CA2296347A1 - 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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- CA2296347A1 CA2296347A1 CA002296347A CA2296347A CA2296347A1 CA 2296347 A1 CA2296347 A1 CA 2296347A1 CA 002296347 A CA002296347 A CA 002296347A CA 2296347 A CA2296347 A CA 2296347A CA 2296347 A1 CA2296347 A1 CA 2296347A1
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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
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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
-
- 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
Abstract
A high internal phase emulsion having an emulsion stabilizing surfactant, one or more insoluble fillers, at least 70 volume percent of a discontinous internal phase; and less than 30 volume percent of a continuous external phase containing one or more vinyl polymerizable monomer(s). Polymerizing the waterin-oil high internal phase emulsion produces an open-cell porous polymeric material having insoluble fillers incorporated into its polymeric backbone.
Description
HIGH INTERNAL PHASE EMULSIONS AND POROUS MATERIALS PREi:'ARED
THEREFROM
This invention relates to high internal phase emulsions and porous polymeric materials produced therefrom.
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; ~:~nd 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). '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 hIIPEs being reported as high as 98 ~~ercer~t G':lca~os.~~:
phr,~:~.
An early application of high internal phase emulsions (HIPEs} is for a suspension medium for sol~ds. See for example U. ~ P:~t~:,~nt 3,9'1 4,~ 16. ~1-he '~;ic~;~ ;static viscosity of HIPEs prevents particles from settling. n a similar appiicatian, HIi'Es 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 ernulsion prevents the solid particles from settling, yet the decreased viscosity while under shear allows the emulsion to be pumped efficiently through a pipeline. l he ability to suspend paiiiculates m HiPts is :;arroewhat surprising given the fact that particulates such as n~;~r~trncr~:ll~nite cia~-s ;,a.n be ~,ed to break emulsions, see for examplk~ K.J. Lissant, Emu'~icn -°W i=~:u.isiov i'ech~~oo~ S~ ;__;-'-; "Making and Breaking Emulsions"; pages 122-123 (ltil4~.
The use of high internal phase ernuisions (HiPEs) in forwang parous polymeric materials is also well known and is described, for example, in U.S. faatents 5,2~i 0, i X74 5,200,433; 4,536,521; 4,7813,225; 5,147,345; 5,331,015; 5,260,345; 5,2bi3,224 and 5,318,554. In the described HIPEs, the external oil phase typically comr~rises a vinyl polymerizable monomer, such as 2-ethylhexyl acryiare and styrene, ana a cross-linking monomer such as divinylbenzene. The iniernai aqueous phase typically comprises water, a radical initiator (if not in the oil phase) and an electrolyte. To form a stable emulsion, a surfactant is added to the a:l phase prior to errmusificui:~n. :~c~mrnc~r;y u~ecl Er~;u.'s~cn stabilizing surfactants inc;ude, for example, nonioi~,ic surfactants, such as sorbiv,:un esters (for example, sorbitan monooleate and sorbitan moncla~rabe;. :~:l~e~ knovrrl s~.a~i~~ivir~y surfactants include certain; polyglycerol aliphatic est~:rs sLCh as l-n~se df:S~i lu8(.l ;rv U.S.
Patent No. 5,500,4~~1.
WO 99/09070 PCTltJS98/16596 Porous polymeric materials prepared cram HIPEs have been shown useful in many applications. For instance, U.S. Patents 5,260,345; 5,268,224;
~~,~~31,015 teach the use of HIPE foams as absorbent materials for use in diaper-type articles. Are attractive feature of HIPE foams for such an application is that their high void volume and low density provides a high capacity for liquid. For example, a 98 weight percent internal phase HIPE
can produce a foam with approximately a 49 gram capacity for water per grain of roam (g/g capacity), assuming a polymer density of 1 g/cc. The g/g capacity of a foam c;an be increased either by increasing the void volurr~r~ ~f :;:E f::am ~r b;~
d:::;rE.~.si;tg i~v..~ Density.
Historically, one was changed by o;~3nging tfu:~ flt'.r~~., _;~;at i ;
increasing fif ~s u.~i_' ~: plume decreased the density. Void volume i;s typically :~'cr.a~-:-r ~ j tt~r~
inte~naph,sw rain of the emulsion, the higher the internal pha~~a ratio tho :~i~n~:r am ti~naa ~~cyid vu!~n:e of tln::~ foam.
One is limited, however, as to how high of an ;~.te: n,::~: f~'r~:=a cap ~w ac«i~.-:er~~ ,a;-.r' polymerized into a foam. :Another method o'ir:craa~iry uc~id ~ro!~:arro; i~3 a f-II!'~:~ 'ra:m is by including an inert oil in the external p,nase. After p;:~ey:rr~r:ri~.,ation, i!tc, pal i~~;rr~~~:v~~:a, leaving voids in the polymer w:~llc :and struts. Co!fe.~ior~ aiv:. ~:~~~:I ~~ø u. ~
'n~.t ;~~, ;;~ ;ewer, must be considered after the ;~oI~A:~neriz~~,i<~n rar~c~;;..s. i=_., : r- :: , n:vrc, ;r c r e:.s;~ i; n: ~.a: i~; volume tends to produce thinner' struts in the foam ~,~rl!s _'~~; ,:;~yr ~,a~~l~~ a i,r ~ ~ :~,~;
structure. Therefore, it ~~ro~ld be ad~.i,~ntageouicr ~:t: aoie to i~~r:=~:~e ':r~~ ~~:.'~~ :~~:.,_acity of a HIPE foam without increasing the internal phase :;t .; c;, ~;.~i:~a ~~rj:': r:
i~~°~;.
Another application for HIPE foams is as thermal and acoustlca! insulating materials. U.S. Patent 5,6,3,291, for instance, teaches the use of Hnf= foams in ti~ese applications. For thermal insulating applications, it is irr~portani to nmder the transport of thermal energy through the insulating material. Une pam or thermal e. ~srgy transport through material is radiative, in which the intrareu wave is cra~nsrrnti:ed tr~rougn the insulation directly to the other sine. 'i'he thermal insulating aLility at a rilFt roam wouic~ be enhanced if the radiative component could be diminisned, or eicminateo by the presence r~r an infrared blocking material. TI'sarm.il anri acoustical irnE~iatin;; .:.,.yiicati~ns ~F~ri:;~~al;~a r~;:,~~;;,-, flame retardant materials. ~ iotvev°er9 ~d;PE fioams ar:~ cc!;,1:.;~~t;uie beoau~~; tr:at ~~r~ :~~ganic.
It would be desirable to provide a pro~ess whereby the rs/g capacity of a H1PE
foam can be increased without increasing the internal phase ratio or uCinq inert oils. Further, it would be desirable to provide water-in-oil high iratQrnai phase Pmulsions and porous polymeric materials produced therefrom which incorr~or~ts ~nfr2red ra~iia$ion blocking materials for enhancing the thermal insulating ability of the foam r~roduct.
tr ~~~cu.s~d also be desirable to provide HIPS foams which incorporatF rlame retardant materia~s WO 99/09070 !'C x',~U~~E/16596 In a first aspect, this invention is a Ir~~;!~ ir~t~rnal p:'~ase ernufsion i~raving an emulsion stabilizing surfactant, an insoluble filler, at least 70 volu,. a percent of an internal phase and less than 30 volume percent of an exterv~al ~;h:~se containing anp r~r more vinyl polymerizable monomers.
In a second aspect, the present invention is a process for prE:parina the high internal phase emulsion of the first aspect which comprises preparing an ex°teE"nal phase, preparyng an internal phase, adding an insoluble filer to one or both phases, and then mixing the internal phase with the external phase under conditions sufficient to form an emulsion.
In a third aspect, 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 tie nil phase under ~onditinns sufficient to form an emulsion and then adding an insoiubee filler to mP emun~on.
In a fourth aspect, this invention is are ope;~-cell porous paiymeric material prepared by polymerizing the high internal phase E~, ul~:,i; ~, -,f tr;a fr~;t :;;,;~;:,c;t.
In a fifth aspect, this invention is do c~p~;r~-cei~ pormas poiy~~eri;;
:~raaterial having insoluble fillers incorporated into its poiyrne~ is bacKbone.
We have di scovered that high inte;r::~ p" ~~r. ~mcyi;ans ;'J!!P~.~ ~~n not only be prepared with inscluble fillers. brrt c~.n ;al~r.~ ba w~al.,~~~~lriz:~;r i~
vc ~~arr~s r:r~;~4yninvr~g insoluble filler in the polymeric backbone. While H'~~~a witn sela3ctecir,soiubita IiilE;rS have been known, we have been able tc prepare i~iFEs ~itr~ a b~°oad~r sp,~crtw~r~ of ir~soiuble fillers including montmorilionite clays which are reporiec: c~3 kareah I-ilf'f_s (sre ~~eference above) and to incorporate them into a HIPE with ~,vr~;l ~c;iyrrc~ri~~oia nor.~o~"r-.~.rr.
Furthermore, the fact that the HIPE can be aolyrns~i~~~info ; ,n ~~: ran ~c~llr~cf f,~am and still retain the insoluble fil!E~ i~; surprising. In orc~ev':r f,:,w, ;, ~;,:~.;.r;!'= ~! :v~,~.,~;:,..;-, °~~nE, must break to a certain extt~nj: CEU!'ing p01;'i'Ti':;TiZ~l~l::! l : ':r ';: ( _,3": ~~~, ;1~ "~. ~,,~ _ ,~nll WaIIS, but not break so muc~ as to result i~~ ;:i;ase Ji:ria,i;a:~t~!~.
'~,,.~;:,:ut,i, G:;Zrr~~::.:~~~~t=.:, .;~; noted above, have been kromn to break ernui:~iuns. '~ J~~:,r:~f~:,yc:, r~;a°;
cs.:ri=~::,~ a '.;il';:=,:r:w:~;:ining an insoluble particulate to an c:pen~~co!J~d str~ict;.;ue c~i:_,~':
r_~~;,.~iis:;,~ i, ur,-;~c~ ~=n~<;~.ii~n is surprising.
The HIPEs of the present invention are useful in preparing polyrner~c foam materials with either increased or decreased densities without increasing or decreasing the internal phase ratio of the HIPS.
~~3 WO 99/09070 ~r~'1,~~.T;;93/16596 The polymeric foams of the present invention are ais o useful as thermal insulating materials and sound abatement materials, as \N2~I as for fluid ~asorptic~rr.
Figurel is a comparison of sound atter;uation spectra foc the foams prepared in Example 6 and Comparative Example B.
The high internal phase emulsion (HI~'E1 of the ~rPspnt invenkion has greater than about 70 volume percent, more preferably, gre~aer than abc~c~t 90 volume percent and, most preferably, greater than about 95 volume percE-nY of an internal phase;
!e°~s ahan about 30 volume percent, more preferably, less than abo~rr !0 volume rsr;~er~and r~°,~ast preferably, less than about 5 volume percent of an external phasr~: sand ~:rt insclubie filler.
i0 Preferably, 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 hase can be made b the resent inve:7tion. The :x~~~°o~ t,~~tacJ
5~~~~~i~° = more P Y p =' c~:wp.,..-, ~r3c.~ ~~r vinyl polymerizable morom~:r. Preferably, the exf:--~ .v pi,:~s :r'~ ~
c~;r~t~..i;w~ ,.; rr~:;~;-linking monomer. The internc.l ~~:;~.se comprises vrater. T~at,,v:c.~i~r ~, ,~~,:,~«~~
t;c,;-~' ~'. ~ :a;i't.a; '~,;kiator is added to the aqueous w>~msc:. If an oil-soluble in~':i;:v'~,r ~a .:-n,; ~-~~=r;, ;f i;; ;,.;,;;,~c; ~, r'1e oil phase. AdditionaEly, tf,~e HIFE comprises a surra~:u;~t ,s.;~~~ ;~'~
~r.r:~.lu'~f;; f''<er.
Vinyl polymerizable rnc~norr~ers whici ~ can ~e empioyeci ir; kne practice of the present invention are any polymerizabfe monomers anav~;sc~ an ethylenic unsat~r~~.;~tn. In general, the HIPEs are advantageously preparea rrLrr: ei~raer Uf c~~tr~ (;) at redst ;one monomer that tends to impart glass-like properties (glassy n-oonornersl ro the resuning porous polymeric material ar;d (ii) at least one rnoncrner irvat tends to ire part rUrr~er-like properties (rubbery monomers) to the resulting porous poyrr;er~c marer~ats.
The glassy monomers are, for the purposes of 'the present invention, defined as monomeric materials which would produce homcpolymers having a glass transition temperature above about 40°C. Preferred glassy m~nom~rs include metha,,r~ta:G-cased monomers, such as, for example, methyl methacrvlate, and styrene-based monomers, such as, for example, various monovinylidene aromatics :;~a;;>> :ros st~/re ~c o-r~nE;tlr;l:a,s~~;~e, chkoromethylstyrene, vinylethylbenzene and vinyl tc~:i~. ~:rr. O,~fwre ivr:;c~r; :~f' r',;~~sy monomers include styrene, o-methylstyrene, and chloromethylstvrene 'the mast ~ra.,ferred glassy monomer is styrene.
The rubbery monomers are, for the _~ wr~~~°,=~c ref tho f~~c~:.E~nt ire' a~r;f~.°~f~, defined as monomeric materials which would pr oduce hcr~~cy :'~~~; n Y., ya , .y:.~ ~
~.: t ~r ~''~;on temperature of about 40°C or lower. Preferred r..a;:: ., ~ ;:~. ;r :;r,;~. ~, ~-v-~l; ,i;: ~ :k ! ;~~?rs of WO 99/09070 l~w/Lrc.9$/16596 ethylenically unsaturated acids ("acrylate esters" or ".~;~e:ha~n~/late" ra~t~
r:~), ';r.r~i~ ~s 2-ethylhexyl acrylate, butyl acrylate, hexyl acrylate, ~c,!y1 a~nethacr,rtcrte, lar~ryl ~7rezi7acrylate, isodecyl methacrylate and mixtures thereof; vinyl ~~i pn~-::i~:° c~rac~
s..:yr~iic try::ro~~:rhons such as butadiene; isoprene; and combinations of these cornc:r~omers. More preferrerl rubbery monomers include butyl acrylate, 2-ethythexyl acrylate, lacrtadiene~ isoprene an~~
combinations of these comonomers. The most prEferrEe" ~ubbey~ man~~:rrc~; is ~-aanylhexyl acrylate.
Preferably, the HiPE emulsion includes at peat one gias.sy monomer and at least one rubbery monomer. Without being bound ~5~y tc~E~ory, it is ;oEaiie~r~~~ tnat the rubbery monomer provides the foams with flexibility and is used in an amaura sufricient to allow compression, bending and twisting during processing, packaging, shipping, :storing and use of articles containing such foams. It is believed the glassy monorr;er provines the foams with structural integrity and is used in an amount sufficient to r~immme ~:rte inrio2rr~ ~at foam tearing or fragmenting encountered when such foams are sul.~jectea to Broth d~!narnic and static forces. The ratio ef it~e g:e.s:;y rrror:~~rrn~~ t~ t'. u:';,t;;.:~A;
r,nJncrr.: ~ c~,E,u-i;. ~i~~ :tinges from 1:25 to 1.5:1, more praferaloly from; 1:9 t~.; 1.~:
White the amount of the vinyl poivrrra~~eiza.hl~~ monomers rarmt ad~iantageously employed depends on a variety of factors, such as 'cl:e sc~ecitii r;r~~~ovr'ers, ir7 general, the vinyl polymerizable monomer is used in an amount ct ~ron~ 5c5 to ~lG~) weig;at ro:~ra°ent, preferably from 80 to 95 weight percem, and most t:referabiy ~irorw? N5 t~~
;~;i jury=rt percent, based on the total ex:ernal phase.
Insoluble filters which can be emrl~~~~y-d i~ F '.i ~: . _. :.;ic; -~ of i'°r _~ ~vrr:~. ~~~~°r invention for preparing the HIPE include both inert and rea.cv'i~=t: fil'~:-~~. ",-lr.-amrt f~' r_:~.; .,r.: r'~ose which do not become copolymerized with the monomers r..~,~~~' ~;, crv~c:~r..ra.s~~~!~ of t~~'.r'!~ fcaam5. The reactive fillers are those which become chemically att:ac; ~F;;: t.~ ti,:a n~oit~ca': r ::I-~,~ins during polymerization. Inert fillers for use in this inver;tvcn i~~vl~Acic: ton :;
a;~w:pB~ :,:: w~ ~°~ Ma;.cK;
graphite; metal hydroxides, such as aluminum hydr>xide, rn:agnAsi~~~r~
hvdr~axic;~~ calcium hydroxide, zirconium hydroxide, manganese hydro;~lcxe :are:! ;rnr:
;.~~c:r~,;.ice; ~;v~t.:~l ;::owders such as iron powdE,; and I-~~~(iovr cE~~rGr~u~~ rvierti:-N~o-:::~: ~~;
:~~~_.:. ; ~:e ~.~1 u-a~~;; :. ':i!~~rs is cross-linked polymeriL ur~aterials vYitlr acy!at~e '.:~~r~..v..~~ :
::.~:~:cua.:;_'.:v::
As used herein, the term "insolu!al~" ~wP~~,r , 4 ~~~;-, a :, tirr~,~, ,~r,~o;,r,t ~f the material introduced into the system does not dissa:'v~=~ :n '=Ftp~e'r ~"-,~-~= KtE?rt~:j! c:i: r~oa;;e or the internal aqueous phase of the HIPS. Prefer«hlv 't ~~~~:,! 'a'r ~::~f:rr~=r~~
~r~ :~7 ~;r, ~r='a!y at least ..r.
WO 99/09070 :P~:;'~ '~~~~'8/16596 80 percent and most preferably 100 percent of the filler ic~ading doe, s ncyq ciisColve in either the external oil phase or the internal aqueous phase.
Hollow fillers, such as ceramic or g'~~ss nar«sp'~=arES ran f: a c.3~s.~ ~:n the practice of the present invention. Hollow fillers care be prepares' ia~.~ing a :~l,~rasity below i g/cc. By incorporating such Pow density fillers into a. HIPr foam, ore me.~° d~~:~=~aGe the density (while simultaneously increasing the g/a ca_a-city] ~ritP~c~~ ~s~~r~a :~~~ W t'~.~ internal phase ratio of the HIPE precursor and without usia:~r e~~P oils in 'f;F~;xtc;,°na! ~iE phase.
Examples of hollow fillers include the various PO r<fci!o~~; .~ly-e~~es auai~;~a;e: tror7 The PQ
Corporation (Valley Forge, PA) which range in dens~;iy~ c:~c~~n~r tc~ :x.1;:3 g/~:c.
Infrared blocking tillers such as car crln y;l«~;1, area :tr-~,~nive pc~..,;Jen .can be used in the practice of the present invention and can rscluce the mrar«d radiation transmitted through the final HIPE foam, increasing the etiectiv;!~~:rnai ir~,:,u~~:irir~ value of the foam.
Organic and inorga;rir con'~pUe_lnc~~ c;m?,~i~ai;yr r;iu~:;t:~or~~~;, r>;°;'~-~;;~~r, boron, bismuth and halogens are !cnovrn as fillers fav i;n::b~.;.:csiry vlar~re retardar~cy (see, for example, G.T. Gmitter, et al. Flexible Polyurethane Foams. in i='i«sti~~ f=r~arr~~=:
F~a>~ l; FrFsc~h, K.C., Saunders, J.H., Eds.; Marcei L7ekker, ins.: i~iew 'c:rk, t ;/2: pa~~e ~ 42) ak-~c~ c:an kae used as fillers in the practice of the present invention. tUther incarqanic compounds useivi as fire retardants in this invention include alumina trihydr«te (also known as A°r~~l, aiurnir~um hydroxide, AI(OH)3) (see, for example, Hawley's Condensed Ci-aernical dictionary, 12'"
Edition, 1993, Rict;ard ~. t..~.vis, ~c.~., p. ~-;~, a; ; ;~~ ,. : ~ ~ , -:i ~: .,~~,; r..:,~ ;aE~ ', f,ese inorganic compo"r.ds can I~c~ u~~;c: .Icn:,~ Jr :~t 1:;:11;.,"a;°~r~
~t~;rl; ~::I~r:r r.r;~3n.c ~; imrganic fire retardants.
Ferromagnetic materials, such say i~!}s, an~i r~i~~'~:.~, ;;,_ r Ge ;nr;~rr~;~3,vtad to render magnetic properties to the fnal foam. A 7r; .T. rw~ ~ a ~ ;;;c~ v:~
~;.r , i~:: ~ v~erials can be useful, for example, in thermal and acous~ic,~l ;~~:J~ct'c;rr c;n ;vezta~
;,ei;;,n~~. w, ~c~~am, for example, can be prepared with the ferrumagne,ic rru~e;«i~ uis(w~eci iE; a ~hi.~ Icyer on one side of a foam. The ferromagnetic materials c;ar~ e;rl~er ;~r~ rr;r~gawti-cc ~:as~e c~~ arter introduction into the foam. The foam cGn'~positi0,~ car'. rir~i~ ~;; Eas~~u atrache~ to a ceiling containing ferromagnetic materials without nails ~;;; !~,:, a t,°.r;;,,.x~,,;;P~~ r,E., .gyp , .,~.,,.~onetic materials in the foarn Amy ,~~:rrain ~iruoag;;~;tizf;i a;w,:a :n:~ r~~,";, t,~;;.: ,~r:::i~: ;:,, ;,~.,; :,~ted to magnetized materials.
-r WO 99/09070 ~'CT!C X598/16596 Water and/or oil swellable fillers, sucr; as cross-lin~r:~:~ ~,oclir,n ~;
polyacrylate can also be used in the practice of the present invereti~~rl r.s k~;~g ;~"~ ,~
I-I ~;~E oGn he made, preferably as long as the HIPE with the filler can he ~~lyrr~e~~i_eri intc;~
;z t;;am.
Metal oxide and metal carbonate cars also iae'r: cased as fillers in tire practice of the present invention. Such materials include calci;_;m ~xi~e, magrtE=Ji~:r;~
Oxide, zirconium oxide, titanium oxide, manganese oxide, iron oxide, aluminum oxide, calcium carbonate, magnesium carbonate, manganese carbonate, iron ~a.rbonate and zirconium carbonate.
Metal nitride, metal carbide and meta= ~~oricis rvafi~a;~;~;~;s sl~~;~ as alur7linum nitride, silicon nitride, iron nitride, silicon carbide, manganese carbide, i°;~n cark,i~~o, iron boride, aluminum boride, manganese boride or other materials Lrsed in the pro~~~=Iration of ceramic materials may also be used in the practice or the present invention for preparing the HIPE. Mixtures of one or more such materials may else ~e employed.
Naturally occurring members of the cEay a-ninera! fa:~ily or syn~heki~:
members of the clay mineral family can also be employed ,.r~ t;ll,~;~ ;t, ;~,o I:,,:,:::i~ :: ~;~.~ :.,~. ,~...i,,;~,nt invention. Such filler s include talc, mica and ~: d~ia';:.~r:~' ~~r :
~n!.;~:~r~ : r : n;: ~:, ~;y r~z;nr;; al family such as montmorillonite, nertorite, k~o!inite, dichie., r,-ic~~~r;, i;~:~:3,~:.. E. . :c.;r,~ko, nJntronite, beidellite, volhonskoite, sauconite, magadiite, medrr~ur~kit~. r;~;s~vaito, s~~.~rnic:~a9it~
serpentines, chlorites, palygorskite, kulkeite, aliettite, sepi.~~l;t~~, aiicpl~an~ aria ir~~aqoiite can also be employed. Mixtures of one or more such nnafier ia:~ Irtay ~:;~~; r~s erni:~loytao.
Other fillers which can be emplo~~s d ~°: ~.~:;- P~r:.cti°;<: a' chi ~;,~n~-~e,~~ n ,vrantion include multilayered inorganic materials (corwencmrmi~y reter~-ec: rc~ as ~rlaflUt~II~YS' ). The multilayered inorganic material woicn may be useu ire c«e ~raciic~ of rile irwaraiars can be any swellable layered inorganic material. 'T'ypluaivy, ~~le Idys~r~u n~c,rgan~~ ir7aiorial is comprised of layers having W o opposing fac~.~ wrn,l r:~a~; '.~E; rr:;ai;v.
~,~ {iz~r ,~r :;i; a"~;3i~i curved.
Such materials are described in ~.S. Patent 4,88ii, ~=~.::~
Representative examples of such sw~liai~le fayerEd inorganic: r~r~~.teriais include members of the clay mineral family such as v'rlose e»souit~~c~
nravs~.~t~siy, i~%her representative examplQS of such swellable layerr~~~ '~a~ ,,;: ,~ir r~~<<.
a:;;~: ~~ ~~~a i;; 'iitl; minerals such as ledikite; the layered double hydroxides ar n i>:f:;i ~-~~:'~~f ~~~~ar:~xi~:~-;a :,~ ~cln =I;:
MggAlg.4(OH)18.8(C03)1.;~'H2a (sEe W. T. Raichl_:, .1:_:~%.--~~:_~:, '~ ' ;~~):~'~l, 5~'~W vl~.ach have positively charged layers and a;<<rhangeat;le ur~i7n;~ an "~~;j :'I-~':v~~l;-::v, ~ ~ ~ ,.-:r~~; ;;A~!;r;i;l;;s such as ReCl3 and FeOCI, chalcagenides such as T~;~;,, ~,'; _~y~ a;~~' "J~ "<~:
r°y:a;;~!< ~_~~c;h as Ni(CN)2; and oxides such as H2Si205, V5013~ ~fTi slLl~;~;, ':r~
t;'s~~,:~~:a.., °.~Vf,.n'v,'~~: x:307, WO 99/09070 P'C'T/US9~8/16596 Cr3Og, Mo03(OH)2, VOP04-2H20, CaP04CH~-hipt~, t,~ifir~As~:.~H--HL t;' ~nrl AtlgMo10033~
Mixtures of one or more such materials may also oe E~rn~iayed.
Depending on the application o'i ahe final foam, the preferred insoluble filters are carbon black, graphite, metal powders, metal hydroxides, hollovv fibers such :as glass or ceramic microspheres, natural or synthetic clays, nanofillz:rs, p(~4~rd~;rs ~y m(~tals, aia.me retardant fillers such as those containing phosphorus. ar;tirTronu. bo=gin.
bvsmutll .and/or halogens, copofymerizable fillers such as acrylate fcanctionalized nolyrrieric palh~ders, oil swellable fillers such as lightly cross-linked polyi'neric po~:vdei~s, and a~aueous swellable materials such as cross-finked sodium polyacrylate. flr more ;a:
~;i~er~°e:a ;n~;oi~ibl~~ fillers are carbon black, graphite pc.~w~~i~r, rnei::>l p~md(;IS, !r;=a~.G
'ryc~r~:;cid~,~: , '~.~::'(;;u ::~.=uv~.;:~w microspheres, nar!ofilf~~rs, arod pc~u~d°er'~~ u= metals. --y~.(, :~:~
_,__ pry fcr.'e;~ 'v:..cv!i:~?r ~~ilE!~s are Carbon black, graphite, r~Siw~r!'7inl:!11 zi'i~-.jrLi'OXlae, r~7S(~':'.~:51i:::_ :~'yC:CVs_:~::~, ~yil",'~_ . .~~'e~-lIC
microspheres, Clayton A.:'r? Montu:orillo~~ite silic~~:. ~r~.y, ex,e~ ii~~!-:
~~~.:"r'~~~:.
Insoluble fillers can modify many cr;_:r~.:~~tr~isti~.~ ~'~,' a 'al~~'~ fo ;i-.o ~n.;'Liding density, modules, tensile Strength, thermal conduct-~rita~. t,~arT~e r~
iarctaio;y, anc~ magnetic property. Typically, more than one property is modified unor~ inc:~rpea~:':F~'-!~ of ~a ~ hole insoluble filler. For example, incorporation or a iarg4~ JGI!ai~ne UT
s°~~va ~a~hP(~er'e~~ili simultaneously increase the density of a foam and increase its terrorr!agnetic property.
Often, large amounts of insoiupie tiller will tend ro aecrease r; ie Tensiir str(o Igr;-. (,~ :fee foam.
This tensile strengih loss is suspecteo i:o arise wont wraic ~drievic~n be;:,~~~~:,~er, the polymer and the filler. A redur~;o;1 in tensile ;~t~.-:ngth can i;f- .~: v.e ~ ~ -: i ~ .!~'~,~ ~: t;~~ - "',-~,.,~, chemically or rnecha.i"v:;S.ii~ hin.l.:i inic the lu!~rr~~r~~~ n.,tv~ .~~, t;
~;,:,r~,~;~ ~ , ~ ~";~~ify the surfaces of the filler v~rith .~ ~,L~upii~~g agent, mart' a;~ ~,~r;~~~'~~
_~~r~ ~~, r:~' y~~,~,, v -, ~i ~: -,,;. Known COUpling agents l3UiU;~~:: QfC:dn~,li;i!iCaiQilF:i 8liiv;(in c;Ci :9~~l,t,l'W
: ~,;;( ;s ~~ ',;:~Z~,ai yt'y;,::;~;-~UXy silane and'y methacryloxypropyi t~irriEt~aoxy Si:ai:e, ar:c~'ita.l:ii::r;
:~~~r~~:;~t_._~in~;~ ~w.:~;,. _:s _:,-:.': :Sopropyl triisostearoyl tita,~aAS arld ISUpI'Oj;.~yi :i lfT;i;thu_:I~ i t!Ei?'~~!;E .
rx9l: i'.Tl. (t ~~:' -y ,;. ~ : .'.l:i'~i ~ct!
coupling agent could ~a especaliy~ efie;:~ive ;:~5 tire ;i',:;v:-:uc:-;~
gi~~:;r~;: ;-..~;L ,~~.rt :: ~ a',,-, .
polymerization react:ca. a:~,cthE~ exarT:ple i, :: u.:~ ~ : ... : ~!'.~:.in !i~ : ;. ~'; _ ~.v~~iich will copolymerize uvith the "~e~~c~~;re:;~ d;~:iog ;~oiy~r;:::.._:_n: . ~,~~r:;
f,.n~:, ~.; ;; ..;.~i(~at;i;; ~:1 the organic monomer;.ai'i :wvo;.~le strr.ng:y ~,our;~ : ".~I.r~r:.c~~;,~ ~~
:..,.,.., ,.,..~ p.~:y:.z~:,:v~~d through the swollEn vi;,;>i ;;y~.;'.i:;l(.
The amount of insol~.it~le filler most a~lman~~ag~c~i.s~in ~n~p'n~~e'i d~~~=~rds on a number of factors including the desired application of the ~!~rF or ~~~~15~r~~Arized RIPE foam and the type of filler used. As previously describAd, otrpr rtmre than aye nroiaer~y of a foam WO 99109070 ~aC~'!f»9~116596 is modified when a filler is incorporated. Thus, the =~mor~~,t of ~~iller e:r,pio;:~s~~:! r~FU~be adjusted to achieve the desired property. For examcle; if or a deeair~,C a ::.rer~sc ~'oUm with ferromagnetic properties they could prepare a HIDE ~n~it!~ 'args a-~~o~wnt: of iron powder.
However, if a person wants ferromagnetic properties but does not de~ira 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 req~sirF
a. ,~i~,~~~r~r concentration than others to reach a desired effect. For ~xample, carbon blank can significantly effect the th~rrnal ccncucivity u~ a iuar : _:r ~.
°.zy.r,' o' '. .~: E',~:.:~ i i ' :~~sight percent while approxin~~:~aE~,~ 30 ~rreg,i2 E;erceot c~;~ .~.. J; ~~ .'. '~ 1 :r.~. :_ ~ ;~ ~:.;,: ~;; is :w~::;~; a significant increase in i:arrnve retard::r::;y. Thewf~:~:, i',;~~ a,~~n ~at7or: ~rn~ l~y~; ~:;i~:i:used plays a role in determi;;ing optic,~,~i ;iffier concs~n,~ati,:;~s. I~:
;~~nEYal, .u:c ~~s;~iuk.~~c: i:lc~r can be employed in an amour~.t up tc a: rd ~~x~;eading iG;'.~ wf:.rr;.: p-:=n~~.ni .~eiati: ~ v~.: oii~ :;c~.tinuous phase. A broader domain o! insGluble fillers cap-: f~e: er,:p~y ;>,.1 :ap to :
i~;? rc i .. ~.°s:,~ percent relative to the continuous phase; an even broads! dcmai:, ~~:f i.~~;~.r~:r:v,=
'.pier:: ..gin own employed up to 50 vo;~.~~:-c; pe;rc~o relativs to the ;, .nin;. ~ ~,.~ ,;;i;
.~:; .; : ~.i'~ ~ ~ r ,;~~e~ ~ ~:_~main of insoluble fillers can be E:rr~f;lcy~;c'. a~~ W 1~ ~~oar"~; Em~ri~::,.~
!.:a..r~ . . . =-~~:'.i:u>:; ~:. phase;
and the broadest domain ~:, i;i:;<.'ur la fii!ew:; ~c~t~, i:i: A,a,;i:z,a ' , ~ ,1_,~~.:.; :c: ,-.,lt relative to the continuous pha~;~:'.
Cross-linking monomers which carr i:~e ~~rryic~yec~ in Tree ~:r-a~:iice o~
;:he present invention for preparing the HIPS rnciude any multiiuncnur,~;i ~_,n~wturateu rnr~, r:.~rr.ers capable of reacting with the vinyl monomers. Multifunctic~na ur~s;~iurazea c;rcss-rirri~mrng monomers include, for example, mvinyibenzene, ethylene giyccn dm~e!nacry~~ae, ~-uuxy~ero~
dimethacrylate, trimethyioipropane iriacryfate and anyi rnranacry~ate. v~tri~e xne amount of cross-linking monomers most advanlageousry emp~oyeo Jr:~.~er~ras on a vr;~riety ci tactors, such as the desired polymer modulus, in general, tt~e cro::S-Iln~clnf~
rranr~amer is a, sed in an amount of from 0 to 5C v~~:ic~trt pE;rcent, p:~eferGl:'.~r i~~:r:- ;. .. , ~
~5 n~~:i~~~v: :u::u:~:,-,:..; :.:n~.i most preferably from 7 to 1 t~ weight percent, bas~~cJ ~:.~:n il~~: _~: _v;
~~a:~.a. .~ .:! ,~: ~:~ ~~:
Radical initiators which can be empicvVed ~n the nractrce of thr~ present invention for preparing the HIPS include the water-solubn in~tiwi~ars s~rrh a~, fop e~cample, potassium or sodium persulfate and various rednx svst~r~ns ~ncr as ammonium .r~ersulfate together with sodium metabisulfite and oil-soluble init;ator s; s!arh a.s ~cr exarxrplrr:, azobisisobutyronitrile (AIBN), benzoyl peroxide., rnet~vl pth~~i ~etc,~~F
ner~Xlne at~ri dl-2-ethyl-hexyl-peroxydicarbonate arod lauroyl peroxide. The iniøiarrr can be av~ed t7 tk-sn «Ypeous phase or to the oil phase, oepending on whether the initiator ~s water-.snicrhle or oil-soluble.
_cf_ *rB
WO 99/09070 PCTr'U~~98/16596 The initiator should be present in an effective an-sos.mt r~~ ,~,:oiym~~;rize fih ~ rronornars..
Typically, the initiator can be present in an amount of frofr~ 0.0':5 to ~~
weight pc;rcent, preferably from 0.1 to 10 weight percent and most preferably frsjrrc 0. t to 5 ~4ei:;~l~t percent, based on total monomers.
The aqueous phase can include a wager-s~~1;~:ale :wiar;lrc: i~,>~:e for r:cciir?g the surfactant in forming a stable emulsion, controlling porosity of the foam andlor ernhancing the hydrophilicity of the resulting polymeric foam material 'f 6ef~ «s a re si~:aa.l ccrnpc;nent of the foam material. Water-soluble electrolytes which can ba ~»~op~oy~so irr t~cc:
~,~r«ctim. of the present invention include inorganic salts (monovafE nt, anraient, o~ivaient ;~
rvixrr~res thereof), for example, alkali metal salts, alkaline earth metal salts anG he«vy metal salts s!~ch as halides, sulfates, carbonates, phosphates and mixtcares ~k~,~.r~nf Sur~h electro~,~tr~s include, for example, sodium c:hiuri:le, sadiurr~ sulfate, ~ct~~:;~:urr. ~,~:~r~~.
~~r.,~,,~,;~m~c : ~i ~~:~~~, lithium chloride, magnesium ct~loriae, c;~lwum c7ioui~:!~~, rr~G~!ee~_::!°:~~
sur~a~::, ~;:u,-:~.u~:;~n ~:iu:ide and mixtures thereof. Moryo~~ or divalsnt salts with m~cncvGie: ~. ::.-ic.~.;, :;u~:; a~~ itu~-W.J, are preferred. While the a3naunt of e6ectrru~fes .lvosi ~:~v-. ,i .~:~:rc:r~.y E~r~,:, ~~:~: i E~~~~ s-i~s on a variety of factors, such ;~~s it~~s sl:-u~ific o.omp~~~c.c~~,', ~' '~::
~~:;x:~,re;x pvr~;~ i~~ c,f 1~~; ~~,~o: and the surfactant employed, ir-: g;zr~~ra!, :he elecirnlyt,~ ca ~ ~:~~ f:r~~ul.~: ::-a ij~, c sir?, --,;~:w ,;preferably up to 5 and most pref~:~a~oly up i~:~ about ~ ~nre;;~'~~~ ,ryri.~wi, ';a~it.._:cf ,,n ; .; ' : ._ ; .. :~:c ~s c mixture.
The aquer~us phase can additior~arly ;;ornprise a r7or~-ecectrc;ryte c:orrnponent, such as, for example, giycerm, as long as a_nIF=r= c;an sciia s~~e praparea arni pocvmenzed into a foam.
Surfactants which can be emplo;roc! ~;~ !rc: ~,.r_~ct;.:~cf thd; pse~.~,;
~,~~vention for preparing water-in-oil high internal phase emulsions inca_~de nonionic surfac'ants, such as, for example, sorbitan esters, including sorbitan monoole«fP and rorlzitan rr=on«i~.urate;
glycerol esters, such as glycerol monooleate; PEG 200 dioleate. partisl fatty acid esters of polyglycerol; cationic surfactants, such as ammonic,~m s~zsts; anr~ anionr~
suriacta.nts, such as certain organic sulfate and sulfonate compounds. ~,i;~c; s:ai:=.aiu.a:w ~;c~~~on-c~;riz.~'c:
surfactants such as those described in copendinp .~,r;cl~-,..~i~~r, ~=~rial ~'to. ~~~s,~;~, filed November 15, 1995. ~u:;~ :~ucfa!:~~~nts irn~ii.~~ra ~ ~r ~;;i~.: ~:: ;:~~.~~ i c I
.s~: :~ . a~:~~y;.~,.'~.~:.i~: ~; ~Y groups and surfactants capahi~ ~.~f ~; dergaing :~ Sraft rc ror: ;u;;:a;;u~:~= ~'.~..-ft'.ct~~cr.,; 4~t ~h,~
conditions of polymeriwiiuc-. A~so :;uitablE~ ar~~ i~~c~ o~;l;v~ ";t~;;;rr=
.u: ~~;i.'~;tc-.~ r~>r=.. ;.,;;:le) sulfate-based surfactants c~esCribecl in ccspEndir.a I? .~,,~,is~:: wx.l n ?r a:;~~.~rrc ~;s-:r:~.i ;~!(_~.
60,046,910 filed May : Ei, 1 ~9~.
..1 r;.
WO 99/09070 PC'1',~~:398/16596 The amount of surtactant used must be suwt~ that a high irvternal pr'rase emulsion will form. Generally, the amount of surfac;ani r~e~;dE~;~ varies W°ithd tic ;>~ecific surtactant and the type of formulation used. As litt~~ as about 0. i25 weight pNrnent, or less, based on continuous phase can be used. More generaii~~, as little as abort !).2~ vr~~~ight percent based on continuous phase can be used. C~ene~,al'yy r~~: x~;~ abc;~t 25 ~,,t~i~a;t percent or more, based on the continuous phase, can be used, if desired.
Methods for preparing water-in-oil emulsions are Known in the art such as, for example, in U.S. Patents 4,522,953 and 5,210,104, and t!"ese n',sthods can !ce employed in the practice of the present invention. Far example, the t~aat~r-in-oil I-~!PE
~ar be prepared in batches. In general, to form a water-in-oil HIDE in batc',~ quantities the watEar phase is gradually added to a mixture of oil phase and surractant ~Nhile the mixture is being agitated.
Agitation can be accomplished any number of ways inclurir~,r, impel°er-r;rpe ~api~.~~.~.~nn.
Alternatively, water-in-oil HIPEs can be prepared in a con,inErou.' flow r..ranner. l~~lethods for COntIntJOUS fIOW HIPS ~,~r:,~pa:r~.ti~..~.il ar'9 aI~L VI~E!~~
~~E,~:ar:~l''i'r_t~ i t'l;ilk.';! Wit:;."E'.. c :i_, '~-,v example, U.S. Patents '",Gt3;~.2.5 and 5,'s9rs,~s7.p Incorporaeion of insoluble fillers intr:, the I-!~~'=~ rare r~P ~;or~a.
;~recr' is c» after emulsification. If incorporated prior to ernulsificaticrs, the inlsUl°.r:~iP v~i!ier ~wr~ yx~ir;aiiv be added to the oil phase or aqueous phase or to boor Ui~ase~. Tfte msci~rflie iinE:r c"~:r7 ue added as a separate phase curing the emulsification prac:~s:, p~..ricunrry ;~
:~ rm ;,-~:,~..uous flow procedure. Alternatively, the filler can be rrixer.~ into _i-re er:~r~rrsion a.~iaer the errruision has been formed. The prefarrea method of incorpara,ing the firie~ aet:renas on a r7r~mber of factors including the ernuisitication procedure used and trrc rsrr~e ar7d ac ~~clcant of riiser used.
For example, an insolcl;le fili~r s~vric?-: d;m:; not ti~,;:~,yrFrc: ~r,w ;,.~-;~ , c~:v ;.,.a~;~y ur: ~ d not be optimally incorporated into iio; errr~nlsiorr b;~ :rc'ca: ~ ~ to 'w,.:
:~rfr!,~c~.rs _.n.--.,~ :; ~ ,; ,; ~,:
emulsification. Such a fiiler.>Youl;i loe iaeite~r incorpE~!aicu :~~ o tu:=
~~n-;~ 1~ ~:.. ~y~ ;i.=;~ adding it to the oil phase, adding it as a sE~c~GratE; phase, -~r :acic~ir~~r .: ::ftcn ~~:~yr-.:,:~~iz~:~:, .
Layered foam compositions can be prepared from the i-itf'E of the present invention in accordance with the rrroc~ess des,~~iher~ ;r: c;:ren~ar-:q i'ro~'i~i,~r,ai fxp:;. ration Serial No. 60/055,852 filed August 15, 199 r. I-or ~x~_'r:p~~. a ~ayerec~ :c;-;n cc°n~io~~nifln can be prepared comprising two or more layers with aiiierr.g u;r"cr:rtt:: or ry~,~::cr~,~ fl~~rs. One application where layered filled foams are useful ~~ i;r s;~.~nc;
al~~::~~~r:r=vnt. iraye:'c;o compositions with iron sponge powder in one la~~rer c.; ~d ~,r!ic~aw r. ~ -arar;, ;~~:i .v'ou;.v; ~t;res in another have demonstrated enhanced sound att~anuatiorr ~~rE:pc:,-ies over sirnilar foams WO 99/09070 lPr~ >~/~:~~9~c116596 prepared without fillers, with only the iron or only the ~~iic:i°c~;=phN!-s=.=:;, .-;r 4"iti: a he,r°iogeneous mix of iron powder and ceramic microspheres.
The following working examples are cfiven to illustrate the i~ver!tiort and should not be construed to limit its scope. Unless ouhervt~ise indca~.ecf, all party a.rrd percentages are by weight.
Example 1 - HIPE Foam with Montmorillonite Silicate Clr~a~
Clayton Ar'A l~lor~trnorill~;~nites Silicate Ltayr sr~ m~:;;
urrlc~t'I~ivtu;tt: ;:Ilii atv clay available from Southern Clay Froaucts, Inc.) was rroxi;e to d 2-v~eight percent concentration into a monomer mix cc" !prising c4. ~.nieight pE~rce-a ~-~~t'~yl~ve~:yr .- : -r;a!r~. -I.1 :,~,i.v;l.,t :,,ercent styrene, and 22 weight io=rce~t ciivi:wl":~enz:~; ~c~ fv ~ ~~~4~.:;; a' :~r:rti~ :-. .s tr-: .c:.a; ~
r i; ~;; :~f the monomer/clay mix wa~liraolved 1.1 grams SP,4NT~ 80 (sorbitan monoofeate) «nd 0.35 g SPANT"" 85 (sorbitan trioleate). A separate aqueous phase was prepared compri ,ing 114 g water, 1.1 g calcium chloride dinydrate and u.~ g pmass~mr~ pe~sulfave. Trre ay_veous phase was added dropwise to ;I~e r,.unc:~:~",~,'c!.~y;'sar«~~ar,: rr,~:: vii il~
~.o!::r:~ ~. ~~~ ' t :~:.,3 u:;ing a three-paddle mixer. A thlcl: .vrtite t~:s:~_: was p;~~~u~~c. '!-rrc:. flir'~~
~u~::::;:cayr~.~er;:~~;~.~' at 60°C
for 16 hours in a PYRE~'~'% uist; covare: Witit Jal~cit~ ~~i'u;:n ° ~~i ru.t;ir=Iftcith: (::1 i fi~c; ;.i~)wv Chemical Company). i~oa sarnp~rr was soakeu J,~r ~-~~roN~n~J u~~~.,~ ,i ~;~:~r~ i3c; c~, ,.;.~;~sed free of the internal aqueous r:"~,ase. 'Throe ;irises wera dune r :';~: ~-o,~oNcl;
;al, ;~?-~:f, r~-ryes in water, and a final rinse ag«in in ~-p;opanoJ. ~~i"t~: Sc:~T~~li: u'd8.;~
;;~.~Gi,1<:C: 'J8t'dV~':;>, ~;aper towels and allowed to d.~r at reu;o te,~;yirature. 'f!~1,: Irnl.:,. vC,c'.!v;
svaS t;~parls:2..:, ,::.i;rf:iessible and resilient.
m - HIP Foam,with Iron P~wde_r An oil pv:a;-..~e v.~a.~ e: a~ed ~;r a .,'n-.., ~: ~, - .~ ;:;y'.,'' .a;'~.,;5. . ~? 9 styrene 1.13 g divinyl~ F~ ;.: ire (;5 cer:~,~r;~: arfii:r = v ~ ~;~~ . t ,..
r r, ~ ~ .
.. , . ', : r- a. . ~. " .-,: : ~ c;: ; T .-,_ ~ eate , and 0.10 g lauroyl perrn:~a~. ~'~n ~t.;: ,~c.;;; ph2 ~, ~. E; ~ _ ;~r~~~ a.._ 4". , i;,.; ~ ;; _ , , .~ ater, 1.35 g calcium chloridE ~Jh,c"n:,~~_, ~:;,~.~ ~.v; s .a~;::i ;,. _~ .
.~;a;~,.. .~. ~ r'v'-~~.1, . y ::pared by adding the aqueous pJ~asr~ dropwrse ao tr;e ~Jl ~"ra~e ~rWr~.~~ ro.;ciry ai ;:~u~ ~riv~ ~w.~ a three-paddle mixer. The ~ IiF'>r was rnixed a~n ar~~lJ~";r;al 2 ~i,rrt~,m5 uiFr'tur!i~~~rr~ 'c; ~r,sure homogeneity. To the l'i i h' c !lu ~c;i niiCf~'G ?C~ g of .~l', :; ~~ ~ i ~' :
~ V 7 ::5; ,. ,: .;~~~ ~, av; a ~, ', ~.~,~_ ~anaes, Inc.; Valley Forge, PA) s:;::e t,:;rt;,-,~~;ng t!~:u ra..u;~u: ~ lr;: u!e; ~,-; ~;r , E .s ~~ ". ;.~.4J
polymerized at 65°C fcr ~~.;~ i;c~ura a: G - t'F,~;~ ;:.i. a:~.v~ ;a.;:
~, ~~
resulting foam was sq~.cu~;.~d ire:; fw ~~ ~ .:u;1 ....~.._ ....~.. .:.~;;:
., ,~~,~ our ;;: iu:.:. .: :; v ~, , : c.;:anol, *rB
WO 99/09070 PCTlUS98/16596 three times in water, and a final time in 2-propanol. The ~~leaned foam was s~rc ~p~zed free of alcohol and allowed to air-dry. The resulting foam ?gas ircar! raow~i~~~
incornoratc~~~i ~n its polymer matrix and was attracted to a magnet.
~ca_mple 3 - HIPE foam with Hollow Ceramic Micron heres An oil phase was prepared by mixing 17.~ :~ 2-e'hyl!~exafl a~;r~iia;f, r2.25 g styrene, 3.00 g divinylbenzene (55 percent active. 5.63 q SPP;N 80 (srrrlait~~n morooleate), and 0.27 g lauroyl peron'clo. An acr~.~eou~:, i.-.f~asF was i~r.~;-,w.r:~t~
r;y ;;~i~.-r ;~ ~C.a.r;- ;,~ ,;.eater, 3.58 g calcium chloride dih~drate, ~~n~~ 1.~~~ g ~~:~~::~ ='c.n~ ,ar~~.'f~=+-.
", ~-"~~: ~,~-,~ ~rf;pared by adding the aqueous ph~is~ _aro~,kv~sr; to th:; oil phase v~h~!a r~ixir:g at X00 h~t;;~ varith a three-paddle mixer. The HIPE was mixed an addit~onal ~ minutes after farming 2o ensure homogeneity. Into the Hlr:'E was rr~ixed 8.55 g c~f i~ui;ovn ,<~~ramic !~nic-'e~spher~as rSl_-150 Extendospheres0, The I=~ Cor,porati«r:) usi~ig "~lE: ~hwe- ~~'~;- ~ ~',,:-e;~ -,t ~.,~,,~ :-~tv. 's"he HIPE was polymerized at 55°C for ~8 hours in r. -'~':?''~; ti::,in ;:~:,~%:~~a~'. ~ai~f: ~~~r_u~a l~lrapTM.
The resulting foam w~:.s :.~~aueeze~! ~:~,:.~ o~ aq~::._:i~: -~:,~;:_ .:v~
:..~:.~~' i;~.-~;, y , :r,. ; , '~
.< , propnaol, three tlmeS :3~ '.ryd:v:E', i:.t?C~ i~ ?,!',sly il~'~Ii' . . ._ ,, J':;: .:' ~i' ' ~j,; ,, ~,~y r~ ~ sn ... _. ~.
squeezed free of alcc':o~ ~..~~~:' a:ac~w~.:ct ;~ :ir~_:.;~.
a le 4 - Foam with_I_rc_~~ Po~rrdt;r ~yr~_I~Icylyv_4~ Gf=:.>:»',!:
l~licrosQh~r_e_s An oil p'~~:~E- was r;~??a: ~c,~! ~., ,~,'.,~ ,. ._. ,. . ~~- ~~tw ; . ~ v . g , ~, ~.: '2.25 styrene, 3.00 g divinylb~r'Brae ~~5 ye!r;ertt ~ct~'~~v. " ~';' . ;-,.~r~ !
w~,.,<;,~ , ;,,,r; ~ ~~ g SPAN
80 (sorbitan monoole<a'a~ ;fin P.n~.!~o~ ~c ~h,: s~ ~.w.- : ;. ..,.. _ ....,, ~_.'. ."p.,_.c. .; "~ ~ .1 ,~,~er 3.58 g calcium chloride dihv,r~r~;~s. ar.~' ? ,af ;t ~:,~,+o,-si!c:~: ~. :s.,.,- -r~-., ~,.~;,. , _~~.~,-a , . . , . . Nas added dropwise while mer~;~r t'-, cc' ,: h~.~.n ~~ ~C~:~ ~'~'VI E~~ia'n a ai,~
a-y,r 'i;, r~!; ~ . ':7nce the aqueous phase was completely addad and wh°le ~;;:,r Air~~ti:~ti,;
~~ri;;:~~:g. ~~.~'~f; g r_~~r ~- ~~c microspheres and 14.33 c~ ircr ; aEm,~ ~~r ~;~w;, t:c ~~.a; ~ ~;::,, , ~,wc t t: -:~-~ ~, ~!~ir~r. TI-w, resulting HIPE was mixed an a.c;c''fiic:n~' ? ~.ri4e:; tc: ~n ;.a.°v ! aY: ' ;~'.
-'~~ : , - ; '~ . <:~ nut into a PYREX dish, coverE~~ wit's 8an.~~~T~" 1'.!ral:~ ~;:_! ~ ;~~ w ~' ~:i~ ~ '.
vr, -.~ :.r, ~'. ~ .... v: ' ~'S°C
overnight. The resulti . J ~.,r: m v~;u =~.:~ .:~~ .' . ~ . . , ~ _ . , _. ..
. ..,: .: , .;. a times in 2-propanol, three ti::~c;~. :r. era °.r, i_'.r ~~ -y:;;; ;;. _ ~;-:,; a .: ~ .;,. :;n. : ~ ';, .; . : ;~ueezed free of most of the 2-~:~,:~:.~~ ~;r.J ~I~~ :.- .,. '~~-~r;, cu :.-~v.
:~~.~a~,;:::~ ~:.::,;..
, m le 5 - And Comn~r~~iy~ ~.~.= ~n~'~;_~', Two HI~'!.'~.:~4n~~ ~~~~~r a ;~: spa ~: : ~. c: :.~~ ~A a.
t. _ : : ~.
,..
WO 99/09070 PCT/U~98i16596 Comt~arative Examlhe AA - Control with no Filler An oil phase was prepared by rnixin~~E.b~ ~ ?-e',;~yll~e;c;~9 r:~cryats', 1.90 g styrene, 2.98 g divinylbenzene (55 percent active), f .45 ~ SPAI°v"~~~
EC (sorbitan n~onooleate), and 0.06 g lauroyl peroxide. A water phase was pi~;;pac~;:d b~;°
nvixir~g 132.96 g water, 1.34 g calcium chl~r~id-~ dihydsate, wr d C. '~ ~, ~c,~usv:;:3~; pc;~ ,.ruy~. The aqueous phase was added dropwise to the oil phaa v~t~i~.; nixing at '3~G~
Rl~i~! ~siy~g a three-paddle mixer. The emulsion was mixed an additior~a! ;3 ;,~u:es aftsr G:IE ~~~
rh~s u~:~a.seous phase was added to ensure homogeneity. -f-he so°3~.rl~io,~ ~w~as ~;~_;
i;~".~ ~1'~I~~C niss~es, covered SaranT~~ wrap, arc: poiyr ;er izc;d ;;i a for~~a G:r ;,u~ r~, arc;"C;
;;..r ; a w~,;,;~;:;. -; he resulting foam was rinsed 3 times in 2-propa~~ov ;INt,), ;; °.r~;~a ir.
wasar, a;;cJ ;~uuv irv IPA.
The final foam was sq;~~eted ,'r;;c of rtm:;r o1 .:.u ~~~.~?. ;:rlu ti~~;r.
c:;;~;: i~~ a vacuurrr oven at 80°C for several hours. 'he ex,~,~r:~,~;fuarr', v'~~;;:; t;.;:"
;.ii~w::cc~ ~~; ,~ r=:~.~; ;~: ::f,;~rature for 2 days.
Exarryle 66 - PE i h ~_Ir~minum Tr~hv~raxi~_[=~,~AI_(f~H~3l,~ille_r An oil pnas~: was,~:ep~.~LU b,/;:::r;:::~ .,~.G~~ a ~-Lu:=yu~:~.ly a.;ry~:~ic:
~.u2 g -, ~
styrene, 1.60 g divinyive:.za~~:e ,,~Jr pEiCF;n: :C:::'Jv:" n 4;: ~'>:-,'~V
~i; (iCSfsJiiat: rfi:Jr~(:~leate), and 0.06 g lauroyl peCl.:~:~'u~. 111tU u:n t,.;: rl'iaoE: :V:a:. ,i~l.:(c:u i:.J~: 1~ ~;,.i,lllllTl~.'C1 t'~:~'.lGrr~il:Yide. An aqueous phase was ~~epa. eci ay r~ n:~;~ .g ; 3:~.::~. ~ v.;~:_e: , :._ : ~ ~
u:;:.~; v~ :,. f; ,w >>drate and 0.64 g potassium persufvata. -;-i~~e a:~uec;~s ptiu;~e v~'ua a~i~e~-, ;:;
c;N~~ist~ to i; ~;: nil phase while mixing with a three-paddle mixer at 3GG ;~1= ~:a ;: a p:riy~;r;;Ny~,~r,E
t;t~,her, r;.r-,,;c all of the aqueous phase was a=:;cled, the enwdsion wG~ r~";:eu c.i i ;zd:.l:iltlfl.~'1 3 tTIrI tLiiC;y :u it iSUrB
homogeneity. The emu'. ~.:~r. ~~~ c::, ~; ~ ~:.~'~d into I ': ~.::;: u;::~:
~:~, ,:L. ~; ~ ~::~ w::i . ~~c.~ ~~o Jl' -apT""
and placed in a forces-uir c~LCSI i:a ~.5'.. :~i: :C ::c~.lfS. : i'1:;
!v;i.:,iir:~ i~c.~;t: 1,'".:~:~;"il,r7rLSSed free of most of the aqu;:;;::; j~llia:i0. '1 i:v; iJt..ri~ i.c3:i ~lri'' ':
r~,!~", '~~; ";,~;;;(;~rt;f;;.; j;;
.: W .a U: t: "~
Comparative Example ~,., w~:f~.;;~y ~:.;. ~;;,Nar;,.~~~: ~;"~:n.
Flame Retardancyr Testing Foarn srrrwp;e;~ of 3=~;;vN~.rL-~ti',~ ~ ~=:~:a: l~i _; .~ _~ . ~.. -:ry:a: ~;
~":: ,..,~,~ i r'_,o strips 8 cm long, 1.5 cm wide; a;r c; a.-~Jro;'~. Ac'~.~ ai r,r,~: : ~.;, ; .c . _ ~
;~ . _ , , r, , . ,. , .,-~. .;_.- ~T:cr.nted vertically, clamped at .~ :~ ~ :~t':~r:~ ~,r ~~ ,x.~- o:ar~~ ..~ ~;..i Lr~ a:
:::. '' ~~~ ,_.,: J~ ~! , ._ ,.. .r/as lit with a match. Obsen ~~::~;', ~ v. ~~ :; rvc:orc~i :,~ i:a,;c ~~ ~r.:." :
;...v,:.~ ,.. fi :, ~r ; ~ w.ynt ,,.s.- . .;
effect of the AI(OH)3.
_-I,;.
Comparative Example B - Foam - Blank The foam was easily ignited and bc~~°~~ec~ c ~~ .ln t~~~ t~rtir~ 7 cm !w~ 17 seconds, with near complete incineration in about 35 second:.
m I 7 - Foam - ATH Filled Foam The foam was difficult to ignite. Onct~ ignit~~c~, -she flame self-extirgnished in 1 minute and 16 seconds having only burned the tee 2 ~:m cf tt~e foam st:-i~'~.
1 xample 8 - and Comparative Example C
Two HIPF ;ozms were n ~eQa~ed a~;~ evaluated for their soc~n~ a'~ter?uation properties.
Comparative Example C - Non-filled Foam An oil phase ~n~as prepared h~~ mixinc 1? 9p c ?-c.!!'!v!he:~0.,~i acylatc;, 12.25 g styrene, 3.00 g divinylbenzene (55 percent active), 0.27 g la uroyl peroxide and 6.63 g SPAN 80 (sorbitan mor;c~olea~:e). ~~rt A~~,~ao~rs pha~~ M!~~. r~rQp;~rar~ y~
.~ixlnct 35.51 g water, 3.58 g calcium :hlcr~r~!e dilh~yra~Q; ~nr~ 1.RF ~~ ~c~,-rs;i;arn rt;~r ;nlfate.. The t,c~°ueous phase was added dropwise while mixing the oil phase at 300 RPM with a three-paddle mixer. The resulting HIF~E was mixed an additional 2 miw.ates to insure homogeneity. The emulsion was put into ~.. PY ;E:~ tlis';, cc,s~prea with ~~ra ~T~" V'~'rao art~i p-~Ivmeriz~:~ irr a forced-air oven at 65°C ~:v/~~~r~:g'~~. T~~,c,, .~Krrj~~t~»~~;;:~.~:~~
e~~:~~° ~:~ ~u.";:~s ;e: i °:Q crf r~-~ ~o.~s phase ,..
and rinsed three times ;~ 2.~~r~pa:,cu, ~i~;r.;~~ L.V::.~J ~.n ~~l~~er ~ ;'~~
~'.l~'::~'. ~r. %..;]i:)J.~ri~,;. '! he rinsed roam was squea~~ei ir~c o~ ;f.c;:~ :~' th, ?..~:. ~:~~;c-~ ~r~r' ~
~~.~~~-" tc~ a:.;r-;a,a t~;v~
expanded foam.
m lei - Layered Fil_I_Pd Foa__m_ TWO H~I"'~:i Vi:irf:' (JI'c;rlar"i::~ 1~~~:rf_'~.'! "rd ~il'ir':
'!C?~'~"''"'r't'f~e=s.'i, j'~,: f:.,F+,r~m layer was prepared similar tw~'h~t v ~srr , ~a~ ~~'ue r-~ ~ r,_ ~~ ~. ,;. ".~_.,t .", -~~ :_ ",,y;~,~ ,r.;,,,-~e B iron . . E
sponge powder was m;,e~J °rtc the :,a ~;I;.~n :~:~:°.f~ sw, -,~
fii...._.;~~' T~~i:, !:._°~,; .-.-. !,.;~;r~; vIIPE
was placed into a PYPr". :~i'~"i. t~o; ;~~- ~.~ tt.r, t,~,.,._ ., ~.,., . ~;
~;-. -a ~ f'-w a,,-,;~ ,uf polypropylene non-woven rnaterial. A :-econd t-"°a~ ,~,,,~; ,~ r,-.;.,~r-_.' ~- ;a-~4,~ri ;e~'; '~~ ~,cample 3. The second HIPE was cGrefu!ly deposited ever" ;':~ p,a!~l:rc~py!enr~ ,-";-~_~,~~.r.,., f.~,,;,ering the bottom layer and tire carn~postion was polymerized in ~ fcrueu.-a'; ;vcr~
u; ~~;~°:
overnight. The final fc;~:~;; s,r;~cr :~; :;rw:, . _, " . ";
w:u~~, .:;:, :,."-.. ,.,: .", .. ', phase and rinsed three times ,~~.vr: ~'p.;:Nu;..;, ;...,:~.. :~rv:c..;: ;,~,:~, ...~
..~_ . ' ~.~; , ~.v;t;.: ;..~~:«nol.
*rB
WO 99/09070 YC:'I NS9t3/16596 The rinsed foam was squeezed free of 2-propanol arid allowed to dry to an expanded layered structure.
The sound attenuation was deterrr~ir~e~! fir the foams ~r~~arec' in Comparative Example B and Example 6 using a lahoratom sour~~l 2ttertaafi~or~
apparatus.
The apparatus basically caamprises a source chamtaer, a .~eceiver ;,hamhe.~, ,end ~ test sample fixture between the source and receiver charbe~~.. ~. ?-in~~h diamPtsr ~~~er:p!re was provided in the fixture. The source cham5er mas en~.aippz~ ~r~;th n~..,~A-«-~, ~r.t~ .~ ~~ir;rophone.
The receiver chamber was equipped with a rnicropt,or.e that ~ec~~r,; ; ~!~"
,n~~,-;:-; ; ~+;~;~,sity in that chamber. Noise was produced ~n yhe sourcF c'-a!~br ~ ~vd the ~.:,o,v-t intPr;;'~r spectrum collected at the microphone ire the recc~~~E:r,:.fw_mi;~e~ wife, - -' ;~~=,,r~;;~;,! ~~ ;:_,rr,~-, ~, ~ packing the aperture. The sound a~aen~;aiicrv uvas cnfn~~,ca as_ 1U log (id~j where to was the sound intensity spectrum. recordPrl with~nt a sa~~r~n in oyce ;~n.~ I was the sound intPnsityspectrr;~r~ ~eLnrd,::~W,,itt, ;3 ~a;~~n!r-. ir; ;~;.~c.. ~-~.,,~, :...;_r,.-: ~~'.=:w.~-,.:i:;~ -,~,ectra for the foam samples mere presRnt~:~~ i.~ ~igur~; , ~,.;~~ .-e;,-~~~~ :~.r ;~t--:~~.~~f ;~.;:.--~ ~.t~cnuation for the layered foam sta!~.~t:~re t~s~~r'!~c~m;,:~-,-,A' ~~ f~~; -~,
THEREFROM
This invention relates to high internal phase emulsions and porous polymeric materials produced therefrom.
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; ~:~nd 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). '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 hIIPEs being reported as high as 98 ~~ercer~t G':lca~os.~~:
phr,~:~.
An early application of high internal phase emulsions (HIPEs} is for a suspension medium for sol~ds. See for example U. ~ P:~t~:,~nt 3,9'1 4,~ 16. ~1-he '~;ic~;~ ;static viscosity of HIPEs prevents particles from settling. n a similar appiicatian, HIi'Es 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 ernulsion prevents the solid particles from settling, yet the decreased viscosity while under shear allows the emulsion to be pumped efficiently through a pipeline. l he ability to suspend paiiiculates m HiPts is :;arroewhat surprising given the fact that particulates such as n~;~r~trncr~:ll~nite cia~-s ;,a.n be ~,ed to break emulsions, see for examplk~ K.J. Lissant, Emu'~icn -°W i=~:u.isiov i'ech~~oo~ S~ ;__;-'-; "Making and Breaking Emulsions"; pages 122-123 (ltil4~.
The use of high internal phase ernuisions (HiPEs) in forwang parous polymeric materials is also well known and is described, for example, in U.S. faatents 5,2~i 0, i X74 5,200,433; 4,536,521; 4,7813,225; 5,147,345; 5,331,015; 5,260,345; 5,2bi3,224 and 5,318,554. In the described HIPEs, the external oil phase typically comr~rises a vinyl polymerizable monomer, such as 2-ethylhexyl acryiare and styrene, ana a cross-linking monomer such as divinylbenzene. The iniernai aqueous phase typically comprises water, a radical initiator (if not in the oil phase) and an electrolyte. To form a stable emulsion, a surfactant is added to the a:l phase prior to errmusificui:~n. :~c~mrnc~r;y u~ecl Er~;u.'s~cn stabilizing surfactants inc;ude, for example, nonioi~,ic surfactants, such as sorbiv,:un esters (for example, sorbitan monooleate and sorbitan moncla~rabe;. :~:l~e~ knovrrl s~.a~i~~ivir~y surfactants include certain; polyglycerol aliphatic est~:rs sLCh as l-n~se df:S~i lu8(.l ;rv U.S.
Patent No. 5,500,4~~1.
WO 99/09070 PCTltJS98/16596 Porous polymeric materials prepared cram HIPEs have been shown useful in many applications. For instance, U.S. Patents 5,260,345; 5,268,224;
~~,~~31,015 teach the use of HIPE foams as absorbent materials for use in diaper-type articles. Are attractive feature of HIPE foams for such an application is that their high void volume and low density provides a high capacity for liquid. For example, a 98 weight percent internal phase HIPE
can produce a foam with approximately a 49 gram capacity for water per grain of roam (g/g capacity), assuming a polymer density of 1 g/cc. The g/g capacity of a foam c;an be increased either by increasing the void volurr~r~ ~f :;:E f::am ~r b;~
d:::;rE.~.si;tg i~v..~ Density.
Historically, one was changed by o;~3nging tfu:~ flt'.r~~., _;~;at i ;
increasing fif ~s u.~i_' ~: plume decreased the density. Void volume i;s typically :~'cr.a~-:-r ~ j tt~r~
inte~naph,sw rain of the emulsion, the higher the internal pha~~a ratio tho :~i~n~:r am ti~naa ~~cyid vu!~n:e of tln::~ foam.
One is limited, however, as to how high of an ;~.te: n,::~: f~'r~:=a cap ~w ac«i~.-:er~~ ,a;-.r' polymerized into a foam. :Another method o'ir:craa~iry uc~id ~ro!~:arro; i~3 a f-II!'~:~ 'ra:m is by including an inert oil in the external p,nase. After p;:~ey:rr~r:ri~.,ation, i!tc, pal i~~;rr~~~:v~~:a, leaving voids in the polymer w:~llc :and struts. Co!fe.~ior~ aiv:. ~:~~~:I ~~ø u. ~
'n~.t ;~~, ;;~ ;ewer, must be considered after the ;~oI~A:~neriz~~,i<~n rar~c~;;..s. i=_., : r- :: , n:vrc, ;r c r e:.s;~ i; n: ~.a: i~; volume tends to produce thinner' struts in the foam ~,~rl!s _'~~; ,:;~yr ~,a~~l~~ a i,r ~ ~ :~,~;
structure. Therefore, it ~~ro~ld be ad~.i,~ntageouicr ~:t: aoie to i~~r:=~:~e ':r~~ ~~:.'~~ :~~:.,_acity of a HIPE foam without increasing the internal phase :;t .; c;, ~;.~i:~a ~~rj:': r:
i~~°~;.
Another application for HIPE foams is as thermal and acoustlca! insulating materials. U.S. Patent 5,6,3,291, for instance, teaches the use of Hnf= foams in ti~ese applications. For thermal insulating applications, it is irr~portani to nmder the transport of thermal energy through the insulating material. Une pam or thermal e. ~srgy transport through material is radiative, in which the intrareu wave is cra~nsrrnti:ed tr~rougn the insulation directly to the other sine. 'i'he thermal insulating aLility at a rilFt roam wouic~ be enhanced if the radiative component could be diminisned, or eicminateo by the presence r~r an infrared blocking material. TI'sarm.il anri acoustical irnE~iatin;; .:.,.yiicati~ns ~F~ri:;~~al;~a r~;:,~~;;,-, flame retardant materials. ~ iotvev°er9 ~d;PE fioams ar:~ cc!;,1:.;~~t;uie beoau~~; tr:at ~~r~ :~~ganic.
It would be desirable to provide a pro~ess whereby the rs/g capacity of a H1PE
foam can be increased without increasing the internal phase ratio or uCinq inert oils. Further, it would be desirable to provide water-in-oil high iratQrnai phase Pmulsions and porous polymeric materials produced therefrom which incorr~or~ts ~nfr2red ra~iia$ion blocking materials for enhancing the thermal insulating ability of the foam r~roduct.
tr ~~~cu.s~d also be desirable to provide HIPS foams which incorporatF rlame retardant materia~s WO 99/09070 !'C x',~U~~E/16596 In a first aspect, this invention is a Ir~~;!~ ir~t~rnal p:'~ase ernufsion i~raving an emulsion stabilizing surfactant, an insoluble filler, at least 70 volu,. a percent of an internal phase and less than 30 volume percent of an exterv~al ~;h:~se containing anp r~r more vinyl polymerizable monomers.
In a second aspect, the present invention is a process for prE:parina the high internal phase emulsion of the first aspect which comprises preparing an ex°teE"nal phase, preparyng an internal phase, adding an insoluble filer to one or both phases, and then mixing the internal phase with the external phase under conditions sufficient to form an emulsion.
In a third aspect, 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 tie nil phase under ~onditinns sufficient to form an emulsion and then adding an insoiubee filler to mP emun~on.
In a fourth aspect, this invention is are ope;~-cell porous paiymeric material prepared by polymerizing the high internal phase E~, ul~:,i; ~, -,f tr;a fr~;t :;;,;~;:,c;t.
In a fifth aspect, this invention is do c~p~;r~-cei~ pormas poiy~~eri;;
:~raaterial having insoluble fillers incorporated into its poiyrne~ is bacKbone.
We have di scovered that high inte;r::~ p" ~~r. ~mcyi;ans ;'J!!P~.~ ~~n not only be prepared with inscluble fillers. brrt c~.n ;al~r.~ ba w~al.,~~~~lriz:~;r i~
vc ~~arr~s r:r~;~4yninvr~g insoluble filler in the polymeric backbone. While H'~~~a witn sela3ctecir,soiubita IiilE;rS have been known, we have been able tc prepare i~iFEs ~itr~ a b~°oad~r sp,~crtw~r~ of ir~soiuble fillers including montmorilionite clays which are reporiec: c~3 kareah I-ilf'f_s (sre ~~eference above) and to incorporate them into a HIPE with ~,vr~;l ~c;iyrrc~ri~~oia nor.~o~"r-.~.rr.
Furthermore, the fact that the HIPE can be aolyrns~i~~~info ; ,n ~~: ran ~c~llr~cf f,~am and still retain the insoluble fil!E~ i~; surprising. In orc~ev':r f,:,w, ;, ~;,:~.;.r;!'= ~! :v~,~.,~;:,..;-, °~~nE, must break to a certain extt~nj: CEU!'ing p01;'i'Ti':;TiZ~l~l::! l : ':r ';: ( _,3": ~~~, ;1~ "~. ~,,~ _ ,~nll WaIIS, but not break so muc~ as to result i~~ ;:i;ase Ji:ria,i;a:~t~!~.
'~,,.~;:,:ut,i, G:;Zrr~~::.:~~~~t=.:, .;~; noted above, have been kromn to break ernui:~iuns. '~ J~~:,r:~f~:,yc:, r~;a°;
cs.:ri=~::,~ a '.;il';:=,:r:w:~;:ining an insoluble particulate to an c:pen~~co!J~d str~ict;.;ue c~i:_,~':
r_~~;,.~iis:;,~ i, ur,-;~c~ ~=n~<;~.ii~n is surprising.
The HIPEs of the present invention are useful in preparing polyrner~c foam materials with either increased or decreased densities without increasing or decreasing the internal phase ratio of the HIPS.
~~3 WO 99/09070 ~r~'1,~~.T;;93/16596 The polymeric foams of the present invention are ais o useful as thermal insulating materials and sound abatement materials, as \N2~I as for fluid ~asorptic~rr.
Figurel is a comparison of sound atter;uation spectra foc the foams prepared in Example 6 and Comparative Example B.
The high internal phase emulsion (HI~'E1 of the ~rPspnt invenkion has greater than about 70 volume percent, more preferably, gre~aer than abc~c~t 90 volume percent and, most preferably, greater than about 95 volume percE-nY of an internal phase;
!e°~s ahan about 30 volume percent, more preferably, less than abo~rr !0 volume rsr;~er~and r~°,~ast preferably, less than about 5 volume percent of an external phasr~: sand ~:rt insclubie filler.
i0 Preferably, 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 hase can be made b the resent inve:7tion. The :x~~~°o~ t,~~tacJ
5~~~~~i~° = more P Y p =' c~:wp.,..-, ~r3c.~ ~~r vinyl polymerizable morom~:r. Preferably, the exf:--~ .v pi,:~s :r'~ ~
c~;r~t~..i;w~ ,.; rr~:;~;-linking monomer. The internc.l ~~:;~.se comprises vrater. T~at,,v:c.~i~r ~, ,~~,:,~«~~
t;c,;-~' ~'. ~ :a;i't.a; '~,;kiator is added to the aqueous w>~msc:. If an oil-soluble in~':i;:v'~,r ~a .:-n,; ~-~~=r;, ;f i;; ;,.;,;;,~c; ~, r'1e oil phase. AdditionaEly, tf,~e HIFE comprises a surra~:u;~t ,s.;~~~ ;~'~
~r.r:~.lu'~f;; f''<er.
Vinyl polymerizable rnc~norr~ers whici ~ can ~e empioyeci ir; kne practice of the present invention are any polymerizabfe monomers anav~;sc~ an ethylenic unsat~r~~.;~tn. In general, the HIPEs are advantageously preparea rrLrr: ei~raer Uf c~~tr~ (;) at redst ;one monomer that tends to impart glass-like properties (glassy n-oonornersl ro the resuning porous polymeric material ar;d (ii) at least one rnoncrner irvat tends to ire part rUrr~er-like properties (rubbery monomers) to the resulting porous poyrr;er~c marer~ats.
The glassy monomers are, for the purposes of 'the present invention, defined as monomeric materials which would produce homcpolymers having a glass transition temperature above about 40°C. Preferred glassy m~nom~rs include metha,,r~ta:G-cased monomers, such as, for example, methyl methacrvlate, and styrene-based monomers, such as, for example, various monovinylidene aromatics :;~a;;>> :ros st~/re ~c o-r~nE;tlr;l:a,s~~;~e, chkoromethylstyrene, vinylethylbenzene and vinyl tc~:i~. ~:rr. O,~fwre ivr:;c~r; :~f' r',;~~sy monomers include styrene, o-methylstyrene, and chloromethylstvrene 'the mast ~ra.,ferred glassy monomer is styrene.
The rubbery monomers are, for the _~ wr~~~°,=~c ref tho f~~c~:.E~nt ire' a~r;f~.°~f~, defined as monomeric materials which would pr oduce hcr~~cy :'~~~; n Y., ya , .y:.~ ~
~.: t ~r ~''~;on temperature of about 40°C or lower. Preferred r..a;:: ., ~ ;:~. ;r :;r,;~. ~, ~-v-~l; ,i;: ~ :k ! ;~~?rs of WO 99/09070 l~w/Lrc.9$/16596 ethylenically unsaturated acids ("acrylate esters" or ".~;~e:ha~n~/late" ra~t~
r:~), ';r.r~i~ ~s 2-ethylhexyl acrylate, butyl acrylate, hexyl acrylate, ~c,!y1 a~nethacr,rtcrte, lar~ryl ~7rezi7acrylate, isodecyl methacrylate and mixtures thereof; vinyl ~~i pn~-::i~:° c~rac~
s..:yr~iic try::ro~~:rhons such as butadiene; isoprene; and combinations of these cornc:r~omers. More preferrerl rubbery monomers include butyl acrylate, 2-ethythexyl acrylate, lacrtadiene~ isoprene an~~
combinations of these comonomers. The most prEferrEe" ~ubbey~ man~~:rrc~; is ~-aanylhexyl acrylate.
Preferably, the HiPE emulsion includes at peat one gias.sy monomer and at least one rubbery monomer. Without being bound ~5~y tc~E~ory, it is ;oEaiie~r~~~ tnat the rubbery monomer provides the foams with flexibility and is used in an amaura sufricient to allow compression, bending and twisting during processing, packaging, shipping, :storing and use of articles containing such foams. It is believed the glassy monorr;er provines the foams with structural integrity and is used in an amount sufficient to r~immme ~:rte inrio2rr~ ~at foam tearing or fragmenting encountered when such foams are sul.~jectea to Broth d~!narnic and static forces. The ratio ef it~e g:e.s:;y rrror:~~rrn~~ t~ t'. u:';,t;;.:~A;
r,nJncrr.: ~ c~,E,u-i;. ~i~~ :tinges from 1:25 to 1.5:1, more praferaloly from; 1:9 t~.; 1.~:
White the amount of the vinyl poivrrra~~eiza.hl~~ monomers rarmt ad~iantageously employed depends on a variety of factors, such as 'cl:e sc~ecitii r;r~~~ovr'ers, ir7 general, the vinyl polymerizable monomer is used in an amount ct ~ron~ 5c5 to ~lG~) weig;at ro:~ra°ent, preferably from 80 to 95 weight percem, and most t:referabiy ~irorw? N5 t~~
;~;i jury=rt percent, based on the total ex:ernal phase.
Insoluble filters which can be emrl~~~~y-d i~ F '.i ~: . _. :.;ic; -~ of i'°r _~ ~vrr:~. ~~~~°r invention for preparing the HIPE include both inert and rea.cv'i~=t: fil'~:-~~. ",-lr.-amrt f~' r_:~.; .,r.: r'~ose which do not become copolymerized with the monomers r..~,~~~' ~;, crv~c:~r..ra.s~~~!~ of t~~'.r'!~ fcaam5. The reactive fillers are those which become chemically att:ac; ~F;;: t.~ ti,:a n~oit~ca': r ::I-~,~ins during polymerization. Inert fillers for use in this inver;tvcn i~~vl~Acic: ton :;
a;~w:pB~ :,:: w~ ~°~ Ma;.cK;
graphite; metal hydroxides, such as aluminum hydr>xide, rn:agnAsi~~~r~
hvdr~axic;~~ calcium hydroxide, zirconium hydroxide, manganese hydro;~lcxe :are:! ;rnr:
;.~~c:r~,;.ice; ~;v~t.:~l ;::owders such as iron powdE,; and I-~~~(iovr cE~~rGr~u~~ rvierti:-N~o-:::~: ~~;
:~~~_.:. ; ~:e ~.~1 u-a~~;; :. ':i!~~rs is cross-linked polymeriL ur~aterials vYitlr acy!at~e '.:~~r~..v..~~ :
::.~:~:cua.:;_'.:v::
As used herein, the term "insolu!al~" ~wP~~,r , 4 ~~~;-, a :, tirr~,~, ,~r,~o;,r,t ~f the material introduced into the system does not dissa:'v~=~ :n '=Ftp~e'r ~"-,~-~= KtE?rt~:j! c:i: r~oa;;e or the internal aqueous phase of the HIPS. Prefer«hlv 't ~~~~:,! 'a'r ~::~f:rr~=r~~
~r~ :~7 ~;r, ~r='a!y at least ..r.
WO 99/09070 :P~:;'~ '~~~~'8/16596 80 percent and most preferably 100 percent of the filler ic~ading doe, s ncyq ciisColve in either the external oil phase or the internal aqueous phase.
Hollow fillers, such as ceramic or g'~~ss nar«sp'~=arES ran f: a c.3~s.~ ~:n the practice of the present invention. Hollow fillers care be prepares' ia~.~ing a :~l,~rasity below i g/cc. By incorporating such Pow density fillers into a. HIPr foam, ore me.~° d~~:~=~aGe the density (while simultaneously increasing the g/a ca_a-city] ~ritP~c~~ ~s~~r~a :~~~ W t'~.~ internal phase ratio of the HIPE precursor and without usia:~r e~~P oils in 'f;F~;xtc;,°na! ~iE phase.
Examples of hollow fillers include the various PO r<fci!o~~; .~ly-e~~es auai~;~a;e: tror7 The PQ
Corporation (Valley Forge, PA) which range in dens~;iy~ c:~c~~n~r tc~ :x.1;:3 g/~:c.
Infrared blocking tillers such as car crln y;l«~;1, area :tr-~,~nive pc~..,;Jen .can be used in the practice of the present invention and can rscluce the mrar«d radiation transmitted through the final HIPE foam, increasing the etiectiv;!~~:rnai ir~,:,u~~:irir~ value of the foam.
Organic and inorga;rir con'~pUe_lnc~~ c;m?,~i~ai;yr r;iu~:;t:~or~~~;, r>;°;'~-~;;~~r, boron, bismuth and halogens are !cnovrn as fillers fav i;n::b~.;.:csiry vlar~re retardar~cy (see, for example, G.T. Gmitter, et al. Flexible Polyurethane Foams. in i='i«sti~~ f=r~arr~~=:
F~a>~ l; FrFsc~h, K.C., Saunders, J.H., Eds.; Marcei L7ekker, ins.: i~iew 'c:rk, t ;/2: pa~~e ~ 42) ak-~c~ c:an kae used as fillers in the practice of the present invention. tUther incarqanic compounds useivi as fire retardants in this invention include alumina trihydr«te (also known as A°r~~l, aiurnir~um hydroxide, AI(OH)3) (see, for example, Hawley's Condensed Ci-aernical dictionary, 12'"
Edition, 1993, Rict;ard ~. t..~.vis, ~c.~., p. ~-;~, a; ; ;~~ ,. : ~ ~ , -:i ~: .,~~,; r..:,~ ;aE~ ', f,ese inorganic compo"r.ds can I~c~ u~~;c: .Icn:,~ Jr :~t 1:;:11;.,"a;°~r~
~t~;rl; ~::I~r:r r.r;~3n.c ~; imrganic fire retardants.
Ferromagnetic materials, such say i~!}s, an~i r~i~~'~:.~, ;;,_ r Ge ;nr;~rr~;~3,vtad to render magnetic properties to the fnal foam. A 7r; .T. rw~ ~ a ~ ;;;c~ v:~
~;.r , i~:: ~ v~erials can be useful, for example, in thermal and acous~ic,~l ;~~:J~ct'c;rr c;n ;vezta~
;,ei;;,n~~. w, ~c~~am, for example, can be prepared with the ferrumagne,ic rru~e;«i~ uis(w~eci iE; a ~hi.~ Icyer on one side of a foam. The ferromagnetic materials c;ar~ e;rl~er ;~r~ rr;r~gawti-cc ~:as~e c~~ arter introduction into the foam. The foam cGn'~positi0,~ car'. rir~i~ ~;; Eas~~u atrache~ to a ceiling containing ferromagnetic materials without nails ~;;; !~,:, a t,°.r;;,,.x~,,;;P~~ r,E., .gyp , .,~.,,.~onetic materials in the foarn Amy ,~~:rrain ~iruoag;;~;tizf;i a;w,:a :n:~ r~~,";, t,~;;.: ,~r:::i~: ;:,, ;,~.,; :,~ted to magnetized materials.
-r WO 99/09070 ~'CT!C X598/16596 Water and/or oil swellable fillers, sucr; as cross-lin~r:~:~ ~,oclir,n ~;
polyacrylate can also be used in the practice of the present invereti~~rl r.s k~;~g ;~"~ ,~
I-I ~;~E oGn he made, preferably as long as the HIPE with the filler can he ~~lyrr~e~~i_eri intc;~
;z t;;am.
Metal oxide and metal carbonate cars also iae'r: cased as fillers in tire practice of the present invention. Such materials include calci;_;m ~xi~e, magrtE=Ji~:r;~
Oxide, zirconium oxide, titanium oxide, manganese oxide, iron oxide, aluminum oxide, calcium carbonate, magnesium carbonate, manganese carbonate, iron ~a.rbonate and zirconium carbonate.
Metal nitride, metal carbide and meta= ~~oricis rvafi~a;~;~;~;s sl~~;~ as alur7linum nitride, silicon nitride, iron nitride, silicon carbide, manganese carbide, i°;~n cark,i~~o, iron boride, aluminum boride, manganese boride or other materials Lrsed in the pro~~~=Iration of ceramic materials may also be used in the practice or the present invention for preparing the HIPE. Mixtures of one or more such materials may else ~e employed.
Naturally occurring members of the cEay a-ninera! fa:~ily or syn~heki~:
members of the clay mineral family can also be employed ,.r~ t;ll,~;~ ;t, ;~,o I:,,:,:::i~ :: ~;~.~ :.,~. ,~...i,,;~,nt invention. Such filler s include talc, mica and ~: d~ia';:.~r:~' ~~r :
~n!.;~:~r~ : r : n;: ~:, ~;y r~z;nr;; al family such as montmorillonite, nertorite, k~o!inite, dichie., r,-ic~~~r;, i;~:~:3,~:.. E. . :c.;r,~ko, nJntronite, beidellite, volhonskoite, sauconite, magadiite, medrr~ur~kit~. r;~;s~vaito, s~~.~rnic:~a9it~
serpentines, chlorites, palygorskite, kulkeite, aliettite, sepi.~~l;t~~, aiicpl~an~ aria ir~~aqoiite can also be employed. Mixtures of one or more such nnafier ia:~ Irtay ~:;~~; r~s erni:~loytao.
Other fillers which can be emplo~~s d ~°: ~.~:;- P~r:.cti°;<: a' chi ~;,~n~-~e,~~ n ,vrantion include multilayered inorganic materials (corwencmrmi~y reter~-ec: rc~ as ~rlaflUt~II~YS' ). The multilayered inorganic material woicn may be useu ire c«e ~raciic~ of rile irwaraiars can be any swellable layered inorganic material. 'T'ypluaivy, ~~le Idys~r~u n~c,rgan~~ ir7aiorial is comprised of layers having W o opposing fac~.~ wrn,l r:~a~; '.~E; rr:;ai;v.
~,~ {iz~r ,~r :;i; a"~;3i~i curved.
Such materials are described in ~.S. Patent 4,88ii, ~=~.::~
Representative examples of such sw~liai~le fayerEd inorganic: r~r~~.teriais include members of the clay mineral family such as v'rlose e»souit~~c~
nravs~.~t~siy, i~%her representative examplQS of such swellable layerr~~~ '~a~ ,,;: ,~ir r~~<<.
a:;;~: ~~ ~~~a i;; 'iitl; minerals such as ledikite; the layered double hydroxides ar n i>:f:;i ~-~~:'~~f ~~~~ar:~xi~:~-;a :,~ ~cln =I;:
MggAlg.4(OH)18.8(C03)1.;~'H2a (sEe W. T. Raichl_:, .1:_:~%.--~~:_~:, '~ ' ;~~):~'~l, 5~'~W vl~.ach have positively charged layers and a;<<rhangeat;le ur~i7n;~ an "~~;j :'I-~':v~~l;-::v, ~ ~ ~ ,.-:r~~; ;;A~!;r;i;l;;s such as ReCl3 and FeOCI, chalcagenides such as T~;~;,, ~,'; _~y~ a;~~' "J~ "<~:
r°y:a;;~!< ~_~~c;h as Ni(CN)2; and oxides such as H2Si205, V5013~ ~fTi slLl~;~;, ':r~
t;'s~~,:~~:a.., °.~Vf,.n'v,'~~: x:307, WO 99/09070 P'C'T/US9~8/16596 Cr3Og, Mo03(OH)2, VOP04-2H20, CaP04CH~-hipt~, t,~ifir~As~:.~H--HL t;' ~nrl AtlgMo10033~
Mixtures of one or more such materials may also oe E~rn~iayed.
Depending on the application o'i ahe final foam, the preferred insoluble filters are carbon black, graphite, metal powders, metal hydroxides, hollovv fibers such :as glass or ceramic microspheres, natural or synthetic clays, nanofillz:rs, p(~4~rd~;rs ~y m(~tals, aia.me retardant fillers such as those containing phosphorus. ar;tirTronu. bo=gin.
bvsmutll .and/or halogens, copofymerizable fillers such as acrylate fcanctionalized nolyrrieric palh~ders, oil swellable fillers such as lightly cross-linked polyi'neric po~:vdei~s, and a~aueous swellable materials such as cross-finked sodium polyacrylate. flr more ;a:
~;i~er~°e:a ;n~;oi~ibl~~ fillers are carbon black, graphite pc.~w~~i~r, rnei::>l p~md(;IS, !r;=a~.G
'ryc~r~:;cid~,~: , '~.~::'(;;u ::~.=uv~.;:~w microspheres, nar!ofilf~~rs, arod pc~u~d°er'~~ u= metals. --y~.(, :~:~
_,__ pry fcr.'e;~ 'v:..cv!i:~?r ~~ilE!~s are Carbon black, graphite, r~Siw~r!'7inl:!11 zi'i~-.jrLi'OXlae, r~7S(~':'.~:51i:::_ :~'yC:CVs_:~::~, ~yil",'~_ . .~~'e~-lIC
microspheres, Clayton A.:'r? Montu:orillo~~ite silic~~:. ~r~.y, ex,e~ ii~~!-:
~~~.:"r'~~~:.
Insoluble fillers can modify many cr;_:r~.:~~tr~isti~.~ ~'~,' a 'al~~'~ fo ;i-.o ~n.;'Liding density, modules, tensile Strength, thermal conduct-~rita~. t,~arT~e r~
iarctaio;y, anc~ magnetic property. Typically, more than one property is modified unor~ inc:~rpea~:':F~'-!~ of ~a ~ hole insoluble filler. For example, incorporation or a iarg4~ JGI!ai~ne UT
s°~~va ~a~hP(~er'e~~ili simultaneously increase the density of a foam and increase its terrorr!agnetic property.
Often, large amounts of insoiupie tiller will tend ro aecrease r; ie Tensiir str(o Igr;-. (,~ :fee foam.
This tensile strengih loss is suspecteo i:o arise wont wraic ~drievic~n be;:,~~~~:,~er, the polymer and the filler. A redur~;o;1 in tensile ;~t~.-:ngth can i;f- .~: v.e ~ ~ -: i ~ .!~'~,~ ~: t;~~ - "',-~,.,~, chemically or rnecha.i"v:;S.ii~ hin.l.:i inic the lu!~rr~~r~~~ n.,tv~ .~~, t;
~;,:,r~,~;~ ~ , ~ ~";~~ify the surfaces of the filler v~rith .~ ~,L~upii~~g agent, mart' a;~ ~,~r;~~~'~~
_~~r~ ~~, r:~' y~~,~,, v -, ~i ~: -,,;. Known COUpling agents l3UiU;~~:: QfC:dn~,li;i!iCaiQilF:i 8liiv;(in c;Ci :9~~l,t,l'W
: ~,;;( ;s ~~ ',;:~Z~,ai yt'y;,::;~;-~UXy silane and'y methacryloxypropyi t~irriEt~aoxy Si:ai:e, ar:c~'ita.l:ii::r;
:~~~r~~:;~t_._~in~;~ ~w.:~;,. _:s _:,-:.': :Sopropyl triisostearoyl tita,~aAS arld ISUpI'Oj;.~yi :i lfT;i;thu_:I~ i t!Ei?'~~!;E .
rx9l: i'.Tl. (t ~~:' -y ,;. ~ : .'.l:i'~i ~ct!
coupling agent could ~a especaliy~ efie;:~ive ;:~5 tire ;i',:;v:-:uc:-;~
gi~~:;r~;: ;-..~;L ,~~.rt :: ~ a',,-, .
polymerization react:ca. a:~,cthE~ exarT:ple i, :: u.:~ ~ : ... : ~!'.~:.in !i~ : ;. ~'; _ ~.v~~iich will copolymerize uvith the "~e~~c~~;re:;~ d;~:iog ;~oiy~r;:::.._:_n: . ~,~~r:;
f,.n~:, ~.; ;; ..;.~i(~at;i;; ~:1 the organic monomer;.ai'i :wvo;.~le strr.ng:y ~,our;~ : ".~I.r~r:.c~~;,~ ~~
:..,.,.., ,.,..~ p.~:y:.z~:,:v~~d through the swollEn vi;,;>i ;;y~.;'.i:;l(.
The amount of insol~.it~le filler most a~lman~~ag~c~i.s~in ~n~p'n~~e'i d~~~=~rds on a number of factors including the desired application of the ~!~rF or ~~~~15~r~~Arized RIPE foam and the type of filler used. As previously describAd, otrpr rtmre than aye nroiaer~y of a foam WO 99109070 ~aC~'!f»9~116596 is modified when a filler is incorporated. Thus, the =~mor~~,t of ~~iller e:r,pio;:~s~~:! r~FU~be adjusted to achieve the desired property. For examcle; if or a deeair~,C a ::.rer~sc ~'oUm with ferromagnetic properties they could prepare a HIDE ~n~it!~ 'args a-~~o~wnt: of iron powder.
However, if a person wants ferromagnetic properties but does not de~ira 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 req~sirF
a. ,~i~,~~~r~r concentration than others to reach a desired effect. For ~xample, carbon blank can significantly effect the th~rrnal ccncucivity u~ a iuar : _:r ~.
°.zy.r,' o' '. .~: E',~:.:~ i i ' :~~sight percent while approxin~~:~aE~,~ 30 ~rreg,i2 E;erceot c~;~ .~.. J; ~~ .'. '~ 1 :r.~. :_ ~ ;~ ~:.;,: ~;; is :w~::;~; a significant increase in i:arrnve retard::r::;y. Thewf~:~:, i',;~~ a,~~n ~at7or: ~rn~ l~y~; ~:;i~:i:used plays a role in determi;;ing optic,~,~i ;iffier concs~n,~ati,:;~s. I~:
;~~nEYal, .u:c ~~s;~iuk.~~c: i:lc~r can be employed in an amour~.t up tc a: rd ~~x~;eading iG;'.~ wf:.rr;.: p-:=n~~.ni .~eiati: ~ v~.: oii~ :;c~.tinuous phase. A broader domain o! insGluble fillers cap-: f~e: er,:p~y ;>,.1 :ap to :
i~;? rc i .. ~.°s:,~ percent relative to the continuous phase; an even broads! dcmai:, ~~:f i.~~;~.r~:r:v,=
'.pier:: ..gin own employed up to 50 vo;~.~~:-c; pe;rc~o relativs to the ;, .nin;. ~ ~,.~ ,;;i;
.~:; .; : ~.i'~ ~ ~ r ,;~~e~ ~ ~:_~main of insoluble fillers can be E:rr~f;lcy~;c'. a~~ W 1~ ~~oar"~; Em~ri~::,.~
!.:a..r~ . . . =-~~:'.i:u>:; ~:. phase;
and the broadest domain ~:, i;i:;<.'ur la fii!ew:; ~c~t~, i:i: A,a,;i:z,a ' , ~ ,1_,~~.:.; :c: ,-.,lt relative to the continuous pha~;~:'.
Cross-linking monomers which carr i:~e ~~rryic~yec~ in Tree ~:r-a~:iice o~
;:he present invention for preparing the HIPS rnciude any multiiuncnur,~;i ~_,n~wturateu rnr~, r:.~rr.ers capable of reacting with the vinyl monomers. Multifunctic~na ur~s;~iurazea c;rcss-rirri~mrng monomers include, for example, mvinyibenzene, ethylene giyccn dm~e!nacry~~ae, ~-uuxy~ero~
dimethacrylate, trimethyioipropane iriacryfate and anyi rnranacry~ate. v~tri~e xne amount of cross-linking monomers most advanlageousry emp~oyeo Jr:~.~er~ras on a vr;~riety ci tactors, such as the desired polymer modulus, in general, tt~e cro::S-Iln~clnf~
rranr~amer is a, sed in an amount of from 0 to 5C v~~:ic~trt pE;rcent, p:~eferGl:'.~r i~~:r:- ;. .. , ~
~5 n~~:i~~~v: :u::u:~:,-,:..; :.:n~.i most preferably from 7 to 1 t~ weight percent, bas~~cJ ~:.~:n il~~: _~: _v;
~~a:~.a. .~ .:! ,~: ~:~ ~~:
Radical initiators which can be empicvVed ~n the nractrce of thr~ present invention for preparing the HIPS include the water-solubn in~tiwi~ars s~rrh a~, fop e~cample, potassium or sodium persulfate and various rednx svst~r~ns ~ncr as ammonium .r~ersulfate together with sodium metabisulfite and oil-soluble init;ator s; s!arh a.s ~cr exarxrplrr:, azobisisobutyronitrile (AIBN), benzoyl peroxide., rnet~vl pth~~i ~etc,~~F
ner~Xlne at~ri dl-2-ethyl-hexyl-peroxydicarbonate arod lauroyl peroxide. The iniøiarrr can be av~ed t7 tk-sn «Ypeous phase or to the oil phase, oepending on whether the initiator ~s water-.snicrhle or oil-soluble.
_cf_ *rB
WO 99/09070 PCTr'U~~98/16596 The initiator should be present in an effective an-sos.mt r~~ ,~,:oiym~~;rize fih ~ rronornars..
Typically, the initiator can be present in an amount of frofr~ 0.0':5 to ~~
weight pc;rcent, preferably from 0.1 to 10 weight percent and most preferably frsjrrc 0. t to 5 ~4ei:;~l~t percent, based on total monomers.
The aqueous phase can include a wager-s~~1;~:ale :wiar;lrc: i~,>~:e for r:cciir?g the surfactant in forming a stable emulsion, controlling porosity of the foam andlor ernhancing the hydrophilicity of the resulting polymeric foam material 'f 6ef~ «s a re si~:aa.l ccrnpc;nent of the foam material. Water-soluble electrolytes which can ba ~»~op~oy~so irr t~cc:
~,~r«ctim. of the present invention include inorganic salts (monovafE nt, anraient, o~ivaient ;~
rvixrr~res thereof), for example, alkali metal salts, alkaline earth metal salts anG he«vy metal salts s!~ch as halides, sulfates, carbonates, phosphates and mixtcares ~k~,~.r~nf Sur~h electro~,~tr~s include, for example, sodium c:hiuri:le, sadiurr~ sulfate, ~ct~~:;~:urr. ~,~:~r~~.
~~r.,~,,~,;~m~c : ~i ~~:~~~, lithium chloride, magnesium ct~loriae, c;~lwum c7ioui~:!~~, rr~G~!ee~_::!°:~~
sur~a~::, ~;:u,-:~.u~:;~n ~:iu:ide and mixtures thereof. Moryo~~ or divalsnt salts with m~cncvGie: ~. ::.-ic.~.;, :;u~:; a~~ itu~-W.J, are preferred. While the a3naunt of e6ectrru~fes .lvosi ~:~v-. ,i .~:~:rc:r~.y E~r~,:, ~~:~: i E~~~~ s-i~s on a variety of factors, such ;~~s it~~s sl:-u~ific o.omp~~~c.c~~,', ~' '~::
~~:;x:~,re;x pvr~;~ i~~ c,f 1~~; ~~,~o: and the surfactant employed, ir-: g;zr~~ra!, :he elecirnlyt,~ ca ~ ~:~~ f:r~~ul.~: ::-a ij~, c sir?, --,;~:w ,;preferably up to 5 and most pref~:~a~oly up i~:~ about ~ ~nre;;~'~~~ ,ryri.~wi, ';a~it.._:cf ,,n ; .; ' : ._ ; .. :~:c ~s c mixture.
The aquer~us phase can additior~arly ;;ornprise a r7or~-ecectrc;ryte c:orrnponent, such as, for example, giycerm, as long as a_nIF=r= c;an sciia s~~e praparea arni pocvmenzed into a foam.
Surfactants which can be emplo;roc! ~;~ !rc: ~,.r_~ct;.:~cf thd; pse~.~,;
~,~~vention for preparing water-in-oil high internal phase emulsions inca_~de nonionic surfac'ants, such as, for example, sorbitan esters, including sorbitan monoole«fP and rorlzitan rr=on«i~.urate;
glycerol esters, such as glycerol monooleate; PEG 200 dioleate. partisl fatty acid esters of polyglycerol; cationic surfactants, such as ammonic,~m s~zsts; anr~ anionr~
suriacta.nts, such as certain organic sulfate and sulfonate compounds. ~,i;~c; s:ai:=.aiu.a:w ~;c~~~on-c~;riz.~'c:
surfactants such as those described in copendinp .~,r;cl~-,..~i~~r, ~=~rial ~'to. ~~~s,~;~, filed November 15, 1995. ~u:;~ :~ucfa!:~~~nts irn~ii.~~ra ~ ~r ~;;i~.: ~:: ;:~~.~~ i c I
.s~: :~ . a~:~~y;.~,.'~.~:.i~: ~; ~Y groups and surfactants capahi~ ~.~f ~; dergaing :~ Sraft rc ror: ;u;;:a;;u~:~= ~'.~..-ft'.ct~~cr.,; 4~t ~h,~
conditions of polymeriwiiuc-. A~so :;uitablE~ ar~~ i~~c~ o~;l;v~ ";t~;;;rr=
.u: ~~;i.'~;tc-.~ r~>r=.. ;.,;;:le) sulfate-based surfactants c~esCribecl in ccspEndir.a I? .~,,~,is~:: wx.l n ?r a:;~~.~rrc ~;s-:r:~.i ;~!(_~.
60,046,910 filed May : Ei, 1 ~9~.
..1 r;.
WO 99/09070 PC'1',~~:398/16596 The amount of surtactant used must be suwt~ that a high irvternal pr'rase emulsion will form. Generally, the amount of surfac;ani r~e~;dE~;~ varies W°ithd tic ;>~ecific surtactant and the type of formulation used. As litt~~ as about 0. i25 weight pNrnent, or less, based on continuous phase can be used. More generaii~~, as little as abort !).2~ vr~~~ight percent based on continuous phase can be used. C~ene~,al'yy r~~: x~;~ abc;~t 25 ~,,t~i~a;t percent or more, based on the continuous phase, can be used, if desired.
Methods for preparing water-in-oil emulsions are Known in the art such as, for example, in U.S. Patents 4,522,953 and 5,210,104, and t!"ese n',sthods can !ce employed in the practice of the present invention. Far example, the t~aat~r-in-oil I-~!PE
~ar be prepared in batches. In general, to form a water-in-oil HIDE in batc',~ quantities the watEar phase is gradually added to a mixture of oil phase and surractant ~Nhile the mixture is being agitated.
Agitation can be accomplished any number of ways inclurir~,r, impel°er-r;rpe ~api~.~~.~.~nn.
Alternatively, water-in-oil HIPEs can be prepared in a con,inErou.' flow r..ranner. l~~lethods for COntIntJOUS fIOW HIPS ~,~r:,~pa:r~.ti~..~.il ar'9 aI~L VI~E!~~
~~E,~:ar:~l''i'r_t~ i t'l;ilk.';! Wit:;."E'.. c :i_, '~-,v example, U.S. Patents '",Gt3;~.2.5 and 5,'s9rs,~s7.p Incorporaeion of insoluble fillers intr:, the I-!~~'=~ rare r~P ~;or~a.
;~recr' is c» after emulsification. If incorporated prior to ernulsificaticrs, the inlsUl°.r:~iP v~i!ier ~wr~ yx~ir;aiiv be added to the oil phase or aqueous phase or to boor Ui~ase~. Tfte msci~rflie iinE:r c"~:r7 ue added as a separate phase curing the emulsification prac:~s:, p~..ricunrry ;~
:~ rm ;,-~:,~..uous flow procedure. Alternatively, the filler can be rrixer.~ into _i-re er:~r~rrsion a.~iaer the errruision has been formed. The prefarrea method of incorpara,ing the firie~ aet:renas on a r7r~mber of factors including the ernuisitication procedure used and trrc rsrr~e ar7d ac ~~clcant of riiser used.
For example, an insolcl;le fili~r s~vric?-: d;m:; not ti~,;:~,yrFrc: ~r,w ;,.~-;~ , c~:v ;.,.a~;~y ur: ~ d not be optimally incorporated into iio; errr~nlsiorr b;~ :rc'ca: ~ ~ to 'w,.:
:~rfr!,~c~.rs _.n.--.,~ :; ~ ,; ,; ~,:
emulsification. Such a fiiler.>Youl;i loe iaeite~r incorpE~!aicu :~~ o tu:=
~~n-;~ 1~ ~:.. ~y~ ;i.=;~ adding it to the oil phase, adding it as a sE~c~GratE; phase, -~r :acic~ir~~r .: ::ftcn ~~:~yr-.:,:~~iz~:~:, .
Layered foam compositions can be prepared from the i-itf'E of the present invention in accordance with the rrroc~ess des,~~iher~ ;r: c;:ren~ar-:q i'ro~'i~i,~r,ai fxp:;. ration Serial No. 60/055,852 filed August 15, 199 r. I-or ~x~_'r:p~~. a ~ayerec~ :c;-;n cc°n~io~~nifln can be prepared comprising two or more layers with aiiierr.g u;r"cr:rtt:: or ry~,~::cr~,~ fl~~rs. One application where layered filled foams are useful ~~ i;r s;~.~nc;
al~~::~~~r:r=vnt. iraye:'c;o compositions with iron sponge powder in one la~~rer c.; ~d ~,r!ic~aw r. ~ -arar;, ;~~:i .v'ou;.v; ~t;res in another have demonstrated enhanced sound att~anuatiorr ~~rE:pc:,-ies over sirnilar foams WO 99/09070 lPr~ >~/~:~~9~c116596 prepared without fillers, with only the iron or only the ~~iic:i°c~;=phN!-s=.=:;, .-;r 4"iti: a he,r°iogeneous mix of iron powder and ceramic microspheres.
The following working examples are cfiven to illustrate the i~ver!tiort and should not be construed to limit its scope. Unless ouhervt~ise indca~.ecf, all party a.rrd percentages are by weight.
Example 1 - HIPE Foam with Montmorillonite Silicate Clr~a~
Clayton Ar'A l~lor~trnorill~;~nites Silicate Ltayr sr~ m~:;;
urrlc~t'I~ivtu;tt: ;:Ilii atv clay available from Southern Clay Froaucts, Inc.) was rroxi;e to d 2-v~eight percent concentration into a monomer mix cc" !prising c4. ~.nieight pE~rce-a ~-~~t'~yl~ve~:yr .- : -r;a!r~. -I.1 :,~,i.v;l.,t :,,ercent styrene, and 22 weight io=rce~t ciivi:wl":~enz:~; ~c~ fv ~ ~~~4~.:;; a' :~r:rti~ :-. .s tr-: .c:.a; ~
r i; ~;; :~f the monomer/clay mix wa~liraolved 1.1 grams SP,4NT~ 80 (sorbitan monoofeate) «nd 0.35 g SPANT"" 85 (sorbitan trioleate). A separate aqueous phase was prepared compri ,ing 114 g water, 1.1 g calcium chloride dinydrate and u.~ g pmass~mr~ pe~sulfave. Trre ay_veous phase was added dropwise to ;I~e r,.unc:~:~",~,'c!.~y;'sar«~~ar,: rr,~:: vii il~
~.o!::r:~ ~. ~~~ ' t :~:.,3 u:;ing a three-paddle mixer. A thlcl: .vrtite t~:s:~_: was p;~~~u~~c. '!-rrc:. flir'~~
~u~::::;:cayr~.~er;:~~;~.~' at 60°C
for 16 hours in a PYRE~'~'% uist; covare: Witit Jal~cit~ ~~i'u;:n ° ~~i ru.t;ir=Iftcith: (::1 i fi~c; ;.i~)wv Chemical Company). i~oa sarnp~rr was soakeu J,~r ~-~~roN~n~J u~~~.,~ ,i ~;~:~r~ i3c; c~, ,.;.~;~sed free of the internal aqueous r:"~,ase. 'Throe ;irises wera dune r :';~: ~-o,~oNcl;
;al, ;~?-~:f, r~-ryes in water, and a final rinse ag«in in ~-p;opanoJ. ~~i"t~: Sc:~T~~li: u'd8.;~
;;~.~Gi,1<:C: 'J8t'dV~':;>, ~;aper towels and allowed to d.~r at reu;o te,~;yirature. 'f!~1,: Irnl.:,. vC,c'.!v;
svaS t;~parls:2..:, ,::.i;rf:iessible and resilient.
m - HIP Foam,with Iron P~wde_r An oil pv:a;-..~e v.~a.~ e: a~ed ~;r a .,'n-.., ~: ~, - .~ ;:;y'.,'' .a;'~.,;5. . ~? 9 styrene 1.13 g divinyl~ F~ ;.: ire (;5 cer:~,~r;~: arfii:r = v ~ ~;~~ . t ,..
r r, ~ ~ .
.. , . ', : r- a. . ~. " .-,: : ~ c;: ; T .-,_ ~ eate , and 0.10 g lauroyl perrn:~a~. ~'~n ~t.;: ,~c.;;; ph2 ~, ~. E; ~ _ ;~r~~~ a.._ 4". , i;,.; ~ ;; _ , , .~ ater, 1.35 g calcium chloridE ~Jh,c"n:,~~_, ~:;,~.~ ~.v; s .a~;::i ;,. _~ .
.~;a;~,.. .~. ~ r'v'-~~.1, . y ::pared by adding the aqueous pJ~asr~ dropwrse ao tr;e ~Jl ~"ra~e ~rWr~.~~ ro.;ciry ai ;:~u~ ~riv~ ~w.~ a three-paddle mixer. The ~ IiF'>r was rnixed a~n ar~~lJ~";r;al 2 ~i,rrt~,m5 uiFr'tur!i~~~rr~ 'c; ~r,sure homogeneity. To the l'i i h' c !lu ~c;i niiCf~'G ?C~ g of .~l', :; ~~ ~ i ~' :
~ V 7 ::5; ,. ,: .;~~~ ~, av; a ~, ', ~.~,~_ ~anaes, Inc.; Valley Forge, PA) s:;::e t,:;rt;,-,~~;ng t!~:u ra..u;~u: ~ lr;: u!e; ~,-; ~;r , E .s ~~ ". ;.~.4J
polymerized at 65°C fcr ~~.;~ i;c~ura a: G - t'F,~;~ ;:.i. a:~.v~ ;a.;:
~, ~~
resulting foam was sq~.cu~;.~d ire:; fw ~~ ~ .:u;1 ....~.._ ....~.. .:.~;;:
., ,~~,~ our ;;: iu:.:. .: :; v ~, , : c.;:anol, *rB
WO 99/09070 PCTlUS98/16596 three times in water, and a final time in 2-propanol. The ~~leaned foam was s~rc ~p~zed free of alcohol and allowed to air-dry. The resulting foam ?gas ircar! raow~i~~~
incornoratc~~~i ~n its polymer matrix and was attracted to a magnet.
~ca_mple 3 - HIPE foam with Hollow Ceramic Micron heres An oil phase was prepared by mixing 17.~ :~ 2-e'hyl!~exafl a~;r~iia;f, r2.25 g styrene, 3.00 g divinylbenzene (55 percent active. 5.63 q SPP;N 80 (srrrlait~~n morooleate), and 0.27 g lauroyl peron'clo. An acr~.~eou~:, i.-.f~asF was i~r.~;-,w.r:~t~
r;y ;;~i~.-r ;~ ~C.a.r;- ;,~ ,;.eater, 3.58 g calcium chloride dih~drate, ~~n~~ 1.~~~ g ~~:~~::~ ='c.n~ ,ar~~.'f~=+-.
", ~-"~~: ~,~-,~ ~rf;pared by adding the aqueous ph~is~ _aro~,kv~sr; to th:; oil phase v~h~!a r~ixir:g at X00 h~t;;~ varith a three-paddle mixer. The HIPE was mixed an addit~onal ~ minutes after farming 2o ensure homogeneity. Into the Hlr:'E was rr~ixed 8.55 g c~f i~ui;ovn ,<~~ramic !~nic-'e~spher~as rSl_-150 Extendospheres0, The I=~ Cor,porati«r:) usi~ig "~lE: ~hwe- ~~'~;- ~ ~',,:-e;~ -,t ~.,~,,~ :-~tv. 's"he HIPE was polymerized at 55°C for ~8 hours in r. -'~':?''~; ti::,in ;:~:,~%:~~a~'. ~ai~f: ~~~r_u~a l~lrapTM.
The resulting foam w~:.s :.~~aueeze~! ~:~,:.~ o~ aq~::._:i~: -~:,~;:_ .:v~
:..~:.~~' i;~.-~;, y , :r,. ; , '~
.< , propnaol, three tlmeS :3~ '.ryd:v:E', i:.t?C~ i~ ?,!',sly il~'~Ii' . . ._ ,, J':;: .:' ~i' ' ~j,; ,, ~,~y r~ ~ sn ... _. ~.
squeezed free of alcc':o~ ~..~~~:' a:ac~w~.:ct ;~ :ir~_:.;~.
a le 4 - Foam with_I_rc_~~ Po~rrdt;r ~yr~_I~Icylyv_4~ Gf=:.>:»',!:
l~licrosQh~r_e_s An oil p'~~:~E- was r;~??a: ~c,~! ~., ,~,'.,~ ,. ._. ,. . ~~- ~~tw ; . ~ v . g , ~, ~.: '2.25 styrene, 3.00 g divinylb~r'Brae ~~5 ye!r;ertt ~ct~'~~v. " ~';' . ;-,.~r~ !
w~,.,<;,~ , ;,,,r; ~ ~~ g SPAN
80 (sorbitan monoole<a'a~ ;fin P.n~.!~o~ ~c ~h,: s~ ~.w.- : ;. ..,.. _ ....,, ~_.'. ."p.,_.c. .; "~ ~ .1 ,~,~er 3.58 g calcium chloride dihv,r~r~;~s. ar.~' ? ,af ;t ~:,~,+o,-si!c:~: ~. :s.,.,- -r~-., ~,.~;,. , _~~.~,-a , . . , . . Nas added dropwise while mer~;~r t'-, cc' ,: h~.~.n ~~ ~C~:~ ~'~'VI E~~ia'n a ai,~
a-y,r 'i;, r~!; ~ . ':7nce the aqueous phase was completely addad and wh°le ~;;:,r Air~~ti:~ti,;
~~ri;;:~~:g. ~~.~'~f; g r_~~r ~- ~~c microspheres and 14.33 c~ ircr ; aEm,~ ~~r ~;~w;, t:c ~~.a; ~ ~;::,, , ~,wc t t: -:~-~ ~, ~!~ir~r. TI-w, resulting HIPE was mixed an a.c;c''fiic:n~' ? ~.ri4e:; tc: ~n ;.a.°v ! aY: ' ;~'.
-'~~ : , - ; '~ . <:~ nut into a PYREX dish, coverE~~ wit's 8an.~~~T~" 1'.!ral:~ ~;:_! ~ ;~~ w ~' ~:i~ ~ '.
vr, -.~ :.r, ~'. ~ .... v: ' ~'S°C
overnight. The resulti . J ~.,r: m v~;u =~.:~ .:~~ .' . ~ . . , ~ _ . , _. ..
. ..,: .: , .;. a times in 2-propanol, three ti::~c;~. :r. era °.r, i_'.r ~~ -y:;;; ;;. _ ~;-:,; a .: ~ .;,. :;n. : ~ ';, .; . : ;~ueezed free of most of the 2-~:~,:~:.~~ ~;r.J ~I~~ :.- .,. '~~-~r;, cu :.-~v.
:~~.~a~,;:::~ ~:.::,;..
, m le 5 - And Comn~r~~iy~ ~.~.= ~n~'~;_~', Two HI~'!.'~.:~4n~~ ~~~~~r a ;~: spa ~: : ~. c: :.~~ ~A a.
t. _ : : ~.
,..
WO 99/09070 PCT/U~98i16596 Comt~arative Examlhe AA - Control with no Filler An oil phase was prepared by rnixin~~E.b~ ~ ?-e',;~yll~e;c;~9 r:~cryats', 1.90 g styrene, 2.98 g divinylbenzene (55 percent active), f .45 ~ SPAI°v"~~~
EC (sorbitan n~onooleate), and 0.06 g lauroyl peroxide. A water phase was pi~;;pac~;:d b~;°
nvixir~g 132.96 g water, 1.34 g calcium chl~r~id-~ dihydsate, wr d C. '~ ~, ~c,~usv:;:3~; pc;~ ,.ruy~. The aqueous phase was added dropwise to the oil phaa v~t~i~.; nixing at '3~G~
Rl~i~! ~siy~g a three-paddle mixer. The emulsion was mixed an additior~a! ;3 ;,~u:es aftsr G:IE ~~~
rh~s u~:~a.seous phase was added to ensure homogeneity. -f-he so°3~.rl~io,~ ~w~as ~;~_;
i;~".~ ~1'~I~~C niss~es, covered SaranT~~ wrap, arc: poiyr ;er izc;d ;;i a for~~a G:r ;,u~ r~, arc;"C;
;;..r ; a w~,;,;~;:;. -; he resulting foam was rinsed 3 times in 2-propa~~ov ;INt,), ;; °.r~;~a ir.
wasar, a;;cJ ;~uuv irv IPA.
The final foam was sq;~~eted ,'r;;c of rtm:;r o1 .:.u ~~~.~?. ;:rlu ti~~;r.
c:;;~;: i~~ a vacuurrr oven at 80°C for several hours. 'he ex,~,~r:~,~;fuarr', v'~~;;:; t;.;:"
;.ii~w::cc~ ~~; ,~ r=:~.~; ;~: ::f,;~rature for 2 days.
Exarryle 66 - PE i h ~_Ir~minum Tr~hv~raxi~_[=~,~AI_(f~H~3l,~ille_r An oil pnas~: was,~:ep~.~LU b,/;:::r;:::~ .,~.G~~ a ~-Lu:=yu~:~.ly a.;ry~:~ic:
~.u2 g -, ~
styrene, 1.60 g divinyive:.za~~:e ,,~Jr pEiCF;n: :C:::'Jv:" n 4;: ~'>:-,'~V
~i; (iCSfsJiiat: rfi:Jr~(:~leate), and 0.06 g lauroyl peCl.:~:~'u~. 111tU u:n t,.;: rl'iaoE: :V:a:. ,i~l.:(c:u i:.J~: 1~ ~;,.i,lllllTl~.'C1 t'~:~'.lGrr~il:Yide. An aqueous phase was ~~epa. eci ay r~ n:~;~ .g ; 3:~.::~. ~ v.;~:_e: , :._ : ~ ~
u:;:.~; v~ :,. f; ,w >>drate and 0.64 g potassium persufvata. -;-i~~e a:~uec;~s ptiu;~e v~'ua a~i~e~-, ;:;
c;N~~ist~ to i; ~;: nil phase while mixing with a three-paddle mixer at 3GG ;~1= ~:a ;: a p:riy~;r;;Ny~,~r,E
t;t~,her, r;.r-,,;c all of the aqueous phase was a=:;cled, the enwdsion wG~ r~";:eu c.i i ;zd:.l:iltlfl.~'1 3 tTIrI tLiiC;y :u it iSUrB
homogeneity. The emu'. ~.:~r. ~~~ c::, ~; ~ ~:.~'~d into I ': ~.::;: u;::~:
~:~, ,:L. ~; ~ ~::~ w::i . ~~c.~ ~~o Jl' -apT""
and placed in a forces-uir c~LCSI i:a ~.5'.. :~i: :C ::c~.lfS. : i'1:;
!v;i.:,iir:~ i~c.~;t: 1,'".:~:~;"il,r7rLSSed free of most of the aqu;:;;::; j~llia:i0. '1 i:v; iJt..ri~ i.c3:i ~lri'' ':
r~,!~", '~~; ";,~;;;(;~rt;f;;.; j;;
.: W .a U: t: "~
Comparative Example ~,., w~:f~.;;~y ~:.;. ~;;,Nar;,.~~~: ~;"~:n.
Flame Retardancyr Testing Foarn srrrwp;e;~ of 3=~;;vN~.rL-~ti',~ ~ ~=:~:a: l~i _; .~ _~ . ~.. -:ry:a: ~;
~":: ,..,~,~ i r'_,o strips 8 cm long, 1.5 cm wide; a;r c; a.-~Jro;'~. Ac'~.~ ai r,r,~: : ~.;, ; .c . _ ~
;~ . _ , , r, , . ,. , .,-~. .;_.- ~T:cr.nted vertically, clamped at .~ :~ ~ :~t':~r:~ ~,r ~~ ,x.~- o:ar~~ ..~ ~;..i Lr~ a:
:::. '' ~~~ ,_.,: J~ ~! , ._ ,.. .r/as lit with a match. Obsen ~~::~;', ~ v. ~~ :; rvc:orc~i :,~ i:a,;c ~~ ~r.:." :
;...v,:.~ ,.. fi :, ~r ; ~ w.ynt ,,.s.- . .;
effect of the AI(OH)3.
_-I,;.
Comparative Example B - Foam - Blank The foam was easily ignited and bc~~°~~ec~ c ~~ .ln t~~~ t~rtir~ 7 cm !w~ 17 seconds, with near complete incineration in about 35 second:.
m I 7 - Foam - ATH Filled Foam The foam was difficult to ignite. Onct~ ignit~~c~, -she flame self-extirgnished in 1 minute and 16 seconds having only burned the tee 2 ~:m cf tt~e foam st:-i~'~.
1 xample 8 - and Comparative Example C
Two HIPF ;ozms were n ~eQa~ed a~;~ evaluated for their soc~n~ a'~ter?uation properties.
Comparative Example C - Non-filled Foam An oil phase ~n~as prepared h~~ mixinc 1? 9p c ?-c.!!'!v!he:~0.,~i acylatc;, 12.25 g styrene, 3.00 g divinylbenzene (55 percent active), 0.27 g la uroyl peroxide and 6.63 g SPAN 80 (sorbitan mor;c~olea~:e). ~~rt A~~,~ao~rs pha~~ M!~~. r~rQp;~rar~ y~
.~ixlnct 35.51 g water, 3.58 g calcium :hlcr~r~!e dilh~yra~Q; ~nr~ 1.RF ~~ ~c~,-rs;i;arn rt;~r ;nlfate.. The t,c~°ueous phase was added dropwise while mixing the oil phase at 300 RPM with a three-paddle mixer. The resulting HIF~E was mixed an additional 2 miw.ates to insure homogeneity. The emulsion was put into ~.. PY ;E:~ tlis';, cc,s~prea with ~~ra ~T~" V'~'rao art~i p-~Ivmeriz~:~ irr a forced-air oven at 65°C ~:v/~~~r~:g'~~. T~~,c,, .~Krrj~~t~»~~;;:~.~:~~
e~~:~~° ~:~ ~u.";:~s ;e: i °:Q crf r~-~ ~o.~s phase ,..
and rinsed three times ;~ 2.~~r~pa:,cu, ~i~;r.;~~ L.V::.~J ~.n ~~l~~er ~ ;'~~
~'.l~'::~'. ~r. %..;]i:)J.~ri~,;. '! he rinsed roam was squea~~ei ir~c o~ ;f.c;:~ :~' th, ?..~:. ~:~~;c-~ ~r~r' ~
~~.~~~-" tc~ a:.;r-;a,a t~;v~
expanded foam.
m lei - Layered Fil_I_Pd Foa__m_ TWO H~I"'~:i Vi:irf:' (JI'c;rlar"i::~ 1~~~:rf_'~.'! "rd ~il'ir':
'!C?~'~"''"'r't'f~e=s.'i, j'~,: f:.,F+,r~m layer was prepared similar tw~'h~t v ~srr , ~a~ ~~'ue r-~ ~ r,_ ~~ ~. ,;. ".~_.,t .", -~~ :_ ",,y;~,~ ,r.;,,,-~e B iron . . E
sponge powder was m;,e~J °rtc the :,a ~;I;.~n :~:~:°.f~ sw, -,~
fii...._.;~~' T~~i:, !:._°~,; .-.-. !,.;~;r~; vIIPE
was placed into a PYPr". :~i'~"i. t~o; ;~~- ~.~ tt.r, t,~,.,._ ., ~.,., . ~;
~;-. -a ~ f'-w a,,-,;~ ,uf polypropylene non-woven rnaterial. A :-econd t-"°a~ ,~,,,~; ,~ r,-.;.,~r-_.' ~- ;a-~4,~ri ;e~'; '~~ ~,cample 3. The second HIPE was cGrefu!ly deposited ever" ;':~ p,a!~l:rc~py!enr~ ,-";-~_~,~~.r.,., f.~,,;,ering the bottom layer and tire carn~postion was polymerized in ~ fcrueu.-a'; ;vcr~
u; ~~;~°:
overnight. The final fc;~:~;; s,r;~cr :~; :;rw:, . _, " . ";
w:u~~, .:;:, :,."-.. ,.,: .", .. ', phase and rinsed three times ,~~.vr: ~'p.;:Nu;..;, ;...,:~.. :~rv:c..;: ;,~,:~, ...~
..~_ . ' ~.~; , ~.v;t;.: ;..~~:«nol.
*rB
WO 99/09070 YC:'I NS9t3/16596 The rinsed foam was squeezed free of 2-propanol arid allowed to dry to an expanded layered structure.
The sound attenuation was deterrr~ir~e~! fir the foams ~r~~arec' in Comparative Example B and Example 6 using a lahoratom sour~~l 2ttertaafi~or~
apparatus.
The apparatus basically caamprises a source chamtaer, a .~eceiver ;,hamhe.~, ,end ~ test sample fixture between the source and receiver charbe~~.. ~. ?-in~~h diamPtsr ~~~er:p!re was provided in the fixture. The source cham5er mas en~.aippz~ ~r~;th n~..,~A-«-~, ~r.t~ .~ ~~ir;rophone.
The receiver chamber was equipped with a rnicropt,or.e that ~ec~~r,; ; ~!~"
,n~~,-;:-; ; ~+;~;~,sity in that chamber. Noise was produced ~n yhe sourcF c'-a!~br ~ ~vd the ~.:,o,v-t intPr;;'~r spectrum collected at the microphone ire the recc~~~E:r,:.fw_mi;~e~ wife, - -' ;~~=,,r~;;~;,! ~~ ;:_,rr,~-, ~, ~ packing the aperture. The sound a~aen~;aiicrv uvas cnfn~~,ca as_ 1U log (id~j where to was the sound intensity spectrum. recordPrl with~nt a sa~~r~n in oyce ;~n.~ I was the sound intPnsityspectrr;~r~ ~eLnrd,::~W,,itt, ;3 ~a;~~n!r-. ir; ;~;.~c.. ~-~.,,~, :...;_r,.-: ~~'.=:w.~-,.:i:;~ -,~,ectra for the foam samples mere presRnt~:~~ i.~ ~igur~; , ~,.;~~ .-e;,-~~~~ :~.r ;~t--:~~.~~f ;~.;:.--~ ~.t~cnuation for the layered foam sta!~.~t:~re t~s~~r'!~c~m;,:~-,-,A' ~~ f~~; -~,
Claims
CLAIMS:
1. A high internal phase emulsion having an emulsion stabilizing surfactant, one or more insoluble fillers, at least 70 volume percent of a discontinuous internal phase, and less than 30 volume percent of a continuous external phase containing one or more vinyl polymerizable monomers.
2. The high internal phase emulsion of Claim 1 wherein the emulsion is a water-in-oil emulsion.
3. The high internal phase emulsion of Claim 1 wherein at least of the insoluble fillers has a density of less than 1 g/cc.
4. The high internal phase emulsion of Claim 1 wherein at least one of the insoluble fillers has a density of greater than 1 g/cc.
5. The high internal phase emulsion of Claim 2 wherein the surfactant is a sorbitan ester, glycerol ester, partial fatty acid ester of polyglycerol; a surfactant having polymerizable vinyl groups; a surfactant capable of undergoing a graft reaction at the conditions of polymerization; or a poly(butylene oxide/ethylene oxide) sulfate-based surfactant.
6. The high internal phase emulsion of Claim 1 wherein at least one of the insoluble fillers is a flame retardant filler, an infra-red absorbing filler, and/or a ferromagnetic material.
7. The high internal phase emulsion of Claim 6 wherein the flame retardant filler is aluminum 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. The high internal phase emulsion of Claim 1 wherein at least one of the insoluble fillers is a metal oxide, metal hydroxide, metal nitride, metal carbide, metal boride, metal powder, hollow ceramic microsphere or hollow glass microsphere.
9. The nigh 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; the 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 iron nitride; the metal carbide is silicon carbide, manganese carbide, iron carbide; the metal boride is iron boride, aluminum boride, manganese boride and the metal powder is iron powder.
10. The high internal phase emulsion of Claim 1 wherein at least one of the insoluble fillers is a naturally occurring or a synthetic member of the clay mineral family.
11. The high internal phase emulsion of Claim 1 wherein of least one of the insoluble fillers is talc, mica, montmorillonite, hectorite, kaolinite, dickite, nacrite, halloysite, saponite, nontronite, beldelite, volhonskolte, sauconite, magadine,meumomie, kenyalte, vermiculite, serpentines, chlorites, palygorskite, kulkeite, a~lettite, sepiolite, aliopnane, imogolite or mixtures thereof.
12. The high internal phase emulsion of claim 1 wherein at least one of the insoluble fillers is a multilayered inorganic material.
13. The high internal phase emulsion of Claim 12 wherein the multilayered inorganic material is a member of the clay mineral family, an illite mineral, a layered double hydroxide, a mixed metal hydroxide, a chloride, or an oxide.
14. The high internal phase emulsion of Claim 13 wherein the illite mineral is ledikite; the mixed metal hydroxide is Mg6Al3.4(OH)18.8(CO3)1.7H2O, the chloride is ReCl3 or FeOCl; and the oxide is H2Si2O5, V5O13, HTiNbO5, Cr0.5V0.5S2, W0.2V2.8O7, Cr3O8. MoO3(OH)2, VOPO4-2H2O, CaPO4CH3H2O, M~As~4H2O, Ag6Mo1~O33 or mixture thereof.
17. The high internal phase emulsion of Claim 1 wherein the insoluble filler is present in an amount of from 1 to 10 volume percent, based on the continuous phase.
18. A multilayer high internal phase emulsion comprising distinct layers wherein one or more layer contains one or more insoluble filler.
19. The emulsion of Claim 18 wherein the filler in each layer is present in an amount which is the same as or different from the amount filler in each of the other layers.
20. A process which comprises preparing a continuous phase containing at least one vinyl polymerizable monomer, preparing an internal phase, introducing an insoluble filler into either the continuous phase or internal phase, introducing an insoluble phase with the continuous phase under conditions sufficient to form an emulsion.
21. The process of Claim 20 wherein the emulsion is water-in-oil emulsion comprising an oil continuous phase and an aqueous internal phase.
22. A process which comprises preparing a continuous phase containing at least one vinyl polymerizable monomer, preparing an internal phase and then mixing the internal phase with the continuous phase while simultaneously adding one or more insoluble fillers under conditions sufficient to form an emulsion.
23. The process of Claim 22 wherein the emulsion is a water-in-oil emulsion comprising an oil continuous phase and an aqueous internal phase.
24. A process which comprises preparing a continuous phase containing at least one vinyl polymerizable monomer, preparing an internal phase and then mixing the internal phase with the continuous phase under condition sufficient to form an emulsion and then adding to the emulsion one or more isoluble fillers.
25. The process or Claim 24 wherein the emulsion is a water-in-oil emulsion comprising an oil continuous phase and an aqueous internal phase.
26. A process comprising preparing at least two high internal phase emulsions, of least one of which contains one or more insoluble filer, and then o~positing each emulsion on top of each other thereby producing a layered high internal phase emulsion.
27. A porous polymeric material prepared by polymerizing the high internal phase emulsion of Claim 1.
28. A porous polymeric material prepared by polymerizing the high internal phase emulsion of Claim 2.
29. A porous polymeric material prepared by polymerizing the multilayer high internal phase emulsion of Claim 18.
30. An open-cell porous polymeric material having insoluble fillers incorporated into its polymeric backbone.
31. An article comprising the porous polymeric material of Claim 28.
32. An article comprising the porous polymeric material of Claim 28.
33. A multilayer polymeric foam comprising at least two layers, each layer being either physically or structurally different from that of a contiguous layer and at least one layer being formed from a high internal phase emulsion having one or more insoluble fillers, 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.
34. An article comprising a multilayer polymeric foam having at least two layers, each layer being, either physically or structurally different from that of a contiguous layer and at least one layer being formed from a high internal phase emulsion having one or more 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.
35. The article of Claim 34 in the form of an acoustical insulating material.
36. The high internal phase emulsion of Claim 1 wherein one or more insoluble filler is water-swellable or oil-swellable.
37. The high internal phase emulsion of Claim ~ wherein at least one of the insoluble fillers has vinyl polymerizable functionalities capable of copolymerizing with the monomers in the emulsion.
38. The high internal phase emulsion of Claim 1 wherein the insoluble filler is present in an amount from less than 3 to 50 volume percent bases on the external phase.
39. A porous polymeric material prepared by polymerizing the high internal phase emulsion of Claim 1 while in contact with a non-HIPE material such that the non-HIPE
material becomes attached to the porous polymeric material during polymerization.
40. The polymeric material of Claim 39 wherein the non-HIPE material is a porous polymeric material, a non-woven material, or a polymeric ~~~ swellable with the external phase of the emulsion.
41. The polymeric material of Claim 40 wherein the porous polymeric material is a polyurethane foam, the non-woven material is a polypropylene non-woven tissue, and the polymeric film-swellable with the external phase of the emulsion is a polystyrene when using a water-in-oil emulsion with styrene in the oil phase.
42. A multilayer polymeric foam comprising at least two layers, each layer being either physically or structurally different from that of a contiguous layer and at least one layer being formed from a high internal phase emulsion having one or more 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 and having a non-HIPE
material between one or more layers and/or one or both surface(s).
1. A high internal phase emulsion having an emulsion stabilizing surfactant, one or more insoluble fillers, at least 70 volume percent of a discontinuous internal phase, and less than 30 volume percent of a continuous external phase containing one or more vinyl polymerizable monomers.
2. The high internal phase emulsion of Claim 1 wherein the emulsion is a water-in-oil emulsion.
3. The high internal phase emulsion of Claim 1 wherein at least of the insoluble fillers has a density of less than 1 g/cc.
4. The high internal phase emulsion of Claim 1 wherein at least one of the insoluble fillers has a density of greater than 1 g/cc.
5. The high internal phase emulsion of Claim 2 wherein the surfactant is a sorbitan ester, glycerol ester, partial fatty acid ester of polyglycerol; a surfactant having polymerizable vinyl groups; a surfactant capable of undergoing a graft reaction at the conditions of polymerization; or a poly(butylene oxide/ethylene oxide) sulfate-based surfactant.
6. The high internal phase emulsion of Claim 1 wherein at least one of the insoluble fillers is a flame retardant filler, an infra-red absorbing filler, and/or a ferromagnetic material.
7. The high internal phase emulsion of Claim 6 wherein the flame retardant filler is aluminum 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. The high internal phase emulsion of Claim 1 wherein at least one of the insoluble fillers is a metal oxide, metal hydroxide, metal nitride, metal carbide, metal boride, metal powder, hollow ceramic microsphere or hollow glass microsphere.
9. The nigh 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; the 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 iron nitride; the metal carbide is silicon carbide, manganese carbide, iron carbide; the metal boride is iron boride, aluminum boride, manganese boride and the metal powder is iron powder.
10. The high internal phase emulsion of Claim 1 wherein at least one of the insoluble fillers is a naturally occurring or a synthetic member of the clay mineral family.
11. The high internal phase emulsion of Claim 1 wherein of least one of the insoluble fillers is talc, mica, montmorillonite, hectorite, kaolinite, dickite, nacrite, halloysite, saponite, nontronite, beldelite, volhonskolte, sauconite, magadine,meumomie, kenyalte, vermiculite, serpentines, chlorites, palygorskite, kulkeite, a~lettite, sepiolite, aliopnane, imogolite or mixtures thereof.
12. The high internal phase emulsion of claim 1 wherein at least one of the insoluble fillers is a multilayered inorganic material.
13. The high internal phase emulsion of Claim 12 wherein the multilayered inorganic material is a member of the clay mineral family, an illite mineral, a layered double hydroxide, a mixed metal hydroxide, a chloride, or an oxide.
14. The high internal phase emulsion of Claim 13 wherein the illite mineral is ledikite; the mixed metal hydroxide is Mg6Al3.4(OH)18.8(CO3)1.7H2O, the chloride is ReCl3 or FeOCl; and the oxide is H2Si2O5, V5O13, HTiNbO5, Cr0.5V0.5S2, W0.2V2.8O7, Cr3O8. MoO3(OH)2, VOPO4-2H2O, CaPO4CH3H2O, M~As~4H2O, Ag6Mo1~O33 or mixture thereof.
17. The high internal phase emulsion of Claim 1 wherein the insoluble filler is present in an amount of from 1 to 10 volume percent, based on the continuous phase.
18. A multilayer high internal phase emulsion comprising distinct layers wherein one or more layer contains one or more insoluble filler.
19. The emulsion of Claim 18 wherein the filler in each layer is present in an amount which is the same as or different from the amount filler in each of the other layers.
20. A process which comprises preparing a continuous phase containing at least one vinyl polymerizable monomer, preparing an internal phase, introducing an insoluble filler into either the continuous phase or internal phase, introducing an insoluble phase with the continuous phase under conditions sufficient to form an emulsion.
21. The process of Claim 20 wherein the emulsion is water-in-oil emulsion comprising an oil continuous phase and an aqueous internal phase.
22. A process which comprises preparing a continuous phase containing at least one vinyl polymerizable monomer, preparing an internal phase and then mixing the internal phase with the continuous phase while simultaneously adding one or more insoluble fillers under conditions sufficient to form an emulsion.
23. The process of Claim 22 wherein the emulsion is a water-in-oil emulsion comprising an oil continuous phase and an aqueous internal phase.
24. A process which comprises preparing a continuous phase containing at least one vinyl polymerizable monomer, preparing an internal phase and then mixing the internal phase with the continuous phase under condition sufficient to form an emulsion and then adding to the emulsion one or more isoluble fillers.
25. The process or Claim 24 wherein the emulsion is a water-in-oil emulsion comprising an oil continuous phase and an aqueous internal phase.
26. A process comprising preparing at least two high internal phase emulsions, of least one of which contains one or more insoluble filer, and then o~positing each emulsion on top of each other thereby producing a layered high internal phase emulsion.
27. A porous polymeric material prepared by polymerizing the high internal phase emulsion of Claim 1.
28. A porous polymeric material prepared by polymerizing the high internal phase emulsion of Claim 2.
29. A porous polymeric material prepared by polymerizing the multilayer high internal phase emulsion of Claim 18.
30. An open-cell porous polymeric material having insoluble fillers incorporated into its polymeric backbone.
31. An article comprising the porous polymeric material of Claim 28.
32. An article comprising the porous polymeric material of Claim 28.
33. A multilayer polymeric foam comprising at least two layers, each layer being either physically or structurally different from that of a contiguous layer and at least one layer being formed from a high internal phase emulsion having one or more insoluble fillers, 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.
34. An article comprising a multilayer polymeric foam having at least two layers, each layer being, either physically or structurally different from that of a contiguous layer and at least one layer being formed from a high internal phase emulsion having one or more 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.
35. The article of Claim 34 in the form of an acoustical insulating material.
36. The high internal phase emulsion of Claim 1 wherein one or more insoluble filler is water-swellable or oil-swellable.
37. The high internal phase emulsion of Claim ~ wherein at least one of the insoluble fillers has vinyl polymerizable functionalities capable of copolymerizing with the monomers in the emulsion.
38. The high internal phase emulsion of Claim 1 wherein the insoluble filler is present in an amount from less than 3 to 50 volume percent bases on the external phase.
39. A porous polymeric material prepared by polymerizing the high internal phase emulsion of Claim 1 while in contact with a non-HIPE material such that the non-HIPE
material becomes attached to the porous polymeric material during polymerization.
40. The polymeric material of Claim 39 wherein the non-HIPE material is a porous polymeric material, a non-woven material, or a polymeric ~~~ swellable with the external phase of the emulsion.
41. The polymeric material of Claim 40 wherein the porous polymeric material is a polyurethane foam, the non-woven material is a polypropylene non-woven tissue, and the polymeric film-swellable with the external phase of the emulsion is a polystyrene when using a water-in-oil emulsion with styrene in the oil phase.
42. A multilayer polymeric foam comprising at least two layers, each layer being either physically or structurally different from that of a contiguous layer and at least one layer being formed from a high internal phase emulsion having one or more 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 and having a non-HIPE
material between one or more layers and/or one or both surface(s).
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 | ||
| PCT/US1998/016596 WO1999009070A1 (en) | 1997-08-15 | 1998-08-10 | High internal phase emulsions and porous materials prepared therefrom |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2296347A1 true CA2296347A1 (en) | 1999-02-25 |
Family
ID=26734694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002296347A Abandoned CA2296347A1 (en) | 1997-08-15 | 1998-08-10 | High internal phase emulsions and porous materials prepared therefrom |
Country Status (8)
| Country | Link |
|---|---|
| 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) |
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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 |
| JP4527384B2 (en) * | 2002-12-06 | 2010-08-18 | 綜研化学株式会社 | Manufacturing method of colored spherical particles using microchannel, and microchannel manufacturing apparatus used in the manufacturing method |
| GB0229810D0 (en) | 2002-12-20 | 2003-01-29 | Vantico Ag | Flame retardant polymer compositions |
| US6750261B1 (en) | 2003-04-08 | 2004-06-15 | 3M Innovative Properties Company | High internal phase emulsion foams containing polyelectrolytes |
| US20120135141A1 (en) * | 2007-08-23 | 2012-05-31 | Agency For Science, Technology And Research | Polymerization on particle surface with reverse micelle |
| 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 |
| US9440255B2 (en) | 2012-11-28 | 2016-09-13 | Eastman Kodak Company | Preparation of porous organic polymeric films |
| US10005917B2 (en) | 2013-04-30 | 2018-06-26 | Kimberly-Clark Worldwide, Inc. | Non-fluorinated water-based superhydrophobic compositions |
| US9803100B2 (en) | 2013-04-30 | 2017-10-31 | Kimberly-Clark Worldwide, Inc. | Non-fluorinated water-based superhydrophobic surfaces |
| CN103849096B (en) * | 2014-02-21 | 2016-04-13 | 中科院广州化学有限公司南雄材料生产基地 | A kind of high strength open cell type cellular plastic and preparation method thereof and application |
| EP2959967A1 (en) * | 2014-06-27 | 2015-12-30 | The Procter and Gamble Company | High internal phase emulision foam associated with polyurethane foam |
| DE102014112672B4 (en) * | 2014-09-03 | 2018-05-09 | Snaptrack, Inc. | Cover for a component and method for producing a cover for a component |
| CN104403242B (en) * | 2014-12-14 | 2016-06-08 | 新昌县澄潭镇康成机械配件厂 | A kind of preparation method of cold-resistant sound absorption heat-barrier material |
| WO2016138272A1 (en) | 2015-02-27 | 2016-09-01 | Kimberly-Clark Worldwide, Inc. | Non-fluorinated water-based superhydrophobic compositions |
| CN106478866A (en) * | 2016-10-07 | 2017-03-08 | 琼州学院 | A kind of preparation method of organic porous material |
| CN109593159A (en) * | 2018-11-21 | 2019-04-09 | 华东理工大学 | A method of molecularly imprinted polymer is prepared for template based on porous material |
| CN110229263B (en) * | 2019-07-02 | 2022-03-04 | 深圳市方科马新材料有限公司 | Light high-strength polymer material and preparation method thereof |
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|---|---|---|---|---|
| DE2256496C2 (en) * | 1972-11-17 | 1983-01-20 | Will, Günther, Dr., 6100 Darmstadt | Process for the production of molded parts with a cell structure |
| DE2851045A1 (en) * | 1978-11-25 | 1980-06-04 | Will Guenther Dr Med | Prodn. of porous articles from water-in-oil emulsions contg. monomers - by catalytic hardening under microwave heating |
| US4473611A (en) * | 1982-11-26 | 1984-09-25 | Lever Brothers Company | Porous polymeric material containing a reinforcing and heat-sealable material |
| US5563179A (en) * | 1995-01-10 | 1996-10-08 | The Proctor & Gamble Company | Absorbent foams made from high internal phase emulsions useful for acquiring and distributing aqueous fluids |
| US5922780A (en) * | 1995-01-10 | 1999-07-13 | The Procter & Gamble Company | Crosslinked polymers made from 1,3,7-octatriene and like conjugated polyenes |
| US5770634A (en) * | 1995-06-07 | 1998-06-23 | The Procter & Gamble Company | Foam materials for insulation, derived from high internal phase emulsions |
-
1998
- 1998-08-10 AU AU86991/98A patent/AU8699198A/en not_active Abandoned
- 1998-08-10 BR BR9811303-8A patent/BR9811303A/en not_active Application Discontinuation
- 1998-08-10 CN CN98807899A patent/CN1265678A/en active Pending
- 1998-08-10 CA CA002296347A patent/CA2296347A1/en not_active Abandoned
- 1998-08-10 WO PCT/US1998/016596 patent/WO1999009070A1/en not_active Application Discontinuation
- 1998-08-10 KR KR1020007001539A patent/KR20010022934A/en not_active Application Discontinuation
- 1998-08-10 EP EP98938468A patent/EP1003788A1/en not_active Withdrawn
- 1998-08-10 JP JP2000509747A patent/JP2001515104A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP1003788A1 (en) | 2000-05-31 |
| WO1999009070A1 (en) | 1999-02-25 |
| CN1265678A (en) | 2000-09-06 |
| BR9811303A (en) | 2000-08-29 |
| KR20010022934A (en) | 2001-03-26 |
| AU8699198A (en) | 1999-03-08 |
| JP2001515104A (en) | 2001-09-18 |
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