United States Patent (19) 11 Patent Number: 4,639,489

Aizawa et al. (45) Date of Patent: Jan. 27, 1987

54 METHOD OF PRODUCING ASILICONE 4,443,359 4/1984 Shimizu et al. ..................... 252/321
DEFOAMER COMPOSITION 4,486,336 12/1984 Pape et al. ...... ... 252A358
4,554,187 11/1985 Grape et al. ........................ 524/588
75 Inventors: Koichi Aizawa; Shingo Sewa; Hideki FOREIGN PATENT DOCUMENTS
Nakahara, all of Kanagawa, Japan
73) Assignee: Dow Corning Kabushiki Kaisha, 23613 1/1970 Japan .
Tokyo, Japan 1602 8/1972 Japan .
21) Appl. No.: 738,922 Primary Examiner-Lewis T. Jacobs
Attorney, Agent, or Firm--George A. Grindahl
22 Filed: May 29, 1985
30 Foreign Application Priority Data 57 ABSTRACT
May 30, 1984 JP Japan ................................ 59-108450 Foam control compositions are prepared by reacting a
mixture of components which include a polyor
51) int. Cl“................................................ C08K 3/36 ganosiloxane fluid bearing one or more hydroxyl and
52 U.S. C. .................................... 524/588; 524/501; /or hydrocarbonoxy groups, a resinous siloxane or a
524/863; 252/321; 252/358 silicone resin-producing silicon compound, a finely
58) Field of Search ....................... 524/588, 863, 501; divided filler material and a catalyst to promote the
252/.321, 358 reaction of the listed components. The compositions
56) References Cited can optionally contain a polyorganosiloxane fluid
U.S. PATENT DOCUMENTS which is substantially free of reactive groups and/or a
polyorganosiloxane fluid bearing two or more hydroxyl
3,455,839 7/1969 Rauner ....... 252/321 and/or hydrocarbonoxy groups.
3,560,401 2/1971 O'Hara et al. ...................... 252/358
4,101,499 7/1978 Herzig ................................. 524/863
4,145,308 3/1979 Simoneau et al. .................. 252/321 18 Claims, No Drawings
 4,639,489
1. 2
drolyzable group and d has an average value of one
METHOD OF PRODUCING A SELICONE or less;
DEFOAMER COMPOSITION (b) a partially hydrolyzed condensate of the con
pound (a);
BACKGROUND OF THE INVENTION 5 (c) a siloxane resin consisting essentially of (CH3)3Si
This invention relates to a method of producing a O1/2 and SiO2 units and having a (CH3)3SiO1/2-
defoamer composition. /SiO2 ratio of 0.4/1 to 1.2/1; and
The foaming of a liquid presents a serious problem in (d) a condensate of the compound (c) with the com
a variety of industrial processes including the treatment pound (a) or (b);
10 (4) 0.5 to 30 parts by weight of a finely divided filler
of the liquid itself or the treatment of something else by for every 100 parts by weight of the components (1) and
the liquid. The foaming of the liquid brings about a (2);
reduction in the efficiency of the treatment or a lower (5) a catalytic amount of a compound for promoting
ing in the quality of the product to be manufactured. the reaction of the other components; and
It is known that the problem of foaming may be 15 (6) 0 to 20 parts by weight, for every 100 parts by
solved by a defoamer having the effect of breaking foam weight of the components (1) and (2), of a polyor
in a liquid or inhibiting or reducing its foamability. A ganosiloxane having a viscosity of 5 to 200 cs at 25 C.
silicone defoamer is particularly suitable, since it is and being expressed by the general formula (R-8(R90)?.
chemically stable and hardly has an influence on the SiO(4-e-f/2 in which R8 is a monovalent hydrocarbon
liquid to which it is applied, and its use in a very small 20 or halogenated hydrocarbon group having 1 to 10 car
quantity produces a relatively large defoaming effect. bon atoms, R9 is hydrogen or a monovalent hydrocar
Various types of silicone defoamers have hitherto bon group having 1 to 10 carbon atoms, e is from 1.9 to
been proposed and are known. For example, Japanese 2.2 on an average and f has a sufficiently large value to
Patent Publication No. 23613/1970 describes a de give at least two -OR9 groups in each molecule at the
foamer composition composed of dimethylpolysiloxane 25 end of a molecular chain.
oil, a specific siloxane resin and silica aerogel. Japanese The invention will now be described more specifi
Patent Publication No. 1602/1972 describes a defoamer cally.
composition obtained by heating polyorganosiloxane According to this invention, a mixture of the compo
with a finely powdered additive, such as silica, in the nents (2) to (5) or a mixture further containing the com
presence of an alkaline substance. The known silicone 30 ponent (1) and/or (6) is reacted under heat to produce a
defoamers have, however, the disadvantage that their defoamer composition.
defoaming effect, particularly their foam inhibiting ef Component (1) is a polyorganosiloxane expressed by
fect, lasts only for a short period of time and fails to the general formula RaSiO(4-a)/2 and having a viscos
satisfy the requirement of a process in which it is neces ity of 20 to 100,000 centistokes (cs) at 25 C. The organo
sary to inhibit foam for a long period of time. 35 groups R of the polyorganosiloxane are the same or
Under these circumstances, it is an object of this different monovalent hydrocarbon or halogenated hy
invention to provide a method of producing a defoaner drocarbon groups having one to ten carbon atoms. Spe
composition which maintains an excellent foam inhibit cific examples thereof are well known in the silicone
ing effect for a long period of time. industry and include methyl, ethyl, propyl, butyl, octyl,
trifluoropropyl, phenyl, 2-phenylethyl and vinyl
DETAILED DESCRIPTION OF THE groups. The methyl group is particularly preferred. In
INVENTION the formula, a is a value ranging from 1.9 to 2.2. The
This invention is characterized by reacting at a tem polyorganosiloxane consists essentially of R2SiO and
perature of 50° C. to 300° C.: R3SiO1/2 units, but may further contain RSiO3/2 and
(1) 0 to 100 parts by weight of a polyorganosiloxane 45 SiO4/2 units if the value of a representing the molar ratio
having a viscosity of 20 to 100,000 cs at 25 C. and being of R1/Si is within the range hereinabove specified. It
does not substantially contain any OH or hydrolyzable
expressed by the general formula RaSiO(4-a)/2 in groups, though it may contain a residual amount thereof
which R1 is a monovalent hydrocarbon or halogenated which may be introduced during the process of produc
hydrocarbon group having 1 to 10 carbon atoms and a 50 tion. It is particularly preferable to use polydimethylsi
has an average value of from 1.9 to 2.2; loxane endblocked by a trimethylsilyl group and having
(2) 5 to 100 parts by weight of a polyorganosiloxane a viscosity of 350 to 15,000 cs at 25 C.
having a viscosity of 200 to several million cs at 25 C. Component (2) is a polyorganosiloxane expressed by
and being expressed by the general formula Rb2CRO)c- the general formula Rb (RO)SiO(4-b-c)/2 and having
SiO(4-b-c)/2 in which R2 is a monovalent hydrocarbon 55 a viscosity of 200 to several, for example 1, 2, 5, 10, 20
or halogenated hydrocarbon group having 1 to 10 car and 50, million centistokes at 25 C. R2 is a monovalent
bon atoms, R3 is hydrogen or a monovalent hydrocar hydrocarbon or halogenated hydrocarbon group hav
bon group having 1 to 10 carbon atoms, b has an aver ing one to ten carbon atoms. Specific examples thereof
age value of from 1.9 to 2.2 and chas a sufficiently large are those hereinbefore given for R. R3 is a hydrogen
value to give at least one -OR3 group in each mole atom or monovalent hydrocarbon group having one to
cule, said -OR group being present at least at the end ten carbon atoms, such as those given for R, and the
of a molecular chain; -OR3 group is present at the end of a molecular chain
(3) 0.5 to 20 parts by weight for every 100 parts by of polyorganosiloxane. The value of b ranges from 1.9
weight of the components (1) and (2) of one or more to 2.2 and c is a sufficiently large value to give at least
compounds selected from the following (a) to (d); 65 one -OR3 group in each molecule. It is particularly
(a) an organosilicon compound of the general formula preferable to use polydimethylsiloxane having an end
RdSiX4-din which R is a monovalent hydrocar hindered by a hydroxyl group and having a viscosity of
bon group having 1 to 5 carbon atoms, X is a hy 1,000 to 50,000 cs at 25 C.
 4,639,489 4.
3
Component (3) is any of the following compounds (a) any of the compounds from which the component (3) is
to (d): selected, the resulting alkali metal silanolate is also suit
(a) An organosilicon compound of the general for able for use as component (3) and if its amount covers
mula RdSiX4-d. R is a monovalent hydrocarbon the quantity required of component (3), it is not always
group having one to five carbon atoms. X is a hy necessary to use any additional component (3). The
drolyzable group, such as -OR5 or -OR6OR7. alkali metal alkoxide is a product of the reaction be
R6 is a divalent hydrocarbon group having one to tween an alkali metal hydroxide and an alcohol having
five carbon atoms and R5 or R7 are each hydrogen one to five carbon atoms. Examples of quaternary am
or a monovalent hydrocarbon group having one to monium hydroxides are beta-hydroxyethyltrimethyl
five carbon atoms. The average value of d does not 10 ammonium hydroxide, benzyltrimethyl ammonium hy
exceed 1. Therefore, this compound is one of the droxide and tetramethyl ammonium hydroxide. Exam
formula RSiX3 or Six4, or a mixture thereof. ples of quaternary phosphonium hydroxides are tet
These organic silicon compounds are well known rabutyl phosphonium hydroxide and tetraethylphos
in the silicone industry and examples thereof in phonium hydroxide. Examples of the metal salts of
clude CH3SiOCH3)3, CH3Si(OC2H5)3, 15 organic acids are dibutyltin dilaurate, stannous acetate
CH2=CHSiOCH3)3, C6H5Si(OC2H5)3, Si or octanoate, lead naphthenate, zinc octanoate, iron
(OC2H5)4, Si(OC3H7)4, CH2=CHSi.(OC2H5)3 and 2-ethylhexoate and cobalt naphthenate.
Si(OC2H4OC2H5)4. Component (6) is a polyorganosiloxane expressed by
(b). A partially hydrolyzed condensate of the com the general formula (Re(RO)/SiO(4-e-f/2 and having
pound (a). This condensate can be prepared by a 20 a viscosity of 5 to 200 cs at 25 C. R8 is a monovalent
known method. hydrocarbon or halogenated hydrocarbon group hav
(c) A siloxane resin consisting essentially of ing one to ten carbon atoms. R is hydrogen or a mono
(CH3)3SiO1/2 and SiO2 units and having a valent hydrocarbon group having one to ten carbon
(CH3)3SiO1/2/SiO2 ratio of 0.4/1 to 1.2/1. These atoms. The value of e ranges from 1.9 to 2.2. It is the
siloxane resins are commercially available. They 25 same as the polyorganosiloxane used as component (2),
are produced by the cohydrolysis and condensa except that component (6) has a viscosity of 5 to 200 cs
tion of (CH3)3SiCl and SiCl4 or the reaction be at 25 C., and except that f is a sufficiently large value to
tween (CH3)3SiCl with a silicate solution. A silox give two or more -OR9 groups in each molecule. It is
ane resin usually contains residual amounts of hy particularly preferable to use polydimethylsiloxane
droxyl groups, e.g., about 2 to 5% by weight. The 30 having an end hindered by a hydroxyl group and having
residual hydroxyl group can be decreased to sub a viscosity of 10 to 50 cs at 25 C.
stantially zero by a known method, if desired. All A mixture of components (2) to (5), optionally con
of these siloxane resins are usable for the purpose of taining components (1) and/or (6) is reacted under heat
this invention irrespective of the amount of the to produce a silicone defoamer composition. The pro
residual hydroxyl group. 35
portions of the components are:
(d) A condensate of the siloxane resin (c) with the Component (1)-0 to 100 parts by weight;
compound (a) or (b). Condensation of siloxane Component (2)-5 to 100 parts by weight;
resins with hydrolyzable silanes can be accom Component (3)-0.5 to 20, preferably 1 to 7, parts by
plished by a known method. weight;
Component (4) is a finely divided filler such as fume Component (4)-0.5 to 30, preferably 1 to 7, parts by
TiO2, Al2O3, Al2O3/SiO2 and SiO2. weight;
Silica (SiO2) can be produced by a dry method such Component (5)-A catalytic amount usually in the
as the thermal decomposition of a silicon halide or the range of 0.03 to 1 part by weight;
reaction of a substance containing silicic acid under Component (6)-0 to 20, preferably 1 to 10, parts by
heat, or silica produced by a wet method such as the 45
weight; the proportion of each of components (3)
decomposition of a metal salt of silicic acid, e.g., sodium to (6) being shown for a total of 100 parts by
silicate, by an acid or the aerogel method. Various
grades of silica having a particle size of several millimi weight of (1) and (2). The proportions of compo
crons to several microns and a specific surface area of nents (1) and (2) depend largely on their viscosity.
about 500 to 50 m2/g are commercially available. 50 Component (2) having a high viscosity, e.g., close
Fume TiO2, Al2O3 and Al2O3/SiO2 can be prepared to that of gum, can be used if it is combined with
by the well-known process of burning TiCl4, AlCl3 and component (1) of low viscosity. It is preferable to
SiCl4 and mixtures thereof. use a mixture of (1) and (2) which has a viscosity of
Component (5) is a compound used as a catalyst for 1,000 to 100,000 cs at 25 C.
promoting the reaction of the other components. It is 55 An appropriate mixture of the components each in an
preferably selected from siloxane equilibration and/or appropriate quantity may be prepared by mixing all the
silanol-condensing catalysts such as alkali metal hy components except (4) and then admixing (4) uniformly
droxides, alkali metal silanolates, alkali metal alkoxides, by an appropriate dispersing device, such as a homo
quaternary ammonium hydroxides and silanolates, qua mixer, colloid mill or triple roll mill. The mixture is
ternary phosphonium hydroxides and silanolates and heated to a temperature of 100° C. to 300° C. and re
metal salts of organic acids. These compounds are well acted for one to eight hours, although the reaction time
known in the field of silicone chemistry and are not varies depending on the temperature. The details of the
considered to need any detailed description. KOH and reaction of the various components is not clear. How
CsCH are examples of alkali metal hydroxides. If one of ever, it is apparent that a reaction takes place because no
them is reacted with low molecular silicone or silicate 65 defoaming effect is expected from a simple mixture of
or a partially hydrolyzed product thereof, there is ob the components which is not heated. It is preferable to
tained an alkali metal silanolate. If the low molecular carry out the mixing and heating of the components in
silicone or silicate which is employed corresponds to an inert gas atmosphere in order to avoid any danger
 4,639,489
5 6
and remove volatile matter (unreacted matter, by-pro C. to 110° C. was reached, 180g of polydimethylsilox
ducts, etc.). ane having an end hindered by a hydroxyl group and
The mixing order of the components and the heating having a viscosity of 12,500 cs at 25 C. were added and
temperature and time as hereinabove stated are not stirring and heating were continued. After several tens
critical, but can be changed as required. of minutes, 30 g of silica of the same type as that used in
The silicone defoamer composition produced by this Example 1 were added and dispersed uniformly by a
invention may be used as it is, or in the form of a solu homomixer, and the mixture was heated to 230 C. It
tion obtained by dispersion in an appropriate solvent or was reacted at 230 C. for two hours and cooled to
an emulsion obtained by a known emulsifying method, ambient temperature to yield a silicone defoamer com
and provides a defoamer having a good defoaming 10 position (Composition D). The whole process was car
effect which lasts for a long period of time. ried out in a nitrogen gas atmosphere.
The invention will now be described with reference EXAMPLE 5
to examples which are merely illustrative of this inven
tion. 384 g of polydimethylsiloxane having an end hin
EXAMPLE 1.
15 dered by trimethylsilyl and having a viscosity of 1,000
cs at 25 C. and 25.8g of a siloxane resin consisting of
A three-necked flask having a capacity of one liter (CH3)3SiO1/2 and SiO2 units and having a (CH3)3Si
and provided with a stirrer and devices for introducing O/2/SiC)2 ratio of 0.4/1 to 1.2/1 were uniformly mixed
nitrogen gas thereinto and discharging it therefrom was with stirring in a one liter beaker. Added to the mixture
charged with 378 g of polydimethylsiloxane end 20 were 180g of polydimethylsiloxane having an end hin
blocked by trimethylsilyl groups and having a viscosity dered by a hydroxyl group and having a viscosity of
of 1,000 cs at 25 C., 180 g of polydimethylsiloxane 12,500 cs at 25 C. After several minutes of stirring, 3 g
having an end hindered by a hydroxyl group and having of a catalyst C, which had been prepared by reacting 90
a viscosity of 12,500 cs at 25 C. and 18 g of ethyl g ofisopropyl alcohol and 10 g of KOH at 80 C. for 20
polysilicate ("Silicate 45' of Tama Kagaku Kogyo Co., 25 minutes, were added and heating was started. When a
Ltd.). They were stirred and heated. When a tempera temperature of 130 C. to 140 C. was reached, 30 g of
ture of 130 C. to 140 C. was reached, 3 g of a catalyst silica of the same type as that used in Example 1 were
A, which had been obtained by reacting at 120 C. for uniformly dispersed by a homomixer. Then, the appara
15 minutes 90 g of polydimethylsiloxane endblocked by tus of Example 1 was used to carry out two hours of
trimethylsilyl groups and having a viscosity of 1,000 cs 30 reaction at 230 C. The reaction product was heated for
at 25 C. and 10g of KOH, were added, and stirring and an hour at 180° C. and a reduced pressure of 400 mm
heating were continued. Then, 30 g of silica ("Aerogel Hg, whereby the unreacted matter and the by-product
#200” of Nippon Aerogel Co. having a surface area of of the reaction were removed. Then, it was cooled to
200 m2/g) and 30 g of polydimethylsiloxane having an ambient temperature to yield a silicone defoamer com
end hindered by a hydroxyl group and having a viscos 35 position (Composition E).
ity of 40 cs at 25 C. were added and dispersed uni EXAMPLE 6
formly by a homomixer. Heating was continued at 180
C. for four hours to complete the reaction. The reaction The apparatus of Example 1 was used to stir and mix
product was heated for an hour at 180 C. and a reduced uniformly 552 g of polydimethylsiloxane endblocked by
pressure of 40 mm Hg, whereby the unreacted matter trimethylsilyl groups and having a viscosity of 1,000 cs
and the by-product of the reaction were removed. at 25' C., 18 g of the same siloxane resin as that used in
Then, it was cooled to ambient temperature to yield a Example 5 and 0.78g of lead octylate. Then, 18 g of the
viscous, colorless and transparent silicone defoamer same silica as that used in Example 1 were added and
composition (Composition A). The whole process was dispersed uniformly by a homomixer. Added to the
carried out in a nitrogen gas atmosphere. 45 mixture were 1.2 g of the same ethyl polysilicate as that
EXAMPLE 2
used in Example 1 and 120 g of polydimethylsiloxane
having an end hindered by a hydroxyl group and having
A silicone defoamer composition (Composition B) a viscosity of 2,000 cs at 25° C. The resulting mixture
was produced by repeating Example 1 except that the was reacted at 200 C. for two hours and the reaction
polydimethylsiloxane having an end hindered by a hy 50 product was cooled to yield a silicone defoamer compo
droxyl group and having a viscosity of 40 cs at 25 C. sition (Composition F). The whole process was carried
was not used. out in a nitrogen gas atmosphere.
EXAMPLE 3 COMPARATIVE EXAMPLE 1.
A silicone defoamer composition (Composition C) 55 A uniform mixture was prepared under stirring from
was produced by repeating Example 1 except that the 570 g of the same polydimethylsiloxane having an end
polydimethylsiloxane having an end hindered by a hy hindered by trimethylsilyl as that used in Example 1 and
droxyl group and having a viscosity of 12,500 cs at 25 3 g of catalyst CofExample 5 and 30 g of the same silica
C. was replaced by one having a viscosity of 2,000 cs at as that used in Example 1 were uniformly dispersed in
25° C. the mixture by a triple roll mill. The resulting mixture
EXAMPLE 4
was placed in the apparatus of Example 1 purged with
nitrogen gas and reacted at 220 C. for two hours to
The same apparatus as in Example 1 was used to stir yield a comparative silicone defoamer composition
and heat 384 g of polydimethylsiloxane endblocked by (Composition P).
trimethylsilyl groups and having a viscosity of 1,000 cs 65
COMPARATIVE EXAMPLE 2
at 25 C. and 6 g of a catalyst B (Silanolate obtained by
reacting 95 g of n-propylorthosilicate and 5 g of KOH A comparative silicone defoamer composition (Com
at 110° C. for 20 minutes). When a temperature of 100 position Q) was produced by repeating Comparative
 4,639,489 8
7
Example 1 except that the reaction was carried out at heated for an hour at 180° C. and a reduced pressure of
280 C. for two hours. 40 mm Hg, whereby the unreacted matter and the by
COMPARATIVE EXAMPLE 3 product of the reaction were removed. Then, it was
cooled to ambient temperature to yield a silicone de
A uniform solution was prepared by dissolving 15 g 5 foamer composition (Composition I).
of the same siloxane resin as that used in Example 5 in COMPARATIVE EXAMPLE 4
525 g of the same polydimethylsiloxane having an end
hindered by trimethylsilyl as that used in Example 1 and The apparatus of Example 1 was used to stir uni
60 g of silica produced by a wet method ("Degussa FK formly 390 g of the same polydimethylsiloxane end
383 DS' of Degussa, USA) were uniformly dispersed in O blocked by trimethylsilyl groups as that used in Exam
the solution by a triple roll mill. The mixture was placed ple 1 and 180 g of the same polydimethylsiloxane hav
in the apparatus of Example 1, purged with nitrogen gas ing an end hindered by a hydroxyl group as that used in
and reacted at 180° C. for two hours to yield a silicone Example 1 and heat their mixture with 3 g of catalyst C
defoamer composition (Composition R). of Example 5 under stirring. When a temperature of
EXAMPLE 7
15 130° C. to 140 C. was reached, 30 g of the same silica
as that used in Example 1 were added and mixed uni
The apparatus of Example 1 was used to stir and heat formly by a homomixer.
378 g of polydimethylsiloxane endblocked by trimethyl The resulting mixture is reacted at 180° C. for 4
silyl groups and having a viscosity of 12,500cs at 25' C., hours, heated at 180° C. under a reduced pressure of 40
180 g of the same polydimethylsiloxane having an end 20 mm of Hg for 1 hour and then cooled to room tempera
hindered by a hydroxyl group as that used in Example ture in order to obtain a silicone defoamer composition
1 and 18 g of the same ethyl polysilicate as that used in designated as Composition S.
Example 1. When a temperature of 130 C. to 140 C. Method of Testing Defoaming Property
was reached, 3 g of catalyst A of Example 1 were added
and stirring was continued for several minutes. Then, 30 25 Each of the compositions produced as hereinabove
g of the same silica as that used in Example 1 were described was emulsified in accordance with the fol
added and dispersed uniformly by a homomixer. The lowing recipe to prepare a 10% emulsion:
mixture was heated at 230 C. for two hours to con
plete its reaction. The reaction product was heated for Composition 10 parts by weight
an hour at 180° C. and a reduced pressure of 40 mm Hg, 30 Polyoxyethylene monostearate 1.4 parts by weight
whereby the unreacted matter and the by-product of Fatty acid ester of glycerin 1.2 parts by weight
the reaction were removed. Then, it was cooled to yield Hydroxyethyl cellulose 1.5 parts by weight
a silicone defoamer composition (Composition G). Antiseptic agent 0.1 part by weight
Water Balance
EXAMPLE 8 35
Total 100 parts by weight
A uniform mixture was prepared by a homomixer
from 528 g of polydimethylsiloxane having an end hin A known amount of the emulsion was added to a
dered by trimethylsilyl and having a viscosity of 1,000 foaming composition and was shaken for 10 seconds by
cs at 25 C. and 30 g of polydimethylsiloxane having an a barrel wrist action shaker under the conditions as will
end hindered by a hydroxyl group and having a viscos hereinafter be set forth. The time t (seconds) between
ity of several million cs comparable to that of gum at the discontinuance of shaking and the disappearance of
25 C. Added to the mixture were 18 g of ethyl polysili large bubbles and the time T (seconds) between the
cate ("Silicate 45' of Tama Kagaku Kogyo Co., Ltd.) discontinuance of shaking and the appearance of the
and they were stirred and heated. When a temperature liquid surface were measured. Then, it was shaken again
of 130 C. to 140 C. was reached, 3 g of catalyst A of 45 for 40 seconds and the time was likewise measured. The
Example 1 were added and stirring and heating were test was further continued by increasing the shaking
continued. Then, 30 g of silica (Aerogel #200) were time to 60, 120 and 180 seconds. The results are shown
added and dispersed uniformly by a homomixer. Then, in Table 1.
Example 1 was repeated for reacting the mixture and Test apparatus: Glass bottle having a capacity of 200
thereby producing a silicone defoamer composition 50 ml;
(Composition H). Foaming agent: 100 ml of a 1% aqueous solution of
EXAMPLE 9 Tween 80;
Amount of defoamer used: Amount giving a silicone .
The apparatus of Example 1 was used to stir and mix content of 20 ppm;
uniformly 384 g of polydimethylsiloxane endblocked by 55 Shaking frequency: 350 cycles per minute;
trimethylsilyl groups and having a viscosity of 1,000 cs Test temperature: 25 C.
at 25 C. and 25.8g of a partially hydrolyzed conden EXAMPLE 10
sate prepared from the same siloxane resin as that used
in Example 5 and ethyl orthosilicate. Added to the The reactor and procedure of Example 1 were used
mixture were 180g of polydimethylsiloxane having an to stir and heat 558g of polydimethylsiloxane having an
end hindered by a hydroxyl group and having a viscos end hindered by a hydroxyl group and having a viscos
ity of 12,500 cs at 25 C. After several minutes of stir ity of 12,500 cs at 25 C. and 24 g of normal ethyl silicate
ring, 3 g of catalyst CofExample 5 were added and the ('Silicate 28' of Tama Kagaku Kogyo Co., Ltd.). The
mixture was heated under stirring. When a temperature heating and stirring of the mixture were continued after
of 130° C. to 140 C. was reached, 30 g of the same silica 65 3 g of an alkaline catalyst, which had been obtained by
as that used in Example 1 were added and mixed uni reacting 90 g of ethyl alcohol and 10g of KOH at 60° C.
formly by a homomixer. The mixture was, then, reacted to 80 C., had been added. When a temperature of 130
at 230 C. for two hours and the reaction product was C. to 140 C. was reached, 30 g of the same silica as that
 4,639,489
9 10
used in Example 1 were uniformly dispersed by a homo (2) 5 to 100 parts by weight of a polyorganosilxoane
mixer. A reaction was caused by heating at 180° C. to having a viscosity of 200 to several million cs at 25
185 C. for about four hours understirring. The reaction C. expressed by the general formula Rb2(RO)Si
product was cooled to ambient temperature to yield a O(4-b-c)/2 in which R is a monovalent hydrocar
silicone defoamer composition (Composition J). 5 bon or halogenated hydrocarbon group having 1 to
The defoaming property of Composition J was tested 10 carbon atoms, R is hydrogen or a monovalent
by the method hereinabove described. The results are hydrocarbon group having 1 to 10 carbon atoms, b
shown in Table 1. has an average value of from 1.9 to 2.2 and c has a
EXAMPLE 11
sufficiently large value to give at least one -OR3
10 group in each molecule, said -OR group being
The reactor and procedure of Example 1 were used present at least at the end of a molecular chain;
to stir and heat 210 g of polydimethylsiloxane end (3) 0.5 to 20 parts by weight for every 100 parts by
blocked by trimethylsilyl groups and having a viscosity weight of said components (1) and (2) of one or
of 100 cs at 25°C., 300 g of polydimethylsiloxane hav more compounds selected from the following (a) to
ing an end hindered by a hydroxyl group and having a 15 (d):
viscosity of 12,500 cs at 25° C. and 24 g of ethyl polysi (a) an organosilicon compound of the general for
loxane ("Silicate 45" of Tama Kagaku Kogyo Co., mula RdSiX4-d in which R is a monovalent
Ltd.). The heating and stirring were continued after 3g hydrocarbon group having 1 to 5 carbon atoms,
of catalyst A of Example 1 had been added. Then, 30 g X is a hydrolyzable group and d has an average
of the same silica as that used in Example 1 were uni 20 value of one or less;
formly dispersed by a homomixer. After 30 g of polydi (b) a partially hydrolyzed condensate of said
methylsiloxane having an end hindered by a hydroxyl compound (a);
group and having a viscosity of 40 cs at 25 C. had been (c) a siloxane resin consisting essentially of
added, the mixture was reacted by heating at 180 C. for (CH3)3SiO1/2 and SiO2 units and having a
about four hours under stirring. The reaction product 25 (CH3)3SiO1/2/SiO2 ratio of 0.4/1 to 1.2/1; and
was heated for an hour at 180° C. and a reduced pres (d) a condensate of said compound (c) with said
sure of 40 mm Hg, whereby the by-product of the reac compound (a) or (b);
tion was removed. Then, it was cooled to ambient tem (4) 0.5 to 30 parts by weight of a finely divided filler
perature to yield a silicone defoamer composition for every 100 parts by weight of said components
(Composition K). 30 (1) and (2);
The defoaming property of Composition K was (5) a catalytic amount of a compound for promoting
tested by the method hereinbefore described. The re the reaction of the other components; and
sults are shown in Table 1. (6) 0 to 20 parts by weight, for every 100 parts by
weight of said components (1) and (2), of a polyor
TABLE 1 * 35 ganosiloxane having a viscosity of 5 to 200cs at 25
Example, t (sec.)/T (sec.) v. Shake Time C. and being expressed by the general formula
Compo-
sition
10
SeC.
40
Sec.
60
SeC. 120 sec. 180 sec, 180 sec.
Re(R90)/SiO4-e-f)/2 in which R8 is a monovalent
hydrocarbon or halogenated hydrocarbon group
3/3 3/3 4/16 8/16 15/30 17/63 having 1 to 10 carbon atoms, R9 is hydrogen or a
2/2
2/2
3/3
3/3
8/2
6/8
15/33
10/17
22/93
16/42
34/120
20/83
monovalent hydrocarbon group having 1 to 10
3/3 3/3 6/7 8/15 24/50 35/82 carbon atoms, e is from 1.9 to 2.2 on an average and
2/2 2/2 4/6 8/15 14/42 19/75 f has a sufficiently large value to give at least two
3/3 3/4 5/8 12/35 20/52 32/78 -OR9 groups in each molecule at the end of a
3/3 3/3 4/6 9/18 16/35 25/80 molecular chain.
3/3 3/4 7/12 15/28 22A83 32/120 45 2. A method according to claim 1 wherein the R
2/2 3/3 4/7 9/16 1.5/54 21/87
groups of component (1), the R2 groups of component

s
2/2 3/3 4/6 12/25 22/56 30/100
3/3 3/3 4/6 9/16 15/50 18/72 (2) and the R8 groups of component (6) are hydrocar
2/2 2/2 4/40 3/104 26/> 120 64/- bon groups; the X groups of component (3) (a) are
2/2 2/3 5/31 16/47 40/> 120 95/.
-OR groups or -OROR7 groups in which R6 is a
2, 50 divalent hydrocarbon group having 1 to 5 carbon atoms
3/4 3/4 7/1. 18/> 120 42/- >120/- and R5 and R7 are each hydrogen or a monovalent
hydrocarbon group having 1 to 5 carbon atoms; compo
2/2 3/4 5/18 13/54 28/> 120 45/> 120 nent (4) is silica; and component (5) is a compound
"The sign "> 120" means that the time was over 120 seconds.
selected from the group consisting of alkali metal hy
The sign "-" means that the time was so long that its measurement was considered 55 droxides, alkali metal silanolates, alkali metal alkoxides
meaningless. and metal salts of organic acids.
3. A method according to claim 2 wherein compo
That which is claimed is: nent (1) is a trimethylsiloxy-endblocked polydimethylsi
1. A method of producing a silicone defoamer con loxane fluid having a viscosity of from 350 to 15,000
position comprising reacting at a temperature of 50° C. centistokes at 25 C.; component (2) is a hydroxyl
to 300 C.: endblocked polydimethylsiloxane fluid having a viscos
(1) 0 to 100 parts by weight of a polyorganosiloxane ity of from 1,000 to 50,000 centistokes at 25' C.; compo
having a viscosity of 20 to 100,000 cs at 25° C. and nent (4) is a silica having a surface area of from 50 to 500
being expressed by the general formula RaSiO(4- m2/g; and component (6) is a hydroxyl-endblocked
-a)/2 in which R1 is a monovalent hydrocarbon or 65 polydimethylsiloxane having a viscosity of from 10 to
halogenated hydrocarbon group having 1 to 10 50 centistokes at 25 C.
carbon atoms and a has an average value of from 4. A method according to claim 3 wherein compo
1.9 to 2.2; nent (5) is a catalyst for the inter-condensation of sili
 4,639,489 12
11
con-bonded hydroxyl groups and/or silicon-bonded 12. A silicone defoamer composition obtained by the
alkoxyl groups. method of claim 6.
5. A method according to claim 3 wherein compo 13. A method according to claim 1 further compris
nent (5) is a catalyst for the rearrangement of siloxane ing mixing a diluent with the silicone defoamer compo
bonds. sition to provide a diluted silicone defoamer composi
6. A method according to claim 5 wherein compo tion.
nent (5) is a reaction product of potassium hydroxide 14. A method according to claim 13 wherein the
and component (3). mixing is accomplished by emulsifying the silicone de
7. A silicone defoamer composition obtained by the foamer composition in water.
method of claim 1.
10 15. A method according to claim 13 wherein the
mixing is accomplished by dispersing the silicone de
8. A silicone defoamer composition obtained by the foamer composition into a solvent therefor.
method of claim 2. 16. The diluted silicone defoamer composition pre
9. A silicone defoamer composition obtained by the pared by the method of claim 13.
method of claim 3. 15 17. The diluted silicone defoamer composition pre
10. A silicone defoamer composition obtained by the pared by the method of claim 14.
method of claim 4. 18. The diluted silicone defoamer composition pre
11. A silicone defoamer composition obtained by the pared by the method of claim 15. sk
method of claim 5.
20

25

30

35

45

50

55

65