 disclosed.
The representative examples of these swellable layered inorganic materials comprises clay pit composition material as described above.The representative examples of other inflatable stratiform inorganic materials has illite class mineral, as the trioctahedron illite; Be lamellated two kinds of metal hydroxidess or mixed metal hydroxides, as Mg 6Al 3.4(OH) 18.8(CO 3) 1.7H 2O (seeing W.T.Reichle, catalysis magazine (J.Catal.), 94 (1985), 547), it has positive electricity layer, and interchangeable negatively charged ion is arranged in interlayer space; Muriate is as ReCl 3And FeOCl; The sulfur family element compound is as TiS 2, MoS 2And MoS 3Prussiate is as Ni (CN) 2Oxide compound is as H 2Si 2O 5, V 5O 13, HTiNbO 5, Cr 0.5V 0.5S 2, W 0.2V 2.8O 7, Cr 3O 8, MoO 3(OH) 2, VOPO 42H 2O, CaPO 4CH 3-H 2O, MnHAsO 4-H 2O and Ag 6Mo 10O 33Also can adopt one or more mixtures of material.
According to the purposes of final foam materials, but the oxyhydroxide that preferred soluble filler is carbon black, graphite, metal-powder, metal, the hollow packing that resembles glass or ceramic microsphere, natural or synthesis of clay, millimicro filler, metal powder, contain the polymer powder functionalized, oily swellable filler as slight crosslinked polymer powder and water-swellable material such as crosslinking sodium polyacrylate just like the fire-retardant filler copolymerization filler of phosphorus, antimony, boron, bismuth and/or halogen such as acrylate.The oxyhydroxide that preferred soluble filler is carbon black, Graphite Powder 99, metal-powder, metal, ceramic microspheres, millimicro filler and granulated metal.Most preferred soluble filler is carbon black, graphite, hibbsite, magnesium hydroxide, ceramic microspheres, Clayton APA montmorillonite silicate clay and iron powder.
Soluble filler can change many performances of hipe foam material, comprises density, modulus, tensile strength, heat conductivity, flame retardant resistance and magnetic property.Typically, the adding of the soluble filler of single variety not only changes a kind of performance.For example, add density and the ferromagnetic property that comparatively large vol fractional iron powder will improve foam materials simultaneously.In the ordinary course of things, the soluble filler of larger amt reduces the tensile strength of foam materials easily.Loss of tensile strength may be because between polymkeric substance and the filler due to the more weak binding property.By add can with the filler of polymer network generation Chemical bond or mechanical bond, can offset reducing of tensile strength.An example is that most of coupling agent is well-known in this area with the surface property of coupling agents to improve filler.Known coupling agent comprises organic functionalized silicon compound, as vinyltrimethoxy silane and γ-propyl methacrylate base Trimethoxy silane; Titanium compound is as sec.-propyl three isostearoyl base titanic acid ester and trimethylammonium acrylic isopropyl ester base titanic acid ester.Methacrylate functionalized coupling agent effect can be better, because methacrylate based group participates in polyreaction.Another example is to adopt the acrylate functional filler, it in polymerization process can with monomer generation copolymerization.Can in organic monomer, can produce firm mechanical bond by the expansible filler, because pass the expansible filler grain during monomer polymerization.
The optimum quantum of utilization of soluble filler depends on series of factors, comprises HIPE or the desired use of polymeric hipe foam material has taken place and the type of the filler that uses.As previously mentioned, behind the adding filler, often more than a kind of foam performance changes.Must adjust the usage quantity of filler like this to reach estimated performance.For example, if expect the ferromegnetism high-density foam material, can produce the HIPE that contains a large amount of iron powders so.If but the ferromegnetism of expecting and do not wish to have high-density just can be used few many iron powders, perhaps prepare iron powder and be distributed in a thin layer, hollow low density filler laminate structure at another layer.Compare with other fillers, some fillers require higher concentration is arranged to obtain required performance.For example, the carbon black add-on during less than 15wt% just with the heat transfer property of remarkably influenced foam materials, but the ATH add-on must be about 30% or the higher flame retardant properties that just can make significantly improve.Therefore, the type decided of purposes and used filler best packing density.In general, the usage quantity of soluble filler can meet or exceed 100% of external phase volume.In broad filler scope, the usage quantity of soluble filler can reach 100% of external phase volume.In wideer filler scope, the usage quantity of soluble filler can reach 50% of external phase volume.In further wide filler scope, the usage quantity of soluble filler can reach 10% of external phase volume.In the wideest filler scope, the usage quantity of soluble filler can reach 1% of external phase volume.
When the present invention prepares HIPE spendable cross-linking monomer comprise any can with the multifunctional unsaturated monomer of vinyl monomer reaction.For example, multifunctional unsaturated cross-linking monomer has Vinylstyrene, ethylene glycol dimethacrylate, 3-butylidene dimethacrylate, Viscoat 295 and allyl methacrylate(AMA).The optimum amount of cross-linking monomer depends on several factors, and as the polymkeric substance modulus of expection, in general, the consumption of cross-linking monomer accounts for the 0-50% of whole foreign minister's weight, more preferably 5-20%, most preferably 7-15%.
Operable radical initiator has water soluble starter when preparing HIPE in the present invention, as Sodium Persulfate or Potassium Persulphate, and various redox system, as ammonium persulphate and sodium bisulfite; Oil-soluble initiator is as Diisopropyl azodicarboxylate (AIBN), benzoyl peroxide, methylethyl ketone peroxide, mistake two carbonic acid diethylhexyl ester and lauroyl peroxides.According to initiator is water soluble starter or oil-soluble initiator, and initiator is added water or oil phase.Initiator should possess effective usage quantity makes monomer polymerization.Typically, initiator can reach the 0.005-20% of total monomer weight, and preferred amount is 0.1-10%, and most preferred initiator amount is the 0.1-5% of total monomer weight.
Water can contain water-soluble ionogen helps tensio-active agent and forms stable emulsion, the abscess rate of control foam material and/or increase the wetting ability of institute's synthetic polymer foam materials.The water-soluble ionogen that can be used among the present invention comprises inorganic salt (monovalence, divalence, trivalent or their mixture), as an alkali metal salt, alkaline earth salt and heavy metallic salt, such as halogenide, vitriol, carbonate, phosphoric acid salt and their mixture.Such ionogen for example has sodium-chlor, sodium sulfate, Repone K, vitriolate of tartar, lithium chloride, magnesium chloride, calcium chloride, sal epsom, aluminum chloride and their mixture.Comparatively it is desirable to univalent anion, as anionic monovalence of halogen or divalent salts.Electrolytical optimum amount depends on several factors, as specific compound, required foam materials abscess rate and used tensio-active agent.In general, electrolytical consumption can be at the most 20% of whole aqueous mixture weight, and more preferably at the most 5%, most preferably about at the most 1%.
As long as HIPE still can be made with polymerization and form foam materials, aqueous phase can also comprise the nonelectrolyte component, as glycerol.
The tensio-active agent that can be used for preparation water-in-oil-type High Internal Phase Emulsion among the present invention comprises: nonionic surface active agent, and for example sorbitan ester has sorbitan monooleate and sorbitan mono-laurate; Glyceryl ester is as XU 61518.10; Two oleic acid Macrogol 200 esters, the partial fatty acid ester of Polyglycerine; Cationic surfactant is as ammonium salt; Aniorfic surfactant is as some organic sulfuric acid and sulfoacid compound.Polymerisable surfactant described in the common pending trial U.S. Patent application No.558333 (applying for November 15 nineteen ninety-five) also is suitable.Such tensio-active agent has the tensio-active agent that has the polymerizable vinyl group; And the tensio-active agent (but grafting tensio-active agent) that graft reaction can take place under polymerizing condition.Other suitable tensio-active agents also have poly-(oxybutylene/ethylene oxide) Sulfates tensio-active agent, describe to some extent in treating U.S. Patent application No.60046910 (applying on May 16th, 1997) jointly.
The usage quantity of tensio-active agent must be enough to form High Internal Phase Emulsion.In general, the type of the kind of the concrete tensio-active agent of the consumption of tensio-active agent basis and prescription is different and different.The consumption of tensio-active agent may be as few as the 0.125wt% of external phase or still less.Under more general situation, the consumption of tensio-active agent may be as few as the 0.25wt% of external phase.In the ordinary course of things, if desired, the consumption of tensio-active agent can reach the 25wt% of external phase.
The processing method of preparation water-in-oil emulsion is known, as U.S. Patent No. 4522953 and No.5210104 are disclosed, can adopt these methods in the present invention.For example, can make water-in-oil HIPE in batches.In the ordinary course of things, for producing water-in-oil HIPE in batches, in oil phase and surfactant mixtures, under agitation progressively add water.Can adopt and comprise that vane type is stirred in interior a lot of methods and realizes stirring.Another kind of alternative method is to produce oil with continuous processing to wrap water HIPE, and the continuous processing of producing HIPE also has a lot of reports in the literature, and is disclosed as U.S. Patent No. 4018426 and U.S. Patent No. 5198472.
Can before or after emulsification, add soluble filler.If before emulsification, add soluble filler, typical, can add in oil phase or water or the two-phase.Soluble filler can particularly in continuous processing, add in emulsion process as independent phase.Another kind of alternative method is to sneak into filler after emulsion forms.The optimal way that adds filler depends on series of factors, for example the type of emulsion process that is adopted and used filler and quantity.For example, for can not before emulsification, soluble filler farthest being mixed its method that adds water with emulsion at the soluble filler of aqueous phase dispersive.Filler like this both can be used as and had been added to oil phase separately, also can add after polymerization, so that make itself and emulsion better mixing.
Use HIPE of the present invention, the method according to described in the pre-first to file No.60/055852 of the U.S. of common pending trial (application on August 15th, 1997) can prepare stratiform foam materials synthetics.For example, can prepare by stratiform foam materials synthetics two-layer or that multilayer is formed, each layer contains the filler of different quantities or type.An Application Areas of stratiform filled and process material is to eliminate the noise.Compare with foam materials similar but that do not contain filler, perhaps with have only iron or have only microballoon or be that the foam materials of filler is compared with iron powder and ceramic microsphere homogenizing mixture, spongy iron powder is distributed in the stratiform synthetics that one deck, ceramic microspheres be distributed in another layer and has been proved to be able to strengthen sound absorbing capabilities.
The present invention will be described to have provided embodiment below, but can not think that the present invention only limits in this scope.Unless otherwise indicated, all marks below and percentage number average are by weight.
Embodiment 1-contains the hipe foam material of montmorillonite silicate clay
Clayton APA montmorillonite silicate clay (from a kind of montmorillonite silicate clay of southern clay-ware company) is that 2wt% adds monomer mixture with concentration, and monomer mixture contains the ethyl acrylate of 64wt%, the vinylbenzene of 14wt% and the Vinylstyrene (activity is 55%) of 22wt%.Dissolving 1.1 gram SPAN in the monomer/clay mixture of 4.6 grams TM80 (sorbitan monooleates) and 0.35 gram SPAN TM85 (Witconol AL 69-66s).Prepare water separately, water contains 114 gram water, 1.1 gram Calcium dichloride dihydrates and 0.3 gram Potassium Persulphate.Under three paddle agitators stir with 300 rev/mins speed, water is added dropwise in monomer/clay/surfactant mixtures.Produce white HIPE.At thermal glass (PYREX *) in the dish, at saran parcel (Saran Wrap TM) covering under, HIPE was 60 ℃ of following polymerizations 16 hours.Sample is immersed in the 2-propyl alcohol, up to the inside water that can squeeze out sample.In the 2-propyl alcohol, clean three times, in water, clean three times then, in the 2-propyl alcohol, clean at last.Sample pushes between paper handkerchief, and is at room temperature dry then.Final foam materials is an equatorial, compressible and flexible.
Embodiment 2-contains the hipe foam material of iron powder
By 6.75 gram ethyl acrylates, 4.62 gram vinylbenzene, 1.13 gram Vinylstyrenes (activity is 55%), 2.50 gram SPAN80 (sorbitan monooleate) and 0.10 gram lauroyl peroxide are mixed, make oil phase.133.65 gram water, 1.35 gram Calcium dichloride dihydrates and 0.70 gram Potassium Persulphate mixing are obtained water.Under three paddle agitators stir with 300 rev/mins speed, water is added dropwise to oil phase and makes HIPE.After forming HIPE, remix 2 minutes is to guarantee uniformity in addition.Continue to mix down, and the spongy iron powder of adding 20 gram ANCOR B in HIPE (Hoeganaes company, Valley Forge, PA).At thermal glass (PYREX *) in the container, at saran parcel (Saran Wrap TM) covering under, resulting grey emulsion was 65 ℃ of following polymerizations 20.5 hours.The foam materials that extruding is synthesized is until not containing inner water.In the 2-propyl alcohol, clean three times, in water, clean three times then, in the 2-propyl alcohol, clean at last.Foam materials after extruding is cleaned dries then up to not containing alcohol.The foam materials that the result obtains contains iron powder in its polymeric matrix, can be by attraction.
Embodiment 3-contains the hipe foam material of ceramic microspheres
By 17.9 gram ethyl acrylates, 12.25 gram vinylbenzene, 3.00 gram Vinylstyrenes (activity is 55%), 6.63 gram SPAN80 (sorbitan monooleate) and 0.27 gram lauroyl peroxide are mixed, make oil phase.354.51 gram water, 3.58 gram Calcium dichloride dihydrates and 1.86 gram Potassium Persulphates mixing are obtained water.Under three paddle agitators stir with 300 rev/mins speed, water is added dropwise to oil phase and makes HIPE.After forming HIPE, remix 2 minutes is to guarantee uniformity in addition.Under three paddle agitators stir with 300 rev/mins speed, in HIPE, add 8.95 gram ceramic microspheres (SL-150Extendospheres *, Pq Corp.).At thermal glass (PYREX *) in the container, at saran parcel (Saran Wrap TM) covering under, with HIPE 65 ℃ of following polymerizations 18 hours.The foam materials that extruding is synthesized is until not containing inner water.Clean three times with the 2-propyl alcohol, water cleans three times then, cleans with the 2-propyl alcohol more at last.Foam materials after extruding is cleaned dries then up to not containing alcohol.
Embodiment 4-contains the foam materials of iron powder and ceramic microspheres
By 17.90 gram ethyl acrylates, 12.25 gram vinylbenzene, 3.00 gram Vinylstyrenes (activity is 55%), 0.27 gram lauroyl peroxide and 6.63 gram SPAN80 (sorbitan monooleate) are mixed, make oil phase.354.51 gram water, 3.58 gram Calcium dichloride dihydrates and 1.86 gram Potassium Persulphates mixing are obtained water.Mix under the oil phase in the speed of three paddle agitators, water is added dropwise to 300 rev/mins.After the water adding finishes, continue to mix down, in emulsion, add 4.48 and restrain ceramic microspheres and the spongy iron powder of 14.38 grams.The HIPE remix that obtains 2 minutes is to guarantee uniformity.Emulsion is added thermal glass (PYREX *) container, at saran parcel (Saran Wrap TM) covering under, in 65 ℃ of baking ovens, one night of polymerization.The foam materials that extruding is synthesized is until not containing inner water.Clean three times with the 2-propyl alcohol, water cleans three times then, cleans with the 2-propyl alcohol more at last.Foam materials after extruding is cleaned dries into foam articles then up to not containing the 2-propyl alcohol.
Embodiment 5-and comparative example A
Prepare two kinds of foam materialss and come their flame retardant properties of comparison.
Comparative example A-no filler
By 8.67 gram ethyl acrylates, 1.90 gram vinylbenzene, 2.98 gram Vinylstyrenes (activity is 55%), 1.45 are restrained SPAN TM80 (sorbitan monooleates) and 0.06 gram lauroyl peroxide mix, and make oil phase.132.96 gram water, 1.34 gram Calcium dichloride dihydrates and 0.64 gram Potassium Persulphate mixing are obtained water.Under three paddle agitators stir with 300 rev/mins speed, water is added dropwise to oil phase.After all waters add, with emulsion remix 5 minutes to guarantee uniformity.Emulsion is added thermal glass (PYREX *) container, at saran parcel (Saran Wrap TM) covering under, in 65 ℃ of baking ovens, polymerization 16 hours.Clean the foam materials that makes for three times with the 2-propyl alcohol, water cleans three times then, uses 2-propyl alcohol (IPA) to clean at last again.The foam materials that finally obtains of extruding, until removing most IPA, in 80 ℃ vacuum drying oven dry several hours then.Foam materials was at room temperature placed two days.
Embodiment 6-contains the HIPE of filling aluminium hydrate
By 4.65 gram ethyl acrylates, 1.02 gram vinylbenzene, 1.60 gram Vinylstyrenes (activity is 55%), 1.45 gram SPAN80 (sorbitan monooleate) and 0.06 gram lauroyl peroxide are mixed, make oil phase.In this oil phase, sneak into 6.30 gram aluminium hydroxides.132.96 gram water, 1.34 gram Calcium dichloride dihydrates and 0.64 gram Potassium Persulphate mixing are obtained water.In the polypropylene beaker, mix down in the speed of three paddle agitators with 300 rev/mins, water is added dropwise to oil phase.After all waters add, continue emulsion remix 5 minutes to guarantee uniformity.Pour emulsion into thermal glass (PYREX *) container, at saran parcel (Saran Wrap TM) covering under, polymerization is 16 hours in 65 ℃ of baking ovens.The foam materials that extruding obtains is until removing most water.Resemble as described in the ginseng comparative example A, foam materials is cleaned and drying, obtain foam materials.
The flame retardant properties experiment
The foam materials sample of comparative example A and embodiment 5 is cut into the batten of 8 cm long, 1.5 centimetres of wide, about 5 mm thick.The vertical batten of installing clamps in the bottom, protrudes upward 7 centimetres.Light the top of foam materials with match.The record observations is as follows, checking Al (OH) 3Influence to flame retardant properties.
The blank foam materials sample of Comparative Examples B-
Foam materials is easy to be lighted, and at 17 seconds whole 7 centimetres of samples of internal combustion, almost all burnouts in about 35 seconds.
Embodiment 6-ATH filled and process material
Foam materials is difficult to light.In case light, flame in 1 minute 16 seconds from putting out, 2 centimetres of the foam materials sample top of only burning.
Embodiment 8-and Comparative Examples C
Prepare two kinds of hipe foam materials, and estimate their sound absorbing capabilities.
The non-filled and process material of Comparative Examples C-
By 17.90 gram ethyl acrylates, 12.25 gram vinylbenzene, 3.00 gram Vinylstyrenes (activity is 55%), 0.27 gram lauroyl peroxide and 6.63 gram SPAN80 (sorbitan monooleate) are mixed, make oil phase.354.51 gram water, 3.58 gram Calcium dichloride dihydrates and 1.86 gram Potassium Persulphates mixing are obtained water.Mix under the oil phase in the speed of three paddle agitators, water is added dropwise to 300 rev/mins.The HIPE remix that obtains 2 minutes is to guarantee uniformity.Emulsion is added thermal glass (PYREX *) dish, at saran parcel (Saran Wrap TM) covering under, in 65 ℃ of baking ovens, one night of polymerization.The foam materials that extruding is synthesized is until not containing inner water.Clean foam materials three times with the 2-propyl alcohol, water cleans three times then, cleans with the 2-propyl alcohol more at last.Foam materials after extruding is cleaned dries the formation foam materials then until removing most of 2-propyl alcohol.
Embodiment 9-stratiform filled and process material
Prepare two kinds of HIPE, layering, polymerization then.The making of bottom is similar to Comparative Examples C, but after emulsion forms, adds the spongy iron powder of 28.76 gram ANCOR B levels.Bottom HIPE places on thermal glass (PYREX) dish.On bottom, place one deck nonwoven polypropylene thin slice.As embodiment 3, prepare second kind of HIPE.With careful the placing on the nonwoven polypropylene that covers bottom of second kind of HIPE, whole composition one night of polymerization in 65 ℃ of baking ovens.The final foam materials of careful extruding to remove phase in the water-based, cleans three times in the 2-propyl alcohol, and water cleans three times then, cleans with the 2-propyl alcohol more at last.Foam materials after extruding is cleaned is dried to the laminate structure foam materials then until removing the 2-propyl alcohol.
Come the acoustic attenuation performance of test comparison example B and embodiment 6 prepared foam materialss with a kind of laboratory acoustic attenuation equipment.Equipment is mainly by sound source room, reception chamber, and between sound source room and the reception chamber, the stationary installation of test sample is formed.It is three inches aperture that a diameter is arranged on the stationary installation.The sound source room is equipped with loud speaker and microphone.Reception chamber is equipped with microphone to write down the intensity of sound wave in the reception chamber.The sound source room produces noise.Having sample to stop up aperture and do not having sample to stop up under the aperture both of these case, the microphone of reception chamber is collected the intensity of acoustic wave spectrum.Acoustic attenuation is defined as:
10 log (I o/ I) I wherein oBe the intensity of acoustic wave spectrum that is write down when not having sample to stop up aperture, I is the intensity of acoustic wave spectrum that is write down when having sample to stop up aperture.Fig. 1 is the acoustic attenuation spectrogram of foam materials sample, illustrates with the contrast foam materials to compare, and the acoustic attenuation performance of stratiform foamy structure improves.

Claims (42)

1.一种高内相乳液，它含有稳定乳液的表面活性剂，一种或多种不可溶填料，体积分数至少为70％的非连续内相，体积分数小于30％的连续外相，连续外相含有一种或多种可聚合乙烯基单体。1. A high internal phase emulsion comprising an emulsion-stabilizing surfactant, one or more insoluble fillers, a discontinuous internal phase with a volume fraction of at least 70%, a continuous external phase with a volume fraction of less than 30%, and a continuous external phase Contains one or more polymerizable vinyl monomers. 2.权利要求1的高内相乳液，其中所述乳液为油包水乳液。2. The high internal phase emulsion of claim 1, wherein said emulsion is a water-in-oil emulsion. 3.权利要求1的高内相乳液，其中，至少有一种不可溶填料的密度小于1g/cc。3. The high internal phase emulsion of claim 1, wherein at least one of the insoluble fillers has a density of less than 1 g/cc. 4.权利要求1的高内相乳液，其中，至少有一种不可溶填料的密度大于1g/cc。4. The high internal phase emulsion of claim 1, wherein at least one of the insoluble fillers has a density greater than 1 g/cc. 5.权利要求2的高内相乳液，其中，表面活性剂是山梨糖醇酯，甘油酯，聚甘油的部分脂肪酸酯；带有可聚合乙烯基基团的表面活性剂；在聚合条件下能够发生接枝反应的表面活性剂；或者聚(氧化丁烯/氧化乙烯)硫酸盐表面活性剂。5. the high internal phase emulsion of claim 2, wherein, surfactant is sorbitol ester, glyceride, the partial fatty acid ester of polyglycerol; Have the surfactant of polymerizable vinyl group; Under polymerization condition A surfactant capable of grafting; or a poly(butylene oxide/ethylene oxide) sulfate surfactant. 6.权利要求1的高内相乳液，其中，至少有一种不可溶填料是阻燃填料，红外线吸收填料，和/或铁磁性材料。6. The high internal phase emulsion of claim 1, wherein at least one of the insoluble fillers is a flame retardant filler, an infrared absorbing filler, and/or a ferromagnetic material. 7.权利要求6的高内相乳液，其中，阻燃填料是三水合氧化铝，或含有磷、锑、硼、铋或卤素的化合物；红外线吸收填料是碳黑，铁磁性材料是铁或镍。7. The high internal phase emulsion of claim 6, wherein the flame retardant filler is alumina trihydrate, or a compound containing phosphorus, antimony, boron, bismuth or halogen; the infrared absorbing filler is carbon black, and the ferromagnetic material is iron or nickel . 8.权利要求1的高内相乳液，其中，至少有一种不可溶填料是金属氧化物，金属氢氧化物，金属碳酸盐，金属氮化物，金属碳化物，金属硼化物，金属粉末，中空陶瓷微球或中空玻璃微球。8. The high internal phase emulsion of claim 1, wherein at least one insoluble filler is metal oxide, metal hydroxide, metal carbonate, metal nitride, metal carbide, metal boride, metal powder, hollow Ceramic microspheres or hollow glass microspheres. 9.权利要求8的高内相乳液，其中，金属氧化物是氧化钙、氧化镁、氧化锆、氧化钛、氧化锰、氧化铁或氧化铝；金属氢氧化物是氢氧化铝、氢氧化镁、氢氧化钙、氢氧化锆、氢氧化锰或氢氧化铁；金属碳酸盐是碳酸钙、碳酸镁、碳酸锰、碳酸铁或碳酸锆；金属氮化物是氮化铝、氮化硅或氮化铁；金属碳化物是碳化硅、碳化锰、碳化铁；金属硼化物是硼化铁、硼化铝、硼化锰；金属粉末是铁粉。9. The high internal phase emulsion of claim 8, wherein the metal oxide is calcium oxide, magnesium oxide, zirconium oxide, titanium oxide, manganese oxide, iron oxide or aluminum oxide; metal hydroxide is aluminum hydroxide, magnesium hydroxide , calcium hydroxide, zirconium hydroxide, manganese hydroxide or iron hydroxide; the metal carbonate is calcium carbonate, magnesium carbonate, manganese carbonate, iron carbonate or zirconium carbonate; the metal nitride is aluminum nitride, silicon nitride or nitrogen Iron carbide; metal carbides are silicon carbide, manganese carbide, iron carbide; metal borides are iron boride, aluminum boride, manganese boride; metal powder is iron powder. 10.权利要求1的高内相乳液，其中，至少有一种不可溶填料是粘土矿物系的天然形成物或合成物。10. The high internal phase emulsion of claim 1, wherein at least one insoluble filler is a clay mineral-based natural or synthetic compound. 11.权利要求1的高内相乳液，其中，至少有一种不可溶填料是滑石粉、云母、蒙脱土、锂蒙脱土、高岭土、地开石、珍珠陶土、埃洛石、皂石、绿脱石、贝得石、铬岭石、锌皂石、麦羟硅钠石、铜皂石、水羟硅钠石、蛭石、蛇纹石、绿泥石、坡缕石、绿泥间滑石、滑间皂石、海泡石、水铝英石、伊毛缟石或者它们的混合物。11. The high internal phase emulsion of claim 1, wherein at least one insoluble filler is talcum powder, mica, montmorillonite, hectorite, kaolin, dickite, nacrite, halloysite, saponite, Nontronite, beidellite, chrome lingite, sauconite, magadiite, copper saponite, hydroxonite, vermiculite, serpentine, chlorite, palygorskite, chlorite Talc, talcite, sepiolite, allophane, imogolite or mixtures thereof. 12.权利要求1的高内相乳液，其中，至少有一种不可溶填料是多层无机材料。12. The high internal phase emulsion of claim 1, wherein at least one insoluble filler is a multilayered inorganic material. 13.权利要求12的高内相乳液，其中，多层无机材料是粘土矿物、伊利石类矿物、呈层状的双金属氢氧化物、混合金属氢氧化物、氯化物或氧化物。13. The high internal phase emulsion of claim 12, wherein the multilayer inorganic material is clay mineral, illite-type mineral, double metal hydroxide, mixed metal hydroxide, chloride or oxide in layered form. 14.权利要求13的高内相乳液，其中，伊利石矿物是三八面体伊利石；混合金属氢氧化物是Mg6Al3.4(OH)18.8(CO3)1.7H2O；氯化物是ReCl3或FeOCl；氧化物是H2Si2O5、V5O13、HTiNbO5、Cr0.5V0.5S2、W0.2V2.8O7、Cr3O8、MoO3(OH)2、VOPO4-2H2O、CaPO4CH3-H2O、MnHAsO4-H2O、Ag6Mo10O33；或者它们的混合物。14. The high internal phase emulsion of claim 13, wherein the illite mineral is trioctahedral illite; the mixed metal hydroxide is Mg 6 Al 3.4 (OH) 18.8 (CO 3 ) 1.7 H 2 O; the chloride is ReCl 3 or FeOCl; oxides are H 2 Si 2 O 5 , V 5 O 13 , HTiNbO 5 , Cr 0.5 V 0.5 S 2 , W 0.2 V 2.8 O 7 , Cr 3 O 8 , MoO 3 (OH) 2 , VOPO 4 -2H 2 O, CaPO 4 CH 3 -H 2 O, MnHAsO 4 -H 2 O, Ag 6 Mo 10 O 33 ; or mixtures thereof. 15.权利要求1的高内相乳液，其中，以连续相为基准，不可溶填料用量的体积分数大于100％。15. The high internal phase emulsion of claim 1, wherein, based on the continuous phase, the volume fraction of the insoluble filler is greater than 100%. 16.权利要求1的高内相乳液，其中，以连续相为基准，不可溶填料用量的体积分数为1-100％。16. The high internal phase emulsion according to claim 1, wherein, based on the continuous phase, the volume fraction of the insoluble filler is 1-100%. 17.权利要求1的高内相乳液，其中，以连续相为基准，不可溶填料用量的体积分数为1-10％。17. The high internal phase emulsion of claim 1, wherein, based on the continuous phase, the volume fraction of the insoluble filler is 1-10%. 18.包含不同的多层的多层高内相乳液，其中，一层或多层含有一种或多种不可溶填料。18. A multilayer high internal phase emulsion comprising different layers, wherein one or more layers contain one or more insoluble fillers. 19.权利要求18的乳液，其中，每层填料的使用量与其它每层填料的使用量，可以相同或不同。19. The emulsion of claim 18, wherein the amount of filler used in each layer can be the same or different from the amount used in each other layer of filler. 20.一种方法，它包括：制备包含至少一种可聚合乙烯基单体的连续相；制备内相；向连续相中或者内相中或者两相中加入不可溶填料；然后在足以形成乳液的条件下将内相和连续相混合。20. A method comprising: preparing a continuous phase comprising at least one polymerizable vinyl monomer; preparing an internal phase; adding an insoluble filler to either the continuous phase or the internal phase or both phases; The internal phase and the continuous phase are mixed under the conditions. 21.权利要求20的方法，其中，乳液是油包水乳液，包含油性连续相和水性内相。21. The method of claim 20, wherein the emulsion is a water-in-oil emulsion comprising an oily continuous phase and an aqueous internal phase. 22.一种方法，它包括：制备包含至少一种可聚合乙烯基单体的连续相；制备内相；然后在足以形成乳液的条件下将内相和连续相混合，同时加入一种或多种不可溶填料。22. A method comprising: preparing a continuous phase comprising at least one polymerizable vinyl monomer; preparing an internal phase; then mixing the internal phase and the continuous phase under conditions sufficient to form an emulsion while simultaneously adding one or more an insoluble filler. 23.权利要求22的方法，其中，乳液是油包水乳液，包含油性连续相和水性内相。23. The method of claim 22, wherein the emulsion is a water-in-oil emulsion comprising an oily continuous phase and an aqueous internal phase. 24.一种方法，它包括：制备包含至少一种可聚合乙烯基单体的连续相；制备内相；在足以形成乳液的条件下将内相和连续相混合，然后向乳液中加入一种或多种不可溶填料。24. A method comprising: preparing a continuous phase comprising at least one polymerizable vinyl monomer; preparing an internal phase; mixing the internal phase and the continuous phase under conditions sufficient to form an emulsion, and then adding a or a variety of insoluble fillers. 25.权利要求24的方法，其中，乳液是油包水乳液，包含油性连续相和水性内相。25. The method of claim 24, wherein the emulsion is a water-in-oil emulsion comprising an oily continuous phase and an aqueous internal phase. 26.一种方法，它包括：制备至少两种高内相乳液，至少其中一种含有一种或多种不可溶填料；然后将一种乳液在另一种乳液上面沉积，由此生产出层状高内相乳液。26. A method comprising: preparing at least two high internal phase emulsions, at least one of which contains one or more insoluble fillers; and depositing one emulsion on top of the other, thereby producing a layer high internal phase emulsion. 27.多孔聚合物材料，通过使权利要求1的高内相乳液聚合而制得。27. A porous polymeric material obtained by polymerizing the high internal phase emulsion of claim 1. 28.多孔聚合物材料，通过使权利要求2的高内相乳液聚合而制得。28. A porous polymeric material obtained by polymerizing the high internal phase emulsion of claim 2. 29.多孔聚合物材料，通过使权利要求18的高内相乳液聚合而制得。29. Porous polymeric material obtained by polymerizing the high internal phase emulsion of claim 18. 30.开孔型多孔聚合物材料，含有与其聚合物骨架相结合的不可溶填料。30. An open-cell porous polymeric material containing insoluble fillers associated with its polymeric backbone. 31.包含权利要求28的多孔聚合物材料的制品。31. An article comprising the porous polymeric material of claim 28. 32.包含权利要求29的多孔聚合物材料的制品。32. An article comprising the porous polymeric material of claim 29. 33.一种多层聚合物泡沫材料，包含至少两层，每层或者在物理上或者在结构上与其相邻层有所不同，并且至少一层由高内相乳液形成，所述高内相乳液含有一种或多种不可溶填料、体积分数至少为70％的内相和含有一种或多种可聚合乙烯基单体的体积分数小于30％的外相。33. A multilayer polymeric foam comprising at least two layers, each layer being either physically or structurally distinct from its adjacent layers, and at least one layer being formed from a high internal phase emulsion, the high internal phase The emulsion comprises one or more insoluble fillers, an inner phase comprising at least 70% by volume and an outer phase comprising less than 30% by volume of one or more polymerizable vinyl monomers. 34.包含多层聚合物泡沫材料的制品，至少有两层，每层或者在物理上或者在结构上与相邻层有所不同，并且至少一层由高内相乳液形成，所述高内相乳液含有一种或多种不可溶填料、体积分数至少为70％的内相和含有一种或多种可聚合乙烯基单体的体积分数小于30％的外相。34. An article comprising multiple layers of polymeric foam having at least two layers, each layer being either physically or structurally distinct from adjacent layers, and at least one layer being formed from a high internal phase emulsion, said high internal phase The phase emulsion comprises one or more insoluble fillers, an inner phase having a volume fraction of at least 70%, and an outer phase comprising less than 30% by volume of one or more polymerizable vinyl monomers. 35.权利要求34的制品，其形式为隔声材料。35. The article of claim 34 in the form of an acoustic insulating material. 36.权利要求1的高内相乳液，其中，一种或多种不可溶填料是水可溶胀或者油可溶胀的。36. The high internal phase emulsion of claim 1, wherein the one or more insoluble fillers are water-swellable or oil-swellable. 37.权利要求1的高内相乳液，其中，至少一种不可溶填料含有可聚合乙烯基官能团，在乳液中能与单体共聚。37. The high internal phase emulsion of claim 1, wherein at least one insoluble filler contains polymerizable vinyl functional groups that are copolymerizable with monomers in the emulsion. 38.权利要求1的高内相乳液，其中，以外相体积为基准，不可溶填料的用量从小于3％到50％。38. The high internal phase emulsion of claim 1, wherein the amount of insoluble filler is from less than 3% to 50% based on the volume of the external phase. 39.多孔聚合物材料，通过使权利要求1的高内相乳液在与非HIPE材料接触的情况下聚合而制得，使得非HIPE材料在聚合过程中附于多孔聚合物材料上。39. A porous polymeric material prepared by polymerizing the high internal phase emulsion of claim 1 in contact with a non-HIPE material such that the non-HIPE material attaches to the porous polymeric material during polymerization. 40.权利要求39的聚合物材料，其中，非HIPE材料是多孔聚合物材料、无纺材料或者遇到乳液外相能够溶胀的聚合物薄膜。40. The polymeric material of claim 39, wherein the non-HIPE material is a porous polymeric material, a nonwoven material, or a polymeric film capable of swelling upon encountering the external phase of the emulsion. 41.权利要求40的聚合物材料，其中，多孔聚合物材料是聚氨酯泡沫材料，无纺材料是聚丙烯无纺织物，当使用苯乙烯在油相中的油包水乳液时，遇到乳液外相能够溶胀的聚合物薄膜是聚苯乙烯。41. The polymeric material of claim 40, wherein the porous polymeric material is a polyurethane foam, the nonwoven material is a polypropylene nonwoven fabric, and when using a water-in-oil emulsion of styrene in the oil phase, the outer phase of the emulsion is encountered A polymer film capable of swelling is polystyrene. 42.多层聚合物泡沫材料，包含至少两层，每层或者在物理上或者在结构上与其相邻层有所不同，并且至少一层由高内相乳液制得，所述高内相乳液含有一种或多种不可溶填料、体积分数至少为70％的内相和含有一种或多种可聚合乙烯基单体的体积分数少于30％的外相，并且在一层或多层之间或/和一个表面或两个表面上有非HIPE材料。42. A multilayer polymeric foam comprising at least two layers, each layer being either physically or structurally different from its adjacent layers, and at least one layer being made from a high internal phase emulsion, said high internal phase emulsion An inner phase comprising at least 70% by volume of one or more insoluble fillers and an outer phase comprising less than 30% by volume of one or more polymerizable vinyl monomers, and between one or more layers Occasionally and/or non-HIPE material on one or both surfaces.
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