# US 10,870,071 B2 · Defoaming formulations containing organopolysiloxanes

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- Number: US 10,870,071 B2
- Document ID: US10870071B2
- Status: Granted
- Kind: B2
- Application number: 16/330,193
- Filed: 2017-06-06
- Published: 2019-07-25
- Granted: 2020-12-22
- Earliest claimed: 2017-06-06
- Assignees: Wacker Chemie AG
- Applicants: Wacker Chemie AG
- Inventors: Christof Brehm; Willibald Burger; Wolfgang Ziche
- Web page: https://patentgrep.com/patent/US10870071B2

## CPC

- B01D 19/0409: {compounds containing Si-atoms}
- C11D 3/0026: {Low foaming or foam regulating compositions}
- C11D 3/373: {containing silicones}
- C11D 3/3734: {Cyclic silicones}
- C11D 3/3738: {Alkoxylated silicones}
- D21C 3/28: Prevention of foam
- D21H 17/59: obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon
- D21H 21/12: Defoamers
- C08L 2205/035: containing four or more polymers in a blend
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- C11D: DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- D21C: PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21H: PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

Defoamer compositions containing a plurality of defined organopolysiloxanes exhibit very short initial foam collapse and yet exhibit long lasting defoaming activity when added to aqueous media prone to foaming.

## Claims

### Claim 1

A defoamer formulation, comprising:
(1) at least one organopolysiloxane containing per molecule at least one structural unit of formula
O1/2R2Si—Y-SiRO2/2 (I)
at least 2 units of formula
R1R2SiO1/2 (II)
and units of formula
R2SiO2/2 (III),
wherein
R each is identical or different and is a monovalent SiC-bonded hydrocarbon radical having
1 to 30 carbon atoms which optionally contains one or more nonadjacent O-atoms and which is free from aliphatic carbon-carbon multiple bonds and
R1 each is identical or different and is R or an alkenyl radical having 2 to 30 carbon atoms, wherein at least one alkenyl radical per molecule is present,
Y each is an identical or different divalent hydrocarbon radical having 2 to 30 carbon atoms,
with the proviso that the at least one organopolysiloxane contains a structural element of formula
R2Y2SiO—(SiR2O)x1—SiRY1O—(SiR2O)x2—SiR2R1 (IV),
wherein
R and R1 are as defined above,
Y1 is a divalent hydrocarbon radical having 2 to 30 carbon atoms which is bonded to a group having the formula SiR2O1/2,
Y2 is a divalent hydrocarbon radical having 2 to 30 carbon atoms which is bonded to a group having the formula SiRO2/2, and
x1 and x2 are, independently, 0 or a positive integer,
with the proviso that the sum of x1+x2 is x,
wherein x is on average more than 5 and less than 100,
(2) fillers, and
(3) organopolysiloxane resins comprising units of formula
R2e(R3O)fSiO(4-e-f)/2 (V),
wherein
R2 is identical or different and represents a hydrogen atom or a monovalent, optionally substituted, SiC-bonded hydrocarbon radical having 1 to 30 carbon atoms,
R3 is identical or different and represents a hydrogen atom or a monovalent, optionally substituted hydrocarbon radical having 1 to 4 carbon atoms,
e is 0, 1, 2 or 3, and
f is 0, 1, 2, or 3,
with the proviso that the sum of e+f is not more than 3 and that the sum of e+f is 2 in less than 50% of all units of formula (V) in the organopolysiloxane resin.

### Claim 2 (depends on 1)

The defoamer formulation of claim 1, wherein R1 is a methyl or vinyl radical.

### Claim 3 (depends on 1)

The defoamer formulation of claim 1, wherein x is on average more than 10 and less than 60.

### Claim 4 (depends on 1)

The defoamer formulation of claim 1, wherein Y and Y1 and Y2 are each a radical of the formula —CH2CH2—.

### Claim 5 (depends on 1)

The defoamer formulation of claim 1, wherein the organopolysiloxanes (1) are produced by reacting:
(A) oligomeric or polymeric organosilicon compounds containing units of formula
R1R2SiO1/2 (II),
units of formula
R2 SiO2/2 (III),
and units of formula
HRSiO2/2 (VII),
with the proviso that
at least one alkenyl radical R1 per molecule is present,
the sum of the units HRSiO2/2 and R1R2SiO1/2 is on average greater than 2.0, and the number of alkenyl radicals R1 is on average greater than the number of Si-bonded hydrogen atoms
and optionally
(B) oligomeric or polymeric organosilicon compounds containing units of formula
R6R2SiO1/2 (VIII), and
units of formula
R2SiO2/2(III),
wherein
R6 is an alkenyl radical having 2 to 30 carbon atoms, in the presence of
(C) catalysts which promote the addition of Si-bonded hydrogen onto aliphatic double bonds, wherein the ratio of aliphatic double bonds in the components (A) and optionally (B) to Si-bonded hydrogen in component (A) is 1.2 to 10.

### Claim 6 (depends on 5)

The defoamer formulation of claim 5, wherein the ratio of aliphatic double bonds in the components (A) and optionally (B) to Si-bonded hydrogen in the component (A) is 1.5 to 5.0.

### Claim 7 (depends on 5)

The defoamer formulation as claimed in claim 5, wherein the organosilicon compounds (A) have the formula
R1R2SiO-(SiR2O)x-(HSiR)y—O-SiR2R1 (IX),
wherein
y is on average at least 0.5, and on average not more than 1.5,
with the proviso that at least one alkenyl radical R1 per molecule is present,
the sum of the units HRSiO2/2 and R1R2SiO1/2 is on average greater than 2.0,
and the number of alkenyl radicals R1 is on average greater than the number of Si-bonded hydrogen atoms.

### Claim 8 (depends on 5)

The defoamer formulation as claimed in claim 5, wherein the organosilicon compounds (A) have the formula
R1R2SiO-(SiR2O)x-(HSiR)y—O-SiR2R1 (IX),
wherein
y is on average at least 0.6, and on average not more than 1.2,
with the proviso that at least one alkenyl radical R1 per molecule is present,
the sum of the units HRSiO2/2 and R1R2SiO1/2 is on average greater than 2.0, and the number of alkenyl radicals R1 is on average greater than the number of Si-bonded hydrogen.

### Claim 9 (depends on 5)

The defoamer formulation of claim 5, wherein the organosilicon compounds (B) employed are those of formula
R6R2SiO—(SiR2O)z—O—SiR2R6 (X),
wherein
R each is identical or different and is monovalent SiC-bonded hydrocarbon radical having 1 to 30 carbon atoms which optionally contain one or more nonadjacent O-atoms and which is free from aliphatic carbon-carbon multiple bonds and
R6 is an alkenyl radical having 2 to 30 carbon atoms,
z is on average more than 5, preferably more than 10, and less than 1000, preferably less than 500, particularly preferably less than 250.

### Claim 10 (depends on 7)

The defoamer formulation of claim 7, wherein the organosilicon compounds (B) employed are those of formula
R6R2SiO—(SiR2O)z—O—SiR2R6 (X),
wherein
R each is identical or different and is monovalent SiC-bonded hydrocarbon radical having 1 to 30 carbon atoms which optionally contain one or more nonadjacent O-atoms and which is free from aliphatic carbon-carbon multiple bonds and
R6 is an alkenyl radical having 2 to 30 carbon atoms,
z is on average more than 5, preferably more than 10, and less than 1000, preferably less than 500, particularly preferably less than 250.

### Claim 11 (depends on 1)

The defoamer formulation of claim 1, further comprising one or more constituents (4) through (7);
(4) polyorganosiloxanes of formula
wherein
R4 each is identical or different and is R or —OR5, wherein
R5 is a hydrogen atom or a monovalent, optionally substituted hydrocarbon radical having 1 to 25 carbon atoms,
m is an integer from 1 to 2500,
n is an integer from 2 to 20,
wherein the polyorganosiloxanes may also contain small proportions of T units (R4SiO3/2) and/or Q units (SiO2),
(5) water-insoluble organic compounds,
(6) polyether-modified polysiloxanes which are linear or branched and contain at least one polyether group,
and
(7) alkaline or acidic catalysts or their reaction products with one of the components (1) to (6).

### Claim 12 (depends on 1)

The defoamer formulation of claim 1, wherein the defoamer formulation has a loss factor (tan delta) at 100 rad/s between 1.0 and 5.0, wherein over the frequency range of 1 to 100 rad/s the difference in the loss factor (A tan delta) is less than 1.5, and the defoamer has a viscosity at 100 rad/s between 1000 mPas and 300,000 mPas, in each case measured at 25° C., wherein the loss factor and the viscosity are determined according to DIN 53019-4.

### Claim 13 (depends on 1)

The defoamer formulation of claim 1, wherein the defoamer formulation has a loss factor (tan delta) at 100 rad/s between 1.5 and 3.0, wherein over the frequency range of 1 to 100 rad/s the difference in the loss factor (Δ tan delta) is less than 1.0, and the defoamer has a viscosity at 100 rad/s between 2000 mPas and 100,000 mPas, in each case measured at 25° C., wherein the loss factor and the viscosity are determined according to DIN 53019-4.

### Claim 14 (depends on 1)

The defoamer formulation, of claim 1, wherein the organopolysiloxane resins (3) are MQ resins comprising units of formulae
SiO2 (Q units) and
R23 SiO1/2 (M units),
wherein
the molar ratio of M units to Q units is in the range from 0.5 to 2.0, the MQ resins optionally also contain in addition to the M units and Q units, R2SiO3/2 or (R3O)SiO3/2 (T) units or R22 SiO2/2 (D) units in amounts of 0.01 to 20 mol % based on the sum of all siloxane units, and the MQ resins may contain up to 10% by weight of free Si-bonded hydroxyl or alkoxy groups.

### Claim 15 (depends on 11)

The defoamer formulation of claim 11, wherein the water-insoluble organic compounds (5) are those having a boiling point greater than 100° C. at 900 to 1100 hPa.

### Claim 16 (depends on 11)

The defoamer formulation of claim 11, wherein the water-insoluble organic compounds (5) include one or more of mineral oils, native oils, isoparaffins, polyisobutylenes, residues from oxo alcohol synthesis, esters of low molecular weight synthetic carboxylic acids, for example pentanediol-1,3-diisobutyrate, fatty acid esters, octyl stearate, dodecyl palmitate or isopropyl myristate, fatty alcohols, ethers of low molecular weight alcohols, phthalates, esters of phosphoric acid and/or waxes.

### Claim 17 (depends on 1, 11)

The defoamer formulation of claim 11, wherein the defoamer formulation contains
(1) at least 30% by weight, and not more than 98% by weight, of organopolysiloxanes of claim 1,
(2) at least 1% by weight, and not more than 15% by weight, of fillers,
(3) at least 1% by weight, and not more than 15% by weight, of organopolysiloxane resins composed of units of formula (V),
(4) greater than 0% by weight and not more than 40% by weight of polyorganosiloxanes of formula (VIa) or (VIb),
(5) greater than 0% by weight and not more than 15% by weight, of water-insoluble organic compounds,
(6) greater than 0% by weight and not more than 15% by weight, of polyether-modified polysiloxanes which are linear or branched and bear at least one polyether group and
(7) greater than 0% by weight, and not more than 1% by weight, of alkaline or acidic catalysts or their reaction products with one or more of components (1) to (6).

### Claim 18 (depends on 1)

An emulsion of defoamer formulation(s) comprising at least one defoamer formulation of claim 1, emulsifiers, and water.

### Claim 19 (depends on 1)

A powder, comprising:
at least one defoamer formulation of claim 1, and support materials.

### Claim 20 (depends on 1)

A washing or cleaning composition containing a defoamer formulation of claim 1, or an emulsions thereof, or a powder thereof.

### Claim 21 (depends on 1)

A process for defoaming and/or preventing foaming of liquid media, comprising:
mixing a defoamer formulation of claim 1, an emulsion thereof or a powder with the liquid media.

### Claim 22 (depends on 21)

The process of claim 21, wherein the aqueous media comprises an aqueous medium generated in chemical pulp production.