Non-aqueous antifoam compositions comprising a lipophilic nonionic surface active agent homogeneously dispersed in a transient non-aqueous siloxanate antifoam agent.

BACKGROUND OF THE INVENTION 
This invention relates to novel non-aqueous antifoam compositions. 
U.S. application Ser. No. 691,394, filed concurrently herewith, entitled 
TRANSIENT ANTIFOAM COMPOSITIONS by M. Rosen and S. Sterman discloses 
transient non-aqueous antifoam compositions based on silica filler and the 
condensation product of a partially hydrolyzed trifunctional silane. Such 
antifoam compositions can not be readily employed in an emulsified form 
due to their hydrolytic instability in water. In order to obtain a high 
degree of effectiveness in aqueous foam systems such antifoam compositions 
generally must be first solubilized using a dispersing solvent. 
SUMMARY OF THE INVENTION 
It has now been discovered that the above mentioned transient antifoam 
compositions can be made more effective in aqueous foam systems as 
witnessed by the novel antifoam compositions of this invention. 
Thus, it is an object of this invention to provide novel improved transient 
non-aqueous antifoam compositions. Other objects and advantages of this 
invention will become readily apparent from the following description and 
appended claims. 
More particularly this invention is directed to a non-aqueous antifoam 
composition consisting essentially of a lipophilic nonionic surface active 
agent homogeneously dispersed in a transient siloxanate antifoam agent, 
wherein the amount of said surface active agent to said antifoam agent 
ranges from about 3 to about 33 parts by weight of the surface active 
agent per 100 parts by weight of the antifoam agent. 
It is of course to be understood that the antifoam compositions of this 
invention read on employing a single component of the type specified or 
any of the various combinations of component mixtures possible. For 
instance, in addition to compositions of a single type of siloxanate 
antifoam agent, the compositions of this invention include mixtures of 
nonionic surface active agents dispersed in a single siloxanate antifoam 
agent, a single nonionic surface active agent dispersed in mixtures of 
siloxanate antifoam agents as well as mixtures of nonionic surface active 
agents dispersed in mixtures of siloxanate antifoam agents. 
DESCRIPTION OF THE PREFERRED EMBODIMENTS 
The present invention is based on the discovery that non-aqueous 
compositions consisting essentially of a lipophilic nonionic surface 
active agent homogeneously dispersed in a siloxanate antifoam agent are 
highly effective in aqueous foam systems. The term non-aqueous as employed 
herein means that the antifoam compositions of this invention contain less 
than 1 percent by weight of water, if indeed they contain any measurable 
amont of water at all. 
Any transient non-aqueous siloxanate antifoam agent disclosed in the 
above-mentioned concurrently filed U.S. applications Ser. No. 691,394 can 
be employed in this invention, the entire disclosure of said application 
being incorporated herein by reference thereto. 
More particularly the transient non-aqueous antifoam agents employed in 
this invention are compositions consisting essentially of the product 
resulting from heating, in the absence of water, a mixture consisting 
essentially of a finely divided silica filler and a condensation product 
of a partially hydrolyzed trifunctional silane, said condensation product 
having a residual alkoxy content of at least about 9 percent by weight, 
said silane being selected from the group consisting of RSiX.sub.3 and 
RSi(OR').sub.3 wherein R and R' are alkyl radicals and X is a halogen 
atom, and wherein the amount ratio of said silica filler to said 
condensation product ranges from about 1 to about 33 parts by weight of 
the silica filler per 100 parts by weight of the condensation product. 
The finely divided silica fillers employed in the preparation of said 
siloxanate antifoam agents are finely powdered materials that are well 
known in the art such as precipitated silica, fumed silica, and the like. 
Such fillers preferably have an average particle diameter size of about 7 
to about 25 millimicrons, preferably in the range of about 7 to about 14 
millimicrons as calculated from the surface area (BET Method), assuming 
spericity of particles, J. Am. Chem. Soc. Vol. 60, page 309. (1938) It is 
to be understood that the fillers are essentially non-aqueous and that 
silica hydrosols are excluded from the definition of the term finely 
divided silica as employed herein. 
The condensation products of partially hydrolyzed trifunctional silanes 
employed and/or methods for their preparation are well known in the art. 
For instance, said condensation products can be prepared by the 
conventional known methods of partial hydrolysis and condensation. As is 
well known in the art, hydrolyzates represent the metathetical reaction 
products of corresponding hydrolyzed silanes, while the condensation 
products represent the siloxanate products obtained upon condensation of 
the hydrolyzed reaction mixture. 
The hydrolyzable trifunctional silanes used in the preparation of the 
condensation products employed are those silanes of the formulas 
RSiX.sub.3 and RSi(OR').sub.3 wherein X represents a halogen atom, 
preferably chlorine, R represents an alkyl radical having from 1 to 5 
carbon atoms and R' represents an alkyl radical having from 1 to 4 carbon 
atoms. Illustrative radicals represented by R include alkyl radicals such 
as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, 
amyl, and the like. Most preferably R is a lower alkyl radical having from 
1 to 3 carbon atoms, especially methyl. Radicals represented by R' include 
methyl, ethyl, propyl, butyl, isobutyl and the like. More preferably R' is 
methyl or ethyl, especially ethyl. Said hydrolyzable trifunctional silanes 
are well known in the art, illustrative examples of same include 
methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, 
amyltriethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane and the 
like. 
Thus, method for obtaining the partial hydrolyzates of said hydrolyzable 
trifunctional silanes is not critical and any conventional method known in 
the art can be employed. For instance, said partial hydrolyzate can be 
obtained by mixing the desired silane or mixtures thereof to be partially 
hydrolyzed with water in the case of trialkoxysilanes or water and an 
alcohol in the case of trihalosilanes and refluxing the mixture until the 
desired degree of hydrolysis is obtained. The reaction conditions are 
conventional and not critical, e.g. normally the reaction temperature may 
range from about room temperature to reflux and the hydrolysis is 
generally completed within three hours. Of course it is to be understood 
that since partial hydrolysis is involved the amount of water employed 
must be less than that required for complete hydrolysis of the silane. The 
amount of water employed need of course only correspond to that amount 
required to furnish the degree of hydrolysis desired as determined by the 
desired degree of residual alkoxy content present in the desired 
condensation product. It should be also understood that in the case of 
trihalosilane starting materials sufficient alcohol is employed to convert 
in situ all the halogen radicals to alkoxy radicals, said alcohols 
corresponding to the residual alkoxy groups on the desired condensation 
product. Likewise in the case of trialkoxysilane starting materials, a 
catalyst, e.g. hydrochloric acid, and a solvent, e.g. an alcohol, such as 
ethanol can be employed if desired. 
The condensation products used in the production of the siloxanate antifoam 
agents are obtained through the condensation of said partial hydrolyzates 
and can of course be recovered in any conventional manner known in the art 
such as by neutralization is desired, followed by stripping all the water, 
as well as the solvent and catalyst if employed, and any undesired 
by-products from the partial hydrolyzed reaction mixture. Thus, said 
condensation products are essentially non-aqueous siloxanate materials, 
the predominant species of which may be represented by the general formula 
##EQU1## 
wherein R and R' are the same as defined above and wherein the value of x 
corresponds to the residual alkoxy content of the condensation product. 
Said condensation products have a residual alkoxy content of at least 
about 9 percent by weight and more preferably from about 40 to 50 percent 
by weight. The preferred condensation products are those that also have a 
viscosity in the range from about 10 to 50 centipoises (more preferably 
about 10 to 20 centipoises) at 25.degree. C. Of course it is to be 
understood that the condensation products encompass those co-condensation 
products obtained on partial cohydrolysis, if desired, of a mixture of one 
or more of said hydrolyzable trifunctional silanes. 
As pointed out above, the transient, nonaqueous siloxanate antifoam agents 
are prepared by heating at an elevated temperature, a mixture consisting 
essentially of a finely divided silica filler and a condensation product 
of a partially hdyrolyzed trifunctional silane, said materials having been 
defined above. Typically the elevated temperature can be about 80.degree. 
C. to about 200.degree. C., preferably about 100.degree. C. to 170.degree. 
C. The period of heating is not narrowly critical and, for example, can 
range from at least about one-quarter hour to about 5 hours or longer if 
desired, with the preferred period being about one-half hour to about 3 
hours. Preferably the mixture is sheared prior to the heating operation to 
thoroughly disperse the filler in the condensation product. If desired the 
mixture can be mildly agitated during the heating operation. After the 
heating operation the mixture need not be further processed in any way, 
the desired transient non-aqueous siloxanate antifoam composition normally 
being recovered merely by allowing the reacted mixture to cool to room 
temperature. However, if desired, the resulting heated mixture may be 
subjected to any heretofore conventional antifoam processing operation. 
Moreover the process employed in preparing the siloxanate antifoams is 
carried out in the absence of water, i.e. there is no deliberately added 
water and the reactants are essentially non-aqueous. The reaction mixture 
of filler and condensation product can be formed in any conventional 
manner such as by simply blending the materials together or employing a 
conventional high shear mixer. 
While the transient non-aqueous siloxanate antifoam agents employed in this 
invention are preferably produced without the use of a catalyst, a 
catalyst can be employed if desired. When employed the catalyst may be any 
of the well known types heretofore employed in the preparation of antifoam 
compositions such as the acid catalysts disclosed in U.S. Pat. No. 
3,235,509 and the basic catalysts of U.S. Pat. No 3,506,401. 
The amounts of the above mentioned silica filler, condensation product and 
catalyst, if employed, that are mixed and heated to produce the siloxanate 
antifoams are not narrowly critical. Typical ranges of amounts of these 
materials, defined above, include from about 1 to about 33 (preferably 
about 3 to about 20) parts by weight of the finely divided silica filler 
per 100 parts by weight of the condensation product employed. Of course, 
if employed the amount of catalyst need only be a catalytic amount. 
Of course, it is to be understood that not every siloxanate antifoam agent 
or antifoam composition encompassed by the instant invention will be 
equally effective and equally transient in their performance. For 
instance, antifoam compositions based on amylsilane and containing about 
10 parts by weight of silica filler have been found to be very poorly 
transient, yet have exhibited hydrolytic instability when containing about 
3 parts by weight of silica filler. The determination of optimum desired 
results for a given antifoam composition is well within the knowledge of 
one skilled in the art and can be met by routine experimentation by 
following the teachings of this invention. 
Any lipophilic nonionic surface active agent can be employed in this 
invention. The nonionic surface active agent can be a nonionic organic 
surface active agent or more preferably a nonionic siloxane surface active 
agent. The term lipophilic as used herein means that the nonionic surface 
active agent has a hydrophilic-lipophilic balance (HLB) of less than 9. 
Said hydrophilic-lipophilic balance, hereinafter referred to as HLB, is a 
measure of the balance of the size and strength of the hydrophilic 
(water-loving or polar) and the lipophilic (oil-loving or non-polar) 
groups of a surface active agent. The HLB of a surface active agent is 
related to its solubility and a surface active agent having a low HLB will 
tend to be oil-soluble, while one having a high HLB will tend to be 
water-soluble. As employed herein surface active agents having an HLB 
number of less than 9 are lipophilic in character (i.e. tend to be 
oil-soluble) while surface active agents having a higher HLB number are 
considered to be hydrophilic in character (i.e. tend to be water-soluble). 
The HLB methods of determining the characteristics of a surface active 
agent are well known in the art and can be found more fully explained e.g. 
in "The Atlas HLB System a time-saving guide to emulsifier selection", 4th 
Printing May, 1971, published by the Atlas Chemical Industries, Inc., 
Wilmington, Delaware, (now known as ICI United States Inc.), the 
disclosure of which is encompassed herein by reference thereto. For 
example HLB values of most polyol fatty acid esters can be calculated with 
the formula 
##EQU2## 
where S = saponification number of the ester (AOCS Cd 3-25) and A = acid 
number of the recovered acid (AOCS Cd 6-38 and AOCS L3a-57). Where the 
hydrophilic portion of organic surface active agents consist of ethylene 
oxide only the formula is simply 
EQU HLB = E/5 
wherein E = weight percent oxyethylene content (Morgan, P.W., 
"Determination of Ethers and Esters of Ethylene Glycol", Ind. and Eng. 
Chem., Anal. Ed., Vol. 18, page 500, 1946). While the above formulas given 
above are satisfactory for many non-ionic surface active agents certain 
other nonionic types exhibit behavior which is apparently unrelated to 
their composition, e.g. those containing propylene oxide, butylene oxide, 
nitrogen and sulfur. The HLB values of these nonionics can be 
experimentally estimated so that their HLB values are aligned with those 
of common nonionic surface active agents. While the experimentally 
determined HLB value will not necessarily indicate the percentage weight 
of its hydrophilic portion, it does indicate its apparent HLB when used in 
combination with other surface active agents. This experimental method of 
HLB determination, while not precise, briefly consists of blending the 
unknown surface active agent in varying ratios with a surface active agent 
of known HLB and using the blend to emulsify an oil of known required HLB. 
The blend which performs the best is assumed to have an HLB value 
approximately equal to the required HLB of the oil, so that the HLB value 
of the unknown can be calculated. A simpler and easier method for 
obtaining a rough estimate of HLB can be made from the water-solubility of 
the surface active agent. This method is especially suitable for screening 
nonionic siloxane surface active agents and merely involves approximating 
their HLB values according to their solubility or dispersibility in water 
as shown in the following Table: 
______________________________________ 
HLB by Dispersibility HLB Range 
______________________________________ 
No dispersibility in water 
1-4 
Poor dispersion 3-6 
Milky dispersion after 
6-8 
vigorous agitation 
Stable milky dispersion 
8-10 
Translucent to clear 10-13 
dispersion 
Clear solution 13+ 
______________________________________ 
The determination of a HLB value for a given nonionic surface active agent 
generally has a precision factor of about .+-.1. 
Of course, as pointed out above, it is to be understood that if desired 
mixtures of two or more nonionic surface active agents can be employed 
herein and that the mixtures can consist of different nonionic organic 
surface active agents, different nonionic siloxane surface active agents, 
or mixtures of nonionic organic and nonionic siloxane surface active 
agents. It is to be further understood that the term lipophilic nonionic 
surface active agent as employed herein includes not only the above types 
of lipophilic nonionic surface active agents and mixtures thereof, but 
mixtures of lipophilic nonionic surface active agents and hydrophilic 
nonionic surface active agents as well, so long as such mixtures are 
lipophilic, i.e. have a HLB value of less than 9. For example, a blend, 
consisting of about 67 percent by weight of a nonionic surface active 
agent having a HLB value of about 4.7 and about 33 percent by weight of a 
nonionic surface active agent having a HLB value of about 16.9, has a 
blended HLB value of about 8.9 and such types of mixtures are included 
within the scope of this invention. 
Nonionic surface active agents and/or methods for their preparation which 
are useful in this invention are well known in the art as witnessed for 
example by "McCutcheon's Detergents and Emulsifiers", North America Ed. 
1975 Annual, McCutcheon Division, M.C. Publishing Co., Ridgewood, N.J., 
the disclosure of which is incorporated herein by reference thereto. Any 
lipophilic nonionic organic or siloxane surface active agent, or mixtures 
thereof can be employed in this invention. Illustrative lipophilic 
nonionic organic surface active agents include polyoxyalkylene alcohols 
such as polyoxyethylylene (2) cetyl ether, polyoxyethylene (2) stearyl 
ether, polyoxyethylene (2) oleyl ether, and the like; mono and 
diglycerides, such as mono and diglycerides from the glycerolysis of 
edible fats, mono and diglycerides of fat forming fatty acids, mono and 
diglycerides from the glycerolysis of edible fats or oils and the like; 
sorbitan fatty acid esters, such as sorbitan monooleate, sorbitan partial 
fatty esters, sorbitan monolaurate, sorbitan monopalmitate, sorbitan 
monostearate, sorbitan sesquioleate, sorbitan trioleate, sorbitan 
tristearate, and the like; and polyoxyalkylene sorbitol esters, such as 
polyoxyethylene sorbitol beeswax derivative and the like, as well as any 
of the other known types of nonionic surface active agents that are 
lipophilic. The precise structural and formula configurations of such 
nonionic organis surface active agents is considered to be immaterial so 
long as the nonionic organic surface active agent is lipophilic in 
character as defined herein above. Illustrative commercial lipophilic 
nonionic organic surfactants include, e.g. certain Atmos, Atmul, Arlacel, 
Atpet, Span, Tween, and Brij surfactants of ICI United States Inc. 
Illustrative lipophilic siloxane surface active agents include 
siloxane-oxyalkylene block copolymers. Such copolymers are composed 
essentially of siloxy units having the formula 
##EQU3## 
wherein R is a monovalent hydrocarbon radical, especially methyl; R' is a 
divalent organic group linked directly to the silicon atom; R" is an 
oxyalkylene group; R"' is a monovalent organic terminating group; n is an 
integer; a has a value of from 1 to 3 inclusive; b has a value of from 1 
to 3 inclusive, and siloxy units having the formula wherein R is the same 
as defined in formula (A) above and c has a value of from 0 to 3 
inclusive. Such types of siloxane-oxyalkylene block copolymers and/or 
methods for their preparation are well known in the art as witnessed for 
example, by U.S. Pat. Nos. 2,834,748; 2,917,480; 3,398,104; 3,402,192; 
3,507,815; 3,741,917; and the like. The precise structural and formula 
configurations of such siloxane-oxyalkylene block copolymers is considered 
immaterial so long as the nonionic siloxane surface active agent is 
lipophilic in character as defined herein above. Illustrative of some of 
the more preferred groups represented by formula (A) and (B) above are 
those wherein R is a lower alkyl radical, especially methyl; wherein R' is 
a --C.sub.d H.sub.2d O-- group where d is an integer and the oxygen atom 
is linked directly to the silicon atom, or more preferably a divalent 
hydrocarbon group linked directly to the silicon atom through a carbon to 
silicon bond, e.g. propylene; wherein R" is the oxyalkylene portion or 
block of the siloxane-oxyalkylene block copolymer said oxyalkylene block 
being composed of an oxyalkylene group of the formula [--C.sub.d H.sub.2d 
O--] where d is an integer, e.g. oxyethylene, oxypropylene, as well as 
mixtures of oxyethylene and oxypropylene, and the like. Preferably the 
oxyalkylene group is composed of oxyethylene or a mixture of oxyethylene 
and oxypropylene radicals; and wherein R"' represents an organic terminal 
group such as hydroxy, alkoxy, aryloxy, arylalkyloxy, alkenyloxy, acyloxy, 
carbamyloxy and carbonate groups the preferred terminal group being an 
alkoxy group of 1 to 4 carbon atoms. Illustrative of the more preferred 
siloxane-oxyalkylene block copolymers are those composed essentially of 
siloxy units of the formula R.sub.3 SiO.sub.0.5, R.sub.2 SiO and 
[R"'(R").sub.n R'--Si(R)O wherein R, R', R", R"' and n are the same as 
defined above, especially those wherein R"' is an alkoxy radical. 
As pointed out above mixtures of the various lipophilic nonionic surface 
active agents can be employed as well as mixtures of such lipophilic 
agents and hydrophilic nonionic surface active agents so long as the 
mixture is lipophilic in character as herein defined above. Such 
hydrophilic nonionic surface active agents that may be employed are well 
known in the art. Illustrative hydrophilic surface active agents include 
those of the same surface active agent classes as defined above having an 
HLB of more than 9, as well as the conventional polyoxyalkylene compounds, 
e.g. the Myrj surfactants of ICI United States Inc., The Tergitol 
surfactants of Union Carbide Corporation, and the like. 
The non-aqueous antifoam compositions of this invention are prepared by 
homogeneously dispersing a lipophilic nonionic surface active agent in a 
transient non-aqueous siloxanate antifoam agent. The term homogeneously 
dispersed as employed herein means that the nonaqueous antifoam 
compositions of this invention are either homogeneous solutions as in the 
case wherein the lipophilic nonionic surface active agent is soluble in 
the siloxanate antifoam agent or homogeneous dispersions wherein the 
lipophilic nonionic surface active agent is completely distributed 
throughout the composition as in the case wherein the lipophilic nonionic 
surface active agent is not soluble in the siloxanate antifoam agent. 
Thus, the two components need only be throughly blended or mixed in any 
conventional known manner for obtaining homogeneous dispersions. In the 
case where lipophilic nonionic surface active agent is not soluble in the 
siloxanate antifoam agent the surface active agent is preferably throughly 
mixed with the antifoam agent at a temperature sufficient to liquify the 
nonionic surface active agent if it is a solid until a homogeneous 
dispersion is obtained. Alternatively, if its a non-soluble solid, the 
lipophilic nonionic surface active agent can be preheated to its melting 
point and then thoroughly mixed with the siloxanate antifoam agent, at a 
temperature sufficient to maintain the nonionic surface active agent as a 
liquid, until a homogeneous dispersion is obtained. It should be noted 
that particular attention should be applied to the amount of work 
(shear-time) expended to optimize the homogeneous dispersions of this 
invention. If too little work is put in surface active agent separation 
may occur with time, while if too much work is put in the performance of 
the base antifoam may degrade. The preferred intermediate work range in 
obtaining the optimized, most stable antifoam compositions of this 
invention will vary depending upon the particular surface active agent and 
antifoam components employed, however, the preferred limits can be easily 
determined by routine experimentation. 
As pointed out above the amount ratio of lipophilic nonionic surface active 
agent to siloxanate antifoam agent can range from about 3 to about 33 
parts by weight of the surface active agent per 100 parts by weight of the 
antifoam agent. More preferably said amount ratio ranges from about 5 to 
about 25 parts by weight of the surface active agent per 100 parts by 
weight of the antifoam agent. In general the preferred surface active 
agents employed herein are the lipophilic nonionic siloxane surface active 
agents. 
Of course, it is to be understood that not every possible lipophilic 
nonionic surface active agent will be optimally suited for every possible 
siloxanate antifom agent and that the antifoam activity of the non-aqueous 
antifoam compositions of this invention will vary depending upon the 
ingredients employed. For example the compatibility of the surface active 
agent/antifoam mixture as evidenced by resistance to gross phase 
separation on standing or poor homogenity resulting in a lumpy appearance 
as well as the nature of the aqueous foaming media to which the antifoam 
is to be applied will play a role in the proper choice of surface active 
agent and concentration in terms of gaining suitable antifoam peformance. 
However, the determination of optimum desired results is well within the 
knowledge of one skilled in the art and can be met by routine 
experimentation involving the proper selection of surface active agent, 
concentration and well known process techniques for preparing stable 
dispersions. 
The transient non-aqueous antifoam compositions of this invention can be 
employed to prevent or destroy the foam formation of an aqueous or 
non-aqueous foam forming media. Thus, the compositions of this invention 
are useful in many applications wherein foaming is not desired, such as in 
the preparation and use of aqueous media systems, e.g. shampoos, 
waste-water treatment, fermentation processing, paper making, paints, 
latex systems, cleaning compounds, laundry and detergent products and the 
like. Moreover, because of the antifoam compositions of this invention are 
based on transient antifoam agents, they can be especially useful in 
applications where short term foaming control is desired such as in 
waste-water treatment and in the processing and packaging of foam liquids 
such as shampoos, liquid cleaners and the like, and possibly even in the 
processing and packaging of beverages, such as beer. Moreover preferred 
antifoam compositions of this invention containing nonionic siloxane 
surface active agents having a HLB value of less than 9 have been found to 
exhibit good stability upon storage both at room temperature and at 
elevated temperature (about 50.degree. C) Of course the utility in a 
specific area will depend upon the foaming media system to which the 
antifoam is to be applied and the resultant antifoam activity desired for 
said system.

The following examples are illustrative of the present invention and are 
not to be regarded as limitative. It is to be understood that all parts 
percentages and proportions referred to herein and in the claims are by 
weight unless otherwise indicated and that Me represents a methyl radical 
(--CH.sub.3). 
As set forth herein below and in the Examples, the following abbreviations 
are used. 
__________________________________________________________________________ 
Nonionic Surface Active Agents 
HLB.sup.+ 
Surfactant Composition Number 
__________________________________________________________________________ 
A *Brij 52 (polyoxyethylene (2) 
5.3 
cetylether) 
B *Brij 72 (Polyoxyethylene (2) 
4.9 
stearylether) 
C *Brij 93 (Polyoxyethylene (2) 
4.9 
oleylether) 
D *Arlacel 20 (Sorbitan monolaurate) 
8.6 
E *Span 40 (Sorbitan monopalmite) 
6.7 
F *Span 60 (Sorbitan monostearate) 
4.7 
G *Arlacel 60 (Sorbitan monostearate) 
4.7 
H *Span 65 (Sorbitan tristearate) 
2.1 
I *Arlacel 83 (Sorbitan sesquioleate) 
3.7 
J *Atmul 124 (Mono and diglycerides 
3.5 
from the glycerolysis of edible 
fats) 
K *Arlacel 80 (Sorbitan monooleate) 
4.3 
L *Span 80 (Sorbitan monooleate) 
4.3 
M *Arlacel 85 (Sorbitan trioleate) 
1.8 
N About a 67:33% by wt. mixture 
7.4 
of Arlacel 20 and Span 60 
O About a 50:50% by weight mixture 
6.7 
of Arlacel 20 and Span 60 
P About a 33:67% by wt. mixture of 
5.9 
Arlacel 20 and Span 60 
Q Arlacel 165 (Glycerol monostearate) 
11.0 
R Brij 30 (Polyoxyethylene (4) lauryl 
9.7 
ether) 
S *Myrj 52 (Polyoxyethylene (4) 
16.9 
stearate) 
T *Tween 61 (Polyoxyethylene (4) 
9.6 
sorbitan monostearate 
U **Tergitol 15S12 (Ethoxylated 
15.0 
C.sub.11 -C.sub.15 alcohols-12 moles 
ethylene oxide) 
V **Tergitol 15S.9(Ethoxylated 
13.8 
C.sub.11 -C.sub.15 alcohols-9 moles 
ethylene oxide) 
W **Tergitol 15S7 (Ethoxylated 
12.8 
C.sub.11 -C.sub.15 alcohols-7 moles ethylene 
oxide) 
X **Tergitol 15S5 (Ethoxylated 
11.3 
C.sub.11 -C.sub.15 alcohols-5 moles ethylene 
oxide) 
Y **Tergitol 15S3 (Ethoxylated 
9.0 
C.sub.11 -C.sub.15 alcohols-3 moles 
ethylene oxide 
Z About a 67:33% by weight mixture 
8.7 
of Span 60 and Myrj 52 
AA About a 67:33% by wt. mixture of 
10.2 
Tergitol 15S3 and Tergitol 
15S7 
BB About a 50:50% by wt. mixture of 
10.9 
Tergitol 15S3 and Tergitol 15S7 
CC About a 33:67% by wt. mixture of 
11.5 
Tergitol 15S3 and Tergitol 15S7 
DD 
##STR1## 6-8*** 
EE 
##STR2## 6-8*** 
FF 
##STR3## 6-8*** 
GG 
##STR4## 6-8*** 
HH 
##STR5## 6-8*** 
II 
##STR6## 10-13*** 
JJ 
##STR7## 10-13*** 
KK 
##STR8## 10-13*** 
LL 
##STR9## 10-13*** 
MM 
##STR10## 10-13*** 
NN 
##STR11## 10-13*** 
OO 
##STR12## 10-13*** 
PP 
##STR13## 10-13*** 
QQ About a 67:33% by wt. mixture of Tergitol 
10-13*** 
15S7 and 
##STR14## 
__________________________________________________________________________ 
.sup.+ Hydrophilic-lipophilic balance number. 
*Product of ICI United States Inc. 
**Product of Union Carbide Corporation 
***HLB determined by the surfactant's dispersibility in water. 
MECHANICAL SHAKING TEST (TEST II) 
About 0.05 grams of the antifoam (1000 ppm) to be tested was placed in an 8 
oz. wide mouth jar to which was added about 50 grams of aqueous Green Soap 
(Eli Lilly and Company) solution (about 0.5% by wt.) The jar was then 
covered and shaken on a wrist action shaker for two minutes. The jar was 
held to the shaker by a three-prong clamp which is 25 cm. away from the 
central shaking bar (measured from the center of the jar). The angle of 
shaking was set at 10 (the maximum). After the two minute shaking period 
the jar was removed and one minute later the height of empty space (cm. of 
foam breakdown) was measured. If no foam was present, the cm. of foam 
breakdown was at the maximum value of 7.3 cm. If the jar was full of foam 
(which happened when just the Green Soap solution was employed), the cm. 
of foam breakdown is 0. The results are reported in terms of percent foam 
breakdown. For example, if there is 5 cm. of foam breakdown then the 
EQU Percent Foam Breakdown = (5/7.3) .times. 100 = 69% 
The control was run with 50 grams of said 0.5% aqueous Green Soap solution 
which gives 0% foam breakdown. The transient behavior of the antifoam 
composition was recorded by repeating the test on the same test mixtures 
after a few days upon standing and oberving the change in antifoaming 
activity with time. 
TEST PROCEDURES 
In the Examples appearing below the following test procedures were used to 
determine the effectiveness of the antifoams. 
Bubbling Test (Test I) 
About 0.1 gram of the antifoam tested was added to about 250 grams of a 
freshly prepared homogeneous 0.5 percent by weight aqueous Green Soap (Eli 
Lilly and Company) solution in a stoppered graduate. The graduate was 
gently inverted several times until the antifoam was dispersed in the soap 
solution. About 100 grams of the liquid mixture (antifoam and soap 
solution) was then added to a 1000 cc. graduate. A nitrogen bubbler 
containing a porous glass frit was then inserted in the graduate and 
nitrogen bubbled into the liquid mixture at a flow rate equal to the flow 
rate that produced 1000 cc. of foam (foam and liquid) in two minutes from 
100 grams of said soap solution in the absence of any antifoam agent. The 
foam volume produced by each liquid mixture (antifoam and soap solution) 
is then recorded by reading the height of the foam in the graduate at five 
and ten minute intervals. The dispersibility and antifoaming activity of 
the antifoam tested is indicated by the recorded volume of foam so 
produced, the lower the foam volume the more dispersed and effective the 
antifoam. The volume of foam generated after five minutes has a 
reproducability of about .+-. 20 cc, while the foam volume generated after 
ten minutes has a reproducability of about .+-. 50 cc. 
ANTIFOAM ACTIVITY IN COMMERCIAL FOAMING LIQUID (TEST III) 
The commercial foaming liquid was diluted to a 50 percent aqueous solution 
with distilled water and 250 cc. of said solution added to about 0.1 gram 
of the antifoam (400 ppm) composition to be tested. After shaking to 
disperse the antifoam, 125 cc. of said solution-antifoam dispersion was 
placed in an 8 oz. wide mouth jar, which was covered and shaken ten times 
(one shake equaling one up and down motion). The antifoam effectiveness 
was then rated as follows: 
______________________________________ 
Rating Qualitative Observation 
______________________________________ 
Complete No foam visible 
Good No foam in center but 
foam visible at the walls 
Moderate Thin foam layer covers 
the liquid surface 
Slight Foam layer over liquid 
surface 
None Foam fills available 
head space-no evidence 
of any breakdown. 
______________________________________ 
EXAMPLE 1 
A condensation product of a partially hydrolyzed silane was prepared on a 
plant scale as follows. About 19750 lbs. of methyltrichlorosilane, 
MeSiCl.sub.3, along with about 7300 lbs. of anhydrous ethanol was feed to 
a reaction kettle. After about 4000 lbs. of the silane had been added, 
about 1700 lbs. of water was simultaneously added to the kettle along with 
the rest of the silane and ethanol. After adding said reactants the 
reaction mixture was cooled to 70.degree. C. and refluxed for 21/2 hours. 
The mixture was then cooled to about 83.degree. to 86.degree. C. and all 
its volatiles i.e. alcohol, acid catalyst, and water, removed by vacuum 
stripping at two pounds pressure. As the stripping rate fell the vacuum 
pressure was increased to just less than about 100 mm. pressure. The 
stripping was carried out over 2 hours at 135.degree. C. The stripped 
mixture was then cooled to 100.degree. C. and activated carbon used to 
remove the color. The mixture was then neutralized with propylene oxide 
until the chlorine content was less than 0.01 percent followed by vacuum 
stripping to remove said propylene oxide. The desired condensation product 
so recovered was a siloxanate which may be considered as having the 
general formula 
##EQU4## 
Analysis of said desired condensation product showed it to have a 
viscosity of about 17 centipoises at 25.degree. C. and contain about 47.1 
percent by weight of residual ethoxy groups. 
EXAMPLE 2 
A series of ten gram samples of non-aqueous antifoam compositions were 
prepared, each composition consisting of about 2 gram of surface active 
agent used homogeneously blended in about 8 grams of a transient 
non-aqueous siloxanate antifoam agent, said antifoam agent consisting 
essentially of the product resulting from stirring about one gram of 
finely divided fumed silica filler into about ten grams of the 
condensation product of Example 1 until the mixture was homogeneous 
subjecting the mixture to high shear by passing it through an orifice and 
then heating it for about two hours at about 150.degree. C. In those cases 
where a single surface active agent was used the compositions were 
prepared by merely throughly mixing the surface active agent and 
siloxanate antifoam at room temperature with a spatula for about 1 to 2 
minutes until the surface active agent was uniformly distributed 
throughout the antifoam. In those cases where a mixture of two surface 
active agents were used, the surface active agents were first blended 
together in the proper ratio (i.e. 2 grams/4 grams for a 1:2 ratio, 4 
grams/4grams for a 1:1 ratio and 4 grams/2 grams for a 2:1 ratio) and then 
heated to make a homogeneous mixture. The proper amount of surface active 
agent mixture was then added to the siloxanate antifoam agent and the 
mixture heated and stirred until the surface active agents melted and were 
uniformly distributed throughout the antifoam. The non-aqueous antifoam 
compositions so prepared are listed below along with the identified 
surface active agent present in each composition. 
______________________________________ 
Non-Aqueous Surface 
Antifoam Active 
Compositions Agent 
______________________________________ 
I D 
II F 
III N 
IV O 
V P 
VI S 
VII W 
VIII X 
IX Y 
X Z 
XI AA 
XII BB 
XIII CC 
XIV II 
XV JJ 
XVI NN 
XVII QQ 
______________________________________ 
EXAMPLE 3 
A series of ten gram samples of non-aqueous antifoam compositions were 
prepared by repeating the procedure of Example 2 except that in this 
instance each prepared composition consisted of about 1 gram of surface 
active agent homogeneously blended in about 9 grams of the same siloxanate 
antifoam agent defined in Example 2. The non-aqueous antifoam compositions 
so prepared are listed below along with the identified surface active 
agent present in each composition. 
______________________________________ 
Non-Aqueous Surface 
Antifoam Active 
Compositions Agent 
______________________________________ 
XVIII A 
XVIX B 
XX C 
XXI D 
XXII E 
XXIII F 
XXIV G 
XXV H 
XXVI I 
XXVII K 
XXVIII L 
XXIX M 
XXX O 
XXXI J 
XXXII Q 
XXXIII R 
XXXIV T 
XXXV W 
XXXVI X 
XXXVII Y 
XXXVIII DD 
XXXIX EE 
XL FF 
XLI GG 
XLII HH 
XLIII JJ 
XLIV KK 
XLV LL 
XLVI MM 
XLVII NN 
XLVIII OO 
XLIX PP 
______________________________________ 
EXAMPLE 4 
A series of ten gram samples of non-aqueous antifoam compositions were 
prepared by repeating the procedure of Example 2 except that in this 
instance each prepared composition consisted of about 0.5 grams of surface 
active agent homogeneously blended in about 9.5 grams of the same 
siloxanate antifoam agent defined in Example 2. The non-aqueous antifoam 
compositions so prepared are listed below along with the identified 
surface active agent present in each composition. 
______________________________________ 
Non-Aqueous Surface 
Antifoam Active 
Compositions Agent 
______________________________________ 
L B 
LI C 
LII F 
LIII J 
LIV Q 
LV S 
LVI U 
LVII V 
LVIII W 
LIX X 
LX Y 
LXI AA 
LXII DD 
LXIII EE 
LXIV FF 
LXV II 
LXVI JJ 
LXVII NN 
LXVIII QQ 
______________________________________ 
EXAMPLE 5 
A series of 10 gram samples of non-aqueous antifoam compositions were 
prepared by repeating the procedure of Example 2 except that in this 
instance each prepared composition consisted of about 0.1 gram of surface 
active agent homogeneously blended in about 9.9 grams of the same 
siloxanate antifoam agent defined in Example 2. The non-aqueous antifoam 
compositions so prepared are listed below along with the identified 
surface active agent present in each composition. 
______________________________________ 
Non-Aqueous Surface 
Antifoam Active 
Composition Agent 
______________________________________ 
LVXIX DD 
LVXX EE 
LVXXI FF 
______________________________________ 
EXAMPLES 6-22 
The 80 percent active antifoam compositions produced in Example 2 above 
were tested according to the Bubbling Test (Test I) defined above and the 
results of said tests are given below in TABLE 1. 
TABLE 1 
______________________________________ 
Foam Volume Foam Volume 
Ex. Antifoam (cc) After (cc) After 
No. Composition 5 Minutes 10 Minutes 
______________________________________ 
6 I 440 580 
7 II.sup.b 427* 570* 
8 III 450 590 
9 IV 525 690 
10 V 490 640 
11 VI.sup.c 510 720 
12 VII.sup.d 540 750 
13 VIII.sup.a 490 700 
14 IX.sup.a 500 660 
15 X.sup.c 520 670 
16 XI.sup.a 450 640 
17 XII 490 690 
18 XIII 560 770 
19 XIV.sup.d 465 650 
20 XV.sup.d 510 720 
21 XVI.sup.d 510 720 
22 XVII.sup.d 450 620 
______________________________________ 
*Average results of three runs. 
.sup.a Low viscosity-some filler separation on bottom. 
.sup.b Viscous-lumpy 
.sup.c Viscous paste 
.sup.d Gross separation 
The above results demonstrate that all 80% active antifoam compositions (I 
to III), save for IV, V and X, containing a nonionic surface active agent 
having a HLB value of less than 9 were very effective in improving the 
antifoam properties of the neat siloxanate antifoam agent, while all the 
antifoam compositions VI to IX and XI to XVII containing a nonionic 
surface active agent having a HLB value of 9 or above were not as 
effective. 
EXAMPLES 18 TO 51 
The 90 percent active non-aqueous antifoam compositions produced in Example 
3 above were tested according to the Bubbling Test (Test I) defined above 
and the results of said tests are given below in TABLE 2. 
For comparison two control antifoams were also tested. 
Control antifoam YY consisted of the neat transient non-aqueous siloxanate 
antifoam agent defined in Example 2, i.e. free of any additives. The same 
Bubbling Test (Test I)defined above was repeated using about 0.1 grams of 
said antifoam YY and about 250 grams of the same soap solution. 
Control antifoam ZZ consisted of about 2 grams of control antifoam YY 
dispersed in about 98 grams of Dimethyl Cellosolve, a dispersing solvent. 
The same Bubbling Test (Test I) was repeated using about 2 grams of said 
antifoam ZZ and about 98 grams of the same soap solution. 
The results of said comparison tests are also given in TABLE 2 below. 
TABLE 2 
______________________________________ 
Ex. Antifoam Foam Volume (cc) 
Foam Volume (cc) 
No. Compositions After 5 Minutes 
After 10 Minutes 
______________________________________ 
18 XVIII 410 580 
19 XIX.sup.c 440 570 
20 XX.sup.a 450 590 
21 XXI.sup.d 435 570 
22 XXII.sup.a 450 600 
23 XXIII.sup.e 435* 562* 
24 XXIV.sup.e 450 590 
25 XXV.sup.e 450 590 
26 XXVI.sup.d 400 580 
27 XXVII.sup.d 430** 550** 
28 XXVIII.sup.d 520 660 
29 XXIX.sup.d 433** 547** 
30 XXX 485 640 
31 XXXI.sup.f 420 550 
32 XXXII.sup.f 460 590 
33 XXXIII 490 700 
34 XXXIV.sup.f 480 680 
35 XXXV.sup.d 515 750 
36 XXXVI.sup.a 470 630 
37 XXXVII.sup.a 453 610 
38 XXXVIII 425 500 
39 XXXIX 420 520 
40 XL 380 520 
41 XLI 470 700 
42 XLII 410 620 
43 XLIII 500 800 
44 XLIV 515 Separated *** 
45 XLV 620 Separated *** 
46 XLVI 650 Separated *** 
47 XLVII 630 900 
48 XLVIII.sup.d 520 780 
49 XLIX.sup.a 450 700 
50 Control YY 755 Separated*** 
51 Control ZZ 420 500 
______________________________________ 
*Average results of five runs. 
**Average results of three runs. 
***Foam column broke. 
.sup.a Low viscosity, some filler separation on bottom. 
.sup.b Slight non-homogenity 
.sup.c Viscous, lumpy 
.sup.d Gross separation 
.sup.e Slightly viscous 
.sup.f Viscous paste 
The above results demonstrate that all 90% active antifoam compositions 
(XVIII to XXVII, XXIX, XXXI and XXXVIII to XL) save for XXVIII, XXX, XLI 
and XLII, containing a nonionic surface active agent having a HLB value of 
less than 9 were very effective in improving the antifoam properties of 
the neat siloxanate antifoam agent, while all antifoam compositions (XXXII 
to XXXVII and XLIII to XLIX), save for XXXII, containing a nonionic 
surface active agent having a HLB value of 9 or more were not as 
effective. Note that antifoam compositions XLI and XLII were in general 
more effective than antifoam compositions XLIV to XLIX. The effectiveness 
of antifoam composition XXXII may be due to the fact that the nonionic 
surface active agent is self-emulsifying. Note also that the performance 
of antifoams XXXVIII to XL is similar to that of control antifoam 
composition ZZ which employs a dispersing solvent. 
EXAMPLES 52 to 70 
The 95 percent active non-aqueous antifoam compositions produced in Example 
4 above were tested according to the Bubbling Test (Test I) defined above 
and the results of said tests are given below in TABLE 3. 
TABLE 3 
______________________________________ 
Ex Antifoam Foam Volume (cc) 
Foam Volume (cc) 
No. Composition After 5 Minutes 
After 10 Minutes 
______________________________________ 
52 L 610 Separated* 
53 LI.sup.a 740 Separated* 
54 LII 460 610 
55 LIII.sup.b 420 560 
56 LIV.sup.c 480 650 
57 LV.sup.f 580 Separated* 
58 LVI.sup.a 550 790 
59 LVII.sup.a 540 750 
60 LVIII.sup.d 490 720 
61 LIX.sup.a 500 700 
62 LX.sup.a 480 620 
63 LXI.sup.a 500 740 
64 LXII 430 540 
65 LXIII 435 550 
66 LXIV 375 520 
67 LXV.sup.d 470 650 
68 LXVI.sup.d 500 690 
69 LXVII.sup.d 630 Separated* 
70 LXVIII.sup.d 490 700 
______________________________________ 
*Foam column broke 
.sup.a Low viscosity, some filler separation on bottom 
.sup.b Slight non-homogenity 
.sup.c Viscous, lumpy 
.sup.d Gross separation 
The above results based on 95% active antifoam compositions demonstrate 
that while antifoam composition LIII was the only composition containing a 
nonionic organic surface active agent having a HLB value of less than 9 
that was very effective in improving the antifoam properties of the neat 
siloxane antifoam agent, all the antifoam compositions (LXII to LXIV) 
containing a nonionic siloxane surface active agent having a HLB number of 
less than 9 were very effective in improving the antifoam properties of 
the neat siloxanate antifoam agent. Moreover all antifoam compositions 
(LIV to LXI and LXV to LXVIII) containing a nonionic organic or siloxane 
surface active agent having a HLB value of 9 or above were not as 
effective. 
EXAMPLES 71-73 
The 99 percent active non-aqueous antifoam compositions produced in Example 
5 above were tested according to the Bubbling Test (Test I) defined above 
and the results of said tests are given below in TABLE 4. 
TABLE 4 
______________________________________ 
Ex. Antifoam Foam Volume (cc) 
Foam Volume (cc) 
No Composition After 5 Minutes 
After 10 Minutes 
______________________________________ 
71 LVXIX 545 850 
72 LVXX 790 Separated* 
73 LVXXI 500 800 
______________________________________ 
*Foam column broke 
The above results demonstrate that antifoam compositions containing only 
about 1 percent by weight of a nonionic siloxane surface active agent 
having an HLB value of less than 9 were not very effective in improving 
the antifoam properties of the neat siloxanate antifoam agent. 
EXAMPLE 74 
Non-aqueous antifoam composition XVIII (as described in Example 3) was 
freshly prepared and tested for its activity according to the Bubbling 
Test (Test I) defined above. Said antifoam composition had a Brookfield 
viscosity (#1 Spindle, 6RPM) of about 161 centipoises at about 25.degree. 
C. The test was then repeated on the same antifoam soap solution after it 
has been aged for various periods of time at room temperature. The results 
were as follows: 
______________________________________ 
Foam Volume (cc) 
Period of Aging After 5 Minutes 
______________________________________ 
Fresh 390 
1 Hour 415 
3 Days 470 
5 Days 800 
______________________________________ 
The above results demonstate the transient nature of antifoam composition 
XVIII. 
EXAMPLE 75 
Non-aqueous antifoam composition LXIII (as described in Example 4) was 
freshly prepared and tested for its activity according to the Bubbling 
Test (Test I) defined above. Said antifoam composition had a Brookfield 
viscosity (#1 Spindle, 6RPM) of about 142 centipoises at about 25.degree. 
C. The test was then repeated on the same antifoam-soap solution after it 
had been aged for various periods of time at room temperature. The results 
were as follows. 
______________________________________ 
Foam Volume 
Period of Aging (cc) After 5 Minutes 
______________________________________ 
Fresh 420 
1 Hour 510 
1 Day No activity at all 
______________________________________ 
The above results demonstrate the transient nature of antifoam composition 
LXIII. 
EXAMPLE 76 
Non-aqueous antifoams XVIII (Example 3) and LXIII (Example 4) were tested 
for their activity on a variety of commercial foaming liquids according to 
Test III defined above. The results of said tests are given in TABLE 5 
below. 
TABLE 5 
__________________________________________________________________________ 
Antifoam LXIII 
Antifoam XVIII Time Till No Anti- 
Foaming Control Time Till No Antifoam Activity 
Foam Activity 
Type Liquid pH No Antifoam 
Fresh 
Hours Fresh 
Hours 
__________________________________________________________________________ 
Shampoo 
*Earthborn 3.9 N G 24 G 24 
**Breck Dry 7.9 N G 72 G 144 
**Breck Oily 8.2 N G 48 G 144 
Dish Detergents 
*** Joy 6.9 N C 144 C 144 
.sup.+ Palmolive 
7.2 N C 96 G M at 144 
Liquid Laundry 
Detergents 
.sup.+ Dynamo 
8.8 N C 48 G 48 
***Era 7.7 N G 48 G 48 
Liquid Hard 
Surface Cleaners 
.sup.++ Chlorox 409 
12.0 
N C 96 C M at 144 
*Product of Gillette Co. 
**Product of American Cyanamid Co. 
***Product of Proctor and Gamble Co. 
.sup.+ Product of Colgate Palmolive Co. 
.sup.++ Product of Chlorox Co. 
Antifoam Activity: C = Complete 
G = Good 
M = Moderate 
S = Slight 
N = None 
Note qualitative description given in Test III, defined above. 
The above results demonstrate the initial effectiveness of antifoam 
compositions XVIII and LXIII in commercial foaming liquids and their 
subsequent hydrolytic instability (transience). 
EXAMPLE 77 
This example demonstrates the stability of the non-aqueous antifoam 
compositions of this invention to room temperature aging. Antifoam 
compositions II, XVIII, XX, XXII, XXIII, XXIV, XXV, LII and LIII were 
stored at room temperature for various time periods and tested for 
effectiveness at the end of said time periods according to the Bubbling 
Test (Test I) defined above. The results of said tests are given in Table 
6 below. 
TABLE 6 
__________________________________________________________________________ 
Non-Aqueous 
Days Aged 
Antifoam 
at Room 
Foam Volume Foam Volume 
Compositions 
Temperature 
(cc) After 5 Minutes 
(cc) After 10 Minutes 
__________________________________________________________________________ 
II.sup.+++ 
0 430 570 
" 11 480 620 
" 18 490 670 
" 43 455 600 
XVIII.sup.+ 
0 410 580 
" 24 400* 560* 
" 60 450 600 
XX.sup.+ 
0 450 590 
" 30 370 520 
XXLL.sup.30 
0 450 600 
" 24 470* 610* 
XXIII.sup.+ 
0 435 590 
" 5 430* 578* 
" 12 460* 610* 
" 35 400 510 
" 36 452* 600* 
XXIV.sup.+ 
0 450 590 
" 24 440 590 
XXV.sup.+ 
0 450 590 
" 30 400 530 
LII.sup.++ 
0 460 610 
" 11 500 660 
" 43 460 640 
LIII.sup.++ 
0 420 560 
" 11 565* 750* 
__________________________________________________________________________ 
.sup.30 Same as described in Example 3 
.sup.++ Same as described in Example 4 
.sup.++ Same as described in Example 2 
*Average results of two runs. 
EXAMPLES 78-84 
Antifoam compositions XVIII, XX, XXIII, XXIV and XXV were prepared on a 
larger scale (200 gram preparations) using the same ingredients and ratio 
of ingredients and compared with larger scale preparations of control 
antifoam compositions YY and ZZ. 
Thus, about a 120 pound preparation of control antifoam composition YY was 
prepared by mixing and shearing about 12 pounds of finely divided fumed 
silica filler with about 108 pounds of condensation product of Example 1 
which was then heated for about two hours at about 150.degree. C. 
The 200 gram preparation of antifoam compositions XVIII, XX, XXIII, XXIV 
and XXV consisted of about 20 grams of Surfactants A, C, F, G, and H 
respectively, homogeneously blended at about 70.degree. C with about 180 
grams of said large scale preparation of antifoam composition YY. Control 
antifoam composition ZZ consisted of about a 2 weight percent solution of 
said large scale preparation of antifoam composition YY in Dimethyl 
Cellosolve (i.e. about 2 grams of antifoam YY in about 98 grams of 
Dimethyl Cellosolve). 
The large scale antifoam compositions so produced were then tested for 
effectiveness according to the Bubbling Test (Test I) defined above, using 
about 0.1 gram of antifoam compositions XVIII, XX, XXIII, XXIV, XXV and YY 
respectively to about 250 grams of the soap solution and about 2 grams of 
antifoam composition ZZ to about 98 grams of the same soap solution. The 
results of said tests are given below in TABLE 7. 
TABLE 7 
______________________________________ 
Ex. Antifoam Foam Volume Foam Volum (cc) 
No. Compositions 
After 5 Minutes 
After 10 Minutes 
______________________________________ 
78 XVIII 775* Separated** 
79 XX 445* 585* 
80 XXIII 400* 575* 
81 XXIV 420 530 
82 XXV 440 590 
83 YY 775.sup.+ Separated** 
84 ZZ 424.sup.++ 498.sup.++ 
______________________________________ 
*Average results of two runs. 
**Foam column broke 
.sup.+ Average results of four runs (Standard deviation after 5 minutes 
about 30). 
.sup.++Average results of nine runs (Standard deviation after 5 minutes 
about 26 and after 10 minutes about 45). 
The data in Table 7 on the larger scale preparations in general 
demonstrates good agreement with the small scale preparation data in Table 
1. The large scale preparation of antifoam composition XVIII for some 
unknown reason did not work as well compared to its small scale 
preparation, however, upon retesting two months later antifoam composition 
XVIII showed excellent performance. 
EXAMPLE 85 
This Example demonstrates the heat stability of the non-aqueous antifoam 
compositions of this invention upon aging at 50.degree. C. Antifoam 
compositions XX, XXIII, XXIV, and XXV were stored at 50.degree. C. for 
various time periods and tested for effectiveness at the end of said time 
periods according to the Bubbling Test (Test I) defined above. The results 
of said tests are given in Table 8 below. 
TABLE 8 
______________________________________ 
Non-Aqueous 
Weeks Foam Volume 
Foam Volume 
Anti-foam Stored (cc) After 5 
(cc) After 
Compositons.sup.+ 
at 50.degree. C. 
Minutes 10 Minutes 
______________________________________ 
XX 1** 490* 695* 
XXIII 1 Precipitate 
Formed 
XXIV After 2 days 
at 50.degree. C. a 
precipitate 
formed 
XXV 1** 510 670 
Control YY 1 400 460 
______________________________________ 
.sup.+ Same as described in Examples 78-84 and freshly prepared 
*Average results of two runs 
**Antifoam degrades 
EXAMPLE 86 
This Example demonstrates the stability of the non-aqueous antifoam 
compositions of this invention upon cooling to 0.degree. C. and then 
rewarming to room temperature. Antifoam compositions XVIII XX, XXIII, and 
XXV were cooled to 0.degree. C. and tested for effectiveness upon being 
rewarmed to room temperature according to the Bubbling Test (Test I) 
defined above. In some instances the antifoam composition went through two 
cooling and rewarming cycles. The results of said test are given in Table 
9 below. 
TABLE 9 
______________________________________ 
Non-Aqueous 
Cooling/ Foam Volume Foam Volume 
Antifoam Rewarming (cc) After 5 
(cc) After 
Composition.sup.+ 
No. Cycles Minutes 10 Minutes 
______________________________________ 
XVIII 1 750 Separated* 
" 2 790 Separated* 
XX 1 430 590 
" 2 440 590 
XXIII 1 430 590 
" 2 420 570 
XXV 1 450 590 
" 2 460 600 
______________________________________ 
.sup.+ Same as described in Exampls 78-84 and freshly prepared. 
*Foam column broke. 
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 the appended claims.