Note: Descriptions are shown in the official language in which they were submitted.
The invention relates to the use of a composition,
consisting essentially of (A) an organopolysiloxane,
(B) a silicon compound having the general formula R2SiZ2,
wherein R is a monovalent hydrocarbon group and Z is a
hy~rolyzable group containing nitrogen, and (C) silica,
for the purpose of controlling foam.
Background of the Invention
Silicones have been widely used as antifoaming agents,
foam preventors, and/or defoaming agents, foam reducers.
However, in systems which require vigorous agitation, such
as aeration vats and jetdyeing, and in alkaline solutions,
such as the pulp digesting process, silicons foam control
agents are not durable.
Great Britain patent number 1,204,383 discloses a
foam control agent consisting essentially of a dispersion
of a dimethyldichlorosilane hydrophobized silica in an
organopolysiloxane fluid, and Great Britain patent number
1,468,896 discloses a foam control agent consisting
essentially of a dispersion of a nitrogen containing organic
silicon compound hydrophobized silica in an organopoly-
siloxane fluid. Besides having problems with durability,
these foam control agents are economically disadvantageous
because a long period of time is required to make the silica
hydrophobic, and a number of treatment processes are required.
Japanese patent Sho 52[1977]-41,184 discloses a
defoaming agent composes of an organopolysiloxane, a
powdered metal oxide, a filler, and amino-
organofunctional silicon compounds. Besides the
. ~
- ''XJ~'
~ .
-- 2
durability problem with this system, it also has a
tendency to precipitate.
It has been found in accordance with this
invention that the aforementioned problems can be
alleviated with the composition of this invention
which consists essentially of (A) an organopolysiloxane,
(B) a silicon compound having the general formula
R2SiZ2, wherein R is a monovalent hydrocarbon group
and Z is a hydrolyzable group containing nitrogen, and
(C) silica.
It is thus an object of this invention to provide
a composition that is durable for the purpose of
controlling foam, particularly for alkaline system and
; systems that are vigorously stirred.
Detailed Description
This invention relates to the use of a composition
consisting essentially of (A) an organopolysiloxane,
(B) a silicon compound having the general formula
R2SiZ2, wherein R is a monovalent hydrocarbon group
and z is a hydrolyzable group containing nitrogen,
and (C) silica, for the purpose of controlling foam.
Specifically, this invention relates to a
compositon to control foaming consisting essentially of
(A) 100 parts by weight of an organopolysiloxane
having (1) at least one terminal group
selected from the
group consisting of alkoxy and hydroxyl
groups, and
(2) a viscosity range of 10 to 100,000
centistokes at 25C,
--3--
(B) .1 to 50 parts by weight per 100 parts by
weight of Component (A) of an organic silicon
compound having the general formula R2SiZ2,
wherein R is an unsubstituted or substituted
monovalent hydrocarbon group, and Z is a
hydrolyzable group containing nitrogen, and
(c) 1 to 50 parts by weight per 100 parts by weight
.: of Component (A) of a silica.
The organopolysiloxane employed in the present
invention has the general formula RaSiO4_a/2 wherein R
is an unsubstituted or substituted monovalent hydrocarbon
group and "a" has a value of 1.9 to 2.1.
So far as is known at this time, the nature of
the substituents on the organopolysiloxane are not
critical. Thus, for example, any of the hydrocarbon or
substituted hydrocarbon substituents normally found on
silicon atoms in silicone fluids can be present.
Speeific examples of suitable substituents or radicals
are alkyl radieals sueh as the methyl, ethyl, propyl,
butyl, and octyl radicals; alkenyl radicals such as the
vinyl and allyl radicals; aryl radieals sueh as the
phenyl and biphenyl radieals; alkaryl radieals and
aralkyl radieals such as the tolyl and benzyl radicals;
and the corresponding substituted hydroearbon radicals
such as the ehloropropyl, 3,3,3-trifluoropropyl,
dichlorphenyl, eyanobutyl, nitrophenyl, mercaptopropyl,
earboxyethyl, and aminoisobutyl radieals.
The organopolysiloxane has to have at least one
: terminal group selected from the group consisting of
alkoxy and hydroxyl groups. Speeific examples of the
alkoxy group include methoxy, ethoxy, and phenoxy
radicals. So far as is known at this time, the nature of
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--4--
the other terminal groups is not critical, but it is
suggested that they be selected from the group consisting
Of alkoxy, hydroxyl, and triorganosilyl groups, and
mixtures of thereof.
It is perferred that the organopolysiloxane be
a straight chain or a partially branched straight chain.
The organopolysiloxane can be simple polymers, copolymers,
or mixtures thereof. Specific examples of suitable
organopolysiloxanes include dimethylsiloxane,
methylphenylsiloxane, methylethylsiloxane,
diethylsiloxane, ethylphenyisiloxane,
3,3,3-trifluoropropylethylsiloxane,
3,3,3-trifluoropropylmethylsiloxane, and
3,3,3-trifluoropropylphenylsiloxane. It is preferred,
however, that the organopolysiloxane be a hydroxyl
terminated dimethylpolysiloxane from the standpoint of
defoaming effects and economy.
Organopolysiloxanes with viscosities of 25C
in the range of 10 to 100,000 centistokes can be used,
but a viscosity range of 100 to 10,000 centistokes is
desirable.
The organic silicon compound used in the present
invention is a water hydrolyzable organic silicon
compound expressed by the general formula R2SiZ2, wherein
R is an unsubstituted or substituted monovalent
hydrocarbon group, and Z is a hydrolyzable group
containing nitrogen.
So far as is known at this time, the nature of
the hydrocarbon substituent, represented by R, on the
silane is not critical. Specific examples of suitable
substituents or radicals include alkyl radicals such as
the methyl, ethyl, and propyl radicals; alkenyl radicals
7~S3~
such as the vinyl, allyl, and butadienyl radicals; aryl
radi(-als such as the phenyl, xenyl, and naphthyl
radicals; cyclohexyl radical; cycloalkenyl radicals such
as the cyclohexenyl radica]; ara]kyl radicals such as the
benzyl radical; alkaryl radicals such as the tolyl and
xylyl radicals; and the corresponding substituted
hydrocarbon radicals such as the chloropropyl and the
3,3,3-trifluoropropyl radicals. It is not critical for
the purpose of this invention that the substituents be
identical.
The hydrolyzable groups containing nitrogen,
represented by Z, on the organic silicon compound can be
represented by amino groups, aminoxy groups, oxime
groups, amide groups, imide groups, and lactam groups, or
their partially hydrolyzed condensation products. The
suhstituen~s on the nitrogen functional hydrolyzable
group do not appear to be critical for the purpose of
this invention. The substituents can be hydrogens or
monovalent hydrocarbon groups, such as the me-thyl, vinyl,
phenyl, benzyl, tolyl, and 3,3,3-trifluoropropyl
radicals. It is preferred that Z be a water hydrolyzable
group select:ed from the group consistig of
R Rl ~ Rl r----~2
N ~ Rl ~ ON ~ R1 ' ON C ~ Rl ' -ON=C~ R
R10 Rl
- -
-N-C-R -N--COR and -N----CO
LR2J
.
:,
.,
.
, 6
:
wherein R~ is a hydrogen atom or a group selected from
monovalent hydrocarbon groups and R2 is an alkylene
group.
Specific examples of the organic silicon
compound, having the general formula R2SiZ2 wherein R is
an unsubstituted or substituted monovalent hvdrocarbon
group, and Z is a hydrolyzable group containing nitrogen,
include amino silanes such as
(CH3)2Si[NH(C4Hg)]2, (CH3)2Si[NH(C6H5)]2,
~CH3)2Si[N(CH3)2]2, (CH3t(C6H5)Si[N(CH3)2]2,
(cH3)(cH2=cH)si[N(cH3)2]2~ ~C2H5)2 ( 2 2
aminoxy si].anes such as
(CH3)2Si[ON(CH3)212, (CE13)(C6H5)Si[ON(CH3)2]2,
(C113)(CH2=CH)Si[ON(CH3)2]2,
(Cll3)2si[ON(c~l3)(c2~ls)]2
(CE~3)(cH2=cll)si[ON(c2~ls)2]2
oxime silanes such as
(CH3)2Si[ON=C(CT~3)2]2,
(CH3)(CH2=CH)Si[ON=C(CH3)2]2,
(CH3)2Si[OM=C(cH3)(c2H5)]2~
(CH3)(C6H5)Si[ON C(CH3)( 2 5 2
(CH3)2si-[oN=c(cH2)3cH2]2
amide si.lanec; such ~s
~ (~1130 1 ~ , "
(C~l3)2si tN-C-C113J2~ (CH3)(CH2=CII)si tN-C-C113~2'
3~
~3.. 1
(CH3)(C6H5)Si tN-C CH3~ 2'
C2H50
(CH3)(CH2=CH)Si -N-C-CH 2'
~6,5,,
(C113)2siL-N-c C113~2'
imicle silanes such as
r CT13
(CH3)2Si -N=COCH3 2'
~ CH~ 1
(CH3)(CH2=CH)si tN COCH3~2'
,2 5
(CH3)2Si -N=COCH3 2'
~ ,6 5 1 r CH3 1
(CH )2siL-N=COcH3~2~ (CH3)(c6H5) t 3J2
an(l la~tam silanes such as
(C113)2Si-~ N - CO
. LC112 - (CH2)4~ 2
.
~,.'`
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.
.: ,
't~
(C~13) (C~l~=CH) S i ~ N _ CO
CH2 (CH2) 4J
(CTI3) (C61T5)Si-- ~ N CO
LCH2 --(CH2 ) 4~ 2
(CH3) (CH2=CH) Si ~ N CO
LCH2 _ ~ CH2 ~ 3
Component ~) is present in the range of .1 to
50 parts by weight pe-r 100 parts by weight of Component
(A). There is no problem at all if the viscosity
increases to a certain degree with the addition of
Component (~), but because there is a tendency to gel
with a chain polymerization reaction, the amount of
Component ~B) to be added should be selected with care.
Therefore, it is preferred that the range be 1 to 10
parts by weight 2er 100 parts by weight of Component (A).
The silica, Component (C), used in the present
;nvention is represented by fumed silica, silica aerogel,
precipitatt-d silica, quartz powtler, fused sili.ca, antl
calcined silica. In terms of defoaming effects, it is
desirahlt- that the surface area of -the silica be greater
than ]00 m2/g. If the amount of silica added is either
excessive or inadequa,te, there is concern that the foam
control wil.l be insufficient, so it is present in the
range of 1 to 50 parts by weight, preferably 3 to 20
parts by weight, per 100 parts bv weight of Component
- (P').
''
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A wide variety of methods for preparing the
components of the present invention are we]l known in the
.~ rt: . ~ pers~n of ordinary skill in the art would be
c~p~ le oE making the componerlts useful in accordance
with this invention by conventional techniques,
especially in view of the disclosure provided in this
app]ication.
The foam control composition of the present
invention is obtained by mixing components (A), (B), and
(C). When mixing, heating and stirring for 2 to 3 hours
at a temperature of 120 to 200C is desirable. It is
desirable that the mixing apparatus be one in which
mixing and heating can be dome simultaneously. Also, the
present composition may be treated with homogenizer, ball
mill, col]o;d mill, 3 roll mill, etc., in order to make
it -rine and uniform. Reduced pressure operations and
inert gases t such as nitrogen, may also be used as
needed. In short, so long as mixing is uniform, any
apparatus can be used.
The mixing method nor the order of mixing is
not known to be critical for the purpose of this
invention, but the following methods, for example, can be
employed:
(1) the method of mixing components (A), (B), and
(C) simultaneously;
(2) the method of mixing components (A) and (C) and
forming a silicone compound, and then mixing
componen-t (B) in this;
(3) the method of preparing a solution of
components (A) and (B) and then adding
Component (C);
.
.
'~:
,
:.
~ A `
~4) the method of treating the silica powder in
advance by mixing components ~B) and (C), and
then mixing with Component (A);
(5) the method of carrying out the mixings
described in Methods (1) to (4~ above in the
presence of an organic solvent which is
inactive with components (A), (B), and ~C), or
diluting the material mixed by methods (1) to
(4~ with an organic solvent; and
(6) the method of adding the material mixed in
methods (1) to (4) described above to water and
a surfactant and emulsifying it.
Methods ~1) to (6) may be adopted arbitrarily according
to the purpose for which it will be used, but the mixing
method is not restricted only to methods described above.
Depending on the organic silicon compound,
Component (B), employed, reaction with the hydroxyl
groups or alkoxy groups which the organopolysiloxane,
Component (A), contains and the hydroxyl groups which the
silica, Component (C), contains may be slow, so
c-)nventiona]ly well known catalysts of or~anic metal
compounds containing tin, zinc, iron, lead, titanium,
etc., may be added to accelerate this reaction.
The foam control composition of the present
invention can be used in various forms depending on the
variety of the foam system. For example, when the foam
system is an oil system or solvent system, it is possible
to dilute the foam control composition with an organic
solvent. The organic solvent referred to here is a
conventional well-known liquid with a boiling point of
250C or below and is selected from hydrocarbon solvents,
haloqenated hydrocarbons, amines, alcohols, ethers,
:
''
3~
11
ketone, and esters. For example, methvlcyclohexane,
xylene, petrolcum naphtha, perchloroethylene,
bromochloroethane, dichlorobutane, triethylamine,
butylamine, tributylamine, isopropyl alcohol, butyl
alcohol, amyl alcohol, hexyl ether, butyl Cellosolve
(C4HgOCH2CH200CCH3)~ dioxane, methyl ethyl ketone,
diethyl ketone, methyl butyl ketone, ethyl acetate,
Cellosolve acetate (CH3COOCH2CH20C2H5), and ethyl
propionate can be mentioned, but it is not limited to
these.
When the foaming system is an aqueous system,
it is pos.sible to emulsify this composition using
conventional wel]-known surfactants and water. The
surfactant referred to here is represented, for example,
by sorbitan aliphatic esters, glycerol aliphatic esters,
propylene glycol aliphatic acid esters, polyoxyethylene
aliphatic acid esters, polyoxyethylene sorbitan aliphatic
acid esters, polyoxyethylene alkyl ethers,
polyoxyethylene castor oil, ethylene oxide, and propylene
oxide, but it is not limited to these. When emulsifying,
protective colloid agents may be used, which produce
thickening effects, stabilizing effects, and are
dispersable or bondable. For example, methyl cellulose,
milk sugar, sodium alginate, cane sugar aliphatic acid
esters, tragacanth gum, polyvinyl alcohols, hydroxypropyl
cellulose, carboxyvinyl polymers, etc., can be mentioned,
but it is not limited to these.
Besides the organic solvents, water,
~;urractants, anA protective colloid agents, mentioned
.Ihove, the Following may also be added -to this
composition: vegetable oi]s such as soybean oil,
rapeseed oil, peanut oil, coconut oil, etc., polyethers,
~,
t3
12
carboxylic acid esters, phosphoric acid esters,
perfluorocarbons, aromatic chlorides, lauric acid,
polyalkylene glycols, organosilanes other than component
(B), organosiloxanes, aluminum hydroxide, calcium
hvdroxide, magnesium hydroxide, metal oxide micropowders,
scale-shaped fillers, organopolysiloxane oils whose
termini are closed with trimethylsilyl groups,
hydrocarbon oils, animal fats, synthetic oils, etc.
The amount of the composition which is employed
will depend on the particular systems in which foam is to
be controlled and the extent to which the user wishes to
control the foaming. The composition can be used as any
kind of foam control agents, i.e., as defoaming agents
and/or antifoaming agents. Defoaming agents are
generally considered as foam reducers whereas antifoaming
agents are generally considered as foam preventors. As
noted, the composition can serve in either or both
capacities.
Now in order that those skilled in the art may
better understand how the present invention can be
practices, the following examples are given by way of
illustration and not by way of limitation. All parts
referred to herein are by weight, and all viscosities are
measured at 25C, unless otherwise specified.
;~..
Example l
'
A test of durability was used to comparatively
cvaluatc various foam control compo.sitions. The test of
ra~-il;ty is as follows:
1. Prepare a ~oaming solution consisting
essentially of a l.O~ aqueous solution of the
13
*
surfactant Octapol 100 (polyoxyethylene
octylphenol ether) manufactured by Sanyo Kasei
~ogyo .
. Prepare a foam control solution by placing .40
grams of the foam control composition into a
100 ml measuring flask, and add tertiary
butanol to the 100 ml mark.
3. Place 100 ml of the foaming solution and 1.0 ml
of the foam control solution into a 300 ml
` covered glass bottle.
4. Forcibly foam the solution on a shaker.
5. Measure the time for the foam to disappear.
6. Continuously repeat steps 4 and 5 until more
than 5 minutes are required for defoaming. The
number of repetitions is the duration
frequency.
7. Repeat steps 1 to 6, 15 times.
The compositions tested and results are:
`:
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;
.:
O
H o O
H O
H ~' O
H ~> O
H ¦ ~> O
m ¦ O H O O
O H O
H O
l ~ ~ O
~ ~ J~ 1
Ul ~ ~ ,~ ~ ~
.C.~ ~) u~ u~ ul al u~ ~U
O 0~ C~
~ (1) U~ 0 ~1 t) O ~ U~ a) u~
U~ ~ U~ ~1 0 ~ U~ ~ O ~1 0 ~ ~S 'C~ C>
O nS ~ o rr~ ~d h ~
X ~ 0 ~ U~ X ~ s~ o X 1~ c~
~: O O-~ O~ O ~1 O o
~, ~I h E~ ~ ~1 U 1~ ~ ~I E~ ~1 ~1 U~ o
~ -~1 ~ ~ H ~
J~ ~n ~ o u~ ~ ~ ~ u~ X a) u~ X
O J~ ~ O O ~
~ a) ~ ~ ~ ~ ~ o ~ ~ ~ ~ ~ ~ s~ o
O ~: O X ~ ~ O ~ Q u~ o ~ ~ ~ o
O ~ O r~ ~ S~ 0 C~ ~ >~-rl rl Ll~
~ ~ ~ ~ ~ ~ ~ ~ ~ ,C ~ 0 ~ ,~
~1 t ~ ~ O ~ ~ ~ o ~ .C o
u~ O ~ ~ ~ o ~ ~ ~ o S ~ ~ v ~ ~ ~, u~
O C~ ~ ~: u~ ~ ~ ~ ~ o ~ ~ u~ ~ ~ ,~ o
1 ~ ~ ~ a~
~ ~ ~ ~ o ~ ~ ~ ~ ~ u~
O rl ~ O '~ rl ~ O ~ ~a a) r1
c~ a-~Q ~ a~ ~ o a~Q ~ a~
14
!- ~
r~S m ~ c) r 1 a~ 5 ~ t ) - t~ I--
S:~ ~ ~ ~ \ / ~. 7 ~ ~) - t)
~ ~0 'U~ ~ '~ ~J ~ ~
~ ~. ~ S CJ ~ ~ _ ~
~'7~S3~
Ul H u~
O H X
H H H u~
t~l t~
, g ~ U') ~_
H ~ 1
H
,, ~ Ln In
~,Ir) Ir)
.' ',` ~_,
t~ ~1 Ir 1~1
O ~
., HU H U~ Ll~
t1 ltt' H 1~> li~
EiE-
r ~
O H u~
t4 1 LO
~,
~0
U
a~
~) O O
U~ ~ ~1 ~ ~
t~_ (I) h ~ ~1
U ~ ~ ~ ~ ~ Z
.~ _ U~ 1~ U~ tLl
~: ~ n~ I ~ tl
C) S: o o .C o K
C!~ ~l:) .IJ O O ~) O t4
,1C~ ~ ~1 ~ ~ ~
~:- ~ 3 ~ 3 ~ Z
U~O r~ 0 C) (~ o H
OU ~1 ~) t~\ O ~
t~-O .~ ~; O -r I ~1 '¢
F~l ~1 ~ s~ ~1 c) K
o ~ a)-~l ~ :~
u~ u~ ~ f~ u~ r~
16
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] 7
I ach of thc foam control compositions tested in I xarnplc I
werc preparcd by mixing -the components a-t roorn
tempcrature for 30 minute.s using a l~obart mixer, ancl then
at 150C for 2 hours using a rnixing apparatus equipped
with a stirri ng device and a heating appa~ratus. 'rhe
Syloid 266 is manufactured by Fiji-Davison and the
Aerogel 200 is manufactured by Nippon Aerodil.
Example 2
A test oi: defoaming properties ~as used to
comparatively èvaluatè various foam control compositi on
emu] sions.
T}1C' C'llIU ] S i on S we r-c prcpared :trom ~OI!lpO '; i t::i on '
I 1, IV, V~`, IX, x, and XI~ fro~n l`xampk~ omi-o~ n
x I :r 1, Sll 5500 manufactured by Toray Si1 icone, was al~io
tested. The emulsions were prepared by mixing for ~n
minutes at 60 to 70C with a homogenizer 20 parts of the
foam control composition, 3 parts of the surfactant Syran
60 (sorbitan aliphatic acid ester) manufactured by Kao
Atlas, 2 parts of the surfactant Atmul P403 (glycerol
aliphati c acid ester) manufactured hy Kao Atlas, and 75
part wa ter .
I'hc tcst of de-Ec)ar~ g propcl-tics -is as '-ol lows:
I. rrcpare a 1.0 wcight pcrcent acluec)ux solut:ion
((-Id justccl to pll I1 with pc~lciss:ium hyc!ro;iclc) (~1-
th~ surl.'actallt Oc-tapo]. 1()() (po~ oxyet!lyle~n(~
octyl phenyl ether) rnanufactur(?d ~y Sanyo Kasci
Kogyo.
2. Pla(c ~()0 ml of the aqueous solution and .lO
qrams oE the foarl control compositions eml1lsion
-in a I liter measurinc3 cylinder.
i3~
18
3. Blow air into the cylinder through a glass ~all
filter at a rate of 600 ml/min. and measure the
time in minutes until the total volume of foam
reaches 800 ml.
The results are as follows
Time, minutes
Compositiorl II emulsion 25
Composition LV emulc,ion 24
Composition VI emulsion 21
Composition IX emulsion 22
*Composition X emulsion 6
, *Composition XII emulsion 11
*Composition XIII emulsion 5
* Comparison compositions
:
.
