Note: Descriptions are shown in the official language in which they were submitted.
D 9107
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
- - ,, .. , , . ... .. . ~. .
-
D-9107
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
R4 R5
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~
29
D-9107
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.
D-9107
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.
...... . ~ . .. , . , . , . . . . _ .. . .. _ .. . . . .. . . . . . .. . . .. ..
.., . _ .., .. .-- --~
D-9107
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
D-9107
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)
Q E2
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
D-9107
~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~ .
D-9107
are: ethylene (-CH CH -); 1,3-propylene or trimethylene
(-CH CH CH -); 1, 2-propylene [-CH CH(CH )- ]; and
2 2 2 2 3
~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.
~,
.. ... , . ,, . , ., ~ . .. .. . . . . . ... . . .
D-9107
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
21 1 2 4 CH
H2C~ ~CH2
jS~
O O
; CH3
2l 1 2 4
H2C~ /CH2
// ~
1 CH
H2C_fH--o ~ CH2CH--CH2 S~02l~
2 ~ ~ 2
0~ ~
, CH3
H2f IH - 0---CH2CH2CH2 SiO2/2
\ ~
,, /~S~O .
~ 22.
- . . ..
D-9107
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
R6 R7
(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
CH3
O -CH2CH2-.SiO2/2
CH
0/--\~1 ~CH2CH2CH2-SiO2/2
CH3 CH3
." ~ I I
H CHCH -SiO2/2
?. 2
24.
.
D-9107
CH3
O h`--CH2CH20-SiO2/2
CH C~l
3 1 3
o~-CH2CHO-SiO2/2
CH3 3
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
-R2CN
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~
D-9107
(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.
D-9107
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
2 E2
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)
3 E
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~
D-9107
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
36
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~
D-9107
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
D-9107
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.
~ -, .
D-9107
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 . .
D-9107
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.
D-9107
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.
.
D-9107
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 .
... . . ~ . .. . ,.. . . ... .. , , . . .. . ~ .. .. . . . ... .. . . . ..... . . . . .
D-9107
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.
D-9107
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.
*.
D-9107
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.
~,.
'.`
.,' ~ ' ' .
D-9107
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
D-9107
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~
D-9107
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
0 I O GH3 O
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.
D-9107
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
62
f~ '
D-9107
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.
D-9107
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.
D-9107
"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~
D-9107
/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.
.
. ~ . _~ ~_ ~ _,_. _ ,,_ ~. _ . .
D-9107
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
3 4
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
3 4
, 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.
EXAMPLE 5
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
3 4
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.
EXAMPLE 7
In a manner s~milar to Ex~mple 6, the
acrylonitrile-capped polyxoyalkylene composition produc~
having the avera~e formula
.. . .. . .... ... . ..
D-9107
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.
EXAMPLE 8
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
2 2 2 4 10 2 2
- :.
~ 73.
D-9107
was prepared using about 300 grams of H C = CHCH 0(C H 0) H
2 2 2 4 10
(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)
- 4 4
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
3 4
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
D-9107
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.
EXAMPLE 10
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
4 4
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.
.
... .. .... .......
D-9107
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
2 5 7 3
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.
EXAMPLE 17
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
3 2 5 8 3
(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
3 2 5 1 8
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
3 2 5 8 3
(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.
-:.
.--. ... ., .. ~ . ...... .
D-9107
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.
EXAMPLE L4
.
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
3 2 5 8 3
(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
2 2 2 4 10 2 2
(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.
.
.
D-9107
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
3 2 5 8 3
(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
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
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.
EXAMPLE 16
-
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
3 2 5 6 3
(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.
- EXAMPLE 17
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
3 2 5 10 3
(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
3 2 5 1 10 3
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.
EXAMPLE 18
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
3 2 3 3
(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
D-9107
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.
D-9107
(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
01
O ~ o
N N N N N ~1 N ~1 ~ r~ r'7
88
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.
89
.. , . .. ... , . , . .. , .. .. .. .. , . .. ., .. , . .. . . . . . . -
.
D-9107
.,,
~ 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 .
.. . . . . . ... .. ..... . ,. ,.. . . . .. ..... .......... , , .. ~.. .
9 D - 910 7
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.
D-9107
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.
EXAMPLES 41- 43
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
2 3
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
2 4
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
.
. ~ . , .. ,~ ... ..... " , .. .... .. ....... .. .. . ....... . .. ... .. . ........... ... .
D-9107
Reactant (1): 16.2 grams, correspondin~ to 0.1 mole of
Me SiOSiMe or 0.2 mole-equivalents of
3 3
Me SiO
3 1/2
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
2 3
~. 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: ~ _ _ ~ ~ _
93
.. . 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.
EXAMPLE 45
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
2 3
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
2 2 2
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
D 9107
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
2 3
(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
3 2 66 1 4 3
~}l CH C~l CN
2 2 2
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.
EXAMPLE 47
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
2 3
(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~ .
:
D-9107
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
3 2 106 1 4
CH CH CH CN
2 2 2
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.
EXAMPLES 48-51
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.
29
`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.
'
9107
~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.
.. . .. ,. , .. , .. . ....... ..... , .. , . ... , , ... , ~ , .. .... . . . . . . . .. , ~ . .. .... .. .... ...... ... ..
.. .. . ....... .
D - 910 7
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.
EXAMPLES 5 6 - 5 7
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.
D-9107
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
D-9107
.. .
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
0 V
'' ~ )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-~) _ _
.
`. ! ' .
D - 910 7
~ 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 .
