CA 02296347 2000-O1-10
WO 99/09070 PCT/US98/16596
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.
CA 02296347 2000-O1-10
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
CA 02296347 2000-O1-10
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
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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
CA 02296347 2000-O1-10
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.
CA 02296347 2000-O1-10
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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
CA 02296347 2000-O1-10
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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,
-7
CA 02296347 2000-O1-10
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
CA 02296347 2000-O1-10
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
CA 02296347 2000-O1-10
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;.
CA 02296347 2000-O1-10
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
CA 02296347 2000-O1-10
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,
-12-
*rB
CA 02296347 2000-O1-10
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. _ : : ~.
,..
CA 02296347 2000-O1-10
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,;.
CA 02296347 2000-O1-10
WO 99/09070 PCT/US98/16596
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
CA 02296347 2000-O1-10
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~~; -~,
-16-
