CA1114829A - Acrylonitrile-capped polyethersiloxanes - Google Patents

Abstract

ACRYLONITRILE-CAPPED POLYETHERSILOXANES

ABSTRACT OF THE DISCLOSURE

Certain acrylonitrile-capped polyoxyalkylene compounds and their polymers are disclosed which are useful in the preparation of flame-retardant cellular urethane products.

S P E C I F I C A T I O N

Description

The present invention relates to a particular novel class of-acrylonitrile capped polyoxyalkylene com-pounds and to acrylonitrile-capped polyoxyalkylene-poly-siloxane polymers, as well as to the use of said polymers in the formation of cellular urethane p~oducts, particularly flexible polyester urethane ~o~m containin~ a flæme-re-tardan~.
It is well kn4wn that the urethane linkages of cellular urethanes are formed by the exothermic reaction of a polyfunctional isocyanate and a polyfunctional active hydrogen-containing compo~nd in the presence of a catalyst, and that the cellular 6tructure is provided by gas evolution and expan~ion during the urethane-forming reaction. ~llus-trative of suitable acti~e hydrogen-containing compounds are polyether polyols and polyester polyols. In accordance with the"one-shot" process which is the most widely u6ed industrial techni~ue, direct reaction is effected between all of the raw materials which include the polyisocyanate, ~0 the active hydrogen-containing oompound, the cataly6t system, bl~win~ agent ~nd ~urfactant. A major function of the 6urfactant i~ to ~tabili7e the urethane foam, that is, prevent coll~pse of the foam until the foamed product has developed sufficient gel stren~th to become ~elf-~upporting. A~ong the variou~ types of ~ilieon~containin~
compo~itions reported in the li~erature a~ effectivP
6tabil~zers of urethane fo~m deri~ed from a polye~ter polyol ~nd a polyether polyol are e.g. those de~cribed in U. S. Patent No. 3,594,334 ~nd Rei6~ue Patent No.

-2-'.

~ D-9107 27,541, respectively~ Other patents relating to the manuacture of flexible polyester urethane foam in-clude U.S. Patents 3,563,924; 3,793,360; 3,796,676 and

3,833,512.
In recent years considerable effort has been expended and continues, to recluce the recognized objection-able characteristic of urethane polymers in their ability to ignite readily ~nd burn with an open fl~me.
One approach to this problem is to include a flame-retarding agent such as various phosphorus and/or halogen-contaLning compounds as a component of the foam-producing reaction mixture, and in this respect, to develop improved ~nd more efficient flame-retarding a~ents.
An As~oc$ated problem i~ to provide surfactants which not only function to stabilize foam containing a flame-retardant but which al80 allow for the formation of such foam which burns at a reduced rate relative to surfactants de6igned for stabilization of non-fl~me retarded foam. For ex~mple, eertain ~iloxane ~urfactants which are excellent stabilizer~ of non-flame-retarded foam and ~hich are Qlso capable of stab~lizing foam containing a flame-retardant ~ppear to have ~n adverse effec on ~he efficlency of ~he flame retarding agent a~ seen from the flamability properties of ~ome re~ulting flex~ble polyester urethane foam products.

. .
~3--; .
.... - i - - ,, .. , , . ... .. . ~. .

-It is desirable, therefore, and is an objec~
of this invention to provide a new clsss of acrylonitrile-capped polyoxyalkylene compounds as well as a new class of acrylonitrile capped polyoxyalkylene-polysiloxane polymers which polymers, in addition to the ability to stabilize non flame-retarded cellular urethanes, . offer particular utility ~s 6tabilizers of flexible polyester urethane foam having a flame-retardant incorporated therein.
Various other objects and advantages of this invention will become apparent to those skilled in the art from the ~ccompanying description and disclosure.

In accordance with one`a6pect of the present invention ~crylonitrile-capped polyo~yalkylene compounds are provided which can be used ~o produce the acrylo-nitrile-capped polyoxyalkylene-polysiloxane polymers employed in thi6 invention, '. Illustrative of the novel cl~ss of acrylo-nitrile-capped polyoxyalkylene compounds of thi6 ~ invention ~re those having the aver~ge formula `~ R~(X)~ 3H~)n~C2H4)m 2 2 1, wherein X ~s a bridging group 6elected from the cla6s :, ~ consisting of -C0- and -NHC0-; wherein R' represents a : ' - - - . --, - :

.

~ D-9l07 monovalent olefinic alkylene radical containing from to 6 carbon atoms and usually not more than four, allyl being preferred; wherein q has a value of 0 or 1;
preferably 0; wherein m has a value of from 4 to 30, preferably 4 to 15; wherein n has a value of from 0 to ~0, preferably 0, and wherein the sum of m ~ n has a value of from 4 to 40, preferably 4 to 15.
Another aspect of this invention provides acrylonitrile capped polyoxyalkylene-polysiloxane polymers, a~id polymers containing at least one silicon-bonded acrylonitrile-capped polyoxyalkylene radical (Q) wherein Q has the average formula -R~(X)q(OC3H6)n(OC2H4)mOCH2 2 wherein X, ~, n and m are the same as defined above and R" represents an alkylene radical, free from unsaturation, and containing from 2 to 6 carbon atoms, ~sually not more than four. The preferred alkylene radical R" being propylene. Of course, it is obvious that said alkylene radical R" is derived from and corresponds to the particular R' group of the above defined acrylonitrile-capped polyoxyalkylene compounds used in the production of the novel siloxane polymers of this inventlon and it i~ of course also understood that said alkylene radical R" is directly bonded to a silicon atom which constitutes ~e of the siloxy units of said acrylonitrile-capped polyoxyalkylene-polysiloxane polymers of this ~ 4 ~ ~ ~ D-9107 in~ention. It is of course also understood that the other siloxy units ~s well as other radicals attached thereto that make up the siloxane pol~mers of this invention are well known in the art and obviously can correspond to those siloxy units and radicals heretofore contained in con~entional siloxane surfactants that may be employed as stabilizers in the prDduction of urethane foAm and therefore are not critical to the generic definition of the siloxane polymers o~ this invention.
1~ Illustrative of a preferred class of siloxane polymers of this invention are acrylonitrile-capped polyoxyalkylene polymers consisting essentially of ch~mically combined (1) monofunctional siloxy units (M) and (2) an average of from bout 0.5 to about 70 moles of difunctional siloxy units (D) for every two moles of M, with the proviso that an average of at least about 0.5 up to about 30 moles of acrylonitrile-capped polyoxyalkylene groups (Q) are present in said acrylo-nltrile-capped polyoxyalkylene-polysiloxane polymers for every two moles of M, wherein Q is the same as defined above.
In the monofunctional siloxy units encompassed ~, by MD of ~aid polymer6 the respective silicon atoms are ' bonded to two monovalent hydrocarbon radi.als (R), preferably alkyl groups, the third silicon-bonded group belng the ~oresaid acrylonitrile-capped polyoxyalkylene ., .

- : :
. . ~
.

D-91~7 group (Q), P monovalent hydrocarb~n grou~ (R) or E
a radical selected from the class consisting of a cyano-containing group (E) of the formula ~0) rR2CN wherein r is 0 or 1, preferably 0 and R~ is an alkylene radical having from 2 to 12 carbon atoms preferably 2 to 4, a cyano-containing group (E3 o the formula -(0) R20R2CN
wherein r and R2 are the ~ame as defined ebove; a sulfolanyloxyalkyl-containing group (E2) of the formula ~4 5 -R3_o~ -H
~6 ~ ~,R7 S ~1 O O
wherein R3 is an alkylene radical having from two to eight carbon atoms and R4, R5, R6 and R7 shown bonded to the carbon atoms in the two to five positions of the ring, respectively, are independently hydrogen or alkyl having from one ~o four carbon atoms, a~ a ~orpholino-containing group (E3) of the ~ormula CH - CH
~0) (R O~R9-N / \
CH - CH
~, l6 l7 '` wherein t is zero or has an average value fr~m about ., one ~o about four; 8 iB zero or one provi.ded s i5 one when t has a value of more than one; R8 is an alkylene radical having from two to four carbon atoms, R9 i8 an alkylene radical having from two to six càrbon atoms and R , R5, R and R are the ~ame as defin d ~7-;.. ., . , . . .. . . . . ......... -,,, ... .~ - - ~ ;.

i ~ . R

D-9lO7 ~bove. Thus, included within the scope of M are mono-functional 8iloxy units having the followin~ unit formulae which for brevity are also individually referred to herein th M Ml M2 M3 M4 and M5 units as shown M ~ R3SiOl12 Ml=(Q)R SiOl/2 M2= (E)R2SiOl/2 M3~ (E~ )R2SiO112 M4-(E )R2SiOl/2 M ~ tE3)R2SiO112 Of course in any givPn polymer composition the M units m~y be the same as or diff~rent from one another. In the difunctional units encompassed by D, at least one of the two groups bonded to the respective silicon atoms is a monovalent hydrocarbon rsdical (R), preferably alkyl, End the 3econd 6ilicon-bonded group is Q, E or R.
Thus, included within the 6cope of D are difunctional units having the following unit fonmulae which for brevity, are also individually referr~d to herein as the D Dl, D2, D3~ D4 and D5 units a~ ~hown D ~R2S~02/2 Dl-(Q)(R)SiO2/2 D2~(E)RSiO2/2 D3-tEl)RSio2l2 : . D4 t~2)RSiO2~2 ., D5~(E3)RSio2/2 Thu6, sa~d preferred cl~ss of the polymers may cont~in any combination or ~u~comb~n~tion of ~8-~ 4~2~ D-9107 the respective siloxy units ~thin the ~cope of M
and D provided the average composition contains from about 0. 5 to about 70 moles of D~ for every two moles of M~ and from about 0. 5 to about 30 moles of Q for every two moles of M.
Consistent with the above definition ~nd from the standpoint of the nature and rela~ive proportion of monomeric ~iloxy units, the above preferred class of acrylonitrile-capped polyoxyalkylene-polysiloxane polymers have the following average composition, as expressed on the normalized basis of a total of two moles of monofunctional units (M), that is, per sverage mole of polymer:
R R R R R R
[RSiOl/2~ [QSiOl/2]btESiOl/2}C[SiO~/2]d~sio2l2] ~SiO2/2]~ (I) R R R R Q E
wherein R, Q and E are the same as defined above, wherein a, b, and e are zero or any positive number havin~ an average value of no more ~han two, and the aver~ge vAlue of the sum a+b+c i~ two; wherein d is zero or ~ny posi ive number ~v~ng ~n average value of up to ~bout 20, e is zero or any positive number having ~n average value of up to about 30, and f i6 zero or any po6itive number having ~n average value ~p to ~bout 20, provided the average value of the sum b~e ~s at ., lea~t i~ou~ 0.5 up to about 30.
It is e~ident, therefore, t~.at the 6um b+e correYpond6 to the total num~er of Q group B coneained in , .
9.

d~

an ~verag~ mole of polymer an(l t'-nc when either b or e is zero, the o~h~r must be a~ least 0.5. It is also evident tha~ when any combination of a, b and c - are posi~ive numbers the pol~mers contain said combination of respeceive monofunctional units.
Ano~her prepared class of acrylonitrile-capped polyoxyalkylene-polysiloxane pol~mers are thosé
polymers consisting essentially of silicon-containing units A, B and C wherein A is SiO4/2, B is a poly-functional siloxy unit in which silicon is bonded toat least one acrylonitrile-capped polyoxyalkylene group (Q) as defined above, and C is a monofunctional triorganosiloxy unit, and in which there are from about 0.4 to about 2 moles of A, and from about 0.2 to about 2 moles of C, per mole of B.
Yet another pre~erred class of acrylonitrile-capped polyoxyalkylPne-polysiloxane polymers are those polymers consisting essentially of silicon~con-taining units, A', B' and C', wherein A' is SiO4/2, B' is a mono functional siloxy unit in which silicon i~
bonded to a~ least one acrylonitrile-capped polyoxyalkylene group (Q) as defined ~bove, and C' is a monofunc~ional trihydroc~rbylsiloxy unit, and in which there are from about 0.75 to about 2 moles of A', and from ~bout 0.1 to abou~ 1 mole of C'~ per mole of B'.
., In ~ccordance wi~h another ~spect of the presen~ invention, ~here is provided a proce~s for produci~g polyurethane foam whl~h comprises reac~ing 10.

.

, ~ Z9 9107 and foaming a reaction mixtur~ of: (a) an organic polyol reactant comprising a polyether polyol or a polyester polyol containing an average of at least two hydroxyl ~roups`per molecule: (b) a polyisocyanate reactant containing at least two isocyanato groups per mo~ecule; (c) a blowing agen~ a catalyst com~rising a tertiary-amine; and (e) a foam stabilizing component comprising the acrylonitrlle-capped polyoxyalkylene-polysiloxane polymers of ~he present invention. In addition to their efficacy as stabilizers of non flame-retarded urethane foam, it has been found that certain polymers described herein possess the further advantageous property of allowing for the formation of flame-retardant containing flexible polyester foam of ac~eptable overall quality, and reduced combustibility relative to unmodified polyalkylsiloxane-polyoxyalkylene copolymers. In accordance with this aspect of the present invention, flame-retardant containing flexible polyester-based ure~hane foam products ~re provided by reacting and fosming respective reaction mixtu~es which additionally includ a flame-retarding age~t.
In providng the pol~ureth~ne foam6 of the invention, the acrylonitrile-capped polyoxyalky'lene-polysiloxane pol~mers can be introduced to the foam producing reaction mixtures either as 6uch, as a blend with v~rious orgsnic additives including organic surfaet~nts or in combination with one or re of th~
polyol re~c~ant9 blowing gent, ~m~ne ca~alyst and, when u~ed, the flsme-retarding agent~

~1~ ' ' 11.

The acrylonitrile-capped polyoxyalkylene compounds of th s invention which are used as reactants to produce the acrylonitrile-capped polyoxyalkylene-polysiloxane pol~ners of this invention can be made by the cy2noethylation reaction of olefinic-started and hydroxyl endblocked polyoxyalkylene compounds.
The olefinic and hydroxyl endblocked polyoxy-alkylene compounds and/or methods for their preparation are well known in the art. For instance by reacting an alkenol, R'OH, an olefinic carboxylic acid R'COOH o;
an olèfinic R'NHCOOH wherein'R' is the same as defined above with ethylene oxide or a mixture of ethylene oxide and 1, 2-propylene oxide in the presence of a base - catalyst, e.g. KOH the corresponding olefinic and hydroxyl endblocked polyoxyalkylene co~pound having the formula R (X)q(OC3H6)n~OC2H4)mOH
.~ can be produced wherein R', X, q, n and m are the same as defined above. Illustrative examples of such hydroxyl starters are H2C=CHOH, H2C=CH-CH2OH, H2C=C~CH3)-CH2OH, H C=CH-CH2COOH, H2C=CH-CH2NHCOOH, and the like. Of course it is unders~ood that when the polyoxyalkylene com-pound contains both oxyethylene and oxypropylene units that such oxyalkylene units can be rando~ly di~trlbuted throu~hout the chain such GS WheD G rixturo 12.

.'i, -d ,, .

'' ''`'` ''' ` - . . .

3'~ r)-9~07 of the alkylene o~ides is polymerized or they can be ~rranged as sub-blocks in any desired rashion such as when the respective alkylene oxides are polymerized sequentially.
Conventional cyanoethylation of such olefinic started and hydroxyl endblocked polyxoyalkylenes in the presence of a base catalyst then produces the corresponding acrylonitrile-capped (i.e. beta--substituted propionitrile) polyoxyalkylene compounds of this invention as illustrated by the following equation Base ( q( 3 6)n( C2H4)mH + CH2 CHCN~
Rl(x~q(oc3H6)n(oc2H4)mocH2 2 wherein R', X, q n and m are the same as defined above.
As pointed out above preferably R' is allyl, q is 0, n is 0 and m is 4 to 15. Thus, the most preferred acrylonitrile capped polyoxyalkylene compounds are those having ~he average formula 2 HCH2(C2H4)mCH CH CN
wherein m is 4 to 15 which compounds are derived from the cyanoethylation of an Pllyl alcohol started and hydroxy end blocked polyoxyethylene. High conversions of said acrylonitrile-capped polyoxyalkylene compounds are readily achleved by using essentially stoichiometric ~mounts of acrylonitrile and (CH3)4NOH or NaOH base catalyst3. The cyanoethylation rate at about 10~C.
to ~bout 20C. is fast and about 90-95 percent complete in less than ~wo hours. The use of (CH3)4NOH catalyst < . . .. . .

~ D-9107 is preferred over NaOH mainly because of capping efficienc)~ and less acrylonitrile homopolymer formation.
As indicated abovc, th~ acrylonitrile ca~ped polyoxy-alkylene compounds of this invention are useful as reactants in preparing ~he acrylonitrile eapped polyoxyalkylene-polysilox~ne polymers of this invention.
The functio~alit~ t~f the ~espective types of structural units encompassed by M, D, A, B, C, and A', B', C', of the siloxane polymers of this invention denotes the number of oxygen atoms to which the silicon atom (Si) of any particular unit is bonded.
Since each oxygen atom is shared by a silicon atom (Si') of another unit, functionality also denotes the number of linkages by which the particular ~nit can be bonded to another portinn of the polymer through -Si-O-Si'- bonds. Accordingly, in expressing the individual formulas of the respective units of the polymers of this invention, fractional subscripts are used in which the value of the numerator ~efines ?0 functionality ~i.e., the number of oxygen atoms associated with the silicon atom of the particular unit), and the denominator, which i~ each instance is 2, denotes that each oxygen atom is shared with another - sili~on atom. Thus, monounctional units e.g. M, are chain terminating or end-blocking units and the respective oxygen atoms ~hereof are shared with 8ilicon of one othe!r unit, e.~. D~. On the other hsnd, D unit~
are difunct:ional and thus the respective two oxygen 14.

...... . ~ . .. , . , . , . . . . _ .. . .. _ .. . . . .. . . . . . .. . . .. ..
.., . _ .., .. .-- --~

atoms flssociated wlth each silicon atom th~reof are shared with resp~ctive silicon aLoms of other units. Thus, the reoccurring difunctional units may be distributed in .the polymer randomly, alternately, as sub-blocks of repeating units of the same type, or in any combination of such arrangements. ~ hou~h the siloxane polymers of ~his invention can be discrete chemical c~mpounds, they are usually mixtures of discreee siloxane ~pecies which differ in molecular w~ight and in the type, arrangement and relative proportions of units. Therefore, as expressed herein, the par~meters employed to denote these variables are average values and are based on the relative proportions of reactants from which the various ~nits are derived. It is to be further understood that, consi~tent with convention in the art to which the present invention pertains, as expressed herein, ~he formulas of the polymers indicate their overall average emperical composition rather than any particular polymer ~pecies.
With this understanding the average composition of some of ~he more preferred respective types of polymers encompas~ed by ~iloxane polymers of this lnvention the following formulae wherein the var~ous siloxy units ~re ~hown in chemically combined form:

~3SiO[RSiO~y~iR3 (I-~) O Q
R3SiOER2SiO~ ~RSiOly~R3 (I-B) Q

QP~2SiO[~2SiO]XSiR2Q (I-C) QR2SiO[R SiO] [RSiO] SiR Q (I-D) Q

QR2SiO[RSiO]ySiR2Q (I-E) ~ Q

R3SiO[RSiO]y[RSiO]zSiR3 ~I-F) Q E

; R3SiO[R2SiO] [RSiO] [RSiO] SiR3 (I-G) Q
R3SiO[RSiO] [RSiO]zSiR3 (I-H) Q El R3sio[R2sio~x[Rsio] [RSiO]~iR (I-I) El R3SiO[RSiO] [R.SiO] SiR3 (I-J) R3sio[R2sio]x[Rsio]y[Rsio]zsiR3 (I-K) Q E
R3SiO[RSiO] [RSiO]ZsiR3 (I L) . Q E3 R3sio[R2sio]x[Rsio]y[Rsio] SiR3 (I-M) . Q ~3 wherein R, Q, E, E , E snd E are the same as defined above, x has an average value of 0.5 to 20; ~ has sn average value of 0.5 to 30 and z has an average value of 0.5 to 20.
Another illustrated class of siloxane polyme~s of this invention are those having the average formula [sio4/2] [RSiO2/2]h[R3S101/2] (I~N) Q

,.~, 16.

s .. ~

. ' -''. ' :-, ~

~il4B~9 D-~107 wherein R and Q are the same as defined above and wh~rein the mole ratio of the SiO4/2 units to total po~yfunctional units to total monofunctional units is defined by ~ in which the ratio Of &~ is from about 0.4:1 to about 2 :L, and the ratio of i.h is from about 0.2:1 to about 2:1.
Yet another illustrated class of siloxane polymers of this invention are those having the average formula [SiO4/2]j[RSiOl/2~k[R SiOl/2]p (I-O) ! Q
wherein R and Q are the same as defined above and wh~rein the mole ratio of the SiO4/2 units to total Q substituted siloxy units to total trihydrocarbylsiloxy units is defined by J:k:p in which the ratio of i~
is from about 0.75:1 to about 2:1, and the ratio of p:k is from about 0.1:1 to about 1:1.
The silicone-bonded R groups are monovalent hydrocarbon radicals containing from 1 to about 20 carbon atoms and prefer~bly are alkyl radicals having from one to ten carbon atoms including linear and branched alkyls. Illustrative of suitable groups encompassed by R
are methyl, ethyl, n propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, octyl,decyl and the like. Of the various groups represented b~T R, the lower alkyls ~that is, those ha~Ting from one to four carbon atoms) are , ~ more p~eferred of which methyl ~6 especially ~ui~able.
f~ It is to be understood that the R groups may be :~ the 6ame throughout the polymers or they may differ , `s 17.
k i 'B~3 ~s between or ~ithin units without departing from the scope of this inven~ion For example, when the endblocking monofunctional units zre M, that is, R SiOl/2-, they may be trimethylsiloxy units and the difunctional units, R2SiO2/2, when present, m~y be diethylsiloxy and/or methylethysiloxy units. The most preferred M and D ~iloxy units are ~CH3)3SiOl/2 and (CH3) SiO2/2 respectively.
In the Q substituents of the siloxane portion of the polymers of this invention, that is in the silicon-bonded acrylonitrile-capped polyoxyalkylene radical.
-R"(X3 (OC H ) (OC H ) OCH CH CN
q 3 6 n 2 ~ m 2 2 R", X, ~, n and m are as previously defined. As stated R" represents an alkylene radical including linear and branched radicals of ~he series -C H2 ~ wherein w is an integer having from a value of two to eight, prefer-ably not more than four, such as ethylene, 1,~-propylene, 1,3-propylene, 1-4-butylene and the like.
It is ~lso preferred that ~ and n are zero and m has a value of 4 to 15 and most preferably R" is a propylene radical. It is also to be understood that the Q groups may be the same throughout the polymers r ~hey may differ as between ~r within units without teparting from the scope of this invention. Likewi~e, as stated the ~xyethylene and oxypropylen2 units when both ~re presént may be randomly distributed or arranged as sub-blocks in any desired fashion.

.. .
18 .

.i ~1~4~ D-9107 Illustrative of such preferred M', D' and [RQSiOl/2]
~iloxy units are (CH3)2~il/2 t~H2 (0C2H4) 0cH2cH
CH3~iOl/2 CH2CH2CH2(0C2H )mOCH2CH CN

CH liO2l2 2 2( c3H6)n(oc2H4) OCH2CH2CN
CH3SiO2/2 10CH2CH NHCO(OC2H4)mOCH2C 2 CH liO2/2 CH CH2CH2(C3H6) (OC2H4~m 2 2 CH liO2/2 CH CH2cH2co(oc2H4)mocH2cH2 .
CH3~iO2/2 ., H2~HCH2(0C2H4) OCH2CH CN
~ H3 CH3~iO2/2 t H CH2CH (C2H ) QCH2CH2CN

~ and the like, wherein n and m are the &ame as defined ? 20 above.
' J In the silicon-bonded, cyano-~ubstituted ~O) R2CN groups, (group E above~, R2 represents r an alkylene radical including linear and br`anched ; radicals of ~he series, -C H2W-, where w has a value of from 2 to 12, and is usually no more than 6.
Illustrative of 6uitable groups represented by R

1~ .

are: ethylene (-CH CH -); 1,3-propylene or trimethylene (-CH CH CH -); 1, 2-propylene [-CH CH(CH )- ]; and ~etram~thylene Most preferably; -R2- is a lower alkylene group having from two to four carbon atoms. It is to be understood that the -R2- groups may be the same throughout the polymer or may differ and that t~le polymer may contain any combination of cyanoalkyl (-R2CN) and cyanoalkoxy (-OR2CN) 6ubstituted siloxy units. Illustrative of such preferred ~2 and D2 siloxy units are (gamma-cyanopropyl)di-methylsiloxy; ~eta-cyanoethoxy) methylsiloxy: (beta-cyanoethyl) methylsiloxy; ~beta-cyanopropyl) methylsiloxy;
(gamma-cyanopropyl) methylsiioxy; (gamma-cyanopropyloxy) methylsiloxy; (gamma-cyanopropyl~ethylsiloxy; (gEmma-cyanobu~yl) methylsiloxy; (delta-cyanobutyl) methylsiloxy, and the like. The most preferred D2 siloxy unit is (gamma-cyanopropyl~ me~hylsiloxy.
In the silicon-bonded, cyanosubstituted ~0) R20R2CN groups, (group E above), R and r are the same as defined above. Among the more preferred groups are ~0) C H2 OC H2V~CN wherein r i6 0 or 1, u has R value of 3 to 8 and v has a value of 2 to 4.
It i~ to be understood that the ~iloxane polymer may contain any combination of cy~noalkoxyalkyl (-R20R2CN) ~nd/or cyanoalkoxyalkoxy (OR20R2CN) ~ubstituted siloxy units. Illustrative of ~uch preferred M3 and D
ailoxy unit~ are 3-(2-cyanoethoxy)propyl methylsiloxy;
3-(3-cyanopropoxy)propyl methyl~iloxy; 3-(2-cyanoethoxy~
propoxy methylsiloxy; 3-(2-cyanoethoxy)propyl ethylsiloxyi 20.

........ ~ .. , - - :

~ ~ ~ 4 D-9107 3-(2-cyanoethoxy)-2-methylpropyl methylsiloxy; 8-(2-cyanoethoxy)octyl methylsiloxy; 3-(2-cyano-2-methylethoxy)propyl methylsiloxy,; 3-~2-cyano-2-ethyl-ethoxy)propyl ~e~hylsiloxy; 3-(2-cyanoethoxy)propyl di~ethylsiloxy; 3-(2 cyanoethoxy)propoxy dimethylsiloxy;
3-(2-cyanoethoxy)propyl diethy:Lsiloxy; 3-(2-cyanoetho~y)propyl methylethylr,iloxy; and the like.
The most preferred D3 ~iloxy ~lit is 3-~2-cyanoethoxy) propyl methylsiloxy, In the silicon-bonded, sulfoanyloxyalkyl groups 4 5 3 ~ ~ --R -0- -~-H
~-~, ~ ~ \ R7 H ~ H
~0 (group E2 above) the R4 through R7 groups are, as previously defined, hydrogen or Cl to C4 alkyls.
Usually, no more than two are alkyls as in the 2,4-dimethylsulfolan-3-yloxyalkyl nucleus. Preferably each of R4, R5, R6 and R7 is hydrogen. The R3 group iB an alkylene radic~l including linear and branched radical~, of the serles, -C H2W-, wherein w ~s an in~eger having a value from two to eight. Illustrative of ~he linear and branched 8aturated alkylene radicals encompa~sed by ~R3- are ethylene; 1,3-propylene or ) trime~hylene; 1,2-propylene; 2-methyl-1, 3-propylene l-methyl-l, ~-propylene; l-ethyl-ethylene; 1-4-butylene 21.

~, .. ... , . ,, . , ., ~ . .. .. . . . . . ... . . .

or tetramethylene; 3-methyl-1, 3-propylene; 3-ethyl-1, 3-propylene; 1,5-pentylene or pentamethylene; 4-methyl-1,

4-butylene; 1,6-hexylene or hexamethylene; 1-methyl-3, ; 3-dimethyl-1, 3-propylene; ~-et~yl-2, 2-dimethyl-ethylene;
4,4-dimethyl-1, 4-bu~ylene; 3-propyl-1, 3-propylene;
l-ethyl-l; 4-bu~ylene; l-propyl-l, 3-propylene; 1,8~
octylene or octamethylene; and the like. Preferably, -R3- has from 2 to 6 carbon atoms ~nd most preferably has three or four carbon atoms.
Illustrative of such preferred M4 and D
siloxy U~ts ar2 C~
, 1 3 H C _ CH - 0 - C H - SiOl/2 H2C~ ~CH2 jS~
O O
; CH3 2l 1 2 4 H2C~ /CH2 // ~

H2C_fH--o ~ CH2CH--CH2 S~02l~
2 ~ ~ 2 0~ ~
, CH3 H2f IH - 0---CH2CH2CH2 SiO2/2 \ ~
,, /~S~O .

~ 22.

- . . ..

and th~ like. The most prefeL-red D4 siloxy unit being one wherein R4 through R5 are hydrogen, R is methyl and R3 is propyl. It is to be also understood that the siloxane polymers of this invention may contain any one ; of the various types of M4 and D4 siloxy units illustrated above or any combination thereof.
In the silicon-bonded morpholino groups ,R4 R5 ~0)s(R80) R9-N~ CH~o CH- CH

(group E3 above) the R4 through R7 groups are, as previously defined, hydrogen or Cl to C4 alkyls. Usually, no more than two are alkyls as in the 2,6-dimethyl-morpholino nucleus. Preferably, each of R4, R5, R6 and R7 is hydrogen. The R8 and R groups are alkylene radicals, of the ~eries, -CuH2u- and ~ ~ H2v~~
r~spectively, where u is an integer having a value ~rom 2 eo 4 (R8) and v is an integer having a value from 2 to 6 (R9). Illustrative of the linear and branched bivalent alkylene radicals encompassed by R8 and R9 are: ethylene; 1, 3-propylene; 1,2-propylene;
1,4-butylene; 1,2-butylene; 2,3-butylene; ~nd, in addition R9 can be 1,5-pentylene, 1,2-pentylene, 1,6-hexylene ~nd the like. Preferably, -R~- has from 2 to 3, and R9 has from 2 to 4, carbon atoms. It is to be understood ~hat when t of the morpholino-bear~ng group has an average value from about one to about four, 23.

k .

~ 4 ~ ~13 D-9107 -(R~O)t- may be ethyleneoxy, poly(ethyleneoxy), propyleneoxy, pGly(pro?yleneo~), or a cor~bination of different alkyleneoxy units.
Illustrati~.of such preferred M5 and DS
siloxy units are CH
~ 1 3 o ~ ~-CH2-CH2-SiOl/2 O -CH2CH2-.SiO2/2 CH
0/--\~1 ~CH2CH2CH2-SiO2/2 ." ~ I I
H CHCH -SiO2/2 ?. 2 24.

.

O h`--CH2CH20-SiO2/2 CH C~l o~-CH2CHO-SiO2/2 r~ ~ 'I .
o --CH2CHOCH2cH2cH2-siO2/ 2 CH

~CH2cH20cH2cH2cH2-siozl2 \_/ ' and the like. The most preferred D5 siloxy unit being one wherein R4 through R7 are hydrogen, R is methyl, R9 is propylene, ~nd s and t are zero. It i~
to be unterstood thst the siloxanepolymers of this invention may contain ~ny one of the various types o M5 and D5 siloxy unit~ illustrated ~bove or any combinat1On ~hereof.

25.

. ' .

~ 9107 Of the preferred acrylonitri:Le-capped polyoxy-alkylene po].ysiloxane pol~ners of this invention having utility as stabilizers of flexible polyester polyol-: based urethane produced with a flame retardant are those with the scope of Formulas (I-B), ~nd (I-G) t~herein R is a methyl radical; x has an average va'ue of about O.S to about preferably 1 to about 10;
has an sverage value of about 0.5 to about 30 preferably about 1 to about 10; z has an average value of about 0.5 to about 20, preferably about 1 to about 10; and the acrylonitrile-capped polyoxyalkylene radical (Q), is preferably -CH2,CH2CH2 (OC3H6)n(0C2H4)mocH2cH2c~
wherein n has an average value of O to 10, preferably O and m has an average value of from about 4 to ~bout 30, preferably about 4 to 15; and the cyano-containing group (E), is pre~erably wherein R .is an alkylene radical having from 2 to 4 carbon atoms, preferably propylene.
The most preferred of all of ~he acrylonitrile-capped polyoxyalkylene-polysiloxane polymers of this invention are those having the average formula (CH3)3siO[(cH3~2sio~ [CH31iO~ySi(C~3)3 ~H2CH2CH2 (oc2H4)mo~H2cH2cN
, ~

26.

~S

,.. ,., ... . .... --- - .~ :

~ D~107 wherein ~ and y h~ve ~ value of about 1 to about 10 and m has ~ value of nbout 4 to about 15.
The scryloni~rlle~capped polyoxyalkylene-polysiloxane polymers of ~his Inven~ion ~re prep~red by the platinum catalyzed hydrosilation of the Acrylon-ltrile-capped polyo~yalkylene compounds of thl~ in-vention a~ defined above with s~licon-hydr3gen cont~in-ing slloxane ~tarting mæterlals ~.s illustrated e.g. by the following equa~ion R R R R R R
[RSiO1/2]a 1HS1O1I21b [~S101t2~C [Si02/2]~ ESiO2/21e~SiO2121f R R R R H E

(~ormula II) ( )q(0C3H6)n (0C2H~)mOCH2CH CN ~
R R - R
R
RSiO1l2]a ~QSiOl/2]b [E S101/2]~ lSiO2/2ld ~SiO2/2]e lSiO2/2lf R R R R Q E
(Formula I) I~ which R, R', E, a, b, c~ d, e9 f, n, m and ~ are the ~ame as defined above.
~ore particularly, by way of ex~mple, the most preferred aerylonitrile-capped polyoxyalkylene-polysiloxane compound~ of Formula I-A above may be illu~trated by th~ followlng equation 27.

Z~

(CH ) SiO[ (CH ) SiO] ~CH SiO] Si (CH ) 3 3 3 2 x 31 y 3 3 -~ H C = CHCH t C H ) OCH CH CN - -2 2 2 4 m 2 2 (CH ) SiO [ (CH ~ SiO ] [CH SiO] Si (CH ) 3 3 3 ~ x 3~ y 3 3 CH CH CH ( OC H ) OCH CH CN
2 2 2 2 4 rn 2 2 wherein x and y have a value of about 1 to 10 and m has a value of about 4 to 15.
This general hydrosilation reac~ion it con-ventional and well known in the art. Particularly ef~ective is pl~tinum in the form of ~hloroplatinic acid dissolved if desired, in a solvent such as tetrahydrofuran, ethanol, butanol, 1,2-dimethyoxyethane or mixed solvents such as ethanol/1,2-dimethoxyethane, It is to be understood, ho~ever, that other platinum deriv~tives known to the art as hydrosilation catalysts may also be used. For exxmple, also suitable as promoters of the hydrosilation reaction are the platinum catalysts prepared by reaction of chloroplatinic acid and an alcohol such ~s octanol as describ~d in U.S. Patent No. 3,220,972. The platinum is present1in a catalytic amount such as, or example, from a~out 5 to about 400 parts by weight per million (p.p.m.) part~ of ~he combined weight of the silicon-containing and organic reactants. The more usual platinum concentrat~on is no more ~han about 200 p.p.m. preferably

5 to 50 p.p.m. The preferred temperature range for the reaction is 60 to 13BC. Lower temperàturP& may be used but the reaction times sre slower. Higher ~emperatures may also be used up to 200C.

28 .

` F ~ - -( - t,~

D-~107 In carryin~ out the process to prepare the s~loxane polyr.ers of this invention it is generally preferred to mix all the ingredients, except the platinum catalyst, at about 25C. and allow the mixture to warm up to 80C. (with external heatin~) At this temperature the platinum catalyst i5 added and usually an exothermic reaction is observed. The hydrosilation reaction may be conducted in the absence or presence of a solvent. Of course, solvents which themselves are reactive with SiH under the conditions of this invention should not be employed.
Illustrative solvents are ~he normally liquid aromatic hydrocarbons such as benzene, toluene and xylene;
alcohols s~ch as methanol, ethanol, n-propanol, isopropanol;
ethers; ether alc~lhols; and the like. The solvents may be used individually or in combination with one another. Upon completion of the reaction, excess reactant and any org~nic solvent employed in the polymer preparation, may be removed by conventional separation techniques to obtain the final produc~ comprising the polymer compo-sitions of the invention. It is to be understood, however, that some portion or all of the solvent and excess reactants including by-products thereof and the polyether reactant may remain in the product and tha~ such diluted polymer compos tions are within the scope and may be used in accordancP ~ith the teachings of this invention. In the hydrosilatio~ reaction, the removal or neutralization of the platinum catalyst ~s usually desirable for long range product stability. Neutralization is ~eadily effected by adding sodium bicarbona~e to the reaction ,., .. ...... ,.. ...... - - - ~

~-9107 mixture followed by filtration of the resultant slurry to remove the neutralizing agent and platinum residues.
The hydrosilation reaction comprising the addition of Si-H to the respective acrylonitrile-capped polyoY.yalkylene compounds of this invention is carried out by employing said respective acrylonitrile-capped polyoxyalkylene compounds in an amount at least sufficient to react with a predetermined proportion of the 6ilicon-bonded hydrogen of the SiH reactant. From the standpoint of more effective and more complete reaction of silanic hydrogen the acrylonitrile-capped polyoxyalkylene compounds are usually employed in excess of stoichiometric require-ments e.g. the acrylonitrile-capped polyoxyalkylene compounds may be employed in amounts up to a 100 or more mole percent excess.
The silicon-hydrogen containing siloxanes used as ~tarting materials in the hydrosilation reaction of this invention and/or methods for their preparation are well known in the art. For example, such siloxane starting m~terial~ can be produced by cohydrolyzing and condensing the appropriate hydrolyzable silanes or by equilibrating appropriate silo~anes using conven~.ional techniques. Obviously the particular siloxane starting m~tPrial used in a given hydrosilation process will correspond to and merely depend upon the particular type of acrylonitrile-capped polyoxyalkylene-polysiloxane product desired.

30.

, BZ~ D-glO7 For instance the siloxane products of Formulas (I-A), (I-B), (I-C), (I-D) and (I-E) ~bove can be produced by reacting the above defined acrylonitrile-capped polyoxyalkylene compounds of this invention with the following silicon-hydrogen containing ~iloxane starting materials, respectively R3SiO[RSiO~ySiR3 (II-A) , ~1 R3SiO[R2SiO]X[RSiO]ySiR3 (II-B) `. H
HR2SiO~R2SiO]XSiR2H (II-C) HR2sio[R2sio]x[Rlio~ysiR2H (II-D) H
HR2SiO[RSiO]ySiR2H (II-E) . H
wherein R, x and ~ are the same as defined above. Such staring materials are well known in the art.
The siloxane products of Formulas (I-F) and G) above can be produced by reactin~ the above defined acrylonitrile-capped polyoxyalkylene compounds of this invention with the following silicon-hydrogen con-taining siloxane startin~ materials, respectively R3SiO[RSiO]y[RSiOJzSiR (II-F) H E
R3sio[R2sio]x[Rsio]y[Rsio]zsiR3 (II-G~
H E
wherein R, E; x, ~ and z are the same as defined above.
Such starting materials as well as others may be produced e.g. as disclosed in U . S . Patent No ~ 3, 954, 824 .
31.

The siloxane products of Formulas (I-H) and (I-I) above can be produced by reacting the above defined acrylonitrile-capped polyoxyalkylene compounds of this invention with the following silicon-hydrogen containing siloxane starting materials, respectively, R3SiO[RSiO]y[RS O]z';i~3 (II-H) H E
R3SiO[R2SiO]X[RSiO]y[RS O]zSiR3 (II-I) H
wherein R, E , x, ~ and z are the same as defined above.
Such starting materials as well as others may be produced e.g., as disclosed in U.S. Patents Noæ,3,943,156 and 3,979,419.
The siloxane produ~cts of Formulas (I-J) and (I-K) above can be produced by reacting the above defined acrylonitrile-capped polyoxyalkylene compounds of this invention with the following silicon-hydrogen containing siloxane starting materials, resp~ctively, R3SiO[RlSiO]y[RIiO]zSiR
H E
R3SiO[R2SiO]x[RSiO]ylRSi~)]zSiR3 wherein R, E , x ~ and z are the same as defined above.
Such starting materials as well as others may be produced e.g., as disclosed in U.S. Patent No. 4,049,674.

32.

1~ ~ 4~2~ D-9107 The siloxane products of Formulas (I-L) and M) abo~e can be produced by reactirlg ~he above defined acrylonitrile-capped polyoxyalkylene compounds of this invention with the following silicon-hydrogen containing siloxane starting materials, respectively R3Si~[RIiOiy[RIiO]SiR3 (II-L) H E
R3SiO[R2SiO]~[RIiO]y[RI io~zsi 3 (II-M) wherein R, E , x 2 and z are the ~ame as defined above.
Such starting materials as well as others may be produced e.g. as disclosed in U.S. Patent No. 4,018,723.
The siloxane products of Formula (I-N~ above can be produced by reacting the above defined acrylonitrile-!, capped polyoxyalkylene compounds of this invention with the following silicon-hydrogen containing siloxane starting materials, ~ [sio4/2]g[Rsio2l2]h~R3sioll2]i (II-N) F H
; wherein R, ~, h and i are the same as defined above. Such starting materials as well as others may be produced ~ 20 e.g., as disclosed in U.S. P~tents Nos. 3,793,360, and ,c 3,833,512.
. The siloxane products of Formula (I-0) above can be produced by reacting the above defined acrylonitrile-capped polyoxyalkylene compounds of this invention with the following silicon-hydrogen containing siloxane starting materials 33.

~ 2~ D-9107 [SiO4/2] [RSiOl/2] [R SiOl/2] (II-O) i I k 3 p H
wherein R, i, k and ~ are the same as defined above. Such starting materials as well as others may be produced e.g.
as disclosed in U.S. Patent No. 3,796,676.
The acrylonitrile-capped polyoxyalkylene-polysiloxane polymers of this invention are normally liquid compositions and as previously described normally comprise mixtures of polymer species which may differ in molecular weight, polyether and siloxane contents and relative number of monomeric units. It is to be unde~stood t~at two or more polymers or two or more silicon-hydrogen polymers having a particular average composition encompassed by respective ~ormulas I and II
may be admixed in suitable relative proportions to adjust the average values of x, ~ and z as de6ired. For example, a siloxane polymer wherein ~ has an average value of about 5 may be admixed with another wherein has an average value of about 2 to provide a siloxane polymer wherein ~ has an average vlaue of about 3.5.
Similarly a silicon hydrogen containing siloxane in which no R2SiO2/2 units are present (that is in which x is zero) may be admixed in any relative proportion with another in which x is one, thereby providing a siloxane in which the average value vf .~ . x is less than one (such as 9.5 etc.) which is then reac~ed as deqcribed herein to provide the acrylonitrile-capped 34 .

D~9107 polyoxyalkylene-polysiloxane polymer in which x has a corresponding average value. It is to be alsv understood that a sm~ll percentage (on the average, usually about 15 mole percent or less preferably less than 10 mole percent) o~ the acrylonitrile-capped polyoxyalkylene bloeks of the siloxane polymer may com-prise residual, uncapped hydroxyl-terminated groups introduced with the acrylonitrile-capped polyoxyalkylene reactants. Likewise, it is understood that the acrylonitrile-capped polyoxyalkylene-polysiloxane polymers of this invention may be graft or block polymers and tha~ it may be possible for some polymers to contain a sm~ll portion of residual unreacted Si-H groups.
The ~crylon~trile capped polyoxyalkylene-polysiloxane polymers of thi~s invent~on are generally useful as surfactants and find particular application in the manufacture of urethane foam. The normally liquid polymers can be used as ~uch, for ctabilization of urethane foam without the need for eombination with 2Q other surfactants or other type of organic add~ti~e.
The polymer~ can be employed as a 100 percent active stream, or they can be employed in dilute form as a .~ 601ution in polar Golvents (e.g.~ glycols~ or non~
pol~r organic solvents ~uch as norm~lly liquid aliphatic and aromatic unsubstituted and halogen-substituted hydrocarbons (e.g., heptane~xylene, toluene, chloro-benzenes and t:he like).
.

- ~

2~

In addition to the acr~lonitrile-capped polyoxyalkylene-polysiloxane polymers of this in-vention used as foam stabilizers, the other essential types of components and reactants employed in the production of urethane foam in accordance with the process of this invention are an organic polyol comprising a ~olyether polyol or a polyester polyol, an organic polyisocyanate, an amine catalyst and a blowing agent. The foam-producing reaction mixtures may also contain a flame-retardant. The amount of the acrylonitrile-capped polyox~alkylene-polysiloxane polymers of this invention present in the final foam-producing reaction mixture may vary over a relatively wide range such as from a~out 0.~ to about 5 parts by weight per 100 parts b~ weight of the polyol reactant, and are usually present in an amount of at least about 0.2 and no more t~an about 3 parts.
In producing polyether polyol-based urethanes one or more polyether polyols is employed for reaction with 2~ the polyisocyanate reactant to provide the urethane linkage. Su~h polye~her polyols as well as me~hods for their manufacture are well known in the art and eontain an average of at least two, and usually not more than six, hydroxyl groups per molecule and include comp~unds which con3ist of carbon, hydrogen and oxygen and compounds which also contain phosphorus, halo~en and!or nitrogen.
~ nong the 6uitable polyether polyols that can be employe~ are the poly(oxyalkylene) polyols, that is, alkylene oxide adducts of water or 8 polyhydric organic compound as the iniiator or ~tarter such as disclosed D- s ln7 ' ~ . in U.S.P. 3,~46,462. ~llustrat:iv~ of suitable polyhydric or~anic initiators are any one of the follo~ing which may be em~,loyed individually or in combination;
ethylene glycol; diethylene glycol; propylene glycol; 1,5-pentanediol; hexylene glycol; dipropylene glycol;
trimethylene glycol; 1, 2-cyc:Lohexanediol; 3-cyclohexene-1, l-dimethan~l and the 3, 4-dibromo-derivative thereof;
glycerol; 1, 2,6-hexanetriol; 1, 1, l-trimethylolethane;
1, 1, 1 trimethylolpropane; 3-(2-hydroxyethoxy~- and 3-(2-hydroxypropoxy)-1, 2-pr~panediols;2, 4-dimethyl-2-( 2-hydroxyethoxy)methylpentanediol-1,5; 1, 1, 1-tris~(2-hydroxyethoxy)methyl]ethane, 1, 1. 1-tris~(2-hydroxypropoxy)methyl]propane; pentaerythritol; sorbitol;
su~rose, alpha-methyl glucoside; and other such polyhydric compounds consisting of carbon, hydrogen and oxygen and having usual.ly not more than,-about 15 carbon atoms per molecule. The alkylene oxides usually employed in providipg the polyether polyol reactants are the lower alkylene oxides, that is, compounds having from 2 to 4 carbon atoms includin~ ethylene oxide, propylene oxide, butylene oxides (1, 2- or 2,3-) and combinations thereof.
Another class of polyether polyolq are polymer/
polyether polyols which are also well known in the ~rt.
Such reactants arP produced by polymerizing one or more ethylenically unsaturated monomer~ dissolved or dispersed r in a polyether polyol in the presence of a free radical eatalyst. Illustrative of suitable ethylenically unsaturated monomers are those encompassed by the form~la 37.

~4~2~

noooo ~ R~-C=CH

where: R is hydrogen, ~ethyl or any of the halogens (i.e., fluorine, chlorine, bromine or iodine); and Ris R, cyano, phenyl, methyl-substituted phenyl, or alkneyl radicals havin~ from 2 to 6 carbon atoms such ; as vinyl, allyl and isopropenyl groups. Typical examples of such polymerizable monomers are the following which m~y be employed individually or in combination; ethylene, propylene, acrylonitrile, me~hacryloni~rile, vinyl chloride, vinylidene chloride, styrene, alpha-methylstryene, and butadiene. These and other polymer/polyol compositions which are suitably employed either individually or in combination with each other or with poly(oxyalkylene)polyols are those described in British Patent 1,063,222 and U. S.
Patent No. 3, 383,351, the disclosures of which are incorporated herein by reference there~o.
The particular polyether polyol or mixtures thereof ~mployed merely depend upon the end-use of the polyurethane foam desired. Usually diols provide sof~
foams. Firmer oams are obtained by ~he incorporation of polyether polyols having more than two hydroxyl groups, including triols~ tetraols, pentols and hexols. When it is desired to produce polyurethanes havi~ comparatively high load-bearing properties and/or diecutability, polymer/polyether polyols of the aforesaid type are u~ed.
In the production of flexlble polyurethane foams the 38.

.. ... .. ~. ~.. . ..... . ........ .. .

- -- - .. .. ... ..... , ... ; ,. .. ..

- ' D-9107 `. hydroxyl number of the polyether polyol reactan~
including mixtures of polyols m3y vary from a~out 20 to about 150 and is usually no higher than about 80.
More particularly t~is invention is direc,ted to the production of poly~ster polyol-b~sed urethane foam, especially flexible polyester polyurethane foa~
which most preferably also contains a flame retarding ' agent. As indicated above the acrylonitrile-capped ',~ 10 polyoxyalkylene-polysiloxane polymers of this invPntion intended for use as stabilizers of polyester polyol-de-rived foam can be used as ~uch without the need for combinatior with an anionic or cationic organic surfactant or other type of organic additive.
However, it is often the preferred practice of foam manufacturers to premix the foam stauilizer, amine catalyst and water (which is the usual source of at least part of the blowing action) and to eed the ' aqueous premixture to the polyester foam-producing reaction 20 mixture as a single ~tream. Thus, it is desirable ~o employ the acrylonitrile-capped polyoxyalkylene-polysiloxane polymer foam ~tabilizers of this inv ntion in solution in combinat~on with an organic acidic component, a water ~oluble organic ~urfactant and/or a wa~er soluble ~,, . glycol in order to avoid premix incompa~ability, Although these various organic additives can be lntroduced direc~ly to the aqueous premixture of foam s~abilizer snd catalyst, the formation of clear homo~eneous 39.

~ , 1~L4~
~-9107 aqueous ~olutions is facilitated by blending the additi~res with the foam stabilizer (that is the acrylonitrile-capped polyoxyalkylene-polysiloxane polymers of this invention) and combining the resulting blend with water and the ~mine catalyst system.
Thus, in accordance with another embodiment of ~his inv~ntion, therefore~, solution compositions are provided comprising the acrylonitrile-capped poly-oxyalkylene-polysiloxane polymers of this invention, the aforesaid organic acid component, and one or both of an organic surfactant and glycol. The acrylonitrile capped polyoxyalkylene-polysiloxane polymers of this invention may be present in the solution compositions in an amount of from about 10 to about 80 parts by weight per lQ0 parts by weight of the solution. Suitable organic acidic components, organic ~urfactants and glycols for this purpose are as described in U.S. Patents 3,793,360 and 3,833,512, the disclosures of which are incorporated herein by reference thereto.
For instance the aforesaid organic acidic component comprises the saturated and unsaturated aliphatic and cycloaliphatic carboxylic acids containing from 15 to 20 carbon at~ms. Illustrative of ~uitable acidic com-ponents are the fatty ac$ds such a~, for example, palmitic, stearic,palmitoleic, oleic, linoleic,lin~lenic and ricinoleic acids; resin acids of the abietic and pimaric type; and any combination of the aforesaid acids as well as industrial by-products and naturally-occurring materials 40.

~ D-9]07 :
comprising such acids. An especially suitable acidic component of the solution compositions and aqueous p-emixtures of this invention is tall oil which is a by-product of sulfate digestion of wood pulp and is composed largely of fatty acicls (oleic, linoleic, linolenic and palmitic acids) and resins acids, and a t minor amount of neutral material ~uch as fatty acid esters.
The above-described organic acidic cumponent can be present in the solution compositions of this invention in an amount of from about 5 to about 90 parts by weight per 100 perts by weight of silicone polymer pres~nt in the solution.
The water-soluble organic surfactant which can be a component of the ~olution compositions of this invention may be of the nonionic, anionic, cationic or amphoteric types, including combinations thereof.
; Preerably, the organic surfactant~is a nonionic surfactant such as: the poly(oxyalkylene) ethers of the higher alc~hols having from 10 to 18 carbnn atoms including mixtures thereof; polyoxyalkylene ethers of alkyl-substituted phenols in which the alkyl group can have from

6 to 15 carbon atoms; and corresponding polythioalkylene adducts of the aforesaid higher ~lcohols and phenols.
The length of the ether chain i& such that appropriate hydrophilic charact~r is provided ~o balance the hydro-phobic portion derived from the alcohol or phenol and 41.

1$14B29 render the compound soluble in water. The chain may contain oxyethylene units either as essentially the sole type of unit or oxyethylene in combination with a minor amount of oxypropylene. It is preferred that the hydrophilic portion of the nonionic surfactants be composed essentially of oxyethylene monomeric units. Usually the average nu~ber of such -~C2H4- units ranges l.rom about 4 to about 20, although upwards of 40 such units can also be present.
; Typical examples of nonionic surfactants w~ich can be used as components of the solution compositions of this invention are the adducts produced by reaction of k moles j of ethylene oxide (wherein k has a value of from about 4 to about 40, inclusive of whole and fractional numbers) per mole o ~ny of the following hydrophobes i~cluding mixtures thereof; n-undecyl alcohol, myristyl alcohol, lauryl alcohol, trimethyl nonanol, tridecyl alcohol, pentadecyl alcohol, cetyl alcohol, oleyl ~lcohol, stearyl alcohol, nonylphenol, dodecylphenol, tetradecylphenol, and the like.
Other illustrative water soluble organic ~ur-factants which can be present as a component of the solution compositions of this invention are: sodium, potassium ammonium and quaternary ammonium salts of ~ulfonic acids wherein the hydrocarbyl portion can be alkyl or alkaryl groups containing from 10 to 20 carbon a~oms. Examples of such organicisurfactants are: ~odium t~tradecyl sulfonate and sodium dodecylbenzene ~ulfonate; sodium 42.

~ D-9107 and potassium salts of s~llfonated petroleum fractions such as mineral oil; diethylamine salts of sulfonated v~ Clo-C15 alkylated aromatic hydrocarbons; taurine compounds having at least one long chain hydrocarbyl group bonded to nitrogen; and the like.
The solution compositions of this invention may also contain as a third type of organic component, a glycol of from 2 to about lG carbon atoms, or low molecular weight Carbowax polyethylene glycols, Especially suitable is hexylnne glycol (2-methyl-2, 4-pentanediol).
When both the organic surfactant and g~ycol components are present in the solution compositions of this invention, the combined concertration thereof ranges from about 5 to about 90 parts by weight per 100 parts by weight of the silicone polymer contained herein.
When only one of these components is present, the con-centration thereof is also within this latter range.
When the aforesaid solution compositions of the silicone polymers of this invention are combined water ~nd amine catalyst such as the catalysts described hereinbel~ow, clear, homogeneous ~queous 601utions are obtained which can be added directly to the foam-producing reaction mixture. From the standpoint of retaining these desi~able characteristics of clarity and homogeneity under otherwise adverse ambient temperatures which may be encountered upon standing, storage or shipment prior to use in the foam-producing reaction, ~he preferred ~3.

~ -, .

aqueous premixtures are those containing both the organic ~urfactant (of which nonionics are preferred) and the glycol, in addition to the organic acidic component. It is to be understood that the aforesaid invention are also useful when added ~irectly to the final foam-producing reaction mixture rather than being premixed with water and a~ine catalyst.
In producing polyester polyol-based urethanes one or more polyester polyols is employed for reaction with the polyisocyanate reactan~ to provide the urethane linkage. Such polyester ~olyols as well as methods for ~heir manufacture are well known in the art ~s seen for example, by U.S.P.3,793,360. For instance, polyester polyols e~ployed in producing flexible polyester ure-thane foams in accordance with the method of this in-vention are the reaction products of~ a polyfunctional organic carboxylic acid, and (2) one or more of the aforesaid polyether polyols or one or more of the ~foresaid polyhydric organic initiators which are re-acted with alkylene oxide to produce ~uch polyether polyols. The polyester polyols contain at least two hydroxyl groups per ~olecule (as alcoholic OH or as OH
in COOH groups). The functionality o~ thesP acids Bi p~eferably provided by carboxy ~roups (COOH) or by both carboxy groups and aacoholic hydroxyl groups.
The polyesters can have hydroxyl numbers 44.

~ B~3 D-9107 fro~ about 20 to about 150, and preferably have hydroxyl n~ers between about 35 and about 80. These hydroxyl numbers are readily determined according to the procedure described by Mitchel et al., Organic Analysis Vol (Interscience Publishers, New York 1953) Typical of the polyfunctional organic carboxylic acids that can be employed in producing polyester polyols useful in preparing the foams of this invention are: dicarboxylic aliphatic acids such as succinic, adipic, sebacic, azelaic, glut~ric, pimelic, malonic and suberic acids; and dicarboxylic aromatic acids such as phthalic acid, terephthalic acid, isophthalic acid and the like. Other polycarbo~ylic acids that can be employed are the "dimer acids" such as the dimer of linoleic acid. Hydroxyl-containing monocarboxylic acids (such as ricinoleic acid) can also be used. Alternatively, the anhydrides of any of these various acids can be employed in producing the polyester polyols. The polyhydric alcohols (organic polyolsj ~hat can be employed in producing the polyester polyol starting material u6ed in the process of this invention include the monomeric polyhydric alcohols such as for example, glycerol; 1, 2, 6-hexanetriol; ethylene glycol; dlethylene glycol; trimethylol propane;
trimethylolethane; pentaerythritol; propylene glycol;
l, 2-, 1,3- and 1,4-butylene glycols; l, 5-pentanediol;
sorbitol; and the like, including mixtures thereof.
"

~ " ~ ~ 1 r r . .

Oth~r polyhydric alcohols that can be employed in producing the polyester polyols usef-ll in this invention are the polymeric polyhydric alcohols which include the linear and branched chain polyethers having a plurality of acyclic ether oxygens and at least two alcoholic hydroxyl radicals. Illustrative of such polyether polyols are the poly(oxyalkylene) polyols containing one or more chains of connected oxyalkylene radicals which are prepared by the reaction of one or more alkylene oxides with acyclic and alicyclic polyols. Examples of the poly(oxy-alkylene) polyols include the poly(oxyethylene) glycols prepared by the addltion of ethylene oxide to water, ethylene glycol or diethylene glycol; glycols pr pared by the addition of propylene oxide to water, propylene glycol or dipropylene glycol; mixed oxyethylene-oxypropylene polyglycols prepared in a si~ilar ma~er utilizing a mixture of ethylene oxide and propylene oxide vr a sequential addition of ethylene oxide and propylene oxide;
and the poly(oxybutylene)glycols and copolymers ~uch as poly(oxyethylene-oxybutylene) glycols and poly(oxypropyl-ene-oxybutylene) glycols. Included in the term "poly(oxy-butylene) ~lycols" are polymers of 1, 2- butyleneoxide and 2,3-butyleneoxide.
Illustrative of further polyester polyol reactants that are useful in producing flexible polye5ter ure-thane foam in accordance with the process of this inven~ion are the reaction products of Eny of the aforesaj.d polycarboxylic acids and the polyhydric alcohols prepared by the reaction of one or more alkylene oxides such as ethylène oxide, . .

~ 46.

propylene oxide, butylene oxide and mixtures thereof, with any of the following: glycerol; trimethylolpropane;
,6-hexanetriol; pentaerythritol; sorbitol;
glycosides such as methyl, ethyl, propyl, butyl and 2-ethylhexyl arabinoside, xyloside, fructoside, glucoside, and rhammoside; sucrose; mononuclear polyhydroxylbenzenes such as resorcinol, pyragallol, phloro~lucinol, hydro-quinone, 4, 6-di-tertiary-butylcatechol, and catechol;
polynuclear hydroxylbenzenes(" polynuclear" designating at least two benzene nuclei) ~uch as the di-, tri-and tetra-phenylol compounds in which two to four hydroxybenzene groups are attached either directly by means of ~ingle bonds or through an aliphatic hydrocarbon radieal containing one to twelve carbon atoms, such compounds being typically illustrated by 2,2-bis(p-hydroxyphenyl)-propane, bis(p-hy~roxyphenyl)-methane and the various diphenols and diphenol methanes disclosed in U.S. Pat. Nos. 2,506,486 and 2,744,882, respectively. Another type of polyester polyol ~0 reactant i~ that produced by reaction of a polycarboxylic acid ~nd the polyether adduct~ formed by reaction of ethylene oxide~propylene oxide or butylene oxide wlth phenol-formaldehyde condensation product6 ~uch as the novolak~.

47.
.

The organic polyisocyanates that are useful in producing polyether and polyester foa~ in accordance with the process of this invention are or~anic compounds that contain at least two isocyanato groups. Such compounds are well known in the art for producing polyurethane foams and are conveniently repr sented by the general ~ormula Q'(NCO)i wherein i is an integer of two or more and Q' is an organic radical having the valence of i. Q'can be a substituted or unsubstituted hydrocarbon group te.g. alkylene, cyclo-alkylene, arylene, alkarylene, aralkylene and the like).
Q' can also be a group having the formula Q"-Z'-Q"
wherein Q" is an alkylene or arylene group and Z' is a divalent moiety such as ~0-, -0-Q"-0-, -C(0)-, -S-, -S-Q"-S-, or -S02-.
Illustrative of &uitable organic polyisocyanate react~nts are the following including mixtures thereof:
1,2Ydiisocyanato-ethane;
1,3-diisocyanato-propane;
1,4-diisocyanato-butane;
1,5-diisocyanato-pentane;
1,6-diisocyanato-hexane;
1,5-diisocyanto-2,2-dimethyl-pentane;
, - 1,7-diisocyanato-heptane;
lj5-diisocyanato-2,2,4-trimethyl-pentane;
1,8-dii60cyanato-octane;
l,9-diisocyanato-nonane;

48~

D-~107 l, lO-diisocyanato-decane;
l,ll-diisocyanato-undecane;
1,12 diisocyanato-dodecane;
: 1,6-diisocyanato-3-methoxy-he~ane;
1,6-diisocyanato-3-buto~y-hexane;
; bis(3-isocyanato-propyl)ether the (bis(3-isocyanato-propyl)ether of 1,4-butylene glycol;
(0C~CH2CH2CH20C~2)20;
bis(2-isocyanatoethyl)carbonate;
l-methyl-2,4-diisocyanato-cyclohexane;
1,8-diisocyanato-p-methane;
mixtures of 2,4-and 2,6-tolylene-diisocyanate;
2,4-tolylene-diisocyanate;
2,6-tolylene-diisocyanate;
crude tolylene-dii60cyanates;
- ~is-5-6(2-isocyanatoethyl)bicyclo[2.2.1]hèpt-2-ene;
bis(3-isocyanato-propyl)sulfide;
bis(isocyanato-hexyl)sulfide;
1,4-phenylene-diisocyanate;
xylylene diisocyanates;
4-chloro-1,3-phenylene-diisocyanate;
4-bromo-1, ~-phenylene-diisocyanate;
4-nltro-(1,3 or 1,5)-phenylene-diisocyanate;
4-ethoxy-1,3-phenylene-diisocyanate;
benzidine diisocyanate;
toluidine diisocyanate;
dianisidine diisocyanate;
2,4'~ or 4,4'-diisocyanato-diphenyl ether;
diphenylmethane-4,4'-diisocyanate;
4,4'-dissocyanato-dibenzyl;
, 49 .

... . . ~ . .. . ,.. . . ... .. , , . . .. . ~ .. .. . . . ... .. . . . ..... . . . . .

isopropyl-benzene-alpha-4-diisocyanate;
1,5-diisocyanato-naphthalene;
1,8-diisocyanato-naphthalene;
9,10-diisocyanato-anthracene;
triphenyl~cthane-4,4'4"-Lriisocyanate;
2,4,6-toluene triisocyanate;
and many other organic polyisocyanates that are known in the art such as those disclosed in an article by Sie~ken, Ann., 565, 75 (1949). In general, the aromatically ;un-saturated polyisocyanates are preferred.
Further included among the isocyanates useful in the process of this invention are dimers and trimers of isocyanates and diisocyanates and polymeric diisocyanates such as those having the general formula:
[Q(NCO)i]jin which i and j are integers of two or more and/or (as additional component in the reaction mixtures) compounds of the general formula:
L'(NCO)i in which i is one or mroe and L' is a monofunctional or polyfunctional atom or radical. Examples of this type include ethylpho~phonic diisocyanate, C2H5P(O)(NC0)2;
phenylphosphonic diisocyanate, C H5P(O)(NC0)2; compounds containing an sSi-NC0 group, isocyanates derived from sulfonamide6 (QS02NC0), cyanic ~cid, thiocyanic acid, and compounds containing a metal-NC0 radical such as tributyltin i~ocyanate.

~0 .

' D-~107 Also ~nc~u ~ ~ as useful in the preparation of the flexible polyester urethane foa~s in accordance with the process of this invention are the polyisocyanates of the aniline-formaldehyde polyaromatic type which are produced by phosgenation of the polyamine obtained by acid-catalyæed condensation of aniline with formaldehyde.
Poly(phenylmethylene) polyisocyanates of this type are available commerically under such trade names as PAPI, AFPI, Mondur MR, Isorate 390 P, NCO-120 and NCO-20. These products are low viscosity (50-500 centipoises at 25~C.) liquids having average isocyanato functionalities in the range of about 2.25 to about 3.2 or higher, depending upon the specific dniline-to-formAldehyde molar ratio used in the polyamine preparation.
Other useful polyisocyanates are combinations of diisocyanates with polymeric isocyanates containing more than two isocyan~o groups per molecule. Illustrative of such combinations are: a mixture of 2,4-tolylene diiso-cyanate, 2,6-tolylene diisocyanate and t:he aforesaid poly(phenylmethylene) polyisocyanates; and a mixture of isomeric tolylene diisocyanates ~ith polymeric tolylene diisocyanates obtaine-1 as residues from the manufacture of the diisocyanates.
On a combined basis, the polyether or polyester polyol and organ c polyisocyanate usually constitute the major propor~ion by weight of the polyurethane-forming .~ reaction mixture. In general, the polyisocyanate and polyol reactants are employed i~ relative amounts such tha~ the ratio of total -NCO equivalents to total active hydrogen equi~alent (of the polyol and any water, when used) is from about 0.8 to about 1.5, preferably from 51.

about 0.9 to about 1.2, equivalents of -NC0 per equivalent of active hydrogen. This ratio is known as the Isocyanate Index and is often also expressed as a percent of the stoichiometric amount of polyisocyanate required to react with total active hydrogen. When expressed as a percent, the Isocyanate Index may be from about 80 to about 150, and i5 preferably within the range ~rom about 90 to about 120.
The urethane-orming reaction is effected in the presence of a minor amount of a catalyst comprising an amine. This component of the polyurethane-forming reaction mixture is usually a tertiary-amine as disclosed for example in U.S.P. 3,793,360. Suitable amine catalysts include one or more of the following: N-methyl-morpholine; N-ethylmorpholine; N-octadecylmorpholine;
triethylamine; tributyla~ine; trioctylamine; N, N, N', N'-tetramethylethylenediamine; N,N,N',N'-tetramethyl-l, 3-butanediamine; triethanolamine; N,N-dimethylethanolamine;
triisopropanolamine; N-methyldiethanolamine; hexadecyl-dimethylamine; N,N-dimethylbenzylamine; trimethylamine;
bis[2-(N,N-dimethylamino)ethyl]ether; triethylenediamine (i.e.~ ~4-diazabicyclo[2.2.2.]octane); the formate and other salt6 of triethylenediamine; oxyalkylene adducts of the amino groups of primary and æecondary amines and other such amine catalysts which are well known in the art of polyurethane manufacture. Also useful are the beta-tertiary amino amides and esters described in U.S. Patent No. 3,821,131, as exemplified by 3-52.

' ', ' , ~ ~ 4 ~ D-9107 (N,N-dimethylamino)-N',N'-dimethylpropionamide Also useful as the amine catalyst are the beta-tertiary-amino nitriles described in U.S. Patent No. 3,925,268, such as in particular, 3 (N,l~-dimethylamino)propionitrile ~s such or in combination with ot'her tertiary ~mines ~uch as bis-[2-N,N-dimethylamino)ethyl] ether. The amine catalyst may be introduced ~o the polyurethane producing reaction mixture as such or as a solution in suitable carrier solvents such as diethylene glycol, dipropylPne glycol, and 2-methyl-2, 4-pentanediol ("hexylene glycol"), and the like.
The amine catalyst is present in the final urethane-producing reaction mixture in a catalytic amount such as from about 0.05 to about 8 parts by weight Qf active catalyst (that is, the amine exclusive of other components present in solutions thereof) per 100 parts by weight of the polyol reactant. In forming polye~her polyol urethane foam, the amine catalyst concentration is usually no higher than about 3 parts. In forming polyester polyol urethane foam, the preferred concent-ration of total amine catalyst is at least about 0.2 up to about 8 parts, although more than about 5 parts is usually not required.
- In producing polyurethanes from polyether polyols the usual practice is to include as a further com-ponent of the reaction mixture a minor amount of cer~ain metal eatalysts which are useful in promoting gellation of the foaming mixtureD Su~ supplementary catalysts are well known to the art of flexible polyether-based polyurethane foam manufacture. For example, useful 53.

*.

me~al catalysts include organic derivatives of tin, pa~ticularly stannous salts of carboxylic acids, dialkyltin dicarboxylates, polyalkyl tin oxides and tin mercaptides. Typical of such cocatalysts are stannous oc~oate, stannous oleate, stanrous acetate, stannous laurate and dibutyltin dilaurate. Additional met~l catalysts are organic derivatives of other polyvalent metals such as zinc and nickel (e.g., nickel acetylacetonate).
In general, the amount of such metal co-catalysts which can be present in the polyurethane-producing reaction mixture is within the range from about 0.05 to about 2 parts by weight per lO0 parts by weight of the polyether polyol reactant. Although such metal catalysts are suitably employed in the preparation of polyether polyol urethane foam, their use is generally avoided ~n the manufacture of foam derived from a polyester polyol.
The amine catalyst m~y also be used in combination with other additives such as any of the nonion~c organic surfactants de~c~ibed above in connection with the 601ution composi~ions of this invention. Examples of non-ionics which are espec~ally useful as components of the catalyst solu~ions ~re the oxyethyla~ed nonylphenol compounds represented by the general formula ., CgHl9-C4H4_ (OC 2H4) k-OH, wherein k is a number having an average value of from ~bout 9 up to about 20 or more, including average values of k which are either whole or fractional numbers such 54.
~,.

'.`
.,' ~ ' ' .

as 9, 10.5, 15 and the like. When used, the non-ionic organic surfactant may be present in ~n amount from about lO to about 80 weight percent, based on the total weight of the catalyst solution. The catalyst 601ution n~y also include minor amounts of polysiloxane-polyoxyalkylene block copolymers and/or the organosilicone polymers of U.S.P. 3,793,360.
It is to be unde~stood that any of the aforesaid amine catalysts or soluti.ons thereof can be added directly to the foa~-producing reaction mixture or they can be added in premixed form with water and the polymeric organsilicone foam stabilizers of this invention. In ~he. latter event, the catalyst is preferably added as a component of the above described homogeneous aqueous premixture of this invention.
Foaming is accomplished by the presence in the reaction mixture of varying amounts of a polyurethane blowing agent such as water which, upon reaction with isocyanate generates carbon dioxide in situ, or through the use of blowing agents which are vaporized by the exotheYm of the reaction, or by a combination of the two methods. These various methods are known in ~he art. Thus, in addition to or in place of water, other blowing agents which can be employed include methylene chloride, liquefied gases which have boiling points below ~0F. and above-60F., or other inert gases such as nitrogen, carbon dioxide added as such, methane, helium and argon. Suitable liquefied gases incLude aliphatic and cycloaliphatic fluorocarbons which vaporize at or below the tempera~ure cf L~l- foaming mass. Such gases are at least partially fluorinated and may also be otherwise haloge~ated. Fluorocarbon blowing agents suitable for uRe in foaming the formuiations ~f this invention include trichloro-fluoromethane, dichlorodifluoromethane, l,l-dichloro-l-fluoroethane, l,l,l-tribluoro-2-fluoro-3,3-difluoro-4,4,4-trifluorobutane, hexafluorocyclobutene and octa-fluorocyclobutane. Another useful class of blowing agents include thermally unstable compounds which liberate gases u-pon heating, such as ~, N'-dimethyl-N, N'-dinitrosotere-phthalamide and the like. Ihe generally preferred method of foaming for producing flexible foams is the use of water or a combination of water plus a fluorocarbon blowing agent such as trichloromonofluoromethane.
The amount of blowing agent employed will vary with factors such as the desired density of the foamed product. Usually, however, from about 1 to about 30 parts by weight of the blowing agent per 100 parts by weight of the polyol reactant is preferred. It is to be ~nderstood, however, that these are general guidelines and that the choice of the particular amount of blowing agent employed to obtain a desired foam density specification varies from formulation to formulation and ~s well wlthin the skill of the art to which the present invention pertains.
The organic flame retardants ~hat can be employed in producing urethane foam stabilized with ~he 56.
~-~ ~ ~4~2~ D-9107 acrylonitrile-capped polyoxyalkylene-polysiloxane polymers of the invention, can be chemically combined in one or more of the other materials used (e.g., in the polyol or polyisocyanate), or they can be used as discrete chemical compounds added as such to the foam formulation and are well known in the art as seen by U.S.P. 3,793,360. The organic flame-retardants usual].y contain phosphorus or halogen, both phosphorus and halogen or phosphorus and nitrogen. Usually, the halogen, when present, is chlorine and/or bromine. Flame-retardants of the discrete chemical variety include: 2,2-bis(bromomethyl)-1,3-propanediol (also known~as dibromoneopentyl glycol);
2,3-dibromopropanol; tetrabromophthalic anhydride; brominated phthalste ester diols such as those produced from tetra-bromophthalic anhydride, propylene oxide and propylene glycol; tetrabromobisphenol-A; 2,4,6-tribromo-phenol; pentabromophenol; brominated anilines ~nd dianilines; bis(2,3 dibromopropyl)ether of sorbitol;
tetrachlorophthalic anhydride; chlorendic acid; chlorendic anhydride; diallyl chlorendate; chlorinated maleic anhydride;
~ris(2-chloroethyl)phosphate [(ClCH2CH20)3P(0~]; tris(2,3-dibromopropyl)phosphate; tris(2,3-dichloropropyl)phosphate;
tris(l-bromo-3-chloroisopropyl)phosphate; bis(2,3-dibromo-propyl~phoBphoric acid or salts thereof; oxypropylated phosphoric and polyphosphoric acids; polyol phosphites ., such as tri8(dipropylene glycol) phosphi~e; polyol phosphonates such as bis~dipropylene glycol)hydroxymethyl phosph~nate; di-poly(oxyethylene)hydroxymethyl phosphonate;

57.

~4~

di-poly(oxypropylene)phenyl phosphon~te; d_-poly(oxypropylene)-chloromethyl phosphonate; di-poly(oxypropylene)butyl phosphonate; and 0, 0-diethyl-N, N-bis(2-hydroxyethyl)-sminomethyl phosphonate. Also suitable are compounds having the formulas:

(ClCH2)2C[CH2 ~ (OCH CH~C1)2]2 and ClCH2CH20-~-O-IH _ - ~-0-CH ~ ( 2 2 )2 2 2 ¦
CH3 CH2CH Cl n -which are available from Monsanto Chemical Company under the names Phos~ard 2XC-20 and Phosgard C-22-R, respectively~
Other ~uita~le flame-retardants comprise halogen-containing polymeric resins such as polyvinylchloride resins in cvmbination with antimony trioxide ~nd/or other inorganic metal ox~des such as zinc oxide, as described in United States PRtents 3,075,927; 3,075,928; 3,222,305 and 3,574,149. Illustrative of suitable inorganic phosphorus-containing flame-retardants is the ammonium polyphosphate available from Monsanto Chemical Company under the name Phoscheck P30. The latter is espeeially useful as a flame-retardant for polyester urethane foam.
It i6 to be understood that other flame-retardants known to the art may be used and that the aforesaid compounds may be employed individually or in combination with one another.

58.

.

~-9~07 Of the above flame-retardantc, th~se of the discrete chemical compound variety which contain groups reactive with hydroxyl or isocyanato groups can be used as reactants in producing the polyether polyol or poly-ester polyol or they can be reacted with organic polyi~-cyanates, to produce corresponding modified polyols or polyisocyanates having chemically combined flame-retarding groups. Such modified polyols and polyisocyanates are also useful as reactants in the process of this invention.
In such cases, due regard must be given to the possible effect of the functionality of the compound on the o~her properties (e.g., degree of fl~xibility of the resulting foam.
The flame-retarding agent can be present in the foam formulations described herein in an amount fr~m about 1 to about 30 parts by weight per one hundred parts by weight of the polyol reactant. Usually the flame-retardant is employed in an amount of at least about 5 parts by weight perlOO parts by weight of polyol. As will be evident to those having ~kill in the art, the particular amount of flame-retardant employed depends largely on the efficiency of ~ny given agent in reducing fl~mmability of polyurethane foam.
The polyurethane foams may be formed in accordance with any of the processing techniques known to the art.
' J Usually the l'one-shot" process is used. In this method, ~he polyol and polyisocyanate reactants are independently added to the foam-producing reaction mixture and ~he 59.

~ 1 4~ ~ ~ D-9107 -OH/-NCO reaction is effected simultaneously with the foaming operation. It is often convenient to add the foam stabilizing component comprising the acrylonitrile-eapped polyoxyalkylene-polysiloxane polymers of the present invention to the reaction mixture as a premixture with one or m~re of the blowing agent, polyol, amine catalyst and, when used, the flame-retardant. The foaming ,and urethane-forming reactions occur without the application of external heat. Often the resulting foam is cured by heating the foam at a temperature between about 100~C. and about 150C. for about 5 to about 60 minutes to eliminate any surface tackiness, as desired. It is to be understood tha~
variations in process conditions and manipulative steps can be used as known in the art. For example, the v2rious ingredients of the reaction mixture can be combined and the foaming reaction mixtu~e poured into a mold, or the various ingredients can be combined and the foaming reaction mixture commenced and cMmpleted in a mold.
The relative amounts of the various components present in the foam-producing reaction mixture are not narrowly crltical. The polyol and polyisocyanate &re present in the oam-produeing formulation in ~ major amount. The relRtive amount~ of these two CGmpOnentS
is the amount required to produce the urethane 6tructure of the foam and such relative amount6 are well known in the art. The source of the blowing action ~ueh as water, au~iliary blowing agents, catalyst ~nd the foam stabili7-er are each presen~ in a minor amoun~ necessary to achieve the function of the component.

~ rj ~ D-9107 Thus, the blowing agent is present in a minor amount sufficient to foam the reaction mixture, the amine catalyst is present in a catalytic amount (i.e., an amount 3ufficient to catalyze the reaction to produce the urethane at a reasonable rate), and the acrylonitrile-capped polyoxyalkylene-polysiloxane polymers of this invention are present in a foam--stabilizing amount, that i~, in an amount sufficient to stabilize the foam. The preferred ~mounts of these various cOmponenEs are as given hereinabove.
If desired, other additional ingredients can be employed in minor amounts~in producing the polyurethane foams in accordance with the process of this invention.
For example, the solution compositions of the silicone polymer foam stabilizers of this invention as well as the aqueous premixtures can contain such components as inhibitors such as e.g., d~tartaric acid, tertiary-butyl pyrocatechol and di-tert-butyl-p-cresol ("Ionol"), which reduce any tendency of the foamed product to oxidative ~0 or hydrolytic instability. Further, when the foam stabilizers of this invention and/or the amine catalyst are employed BS respective solutions, water soluble carrler solvents and components thereof are, of course, introduced into the aqueous premixtures without however, any dele~erious affect on the effectiveness of ho~o-geneity of the aqueous solution premixtures. Additional illustra~ive additives are: cross-linking a~ents such 61.

as ~lycerol, triethanolamine and tlleir oxyalkylene adducts;
compression set additives (e.g., hexylene glycol); additives ~o regulate cell structure ~o as to coarsen cells and hereby reduce the telldency of the foam to split (e.g., paraffin oil); fillers; dyes; pigments; and particularly in regard to polyester polyol-derived f~am, anti-discoloration additi~res including anti-scorch and antioxidation agents such as phenols substituted with tertiary-butyl groups as exemplified by 2,6-di-tert-butyl-4-methyl-phenol ~"Ionol"), oxirane-containing compounds (e.g., propylene oxide), triorgano-(e.g., triphenyl-)substituted phosphites and phosphines, and other anti discoloration additives known ro the art.
The flexible urethane foams produced in accordance w*th this invention can be used in the same areas as conventional polyether and polyester urethane foams, the products formed with a flame-retarding agent being especially useful where reduced combustibility properties are beneficial. Thus, the foam products are useful as textile interliners, oushioning m~terials for seating and mattresses, for packaging of delicate objects, as gasketing materials, and the like.
As seen by the foLlowing examples the acrylonitrile-capped polyoxyalkylene-polysiloxane polymers ~f this invention possess a highly desirable combination of properties. For instance even when employed in the absence of additional organic surfactants they have been f~ ' found to be effective stabilizers for fleY.ible polyester foam and further allow for the formation of ~aid foam having a low burning extent when said foa~ contains a flame retardant. Moreover, said siloxane 'polymers of this invention can also be blenc~ed with organic ~urfactants whic~.
blended surfactants can form clear homogeneous premixes, effPctively stabilize flexible polyester foam, and further allow for the ormation of said foam having a low burning extent when said foam contains a flnme-retardant.
In addition said siloxane polymers of this invention have excellent potency as stabilizers for flexible polyester foam and thus furnish a wide processing latitude for the production of 6aid foam.
The following examples illustrate the present invention and are not to be regarded ~s limitative. It is to be understood that all parts, perc~ntages and proportions referred to herein and in the claims are by weight unless otherwise indicated. Moreover, as u~ed herei~ the following terms have the indicated significance:
In the formulas '~e" designates a methyl ~roup, -C~3.
"GPCI' denotes that the number average mt)lecular weight (MN) for various polymer compositions of this invention were mea~ured by Gel Permeation Chromato~raphy (abbreviated in t~e examples as "GPC"~ using a calibration curve showing the relationship between the res~ective elution volu~e&
established for dimethylsiloxane fluids of different 63.

molecular weights and the respective known molecular weights of such fluids. In establishing the calibration curve, ~he various dimethyl-siloxane fluids were in solution in trichloroethylene ~olvent using styragel packed columns. In measuring the molecular weights of the polymers described herein, the elution volume observed for any particular pol~mer product (in trichloro-ethylene solvent) was equated with the corresponding elution volume ~f the calibration curve, and the molecular weight associated with thAt particular elution volume was assigned as the molecular weight of the polymer pro~uct. Gel Permeation C~r~mato~raphy as a technique for measuring molecular weight is discussed in "Polymer Fractionation" (ed. Manfred J. R. Cantow, Acedemic Press, Inc. New York 1967), pages 123 173, Chapter B4, entitled "Gel Permeation Chrom~tography," by K.H. Altgelt and J. C. Moore. In determining the molecular weights given in the examples, the particular procedure employed was that described in the article enti~led "Character-ization ~f Silicones by Gel Permeation Chromatography"
by F. Rodriguez et al. ~ ~ & EC Product and De~elo~
Vol. 5, No. 2, page 121 CJune 1966) usang five ~tyragel packed column6 CWater Associates, Inc.) having a pore size of 103AC ~ x 103A 104A 3 x 104A ~nd 8 x 103A
respect~vely.
"Ri5e" !denotes the foam height and is direetly proportional t~ potency of the surfactant.
"Breathability" denotes the porosity of a foam, being roughly propor~onal to the number of open cells in a fo~m, and was measured in accordance with he NOPCO

,t 64.

~ D-9107 h~ X~

breathabili.ty test procedure described by R. E. Jones and G. Fes~an, "Journal of Cellular Pl~stics" (January, 1965).
In accordance with this test, breathabili~y is measured as follows: A 2 inch x 2 inch x 1 inch piece of foam is cut from near the center of the bun. V~ing a Nopco Foam Breathability Tester, Type GP-2 Model 40GD~O, air is drawn through the foam sample at a pressure differential ~ of 0.5 inches of water less th~l atmospheric pressure.
: The air flow is parallel to tne direction of original foam rise. The degree of openness of the fo~m (or foam breathability) is measured by the rate of air flow through the foam Bnd i6 reported in standard cubic feet per minute (SCFM).
"CPI" denotes "cells per inch", that is, the number of cells per linear inch of the foam. CPI is directly proportional to the fineness of tl:e cell structure.
"Burning Extent" was determined in accordance with standard flammability test procedure AS~M D-1692-68.
Burning extent denotes the burned length (in inches) of the foam and is reported as the average of the result6 obtained with the various test specimens of a given foam. On the basis of this test, an averagc burning extent of less than 5.0 inches qualifies the foam for a sel-extingui~hing ("SE") rating. When the burning extent of at least one tes~ specimen iB 5.0 inches or greater, the foam is assigned a burning ("B") rating and usually no further specimens of that foam are ~es~ed.
"Burning Time" denotes the average time (in seconds) taken to give the ~pecified burning ex~ent.

65.

"Top Collapse" denotes settling of the foam height upon cooling.
SURFhCTANTS OF THIS INVENTION
_ _ _ 'ISurfactant M " denotes a blended composition consisting of 50mponent Siloxane Surfactantll/ 52 Nonionic Surfactant /2/ 10.4 Tall Oil 15.6 Hexylene Glycol 21.0 . Ionol /3/ l.O

/1/ A siloxane polymer having the average co~position formula ; [Me SiOl/2] [C H CH O(C H O) C H Si~Me)O] [SiO4/2]
3 l.O 6 5 2 2 4 7.7 3 6 1.0 0.9 . /2/ An organic nonionic surfactant in ~hich the hydrophobe iS 8 mixture of Cll to Cls alcohols and the hydrophile is ethylene oxide ~avg.9 mols/mol of ~Iydrophobe).
. /3/ 2,6-di-tertiary-butyl-p-cresol.
"Surfactant BB'i denotes a siloxane polymer having ~he average composition formula 2D Me SiO(Me SiO) (C H CH O(C H O) C H Si(Me)O) SiMe 3 2 5 6 5 2 ~ 4 7.7 3 6 8 3 "Surfactant CC" denotes a blended composition consi~ting of : Component Parts by Weight Siloxane Surfact~nt /l/ 35 Anionic Surfactant /2/ 35 Tall Oil 15 Hexylene Glycol 15 Ionol /3/ 25~ p~m 6.

.. . .... ~..... ... ... ...... . ... ,, . . .. . .. . . .. . ... ...... ... . .... ~ . .

-~ !
B~

/1/ A siloxane polymer having the average composition formula Me SiO ~e SiO) [MeO(C H O) C H Si(l~e)O] Sil1e 3 2 5.1 2 4 7.2 3 6 7.5 3 /2/ An organic anionic surfactant which is a sodium sulfonate of a petroleum hydrocarbon mixt~re a typical analysis of which is (wt. %) 62.0 sodium sulfonate; 32.7 mineral oil, 4.5 water; 0.7 inorganic salt; avg. mol. wt. of sulfonate por~i~n to 435;
flash point, C. O. C. 400F,; ~vailable com-mercially as "Bryton 430'l.
/3/ Parts per million parts of the other four components.

'ISurfactant DD" denotes a siloxane polymer having the average co~position for~ula Me SiOCMe SiO) [MeO(C H O) C H Si(Me)O] SiMe ~ 5 .

67.
.

. ~ . _~ ~_ ~ _,_. _ ,,_ ~. _ . .

EXA~PLE 1 In a three nec~ round bottom flask fitted with a mechanical stirrer, nitrogen sparge tube, thermometer, addition funnel, reflux column and cold water bath, about 5 grams of a 20 weight percent aqueous ~olution of NaOH (about 0.22 wt. % NaOH in the reaction mixture) were added to about 400 grams of an allyl and hydroxyl end-blocked polyoxyalkylene having an average molecular weight of about 388 and an average co~position formula 2 CHCH20 (C2H40)7 5H
(wt. % OH about 4.36) covered by an atmosphere of nitrogen.
About 53.1 grams (about 100V/o of theory) of acrylonitrile (H2C e CHCH2CN) was then fed to the mixture over a two hour period with constant stirring. The temperature of the mixture was maintained by occasional cooling at about 25C to 30C. After this time the mixture was neutralized by the addition of about tw~ grams of 85 weight percent aqueous phosphoric acid (H3PO4). The neutralized mixture was then mixed with Magnesol ~magnesium 6ilicate) and then filtered to g~ve a clear off-colorless produot filtrate. The filtrate was de-solvated by rotary evaporation at a temp~rature not exceeding about 100C. under reduced pressure to a constant weight. There was obtained about 498.5 grams of the desired polyether product having the average c~mposi~ion ~ormul~
H C ~ CHCH 0(C H 0) CH CH CN
2 2 2 4 7.5 2 2 Analysis of the desired product showed about 0.8 weight %
residual hydroxyl groups and that about 85 percent of the staxting polyether was cyanoethylated.

68.

... ........... ... .. ... .. . . ........ . . . .. . . .. . . . .
. .

~4B~`~
- ~ 9107 E ~fPLE 2 In a manner similar to Example l, the ~crylo-nitrile-capped polyoxyalkylene composition product having the average formula H C = CHCH 0(C H 0) CH CH CN
~ 2 2 4 7.9 2 2 was prepared using about 400 grams of H C G
CHCH 0(C H 0) H (average mol. wt. abDut 406; wt. %
2 2 4 7.9 OH about 4.36), about 0.5 grams of Ionol, about 2.5 grams of 20 wt. % aqueous NaOH (about 0.10 wt. % NaOH in the reaction mixture) and about 106.1 grams of acrylonitrile (about 200% of theory). The reaction was conducted at about 15C. to 25C. over l 1/4 hours. Ater an additional 1 2/3 hours the orange colored product composition was neutralized with about 1.0 gram of 85 wt. % aqueous H PO and vacuum desolvated at 90C/1.0 mm Hg. The neutralized resction product was then mixed with about 60 grams of Magnesol, diluted with toluene and pressure filtered. The filtrate was then desolvated by rotary evaporation. Analysis of the desired polyether product showed about 0.03% residual hydroxyl groups and that about 99.3 percent of the starting polyether was cyanoethylated.
; EXAMPLE 3 In a manner similar to Example 2, the acrylonitrile-capped polyoxyalkylene composition product having the average formula ; H C = CHCH 0(C H G) CH CH CN
2 2 ~ 4 7.9 2 2 ' was again prepared using about 400 grams of H C=
CHCH ~(C H 0) H (avg. mol. wt. about 406; wt. % OH
2 2 4 7.9 about 4.36), about 0.05 grams of Ionol, aboùt 10 grams of 20 ,. . .
69.

~ X~ D-9107 wt. V/o ~aOH (about 0.04 wt. ~/~ NaO}I in the reaction mixture), and about 58 grams of acrylonitrile (about 110% of theory).
The reactio~ was conduc~ed at about 10DC to 13C over 1 3/4 hoùrs. After about an additional hour the pale yellow colored product composition was neutralized with about 1.0 gram of 85 wt. % aqueous H PO and the neutralized product mixture then rotary evaporated and stripped at 90~C/0.3 mm Hg. ~le desired polyether product developed a deep orange to reddish color and analysis showed about 0.27 wt. ~/O residual hydroxyl group and that about 93.8 percent of the starting polyether was cyanoethylated.
EX~MPLE 4 In a manner similar to Example 3, the acrylonitrile-capped polyoxyalkylene composition product having the average formula H C = CHCH 0CC H 0) CH CH CN
2 ~ 2 4 7.9 2 2 was again prepared using about 400 grams of H C=
CHCH 0(C H 0) H (average mol. wt. about 406; wt. ~ OH
2 2 4 7.9 about 4.36), about 0.05 grams of Ionol, about 1.0 grams of 20 wt. % aqueous NaOH (about 0.044 w~. % NaOH in the reaction mixture) and about 53 grams of acrylonitrile (about 100~/o of theory). The reaction was conducted at about 8C to 10C. over 1 hour. After an additional hour the light yellow product compositiqn was neutralized with about 0.5 grams of 85 wt. % aqueous H PO and , J the nPutralized mixture desolva~ed by rotary evaporation at 75C/0.3mm. Hg. The product composition was ~hen diluted with an equal amount of toluene, pressure filtered and the 70.
i.

~ B~ D-9107 . " `

filtrate desolvated by rotary evaporation at 90C/
0.3 mm Hg. Analysis of the desired polyether product showed about 0. 35% residual hydroxyl groups, that about 92 percent of the starting polyether was cyanoethylated and the product to have a Brookfield viscosity (at room temperature) of about 43 centipoi6es.

In a manner similar to Example 4, the acrylo-nitrile-capped polyoxyalkylene composition product having ; i0 the average formula H C ~ CHCH O(C H O) CH CH CN
2 2 2 4 7.9 2 was again prepared using about 992 grams of H C =
CHCH O(C H O) H (avg. mol- wt. about 406; wt. % OH
2 2 4 7,9 about 4.36), about 2.5 grams of 20 wt. % aqueous NaOH
(about 0.045 wt. % NaOH in the reaction mixture), and about 131.5 grams of acrylonitrile (about 97.6% of theory).
The reaction was conducted at about 3~C. to 5~C. over 3 hours. After an additional half hour the product composition was neutralized wqth about 1.25 grams of 85 wt. ~ aqueous H PO . About 50 grams of toluene w~re added to the neutralized reaction mixture which was then desolvated by rotary evaporation at 85C/1.5 mm Hg.
During this treatment the product turned wine-red in color. About 40 grams of Magnesol was then added to the product which was then pre~sure filtered. The filtrate was wine-red in color and analysis of the desired product showed about 0.34% residual hydroxyl groups, that about 92.2% of the starting polyether was cyanoethylated and the product to have a Brookfield viscosity (at room temperature) of about 37 centipoises.
.

71.

~4~ D-9107 E~ ~LE 6 .
In a manner similar to Example 5, the acrylo-nitrile-capped polyoxyalkylene composition product having the average formula H C = CHCH O (C H O) CH CH CN
2 2 2 4 7.9 2 2 was again prepared using about 400 grams of H C =
CHCH 0(C H 0) H (avg. mol. wt. ~bout 406; wt . % OH
2 2 4 7.9 about 4.36), about 1.0 gram of 20 wt. % aqueous NaOH
(about 0.044 wt. % NaOH in the reaction mixture), and about 49.0 grams of acrylonitrile (about 92% of theory).
The reaction was conducted at about 3C to 8C over 2 3/4 hours. After an additio~al half hour the light yellow colored product composition was neutralized with about 0.45 grams of 85 w~. % aqueous H PO and the neutralized mixture desolvated by rotary evaporation at 95C/0.5 mm Hg. About 40 grams of Magnesol and about 400 grams of toluene were then added to the neutralized product which was then pressure filtered and the filtrate desolvated by rotary evaporation at 95C/0.5 mm Hg. Analysis of the de6ired polyether product wh~ch wa~ light yellow-brown in color showed about 0.5 residual hydroxyl groups, that about 88.7 percent of the start~ng polyether was cyanoethylated and the product to have a Brookfield vi6co~y ( at room temperature) of about 37 cen~ipoises.

In a manner s~milar to Ex~mple 6, the acrylonitrile-capped polyxoyalkylene composition produc~
having the avera~e formula .. . .. . .... ... . ..

H C = CHCil 0(C H 0) CH CH CN
2 2 2 4 7.9 2 2 was again prepared using about 1000 grams of H C = CHCH 0(C H 0) H
2 2 2 4 7.9 (avg. mol. wt. about 40~; wt. % ~H about 4.36), about 3.0 grams of a 20 weight percent aqueous solution of Me NOH ~about 0.05 wt. % Me NOH in the reaction mixture), and about 143 grams of acrylonitrile (about 105% of theory). The reaction was conducted at about 10~C. to 18~C. over a one hour period. Infrared analysis at this time showed the presence of a slight amount of unreacted hydroxyl,moiety. Stirring was m~intained for an additional one half hour at about 18C.
after which infrared analysis indicated essen~ially a complete reaction. After this ~ime the mixture was neutralized by addition of about 3.05 grams of 85 weight percent aqueous H PO . About 50 grams of Magnesol were added to the neutralized mixture which was then pressure ; filt~red. Then about 200 grams of toluene were added to a 400 gram portion of the filtrate which was then desolvated by rotary evaporation at 90C/~ 0.5 mm Hg.
Analysis of the desired polyether product thus obtained showed about 0.185 wt. % residual hydroxyl groups, that about 95.8 p~rcent of the starting polyether was cyano-. ethylated and the produc~ to have a Brookfield viscosity , (at room temperature) of about 40 centipoises.

In a manner 6imilar to Example 7, the ~_ acrylonitrile-capped polyoxyalkylene composition product '~ having t~e average formula i~ H C - CHCH O(C H 0) CH CH CN

- :.

~ 73.

was prepared using about 300 grams of H C = CHCH 0(C H 0) H

(avg. mol. wt. about 500; wt. % OH about 3 L0) in about 200 grams of toluene, about 0.65 grams of 20 wt. % aqueous Me NOH (about 0.023 wt. % Me NOH in the reaction mixture) and about 33.2 grams of acrylonitrile (about 110% of theory) in about 33.2 grams of toluene. The reaction was conducted at about 7C to 17C for about two hours. After an additional 1 1/2 hours the light brown colored product composition was neutralized with about 0.75 grams of 85 wt. % aqueous H PO . About 30 grams o~ Magnesol was added to the neutralized mixture which was then pressure filtered. The filtrate was then desolvated by rotary evaporation at 90C/~ 1 mm Hg. Analysis of the desired - polyether prod~ct which had a yellow color showed about 0.17 wt. % residual hydroxyl groups, that about 95 percent of the starting polyether was cyanoethylated and the product to havea Brookfield visco~ty (at room tem~erature) of about 55 centipoises.
EXAMPLE_9 In a manner similar to Example 8, the acrylo-nitrile-capped polyxoyalkylene composition product having the average for~ula H C ~ CHCH 0(C H 0) (C H 0) CH CH CN
2 2 2 4 ~.5 3 6 0.8 2 2 was prepared using about 483 grams of H C = CHCH 0(C H 0~ -2 2 2 4 9.5 (C H 0) H (average mol. wt. about 501.5; w~. % HO about 3 6 0.8 3.39; the oxyethylene and o~ypropylene groups being present in a random ~ashion) in about 100 grams of toluene, about 1.5 grams of 20 wt. % aqueou~ Me NOH (about 0.047 wt. %
Me NOH in the reaction mixture) and about 53.0 grams of acrylonltrile ~about 110% of theory). The reaction was conducted at about 8C to 18C for about 2 3/4 hours The light ~rown cclored prod~ct compositio~ W2S neutraliz~d without 1. 8 grams o~ 85 wt. % aqueous H P04 and the product turned light-yellow in color. About 30 grams of Magnesol was added to the neutrali~ed mixture and the mixture pressure filtered. The filtrate was then desolvated by rotary evaporation at 90C/< 0.5 mm Hg. Analysis of the yellow colored desired polyether product showed about 0. 25 wt. ~/~ residual hydroxyl groups and that about 92.5 percent of the starting polyether was cyanoethylated.

In a manner similar to Example 9, the acrylo-nitrile-capped polyoxyalkylene composition product having the average formEla CH ~CHCH 0(C H 0) (C H 0) CH CH CN
2 2 2 4 21.2 3 6 5.35 2 2 was prepared using about 300 grams of CH =CHCH 0(C H 0) (C H O) H
2 2 2 4 21.2 3 6 5.35 (avg. mol. wt. about 1250; wt. % OH about 1.36; the oxyethylene and oxypropylene groups being present in a random fashion3 in about 200 grams of toluenej ~bout 1.0 grams of 20 wt. % aqueous Me NOH (about 0.04 wt. ~ Me NOH in the reaction mixture) and about 15 grams of acrylonitrile (about 92% of theory) in about 15 grams of toluene. The reaction was conducted at about 15C to 23C for about 2 hour~. The reaction produc~ was neutralized with , about 1.05 grams of 85 wt. % aqueous H PO . About lS
grams of Magnesol was added to the neutralized mixture and the mixture pres6ure filtered. The filtrate was ~hen desolvated by rotary evaporation at 90C/~ 0.5 mm Hg.

.

... .. .... .......

Analysis of the yellow-light brown colored desired polyether product showed about O.23 wt. % residual hydroxyl groups, that about 83 percent of the starting polyether .
was cyanoethylated an~ the product ~o have a Brookfield viscosity (at room temperature) of about 220 centipoises.
EX~LE ll In a three-necked reaction ~lask equipped with a mechanical stirrer, distilling take-off head and thermometer a mixture of about 30.0 grams of a hydrosilo~ane polymer having an average molecular weight of about 952 and the average formu'a Me SiO(Me SiO) (MeHSiO) Si~e 3 2 5 , 7 3 (Anal: Si-H, 165 cc H /gram; Calc: 0.2211 mole MeHSiO) and about 104.7 grams (0.2379 mole) of the acrylonitrile-capped polyoxyalkylene product of Example 1 ha~ing the average formula H C - CHCH O(C H O) CH CH CN
2 2 2 4 7.5 2 2 (about 7.7% excess of theory), and about 50 ml. of xylene was heated rapidly to 45~C. with constant stirring. At that temperature about 20 parts per million of platinum as chloroplatinic acid was added to the ~ystem. There was an exothermal reaction noted. The reaction mixture was maintained at 85C 95C for one hour after which analysis of the reaction mixture for residual Si-H was negative, ~ indicating that the reaction had gone to completion.
The reaction mixture was then cooled, neutralized with NaHCO , filtered and the filtrate ~esolvated by rotary evaporation at 50DC/5 mm Hg. The desired aryloni~rile-capped polyoxyalkylene-polysiloxane product was a clear ~mber liquid having the average formula 76.

... .

~ 9107 MeSiO(Me SiO) (Me~iO) Sil~e CH CH CH O(C H O) CH CH Cl~
. 2 2 2 2 4 7.5 2 2 This ~iloxane product, designated herein as Surfactant A, had a Brookfield viscosity (a~ about 25C) of 480 centipoises and a GPC average molecular weight of 4,400.

In a m~nner similar to Example 11 a mixture of about 24.1 grams of a hydrosiloxane polymer having an average molecular weight of about 1012 and the average formula Me SiO(Me SiO) tMeHSiO) SiMe (Anal: Si-H, 176.3 cc H /gram; Calc: 0.1898 mole MeHSiO) and about 119.5 grams of the acrylonitrile-capped polyoxy-alkylene product of Example 4 having the average formula H C = CHCH O(C H O) CH CH CN
2 2 2 4 7.9 2 2 (about 37% e~cess of theory) and about 110 grams of toluene was heated to about 79C with stirring. The reaction mixture was then catalyzed with about 25 parts per million of platinum as chloroplatinic acid catalyst and the reaction conducted at 79C to 115C for 6iX hours. Additional platinum catalyst, 20 ppm platinum after 10 minutes, and about 25 ppm platinum after three hours, was added during the reaction. After 6aid six hours the reaction mixture was analyzed for residual Si-H and yielded 0.60 cc H /4.0cc sample, indicating that the reaction had gone to 99.0 percent com-pletion. The reaction mixture was then cooled, neutralized J with NaHCO and filtered. The filtrate was then deso~vated by rotary evaporation at 95C/~0.3 mm Hg. The desired acrylonitrile-capped polyoxyalkylene-polysiloxane product was a cl~ar brown liquid having the average formula Me SiO(~e SiO) (Me~iO) SiMe3 CH CH CH O~C H 0~ CH CH CN
2 ~ 2 2 4 7.9 2 2 This siloxane product, de6ignated herein as Surfactant B

' ' ' ' :

'~ D - 910 7 had a GPC averag,e molecular weight of about 4 ,400, EX~MPLE 13 ! In a manner similar to Example 12, a mixture of about 24.1 grams of a hydrosiloxane polymer having an average molecular weight of about 1012 and the avera~e formula Me SiO(Me SiO) (MeHSiO) SiMe (Anal: Si-H, 176.3 ccH /gram; Calc: 0.1898 mole MeHSiO) about 119.5 grams of the acrylonitrile-capped polyoxyalkylene product of Example 6 having the average formula H C ~ CHCH O(C H O) CH CH CN
2 2 2 4 7.9 2 2 (about 37~/0 excess of theory), and about llO grams of toluene was heated to about 81C with stirrin~. The reaction mixture was then catalyzed with about 25 parts per million of platinum as chloroplatinic acid and the reaction conducted at 81C to 100C for th~ee hours. Additional platinum catalyst, about 20 ppm platinum after one-half hour and aoout 15 ppm platinum after two hnurs, was added during the reaction. After said three hours, the reaction mixture was analyzed for residual Si-H and yielded 0.2 cc H /4cc sample, indicating that the reaction had gone to 99.7 percent completion. The reaction mixture was then cooled, neutralized with NaHC03 filtered and the filtra~e desolvated by rotary evaporation at 95C/~0.3 mm Hg. The desired acrylonitrile-capped polyoxy~lkylene-polysiloxane product was a clear light brown liquid having the average formula Me SiO(Me SiO) (MeSio) SiMe ' 3 2 5 1 8 3 CH CH CH O(C H O) CH CH CN
2 2 2 2 4 7.9 2 2 78.
-:.

.--. ... ., .. ~ . ...... .

This siloxane product, desi~nated hereill as Surfactant C, had a Brookfield viscosity (at room temperature) of about 300 centipoises and a GPC average molecular weight of j about 4500.

.
In a similar manner to Example 13, a mixture of about 25.4 grams of a hydrosiloxane poly~er having an average molecular weight of about 1012 and the average formula Me SiO(Me Si~) (MeHSiO) SiMe (Anal: Si-H 176.3 cc H /gram; Calc: 0.20 mole MeHSiO), about 161 grams of the acrylonitrile-capped polyoxyalkylene product of Example 8 having the average formula H C = CHCH O(C H O) CH CH CN

(abou~ 40% excess of theory), and ~bout 186.4 grams of toluene was heated to about 82C with stirring. The reaction mixture was then catalyzed with about 25 parts per million platinum as chloroplatinic acid and the reaction ; conducted at 82C to 9~C for 3 1/2 hours. Additional ~0 platinum catalyst, about 20 ppm platinum after 20 minu~es, about 20 ppm platinum after 1 1/2 hours and about 25 ppm platinum after 3 hours was added dur~g the reaction.
AftPr ~aid 3 1/2 hours the reaction mixture was analyzed for residual Si-H and yielded 0.60 cc H /5.0cc. ~ample indicating that the reaction had gone to 99 percent completion. The reaction product was cooled to room temperature, neutralized with NaHCO and filtered. The filtrate was then desolvated by rotary evaporation Rt 95 C/~ 0 5 mm Hg. The desired acrylonitrile-capped poly~xyalkylene-polysiloxane product was a clear brown liquld having the average formula 79.

.
.

Me SiO(Me SiO) (MeSiO) S~e 3 2 5 1 ~ 3 CH C'n Cl, O (C H O) CH CH C~
2 2 7 2 ~ 10 2 2 This siloxane product,d~signated herein as Surfactant D, had a Brookfield viscoity (at room temperature) of about 500 centipoi6es and a GPC average molecular weight of about 7500.
EX~MPLE 15 In a similar manner to Example 14, a mixture of about 31.75 gra~s of a hydrosiloxane polymer having an average molecular weight of about 1012 and the average formula Me SiO(Me SiO) (~Ie~SiO) SiMe (Anal: Si-H, 176.3 cc. H /gram; Calc: 0.2501 mole MeHSiO), about 143.75 grams of the acrylonitrile-capped polyoxyaLkylene product of Example 7 having the average formula H C = CHCH O(C H O) CH CH CN
2 2 2 4 7.9 2 2 (about 25% excess of theory~ ~nd about 175.5 grams sf toluene was heated to about 90C with stirring. The reaction mixture was then catalyzed with about 20 parts per mi~lion of platinum as chloroplatinic acid catalyst and the react,on conducted at 90~C to 110C for 2 1/2 hours. Additional platinum catalyst, about 20 ppm platinum after 1/4 hour, about 10 ppm platinum after 1/2 hour and about 10 ppm platinum after 1 hour was added during the reaction. After ~aid 2 1/2 hours the r~actionmixture was analyzed for residual Si-H and yielded 1.0 ccH /4.0cc, sample, indicating that the reaction had gone to 98.5 percent`completion. The reaction pr~duct was cooled to room temperature, neutralized 80, ~ r~ D-9107 with NaHCO and filtered. The filtrate was then desolvated by rotary evaporation at 90C/< 0.5 mm Hg. The desired acrylonitrile-capped polyoxyalkylene-polysiloxane product was a clear dark brown liquid having the average formula Me Si0CMe Si0) tMe$iO) SiMe CH CH CH O(C H O) CH CH CN
2 2 2 2 4 7.9 2 2 This siloxane product desi~nated herein as Surfactant E, had a Brookfield viscoslty (a. room temperature) of about 496 centipoises and a GPC average molecular weight of about 4700.

-In a similar manner to Example 15, a mixture of about 35.0 grams of a hydrosiloxane polymer having an average molecular weight of about 892 and the average formula Me SiO~Me SiO) (MeHSiO) SiMe (Anal: SiH, 1S3.6 ccH /gram; Calc: 0.240 mole MeHSiO), about 138.0 grams (0.3 mole) of the acrylonitrile-capped polyoxyalkylene product of Example 7 having ~he average formula H C = CHCH O(C H O) CH CH CN
2 2 2 4 7.9 2 (about 25% excess of theory) and about 173. 0 grams of toluene was heated to about 90C with stirring. The reaction mixture was then catalyzed with about 30 par~s per million of platinum as chloroplatinlc acid catalyst and the reaction conducted at 90C to 109C for 1 1/2 hours. The reaction mixture was ~hen analyzed for residual Si-H and yielded 0.75 cc H /4.0 cc sample, indicating that the reaction had gone to 98.8 percent 81.

:
. ~:
.

~ ~ ~ 4 ~ ~ ~ D-9107 completion. The reaction product was cooled to roo~
temperature, neutralized with NaHCO and fi~tered. The ~, filtrate was then desolvated by rotary evaporation at 90C/CO.S mm Hg. The desired acrylonitrile~capped ' polyoxyalkylene-polysiloxane product was a clear brown liquid having the average formula . Me SiO(Me SiO) (MeSiO) SiMe ~ 3 2 5 1 6 3 : CH CH CH O(C H O) CH CH CN
2 2 2 2 4 7.9 2 2 The siloxane product, desi~nated herein as Surfactant F, had a Brookfield viscosity (at room temperature) of about 335 and a GPC average molecular weight of about 3900.

In a manner similar to ~xample 16, a mixture of about 27.9 grams of a hydrosiloxane polymer having an . average molecular weight of about 1,13~ and the average formula Me SiO(MP SiO) (MeHSiO) SiMe (Anal: Si-H, 205.0 cc H /~ram; Calc; 0.2555 mole MeHSiO), about 146.6 grams of the acrylonitrile-capped polyoxyalkylene product of Example 7 having the average formula H C=CHCH O(C H O) CH CH CN
; 2 2 2 4 7.9 2 2 (about 25% excess of theory) and about 174.5 grams of toluene was heated to about 90C with stirring. '~he reaction mixture was ~hen catalyzed with a~o~t 30 parts per million of platinum as chloroplatinic acid catalyst and the reaction con~ucted at 90C to lO9~C. for 3 1/2 hours. Additional platinum catalys~, about 10 ppm platinum after 1/6 hour and about 10 ppm pla~inum after one hour was added during the reaction.
After said 3 113 hours the reaction mixture was analyzed 82.

.. . .. .. ... ~. ~ . ... ... .. . ..

4 ~ ~ ~ D-9107 for re~idual Si-H an~ yielded 0.75 cc H /4.0 cc sample, indicating that the reaction had gone to 98.9 percent completion The reaction product was cooled,neutralized with NaHCO
and filtered. The filtrate was then desolvated by rotary evaporation at 90DC/~ 0.5 mm Hg. The desired acrylonitrile-capped polyoxyalkylene-polysiloxane product was a cl~ar light brown liquid having the average formula Me SiO(Me SiO) CMeSiO) SiMe CH CH CH O(C H O) CH CH CN
2 2 2 2 4 7.9 2 2 ThiS siloxane product, designated herein as Surfactfint G, had a Brookfield viscosity (at room temperature) of about 478 and a GPC average molecular weight of about 4700.

In a manner similar to Example 11, a mixture of about 10.4 grams of a hydrosiloxane polymer ha~ing an average molecular weight of about 416 and the average formula Me SiOCMo SiO)(MeHSiO) SiMe (Anal: Si-H, 161.3 cc H )gram; Calc: 0.07498 mole MeHSiO) and about 42.2 grams of the acrylonitrile-capped polyoxyalkylene product of Example 1 ha~ing the average formula H C c CHCH O(C H O) CH CH CN
2 2 2 4 7.5 2 2 (about 28% excess of theory) and about 30 ml. of xylene was heated to 45C with constant 6tirring. At that temperature about r~o parts per million of platinum as chloroplatinic acid catalyst was added to the system. There was an exothe~al reaction noted. The reaction mixture was 83~

. , , .. , . . ~ .... , . . ., ~ .. . .
. ...,..~,.~ ~ ..

~ ~ ~ 4~ D-9107 maintained at 85C-95C ~or one hour until completed.
The rcactioll mixture was then cooled, neutralized with NaHCO , filtered and the filtrate desolvated by rotary evaporation at 50C/5 mm Hg. about 50.1 grams of the desired acrylonitrile-capped polyoxyalkyle~e-polysiloxane produc~ having the average formula Me SiO(Me SiO~CMe~iO) SiMe 3 2 ~ 3 3 CH CH CH OtC H O) CH CH CN
. 2 2 2 2 ~ 7.S 2 2 was obtained. Ssid siloxane product is designated herein ss Surfactant H.

-Il 84.

. ~

D-gl07 EXA~LES 19-32 In these examples, fle~:ible polyester polyurethane foam containing a flame-retardin~ agent wer~
produced using the above-described Surfactants A through H of this invention (and with the above~described Control Surfactants AA, BB and CC, not of this invention) as the respective fo~m stabilizi~g surfactant compon~nt of the foam-producing reaction mixture, designated herein as Foam Formulation A, which had the ~.omposition given in Table I, which follows.
TABLE I-F0AM FOR~ULATION A
Component Parts by Weight Surfactant 'Varied (0.5 to 1) Polyester Polyol /1/100.0 N-ethy~morpholine 1.9 Hexadecyldimethylamine0.3 Water 3.6 Tolylene diisocyanate45.2 (Index 105) /2/
Tris(2-chloroethyl)phosphate 7.0 /1/ The polyester polyol e~ployed was a commercially available polyester resin produced from adipic acid, diethylene glycol and tri-methylol propane in a mole ratio of approximately 1:1:0.2. This polyester has a hydroxyl number of about 50 to 56, a molecular weight of about 2,000, an acid nu~ber not greater than 2 and a viscosity of about 17,000 centistokes at 85.

.. . ., ., .,, .. ~

x~ l about 25C. This par~icular polyester is known as "litCO ~omr~ No. 50" (Witco Chemical Corporati~n).
/2/ This component was a mixture of 2,4-tolylene diisocyanate (80 weight percent) and 2,6-tolylene diisocyanate. Index 105 means that the amount of mixture employed was 105 percen~
' of the stoichiometric amount required to react with the polyester polyol and water present in the oam formulation.
_.
The runs of Examples 19-32 were narried out in ~ccordance with substantially the same ge~er~l procedure which entailed the following steps. The surfactant, amine catalysts and water were premixed in a 50 milliliter beaker.
The polyester polyol reactant was weighted into a tared : 32-ounce capacity container The flame-retardant [tris(2-chloroethyl)phosphate] and tolylene diisocyanate reactant were also weighed into the container and mixed with a spatula until homogeneous. Further mixing was done on a drill press equipped with ~ double three-bladed marine-type propeller about three inches in dia~eter. The mixing in the drill press was accompli~hed at 1000 revolutions per minute for eight seconds. Then the premixture of surfactant, catalyst and water was added and mixing wascontinued for seven additional ~econds. The reaction mixture was poured into a 12 in. x 12 in. x 12 in. cardbo~d box, was allowed to rise and was then cured for about 30 minutes at 130C. Samples of the foam products prepared for breath- -ability and for a determination of burning resist~nce ~6.

(burnin~ extent and flame rating) in accordance with AST~ D-'692-68 and the results are ~iven in Table II
whlch f~llows:

. , .
87.

- .. - ~ ~ . - ., . . . . . . . . ~ . " .... .. ... .
. ; - :, , ... .

D- 91û7 U ~
~ e w ~ ~ , w hl lq ~ ~C
~U ~ ~ O O
U N _I N N ~ N N Itl ~ N ~ C:i ~I N N 0~ --~ O O O
1~ N N N --~ N N _I N N Nl N
~1 ~ ~7 ~ N ~
~ O ~ O O O ~ ~ O ~ Z ~ ~ O ~
:~

_ ~ O O ~ ~ O OD
~3 ~ h N ~ l ~ N U) ~ LO N N ~ N C~ D O C
~ Ul I I O

C
:~, O O ~
.n o o In ~ ~ u~ o Ll ~ u ,~ o o o o ~ o O -~ ~
C

O ~ o N N N N N ~1 N ~1 ~ r~ r'7 B~ P-9107 .. .

Thc data in Table II above demonstrates that the acrylonitrile-capped polyoxyalkylene-pol~silox.ane sur-factant polymers of this invention are effective stabilizers of flexible polyester foam and possess the further desirable property of allowing for the formation of flexible polyester foam containing a flame retardant which foam has a self-extinguishing flammability rating as tested above.
EXAMPLES 3~-36 In acc~rdance with these examples, a repeated preparative example of Surfactant E, herein desigaated Surfactant E', was blended with various organic compounds to provide illustrative ~olution compositions of this invention~ These blended compositions are designated herein as Blended Surfactants I through L and each was used as the surfactant component of Foam Formulation A
above in a concentration of one part by weight, following the general procedure described above with reference to Examples 19-32 In using the blended surfactants, clear, homogeneous aqueous premixtures w~re obtained when the water and amine c~talysts of Foam Formulation A were combined therewith. The composition of the blended surfactants and the results of these exomples ~re given in the followin~ Table III.

.. , . .. ... , . , . .. , .. .. .. .. , . .. ., .. , . .. . . . . . . -.

.,, ~ W ~ 1 0~ Y
_ ,c .c: '' '~oc ,i ~ sO ~ ~

o ~ ~ o ~ U

u ~ ~ = o u ~ o co o o ~ o ~ o ~ ~ ~ u o o ~ ~ 8 ~
2 C~ u ~ ~ ~ W U . S

8 ~j y ~ o~ o~ y ~ o~ o ~,U~ Uo o~
o ~ o U~ , u Z ~ `

~4~J~9 D-9107 The date in Table III demonstrates that s~lution compositions of the arylonitril~-c2~ped polyoxy-alkylene-polysiloxane polymers of this inven~,on in addition to forming clear homogeneous premixtures with water and amine catalysts, also possess good poter.cy as effective stabilizers of flexib:Le polyester foam and further possess the desirable property of allowing for the formation of said foam containing a flame-retardant which foam has a self-extinquishing flammability rating as tested above.

In these examples a potency determination was made of above-described Surfactants A and C of this inven~ion (and above-described Control Surfactants AA
and DD, not of this in~ention) as the foam stabilizing surfactant in the production of flexible polyester poly-urethane foam using Foam Formulation B as identified in Table IV, which follows:

TABLE IV - FOAM FORMULATION B
Component Parts by Wei~ht Surfac~ant (varied~ Varied ~0.5 to 1) Polyester Polyol tl/ 100 N-ethylmorpholine 1.9 Hexadecyldimethylamine 0.3 Water 5.0 Tolylene Diisocyanate 59.4 (Index 105) /2/

/lJ As identifi~d in footnote /1/ ~of Table I
2/ As indicated in footnote /2/ of Table I

91 .

.. . . . . . ... .. ..... . ,. ,.. . . . .. ..... .......... , , .. ~.. .

As indicated, Foam Formulation B contains 5 parts by weight of water per 100 parts by weight of polyol reactant. The 5 parts water system i6 usually more difficult to stabilize than the more conventional formulations containing less water and thus provides a relatively sensitive test of potency. The foams were prepared following the above-described foaming procedure except that no flame-retardant was used. The 9 results are given in Table V which follows.

92.

93 .

h ~ u~
,_1 g ~ ¢ C
~ C~

¢ ~1 O ~ O C~

~ ~ O
U~ ~ ~ ~
.,1 rl J-~ ,C

h C) ~ J_) 1~ ~ ~1 ~
~n J-C
¢ ~) U~ l . ' ,, i~;

I~

.

'. D-9107 The data of Table V demonstrates thAt t..!e acrylonitrile-ca~ped polyoxyalkylene-polysiloxane sur-factants of this invention have excellent potency as reflected by the rise values of the flexible polyester foam pr~ducts which do not contain a flame-retardant.

In accordance with these examples, 3-' cyanopropyl-substituted polymethylpolysiloxane hydride : fluids, designated in the examples as Si-H Internediate Fluids I-III were prepared having the average composition . formula - Me SiO~Me SiO] ~MeSiO] ~Me~iO] SiMe (1H ) CN

wherein the particular values of x, ~ and z are given in Table VI below. The respective fluids were prepared by the acid-cataly2ed equil~bration of reactants (1)-~4) listed below employing trifluoromethylsulfonic acid.
Reactant ~ Hexamethyldisiloxane, Me SiOSiMe , . 3 3 , as the source of the endblDcking trimethylsiloxy units, j Me SiO -.
r 3 1/ 2 Reactant (2): Cyclic polymers of d~me~hylsiloxane dis-tilled to pro~ide the cyclic tetramer, [Me SiO] , as the predominant Component (boiling point, 175C./760 mm Hg.), as the sour~g of ~he dime~hylsiloxy units.

. . 94.

i ~, .

.
., ~ .

'.

~ ~1 48 2~ D--9107 Reactant~ Cyclic 3-cyanopropylmethylsilo~ane polymer, as the source of the 3-cy~nopropyLmethylsiloxy units. This reaction is prepared by the hydrolysis of 3-cyanopropylmethyldichlorosilane, MeSiC12(CH2)3CN, at ~q temperature of about 10-15C. and subatmospheric pressure (40-110 mm.) employing toluene diluent and neutralizing the hydrolyzate with 60dium bicarbonate, followed by dehydration and cyclization of the hydrolyzate in the presence of sodium bicarbonate at reflux temperature, and removal of toluene from the cyclizate.
Reactant (4): Polymer~c methylhydrogensiloxane (Si-H
analysis, 355-365 cc. H per ~ram), as the source of the methylhydro~en~iloxy units.
The respective amounts of the a~oresaid reactants (1)-(4) and catalyst employed in providing and a~alytical data pertaining to the respective reaction products are given in Table VI; the procedure and reaction conditions 2D employed are as typically illustrated by the following detailed description of the preparation of Intermediate Fluid I.
Preparation of Intermediate Fluid I
The aforesaid Reactants (1)-(4) were charged in the following amounts to a 500 ml. capacity, three-necked flask equipped with a thermometer, mechanical stlrrer, condenser and nitrogen blow-by:

95.

i .
. ~ . , .. ,~ ... ..... " , .. .... .. ....... .. .. . ....... . .. ... .. . ........... ... .

Reactant (1): 16.2 grams, correspondin~ to 0.1 mole of Me SiOSiMe or 0.2 mole-equivalents of Me SiO

Reactant (2): 44.5 grams, corresponding to 0.6 mole-equivalen~ (x') of the unit, Me SiO

Reactant (3~: 101.78 grams, corresponding to 0.8 mole-equi~alent ~z') of the unit, NC(CH ~ Si(Me)O
2 3 2l2 and Resctant ~ 36.0 grams, corresponding to O.6 mol~-- equivalent (~I) o~ the unit, MeHSiO
~ 2/2 ~ Also added was 0.8 gram of anhydrous trifluoromethyl sulfonic acid catalyst corresponding to about 0.4 weight percent of the total weight of reactants. The heterogeneous reaction mixture was ~tirred at room temperature overnight ,. ,~
; ~about 18 hours). The clear liquid equilibrate was neutralized with sodium bicarbonate while stirring for s about one hour, and ~iltered. The liquid product had a viscosity of 116 cen~ipoise. Based upon the method and proportions of reactants employed expres~ed on the nor~alized basis of two moles of M units, the fluid ~. product, designated Si-H Intermediate Fluid I, has the ': average composition:
Me SiO[i~e SiO] [MeSiO~ ~MeSiOl SiMe 3 2 6 ' 6 ' 8 3 H ~CH ~ CN

~. g ~i .

.' ., ~, .
.,, ~ .

4~ D-9107 corresponding to a theoretical MeHSiO content of 18.1 weight percent. Upon Si-H analysis ~ the product provided 64.0 cc, H2/gram on the basis of which the found MeHSiO
content is 17.4 weig~Lt percenl,.
As used herein, the weight percentages expressed as "% MeHSiO, Found" are derived ~rom the Si-H Analysi6 (cc. H2 pe- grr~) in accordance with the con~rs~on:
Weight ~ercent MeHSiO Found c cc H2 per gram ~ 100 373.3 where the factor 373.3 is the theore~ic~l number of cubic centimeters o hydrogen provi~ed per ~r~m of fluid consist-ing of 100 percent MeHSiO (that is, 22,400 c~. of hydrogen divided by the unit molecular weight of 60).
; The weight percen~ages expréssed as "7~eHSiO, Theoretical"
correspond to ~he weight ~60 y) con~ributed by MeHSiO
divided by the calculated molecular weight o the fluid product times 100.
The above data pertaining ~o Sl-H Intermedi~te Fluid I, as well as corresponding data for Si-~ Fluids II
and III are given in Table VI which follows.

., ..
à

'i ,?, 97.
., .

~ .
,. . .

-., -r~

~1-9107 o "~ ~ o Ul Z
5 " U
q~ ~ ~ ~0 ;~ ~ OF~O ~;t~ rt o~O ~ ~ ~ .C
U o U
U o o ~o ,, 0 , ~oV~~ o ~ t~ ~ a~
~ ~, ~
~ ~o ~ 8 C
s c o c ~ ~
~rl d r~ ~ ~ el ~
C O
O ~ _ ~ ~o r~ ~ ~ ~ o ~t _~ ~ o O J
e _ ~oo~o~ o~oo o Y~o~ ~tr~0~
O Nl ` t 1~ ~ ~ t O ~ `O ~ ~ llU O
~ ~ ~ e ~ o ~3 o X I b b h O 0 8 ,-4 ~
X ~ ~ ~ .
~s 3 .. ,~ ~ ~ 9 C 5 ~ ~
__ ~ ~ o _ o ~
O lil O ~ t O
Q, a ~, 0 0 .. ~
u b j~ 1 9 ~ ~3 b 9 t.i 1~ E~ * e: O O O C
a a~ oo O ~r8~ lo - C
'0 ~I . O ~ 110 ~9 1~
q .. u b ~ d :~ O a ~ a o ; ~ ~ ~ ~~11~ ~_~ b I 3 z~ ~ ~ ~ O ~ s~ ~ s ~ ~ ~ a ~
~ ~ ~ O O U~ ~ O--~ O b ~ b ,~ ~ ~ O b b ~ O
~s ~ 4, ~ u~ a~ 8~ 8 ~ ,u ~ ~_ _ O ~ IC ~1 MI ,æi: ~ _ _ ~ ~ _ .. . h~ D-9107 EXA~PLE 44 In a manner similar to Examp Le ~, the acrylo-nitrile-capped polyoxyalkylene composition product having the average forrnula H C = CHCH O (C H O) CH CH CN
2 2 2 4 7.5 2 2 was prepared using about 4000 grams of H C ~ CHCH O(C H O) H;
about 800 grams of toluene; about 24 grams o 10 wt. % aqueous Me ~OH and about 572 grams of acrylonitrile.
The reaction was conducted by Rdding the acrylonitrile dropwise to the reaction mixture over 40 minutes while the reaction temperatur~ was maintained with an ice bath at about-18C. After all of the acrylonitrile had been added and the exothermic reaction completed the reaction mixture was then warmed to ro~m temperature and allowed to sit for two hours and then was neutralized with about 12 grams of 85 wt. % aqueous H PO , ~hout 200 grams of Mag~esol was added to the ne~tralized mixture and the mixture allowed to stand over night. The reaction mixture was then filtered ~nd the filtrate desolvated.
Analysis of the desired polyether product ~howed about 0.27 wt.
% residual hydroxyl groups and ~hat about 93 p~rcent of the starting polyether was cyanoethylated.

Into ~ 500 ml., 3 necked flask equipped with a mechanical stirrex, thermometer ~nd N cover was charged .~ about 39.7 gr~ms (0.12 mole) of the hydrosiloxane polymer product of Example 41 having the avera~c formula Me SiO(Me 5iO) ~MeHSiO) tMeSiO) SiMe : 3 2 6 6 ' 8 3 (eH ) CN

9g.
~.

2~
. D-9107 (Si-H Intermediate Fluid I), ~bout 70.8 grams (0.156 mole) of the acrylonitrile-capped polycxyalkylene p-oduct of Example 44 having the average for~lla H C ' CH~H O (C H O) CH CH CN
2 2 2 4 7.5 2 2 (abo~t 30% excess o theory); and about 100 ml. of toluene. The reac~ion mixture was heated to about 85C. at which time 50 ~arts per million of platinu~
as chloroplatinic acid ca~lyst (about 0.0005 gram) was added. The reaction exothermed to 103C. and was stirred over night as it cooled to room temper~ture.
The reaction mixture was analyzed for residual Si-H and yielded 0.0 cc H /2 ml. aliquot, indicating - that the reaction had gone to completion. The reaction mixture was then neutralized by adding about 2 grams of NaHCO and 1 gram of ATTACOTE and s~irring for one hour. The neutralized reaction mixture was ~hen filtered ; and ehe filtrate desolvated b~ sotary evaporation at 50C/l mm Hg. The desired acryloni~rile-capped polyoxyalkylene-polysiloxane product was a liquid having the ~verage formula Me SiO(Me SiO) (MeSiO) (MeSiO) SiMe 3 2 66 1 ~ 3 CH CH CH CN

H CH CH O(C H O) CH CH CN
2 2 ~ 2 ~ 7.5 2 2 The siloxane product, designated herein as Surfactant M, had a Bro~kfield viscosity tat room temperature)of abou~

400 centipoises and a GPC aver3ge molecular welght of about 4,600.
, 0.

,~ .

~i EXh~PLE 46 Into a 500 ml., 3-necked flask equipped with a mechanical stirrer, thermometer and N cover was charged about 29.5 grams (0.12 ~ole) of the hydrosiloxane polymer product of Example 42 having the average formula Me SiO(Me SiO) CMeHSiO) (Me$iO) SiMe 3 ~ 6 6 1 4 (Si-H Intermediate Fluid II); about 70.8 grams (0.156 mole) of the acrylonitrile-capped polyoxyalkylene product of Example 44 having the average formula H ~ = CHCH O(C H O) CH CH CH CN
2 2 2 4 7.5 2 2 2 (about 30% excess of theory); and about 100 ml. of toluene.
The reaction mixture was he~ted to about 85C at which time 50 parts per million of platinum as chloroplatinic acid catalyst (about 0.0005 gram) was added. The reaction exothermed to 100C. and was stirred overnight as it cooled to room temp~ra~ure. Analysis of the reaction mixture indicated that the reaction had gone to rompletion. The reaction mixture was then neu~ralized by adding ~bout 2 grams of NaHCO and 1 gram of ATTACOTE and stirring for one hour. The neutralized re~ction mixture was then filtered and ~he filtrate desolvated by rotary evaporation at 50~C/l mm Hg.
The desired acrylonitrile-capped polyoxyalkylene-polysiloxane product w~5 a liquid ha~ing the average formula 101.

. di~
.

.. ... . ..... , . ~ .. ~ . .. .-- .. ... ... . . ... . . .. .
.. .. . .. . . . . . . . . . ,. . ., ., .. . , ., . . -- .

~ ~ ~ 4 ~ ~ ~ D-9107 Me SiO(Me SiO) (MeSiO) (Me~iO) SiMe ~}l CH C~l CN

CH CH CH O(C H O) CH CH CN
2 2 2 2 4 7.5 2 2 The siloxane product, designated herein as Surfactant N, had a Brookfield viscosity (at room temperature) of about 175 centipoises and a GPC average molecular weight of about 3,300.

Into a 500 ml., 3-necked flask equipped with a mechanical stirrer, thermometer and N cover was charged about 35.4 grams (0.12 mole) of the hydrosiloxane polymer product of Exampl~ 43 having the average formula Me SiO(Me SiO)10(MeHSiO) (MeSiO) SiMe (CH ) CN

(Si-H Intermediate Fluid III), about 70.8 grams (0.156 mole) of the acrylonitrile-capped polyoxyalkylene product of Example 44 having the average formula H C ~ CHCH O(C H O) CH CH CH CN
2 2 2 4 7.5 2 2 2 (about 30% excess of theory); and about 105 ml. of toluene.
The reaction mixture was heated to about 85C at which time 50 parts per million of platinum as chloropla~inic acid catalyst (about 0.0005 gran~ was added. The reaction ex~thermed and was stirred over night as it cooled to room temperature. Analysis of the reaction mixture in-dicated that the reaction had gone to completion.
The reaction mixture was then neutralized by adding about 2 grams of NaHCO and 1 gram of ATTACOTE and stirring 10~ .

:

for one hour. The neutralized reaction mixture was then filtered and the filtrate desolvated by rotary evaporation at 50C/5~m Hg. The desired acrylonitrile~eapped polyoxyalkylene-p~lysi~.oxar.e product was a liquid having t:he a~eragc formula Me SiO(Me SiO) (Me5iO) CMe~iO) SiMe CH CH CH CN

CH CH CH O(C H O) CH CH CN
2 2 2 2 4 7.5 2 2 The siloxane product, deslgnated herein as Surfactant 0, had a Brookfield visco~ity ~at room temperature) of about 505 centipoises and a GPC average molecular weight of about 5,200.

In these exæmples, flexible polyester polyurethane foam containing a flame retardant w~re produced using the above de~cribed Surfactants M
through O of this in~ention ~and the above de~cribed Control Surfactant AA) AS the respective foam stabilizin~ surfactant component of the foam~producing reaction mixture. Said foam-producing reacti~n mixture was the same as Foam Formulation A described abo~e and the foams were prepared and ~amples analyzed following the above described procedures. The results a~e given in Table VII which follows.

103.

`104. D-9107 ~ C

v K `
_ C'JI
~ _ C
_ v j ~ ~D C r~
~ ~ wl ~1 Q~

h ' ~1 " `
Cl C~

-- ¦

,~

21 ~1 ~ r ~ C

~ e ro ~j ~ ~ rl o c 31 0 0 0 _ ~v1 vl v ~1 ~ z ~ ~ .
U

C _ C

.. ~

~ lL4i~32~
r D-9107 The data in Table VII above demonstrates that the acrylonitrile-capped poly~xyalkylene-polysiloxane polymers of this invention are effective 6tabilizers for flexible polyester polyurethane foam that contain a flame-retardan~.
` EXAMPLES 52-54 - In these examples, flexible polyester polyurethane foam, not containing 8 flame-ret~rdant, were produced using the above described Surfactants M
10and N of this invention (and the above described Control Surfactant AA) as the respective foam stabilizin~
surfactant component of the foam-producing reaction mixture. Said foam-producing reaction mixture was the same as Foam Formulation B described above and the foams were prepared and samples analyzed following the above described procedures except no flame-retardant was used. The results are given in Table VIII which fallows:

.

.
c 105.

' ~1 h ' ~ ~
~ . . .

? ~
U~ U~
, .~ ~ ~ o C ~
,~, ,, ~( :~
.; ~ ,1 3 ~ ~ .,.1 ~' ~ P
~i ~ ~ Y~
~ ~ U~ O _~ ~
.. ~
-' U~
" 01 CJ ~)~11'1 ~.3 ~ O~

~ O
., J~ ~
~ ~ U~ U~
r~
2 C\ O--~ .~:
~ .
~3 ~
~ V

~, ~ z ~ a ~,~
',. , ~
- G~ U~ .

~æ ~u.ul . . .. .. .. , .~" .. ~ . , .. . .. ., .. , .. ,,, .. . . ,,.. , .,, ".. ,.~
. .
, ~ d~ D-9107 The data in Table VIII above demonstrates that the acrylonitrile-capped polyo~yalkylene-poly-siloxane polymers of this invention are effective stabilizers for flexible polyester polyurethane foam that does not contain a flame-retardant.
~XAMPLE 55 An acrylonitrile-capped polyoxyalkylene composition was prepared in a similar manner as des-cribed above by reacting a mixture of about 350 lbs. of a polyet~er having an average molecular weight of about 390 (allyl analysis) and the average composition for-mula H C=CHCH O(C H 0) H and about 52.5 lbs. of acrylo-2 2 2 4 7.5 nitrile (5~/O excess of theory) along wi.h about 135 grams of 10% aqueous H P0 . The reaction was conducted at 26C to 32C over 3 l/2 hours. Then about 20 lbs. of benzene was added, the reaction mixture~ vacuum stripped at about75G ~2 mm Hg. and filtered, to yield the desired allyl and acrylonitrile endblocked polyether having the average composition formula H C~CHCH O(C H 0) CH CH CN
' 2 2 2 4 7.5 2 ?
(Anal. 9.04% ~llyl).
An acrylonitrile-polysiloxane polymer was then prepared in a ~imilar manner as described above using about 197 lbs. of the above allyl and aryloni~rile endblocked polyether product, about 30 lbs. of isopropanol, abou~ 14 gal. of toluene, about 40 lbs. of hydros~loxane polymer having the average~compos;tion 107.

.. . .. ,. , .. , .. . ....... ..... , .. , . ... , , ... , ~ , .. .... . . . . . . . .. , ~ . .. .... .. .... ...... ... ..
.. .. . ....... .

formula Me SiO (Me SiO) (~leHSiO) SiMe 3 2 5.2 7.6 3 ~Anal. Si-H, 17~ ccH /gr.; Visc. 7.1 centistoke) and about 84 ml. of chloroplatinic acid catalyst (10% ethanol-1,2 dimethoxy-ethane solution). The reaction was conducted at about 95~C to 104~C for abuut 12 hours after which analysis of the reac~ion mixture for residual Si-H
showed 1.4 ccH /gr. The reaction mixturc ~-as then sparged with ethylene for one hour an~ analysis yielded only a trace of Si-H indicating the reaction was essentially completed. The,reaction mixture was then vacuum stripped at about 29C./80-120 mm Hg. to remove the toluene and isopropanol, cooled and filtered. The desired acrylonitrile-capped polyoxyalkylene-polysiloxane product was an amber liquid,~aving the average composition formiala Me SiO~Ie Si~) ~MeSiO) SiMe 3 2 5.2 ' 7.6 3 CH CH CH O(C H O) CH CH CN
2 2 2 2 4 7.5 2 2 This siloxane product, designated herein as Surfactant P, had a Brookfield viscosity (at 25C) of about 372 and ~ j specific gravity of 1.089. Analysis also showed 6.4C/oCN, 2%
allyl and 0.53% OH.

In accordance with these examples sbove described Surfactant P was blended with various organic compounds to provide illustrative solution~compositions of this invention. These blended compositions are de-108 .

... .. ~ . ~, . .. . .. . . .. .

~ . D-9107 .
signated herein as Blended Surfactants Q and R. The solution composition of said blended surfactants is given ~n Table IX which is as follo~.~s:

: TABLE IX
' Example Blended - Wt.% of Number Surfactant Components Components~
. .
56 Q Surfactant P 35 Anionic /1/ 35 Tall O~l ~5 Hexylene Glycol 15 57 R Surfactant P 52 Nonionic /2/ 10.4 Tall Oil 15.6 Hexylene ~ , Glycol 21 * Ionol was also present in Blended Surfactants Q (10000 ppm) and R ~1%).
/1/ An organic anionic surfactant which is a sodium sulfonate of a hydrocarbon mixtur~ available commercially as "Petronate L" CWitco Chemical Company).
/2/ An organic nonionic surfactant in which the hydrophope is a mixture of C 1 to Cl alcohols and the hydrophile is e~hylene oxid~ ~avg. ~ molslmol of hydrophobe).

EX~IPLES 58 _67 In accordance with these examples, a series of machine scale flexible polyester urethane foams were prepared ~mploying above-described Blended Surfactants Q and R of this invention land above described Control Surfact~nts AA and CC, not of ~h~s invention) as the foEm stabilizing component~ of Foam Formulations C and D which contained 5.0 and 3.6 par~s water pe~; 100 parts of 1~9.

poly~ter polyol, res~ectively. The purpnse of th~se examples was to detenmine whc~her the acrylonitrile-capped polyoxyalkylene-polysiloxane polymers of the invention as illustrated by Surfactant P contained in Blended Surfactants Q and R are capahle of providing semicom~ercial size foam buns having acceptable physical properties. In these exEmples, a Hennecke UBT-63 high pressure conti~uo~ polyurethane foam ~achine was used to which ~he following three streams was added ~1) the polyester polyol; (2) the acrivator stream containing water, amine catalysts and foam-stabilizing surfàctants; and (3) the polyisocyanate reactant. The mixer speed was about 5000 revolutions per minute and the head pressure was 12-17 pounds per square inch. At ambient temperature the emerging foam mixture was poured onto paper on a continuou61y~moving conveyor belt. The foams were allowed to set and cure in the form of large slabs (12 feet in length, 22 inches wide and 18 inches high). After 24 hours of aging at ambient temperatures the foams were cut and submitted for physical property measurements. In usin~ Blended Surfactants Q and ~, clear homogeneous aqueous premixtures were obtained when the water and amine catalysts of the foam formulations were combined therewith. The com~osition of Foam Formulations C and D, the amount of the blended surfactants ' f employed in each example, and the resuits are given in Table X and XI which follow.

110.

111. D-9107 ~10 U~~ ~ O t'') ~ ~ ~1 N
O ~ U-) OO O t~ O~ r~l O CD `O ~ Itl ~rl o 0~ O

~ ou~ o ~ ~ ~ , O ~1~ 00 0 N O l"\ ~ 1 ~ O O ~ N ~ ~ N V~
~.
~l o V~~ N O ~ ~ N ~ O ~ O ~
_1 1o o~ U~ O O O ~i O t~ i O 1~ i 0~O ~ O

~ ~ O OUl C~ o t~ o ~ ~ C~
Q _I o U~ - O o ~ o f ~ o ~ ,~ u~ ~ o ~ o ~oo ~ o~
l~ ~ ~, u~
;~
o o o o ~ ~ ~ ~ U

O I O ~ u~ I~ O ~ ~ _ ~ O ~ 0 O ~ ~
X ~ .
c~looo or~ ~ ~o r~
l o~uir.ir i ~io ~ ~o o~ o~O e e ~ . o o . CO ~

,~, 2~ t33 .. .

c~J ~ o ~ u~ o ~ u~ o o oo ~ r--u~
~ I o ~ ~ ~ ' ' ~ o ~ t7 o to .,, 1~ , ..
X
~' ~-~ ~a` , U) D O 0 0 0 ~ u~ ~O U~ 1~ ~ ~0 ~ ~ ~ u~
~n o u~ i O ~ ~ i ~ O ~ ~ ~ ~ C;~

a ~C

o o O ~ ~ O ~ ~ ~ ~ O ~ ~ 00 0 C~ ~ O
X

6 Z r V
oq _ o 3 0 ~ a~ ~ X

,~, e ~ e,, ~ ~
~S ~ ,n '' ~ )o ~ ~ o ~ C q~ ~ ~ ~
. ~ v ~ v ~ ~~ rl ^ ~ ~ S~ C
ta ~ ~ E; E e ~ ~JJ,n ~ d ~1 :i~!; ~ P'~ ~ C ~ ~ P. V~ ) , a~ ~ E~ ~1 O ~
5~ O ~ c~ ~ o_~ u ~ ~1 1~ ~ aJ ~ 0 ~ U~ ~1 U, ~3 ~ ~ E~ ;~ t:4 ~ ~ ~ ¢ ~;
C~ ~ 1 E3 ~ 1.. )~ 1 bS) ~ 6 ~ ~ ,~ ~ ~ ~a ~ ~0 h~_~
X o o t) 0 o I d) ~1 rl O O O ~ ~1 0 11~ C~ ~
tl~ ~4 ~ P~ ) ~ C~ ~4 ~ Pq ~ ~ E-1 WE-~) _ _ .

`. ! ' .

~ e data of Tables X and XI above demonstrate that the acrylonitrile-capped polyoxy-alkylene-polysilo~ane polymers of this invention posses6 a highly desirable combination of properties ~uch as ~he ability to form clear homogeneous premixes, potency and the ability to provide over a wide processing lstitude flexible polyester polyurethane foam having good physical prop~rties.
Various modifications and variations of this invention will be obvious to a worker skilled in the art and it is to be understood that such modifications and variations are to be included within the purview of this application and the spirit and scope of ~he appended claims.

~, ., 113 .

Claims (6)

WHAT IS CLAIMED IS:

1. An acrylonitrile-capped polyoxyalkylene compound having the average composition formula:
R'(X)q(OC3H6)n(OC2H4)mOCH2CH2CN
wherein X is a bridging group selected from the class consisting of -CO- and -NHCO-; wherein R' represents a monovalent olefinic alkylene radical containing from 2 to 6 carbon atoms; wherein q has a value of 0 or 1, m has a value of from 4 to 30; and n has a value of from 0 to 10.

2. A compound as defined in claim 1, wherein R' is an allyl radical, q is 0, m has a value of 4 to 15; and n is 0.

3. A compound as defined in claim 1 having the average composition formula:
H2C = CHCH2O(C2H4O)7.5CH2CH2CN

4. A compound as defined in claim 1 having the average composition formula:

H2C' = CHCH2O(C2H4O)7.9CH2CH2CN

5. A compound as defined in claim 1 having the average composition formula:
H2C = CHCH2O(C2H4O)21.2(C3H6O)5.35CH2CH2CN.

6. A compound as defined in claim 1 having the average composition formula:

H2C = CHCH2O(C2H4O)9.5(C3H6O)0.8CH2CH2CN.