Process for the preparation of organopolysiloxane surfactants

An improved process is provided for the preparation of siloxane-oxyalkylene block copolymer surfactant compositions which utilized a hydrosilation reaction with high boiling point polar polyols as the reaction solvent. The reaction solvent need not be removed from the block copolymer, particularly when the block copolymer is used as a surfactant for polyurethane foam formulations. Dipropylene glycol is the preferred polar solvent and when used in the preparation of the surfactants need not be removed when the surfactants are employed in the preparation of urethane foams.

FIELD OF THE INVENTION 
This invention relates in general to an improved process for the 
preparation of organopolysiloxane surfactants. In one aspect, this 
invention is directed to a process for the preparation of improved 
siloxane-oxyalkylene copolymer compositions. In a further aspect, the 
invention is directed to siloxane-oxyalkylene copolymers that are suitable 
for use as surfactants in urethane foam applications. 
BACKGROUND OF THE INVENTION 
The preparation of siloxane-oxyalkylene copolymers by the hydrosilation 
reaction of an organohydrogensiloxane and an olefinically substituted 
polyoxyalkylene is well known and reported in the literature. The 
hydrosilation reaction is typically performed in a low molecular weight 
volatile hydrocarbon solvent such as benzene, toluene, xylene or 
isopropanol so as to aid in handling the reactants, to moderate an 
exothermic reaction or to promote the solubility of the reactants. 
Less typically, the hydrosilation reaction between the 
organohydrogenpolysiloxane reactant and the olefinically substituted 
polyoxyalkylene reactant may be conducted without a solvent such as 
disclosed in U.S. Pat. No. 3,980,688 or conducted in an oxygen containing 
solvent such as an ether, a polyether, or a lower or higher molecular 
weight alcohol. 
For instance, U.S. Pat. Nos. 3,280,160 and 3,401,192 disclose the 
preparation of copolymers in n-butylether and in a 50/50 mixture of 
isopropyl alcohol/toluene, respectively. Also in U.S. Pat. No. 4,122,029 
the use of isopropyl alcohol is disclosed and in U.S. Pat. No. 3,518,288 
the patentee teaches the use of n-propanol/toluene as a suitable solvent 
for the preparation of siloxane-oxyalkylene copolymers. 
In the majority of the aforementioned processes, the hydrocarbon solvent is 
removed after the hydrosilation reaction is completed, since in most 
cases, the solvent is too flammable, toxic or otherwise detrimental to the 
final product or further processing steps in which the copolymer is 
utilized. Thus, in the processes disclosed in most of the above patents 
the solvent was removed from the reaction product after completion of the 
hydrosilation. A few instances have been reported in the literature where 
for one reason or another it was not necessary nor desirable to separate 
the copolymer from the reaction medium. For example, U.S. Pat. No. 
4,520,160 disclosed the use of saturated higher alcohols as a reaction 
solvent which purposely need not be removed from the resulting copolymer 
when it is used subsequently in personal care compositions as emulsifiers. 
U.S. Pat. No. 3,629,308 also disclosed the use of polyethers having a 
formula R'O(C.sub.3 H.sub.8 O).sub.x H where R' is a lower alkyl group and 
x has a value of from 1 to 20 as a suitable solvent for the preparation of 
copolymers. When the resulting siloxane-oxyalkylene is to be used as a 
stabilizer for urethane foams, the patent teaches that it is not necessary 
to isolate the copolymer from the solvent but rather to use it as a 
solution. 
In many instances, however, the solvent does not enter into any further 
reactions but remains in the final product as is, and hence, there is no 
need for its removal if it does not adversely affect the product. Thus, in 
some products, such as personal care products it may even be beneficial to 
have some of the solvent present in the final product. However, if the 
copolymer is to undergo further reactions before preparation of the final 
product is complete, its presence might adversely affect such reactions 
and hence its removal after the hydrosilation step is desired. For 
example, if one were to use copolymers containing monohydric higher 
alcohols in urethane foam applications, these alcohols will enter into the 
urethane reaction and act as reaction chain terminators in a detrimental 
fashion because they contain only one hydroxyl group. Also as previously 
indicated, such solvents may be toxic or otherwise undesirable in further 
processing of the copolymer. 
It is therefore an object of the present invention to provide an improved 
process for the preparation of siloxane-oxyalkylene copolymers. Another 
object of this invention is to provide a process for the preparation of 
siloxane-oxyakylene copolymers which are useful in the formulation of 
urethane foams and wherein it is not necessary to remove the reaction 
solvent. A further object of the invention is to provide a process for the 
preparation of urethane foams which have improved flow properties and 
other desirable features. These and other objects will readily become 
apparent to those skilled in the art in the light of the teachings 
contained herein. 
SUMMARY OF THE INVENTION 
In its broad aspect, the present invention is directed to an improved 
process for the preparation of siloxane-oxyalkylene copolymers, their use 
as surfactants in the preparation of urethane foams, and the resulting 
foams obtained therefrom. 
These copolymers are prepared by a hydrosilation reaction between an 
organohydrogenpolysiloxane and an olefinically substituted 
polyoxyalkylene, in the presence of a polar high boiling point polyol 
containing more than one hydroxyl group and, optionally, in the presence 
of a carboxylic acid salt. The saturated polar high boiling point polyol 
and carboxylic acid salt not only aid in the preparation of the copolymer, 
but if left in the copolymer, aid in the subsequent handling and serve as 
a necessary component of a composition containing the siloxane-oxyalkylene 
copolymer. 
The process of the present invention comprises the steps of: 
(1) forming a mixture of: 
(a) an organohydrogensiloxane having the average formula: 
EQU R.sub.a H.sub.b SiO.sub.(4-a-b)/2 
(b) a polyoxyalkylene having the average formula: 
##STR1## 
wherein R, R1 and R2 are as hereinafter indicated, (c) a liquid, 
saturated, polar, high boiling point, polyol solvent, and 
(d) optionally a carboxylic acid salt reaction promoter, 
(2) maintaining the mixture in an inert atmosphere to a temperature which 
does not exceed the temperature at which the organohydrogensiloxane reacts 
with the solvent, 
(3) adding to said heated mixture, a catalytic amount of a noble metal 
hydrosilation catalyst, 
(4) maintaining the temperature of said mixture below about 92.degree. C., 
and 
(5) recovering said surfactant in admixture with residual polyol solvent. 
DETAILED DESCRIPTION OF THE INVENTION 
As indicated above, the present invention provides an improved process for 
the preparation of organosiloxane copolymer surfactants which are 
particularly useful in the preparation of urethane foams. The process 
involves the hydrosilation reaction of an organohydrogenpolysiloxane and 
an olefinically substituted polyoxyalkylene, in the presence of a polar 
high boiling point polyol containing more than one hydroxyl group, and 
optionally in the presence of a carboxylic acid salt. The saturated polar 
high boiling point polyol and carboxylic acid salt not only aid in the 
preparation of the siloxane-oxyalkylene copolymer, but the former when 
left in the copolymer, aids in the subsequent handling and serve as a 
necessary component of a composition containing the siloxane-oxyalkylene 
copolymer, particularly when such copolymers are used as surfactants in 
the preparation of urethane foams. 
The organohydrogensiloxane compounds employed in the present invention for 
the preparation of the surfactants are those represented by the formula: 
EQU R.sub.a H.sub.b SiO.sub.(4-a-b)/2 
wherein R denotes a monovalent hydrocarbon radical free of aliphatic 
unsaturation, a has a value of from 1 to 3.0, b has a value of from 0 to 1 
and the sum of a+b has a value of from 1.0 to 3.0. The 
organohydrogenpolysiloxane can contain any combination of siloxane units 
selected from the group consisting of R.sub.3 SiO.sub.1/2, R.sub.2 
HSiO.sub.1/2, R.sub.2 SiO.sub.2/2, RHSiO.sub.2/2, RSiO.sub.3/2, 
HSiO.sub.3/2 and SiO.sub.4/2 provided, of course, that the 
organhydrogenpolysiloxane contains sufficient R-containing siloxane units 
to provide from about 1 to about 3.0 R radicals per silicone atom and 
sufficient H-containing siloxane units to provide from 0.01 to 1 
silicon-bonded hydrogen atoms per silicon and a total of R radicals and 
silicon-bonded hydrogen atoms of from 1.5 to 3.0 per silicon. The 
R-R.sub.3 groups represent hydrocarbon radicals. 
Illustrative of suitable R radicals are alkyl radicals such as methyl, 
ethyl, propyl, butyl, decyl and cycloaliphatic radicals such as cyclohexyl 
and cyclooctyl, aryl radicals such as phenyl, tolyl, and xylyl. R 
typically is the methyl radical. The olefinically substituted 
polyoxyalkylene reactant which can be employed in the process of this 
invention has the formula: 
##STR2## 
wherein R.sup.1 denotes an alkylene group containing from 3 to 6 carbon 
atoms; R.sup.2 is selected from the group consisting of hydrogen an alkyl 
group containing one to five carbon atoms, an acyl group containing 2 to 5 
carbon atoms or a trialkylsilyl group, preferably R.sup.2 is hydrogen or 
methyl group or acetyl group. Z has a value of 0 to 70 and w has a value 
of 0 to 120. The olefinically substituted polyoxyalkylene may be a blocked 
or randomly distributed copolymer. 
In contrast to the prior art processes, the present invention utilizes a 
liquid saturated, polar, high boiling point polyol solvent in which the 
hydrosilation reaction is conducted and which need not be removed from the 
reaction mixture, particularly when the copolymer reaction product is 
subsequently used in the preparation of urethane foams. 
The particular solvents which are employed in the present invention are 
saturated polyols containing at least about 4 carbon atoms, two or more 
hydroxyl groups, which have a boiling point of greater than 175.degree. C. 
at atmospheric pressure and which meet the definition defined by the 
formula below. The solvents are inert to the reactants and are essentially 
non-toxic. These solvents are for the most part composed only of carbon, 
hydrogen and oxygen and are aliphatic, cycloaliphatic or aromatic polyols. 
The polar solvents of the present invention can be defined by the 
following equation: 
##EQU1## 
wherein: H=weight fraction of hydroxyl (OH) in the solvent molecule. 
E=weight fraction of ethylene oxide units (CH.sub.2 CH.sub.2 O) in the 
solvent. 
Illustrative polar, high boiling solvents which can be used in the practice 
of the present invention, include, but are not limited to, the glycols, 
such as, diethylene glycol, 3-hydroxypropyl ether, diisopropylene glycol, 
dibutylene glycol, di-tertiary butylene glycol, 
1,6-dihydroxymethyl-cyclohexane, 1,6-dihydroxymethoxy-cyclohexane, 
1,4-dihydroxyethoxy-cyclohexane, 1,6-dihydroxymethyl benzene, 
1,4-dihydroxyethoxy benzene, and the like. The preferred polyol for use in 
the process of the present invention is dipropylene glycol. 
As indicated above, it is important that the polyol have a boiling point 
greater than about 175.degree. C. 
As previously indicated, the hydrosilation reaction is conducted in the 
presence of a noble metal hydrosilation catalyst. Thus, the hydrosilation 
reaction between the organohydrogenpolysiloxane and an olefinically 
substituted polyoxyalkylene reactant is facilitated by using a catalytic 
amount of a noble metal-containing catalyst. Such catalysts are well known 
and include platinum, palladium and rhodium-containing catalysts. 
Chloroplatinic acid is particularly preferred. 
The catalyst is employed in an catalytic amount sufficient to promote the 
hydrosilation reaction. In practice the amount of catalyst will usually be 
within the range of from about 1 to about 100 ppm of noble metal based on 
the total parts of the mixture of reactants and solvent. 
The hydrosilation reaction, as previously noted, can be optionally 
conducted in the presence of salts of carboxylic acids as promoters, and 
which can be present when using polar solvents for the hydrosilation of 
polyethers with organohydrogenpolysiloxanes. A low, but sometimes adequate 
level of carboxylic acid salts may already be present in olefinically 
substituted polyoxyalkylenes due to inadvertent exposure to traces of 
oxygen during subsequent capping of hydroxyl groups with allylic, methyl 
or acyl groups. In such instances, the use of the acid salt may not be 
necessary. However, it has been noted that if the polyoxyalkylene reactant 
is free of oxidation by-products, the use of a promoter is necessary in 
conjunction with the high boiling polyol if an efficient and rapid 
reaction of the ogranohydrogenpolysiloxane and polyoxalkylene reactant is 
to occur. These promoters can be represented by the formula: 
EQU RCO.sub.2 M 
wherein M is H, alkali or alkaline earth metals or alternately ammonium or 
phosphonium salts and R represents a monovalent hydrocarbon group of from 
2 to 20 carbon atoms. The preferred carboxylic acids contain 3 or more 
carbon atoms and are composed of carbon, hydrogen and oxygen. Particularly 
preferred are the monocarboxylic acids containing from about 3 to about 20 
carbon atoms. Due to traces of carboxylic acid impurities in the 
polyoxyalkylenes it is sometimes only necessary to add some source of M as 
an amine or weak base such as sodium bicarbonate to achieve the desired 
effect. The promoter level needs to be at least about 100 ppm and 
typically at about 0.1 weight percent of reactants. Concentrations of from 
about 100 ppm to about 10,000 ppm can also be employed and the actual 
amount will be dependent to some degree on the particular acid salt 
employed. 
By conducting the hydrosilation reaction in the manner indicated above, and 
employing the saturated high boiling point polyol and carboxylic acid 
salt, improvements are obtained in one or more aspects of the reaction, 
such as reaction rate, reaction yield, reaction selectivity, reaction 
processes or reaction product processing in urethane foam applications. 
For example, when dipropylene glycol is used it has been found that the 
use of at least 10 percent by weight, based on the weight of the 
reactants, of the polyol and 0.05 percent of an acid salt such as sodium 
oleate will aid in the handling of the reactants and moderate the reaction 
exotherms. Of course, amounts of saturated polar high boiling polyol 
larger than 10 percent can be used and greater than 0.05 percent of the 
sodium oleate can be used if desired. In general, from 5 to about 35 
weight percent and more preferably from about 15 to about 25 weight 
percent of the polyol have been found to give good results. 
The organopolysiloxane surfactants prepared by the process of the present 
invention are particularly useful and have been found to be excellent and 
efficient surfactants for the preparation of flexible polyether 
polyurethane foams. It has been found that the surfactants of this 
invention provide improved levels of performance to polyurethane foams and 
avoid the necessity of solvent removal from the reaction mixture in which 
the organopolysiloxane was prepared. Since a relatively non-toxic solvent 
is used and its removal from the reaction mixture avoided, the surfactants 
are prepared under desirable environmental conditions. 
In producing the polyurethane foams using the surfactants of this 
invention, one or more polyether polyols is employed for reaction with the 
polyisocyanate reactant to provide the urethane linkage. Such polyols have 
an average of at least two, and typically 2.0 to 3.5, hydroxyl groups per 
molecule and include compounds which consist of carbon, hydrogen and 
oxygen and compounds which may also contain phosphorus, halogen, and or 
nitrogen. Such polyether polyols are well known in the art and are 
commercially available. 
The organic polyisocyanates that are useful in producing flexible polyether 
polyurethane foams in accordance with the process of this invention are 
also well known in the art and are organic compounds that contain at least 
two isocyanate groups and any such compounds or mixtures thereof can be 
employed. The toluene diiisocyanates are among many suitable isocyanates 
which are commercially used in the preparation of foams. 
The urethane-foaming reaction is usually effected in the presence of a 
minot amount of a catalyst, preferably an amine catalyst and usually a 
tertiary amine. 
It is also preferred to include a minor amount of certain metal catalysts 
in addition to the amine catalyst in the component of the reaction 
mixture. Such supplementary catalysts are well known to the art of 
flexible polyether-based polyurethane foam manufacture. For example, 
useful metal catalysts include organic derivatives, of tin, particularly 
tin compounds of carboxylic acids such as stannous octoate, stannous 
oleate and the like. 
Foaming is accomplished by employing a small amount of a polyurethane 
blowing agent such as water in the reaction mixture, which upon reaction 
with isocyanate generates carbon dioxide in situ, or through the use of 
blowing agents which are vaporized by the exotherm of the reaction or by a 
combination of the two. These methods are well known in the art. 
The polyether-based polyurethane foams of this invention may be formed in 
accordance with any of the processing techniques known to the art such as, 
in particular, the "one-shot" technique. In accordance with this method, 
foamed products are provided by carrying out the reaction of the 
polyisocyanate and polyether polyol simultaneously with the foaming 
operation. It is sometimes convenient to add the surfactant to the 
reaction mixture as a premixture with one or more of the blowing agents, 
polyether, polyol and catalyst components. 
It is understood that the relative amounts of the various components of the 
foam formulation are not narrowly critical. The polyether polyol and 
polyisocyanate are present in the foam-producing formulation in a major 
amount. The relative amounts of these two components in the amount 
required to produce the desired urethane structure of the foam and such 
relative amounts are well known in the art. The blowing agent, catalyst 
and surfactant are each present in a minor amount necessary to achieve the 
function of the component. Thus, the blowing agent is present in an amount 
sufficient to foam the reaction mixture, the catalyst is present in a 
catalytic amount which is that amount necessary to catalyze the reaction 
to produce the urethane at a reasonable rate, and the surfactant is an 
amount sufficient to impart the desired properties as indicated in Tables 
I and II below. 
The polyurethanes produced in accordance with the present invention can be 
used in the same areas as conventional flexible polyether polyurethanes. 
For example, the foams of the present invention can be used with advantage 
in the manufacture of textile interliners, cushions, mattresses, padding, 
carpet underlay, packaging, gaskets, sealers, thermal insulators and the 
like. 
The following examples illustrate the best mode presently contemplated for 
the practice of this invention. 
Examples 1-4 below, employed one set of polyethers and were carbon treated 
prior to use in order to demonstrate the production of surfactants in a 
polar high boiling point polyol solvent without the presence of carboxylic 
acid salts. As the solvent level increased beneficial increase in foam air 
flow is obtained. The results are summarized in Table I.

EXAMPLE 1 
A well stirred mixture of 145.6 grams of an olefinically substituted carbon 
treated polyoxyalkylene having the average formula CH.sub.2 
.dbd.CHCH.sub.2 O(CH.sub.2 CH.sub.2 O).sub.18 (CH.sub.2 CHCH.sub.3 
O).sub.20.7 OCCH.sub.3, 34.4 grams of an organohydrogen polysiloxane 
having the average formula Me.sub.3 SiO(Me.sub.2 SiO).sub.60 
(MeHSiO).sub.7 SiMe.sub.3 and 20 grams (10 wt %) of dipropylene glycol was 
degassed by nitrogen sparge and heated to 85.degree. C. A solution of 
H.sub.2 PtCl.sub.6.6H.sub.2 O in ethanol was added to the mixture in 
sufficient amount to provide 15 ppm Pt. The heat source was removed and 
the exothermic hydrosilation reaction was allowed to proceed until no 
further temperature increase was noted. Heat was then added to the mixture 
as needed to keep its temperature at 85.degree. C. for 15 minutes. Care 
was taken never to allow the reaction pot to exceed 94.degree. C. A 
siloxaneoxyalkylene copolymer containing no gel particles was obtained The 
copolymer was then back diluted to a total of 40 weight percent with 
dipropylene glycol and a resulting viscosity of 686 cSt was obtained. 
EXAMPLE 2 
A well stirred mixture of 129 grams of an olefinically substituted carbon 
treated polyoxyalkylene having the average formula CH.sub.2 
.dbd.CHCH.sub.2 O(CH.sub.2 CH.sub.2 O).sub.18 (CH.sub.2 CHCH.sub.3 
O).sub.20.7 OCCH.sub.3, 30.6 grams of an organohydrogen polysiloxane 
having the average formula Me.sub.3 SiO(Me.sub.2 SiO).sub.60 
(MeHSiO).sub.7 SiMe.sub.3 and 40 grams (20 wt %) of dipropylene glycol was 
degassed by nitrogen sparge and heated to 85.degree. C. A solution of 
H.sub.2 PtCl.sub.6 H.sub.2 O in ethanol was added to the mixture in 
sufficient amount to provide 15 ppm Pt. The heat source was removed and 
the exothermic hydrosilation reaction was allowed to proceed until no 
further temperature increase was noted. Heat was then added to the mixture 
as needed to keep its temperature at 80.degree. C. for 1 hour. Care was 
taken never to allow the reaction pot to exceed 91.degree. C. A 
siloxane-oxyalkylene copolymer containing no gel particles was obtained. 
The copolymer was then back diluted to a total of 40 weight percent with 
dipropylene glycol and the resulting viscosity of 642 cSt was obtained. 
EXAMPLE 3 
A well stirred mixture of 113.2 grams of an olefinically substituted carbon 
treated polyoxyalkylene having the average formula CH.sub.2 
.dbd.CHCH.sub.2 O(CH.sub.2 CH.sub.2 O).sub.18 (CH.sub.2 CHCH.sub.3 
O).sub.20.7 OCCH.sub.3, 26.8 grams of an organohydrogen polysiloxane 
having the average formula Me.sub.3 SiO(Me.sub.2 SiO).sub.60 
(MeHSiO).sub.7 SiMe.sub.3 and 60 grams (30 wt %) of dipropylene glycol was 
degassed by nitrogen sparge and heated to 85.degree. C. A solution of 
H.sub.2 PtCl.sub.6.H.sub.2 O in ethanol was added to the mixture in 
sufficient amount to provide 15 ppm Pt. The heat source was removed and 
the exothermic hydrosilation reaction was allowed to proceed until no 
further temperature increase was noted. Heat was then added to the mixture 
as needed to keep its temperature at 85.degree. C. for 15 minutes. Care 
was taken never to allow the reaction pot to exceed 92.degree. C. A 
siloxaneoxyalkylene copolymer containing no gel particles was obtained. 
The copolymer was then, back diluted to a total of 40 weight percent with 
dipropylene glycol and the resulting viscosity of 638 cSt was obtained. 
EXAMPLE 4 
A well stirred mixture of 97.1 grams of an olefinically substituted carbon 
treated polyoxyalkylene having the average formula CH.sub.2 
.dbd.CHCH.sub.2 O(CH.sub.2 CH.sub.2 O).sub.18 (CH.sub.2 CHCH.sub.3 
O).sub.20.7 OCCH.sub.3, 23 grams of an organohydrogen polysiloxane having 
the average formula Me.sub.3 SiO(Me.sub.2 SiO).sub.60 (MeHSiO).sub.7 
SiMe.sub.3 and 60 grams 40 wt %) of dipropylene glycol was degassed by 
nitrogen sparge and heated to 85.degree. C. A solution of H.sub.2 
PtCl.sub.6.H.sub.2 O in ethanol was added to the mixture in sufficient 
amount to provide 15 ppm Pt. The heat source was removed and the 
exothermic hydrosilation reaction was allowed to proceed until no further 
temperature increase was noted. Heat was then added to the mixture as 
needed to keep its temperature at 80.degree. C. for 1 hour. Care was taken 
never to allow the reaction pot to exceed 91.degree. C. A 
siloxane-oxyalkylene copolymer containing no gel particles was obtained. 
The copolymer was then back diluted to a total of 40 weight percent with 
dipropylene glycol and the resulting viscosity of 603 cSt was obtained. 
In Examples 5-12 below, the experiments were performed with a second lot of 
polyethers and demonstrate the benefits of carboxylic acid salts. Example 
5 has no carboxylic acid salt present and possesses low air flow. The 
presence of carboxylic salt from oxidation of polyethers is present in 
Example 6 and the resulting surfactant affords higher air flow as 
summarized in Table II. 
EXAMPLE 5 
A well stirred mixture of 111.1 grams of an olefinically substituted carbon 
treated polyoxyalkylene having the average formula CH.sub.2 
.dbd.CHCH.sub.2 O(CH.sub.2 CH.sub.2 O).sub.17.3 (CH.sub.2 CHCH.sub.3 
O).sub.19.7 OCCH.sub.3, 29.0 grams of an organohydrogen polysiloxane 
having the average formula Me.sub.3 SiO(Me.sub.2 SiO).sub.60 
(MeHSiO).sub.7 SiMe.sub.3 and 60 grams (30 wt %) of dipropylene glycol was 
degassed by nitrogen sparge and heated to 75.degree. C. A solution of 
H.sub.2 PtCl.sub.6.H.sub.2 O in ethanol was added to the mixture in 
sufficient amount to provide 15 ppm Pt. The heat source was removed and 
the exothermic hydrosilation reaction was allowed to proceed until no 
further temperature increase was noted. Heat was then added to the mixture 
as needed to keep its temperature at 80.degree. C. for 15 minutes. Care 
was taken never to allow the reaction pot to exceed 81.degree. C. A 
siloxaneoxyalkylene copolymer containing no gel particles was obtained. 
The copolymer was then back diluted to a total of 30 weight percent with 
dipropylene glycol and the resulting viscosity of 703 cSt was obtained. 
EXAMPLE 6 
A well stirred mixture of 111.1 grams of an olefinically substituted carbon 
treated polyoxyalkylene having the average formula CH.sub.2 
.dbd.CHCH.sub.2 O(CH.sub.2 CH.sub.2 O).sub.17.3 (CH.sub.2 CHCH.sub.3 
O).sub.19.7 OCCH.sub.3, 29.0 grams of an organohydrogen polysiloxane 
having the average formula Me.sub.3 SiO(Me.sub.2 SiO)60(MeHSiO).sub.7 
SiMe.sub.3 and 60 grams (30 wt %) of dipropylene glycol was degassed by 
nitrogen sparge and heated to 80.degree. C. A solution of H.sub.2 
PtCl.sub.6.H.sub.2 O in ethanol was added to the mixture in sufficient 
amount to provide 15 ppm Pt. The heat source was removed and the 
exothermic hydrosilation reaction was allowed to proceed until no further 
temperature increase was noted. Heat was then added to the mixture as 
needed to keep its temperature at 80.degree. C. for 15 minutes. Care was 
taken never to allow the reaction pot to exceed 91.degree. C. A 
siloxane-oxyalkylene copolymer containing no gel particles was obtained. 
The copolymer was then back diluted to a total of 30 weight percent with 
dipropylene glycol and the resulting viscosity of 807 cSt was obtained. 
Examples 7-9 which follow, demonstrate the clear benefits of the back 
addition of carboxylic acid salts to systems employing treated polyethers 
Increased flows are obtained while retaining normal potency. Example 9 
demonstrates that carboxylic acid salts with less than 3 carbon atoms are 
not as effective as those containing greater than 3 carbon atoms in that 
examples 7 and 8 possess normal potency and increased air flows over that 
of example 9. 
EXAMPLE 7 
A well stirred mixture of 111.1 grams of an olefinically substituted carbon 
treated polyoxyalkylene having the average formula CH.sub.2 
.dbd.CHCH.sub.2 O(CH.sub.2 CH.sub.2 O).sub.17.3 (CH.sub.2 CHCH.sub.3 
O).sub.19.7 OCCH.sub.3, 29.0 grams of an organohydrogen polysiloxane 
having the average formula Me.sub.3 SiO(Me.sub.2 SiO)60(MeHSiO).sub.7 
SiMe.sub.3 and 60 grams (30 wt %) of dipropylene glycol and 0.11 grams of 
the carboxylic acid salt sodium oleate was degassed by nitrogen sparge and 
heated to 75.degree. C. A solution of H.sub.2 PtCl.sub.6.H.sub.2 O in 
ethanol was added to the mixture in sufficient amount to provide 15 ppm 
Pt. The heat source was removed and the exothermic hydrosilation reaction 
was allowed to proceed until no further temperature increase was noted. 
Heat was then added to the mixture as needed to keep its temperature at 
80.degree. C. for 15 minutes. Care was taken never to allow the reaction 
pot to exceed 81.degree. C. A siloxane-oxyalkylene copolymer containing no 
gel particles was obtained. The copolymer was then back diluted to a total 
of 30 weight percent with dipropylene glycol and the resulting viscosity 
of 839 cSt was obtained. 
EXAMPLE 8 
A well stirred mixture of 111.1 grams of an olefinically substituted carbon 
treated polyoxyalkylene having the average formula CH.sub.2 
.dbd.CHCH.sub.2 O(CH.sub.2 CH.sub.2 O).sub.17.3 (CH.sub.2 CHCH.sub.3 
O).sub.19.7 OCCH.sub.3, 29.0 grams of an organohydrogen polysiloxane 
having the average formula Me.sub.3 SiO(Me.sub.2 SiO).sub.60 
(MeHSiO).sub.7 SiMe.sub.3 and 60 grams (30 wt %) of dipropylene glycol and 
0.11 grams of the carboxylic acid salt sodium butylate was degassed by 
nitrogen sparge and heated to 75.degree. C. A solution of H.sub.2 
PtCl.sub.6.H.sub.2 O in ethanol was added to the mixture in sufficient 
amount to provide 15 ppm Pt. The heat source was removed and the 
exothermic hydrosilation reaction was allowed to proceed until no further 
temperature increase was noted. Heat was then added to the mixture as 
needed to keep its temperature at 80.degree. C. for 15 minutes. Care was 
taken never to allow the reaction pot to exceed 80.degree. C. A 
siloxane-oxyalkylene copolymer containing no gel particles was obtained. 
The copolymer was then back diluted to a total of 30 weight percent with 
dipropylene glycol and the resulting viscosity of 851 cSt was obtained. 
EXAMPLE 9 
A well stirred mixture of 111.1 grams of an olefinically substituted carbon 
treated polyoxyalkylene having the average formula CH.sub.2 
.dbd.CHCH.sub.2 O(CH.sub.2 CH.sub.2 O).sub.17.3 (CH.sub.2 CHCH.sub.3 
O).sub.19.7 OCCH.sub.3, 29.0 grams of an organohydrogen polysiloxane 
having the average formula Me.sub.3 SiO(Me.sub.2 SiO).sub.60 
(MeHSiO).sub.7 SiMe.sub.3 and 60 grams (30 wt %) of dipropylene glycol and 
0.11 grams of the carboxylic acid salt potassium acetate was degassed by 
nitrogen sparge and heated to 75.degree. C. A solution of H.sub.2 
PtCl.sub.6.H.sub.2 O in ethanol was added to the mixture in sufficient 
amount to provide 15 ppm Pt. The heat source was removed and the 
exothermic hydrosilation reaction was allowed to proceed until no further 
temperature increase was noted. Heat was then added to the mixture as 
needed to keep its temperature at 80.degree. C. for 15 minutes. Care was 
taken never to allow the reaction pot to exceed 80.degree. C. A 
siloxane-oxyalkylene copolymer containing no gel particles was obtained. 
The copolymer was then back diluted to a total of 30 weight percent with 
dipropylene glycol and the resulting viscosity of 875 cSt was obtained. 
In examples 10 through 12 which follow, the reactions were carried out 
either in polar low boiling solvents (IPA) or non polar solvents 
(toluene). Although normal surfactant may be made in toluene solvent, the 
solvent is volatile and requires removal to increase the resulting 
copolymer's flash point for safety considerations. 
EXAMPLE 10 
A well stirred mixture of 111.1 grams of an olefinically substituted carbon 
treated polyoxyalkylene having the average formula CH.sub.2 
.dbd.CHCH.sub.2 O(CH.sub.2 CH.sub.2 O).sub.17.3 (CH.sub.2 CHCH.sub.3 
O).sub.19.7 OCCH.sub.3, 29.0 grams of an organohydrogen polysiloxane 
having the average formula Me.sub.3 SiO(Me.sub.2 SiO).sub.60 
(MeHSiO).sub.7 SiMe.sub.3 and 60 grams (30 wt %) of toluene was degassed 
by nitrogen sparge and heated to 80.degree. C. A solution of H.sub.2 
PtCl.sub.6.H.sub.2 O in ethanol was added to the mixture in sufficient 
amount to provide 15 ppm Pt. The heat source was removed and the 
exothermic hydrosilation reaction was allowed to proceed until no further 
temperature increase was noted. Heat was then added to the mixture as 
needed to keep its temperature at 80.degree. C. for 15 minutes. Care was 
taken never to allow the reaction pot to exceed 90.degree. C. A 
siloxaneoxyalkylene copolymer containing no gel particles was obtained. 
The copolymer was then back diluted to a total of 30 weight percent with 
dipropylene glycol and the resulting viscosity of 880 cSt was obtained. 
Examples 11 and 12 demonstrate the need for beneficial amounts of 
carboxylic acid salts in polar solvents such as IPA. However, isopropanol 
solvent also requires removal prior to use due to low flash point safety 
concerns. 
EXAMPLE 11 
A well stirred mixture of 111.1 grams of an olefinically substituted carbon 
treated polyoxyalkylene having the average formula CH.sub.2 
.dbd.CHCH.sub.2 O(CH.sub.2 CH.sub.2 O).sub.17.3 (CH.sub.2 CHCH.sub.3 
O).sub.19.7 OCCH.sub.3, 29.0 grams of an organohydrogen polysiloxane 
having the average formula Me.sub.3 SiO(Me.sub.2 SiO).sub.60 
(MeHSiO).sub.7 SiMe.sub.3 and 60 grams (30 wt %) of isopropanol and 0.12 
grams of sodium butyrate was degassed by nitrogen sparge and heated to 
75.degree. C. A solution of H.sub.2 PtCl.sub.6.H.sub.2 O in ethanol was 
added to the mixture in sufficient amount to provide 15 ppm Pt. The heat 
source was removed and the exothermic hydrosilation reaction was allowed 
to proceed until, no further temperature increase was noted. Heat was then 
added to the mixture as needed to keep its temperature at 75.degree. C. 
for 15 minutes. Care was taken never to allow the reaction pot to exceed 
79.degree. C. A siloxane-oxyalkylene copolymer containing no gel particles 
was obtained. The copolymer was then stripped to remove isopropanol (IPA). 
The resulting neat copolymer possessed a viscosity of 1715 cSt. 
EXAMPLE 12 
A well stirred mixture of 127.5 grams of an ion exchanged olefinically 
substituted carbon treated polyoxyalkylene having the average formula 
CH.sub.2 .dbd.CHCH.sub.2 O(CH.sub.2 CH.sub.2 O).sub.17.3 (CH.sub.2 
CHCH.sub.3 O).sub.19.7 OCCH.sub.3, 32.5 grams of an organohydrogen 
polysiloxane having the average formula Me.sub.3 SiO(Me.sub.2 SiO).sub.60 
(MeHSiO).sub.7 SiMe.sub.3 and 40 grams (20 wt %) of isopropanol was 
degassed by nitrogen sparge and heated to 65.degree. C. A solution of 
H.sub.2 PtCl.sub.6.H.sub.2 O in ethanol was added to the mixture in 
sufficient amount to provide 45 ppm Pt. The heat source was removed and 
the exothermic hydrosilation reaction was allowed to proceed until no 
further temperature increase was noted. Heat was then added to the mixture 
as needed to keep its temperature at 65.degree. C. for 15 minutes. Care 
was taken never to allow the reaction pot to exceed 70.degree. C. A 
siloxaneoxyalkylene copolymer containing no gel particles was obtained. 
The copolymer was then stripped to remove isopropanol (IPA). The resulting 
neat copolymer possessed a viscosity of 1372 cSt. 
The above-prepared reaction products were evaluated as surfactants in a 
polyurethane foam composition in the following manner: 
A mixture of 100 parts of a polyol base, 1.26 parts of the above surfactant 
(not counting dipropylene glycol) and 0.23 parts of stannous octoate, 0.2 
parts A-200, 5.5 parts water, and 10 parts methylene chloride were 
thoroughly mixed. To the above mixture was added 112 Index of toluene 
diisocyanate and the resulting mixture was mixed for 7 seconds and then 
poured into a plastic bucket. The mixture was allowed to foam and rise to 
maximum height and was then cured at 110.degree. C. for 10 minutes. 
The cured foam was evaluated by measuring foam height, air flow through the 
foam and foam cell quality in a well known manner. The results are shown 
in Tables I and II below. It is evident from the data presented that the 
surfactant made by the improved method of this invention was equal or 
superior to the surfactant made in toluene solvent without carboxylic acid 
salt, according to one or more test criteria. 
TABLE I 
__________________________________________________________________________ 
Surfactant Foam 
Surfactant Solvent 
Carboxylic 
Foam Foam Cell 
Example # 
Amount.sup.1 
Identity.sup.2 
Acid Salt 0.1%.sup.3 
Height.sup.4 
Airflow.sup.5 
Uniformity.sup.6 
__________________________________________________________________________ 
1 10 DPG None 39.5 1.4 7 
2 20 DPG None 38.0 2.3 5 
3 30 DPG None 39.5 3.0 8 
4 40 DPG None 39.0 3.5 6 
__________________________________________________________________________ 
.sup.1 Weight percent of polysiloxane + polyoxyalkleneoxide 
.sup.2 DPG is dipropylene glycol 
.sup.3 Polyethers were carbon treated to remove any carboxylic acid 
oxidation products except Example #6 wherein IR confirmed presence of 
oxidation products. 
.sup.4 Centimeters .+-. 0.5 
.sup.5 ft.sup.3 /Min. .+-. 0.2, higher airflow more desirable 
.sup.6 Visual rating lower values more desirable, scale 1 to 12 
TABLE II 
__________________________________________________________________________ 
Surfactant Foam 
Surfactant Solvent 
Carboxylic 
Foam Foam Cell 
Example # 
Amount.sup.1 
Identity.sup.2 
Acid Salt 0.1%.sup.3 
Height.sup.4 
Airflow.sup.5 
Uniformity.sup.6 
__________________________________________________________________________ 
5 30 DPG None 36.6 2.5 2 
6 30 DPG (3) 39.6 3.8 3 
7 30 DPG Sodium Oleate 
38.5 5.6 5 
8 30 DPG Sodium Butyrate 
37.5 4.9 2 
9 30 DPG Potassium Acetate 
37.3 3.6 3 
10 30 Toluene 
None 37.5 4.2 3 
11 30 IPA Sodium Butyrate 
36.2 2.0 3 
12 20 IPA None 31.0 2.2 6 
__________________________________________________________________________ 
.sup.1 Weight percent of polysiloxane + polyoxyalkleneoxide 
.sup.2 DPG is dipropylene glycol 
.sup.3 Polyethers were carbon treated to remove any carboxylic acid 
oxidation products except Exmple #6 wherein IR confirmed presence of 
oxidation products. 
.sup.4 Centimeters .+-. 0.5 
.sup.5 ft.sup.3 /Min. .+-. 0.2, higher airflow more desirable 
.sup.6 Visual rating lower values more desirable, scale 1 to 12 
Although the invention has been illustrated by the preceding examples, it 
is not to be construed as being limited to the materials employed therein, 
but rather, the invention is directed to the generic area as hereinbefore 
disclosed. Various modifications and embodiments can be made without 
departing from the spirit and scope thereof.