CA1262592A - Polyether silicone copolymers with mixed hydroxy alkoxy capping for stabilizing high solid content, molded, flexible, urethane foam - Google Patents

Abstract

ABSTRACT
This invention describes novel molded flexible polyurethane foam surfactants which can be used in foam having high concentrations of reinforcing graft copolymer solids. The invention also describes an improved process for making these foams using the novel surfactants.

Description

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POLYETHER ~ILICONE COPOLYMERS WI~ MIxæD
HYDROXY ALKOXY CAPPINB FOR STABILI~ HI~
~OLID CONTENT,_MOLDED, FLEXIBLE URET ~ FO~M

BACR~ROUN~ OF THE INVE~rI~N
ield of the Invsn~ion This ~nvent;on ~ela~e~ ~o polyure~hane oam surfac~ants. ~OE~ ~pecifically, ~hi~ ~nven~ion relates ~o ~ovel ~urfa~tan~s mad~ ~rom polydialkyl~loxane-polyoxyalkylene copolymer~ whi~h have both hydrocarbon and hydroxy capped polyoxylal~ylene pendant6 on ~he 6ame copolym~r.
~hese 6urf~ct~nt~ have particular a~vantage in manufacturing flexible polyurethan~ foam with higher ~han normal amount~ of ~olid polymer.
Prior Art Molded, flexible polyurethane foams ar~
pr3du~ed by the reaction of high molecular weight polyols, which polyols have greater than ~0% o primary hydroxyl capping, with orqanic isocyanat~s and water. Molded, flexible polyurethane ~oams are distingui~hable, in part, from c3nvention~1 hot eure polyurethane foams by ~he use of such a high percentage of primary hydro~yl gr~up6 a~ well a~ by the act ~hat molded flexible polyur~thane foam6 reguilre li~tl~ or no ov~n euring ~nd thu~ ~re often ~eferrecl to ~ cold cure f~ams. 8uc~ foams are extremely desirable or ~u~h~oning applica~ion6 becau6e of their ~xcellent phy~ical prop~r~
e.g., ~ry high oam r~6iliency, Op~F~ cell~d structur~, low flex fati~u~, i.e., long lif~ d high 6AC f~ctor~, ~.e., load ~earing propert~e6.
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Becau~e of the high r~activi~y of ~olded, flexible foam ingredient~ and their rapid bulldup of gel ~treng~h, ~ome~imes ~h~ fo~m can b~ o~t~i~e~
w;thout a cell stabili~er. ~owever, ~u~h fo~
typically have very irregul,ar, ~oar~e ~ell ~truc~ure as partieularly evidenced by ~urface vo~d~. A
var~ety s~f att~mp~ haYe been made ~o ~olve ~
probl~m through the u~e o ~tabilizer~ con6i~ting of ~ubstitu~ed polydimethyl- or polyphenylmethyl-siluxane~.
One group of 6tabiliger~, de~cribed in U.S.
Pat. Nos. 3,741,917 ~o Morehouse e~ ~1 and 4,031,0 ~o ~o~l~n et al., i6 ba~ed on polydimethyl6iloxane-polyoxyalkylene ~o2olymers. The polyoxyalkyl~ne pendant group6 on the 6tabilizer~ in the~e ~at~nt~, however, are alway~ hydrocarbon cfipped.
Other poly611Oxanes b~aring pendant gr.oup6 have al~o ~een claimed a~ stabilizers ~or molded flexible urethane foam. In general ~hey ~re copolymer~ consi~ting of a polydimethyl~iloxane to which ~cre attached organic pendant group~ that include: methyl groupfi (U.~. Pat. No. 2,901,~45);
cyanoalkyl ~ro~ps (U.~. Pat. No. 3,90S,92~);
phenylethyl group~ (U.~. Pat. ~o. 3,839,~4); alkyl groups (U.~. ~at. ~o. 4,306,035); trimethylsilo~y groups (U.~. ~at. No. 3,~8~,847~; ~ulfolanyloxyalkyl ~roup6 (U.~. Pat. No. ~,110,272); morpholinoalko~y-alkyl groups (U.S. Pat. ~o. 4,067,828~, ~nd ~he tertiary hydro~yalkyl grou~ (U.8. Pat. No.
~,039t~9D~. ~one of these patent~ 6u~ges~ hydro~y terminated polyoxyalXyle~ p~ndant group6 attached to the siloxane ~ha~n le~ ~lane ~ ~opolymer wi~

3 --mix~ure of both hydroxy ~ndl hydrocarbon ~erminated pendant~ on the same copolymer.
Re~en~c U.~. :?a~. ~o. ~,~78,957 co ~liet~h et al does de~cribe poly~iloxane-polyoxyalkylene co}?olymer~ wherein ~he polyoxyalkylene portïoas of the copolymer llre e~ther ~o~ally hydroxy terminat~d or totally alkyl, c8r~0xy, OI: alkylary~ cappe~.
Again, however, ~hi~ patent does no~ con~emplace u~ing a ~ingle cop~lymer which ha~ bo~:h hydroxy terrninated ~nd hydrocarbon 'cerminated polyoxyalkylene pendant~ a~tached ~o it. ~r doe~
the paten~ contemplate the u~e of hydroxy capped pendant~ when the copolymer might be u6ed in a blend wi~h ~nother copolymer.
Moreover, all of ~che above mentioned 6t~b~1izers have been designed for molded flexible polyurethane ~oam containing low level6 of reinforclng grafted copolymer rather than tho6e conts~ning h~gh concentration~ of the6e soli~6.
This di~tinction is ~mportant for rea60ns di~cu~sed below.
Reinforcing qrafted copolymer polyol6 are typically prepared by pol~merizing one or more ethylenically un~aturated monomer~, ~or example ~tyrene and acrylonitrile, in a polyether polyol, or by react~ng ~ diisocyanates wit~ polyamines or hydrazine6 ~n a polyether polyol. Typically, t~e reinforcing gr~fted c~polymer ~olyol~ for current mold~d polyure~hane formula~on6 co~ A in about 20 percent solid6 in the polyol. This i~ normslly formulated a~ ~bou~ 50 perc~nt ~f ~he inal grafted ~o~olym~r content, thu~ bringing the ac~ual ~ol~d~
content to about 10 percent.

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Recen~ly, however, i~ has b~com~ desir~ble to manu~acture molded, ~lexible foam wi~h ~ncrea~d fir~nes Xncress~d firmne~ ~s de~irable $~ that ~hinner or lower densi~y foam ~ec~ion6 can ~e manuactured w~th load bear~ng proper~ie6 egual to 6ection~ currently being made~ or for ~h~
manufacture o section6 with ~reater irmne~ where hiqher load bear~g oam i~ desired. ~uch improved foams are e6pecially de~irable ~n the automotive ~eat market where reduced æize and weight ar~
important con~ideration~ in the design of ~maller automobiles. One important method of achieving ~reater foam firmnes6 is ~o increase the concentration of 601ids used in the urethane ~ormulat~on.
Most recently, blends of conven~ional flexible polyurethane foam surfactant~ ~nd high resil~ency polyure~hane foam surfactant~ ~U.~. Pat.
Nos. 4,3Dg,508 ~d ~,477,601) have been taught as a me~hod of increasing the concentration of ~hese ~olid~ in ~he total polyol mixtureO ~he ~mall amount6 of a ~onventional urfac~ant reguired presents con6iderable difficul~i~s a~ minor ~rrors in preparing the~e ~tabilizer~ ~an have significant, adverse effec~s on the performance characteristicfi of foam ~tability or foam brea~hability. Also, ~s in tho~e 6ystem~ for 6tabilizing low levels of reinfor~inq grafted copolymer 601ids, hydroxy group~
~r~ no~ pr~sent AS the capplng gr~up in the p~ndan~
chain of the~a copolymer~.
Of ur~her concern in 6el~cting ~abilizer i~ ~he brQathabili~y or o~en cell~

character of fou7. Greater brQathability, i.~., more open celled chsracter, of the foam 16 de~irable becau6e i~ provide~ a grea~er processirlg lat~tude.
A narrow prooe~6ing la~ituae for~e6 ~he foa~ner to adhere ~o very c1060 ~Oler}lnGe~; ill me~tering ou~ the foaming lngredients which can not alwiay~ b~
accompl~hed. F~ur~her, grea~cer br~a~habili~y provides f~am that ls con~iderably more a~a~y to crush, thu6 avoiding ~plits that might occur dllring crushiny. Thi6 charac~ceristic i~ particularly desirable in foamed part~ that incorpora~ce wir~
insert6 which are difficult to crush.
This invention provides ~tabilizer~ tha~c are capable of providing foam ~tabil~ty for ~he desired higher level~ of reinforcing grafted copolymer ~olid6 in high resiliency molded polyurethane foam. This ~nv~ntion alfio provid~s ~tabiliz~r~ that meet ~he above criteria and provlde high breathabili~y foam~. ~ method is provided for preparinc3 these stabiliz~r~. A method ~6 further provided for meeting the 6tability and breathabili~y requ~rement~ of particular firm foam formulation~
o~er a wide range of reinforcing graf~ed copolymer concentrations.
Objectives I~ i6 thus an object of thi~ anvention to provide ~ncreased ~oam 6tabilization and fo~m breath~bility ~y utili2ing a 6ingle polydialkyl-siloxane-polyoxyalkylene ~opolymer havin~ ~wo or ~o~e polyoxyalkylene pendants capped at leask one of whi~h ~ capped with a hydroxy group and ~t l~a~k D-153.62 6 ~

one of which 1~ capped wi~h ei~her ~n ~l~yl gr~up or with an acyl qroup.
~ nother obj~ct of this invent~o~ ~ to provide a proce~s ~or ma~;ng an improved ope~
~elled, i.e., high breathahility, pol~yurethane ~oam from the copolymer describedO
It ~ a 6till further object of thi~
inven~io~ to provide surfactant~ which can be u~ed in manufactur~ng foam with higher than normal ~mounts of 601~d polymer.
It ~ yet another objec~ of thi6 invention ~o provide foams having fewer surface void6.
I~ is still another object vf ~hi6 invention to provide ~ proc~ss ~or manufacturing fo~m utilizl~g broad processing la~itude.
Other ob~ect6 and advant~ge~ o~ ~he invention will become apparent a6 the ~escription ~hereof proc~eds.
BRIEF ~;U~ARY OF THE ~ION
Thi~ inven~ion i6 based on the discovery that a polydialkyl6iloxane co~olymer bearing both hydroxy capped and hydrocarbon capped polyoxyalkylene pendant~ a~tached ~o the ~ree e~d of the polyethers on the ~iloxane, can be used ~o control the ~ell 6tructure of m~lded, ~lexible polyurethane foam, particularly foam containing a h~gh conten~ of rein~orcing graft cop~lymer.
~oreoYert void~ in th~ oam ~re eliminated or greatly reduced by ~he in6t~n~ ~nYentio~, Further, the6e stab~llzing ~dvan~ag~ are gained w~ t the ~ame time broad proce~6ing lati~ude ~nd ope~ cell~d, i.e.0 ~igh ~reathabil~ty, fGam i~ produce~

PSor~ particularly, the stabilizer~ o ~he l?resent ~nvention are polydial~ylsiloxane-po lyoxya 1 kyl ~n8 copo lymer ~ wher e3 ia ~3 polydial~yl6110xane backbone con~ain~ no msr~ ~han ten 6ilicon atom~ and the Ibackbone i~ 6ub~t~cuted with an average of at lea~ O . S polyoxyalkylene ~ub6tituen~ whereis~:
1. 5 ~ 95 percen~ by weight of ~he pendant~ at~cached to the backbone have ~che formula -~(R' ~a(R' ~bX

wherein R i~ ~ alkylene ~roup of 1 to 4 carbons linked to the 6ilicon a~om, ~' ~s ~n oxyalkylene group of 1 ~o 4 ~arbon6, ~" i6 a second oxyalkylene group of 1 to 4 carbons which i6 different from R', a plu~ b r~nge~ from 1 ~o about 15, and X ~ OR~
or oCR3 where R3 16 a monovalent alkyl group of o 1 to 4 c~rbon6; and 2. 95 ~o 5 percent by weight of the pendant6 attached to the backbone have ~he formula -~ R ' ) c (R" 3 dC)H

wherein R i~ a alkylene group of 1 to ~ carbone li~ked ~o l~he silicon atom, ~' i6 an oxyalkylene group of 1 to ~ carbon6, R" i6 a ~econd oxyalkylene group of 1 to 4 car1~on~ which is dif~erent ~rom R', ~nd ~ plus d range~ from 1 to 3bout 1~.
This invention further relate~ go t~e ~e~chod of the control of foan ~ell structure ~nd ;

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foam br~athability through the 6elect~0n o the rela~ive am~un~ ~f 1 ~nd 2 in the abo~ dessribed ~abilizer~.
Detailed Des~ri~tion of the Invent~on Thi~ inven~ion 1~ ba~ed on th~ di~covery ~hat ~oly6iloxane copolymer~ whioh c~n~ain both hydroxy and hydrocarbon ~erminated polyoxyal~ylen@
pendant~ provide ~nexp~cted improv~ment6 an foam ~tabilizing and foam breathability contributions o~
th~ ~tabilizer. ~lend~ of polydialkylsiloxan0-polyoxyalkylene ~opolymer~ wher~ one l~opolymer contains hydroxy terminated polyoxyalkylene pendant~
and another ~opolymer contain6 alkyl or acyl terminated polyoxyalkylene pendants are al~o described although the advan~ages attained u6ing ~hese blends sre not a~ grea~ a6 with the ~ingl~
copolymer having mixed pendants. A method has ~l~o been discovered for controlling the amount of foam ~abilization and foam breathabili~y by controll~ng the r~lative amount~ of hydroxy or hy~rocarbon ~apping on ~he pendants. These di6coveries allow for the produc~ion of high breathability, i.e., open-celled, molded, ~lexible, ~olyurethane ~oam having l~vel6 of reinforcing grafted copolymer frQm essentially none to concentra~ion~ well ~n exces~ of that now possible w~th conventional ~tabilizers. The high 601~ds content ~an be incr~ased by ~ither increasing the concentration of ~onven~ional grafted copolymer polyol~ u~ed ~n making the resul~i~g urethan~ foam gr by increa~lny t~e concentratio~ of copolymer added ~o ~he poly~l used to ma~e ghe foam. Foams wi~h higher reinforcing graft~

copolymer levels ar~ desirable becau~e ~hey ~an be used to m~ke firmer foams wi~h improved lo~d bearing capabili~y.
Reactant~ and Proces~ Conventional~y ~ed For Makinq _he Polyurethane Foam __ Polyure~hene foam ~s~ypically ~ade by combining ethylenically un~atur~ted monomer6 in polyether polyol to form grafted copolymer polyols and combining these grafted copolymer polyol with isocyana~e, catalyst, sur~actant ~nd blowing agen~.
The polyether polyol reactants employed in th~s inven~ion can be any polyether polyol containinq at lea~t 40 mole percent of primary hydroxyl groups and having a molecular weigh~ from about 2JOOO to ~bout 8,000. The preferred polyether polyol6 used in thi~ invent~on are polyalkylene-ether polyol6 obta~ned by the chemical Addition of alkylene oxides to trihydroxyl organic containing materials 6uch as glycerol t 1,2,6-hexanetriol; l,l,l-trimethylolpropane; and ~he like as well as mixtures thereof. The alkylene oxides employed ln producing the preferred polye~her polyol6 des~ribed above normally have from 2 to ~
carbon ntoms, ~nclusive while propylene oxide dnd mixtures o propylene oxide and ethyl~ne ~xide are especially preferred.
The polyether ~olyol reactants ued in ~hi~
invention can be mix~ures consisting essenti~lly of 6aid above defined polyether ~riol~ ~nd other polyether ~olyol6 havin~ an aver~ge o at lea~ ~wo hydroxyl qroups, 6aid above defined polye~r trlols ~ount~rlg ~o at lea6t 40, prefer~bly 50 , ~ei~

percent of ~he ~otal polyeth~r polyol co~ten~ of ~he mixture~. Illu~trat~ve of such o~her polyether polyols sre diol6, ~etrol6, reinforcing gra~t copolymer6 polyol~ and the li~e, ~ well ~ ~1xture~
ther~of. ~xample~ of ~uch polyether polyols tha~ ~an be mixed ~i~h th~ above defin~d polyether triol~
include tho~e ~dductE of al~ylene oxide ~o ~uch polyol~ as diethylene glycol; dipropylene glycol;
pentaerythritol; 60rbi~01; ~ucro~e; lacto~e;
alphamethylqluco~ide; alpha-hydroxyalkyqlucosid~
no~olac re~in; wate~; ethylene glycol; propylene glycol; trimethylene glycol: 102-butylene glycol;
1,3 butanediol; 1,4-butanediol; 1,5-pentanediol;
1,2-hexanediol; 1,2-hexane glycol; l,10-decanediol:
1,2-cyclohexane- diol; 2-butene-1,4-diol;
3-cyclohexane-1,1- dimethanol;
~-methyl-3-cyclohexene-1,1-dimethanol;
3-methyl-1,5-pentanediol; 4-(2-hydroxyetho~y)~l-butanol; and the like a~ well a6 ~ixture~ th~reo.
The reinforcing graf~ed copolymer polyols used in this inven~ion ar~ obtained ~y polymeriæing ethylenically un~aturated monomers in a p~lyether polyol a~ described in Briti~h patent No. 1,063,222 and in U.S. patent ~o. 3,3~3,351. ~uitable grafting monomer6 for producing ~uch compo~ition6 include, for ex~mple, ~cryloni~rile, vinyl chloride, s~yre~e, butadiene, paramethyl s~yrene, vinyliden~ chloride, and the li~e. Suitable polyether polyol~ or produ~ing such grafted copolymer po~yols include, ~r example, thos~ polye~her pslyol~
herei~Abo~2-de~cr~bed. TheEe ~r~ft copolymer/polyether polyol compo~iti~n~ ontain ~1536~

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from about 1 to 70 weight percent, preferably 5 ~o 60 weight peroent, and mo~t I?referably 10 to 50 weigh~ percent of ~he un6a~curated monom~r polymerized in ~he polyether polyol. ~uch compos~t~on~ are conveniently prepared lby polylTeriæing the monomer in the ~el~cted polyether polyol a~ emperature of 40 to 159 Idegrees cerl~igrade ~n the pre~ence of a free radical polymerization ea'caly~t, ~uch as peroxide~, persulfa~es, percarbonz~es, perborate nd azs compound~ a6 more fully described by ~he above patent references. This polymerization is preferably done in 6itu. Especially preferred are the graft polyls)er/polye~cher polyols obtained from mixtures of ~crylonitr~ le and styrene and polyether triol6 .
~ uit~ble reinforcing gr~ft copolymer polyols employed in ~chi6 patent may al60 be obtained from reacting dii60cyanate with poly~mines or hydrazines in polyether polyol 601utions as described in U.~. patent ~o. ~,042,537. Reactants or produciny said grafted copolyrner polyol~ incl~lde among othexs the polyisocyanates l;uch as 2~4- ~nd 2,6-toluene dii60cyanates and mix~ures of 'chese i~omer~, polyphenyl-polymethylene polyi~ocyanates, and hexamethylene dii60cyanate. The i~ocyana~es ~re reacted with either polyamines or hydrazines ~o form the polymez di~per6ed within and grafted to the polyether polyol ~ol~ent for the reaction. ~ui~able polyamine~ inclu~e: divalent and higher polyvalen~
primary or secondary, 81 iphat~c aralipha~ic cycloaliphatic vr aromatic amines. ~peclf~

~-1536 -- ~2 ~xamples include among o~her~, ethylene diamine, hexamethylene diamine~ 4 arninobellzylamine~3

4,~ iaminodicyc1ohexylmethane, phen:yl~n~ di~nines, ~oluene diamines, and the lilse. ~ui~able hydraz~nes ~s~clude hydrazirle, ~ethyl hydraz~ne, hydr~zi~e hydrate, phenyl hydrazine, }~enzyl hydrazine, ar.
cyclohe~yl hydrazine. The level of polyurea~ of poly~ydrazodicarbonamide~ dispers~d in the polyether polyol may vary within wide l~mit6, although it i~
generally ~rom 1 to ~0 percent by weight ~a~ed on 100 part~ by weight of polyether polyol.
A Yariety of organic ~socyanates ~an b~
employed in ~he foam formulations of ~his invention for reac~ion with the polyether polyol s~arting materials above ~escribed to provide polyurethane foam~. Preferred ~socyanate~ are polyi~ocyana~es and polythiocyanate~ of ~he ~eneral formul~:
Q(NCO)i wher~in i is ~1 integer of two or more And Q i~ an organic radical having ~he valence of i. For instance, Q can be a substituted or unsubs~ut~d hydrocarbon r3dical, such a~ alkylene and arylene, having one or more aryl-NC0 bond~ and/or one or more alkyl-NC0 bond6. Q can also include radical6 6uch ~s -RZ0-, where R ~6 æn ~lkylene or arylene group and ~ divalent moie~y ~uch as C0, ~2 and the like. ~XampleE of ~uch ~ompound~ i~clude hexamethyl di~ocyanate~ 1,8-dii~ocyanato-p-meth~ne, ~ylene d~i60cyanates, ~OCNCH~H~CH20~2)~0, l-~ethyl-2,~-dii60cyana~0cyclohexane, phenylene , . ~ ... .... .
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diis3cyanates, ~olylQne diisocyanate~, chlorophenylene dii~ocyanates, diphenylmetha~e-dii~Qcyana~e, naphthalene-,5-dii~ocyanate.
~riphenylmethyl~ '9~"-trii~ocyanate, ~n~
i~opropylbenzene-alpha-4-dil 6 ocyanate. Further included amon~ ~he i~ocyanates u6eful ~n ~h~
~nventior~ are dimer6 and trimQrs of i~ocyanates such a~ those having the general formula:
Q(NCO)i and ~Q(NCO)~);

which i and ; are integers of two or more, and/~r (as addi~ional ~omponen~s in the reaction mixtures) compounds of the qeneral formula:
L(NCO~ -in which i i6 one or more and L is a monofunc~ional or polyfunctional atom or radical. More ~pecifically, ~he polyisocyanate component employed in the polyure~hane foams o thi6 ~nvention ~l~o include the following specific ~ompound~ as well mixtures of two or more of ~hem: 2,~-~olylene dii~ w yana~e, ~rude tolylene dii~ocyanate, bis(~-i60cyanatophenyl)methane, polymetha~e polyphenyli~ocyanates ~hat are produced by pho~ena~ion of ~nil~neformaldehyde condensation products, 2,4,6-tQluenetr~isocyanate, and many other organic polyasocys~ates that are known in the art 6uch a~ th~6e di6closed in an article by ~ief~e~, ~nn.,5~S,75 ~1949). In general, ~he aroma~
polyisocyanate~ ~re pre~er~e~.

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Particularly useful isocyanate components are combinations of isomeric tolylene diisocyanates and polymeric isocyanates having units of the formula:
2~CO

R x wherein R is hydrogen and/or lower alkyl and x has an average value of at least 2.1. Preferably the lower alkyl radical is methyl and x has an average value of from 2.1 to about 3Ø
The amount of polyisocyanate employed will vary slightly depending on the nature of the polyurethane being prepared. In general the polyisocyanates are employed in the foam formulations of this invention in amounts that provide from 80 to 150 percent, preferably from 90 to 110 percent of the stoichiometric amount of the isocyanato groups required to react with all of the hydroxyl groups of the organic polyol starting materials and with any water present as a blowing agent. Most preferably, a slight amount of isocyanato groups in excess to the stoichiometric amount is employed.
The blowing agent~ which can be employed in the process of this invention include water, liguified gases which have boiling points below 80F
and abo~e 60F, or other inert gases such as nitrogen, carbon dioxide, helium and argon.

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~uitable l~guified ga~2s include ~a~:urated alaphatic f l~aorohy~rocarbonE wh~ch vaporize at or ~elow t~ae ~emperature of the foaming ma~s. ~uch g~s~ ~re st lea~t partially fluoronated and oan a'l60 b~
otherwi&e halogenat~d. Fluorocarbon blowing agen~E
6ui~able for use in foaming ~h~ ormulation~ of ~hi~
~nvention ~ncl~de trichlorofluoromethisne, dichlorodifluoromethane, diehlorofluoromethane, l,l-chloro-l-~luoroethane, l,l-difluoro-1,2,2-trichloroethane, and 1,1 t 1 ~ 2,3,3,~,4,~-nona-fluoro-2-chlorobutane. The preferred blowing agen~
for the proce~ of thi~ in~ention ~
trichlorofluorome~hane. The amount of blswing agent u~ed will vary ~he den6ity in the ~oamed product.
Usually from 2 to 20 parts by weigh~ of ~he blowin~
agent per 100 parts by weight of ~he organic polyol 6tarting material6 are preferred.
The cataly6t~ employed in this invention to produce polyurethane~ include any o~ ~he amine~ or metal ca~aly~t6 u6ed in producing molded, flexible polyurethane foam. Illu6tra~ive of ~uch conventional amine catalyst~ are N-methyl morpholine, N-ethyl morphol~ne, hexadecyl dimethylamine, ~riethylami~e, N,~,N',N'-tekrame~hyl-1,3-butanediamine, N,N-dimethylethanol-amine, diethanolamine, 3-dimethylam~no-~,N-dimethylpropionamide, bi6(2-dimethylaminoethyl)ether, N,~,~',N'-tetramethyl ethylenediamine, ~ me~hylene bis(2-chloroaniline~, dimethyl benzyl~mine, N-~oco morpholine, triethylene diamine, the formate 6alt~ of ~r~ethylene diamine, ot~er .. ... . .. . ..

6alt~ of triethylene diamine ~nd oxyalkylene adduc~
t~f pr imary and ~econ~ary ~mino group~ and the like .
Illu~trative ~f conventional meta7 cataly~t~ are the gin E;alt6 of var~ous carboxylic ~cids and ~c~e~
aeetyl~cetorlate~. The preferred ~eta'L catalys'c ~or the proces~ of thi~ ~nventic\n i~ dlbutylti~-dilaur~te. ~uch amine and me~al cata'ly~t~ ar~
preferably employed in the r"ixture~ ~n ~n amount f rom 0 .1 to 2 weight pers:en~c ba~ed on ~he total weight of the organic polyol ~tarting ~naterial.
Other addi~ional ingredient6 can be employed in minor ~mount6 in pr~ducin~ ~he high resiliency polyurethane foam~ in accordance with the proce~s of thi~ invention, ~f desired, for 6pe~ific purpose~. Thu6 flame re~ardant6, e.g., trichloroethylphosphine can be used to reduce any tendency of th~ ~olyure~hane oam to 1ammability.
Of cour~e, any ~ui~able organic ~olven~ ~or the catalysts can be u~ed which does not substantially adver6ely ~ffect th~ operation of the pro~ess or reactant~. Example~ of Euch ~olvent~ for ~he cataly~ts ~nclude polyols, e.g., 2-methyl-2,4-pentanediol, dipropylene gly:ol and the like.
In accordance with this inv~ntion, ths molded, flexible polyurethane o~ms c~n be produced by any ~ui~able technigue. The preferred pro~ess is a o~e~s~ep or one 6ho~ ~echnisue wherein all of ~he reactan~ are reacted 6imultaneou~1y with the fo~ming operation. A second general proce~
~alled ~he prepolymer proces~ whereby a prepolymer

6 formed by reacting the polye~her polyol wi~ ~
~mall excess of th~ isocyana~ and l~ter oami~g the prepol~mer by ~he reao~ion with wa~er or ~ i~ert blowing agent. Another me~hod which ~an be u~e~ i~
~he guasi-prepoly~er technique which i~volve~
reac~ng a large excess of the isocyanate wi~h the polye~her polyol with addi~onal polyether polyol in ~he presence of a blowing agent. Becau~e o~ the high exo~hermid na~ure of ~he reac ion, high re~iliency polyurethane foams ~re rapidly ~roduced wathout the need of ~ny external heat by mixing the reactant6 a~ ~mbient temperature and pouring the ~oamin~ reaction into ~ ~uitable mold and ~llowing the foam to ~ure i~elf. Of course, if desired, the overall reaction can be further accelerated by preheating ~he mold and~or employing conventional high ~emperature po6t cure proceduree. Of cour~e, it i6 to be understood ~ha~ the eold cure polyurethane foams of ttli6 inv~ntion ~an al~o be prepared in ~lab6toc~ f~rm if de~ired.
Stabilizers The e~ential component in forming ~he urethane foam i6 the noY~l polydialkyl6iloxane-polyoxyalkylene ~tabil~z~r~ that are the objeet of thi6 invention. It i~ these polydialkyl~iloxa~e-polyo~yalkylene ~tabilizer~ that provade cured f~am that ha~ fine uniform ~ell~; ~s free of void~, split6, and hole~; ~nd ~ ~ub~tanti~lly free from shrlnka~e. The relative ~mount of polydialkyl-~iloxane-polyoxyalkyl~ne stab~l~zer u~ed to ~ake the polyurethane oam ~n ~ry over wide ranges bu~ ~re qenerally employe~ in ~moun~ ransing ~rom ~bout 0.02 ~o 5 par~s by weight or greater per hun~r~
part6 o the grafted copolymer polyol, l.e.O the ~ 5~

combined added copolymer and polyol. Generally ~here ~s ~o commensurate advant~gQ to u~inq t~e~e ~tabilizPr~ in exces~ of ~ve part~ by weight, while ~he u~e of amoun~ below 0.0~ part~ by wei~ht c~n result ~n ~oam in~tability. Preferably th~
polydialkylsiloxa~e-polyoxyalkylene stabilizer~ are employed in amount6 ranging from 0.02 to 2.0 parts by weight. per hundred par~ by weigh~ of ~he organic polyol. ~he preferred alkyl 6ub~ituen~ on ~he polydialkysiloxane portion of the ~opolymer of thi~
invention i~ me~hyl.
The stabilizer of thi~ ~nYention consists of a polydialkyl iloxane-polyoxyalkylene copolymer wherein ~he poly~iloxane ~ontain~ no more than ten ~ilicon atoms and the polysiloxane 16 substi uted with an avera~e of a~ least 0.~ polyoxyal~ylene substituent pendant~ wherein:
1. 5 to 95 percent by weight of the pendant6 on the copolymer have the ~ormula -R~R')~(R ~bX

wherein R i6 ~n alkylene group of 1 ~o 4 carbons linked t~ the ~ilicon atom, R' i~ an oxyalkylene group of 1 to ~ carbons, ~" is a ~econd oxyalkylene group of 1 to 4 carbons whi~h is different from R'g ~ plu~ b ie 1 to 15, and X ~8 oR3 or oCR3 where o R3 ~ a monovalent alkyl group of 1 to ~ carbon~;
~nd 2. 95 t~ 5 perce~t by weight of the pendan~ on the sopolymer6 have the ~ormula - ~3.9 --~(R'~

wherein R ~s ~n slkylene group of 1 ~o 4 e~rbon~
linked ~D the ~ oon ~tom, R' ls an oxyalkylsne ~roup oF 1 to 4 earbons, R" i8 ~ ~econd oxy~lkylene group of 1 tv 4 carbons whlch is dlfferent from R~, ~nd c plus d 1~ 1 to 15.
M~re p~rtlculsrly, the st~bllizer 1~
compri~ed o~ linear or branched polyd~lkylsl~ox~nes that ~re substltuted wlth ~he ~bove de~cribed mix~ure of polyoxy~lkylene pendsnts. The pendant groups can be attsched either in~ern~lly to one ~
the sllioone ~toms~ to one of the termlnal slllcone ~toms, or some combin~tion of bOthr ~lthough ~he ~tt~ched ~lkyl group c~n h~ve 1 to 60 c~rbsns, prefer~bly, the polydi~lkyl~lloxsne~ ~re polydimethylslloxanes that m~y be llnesr struotures constructed from D (Me2Si(0}/2)2) ch2in extendlng units and M 5Me3SiOl~2) ch~in terminHting units that cont~irl the ~bove ~escribed polyalkyleneoxlde pend~nts either lnternslly on some of the D unlt~, or terminally on ~ome of the M
unit~, or both. Altern~tively, the polydlalkylsllox~nes msy be constr~cted from M, D, Qnd T 5MeSi~01/2)3~ or Q ~S~(01/2)q) thus creatlnQ br~nching wlth the polydlmethylsllox~nes. In these brsnched polydl~lkylsiloxanes, the poly~xy~lXylene pend~nts m~y be attached to the M, D or T unlt~ or sny combln~ion of thes~ three.
Speclflc ex~mples of this ~tabilizer ~nclude:

... . . . . . . . _ .. . _ . .... . . .

!5~3~

Me3Si(OSiMe2)~OSiMeQ~(OSiMeP)jOSiMe3 wherein Me is a methyl group i ha~ a ~alue of 0.025 to 3.~, ~ ha~ an average ~alue of 0.0;25 ~o 3.0 su~h tha~ ~f~ i6 in ~he range of 0.05~0.9$ ~o 0.95~0.05, i plus ~ h~s an average value of 0.5 to 3.0, h plu~
i plus j ha~ an average value o 0.5 l~o 8.0, Q i6 -R(R~atR )bX
and P i 6 -R(~')C~R~)d~H

wherein ~, ~', R", a, b, ~, d, ~nd X, are a6 described as ~bove;

DgSi((OSlMe23h(OSiMeQ)i(OSiMeP)jOSiMe3)4_g wher in ~ is a hydrocarbon free radical ~ree of aliphatic un~aturation and con~ains from 1 ~o ~0 carbon a~oms, g has a value of 0 to 3, and ~e, h, ~, ;, Q, and P are de~;ne~ as above;

(QMe2S~ (OSiMe2)h(0SiMeQ~a(O5iMeP)i(OSiMe2P)1 wherein Q, ~, h, i, and j are as described above, ~
ha~ an average value of O .1 to 1. 9, 1 has an average ~alue of O .1 ~o 1. 9, ~d It plus 1 eguals 2 . 0;

D~g~l ( (osiMe2~h(osiM~2~a)m~siMe2P~)4 wherein D, Me, ~, ~, and g are a6 describe~ above, ha~ a ~ralue of O to 8, sn has ~ v~ue of 0.05 to 5~62 ~ 2:L --D.95~ n ha~ an average value of 0.05 ~o 0.95~ and plu~ n ha6 ~ a~eraye VillU@ 0f 1.11~

Dg~i((OSiMe23~tOSiMeQ)a~OSiMeP)~OSiMe ~ g where Do g, h~,iD ~J~ m and ~ are a~ define~ ~ov~.
Anong.the above de6cribed ~tabilizers, ~he preferred copol~er iæ a lin~ar polysiloxarlepolya~cylene copolymer of ~che general ~ormul Me3Si (OSiMe2)h(OSiMeQ) i(OS;M~P) jO~iMe3 wherein Me i6 a methyl group h ha~ Bn average value of ~.5 to 3.0, i has an average value of 0.025 lto 3 . O, ~ has an sverage value of 0 . 025 to 3 . O, i/; ha~
an average va}ue in the range of 0.55/0.5Q to 0.95/~.05, Q i~;
~R )a(R ~bX

wherein R i6 propyl, R' and R" ~on~titute a polye~her made from oxyethyl, oxypropyl or a mixtur~
of o~ethyl and oxypropyl group~ to gi~lre a to~cal molecular weigh~ of 100 ~o ~50, X is ~ me~ho~
group, ~nd P is R ( ~ R ) d where~ R ~ propyl, and R' and R" constitute a polyethe~r mad~ from oxyethyl, oxypropyl or ~ m~xture of o~ethyl and oxypropyl group~ to ~ive a tot~l mole~ular weight of 100 ~co ~50.

D-l 53 62 - 22 ~

Improvemen~fi in st~bilizer ef~ic~cy can al~o be realized ~y blending two diff~r~nt copolymer~ each h~ving polyoxyalkylene pend~n~s wi~h var~ed capping. One of the polydialkylsilox~ne-polyoxyalkylene copolymers, u~ed rom 5 to 95 percent by weight, ~on~is~s o ~ polycl~ yl~iloxan~
cont~ining ~o more than ~en ~ilicone a~om~ ~n~
havi~g an ~verag~ of 0 . 5 to ~bout 10 polyoxyalkylene sub~ti~uent uni~6 wh;ch are capped w~h an alkyl or acyl gxoup 6uch ~ha~ ~o ~ctive hydro~y group~
remaln. ~pecific ~xample~ of 6uch a copolymer includ~:

I)gSi((OSi15e2)hOSiMe2E)~ g wherein D i6 8 hydrocarbon free radical free of aliphatic unsaturation and contains from 1 ~o 10 carbon ~om~, g has a value of O to 3, h has value of O to 8, Me i~ a methyl group, E is -R~R')~5R")bX

wherein R is an al~ylene group of 1 ~o 4 carbon~
linked to the ~ilicon atom, R' is an oxyalkylene group of 1 ~o ~ carbons. R" is a second oxyalkylene group of 1 ~o 4 carbon~ which i~ di~ferent from R, a plu6 b i~ 1 to 15, and X is oR3 or oCR3 where R3 ~ ~ monovalent al~yl ..

~roup o 1 ~o ~ carbon~;

~ 23 ;

E~Se2Si(OSiMa2)h(0SiMeE)~OSiMe2E

wherein E ~nd Me are defined a~ above, ~n~ ~ ~a~ a value from 0 ~o 4, and h plu6 ~ has a value ~ 0 to ~;
Dg~iS(osiMe2)h~osiMeE)~osiMe39~-~

wherein D, g, Me and E ~re as de~cribed abov~, ~ has an average ~alue of abou~ 0.5 to ~, and h plu~ ~ has an average value of about 0.5 ~o 8; and Me3~i~0Si25e2)h(0SiMeE~kOSiMe3 wherein Me and ~ are ~ de6cribed above, ~nd k has an average value of ~bout-0.5 ~o ~ and h plus ~ has an average value of about 0.5 to 8.
The second polysiloxanepolyoxyalkylene copolymer for making thi~ blended stabilizer i~ u~d from 95 ~o 5 percent by weight and con~i~t~ of a polydimethyl~iloxane containing no more ~han ~wenty ~ilicon atom~, having an average of 0~5 to about 10 polyalkylene ~ubstituent unit6, which ~nit~ ~ntain an active ~ydroxy ~erminal group. ~pecific examples of ~uch ~ ~opolymer inelude:
Dg~ OSi~e2)hOSiMe2F)~g wh~rein D ~ a hydrocarbon ~ree r~dical ~ree of aliphatic un6aturation ~nd contains from 1 ~o 10 carbon atom~, g bn~ ~ value of 9 ~o 3, ~ ~as ~ Yalue of V to ~, ~e ~ a ~ethyl group, F i~
;

.
' ~ 2 -~(R' 9~R~

wherein 3R i~ a divalent org~nic ~roup of 1 to carbons ~in~ced to the ~ con ~tom, R' ~6 ~a oxyal~yl~ne group of 1 ~o 4 carborl~ O R'~ is a 6e~0nd oxyalkylene group of 1 to 4 ~arbon~, which 1 different from R', and a plu~b ~L~ 1 to 15;

F~Se2Si(OS~Me2~h~0SiMeF)jOSiMe2F

wherei~ ~ and ~Se are defirled as above, and ~ ha6 a value from O ko ~, and h plu~ ~ has a value of O ~o 1~;
DgSi ( (OSiMe2)htOS1MeF)kOsi~Se3)4-g wherein D, ~, ~Se and F are ~s described above, 1~ alas an average value of about O . S to 10, and h plu~ k has an aversge value Qf about 0.5 to 1~; and M~3Si (osi~se2~h(osiMeF)~cosi~se3 whPrein Me and ~ are ~ described above, ~nd 1~ ha6 an average value of about 0.5 ~o 8 and h plu~ ~ ha~
an average value o aboulc 0.5 ~o 13.
lWi~hin the above descriptic?n of copol~nner~
gor a blended stahili~er, the preferre~ bl nd i~ 75 to 95 weight percent of a linear polysiloxan0poly-al~yl0n~ ~opolymer with the ormul~:
Me38~ ~osiMe2~h~c)siMe~ o~ e3 -wherei~ ~e i6 a methyl group, k has an average sralue of ~bout 0.~ ~o 2.5, h ha~ an a-r~rage value o a~ou~
9.5 to 2.5 and E ~s an oxyalkylen~ :~adical with a molecular we~gh rom 100 ~co ~50 a the formula:

R~R ~t~ )bX

wherein R i~ propyl, R' and R" con6titute a polyether made from oxyethyl, oxypropyl or a mixture of oxyetllyl and oxypropyl qroups to giYe the desired molecular weight, ~nd X is a methoxy gr~uE?.
Thi~ i~ blended with ~5 ~co 5 weight percen~
o a linear poly~ilQxanepolyalkylene copolymer with ~he ~ormula:
M~3~i (O~iMe2~h~0SiMeF)~OSiPSe3 wherein Me i6 a methyl group, k has ~n ave~age value o about cf O.S ~o 6, h has 2n ~verage value of a~out O . 5 to 6, and F ~ 6 an oxyalkylene radical with a molecu`l.ar weight from 100 to ~50 of the ~ormula:
-~(R ' ) s ~R" )dOH

wherein R ~ propyl, ~' ~nd R" ~on&~citute a polye~her made ~rom oxyethyl, oxypropyl or a mixture of oxyethyl and oxypropyl grou2s to give ~he desired molecul~r weight.
Whil~ the blend~; of polymers describ~d above were found to produce 6urfactants w~ich made more breathable ~d more ~table foams, ~he l~craases ln 6tabil~ty a~d brea~habili~y were sEar more - ~6 -pronounced when utilizing single copolymers with rnixed pendants attached.
Selection of the ratio of alkyl or acyl capped to hydro~y terminated polyoxyalkylene in the stabilizer is dependent on the amount of solids to be used, and the desirability o open celled structure of the foam. It has been discovered that increasing the relative amount of hydro~y terminated material within the structure increases the amount of ~tability offered to the foaming solution. Thus, concentrations of grafted copol~mer solid well beyond those examined in thîs or any other invention, can be stabilized by appropriately increasing the hydroxy level in the copolymer.
Of further concern in selecting a particular stabilizer structure, is the breathability or open celled character of the foam as influenced by the stabilizer. The breathability of the foam can be controlled by adjusting the ratio of hydroxy terminated to alkyl or acyl capped polyoxyalkylene used in making the copolymer. Thus increasing the amount of alkyl or acyl capped material increases the breathability of the foam.
EXAMPLES
The following examples and procedures are presented to illustrate the invention, but are not to be constru~d as lirniting thereon. Those examples considered to be examples of the invention are numbered and comparative examples are lettered.
~efinitions " inch pphp parts per hundred parts of polyol used Polymer polyol ~ A polymer polyol consisting of about 40~ by weight of an acrylonitrile/
styrene polymer and the remaining 60% by weight of a base polyol such that th~
polymer polyol has a hydroxyl number of 31, and a functionality well understood by those practicing in the art.
Polyether Polyol B A polyether polyol based on ethylene and propylene oxides which polyol has a hydroxy number of about 35, about ~0% primary, and a functionality well understood by those pra~ticing in the art.
Polymer polyol C A polymer polyol consisting of about 21~ by : weight o~ an acrylonitril~ in styrene polymer and t~e remaining 79% by weight of polyol based on ethylene and propylene oxides which polyol has a hydroxy number of 28, and a functionality well understood by those practicing in the art.
~`:
;

: :

,;
: - . ,:

,,,,, ~

~2 Amine catalyst A An amine catalyst made from bis(2-dimethylamino-ethyl~ether and dipropylene glycol in a ratio o 30 to 70.
Amin~ cataly~t B An amine catalyst made from triethylenediamine and dipropylen~ glycol in a ratio o~ 33 to 67.
TDI Tolylene diisocyanate.
MDI Diphenylmethane diisocyanate Surfactant L-5309 A short chained silicone surfactant which is commonly avallable from Union Carbide under this trade designation.
Surfactant L-5303 A short chained silicone which is commonly available from Union Carbide under this trade designation.
Surfactant L-5307 A short chained silicone which is commonly available from Union Carbide under this trade designation.
Surfactant L-5311 A short chained silicone which is commonly available from Union Carbide under this trade designa~ion.
~urfactant L-5312 A short chain~d silicone which is commonly available from Union Carbide under this trade designation.
AMTG allylmethoxytriglycol , :

3~
-- ~29 --APE& allyl started polyethylene oxide APP~ allyl started polypropylene oxide ~CH3)3SiOl~2 ( CH3 ) 2S iO
~* The hydrosilation product of CH3SH)SiO and an allyl started polyethylene-oxide of about 350 molecular weight D** ~H3(cH3o(cH2cH2o33c3H6~sio D The hydrosilation product of CH3(H)SiO and an alkyl started polyethylene-. glycol with an average molecular weight of about 200 D The hydrosilation : product of CH3(H~SiO and a mixture of an allyl started poly-ethyleneoxide with an average molecular weigh~ o 350 a~d allylmetho~ytriglycol D5 Th~ hydrosilation product of CH3(H)SiO and : allylmethoxy-triglycol blended with an allyl started polyethylene-o~ide of molecular w ight 350, in the ratio designated in the adjacent column ~-~5362 ...
, ~ ~
,., .:
'.: .. .
. ~ , ' , 3~ 5~

I~6 The hydro~ilat~on pr od~act of CH3 ~ H ) S ~ O and al lylmethoxy- r iglycol blended with an allyl ~tar~ed polypropylene-glycol o~
mol~cular weigllî 200, ln ~he ratio ~lesiqna~ed ~n the ad~ aoent colwns~
D7 The hydro~ilation pr ~du~t of ~13 ~ H ) S iO and al lylmethoxy-~r iqlycol ~AMTG) blended with either an allyl ~tarted polyethylerle o~cide G) of ~olecu~ ar weight 200 (GG, HH and II), or ~
~llyl ~tarted polyEropyl~ne oxide 5APPG ~ of molecul ~r we i ght 2 0 0 ( JJ, ~X and LL ) in the ratio li6ted in the adj acent ~olumn (AMTG/APEG or AMT~/APPG ) D~ The hydro6 i 1 at io~
produc~ o~ CH3(H)SiO and al lylmethoxy-tr iglycol (AMTG) blended with ~ither an allyl ~tarted polyethylene oxide (APEG) of molecular weight 200 gBB and CC), or au~ allyl 6t~r~ed polypropylene ~xide (P~PPG) of molecular wei~ht 200 ~DI~ and EE3 in ~he ratio 1 isted ~rl the a~j aceng column (~TB~APEG or AMTt~

;

~L2~

g D The hydrosilation product of CH3(H)SiO and allylmethoxy-triglycol (AMTG~
blended with either an allyl started polyethylene oxide (APEG~ of molecular weight 200 ~CC and ~M through PP), or an allyl started propylene oxide ( APPG ~ of mo lecul ar weight ~00 (QQ and RR) in the ratio listed in the adjacent column (AMTG/APEG or AMTG/APPG ) General Procedure A general foaming procedure was adopted for all of the foaming tests presented in this patent.
With the exception of the isocyanate, all of the ingredients listed in a particular formulation were weighed into a cup. This solution was then stirred for 60 seconds. The solution was allowed to degas for 15 seconds. The isocyanate was added and the solution stirred for another 5 seconds. Finally, the rnixture was poured into the appropriate, preheated mold which was then sealed during the foami~g reaction. ~fter a five to ten minute cure, the mold was opened and the foam evaluated.
~lock Mold Test and Evaluation ; The ability of a surfactant to stabilize foam against shear collapse in a mold was evaluated in a block mold tes~. A 15" X 15" X 4" aluminum mold was fitted with an 11.5" X 6" X 3" aluminum ~:
. ~
~ ~-15362 :

~ `

.

~ 5 block. The bloc~ w~ 6i~uated on the bottom of ~he mold with each ~hort ~ide o ~he block 1.75" ~rom ~;de of ~he mold, and on~ long s~de o~E the blQck 1.0" rom the ~ide ~f the mold. The ~Fo~mi~g ~olution wa~ poured into the open portion of th~
mold. Af~er ~ealing the mold, ~he ~,~m wa~ ~llowed to 10w around and over the block to Eill the entire m~ld.
After curing, the ~oam was rlemo~ed and the top 0.~" cu~ of~. This allowed internal evalua~io of 6hear collapse over the block and under ~he ~en~
in the lower portion of the ~oam. The foam was evalua~ed from one to nine based on ~he amount of observed collapse, with one representing ~otal collap~e and nine representing little or no collapse. Thu6 the higher the rating ~he more effective the ~ur~actant was ~n 6tabilizing khe ~o~n.
Foam Breathability Test Foam breathabili~y wa~ measured usi~g Formulatlon 2 to make foams in a 15" X 15" X 4" box mold. The foaming ~olu~ion including a ~elected concentration o~ ~urfac~ant was prepared as described above and poured into the mold which was sealed while ~he oam cured. ~pon removal, the fo~m was allowed to ~tand for 15 minu~s. At this time the foam wa~ ob6erved for 6hrinXa~e. If no 6hrinkage had occurred, then a ~econd oam was prepared using a higher concentration of ~urfactant. Thi~ ~roce~s is repeated un~il a ~reak point ~ termined that coinc~des wi~h t~e on~e~ of ~hrin~age with ~ncrea~ed surf~ctant ~oncentr~t~o~.
~ince shrinkage i6 relat~d to ~he number of open ~-153~2 ..

s~

~ells ~n ~he 3Eoam, th2 breathability ~mparted to th~
foarn by the surf~ct~rlt can b~ d~tsrmined ~ 1;he amount o ~urfactant reguired, to cause fou~
~hrinkage. Thu~, the higher the re~ired ~urf~c~an~
c~ncentration for 6~rinkage, She more ~breathable and bet~er ~che ~urfac~ t. The concentration of ghe surfac~arl'c re~ired for 6hrinkage i~ referred ~co a~
~che ~op ~nd. ~ higher ~op end being be~t~r.
Copolymer Prepara'cion The copolymer~ ~e~ted in ~hi6 patent were prepared by fir~'c eguilibrating a ~our~e of (CH3)3SiO~ S), (CH3)2SiO (D), ~d CH3(~SiO ~D') ~o make a di~tribu~ion of oligsmers with a nominal structure of MDX~ uch tha~ x and y are dependent on the initial amounts of 1~, D
and D' u6ed. An ~llyl star~ed polyalkylether pendant ~me~hyl and/or hydroxy ~ermina~ed) is ~hen hydro6ilylated onto the siloxane ~o form ~h~
copolymer, MDX~ ~ , where M, D, ~ and y are defined ~ above, ~nd D* i~ the monomer unit bearing the pendant group.
Although thi~ method was used for ~he examples illustrated i~ thi6 patent, it i~ n~t ~he only procedure for preparing the 6tructures ~alled f or in the patent .
Foaminq Formulation~
~ sts on the 6ur~actan~ presented ~n this patent were ba~ed on one of the followi~y formulation6:

.. . .. . .

_ 34 ~

Formul at ion Cc)m~?onentS: oncentrat~or Pol~mer polyol ~ 50 Polyether polyol ~3 50 Amine cataly6t A 0.1 Amine cataly~t E~O . 5 D i eth ano 1 amin~ 0 ~ 9 ~tater 3 ~
TDI /MDI ~ 8 û~'20 ) 3 6 . 9 ~urfactan~ Varied Concentra~ion i~ express in part~ per hundred par~ of polyol.
Formul at i on 2 _ Component Concentration Polym~r polyol C70 to 100 Polyether po}yol B 30 to 0 Arnine ca~alyst A0.1 Amine cataly6~ B0 . 5 Diethanolamine 0 . 9 Water 3 TDI ( 103 index)36 . 8 ~ur f act ant Var i ed Concentration is expres~ in part p~r hundred parts of polyol.
Comparative ExamPles A-I
These Example~ demons~ra~ce the need for ~e~ Cla6S of ~;urfactants ~ha~ is able to 6t~biliz~
high solid6 concentration~ iqh 601id contenk molded, flexible urethane ~oam. The ~e6t~ wer~ run using Formul~cion 17 a~E; des~r~bed aboveO whi~h employ~ ~olymer polyol ~ ~ he polym~r po~yol. It ~s impor'can~ ~o ~:o~ ~hst ~he polyol ~on~a~& 40P~

3~2 .. . . ..... _ .. ... ..

35 ~

~crylonitrilei~tyrene p~lymer. ~hen used a~ SO pphp ~he ~olld~ oonten~ o ~h~ re6ul~ing foam i~ ~bout twice the level normally found in h~gh and ~ol1 conten~, ~olded, flexible urethane fo~m.
Table 1 6hows ~he re~ul~ rom a 8~rle6 of surfactan~s evalua~ed in the bloc~ mold ~t descr~bed above. Material~ claimed as suractant~
for molded, flexible ursthane foam generally con~i of a ~hort cha~n 6ilicone conta~ning an ~lkyl or functional alkyl qroup as a pendantO The series ~hown in Table 1 i6 a representa~ive 6ampling of ~he surfactant 6tructures currently available. This inCludes ~truc~ures that have methyl capp~d polyalkyleneoxide pendant groups. The initi~l test~
(Comparative Examples A E) were run with 1.5 pphp ~uractant, which i~ the normally recommended concentration. The low rating6 (2 or 3) ~or all the ~urfactan~ ~6 ~he re~ul~ o extensive foam collap~e due to the inabil1 ty of these ~urfac~ant~, regardles~ of pendant group, ~o ~tabiliz~ the oam.
The ~econd ~et of te~ts (Comparative Examples F-I3 were run with 3.0 pphp &urfactant. ~t b~, only modes~ gains in perormance were ob~erved for of th~ ~ur~actant~. One receiYed a rating o 4, while th~ re~t were ra~ed a~ 3, which ~enote~ a con6iderabl~ amount of collap~e. Increasing ~he ~ur~actant concentration beyona thi~ level migh~ be po6sibl~, but would have obviou~ economic ~i~adv~n~age~ a~ well ~s potential per~ormance pr~blem~. Thes~ result& demonstra~e that lt i8 the 6urfactant 6tructure ~n~ not the concentration oE
~urfactant u~ed that 16 limiting performanc~.

- 36 ~

Table 1 Block Mold Test wi~ll Formulation 1 Compara~lve Conc. Added C~n~. Foam Examl?l ~~ur f ac~ an~ ur f act ant pp~ Ra~ ing A L-5309 1~ 5 ~oa~ ~w 2 B f~-s303 ~ . 5 ~, ~on~ - 3 ~ -53~7 ~ . S aloT~ ~ 3 D L-5311 1. 5 none - 2 E ~-5312 1~ ~ none A 3 F I.-5309 ~ . O nos~e - 3 L-5303 3 . 0 none - ~
H ~-5307 3 . O I~one - 3 5311 3 . 0 a~one - 3 6urfaet~nt concentratiorl i6 expre~sed in parts per ~undred parts oiE polyol u6ed in the ~ormul ~t ion ~pphp) .
.C parative Exarnples J-O
These Examples demonstrate lthat although many o th~ hy~roxy ~erminated pendant copolyme~
u~eful irl thi~ inventior~ ~re cap~ble of 6~abilizing high ~olid content~ rnolded, flexible~foams agairast ~ur~a~e voids, 60me 6truc~ure6 that are useful in thi6 invention ~an not 6tabilize ~oam ~gain~t ~urface ~ids. The use of a ~polymer blend~ i.e., copolymer6 which have hydroxy capped polyoxyalkylene pendant~ blende~ with tho6e which have hydrocarbon capped pendants, provide6 a useful 6tabilizer for both ~ell 6tructure c~trol ~nd ~hear ~ollapse.
~ able 2 ~hows th~ results rom ~ ~oaming test w~th three hydroxy terminated pendant ~opolymer~. Foam pa~ were made u~ing For~ulatio~ 2 at 100 pphp of Pol~mer polyo~ C ~nd 0 pphp ~olyether ~-~5362 .. ... . .

:

- 37 ~ 5~3~

poly~l B~ The te~t wa~ perormed ir~ a 15" X 15" X
~" mold containing no blocl~ sert. Wherea~ ~he b~ock molà . e~t was u~ed ~co ~xplor~ shear ~bili~y, ~h2 ~e~ ~n thi6 ex~ple was performe~ t~
demonstra~ce ~urfac~ cell ~truc~ure csntrol ~ a foam. Normally, a ~aseful ~urfac an~ will l;tar~ go provide f~ne 6ur~ac~ ~ell s1;ruc ure when the ~urfactant ~oncentration reaches about O.5 ~o 1 .O
pphp, and ~hen contlrlue to provide fine ~ell ~tructure until an ~xtremely high concentra~cion i~
achieved. The copoly;ners shos~n in Table 2 do no~l:
exhibit thi~ feature, rather ~hey provide no fine ~urface cell 6~cructure up to concentrations a~ hi~h ~s 4 . O pphp.

D-l 53 62 . . . . ... ... .. ...

~6 3~ --Table 2 ~polymer ~rllc~:ure and Foamin~ Test Usin~
Hydroxy Terminated Polyoxyal1cylens_Pendant CoE?ol~mer~

Hydro~y Sur~ct-~mparatl~e Termlnated Copolymer ~nt Conc _Examp1e _ Copolymer Structure ~ valuatlon .
J~ G ~ID2D^~M 1.0 S~vere Surface Yolds MD6Db~;M 1.0 Severe urfa~ Volds L~ ~ MD6Dg6M 2.0 Severe Surface Vo~ds M~ B MD6D~M 4.0 Severe Surface Volds N~ D MD3D~6M 1.0 Severe Surface Volds 0~ D MD3Db6M 4.0 Severe Surface Volds The copolylTer surfactant i6 diluted to 1~ .
percent k~r weight ~n a polyol and then used in the designated conCQntration which ls expressed in parts ~er hundred par~6 of the polyol in the formulat~on.
P~ll comparative Examples were run using copolymers having hydroxy terminated pendant~ a~
described ln ~his application. The variou~
letter~ of ~hese hydroxy terminated copolymers represent variations in ~e polydimethylsiloxan~
portion of these copolymer~.

~-15362 25~2 Tabl~ 3 Copoïy~er ~ruc~ure and Blook rlold Test Evaluation U~ln~ Hydroxy Terminated Polyoxyall~yl~n~
Pendant COpOl3rlll~!r6 ~lended W~ t~

Hydroxy. Copolymer/ SurfactaRt ~ ermlnated Copolymer Cosurfactant Bl~nd ~oam Exampl@ CoPlovmer Structure Ratlo - - 0~ 7 ûO~ 2 . 5 3 2 ~ HD4D~,M 1.0/1.5 2.5 5 3 ~ MD6D~6M 1.0/1.5 2.5 7 4 C MD4D~M 1.0/1.5 2.5 4 D MD3Dh6M 1.0/1.5 2.5 4 6 E MD4D~M 1.0/1.5 2.5 4

7 ~ PID2D~ ~M 1 . 0/1 . 5 2 . 5 4

8 ~ MD4D~,M 1.5/l.S 3.0 5

9 B MD6D*~M 1.5/1.5 3.0 4 C MD4D~6M 1.5/1.5 3.0 4 11 B MD~D~6M 0.1/1.5 1.6 5 Th~ hydroxy termina~ed copolymer a~ diluted to 10~6 by weight ln polyol before blendin~ ~n ~he ratio ~hown ~bove.
The methyl cappe~ suractan~ was dilu~ed to approximately 25% ln poly~l before blending in the ratio ~howsl abo~re.
The ~urfactan~ blen~ ~onc~ntratior~
expre~ed ~n p~r~c~ pPr hundred part~ o~E polyol used ~n the ~ormula~oz~.

3~2 ~ ~v~ s9,~

Table ~ -C~PO1~ner ~tructure and Block PSold Test Evaluation Usinq Hydroxy Te~minated Polyo~allcylene Copolyrner~
Blended With Methyl Cap~ed Cosurfactan~ ~DD~M

I~ydroxy Copolymer/ Surfatt~flt Termlnated Copolymer Cosur~ctant Bl~nd Foam Example op~ Structure Ratlo nctp~
~2 - . 01l~OX 2.~ 3 13 G MD2D34M 1 . 011 . 5 2 . 5 4 14 tl MD2D36M 1.011.5 2.5 S
lS I MD4D34M l.Q/1.5 2.5 7 16 J MD4D38M 1 . 0/ i . S 2 . 5 17 K MD6D36M 1.011.5 2.5 7 ~ 8 L MD6D38M 1 . 011 . 5 2 . S 4 19 M MD4D36M 1.0/1.5 2.5 S
G MD2D34M l.~/l.S 3.0 4 21 J MDd~D38M l.S11.5 3.0 22 ~ . MD6D36M 1.5/1.5 3~0 7 23 L MD6D38M 1.511.5 3.0 4 The hydroxy terminated copolymer 16 dilu~ced to 10% by weight in polyol before blendirag in the r at i o ~hown above .
The me~hyl capped surfactant was diluted ~o approxima~ely 25~ ~n polyol before blending in the r at i o ~hown ~bove .
The ~ur~actant blerld concentr~tio~ iæ
expre~sed i3~ par~c~ p~r hundred part~ of polyol u6ed in the fc)rmulati~.

D-l 5362 D S j 92~
~/
o ~, ~amPles 2~L 36 The6e Example~ demon6~crate ~c'hat urth~r unexpec~ced ~vant&qe in ~abilizing ~oam ~ga~n~t ~hear collap~e can be ~ine~ ~ preparing c:opolyrner~
~ase~ on ~he ~verage ~ructur~ ~both sili~one ~a~
perldanoc elroup~,o~ ~h~ s~abilizing bl~nds demor~trated i~ Eacampl~ 23. Thu~ ~opolymer N wa~
prepared ~y fir~t ~guilibrating M, D and D' tG gi' a. nominal structure MD2 5D'1 9~5 ~hat ~s the we;ghted sverage of ~ilicone stru~ture in hydroxy terminated ~opolymer B in Example~ 3 and ~he silicone st~ucture of the methyl capp~d co~urfactant u~ed in Examples 1-23. Thi~ product was then hydro~ilylated with a mixture of allylmethoxy-triglycol and an ~llyl ~tarted polyethylene oxide 3f molecular weight 350. The mix~d pendant copol~ner thu6 ~ormed ~6 an average structure ~ilicone that contain~ a mix~ure of me~hyl capped and hydroxy terminated polye~her pendant~. The stabilizin~
ability o this ~ingle c~pol~mer with mixed pendan~
c~n then be compared to the resul~ for hydroxy terminated cvpolymer 8 blended with the me~hyl capped co6urfactant in Example~ 1~23.
~ imil~rly, copolymer P i~ ~he avera~e 6tructure of the 6urfac~ant blend of hydroxy terminated ~opolymer F and the methyl cappe~
cosurfactant used in Example~ 1-23. Copolym2r 0 i~
ano~her example ~hat demonstrate~ that stab~l~z~ng ~dvantage of having a copol~mer with bo~h hydroxy term~nat~ ~nd methyl ~appe~ p~nda~t6, Th~ r~sult~ of the Blo~k Mold Test u~g Formulatlon 1 for the ~verage 6tructure ~o~ol~mer~

~-153~2 .. . . .. .

5~31~

i~ ~hown is T~ le S. Th~y ~learly demonstrate th~
~urpri~ing advan~age o ~veraging the struc~cur~s.
Thu~ copolymer N ~ rated as 9 7,rer~u~; a ra~q o 7 for ~he physical blend u~ing copolyrner B ~ xampl~
3 . Copolymer ~ ~ s ra~ed a6 7 ver u~ a rating o 4 ~or the phy~ l blend using e~polymer F ~ Example 3. I::opolymer 1~ al~o per`orm~1 well wi~h a r~cln~
of 7.
Table 5 CoPolymer ~truct~re and 13lock Mold Test Evalua~ion Mixed Hydroxy and kSethyl Terminated_ Pendant CopolYmer6 Ml xed Surfactant Pendant Copolymer Pendant Conc. Foam Example Copolymer Structure, Ratlopphp Ratl~
2~ N MD2,sD41.g6M 40/60 2.5 9 25 0 MDl.4sD41.31M40/60 2.S
26 p MDl.76D41.96M 40160 2.5 7 The ~opolymer is diluted to 20~6 by weigh~
~o make ~che ~urf~ctant. The ~urfactan~
concentxation i~ expres~ed in par~ p~r hundr~d part of polyQl.
Examples 27 - 36 Example~ X7-36 ~urther demonstrates ~he ~d~van~ge c~f h~ving pslyoatyalkylene pendant6 whi~h are both hydrox~ terminat~d and methyl capped varying ~ 06 1~1 the 6ame copolymer. These êxample~; al60 8how al;Lyl ~tarted polyalkyl~n~ oxide~
that ln~orporate propylene oxi~e.
;

1~-1 53 ~2 ff3 ~ 5 Tabl~ C
opolymer ~tructur~ ~nd Block M~ld Test Evaluatisn P~ixed HydrQx~r Termis~ated nd ~Se~hyl CapPed Co~oll~Tner~

Ml xed, Fo~m Pendant Copolymer Pendant Surfactant natlng Exampl e _,~y~ Structurr Ratlo Conc .
27 Q MD2.5D52.0M 50/50 l.S 8 28 R M~2 . 5~52 .oM ~9l40 29 S MD3,~D5~.oM 50lS0 1.5 8 T MD2.sD52.oM 7ûl30 1.5 9 31 U MD2.~D62.~M 60J40 l.S
32 V MD3.o~6~.5M 70/30 1.5 9 33 ~ MD3.0D62.0M 50/SO 1.5 7 34 X MD2.5D62.0M SO/50 1.5 B
Y MD3 . oD62 . oM ~0/ 50 1 . 5 7 36 Z MD3.oa62~oM 70/30 1.~ 9 The copolymer is diluted to 25% by weight in ~ polyol and ~hen used in the de~igna~ed concerltration which 1s expres~ed in parts per h~dred parts of polyo1.

D-l s3 62 .

....... .

..

v~

Exampl~ 37 - 44 ~nd Comparative ~xam~le~ P ~
~ xamples 37-4~ demonstrate the une~p~ t~d ~dvan~a~e of increa~ing brea~hability by pr~paring a ~ingle ~urfa~tan~ having bo~h hydro~y t~rminated a~d methyl capped pendant6 comprised of both ~thyle~e oxide and propylen~ oxide uni~. Blend~
~uxfactant6 made ~rom ~gual amount~ of hydro~y ~erminated polyekher pendan~ ~opolymler~ and methyl capped polyether pend~n~ ~opolymer~ lwere foam test~d for ~reathability $n the test de~cri~bed ~bo~e.
Analogous ~urfactan~s were prepar~ from slngle copolym~r~ having equal amount~ of both hydro~y terminated and methyl ~apped poly~thers pendants.
These were al~o te~ted for foam breathability ~n th~
above described te~t. ~he re~ult~ are de6cribed below and demonstrate that the ~ingle mixed ~urfactant6 ~re more open and thu~ more prefera`ble.
Tabl~ 7 shows the result~ ~or ~o~m breathability te6t6 of copolymer6 with pendants made with al3.ylmethoxytriglycol ~MTG~ ~nd either allyl 6tarted polyethylene oxide (~PEG) or allyl started polypropylene cxide (APPG~. The tes~ were run using Formulation 2 with ~00 part~ of Polymer polyol C whi~h ls ~i~nificantly higher than the normal concentration o~ ~0 to 60 part~. In thi6 tes~, the totally ~ethyl capped pendan~ copolymer ~FF~ did ~ot make a ~table foam. For copolym~r p~ndant6 ~ad~
~rom ei~her APEG or ~PPG, ~he mixed penda~t ~opolym~r ~II or LL~ provide~ a more ~reathable PDam ~han ~ither t~e hydro~y ~erminated pendant ~o~oly~r t~G or ~J~ or the blen~ of thP all hy~roxy ~ermin~ted pendant ~opolymer and ~h~ ~11 m~th~l ~apped pe~dan~ ~opolymer (~H and ~K).

*~~ ~ 5~

Table a show~ ~ ~imilAr ~et of oam breathability te~ts for ~ 6econd ~ilicone ~tructure u~ing th~ s~ne pendant groups a~ Table 6.
Formul~t~on 2 wa6 u~ed for ~hese ~e ts, wi~h 70 parts of Polymer polyol t: ~d 30 part~ of ~olye~h~x polyol B. The re~ul~ how the same ~sends a~ ~ho~e in Table 7. The mixed AMTG/APEG and AMTG/APPG
~?endant copolymer~ are more breathab~ e ~han th~
analogou~ blend~ o AMTG pendant copolymer wi~h either ~PEG or APPG pendant ~opolymer.

5~
_ ,~

Tabls 7 CoDolymer ~tructure and Br_athabi~ y Fo~m ~e~t U~xed Hydroxy Terminated ar~ Set~yl C~pped endant Cop~lYmer~

Cop~lymerPendantCo~olymer To~ End Example CoPolymer Structure ~ Ratlo Blend Ratlo _n~

C~npar~tlve ~ MD2~sD72.5M 100/0 ~ no stablQ
Example P ~oa~
Comparatlve GG MD2.5D72.5M 0/100 - 0.75 Example ~
MD2 . sD72 . 5M 100/0 37 H~l 50150 0 . 75 MD2 . 5D72, 5M 0~100 38 II MD2~5D72r5M S0/50 1.0 C~mpar~tlve JJ MD2.sD72.5M 0~100 1.0 Example R
MD2.5D72.5M 100/0 39 KK S0/50 1.0 MD2 . sD72 . 5~ 01100 LL MD2.sD7~.sM S0l50 ~ 2.0 HH ~nd ~R are blends o two ~ndependently prepared copolymers. The eopolymers werQ di6solved to 20 weight percent in a polyol ~nd used a~ lthP
li~ted ~onc~n~ra~ion expressed in part6 per hundred ~art~ of polyol in the formulation.

~-15362 ~` ~'1 v ;~
3~

Tabl~ 8 Copol~ner Structure and Brea~habilit~ Foam Te~t Mixed Hydroxy Terminated and Me~h~
Ca~d Pendant Copul~n~r~

CopolymerPenclant Copolymer Top End Structure Rat:lo B1end Ratlo Conc/pphp Comparatlve M . ~Dl.g5D~1.2M 100~9 3-5 Example S
MDl ~sD81 ~M 100lO
41 BB 50/50 0 . 5 MDl.85D81.2M 01100 4~ ~MDl.~5D~1.2M 50/50 - 0.75 MDl . 85D81.2M 100/0 43 DD 50/50 1.25 MD~85D81.2M 0/100 44 EEMDl,~sD81~2M . SO/50 - l.SO

BB ~nd DD ~re blend6 of two independently prepared Gopoly3Ter6. The copolymer& were dis~olved ~o 20 weiyht percsxl~ in a polyol and u~ed ~t ~he lis~ed ~oncentrat~on expres~ed in ~rt~i per hundred ~: part~ o polyol in the iE~rmula~ion.
;' :

', :

Examples 4 5 - 5 These Examples demonstra~ the abili~y t~
control ~he 2:rea~habili~y of ~he foam by ~hangln~
the ratio of hydroxy terminated pendant groups ~o methyl capped pendan~c groups. A 6erlel~ o copolymer~
were I?repared wi~h difersnt ra~io~ oE a methyl capped pendarlt6 ~o hydroxy ~c~rmina~ed pendant~ usirlg pendan~c ~roups ba~e~ on both ethylene oxi~e e~d propylene oxide. Thes~ were then test in ~he foasn breathability te&t descr;bed ~bove. The resul~ fro~n these tests ~re ~ho~ in Tabl~ 9. They demon~trat~
tha~ the breathabili~y incr~ase6 in a controllable manr~er a6 the ratio of methyl capped pendant ~o hydrQ~ terminated pendant increase~. Thu~ it i6 possible to design a copolymer with the desired foam breathability by adjusting th~6 rat~o.

I)-l 5~ ~2 ... .

Table 9 Copolymer Structure and Foam Breathabil itY Test Mixed Hydroxy T~rminated and Methyl Capped Pendant Cop~?lYmer Formulation 2: 70 pph~ C - 30 pphp B

.Copolymer Pendant Top End Example CopolymerStructure Ratio _n ~e~e CC1,85D 1,2M 50/50 0.75 46 MMMDl.85D91 2M 70/30 0.85 NNMDl,g5D91 2M 80~20 1.0 48 OOMDl 8sD91 2M 85/15 1.75 ppMDl 85D91 2M 90/10 2.75 QQMDl gsD91.2M 50/50 1.50 51 RRMDl 85~91.2~ 80/~0 3.25 The copolymers were dissolved to 20 weight percent in a polyol and used in the listed concentration expressed in parts per hundred parts of polyol in the formulation.

Claims (24)

1. A polyurethane foam surfactant which comprises:
a single polydialkylsiloxane-polyoxyalkylene copolymer wherein the polydialkylsiloxane contains no more than ten silicon atoms and the backbone is substituted with an average of at least 0.5 polyoxyalkylene substituents wherein (a) 5 to 95 percent by weight of the pendants on the copolymer have the formula -R(R')a(R")bX
wherein R is an alkylene group of 1 to 4 carbons linked to the silicon atom, R' is an oxyalkylene group of 1 to 4 carbons, R" is a second oxyalkylene group of 1 to 4 carbons which is different from R', a plus b is 1 to 15, and X is OR3 or where R3 is a monovalent alkyl group of 1 to 4 carbons;
and (b) 95 to 5 percent by weight of the pendants on the copolymer have the formula -R(R')c(R")dOH
wherein R is an alkylene organic group of 1 to 4 carbons linked to the silicon atom, R' is an oxyalkylene group of 1 to 4 carbons, R" is a second oxyalkylene group of 1 to 4 carbons which is different from R', and c plus d is 1 to 10.

2. The surfactant of claim 1 wherein polydialkylsiloxane is linearly construed from R2Si(O1/2)2 chain extending units and R3SiO1/2 chain terminating units that contain the polyoxyalkylene pendants either internally on some of the R2Si(O1/2)2 chain extending units, or terminally on some of the R3SiO1/2 chain terminating units, or both and wherein R is an alkyl group having 1 to 6 carbon atoms.

3. The surfactant of claim 2 wherein R is methyl.

4. The surfactant of claim 1 wherein branched polydialkylsiloxane is constructed from R2Si(O1/2)2 units, R3SiO1/2 units and RSi(O1/2)3 or Si(O1/2)4 units which RSi(O1/2)3 or Si(O1/2)4 units create branching with th polydialkylsiloxanes wherein the polyoxyalkylene chain is attached to the R2Si(O1/2)2 unit, the R3SiO1/2 unit or the R2Si(O1/2)3 unit or any combination of the three and wherein R is an alkyl group having 1 to 6 carbon atoms.

5. The surfactant of claim 4 wherein R is methyl.

6. The surfactant of claim 1 wherein the copolymer is:

Me3Si(OSiMe2)h(OSiMeQ)i(OSiMeP)jOSiMe3 Wherein Me is a methyl group, i has an average value of 0.025 to 3.0, j has an average value of 0.025 to 3.0 such that the ratio of i to j has an average value of 0.5 to 8.0, Q is -R(R')a(R")bX
and P is -R(R')c(R")dOH
wherein R,R',R",a,b,c,d, and X are as described in Claim 1.

7. The surfactant of claim 1 wherein the copolymer is:
DgSi(OSiMe2)h(OSiMeQ)i(OSiMeP)jOSiME3)4-g Wherein D is a hydrocarbon free radical free of aliphatic unsaturation and contains from 1 to 10 carbon atoms, g has an average value of 0 to 3, Me is a methyl radical, i has an average value of 0.025 to 3.0, j has an average value of 0.025 to 3.0 such that the ratio of i to j is in the range of 0.05/0.95 to 0.95/0.05, i plus j has an average value of 0.5 to 8.0,Q is -R(R')a(R")bX

and P is -R(R')c(R")dOH
wherein R,R',R", a, b, c, d, and X are as described in Claim 1.

8. The surfactant claim 1 wherein the copolymer is:
(QMe2Si)k(OSiMe2)h(OSiMeQ)i(OSiMeP)j(OSiMe2P)1 wherein K has an average value of 0.1 to 1.9, 1 has an average value of 0.1 to 1.9, K plus 1 equals 2.0, i has an average value of 0.025 to 3.0, j has an average value of 0.025 to 3.0 such that the ratio of i to j is in the range of 0.05/0.95 to 0.95/0.05, i plus j has an average value of 0.5 to 3.0, h plus i plus j has an average value of 0.5 to 8.0, Q is -R(R')a(R")bX
and P is -R(R')c(R")dOH

wherein R,R', R", a, b ,c, d, and X are as described in Claim 1.

9. The surfactant of claim 1 wherein the copolymer is:

DgSi((OSiMe2)h(OSiMe2Q)m(OSiMe2P)n)4-g wherein D is a hydrocarbon free radical of aliphatic unsaturation and contains from 1 to 10 carbon atoms, g has an average value of 0 to 3, h has an average value of 0 to 8, m has an average value of 0.05 to 0.95, n has an average value of 0.05 to 0.95, m plus n equals 1.0, Me is a methyl group, Q is -R(R')a(R")bX

and P is -R(R')c(R")dOH

wherein R, R', R", a, b, c, d, and X are as described in Claim 1.

10. The surfactant of claim 1 wherein the copolymer is DgSi((OSiMe2)h(OSiMeQ)i,(OSiMeP)j(OSiMe2Q)m(OSiMe2p)n)4-g wherein D is a hydrocarbon free radical o aliphatic unsaturation and contains from 1 to 10 carbon atoms, g has an average value of 0 to 3, Me is a methyl radical, i has an average value of 0.025 to 3.0, j has n average value of 0.025 to 3.0 such that the ratio of i to j is in the range of 0.05/0.95 to 0.95/0.05, i plus j has an average value of 0.5 to 3.0, h plus i plus j has an average value of 0.5 to 8.0, m has an average value of 0.05 to 0.95, n has an average value of 0.05 to 0.95, m plus n equals 1, Q is -R(R')a(R")bX
and P is - R(R')a(R")dOH

wherein R,R',R",a, b, c, d an X are as described in claim 1.

11. A polyurethane foam surfactarnt in a polyurethane foam solution which surfactant comprises: a linear polysiloxanepoly-alkylene copolymer of the general formula:

Me3Si(OSiMe2)h(OSiMeQ)i(OSiMeP)jOSiMe3 wherein Me is a methyl qroup, h has an average value of 0.5 to 3.0, i has an average value of 0.025 to 3.0, j has an average value of 0.025 to 3.0, the ratio of i to j is in the range of 0.50/0.50 to 0.95/0.05, Q is -R(R')a(R")bX

wherein R is propyl, R' and R" constitute a polyether made from oxyethyl, oxypropyl or a mixture of oxyethyl and, oxypropyl groups to give a total molecular weight of 100 to 450, X is a methoxy group, and P is -R(R')c(R")dOH

wherain R is propyl, and R' and R" constitute a polyether made from oxyethyl, oxypropyl or a mixture of oxyethyl and oxypropyl qroups to give a total molecular weight of 100 to 450.

12. A process for making an improved molded, flexible polyurethane foam utilizing the surfactant of claim 1.

13. A process for making an improved molded, flexible polyurethane foam utilizing the surfactant of claim 2.

14. A processs for making an improved molded, flexible polyurethane foam utilizing the surfactant of claim 3.

15. A process for making an improved molded, flexible polyurethane foam utilizing the surfactant of claim 4.

16. A process for making an improved molded, flexible polyurethane foam utilizing the surfactant of claim 5.

17. A process for making an improved molded, flexible polyurethane foam utilizing the surfactant of claim 6.

18. A process for making an improved molded, flexible polyurethane foam utilizing the surfactant of claim 7.

19. A process for making an improved molded, flexible polyurethane foam utilizing the surfactant of claim 8.

20. A process for making an improved molded, flexible polyurethane foam utilizing the surfactant of claim 9.

21. A process for making an improved molded, flexible polyurethane foam utilizing the surfactant of claim 10.

22. A process for making an improved molded, flexible polyurethane foam utilizing the surfactant of claim 11.

23. A process for increasing the foam stability of the polyurethane foam of claim 1 by increasing the amount of hydroxy terminated polyoxyalkylen groups in the copolymer relative to the amount of alkyl or acyl terminated polyoxylakylene groups.

24. A process for improving the breathability of the polyurethane foam of claim 1 by increasing the amount of alkyl or acyl terminated polyoxyalkylene qroups in the copolymer relative to the amount of hydroxy terminated polyoxyalkylene groups.