Note: Descriptions are shown in the official language in which they were submitted.
PCT/L;~S93108299
wo 9~/0s~; ~ 14 2 g 3 0
' w..r.v l n ~'v r.
:~OLiZDr.'_ _._..-.. "",~"" I2;I2w .
pL,~'ET HE~ POLL.., ~i~D '='HEIt"Z USE .
'='ECHNIC~L WELD~
'''his _nvention =elates _.. foundry .;,fixes whicz
corar ise a dr ~- f oundr'. aggr agate , a polyure thane-i orming
foundry 'nder, and a'liquid amine curing catalyst. The
binder comprises -a poiyether polyol comoonen~ and an
organic polyisocyanate component. ~'he foundry mixes are
used to prepare roundry shapes made from foundry mixes by
a no-bake proeess. '"he binders do not contain any free
fcrnaidehyde cr pneno~, and are preTerably,soiventless and
odor less , whic'.~. resul is in less s tress to the environment.
__ The resu -1 =~ ~~_ f ound=°: snaoes are used to cas t metal marts
r or" f e= r ous and non f err ous metals .
BACKGROUND Or THE Tr7V~NTION
20 In the zoundry industry; one cf the processes used
fo= making metal parts is sand casting. In sand casting,
di.sm_osable foundry shapes (usually characterized as molds
and cores) are made by shaping and curing a foundry mix
whic:: is a mixture cf send and an organic or inorganic
.... binder . The binge= is used to s 'r engthen the molds and
cones.
One c' the processes used ~~ sand casting fcr making
molds and cores is the no-bake process. T_n this process, j,
a foundry aggregate, binder, and liquid curing catalyst
E
:30 are mixed and compacted to p:oduce a cured mold and/or
core. In the no-bake process, '_' is imaorta.~.= to E
formulate a foundry mix which wi'_1 provide su:~icient
war?: time to allow shaping . Wor~aime is the time between
when mixinc begins and when the mixture can no longer be
~ eff ec tiveiy shaped t:. f i' 1 a mold cr care .
A binder common:.., toed _.. the no-bake process is ~.
r i~.'1
moivuretnane binder derived ~_° _,.-~~~ a poiyurethave-
fo~-m;ng :,finder wit'.~. a liquid te_-tia=y amine catalyst.
Sucpoiyuretnane-f~'~-ina binders usec _.. the no-pake
:,z ocess . Nave p-oven sa t~ s::ac tea _: -_ __ cas ty:.g sucz metals
re ..rw.,..ni ~ .'~.~~ ~e~~e~~~~~~G
~g _~ ~~ .._ Ste°. nr.:.~: a_ ...._...__
WO 94/05447 ~ 1 ~ ~ ~ 3 ~ PCT/L'S93/08299
exceedinc about ?500 degrees :ahrenheit. They are also
useful =:: the casting c° '_ight-weight metals, such as
aluminum, which have melting points of less than 1500 ,
degrees Fahrenheit.
The polyurethane-for:r,ing binder usually consists of
a ohenolic resin component and polyisocyanate component
which are mixed with sand prior to compacting and curing.
Both the phenolic resin component and polyisocyanate
component generally contain a substantial amount of
organic solvent which can be opnoxious to smell and can
create stress for the environment. Because of this, there
is an interest in _developing binders which do not reauire
the use of organic solvents.
British Patent Specification l 203 943 discloses a
25 foundry binder which purports to be solventless, yet
effective. The foundry molds and/or cores disclosed in
this patent are prepared from a foundry mix consisting of
a (1) a wet foundry aggregate and (2) a, polyurethane
forming foundry binder comprising (a) a poiyether polyol
having a hydroxyl value above 200 milligrams of potassium
hydroxide per gram of polyether polyol and a functionality
of at least 2.5 (b) an organic polyisocyanate, and (c) an
orQano-metallic or amine catalyst. The foundry mix is
comD_acted into a mold and allowed to harden until the mix
has sufficient dimensional stability so that it can be
removed from the mold.
- 'The patent states that the amount of the water in the
foundry aggregate is from 2 to 7% by weight based upon the
weight of the foundry aggregate. The patent suggests that
the water in the aggregate may contribute advantageously
to' an earlier attainment cf dimensional stability in the
foundry shape. wt also s;:ates that excess polyisocyanate .
is desirable to compensate for the presence of water. The
examo_les show an isocyanate index of 130.
The patent is otherwise rather indeffinite. For
instance the amount of the catalyst level is not given in
any cf the examples.
WO 94/05447 PCT/US93/08299
-3-
' ~" -' ~:'Vr.Ni IOPd
S LTM~IAR f ,. . _ .. r, _ ,
This ~.:,ven t=on r elates :.o a ~oundrv :~i}: comnr ising as
a miktur a
~ a j a dr ~: . oundr-: aggregate ;
;b) a pcivurethane binder comnr~smg:
~;) a oolvether polyol component; and
(2j 2n organic palydsocyanate component;
y0 and
~~) a catal.:ticallv effective amount ef a
liauid t'rtiarv amine catalyst
wherein components (1) and (2) are compatible
w f t:: eac~ c then .
15 '~'he invention also relates t~ the use of these foundry
mixes in a no-bake process for, preparing ~oundr,: shapes,
and the use of these foundry shapes to cast metal parts.
The binders of the foundry mixes.do not contain any
free formaldehyde ar phenol and preferably do not use
20 solvents and thus are odorless, which creates less stress
to the environment khan conventional polyurethane-forming
binders . The f oundry shapes prepared with the binders also
show good shakeout -when used to make metal castings.
~inall~.v, 'he metal castings do not exhibit as :;such
... ?.ustrous carbon as taose made with many other commercial
binders. This is signi=icant because lower lustrous
carbon results in reduced casting defects:
BEST MODE AND OTHER MODES OF PRACTICING THE INVENTTON
The polyether polyois which are used in the
polyurethane-forming Foundry binders are liquid polyether
polyols or blends c. w quid polvether polyols having a
hydroxyl number of '=om about 200 to about 600, preferably
about 300 to about 500 r,.illigrams of KOH based upon one
gram of polyether poiyol. The viscosity cy the polyether
polyol is from 100 t~ 1,000 centipoise, preferably _rom
200 to 700 centipo:.se, :post ~rererabiy 300 ..,. 500
centicoise _. '"he poiv a then ~olv~ois may have pr ir.~ar~.: and! or
CA 02142830 2003-05-05
WO 94/D~:l..t ~ ~ 1 ~ ~ ~ ~ O PCT/L~543/08299
-a-
sect.~.aar ~ . _ _. _ _= ouos .
~Ji~ "_c G~.~e ....~,.~.:ISIe=~...G~~.. 31'G.'..~.?r~'J~.e ~'G.iC: ~ile.lr
met..~.oa c= ~epar~.._c>. and deter.-.:~:~:.- their nvdrok~.1 :value
~.s we:.! ::sown. =!:e ~c ~yetner ~oiyols ere ~re~red by
.=_ac~~,r,c a;. zlk;.~'_ene c~:iae kit:. ~ poiv~~~cric a~~cohOi .n
~h= rc=_sence _: _.. ~oc.:c _ vase c::~aivs~ sucas sodium
.'.?et,~.X.lQe 2~.~.~r~_. . ~_. Tle,'.I:O.~'~.5 W~._ :::la'vJi. _.. Li?o ?=v.
:W.y
su_tabi.e alt:-, 1=ne o>:ide cr -i~:tures oa'_~:vlene c}:ides may
be = ea~=tea h i t~:-:e co ~:.~ :~vc= '_.. a'~ cohcl ~o ~r eoare the
_,. oolve they c ~ vo?.s . "_'~e a ~~}:vlena ..:~;ides used __ tr mare
the aolvetne~ c:vo~_s tical~~~: Zave _r o~ two to six
carboy, atoms. ~earesentative examaies include athvlene
oxide , . _-c~ylene oxide , ~;: tylene oxide , amyiene cx~de,
s . v r enE: c};ide , .._ .-..=ya~.:r es : hereof . The tclvhvdr is
alc~hois t:~~zcsll~,~ uses =~ nreoare the ~oivether aolvols
genera~.ly :nave ~ =urctiona':.ic~; greater khan
pre=erably _rom 2.5 to 5.0, :,lost preferably from 2.5 to
Exaraoies i.~.ciude ethylene aiycol, diethylene glyco3,
nropvls:ne glycol, _rimethvlol propane, and glycerine.
20 Although not preferred, ~ainor amounts of phenolic
rasi.:~ and/or amine-based palyals car, be added ~to the
polyether aolyo":.. 9y minor amounts, a is meant that less
that ~a weicht aercent c= phenolic res_.~. and/or amine-
oasec poi~. c_ _s added ~asec upo;, the weiC.-.t .,_ the
_.. aoiyether poiycl, usually: 'Hess r.han :5 weight percent and
preferabl_~ less t:an 5 weiw:.t pence..~.t, said weigh t percent
based upon Lhe weight c' :.he polyether polyol component.
_T_' a phenol=c resin is added to tze nolyether polyoi, the
preferred ahenalic resins used are benzylic ether phenolic
resins which are specificall! dese=ibed in U.S. Patent
;~485,7~7.
:.:Lthouch not preferred, organic solvents may be added
:,w. =he polyether polycl car..ponen:, pa=t:cuiar_y _t a
__ benzyl _c ether pheno~.:ic resin .s used ~,~i=:: the poiyether
oolvoi. The axount of solvent ~aec is aenerallw '_ess
=ha.~. =~ weich ~ Mercer.-., usu~ll_ less Khan _., weigh t
CA 02142830 2003-05-05
WO 94I054~7 ~ ~ ~ 2 ~ 3 0. PCT/C.~S93/08299
percent, rreferablv Hess t:.an ~ wezar.t aercent based ::pon
whe ~o~al weight c~ she poiyether polyol component.
Other optional =ngredients ::hic;z .:~ay be added to the
aolyether include release agants and adhesion p:o~oters,
_ such as silanes described ~n '~.~. Paten. x,540,°a:.
Organic polyisocvanates used in the organic
polyisocyanate component, ;which act as a hardener, are
icuid oolvisocvanates having a iunctionalitv cf two cr
more, preferably _ to ... They zay be aliphatic,
cycloaliphatiy, aroz~atic, or a hybrid polyisocyanate.
:~:ixtures c: suc;: 5olyisocyanates nay be used. The
polyisocyanates s:~~ouid have a ~~:.scosit_; cf about :,00 to
_., about =,000, preferacly aoout 200 to about 600:
Representative examples o~ polyisocyanates which can
be used are aliphatic palyisocyanates such as
hexamethylene diisocyanate, alicyclic polyisocyanates such
as ~,4'-dicyclohexylmethane diisocyanate, and aromatic
20 polyisocyanates such as 2,4- and 2,6-toluene diisocyanate,
diphenylmethane diisocyanate, and dimethyl derivates
thereof. Other examples of suitable polyisocyanates are
1,5-naphthalene diisocyanate, triphenylnethane
_~ iisocyanate , xylylene ~iisacyanate , and ~:~e "e t::yl
derivaces thereof, polymethylenepclyphenyl isoc_~~anates,
chlorophenylene-2,4-diisocyanate, arid the like.
The polyisocyanates are used in sufficient
concentrations to cause the cu:ing of the palyether p~lyol
when cured with the liquid amine curing catalyst. In
30 general the isocyanate ratio of the polyisocyanate to the
hydroxyl of the polyether polyol resin .s from y.2~:1.0 to
0.75:1.0, preferably about 0.~:~,.o to 1.1:1.0, an3 ~ost
preferably about 1.0:1:0.
The polyisocyanate preferably contains a natural cil
35 ~ahich may include unmodified natural oils as yell as :hei_
various i~nown modifications, e.g., the heat bodied ai=
blown, or oxygen-blown oils suc:~ as blown linseed c__ and
WO 9~/OS=14 ~ , PCT/L~S93/08299
X14283(1
-6-
cio~,~n sowean .._~. =:~e:' ar°- generally ciassiyied as
esters .._ ethvie~~cali~.~ ~.:nsaturated 'att.: acids.
~re~eraby~: ;.he viscosm_: .._ ~:~.e natural oil is from A to
~.~.de~: :yore preferably
on t:~e ~:ar finer ?-?o~ t . ~scos~ t_: _ , ,
.. _r cm .. to ~ , and ;,ios t _ : e~eraDlV' r to 5. ar efer ably the
acid value c: the natural ci'_ ;s ficm about 0 to about IO,
rare prererably about 0 to about -~ , and most preferably
about 0 to about ~ as neasured by the number c~ milligrams
c~ potassiu:.l h~:dr~i::.de needed .... neutral ize a ~ gram
:0 samnie o~ tze natura'~ cll.
The natural oils are used _.. an effective amaunt
sufficient to ~ ;,prove 'he tensila strength of the foundry
shapes _maae wi t the c:.nder s . =:~is amount w ill generally
range from about . percent by weight to about IS percent
1 J w y we igh t , :cos t prey erably about 2 per cent to about IO
percent by weight, based upon the weight of the organic
polyisocyanate. Repzesentative examples of naZUral oils
which are used in the isocyanate component are linseed'oil
including refined ;inseed oil, epoxidized'linseed oil,
20 alkali refined linseed oil; soybean oil, cottonseed oil,
RBD Canola oil, =efined sunflower oil, rung oil, and
dehydrated castor cll.
Pr ef er ably used as the ha tur al c l 1 are pur e. f crms of
natural o;is which are -seated to remove fatty: acids and
azher impurities. These purer forms of natural oils
typically consist cy trigiycerides~and less. than l weight
percent cy impurities such as fatty acids and other
impurities. Speciyic exampie~ cf these purer natural
oils are purified linseed oils, such as Supreme Linseed
30 Oil manufactured by Cargill Corporation, having an acid
value of aDOUt 0.30 maximum and a viscosity of ~. and
pure=led soybean cils such as refined soybean oil having
an acid value of less than 0.1 and viseasity~ of ~ to 8.
Drying oils, ~c~ example those ~isciosed ..~. ~.S.
__ Patent :~,260.~25, may also be ~,aed i.~. the poiyisocyanate
component. Drying ells may be synthetic o= natural
W IWV~'~in~ a~4 r.~1W 1~? Va~~eTi~e~ .re al~W.nl.y aI~~Lj YYn~V~
PCT/US93/08299
WO 94/0a44.
~;.:,ta~:: .-.;o == ..,crc :J::..:~we coeds ~.:nerebv ~:;vgen on
JYposure ~_ a~- ca:~ --c G.:sCrDed to give pert}:ides whit::
catalv~= ~:e poivmer~~a-~on c~ t~e unsaturated portions.
~~ct~onai :..~red~.ents suc:: as ~eiease agents and
solvents -a~' a~;so ce used ;.. the organic ~olyisacyanate
~;,ma_ onen t .
l t:.oucn ~ct _ re~err°d. solvents ",ay be used .:: the
organic :,oiv;soc~_ anate co:.~.ponent andlo~ poiyether polyol.
__ solvents are ~~sed _., ether , t:ZOSe sf:illed in the ar~
'.;ill r:noc; now _.. select then.:. ~.ypical organic solvents
whit:. are used _~:clude aromatic solvents, esters, or
a ther s , ~-e ~ era~c 1 ~ .::' %: ;.ores ,: ~ these so l vents . ~ener a l iv
,
=::ese s:~ive.~.ts e''° t=SeC ... a:~ounts '.Hess trap about
ercent cased uDOn the weight cL t:Ze organic
weigi:,.
_5 poiyisocyanate component, ~,rezerably less than :. weight
percent.
The binder .s preferably made available as a three
package system with the nolvether polyol component in one
package, ~he organic aolyisocyanate component in the
20 second package, and the catalyst in the Third package.
when making foundry mixes, usually the binaer components
are combined and then nixed with sand or a similar
acc_ rotate t.. f cr:~ the f oundr :~ix cr the :,~,ix. can be ~ crmed
by sequent~ali.: .-,;fixing the ccr,:ponents wit:: he aggregate.
- Droferably the poiyether poivol and catalyst are first
GJ
.~"ixed~ wi t:: t:.e sand bef cr = :~i}:ing the isocyanate component
w i th the sand . !r!ethods of ::is tr ibuting the binder on the
aacreaate par titles are well-'mown tc those 'skilled in the
art. The r,.ix can; optionally contain other ingredients
30 such as iron oxide, Ground flax fibers, wood cereals,
D_ itc::, refractory f lour s , and the like .
The ' ~~uid a:,,ine cataiys~ is a base having a phi value
general 1y ~ ; the range c f abou t '' ~ o abou t _ _ . 'r'he ter ~:
"'_icuid amine" is meant tc i~~'ode amines which are :.'_quid
:.'-, at ambient ~e:~p°_r=Lure ~_. t:.ose in solid farm, whit : are
;:issolved _.. app~opristo solvents. '"he et;:. ~-aiue .s th°-
neca t~ ~: a _ far _ _.-.: .. _ _::e _isscci:: tic., cons ta.~.. .._
=:=°_
CA 02142830 2003-05-05
214~83C~ ,.._
WO 94/05.x=i. PCT/L~S93/08299
base and is a we:L:.-known raeas,ure of ;.he basiciw.~ c: a
basic material. fhf: s~igher this number is, the weal~:er the
base. The bases fa.ll.ng witain this range are generally
organic r_ompounds containing one or more ni.tragen atoms.
Pref erred bases are :~~eterocyclic compounds containing at
least one nitroge:a atom in the ping structure.
Specific examples of bases which have pKb values
within t:he necessary range include 4-alkyl pyridines
wherein t:he alkyl g:rou~o has :rom one to four carbc:. atoms,
isoauino:line, ar~rlpyridines such as phenyl pyridine,
pyridine, acridine, ~-methoxypyridine, pyridazine, 3-
chloro pyridine, guinoline, N-methyl imicazole, N-ethyl
imidazole, =,,~'-dipyridine, 4-pheny'propylpyridine,
methylbenzir.:idazoie, and 1,4--thiazine. Preferably used
1~ are bicyclic ter t.iary amines such as DABCC~~3 LV and DBU
sold by ~~ir Produca;s Company, and diethylenetriamine. The
amines have boi,..ing points of at least 100'C, most
preferably at least 200'C.
In view of the varying catalytic activity and varying
catalytic effect desired, catalyst concentrations will
vary widely. In general, the lower the pI~ value is, the
shorter will be the worktime of the compasition and the
faster, more comple:te will be the cure. solvents and any
acidity present in added ingredients su~h as sa:.d may
2., affect the catae..ytic act~.vity . In general, however,
catalyst concentrations will be a catalytically effective
amount which generally will range from about 0.5 to about
5.0 percent by weight of the polyether polyol, preferably
1.0 percent by weight to 3.0 percent by weight, most
preferably 1.0 percent by weight to 2.5 percent by weight
based upon the weight of the polyether polyol.
In a preferred embodiment of the inventio~, the "
catalyst. level i. adjusted to provide a worktime for the
foundry mix of minutes to 1o minutes, preferably
3 ~ minutes to about 10 minutes , and a striptime o f abou ~ -:
minutes to 12 minutes , pref erably 9 minutes to aboL ~ 10
minutes. Wori:time is defined as the time inteesa".: alts=
WO 9.~/05:~:1. PCT/L'S93/t18299
_g_
~ixinc t:-:e p:,~~.'.':.socvanate, poivrether , and catalyst and the
time when the =oundr~,~ shape reaches a level cf 60 on the
Green Hardness "n" Scale Gauge sold by.Harry W. Dietert
Co. , Detroit, '.~'.ichigan. Striptime is time interval after
~ixing ~he poll-i socyanate, polyether , and catalyst"and the
time when the foundry shape reaches a level of 90 on the
Green Hardness "3" Scale Gauge.
In this preferred embodiment, the ratio of the
socyanate gr ouDS cf the pol}~isocyanate to hydroxyl groups
l0 of the polyether polyol is preferably about 0.9:1.0 to
about 1.1:1.0, post preferably about 1.0:1:0, the hydroxyl
number cf the polyether polyel is from about 200 to about
500, and the weight ratio of polyisocyanate to polyether
~olyol is from about 55:45 to about 45:55, preferably
1~ about 50:50. These parameters provide optimum worktime,
striptime; and tensile properties.
Various t~~pes cf aggregate and amounts of binder are
used to prepare foundry mixes by methods well known in the
art. ordinary shapes, shapes nor precision casting, and
20 refractory shapes can be prepared by using the, binder
systems and paoper aggregate. The amount of binder and
the type of aggregate used is known to those skilled in
the art. The preferred aggregate employed for preparing
foundry nixes is sand wherein at least about 70 weight
25 percent, and preferably at least about 85 weight percent,
of the sand is silica. Other suitable aggregate materials
for ordinary Foundry shapes include zircon, olivine,
aluminosilicate, chromite sand, and the like.
In ordinary sand type foundry applications, the
30 amount of binder is generally no greater than about 10% by
weight and ~reauently within the range of about o.5% to
about 7% by weig'.~.t based upon the weight c' the aggregate.
Mos t often , the binder conten ~ f o~ c~ dinary sand f oundrlr
shaaes ranges 'rpm about 0.6% to about 5o by weight based
:;:. upon the weig::- of the aggreaa~e .n ordinar:~ sand-type
foundry shapes.
The aggregate employed w~~.. the catalyzed binder in
CA 02142830 2003-05-05
vt~p g,~lp~; PCT/L~S93108299
_ y~,_
_"..~_.~. ..::°_ _..::~~-, .-..:.:~. s:,cu:.e ce s:::__..~er.:,_. ,. _
so
.-::at ? handleabie _csnar; s.~.ape =esults ef:.er a wcrJ:time
to ... n~nutes ana 2. st=_p time o~ f t.o 1~ ::inures.
N
~~ene=gi_v the a~.ou.~,~.s ~_ ...~zst:.re _:, to aacreaate is less
_ =::a:, . -about ~.5 per cant , ~.~mc:.t, pYeferabl~~ '.ess than
abou= ~.~ fierce~t ~y weight. and roost p=eferablv 'Hess than
about o.: percent ~y weic:.t cased on t::e weig::t cf the
sand.
_ n L~:.~MP LLS
The examples uhic:. _cllow wii= _llustrate specific
emboi::ents .o' the _nve.~.ticn. '"hens examples a:ong ~:ith
_a u,r_..:.e:~ descr:-_i;,.~. ~::_1 enable one sr::.l'_ed ~_. :he art
__ to -practice the invention. '_. is contemplated that many
other embodiments of the _nvention will be operable
besides those spec:.'~.caly- cisc;osed.
:n all cf the examples, ~he test specimens, unless
otherwise indicated, were produced by the no-bake process
2~ using DABC0~3 L~ , a bicycl:.c te: nary amine sold by Air
?roducts Company, as a ~3 percent solution in dipropylene
glyco 1. All parts are by weight and all temperatures are
in °C unless otherwise specified.
Unless c~herwise .: cic~ted. -he faundrw :.-axes were
..., p= spared ~.y . :.r s t ~ixin~ ~ fiDRO ;~ 5C 0 sane . w f t:: the
ooiyether ~lyoi anC catalyst for about ~ minutes. Then
the MONDlJR ?fit was nixea -with the ~ixzure c' sand,
poiyether, and catalyst fcr about 2 minutes. The amount
of polyether polyol and polyisocyanate was such that the
;;: ratio of hydroxyl Groups cs the polyether polyol to
isacyanato Groups cf the pelyisocyanate was about .:1 and
the weight r grip of poiyether polyol to polyisocyanate was '
abou4 ~0:.'-.~. ':he binder :.evel and amounts of
poly~socyanate arid p:,lyethe=, pl~.a any other components
__ are given :..~. the rabies wnic~ _cllow.
Meant... _ ' ''se aog bone shapes
the ~e.~.Sl:.e 5 ~~ en~..~. C.
enables one .:. Drec~c_ '.;o;; the ~ixt;:re cf sand ana finder
~.:or:: a ::.ua~ -......d'.. :.perat:.:.rs. Lows= ters_~.e
::.__ _..
CA 02142830 2003-05-05
~~4283U
w0 9aio5aa; PC?/L~S93/08299
_"_
.. _r e:~g-::s _ ~_ Y~:e . :ape= _...._ca ~.e _ a t the ~~ls~eLher
oolvc'; Gad c.._._sccvanate ~e~cteh ~ore eia ensivelv during
~axina :: l ~_.._ sane p. _.._ cc y.,_.-"mg . ounarv snapes, ana
=':us wer n ::..,. _ __ ~a~~e . __ _ __..._. _ _ sundry shapes
_ ;'e _-..:::.~-_ shapes were s4ored :. :.our , ~ hours and 2.:,
haur s :..~. ~ ..cps tar. t -°_I(tDe="'c.. tur a = oom at a relative
humicit.: c. ~;;~ and,a cems~erature c~ _~°C before -measuring
their tensile ==rengths. :;nless otherwise specified, the
Tensile st~en~~.~.s were also measured C:1 SllabeS S;.ored 24
hours a' a re~_a_:.ve ::unidit. ;nri) c~ :.000.
m::e ~ cl'_o:; inc ter~s 'were used _., the e~:ar:ales:
'~iOt:D'~ '~a - an _=canic coivisocvanate
commercially available _rom MILES. T_NC. paving
.5 a t::nctionalitv o~ 3.5 to 2...
?LL'~raCO:. :OLYGL '_'?-440 - a polyether polyol,
sold commercially by BASF, having an OH value of
398, prepared by reacting propylene oxide with
t: iraethyo loronane .
20 RF'. - relative humidity.
SLO = Supreme i.inseed Oil
Sm - stri:.ti:ne.
tc'?~ - wor:r: ti:aa .
0/W = on weig~~ ~_.
:.5 BOS = based on sand.
at~s~T ~ . ansl y"~Mpsri,.a=.~iIT~~ F~L.T~s~i~ h:~L'
Examples :. and 2 are w l t::in the scoae of the subj ect
invention and were prepared with dry sand. Comparative
30 Examples h-F are t,.he same as Example 1 except varying
amounts cr:ois;.ure were added to the sand as indicated in
Table I. :.dcit:.onally, :.n Co:,iparative Examales B and D,
the isocvanate :.nde>; was varied _ror" .: ~ to 1. 3 : ~ to
cor r esDOnd w l t' whe .ade~; shown _.. B, :, fish aten t
_~ ~ .. spe=_.__ examai~ _, anon.~.er t=.-,~sterc_a:'_ ava:'~a~ie
~5?ve=~mr . ....__.. -s e'~e~~_~:e _,. u_:.=Rn::C~ .___
~oiye::~gr . ..~:,'. sc'_~ , ~:.~_es. _..,..
~1~2830
WO 94/OS:i4 ~ . PCT/L~S93/08299
-1?-
Soec~ficatic:~ ~ 303 943.
The data _.. Table _ _::dicate t:~at the foundr;~ .;,fixes
:,renared with ~~v sand and soiventless binders perform
effectiveiv. ;hev furt:~er indicate that these same
~cinciers do not pe_form effectively on wet sand which is
surtrisina '~ view c' the teachinas as shown in Brwtish
Patent Speci~ication 1 203 943. This indicates that there
;s a difference between the subject invention and the
_nvention described i.~. the B.~itish patent.
PCl'/US93/08299
N
WO 94/0~~ ~ .
-.
l: J'
f
:/'.
..
~ '
. i
'
~
,
.
~
J :J
'J
_ ~ 3
$
~
~J ~c
_
~
S
i,' N v1
... f .~.
v i
~
~'.
N
V T V
~
N
...
.
J J J' V 'J
1~ ~_'~~ V :J
_
...
-
G M
-
H ~
__..
v. i~ r T H ~ Y1
T T
7
o v; Z ~ 7 ~. . v
' . 7 "
_
~ r . N N r~, f N _
'~ N '~ .
..~ n A /~ ~ ~ x'
n ~
ao
E E,, ~ ~, ~
.~
V
'.. . .. r _
W ;
j
~t 0C ~d 0D 00 00
' C.D
J N N r ' ~ N N
N N e; N . ~/
N .
t ~ G < < C
L G L G < G G
_ 1
~
I
... i ~=
=
~~
'v,, . _ . .
~ x oc x ~i
. r. _
_
y
-
i - ~ m ~ = ~ =
:i = _ :
_c ~ io
_
-
. ~ _ i i.e i.
r. i H
i W~
r
~...
- - , . ,
_
a - ! . .. . - -
'~
.~
~ ~ :J .~
J' . .r
L . .. .. .
r. -. f v
WO 94/0S44 ~ ~ ~ ~ ~ ~ ~ ~ PCT/L:~S93/08299
='Y MD7 rC ~
..A._ _~ and
In Example ~, the procedure of ~'xample 1 was
repeated. Example 3 ~.s a repeat of Example 2 except five
weight percent cf t:~e MONDLR MR organic polyisocyanate ~ ,
was replaced with SLC, Supreme Linseed Oil. Obviously the
weight ratio of polyisocyanate to polyether was affected
by this addition. The weight ratio of polyether to
polyisocyanate for Example 2 was 51.6/48.4 while the
weight ratio for Example 3, the formulation containing the
SLO, was 50.3/49.7. The results of yhe experiment are
show in TABLE I.I. '"he experiments indicate that the
tensile strengths of the test specimens are improved with
the addi tion of the SLO.
i5
~~1~~~30
WO 94/04:1 ~ - PCT/L~S93108299
-1 ~-
H
V
.J
O oC
_
H r c ~~ e:~,
~ N
x 3
= ' ,~
M
O
E, = _ ~
_
H
O
H . ~
H C3 ~~ ~ ~ N
c ro
w 3 ~ '' ~ _ ;-.
'~ :
w w ., .
E a ~
.~
Z ' ~; _
w
w
x m
_ ~ 00
z
a ~ N < .:
N
' ' ~ ~ ~ v
p ~ L ~,
O
H i
E
a .: ~, _ -
~' _
_ ~ ,o
r~
~;, _
=o "c 1
= irt ,G:
f ~ .,
L'1 . C L .
o-
EXAMPLES 4-b and COMPARATI~'~ EXAMPLES G--
Again the procedure of Example 1 was (allowed except
the catalyst level was varied. These examples show the
effect of catalyst levels on worktime and striptime.
Table _TII indicates that, in order to obtain adequate
worktime and striptime, the catalyst level must be from
about 0.75 weight percent to about 2.25 weight percent
based upon the total weight of the polyether polyol.
PCT/L:~S93/08299
w0 9aio~.~a; ~ 1 ~~~. ~:3:~
-1i-
J
~ x
_ sn r mr
'~. .
. . ~ x y v,
~. H
. ~
~ N N
~
t0 en m
.
~ 4 _
~ ~ ~
. ~' ~ w
I
~ ~
, r 0 ~
C ~
1 ~ . f~J .
~ .~
! .
_ ~ N (sJ N r :!
-
. ~ N
.
H
'1
H n W N
T C
~
~ ~ "_ N , x
, ,
a V
~
E w
p
~
E ~ ~ ~ .~ ~ .~
_ _
w V ~~ ~ ~~T ~ p:T J ?~
?. r T
~, ~ . = ~ ~, a
-
,, ,O ~ ~. N N . PS
. ~
w .
pp _~G :0 CO 00 CO
c a : . c:
_;~ N r'! PJ N N N
N N r ~ r
t, ~, ,G G G G
.
L G L ~ G. G
-
~
7
.
i ~ -
. . ~ :,I J
_:d '; .L ' 0p CG CD 0G
x - 70
~ ~ '
'
~ N ~ ~ ~ ~~'7,
'
,~, ~ f~ ~ c~. . . h .. t-1
M e
~
, ~ r. ~
1
L1 ~r
n
WO 94/0~~? ~ 1 ~ ~ ~ PCT/L,~S93/08299
-i8-
COMPAR3TIVE z'XAMPLES J-L
Comparative Examples J-L illustrate the effect of
using polyether polyols with hydroxyl numbers outside the
claimed range. VORANOL 230-660 polyether polyol, used in
f' :.
Comparative Examples J and h, is a trifunctional polyether
~s
polyol having a hydroxyl number of 660 and a viscosity of
850 cps. PLURACOL 726 pol ether
y poiyol, used in
Comparative Example L, is a trifunctional polyether polyol
t
having hydroxyl number of 55 and a viscosity of 420 cps. E
The data in Table IV which follows indicates that
these polyols are not effective in achieving the results ,.:
demonstrated by the subject invention.
".
~1~Z~~C! r
WO 94/054.7
;.
PCT/US93/08299
r
-1a-
2
rl
~0
_ ... '~
n O
N
7
n h
r
f.1
.O N1.-p
V1
G P
N
O
~
a ' '
> " ~ ~:=~ .o
~ =
- . _ H _
_ ~,
> ~
x ..
p . ~
.fix
H
w o 3 ~ ~ ~
a
c
a ~
ca
x
H
w ~;
~
0
4.,
E 0.
w
haft ha0 .
W ~ N
W h
N ~I,
a z c i
5
x ~ a
i
O - - ~ ~ 7
", x '
N J
' v J
> J ~ ,
~ ~' YJ
_ 5 ,-,. N .,T., j
;/) N f'! P. ,J f t'! h -
i
J
r
,
,
_. ~, _ t~ ' II i
~ v r v
~. '7 ! J PJ _ _
- _ _ N _ ~' J ~.
~ 4
: _ ~ ~-
,
!: ~ v
In d lf7
~"1 n N
