United States Patent 0 ICC 3,235,509

Patented Feb. 15, 1966

1 2
3,235,509 where n has an average value from 1.8 to 2.0 [i.e. di
METHOD FOR PRODUCING ANTIFOAM AGENTS methylsiloxane polymers containing limited amounts of
Siegfried Nitzsche and Ewald Pirson, Burghausen, MeSiO3/2 and/or SiO4/2 units such that Me/Si is from
Bavaria, Germany, assignors to Wacker-Chemie 1.8/1 to 2.0/ 1]. In these siloxanes the valences of the
G.m.b.H., Munich, Bavaria, Germany Si atoms which are not satis?ed by oxygen in the form
No Drawing. Filed Oct. 3, 1962, Ser. No. 227,990 of siloxane bonds or by methyl substituents are satis?ed
5 Claims. (Cl. 252358) by any other atoms or radicals commonly appearing as
This invention relates to a novel method for preparing substituents on silicon in siloxane polymers, e.g. -~OH,
antifoam agents and to a new class of antifoam agents alkoxy radicals and acyloxy radicals with fewer than 13
effective in alkaline systems. carbon atoms each.
The use of organosiloxane polymers particularly in mix 10 It is to be understood that homopolymers, copolymers
ture with silicas as antifoam agents in aqueous systems and mixtures can be employed so long as the viscosity,
is well known. A variety of commercial antifoam agents CH3/Si ratio and proportions and identity of units present
based on organosiloxane polymers are presently available are within the limits set forth herein.
on the open market. However, the known antifoam 15 The inorganic ?llers employed herein are ?nely pow
agents exhibit little effect or rapidly lose their effective dered materials such as aluminum oxides, titanium di
ness in aqueous systems containing alkaline or alkaline oxides and particularly silicas exhibiting average particle
reacting materials. size within the range 0.01 to 25 microns. The silicas
It is the object of this invention to introduce a novel are preferred and include precipitated silicas, silica aero
method for preparing improved antifoam agents. An 20 gels, silica xerogels, and fume silicas. The inert inor
other object is an antifoam agent which is effective in ganic ?ller is employed in amounts of from 1 to 30 per
alkaline systems. Other objects and advantages of this cent by weight of the reaction mixture of siloxane and
invention are detailed in or will be apparent from the ?ller. Preferred products are obtained with from 3 to
disclosure and claims following. 10 parts by weight ?ller and 90 to 97 parts by weight
This invention consists of a method of preparing anti 25 siloxane polymer.
foam agents consisting essentially of heating a mixture The acid catalysts employed in the method of this
of ( 1) a methylsiloxane polymer having a viscosity in invention are those acid condensation catalysts common
the range 5-3000 cs. at 25 C., said polymer containing ly employed in organopolysiloxane chemistry. Operative
.25 to 25 mol percent Me3SiO1/2 units, up to 10 mol per acids are protonic acids and Lewis acids (see Chemie
cent of units selected from MeSiO3/2 and SiO4/2 units and 30 und Technologie der Silicone by W. Noll, published by
65 to 99.75 mol percent MeZSiO units and (2) a pulver Verlag Chemie G.m.b.H., Weinheim, Germany, 1960,
ulent inorganic ?ller having an average particle size of pages 138-144) as well as compounds splitting off pro
from .01 to 25 microns in the presence of (3) an acid tonic acids in the presence of water. The dissociation
condensation catalyst. constant of the operative protonic acids in dilute water
The methylsiloxane polymers employed herein are solution at 25 C. is preferably not under 1><10-5. In
known materials. The basic unit in these polymers is a addition to effecting the condensation of hydroxyl groups,
dimethylsiloxane unit of the formula (CH3)2SiO. The the acid catalysts effect a rearrangement or equilibration
dimethylsiloxane units comprise at least 65 mol percent of the siloxane polymer. Preferred acid condensation
and preferably 97.9 mol percent or more of the siloxane
catalysts are: AlCl3, FeCl3, SnCl4, TiCl4, BF3, ZnCl2 as
polymer. The balance of the units present can be tri 4.0 well as phosphorous nitrile halides and organo nitrogen
methylsiloxy units of the formula (CH3)3SiO1/2 which derivatives of phosphorous acid or phosphoric acid in
units can comprise up to 25 mol percent of the polymer which the nitrogen is substituted by organic radicals as de
but are preferably present in amounts of from 0.8 to 2 scribed in United States Patent No. 2,830,967, issued
mol percent of the polymer. Other units which can be April 15, 1958. Other acid catalysts employedto effect
present are monomethylsiloxane units of the formula condensation of organosiloxanes are also suitable foruse
CH3SiO3/2 and unsubstituted siloxane units of the formula herein. The examples of acid catalysts given are pre
SiO4/2 but such units are preferably kept to a minimum ferred over the sulfuric acid and alkyl sulfuric acids, for
of less than 10 mol percent and desirably below 0.1 mol instance, because the hydrogen halide formed during the
percent of the siloxane polymer. Thus, the preferred condensation reaction can be removed from the reaction
polymer is a trimethylsiloxy endblocked dimethylsiloxane mass simply by heating. The acid catalysts are employed
of the polymeric formula herein in quantities of from .01 to 5 percent by weight
based on the weight of methylsiloxane polymer present.
where n is such that the viscosity of the polymer at 25 The method of this invention can advantageously be
C. is from 5 to 3,000 cs. The ratio of methyl radicals carried forward in inert auxiliary ?uids preferably organic
to silicon atoms in the operative siloxane polymers is solvents. Examples of useful solvents for this inven
from 1.8/1 to 2.2/1. tion are aliphatic hydrocarbon solvents, aromatic hydro
The acid catalysts employed in the method of this in carbon solvents, ethers, ketones, and chlorohydrocarbons
vention effect a rearrangement of siloxane polymers under boiling at 50250 C. Speci?c examples are benzene,
the reaction conditions employed. Accordingly, mixtures toluene, xylene, ethylene glycol dimethylether, n-butyl
of methylsiloxane polymers having different viscosities 60 ether, diethyl ether, acetone, dibutyl ketone, methylene
. and different polymeric units present can be employed chloride, chlorobenzene, benzine, n-heptane, octene and
so long as the average viscosity, average ratio of methyl petroleum hydrocarbon solvents.
to silicon and percentages of the various units permitted The siloxane polymer, inorganic ?ller and acid cata
are within the limits set forth above. For example, one lyst are admixed in any desired order with or without
can employ mixtures of low viscosity trimethylsiloxy con 65 an inert organic solvent. The mass is then heated at
taining siloxanes such as Me3SiOSiMe3 and 60 to 250 C., preferably 110 to 240 C. The de
Me3SiOMe2SiOSiMe3 sired reaction will occur at room temperature but the
and higher viscosity cyclic or linear siloxanes of unit reaction time becomes impractically long, hence heat
formula ing is preferred. The reaction can be carried forward
70 under any desired pressure from sub-atmospheric to super
MenSiO4_n
2 atmospheric but the reaction goes forward satisfactorily
 3,235,509
4
at atmospheric pressure, hence excess or partial pressure In the above test for alkali resistance, there was no
is not required. foam formation to be observed after re?ux boiling for
The reaction of the siloxane polymer and ?ller mix 16 hours. 3 ml. of a 1 percent by weight dispersion
ture is carried forward for from 1 to 24 hours until of the antifoam in benzine boiling at 80 to 120 C.
the desired degree of alkali resistance is achieved. The will immediately depress the foam of a 1 percent by weight
alkali resistance of the product is tested as follows: A aqueous solution of Na-laurylsulfate.
test mixture is prepared from 175 ml. of water, 25 ml.
of a 30 weight percent water solution of a sodium par Example 3
a?in sulfonate prepared by sulfo chlorination of a par A mixture was prepared from 50 g. of precipitated
af?n mixture with an average of 1415 carbon atoms 10 silica with a kernel size of 0.02 to 1.0 microns, 600 g.
per molecule and subsequent saponi?cation with caustic of a trimethylsiloxy endblocked dimethylpolysiloxane,
soda, and 50 ml. of an aqueous l-N solution of NaOH. 50 cst., and 0.7 g. phosphorus nitrile chloride and heated
To this test mixture there is added 1 ml. of a 10 per for 10 hours at 130 C.
cent dispersion in toluene of the reaction product to be The mixture obtained is emulsi?ed with 85 g. poly
tested as an antifoam agent. The test mixture is then 15 ethylene glycol stearate with 500 ml. water in a high
re?uxed for 1 hour and if no foam appears during the speed mixer. 2 ml. of this dispersion in 1 liter of boil
re?uxing, the reaction product is considered to be an ing aqueous solution of 5 g. Na-oleate and 1 g. Na-sili
alkali resistant antifoam agent. cate will inhibit all foam formation for more than 10
After the siloxane ?ller reaction has been completed, hours.
the product can be homogenized on a 3-roll mill or in a 20 That which is claimed is:
high speed mixer if desired. 1. A method for preparing alkali-resistant antifoam
The antifoam agents prepared according to this in agents consisting essentially of heating at 60250 C.,
vention exhibit excellent resistance to alkali. They can for a period of from 1 to 24 hours, a mixture of (1)
be employed in undiluted form or as a dispersion, in 70 to 99 percent by weight of a methylsiloxane poly
inert organic solvents or as aqueous emulsions of the 25 mer having a viscosity of 53000 cs. at 25 0., having
oil in water type. The aqueous emulsions require the a methyl to silicon ratio in the range from 1.8/1 to
use of surface active emulsi?ers such as methyl cellu 2.2/1 and containing .25 to 25 mol percent (CH3)3SiO1/2
lose, sorbitol monostearate propylene glycol mono_ units, up to 10 mol percent of units selected from the
laurate, polyethylene glycol monostearate, polyethylene group consisting of CH3SiO3/2 and SiO4/2 units, and 65
glycol trimethyl nonyl ether and other protective col 30
to 99.75 mol percent of (CH3)2SiO units, (2) 1 to 30
loids, esters of polyalcoholates, and esters and ethers of percent by weight of a pulverulent inorganic ?ller se
glycols and polyglycols. lected from the group consisting of silicas, aluminum
The antifoam agents prepared by the method of this oxides and titanium dioxides having a particle size of
invention retain their effectiveness even when stored in from .01 to 25 microns in the presence of (3) .01 to 5
mixtures containing alkali materials. Thus, they are 35
percent by weight based on the polymer (1) of an acid
particularly useful as additives for alkaline cleaning prod condensation catalyst selected from the group consisting
ucts such as commercial soap and detergent laundry of Lewis acids and protonic acids.
products for use in automatic washing machines wherein 2. The method of claim 1 wherein the methylsiloxane
the development of foam is undesirable. The antifoam polymer contains 0.8 to 2 mol percent (CH3)3SiO1/2
agent can be added to powdered materials such as laun 4:0
dry powders in the form of dispersions in organic sol units, up to 0.1 mol percent of CH3SiO3/2 units, up to
0.1 mol percent SiO4/2 units and the balance of the units
vent or water with subsequent drying. being (CH3)2SiO units, the inorganic ?ller is a silica
The examples which follow do not limit the scope and the acid condensation catalyst is selected from the
of the invention which is fully de?ned in the claims. group consisting of Lewis acids and protonic acids.
The examples are merely to aid in understanding and 45 3. The method of claim 1 wherein the siloxane poly
practicing the invention. All parts and percentages in mer is a trimethylsiloxy endblocked dimethylsiloxane
the examples are based on weight unless otherwise speci polymer, the ?ller is selected from the group consisting
?ed and all temperatures are in degrees centigrade. The of silicas, aluminum oxides and titanium dioxides and
symbol Me represents the methyl radical throughout the acid catalyst is A1013.
this disclosure. All viscosities herein were measured at 50 4. The method of claim 1 wherein the siloxane poly
25 C.
mer is a trimethylsiloxy endblocked dimethylsilox-ane
Example] polymer, the ?ller is selected from the group consisting
A mixture of 900 g. of trimethylsiloxy endblocked of silicas, aluminum oxides and titanium dioxides and the
dimethylpolysiloxane with a viscosity of 50 cst., 200 g. acid catalyst is SnCl4.
dimethylpolysiloxane with a viscosity of 400 cst., dis 5. The method of claim 1 wherein the siloxane poly
playing terminal Si bonded OH groups, and 65 g. silica mer is a trimethylsiloxy endblocked dimethylsiloxane
aerogel with a particle size of 0.3 to 3 microns was polymer, the ?ller is selected from the group consisting
mixed with 1.5 g. mortar-ground AlCla and heated for of silicas, aluminum oxides and titanium dioxides and
10 hours at 180 C. 60 the acid catalyst is a phosphorous nitrile halide.
In the alkali resistance test described above, no foam
could be observed after 16 hours of re?ux boiling. An References Cited by the Examiner
otherwise identical mixture of organopolysiloxanes and UNITED STATES PATENTS
silicon dioxide not treated with aluminum chloride was
2,389,477 11/1945 Wright et al. ____ __ 260-465
ineffective after 2 minutes when tested for alkali resist 65
ance. 2,457,688 12/1948 Krieble et al. ____ __ 26037
ExampleZ 2,568,672 9/1951 Warrick __________ _... 260-37
2,632,736 3/1953 Currie ____________ __ 252358
1,000 g. of a dimethylpolysiloxane displaying terminal 2,894,913 7/1959 Sullivan et a1. __;__.__ 252-358
OH groups, with a viscosity of 800 cst., 250 g. hexa 2,972,579 2/1961 Delfel ____________ __ 252-358
methyldisiloxane and 200 g. aluminum oxide with an 70
average kernel size of 10 microns were mixed with 8 JULIUS GREENWALD, Primary Examiner.
g. SnCl4 and heated for 3 hours at 220 C. After cool
ing, the mixture was conducted through a 3-roll mill to MORRIS LIEBMAN, Examiner.
obtain a product of maximum uniformity.