DE2310039B2 - ANTI-FOAM AGENT - Google Patents

Description

(A) R ₀ SiC (OSiMe ₂ UOSiMeG) ₁₁ OSJMe ₂ G] ₄ . "

(B) R ₀ SiC (OSiMe ₂ WOSiMeG) ₁ OSiMeJ] ₄ ..

(C) GMe ₂ Si (OSiMeJ) ₁₁ (OSiMeG) ₄ OSiMe ₂ G and

(D) Me ₃ Si (OSiMe ₂ UOSiMeG) ₁ OSiMe ₃ ,

wherein

R is a hydrocarbon group free of aliphatic multiple bonds and having 1 to 10 carbon atoms,

called a methyl group and

G denotes a group of the structure -D (OR ') mA, in which D denotes an alkyl group with 1 to 30 carbon atoms, R' denotes an alkyl group with 2 to 10 carbon atoms, m denotes a value of at least 1 and A denotes a protective group,

a has a value of 0 or 1,

η has a value of at least 1,

b has a value from 0 to 50 and

c have a value from 1 to 50,

(2) 5 to 35% by weight of a SchauinreguHermittels, which consists of 85 to 96 parts by weight of a liquid triorganosilyl-endmasked polydimethylsiloxane with a viscosity of at least 20 cSt at 25 ° C, 4 to 12 parts by weight Silicon dioxide and 0 to 3 parts by weight of a siloxane resin, which consists of SiO ₂ units and (CH ₃ ) 3SiOi / _r units, the ratio of (CH ₃ ) ₃ SiOi; ₂ units to SiO units in the range from 0.4 / 1 to 1.2 / 1, and

(3) 5 to 35% by weight of a liquid hydroxyl endmasked Polydimethylsiloxane with a viscosity of 50 to 200 cSt at 25 ° C

2. Antifoam agent according to claim 1, characterized in that the component (1) in one Amount of 50 to 70 wt .-% is present and has the general formula (D), and that the Component (2) in an amount of 15 to 25% by weight is present and that the triorganosilyl-end masked polydimethylsiloxane has a viscosity in the range from 20 to 2ÖÖG c3i and that the Ingredient (3) is present in an amount of 15 to 25 percent by weight.

3. Antifoam agent according to claim 2, characterized in that (1) is present in an amount of 50 wt .-% and has the general formula Me ₃ SiO (OSiMe ^ s- (OSiMeG) T-OSiMe ₃ , wherein G - - (GHz) ₃ (OC ₂ HO ₂ * - (OC ₃ K ₆ ) Z ₄ -OOCCH ₃ means, (2) is present in an amount of 25% by weight and consists of 88 parts of a trimethylsilylendmaskierte Polydimethylsüoxans with a viscosity of about 1000 cSt, 10 parts of silica airgel and 2 parts of a siloxane resin is selected from (CH _{3) 3} SIOI / z units and SiO ₂ -A ^k nits, wherein the units in a ratio of 0.4 / 1 to 1, 2/1 are present and wherein (3) in an amount

of 25% by weight and has a viscosity of about 75 cSt

4. Antifoam agent according to claim 2, characterized in that (1) is present in an amount of 70 wt .-% and has the general formula Me ₁ SiO (OSiMe ₂ ) T ₅ - (OSiMeG) ₇ -OSiMe ₃ , wherein G - (CHi) ₃ (CK ^ H ₄ ) H- (OC ₃ H ₆ ) W-OOCCH ₃ means, (2) is present in an amount of! 5% by weight and from 88 parts of trimethylsilyl-endinasked polydimethylsiloxane with a Viscosity of about 1000 cSt, 10 parts of silica airgel and 2 parts of a siloxane resin consisting of (CHj) jSiOi / r and SiO ₂ units, the units being present in a ratio of 0.4 / 1 to 1.2 / 1 and (3) is present in an amount of 15% by weight and has a viscosity of about 75 cSt

5. Antifoam agent according to claim 2, characterized in that (1) has the general formula Me ₃ Si (OSiMe ₂ ) T ₅ - (OSiMeG) T-SiMe ₃ , wherein G - (CH ₂ ) ₃ (OC ₂ H ₄ ) denotes 24- (OC ₃ Il6) ₂ + -OOCCH ₃ , and (2) consists of 95 parts of trimethylsilyl-endmasked polydimethylsiloxane and 5 parts of silica airgel

6. Use of the antifoam agent according to any one of claims 1 to 5 in a carpet dyeing process.

The invention relates to an antifoam based on liquid polydimethylsiloxane, a siloxane resin made from (CH ₃ J ₃ SiOo ^ and SiO ₂ units, and silicon dioxide.

Direct and indirect losses from fire run into the billions every year. One has under Great effort was made to find ways and means to prevent these losses and damage. In The United States of America requires the Federal Standard DOC-FF-1-70 that all according to the April 15, 1971 carpets manufactured the »Methenamine Pass the Tab'et Test «for the fire hazard. This test is commonly referred to by the industry as the "Bitter Pill Test"

When dyeing carpets, an antifoam agent must be used to regulate foaming in the dye bath be used. r ", erzu are already being used by different Anti-foam agents derived from poly-dimethylsüoxanes However, there are reports that the silicone antifoams used in polyester dyeing processes should increase the fire hazard of carpets. A corresponding investigation then showed, however, that the "n time as Silicones used in antifoam are inherently inert and not flammable. Correspondingly plausible Mechanisms, however, also showed why such agents increase the fire hazard of polyester carpets could contribute. There has therefore been a difficulty in providing a carpet dyeing process effective antifoam agent ”, which doesn’t somehow make the carpet dangerous to fire adversely affected, with this agent on the carpet at the same time no stains or streaks

6s education should cause.

From US-PS 34 02 192 are polyoxylalkyleneciloxane copolymers known to be used as surfactants and emulsifiers in the manufacture of polyurethane

23 IC 039

foams can be used. In US-PS 3455 839 preparations of a liquid polydimethylsiloxane, a siloxane resin and a silicon dioxide airgel described, which are dispersed in aqueous Systems have a foam-inhibiting or defoaming effect. On the basis of appropriate investigations it was shown However, because of certain serious disadvantages, these agents are used as antifoams when dyeing Carpets cannot be used.

The object of the invention is therefore to provide antifoam agents which can be used in dyeing carpets based on silicone, which do not have the disadvantages of known agents for this purpose.

This object is achieved according By J ¹ 'an antifoaming agent of the type mentioned solved, which is characterized in that it consists of

(1) 30 to 90% by weight of a siloxane-glycol copolymer of the general formulas

(A) R _a SiL (OSiMe ₂ ) "(OSiMeG) ₆ OSiMe ₁ G] _4. "

(B) I ^ SirjOSiMe ^ OSiMeGkOSiMea-U. ,,

(C) GMe ₂ Si (OSÄMe ₂ ) "(OSiMeG) _i , OSiMe ₂ G and

(D) Me ₃ Si (OSiMe ₂ ) _n (OSiMeG) _f OSiMe ₃ ,

wherein

R eir <; free of aliphatic multiple bonds Hydrocarbon group with 1 to 10 carbon atoms,

Me is a methyl group and G is a group of the structure - D (OR ') mA beuei.itL., Where D is an alkylene group having 1 to 30 carbon atoms, R' is an alkylene group having 2 to 10 carbon atoms, m is at least 1 and A is Protecting group means

a has a value of 0 or 1,

η has a value of at least 1,

b a value from 0 to 50 and

c have a value from 1 to 50,

(2) 5 to 35% by weight of a foam regulating agent, the 85 to 96 parts by weight of a liquid triorganosilyl-end masked polydimethylsiloxane with a viscosity of at least 20 cSt at 25 ⁰ C, 4 to 12 parts by weight of silicon dioxide and 0 to Contains 3 parts by weight of a siloxane resin which consists of SiOj units and (CHjJjSiOm units, the ratio of (CH3) 3SiOi / ₂ units to SiO2 units in the range from 0.4 / i to 1.2 / 1 lies and

(3) 5 to 35% by weight of a liquid hydroxyl endmasked PoiydimeinyianuÄani with a viscosity of 50 up to 200 cSt at 25 ° C.

The antifoam agent according to the invention is neither due to the prior art mentioned at the beginning anticipated still suggested. The first component of this agent is roughly from the above US-PS 34 02 192 known, while the preparation described in US-PS 34 55 839 roughly seen the corresponds to the present second component, but still contains the antifoam agent according to the invention another essential third component which is a liquid polydimethylsiloxane with the specified viscosity. This third component is soluble in the second component and controls in this way the increase in flammability actually caused by the second component, and that

The present agent can therefore be used in particular for dyeing processes for polyester carpets. in the In contrast to known foam regulating agents, this agent can be used in individual systems directly in 100% concentrated form, d. H. be added as such. Of course, you can also use an emulsion or make a solution from this preparation, and much more easily than with received methods. Just this balanced combination of the above

However, ίο three ingredients also yields one Antifoam agent that can be used particularly well when dyeing carpets without affecting flammability to increase such materials, as emerges from the test report which follows later

In the case of the siloxane glycol polymer used as component (1) of the general formulas (A), (B), (C) and (D), R can be any of aliphatic Multiple bonds with free hydrocarbon group 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, decyl, phenyl. Tolyl, benzyl, xylyl, methylcyclohexyl, cyclohexyl, Cyclopentyl, 0-phenylpropyl or 0-phenylethyl.

Specific examples of alkylene groups D connecting the glycol portion of G with the silicon atom are

Methylene, ethylene, propylene, isopropylene, butylene, octylene, decylene, octadecylene and Mj.icylene groups. D preferably contains from 1 to 18 carbon atoms.

R 'in the above formulas denotes any alkylene group. which contains 2 to 10 carbon atoms

R 'can thus be an ethylene, propylene, isopropylene, butylene, hexylene, octylene or decylene group. Most preferably R 'contains 2 to 4 carbon atoms. It should be noted that R 'voi. one can be derived from a single glycol or from a mixture of glycols, d. i.e., for example, OR 'can only

Ethylene oxide units, propylene oxide units or butylene oxide units mean or OR 'can be a Represent a combination of such units.

The symbol m, which indicates the number of OR 'units in the glycol portion of the molecule, can have a value as low as 1 and in the range up to 1,000 or greater. In general, m will have an average value in the range from 10 to ICO.

The glycol or polyoxyalkylene unit contains the group A as a terminal group or is replaced by the Group A ended. The specific nature of this group is not critical to the present invention. The glykoi can be replaced by a hydroxyl group (A.

means a hydrogen atom), through an ether group (A means a monovalent hydrocarbon group such as a methyl, butyl, vinyl or phenyl group), Hiirrh a carboxyl group, through the salt or the Ester of a carboxyl group or through a carbonate ester group or terminated by an isocyanate group.

The symbol n, which indicates the number of dimethylsiloxane units in the molecules, can have a value of at least 1 and can be in the range up to 1500 or higher. It is believed that the number of dimethylsiloxane units in the molecule relative to the glycol containing G units should be at least 10: 1 for best results. The upper ratio of OSiMej units to G-containing units can be 50: 1 or more.

The siloxane-glycol copolymers useful for this are well known, commercially available materials. For those who don't have these connections

know, should be referred to the US Patents 34 02 192, 35 18 288 and 36 37 783, where the Making these connections and other details are illustrated.

The siloxane-glycol copolymer can be from 30 to 90 Make up wt .-% of the agent.

The second component of the agent is the foam control agent. This agent can constitute from 5 to 35% by weight of the composition. The foam control agent consists of 85 to 96 parts by weight of a liquid ίο triorganosyl-permanently masked polydimethylsiloxane with a viscosity of at least 20 cSt at 25 ° C, 4 to \? Qm. " -Ilen silicon dioxide and 0 to 3 parts by weight of ice eiu -; - iüoxanharzes, consisting of (CH ₃ ) JSsOiU-EH ¹ -; - ^ n and SiO ₂ units, where in the resin d * ratio of (CH3) 3SiOi / 2 units to the SiO E »nPerten is in the range from 0.4: 1 to 1.2: 1

The i ',. "- triorganosilyl-endblocked polydimethylsibxanes are well known compounds and are commercially available in many places. They can be prepared by various processes such as the joint hydrolysis and subsequent condensation of triorganomonohalosilanes and dimethyldihalogen silanes, or by cracking and subsequent condensation of the dimethylcyclosiloxanes. The organic end-blocking (= masking) groups can be any well-known hydrocarbon groups, but it is preferred that they contain 1 to 6 carbon atoms. The trimethylsilyl end-masking group is likely the one that is commercially available. Dimethylphenylsilyl and dimethylvinylsilyl groups are also quite common Examples of other organic groups include ethyl, propyl, butyl, amyl, hexyl, cyclohexyl, allyl and oxadecyl groups In order to obtain a significant anti-foam or defoaming effect, the viscosity of the triorganosilyl-e The masked polydimethylsiloxane is at least 20 cSt at 25 ° C; i. The upper viscosity limit of this compound is not critical and can be in the range up to 1,000,000 cSt or higher, determined at 25 ° C. It is assumed that various best results are obtained if the viscosity of the triorganosilyl-egg-masked polydimethylsiloxane ^! m range from 20 to 2000 cSt at 25 ° C

The siloxar resin that can be used in the composition is also a standard compound that is commercially available from various sources. It can be obtained by cohydrolysis and condensation of (CH3) 3SiCl and SiCl ₄ or by reaction of (CH3) 3SiCl with acidic silica sulf. Its manufacture is detailed in many

present application not explained in detail.

A silica airgel is a type of silica that can be used in the composition. In short, such materials are made by putting the water in a silica hydrogel or silica hydrogel with a low-boiling organic liquid such as ethyl alcohol, which treated gel in an autoclave down to approximately the critical temperature of the organic liquid dun autoclave to escape, woourch an excessive shrinkage or breakage of the cellular Structure of the silicon dioxide or the silica is avoided. The details of this procedure are described in the literature and silica aerogels are commercially available. Other silicas or pebbles Soils that can be used are precipitated silicas, kieselxerogels, pyrogenic Silica and treated silicas containing organic silyl groups on their faces. can also be used. These and other silicas that can be used are all well known and easily selected by those skilled in the art.

The third major ingredient of the composition is a liquid hydroxyl-endmasked polydimethylsiloxane having a viscosity of 50 to 200 cSt at 25 ° C, which can be present in the composition in an amount of 5 to 35% by weight. This component can be prepared by well known methods such as e.g. B. by hydrolysis and condensation of dimethyldichlorosilane or by cracking and subsequent condensation of dimethykyclosiloxanes. It has been found that it is necessary that this third ingredient! in the component (2), the foam control agent, dissolves, so that the carpets, which are supposed to pass the pill test, are not adversely affected. It has been found that the materials containing e ^; ne have a viscosity in the range given above,:, e have the required solubility.

The composition according to the invention is produced by simply mixing the three ingredients together in the correct proportions. So far is known to this day, there is no particular order in which the ingredients are mixed have to. As far as we know today, the best method is to produce the mass according to the invention, in adding the hydroxylated dimethylsiloxane to the siloxane-glycol copolymer and well Mix. Then the foam control agent is added and mixed well and finally the Composition passed through a colloid mill.

The amount of the composition of the invention that is used depends on the particular one System in which the foam is to be controlled, from and to the extent to which the consumer has the Want to control foam. Thus, the amount will vary depending on whether the composition in an alkaline soap solution, when evaporating alkaline paper black liquid, when Concentration of synthetic rubber dyes in the steam distillation of styrene butadiene emulsions, in refining sugar, dyeing textiles, treating waste to be thrown away or to be used in other processes. In general, 20 to 150 ppm of that according to the invention are sufficient Composition based on the volume of the system in which the foam is controlled should, for most applications. The compositions of the invention can be used as any Types of foam control agents, for example as defoamers and / or as antifoam agents be used. Defoaming agents are generally considered to be agents that reduce foam, whereas antifoam agents are generally considered to be anti-foaming agents as before indicated, the compositions according to the invention can be used for one or both uses will. It should be noted that the compositions of the invention can be used as 100% solids, i.e. neat, can be used, or emulsions or solutions thereof can be used in suitable Prepare and use solvents when handling and adding to the system

ie

simplified.

The following examples illustrate the invention without restricting it. All parts and percentages are Expressed by weight and all viscosities are determined at 25 ° G unless otherwise stated.

example 1

A composition is made from that
(1) 50% of a Sjloxan-GiykoUGopplyrneren of the general foliage

, —Si (CHJ ₃

(2) 25% of a foam control agent which consists of 88 parts of trimethylsilyi-end-masked polydimethylsiloxane with a viscosity of approximately 1000 cSt, 10 parts of silica airgel and 2 parts of a siloxane resin which consists of SiO ₂ units and (CH3) 3SiOi / ₂ units in a ratio of 1: 0.4 to 1; 1,2 are present, and

(3) 25% of a hydroxyl-end masked polydimethylsiloxane having a viscosity of about 75CS ₁

The above composition is prepared by adding the component (3) to the component (1), mix well, then the component (2) ^ u of the reaction mixture there, mix well again and then pass the mixture once through a colloid mill with a low Speed and a setting of approximately 381μ (15 mils) and an exit temperature of conducts about 55 ° C

This composition is used to control foam in a polyester carpet dyeing process. The composition is diluted with cold water and about added in an amount of from 0.02% solids to the Teppichfärbebekken During the usual dyeing cycle was the anti-foaming effect is good, the various types of carpet, which were stained in the presence of this anti-foaming agent, were tested for their flammability -CCH ₁
O

using the Methenamine Tablet Test Procedure examined

The Pilltest method is as follows: Eight samples of the carpet to be uniersucht be in 22.9 cm (9 inch) squares cut and placed in a drying oven in which a free flow of air is present to be 2 hours at 105 ⁰ C. and then cooled in a desiccator room for at least 1 hour. The carpet samples are then removed from the desiccator with gloved hands, and the stack is brushed in a vertical direction. It is placed in the test chamber and placed Steel ring with a diameter of 203 cm is placed on the samples A methenamine tablet is placed on the samples in the center of the ring and ignited with a match.If the area of the carpet that is burned is not up to 2.5 cm ( 1 inch) to the steel ring (3 inches in any direction), the sample passes the test Six out of eight samples must pass the test for the carpet to pass government requirements demis-

35 se met Test results when dyeing carpets with the composition according to the invention are in the given in the following table:

Type of carpet Pill attempt

Number of samples that pass number of Samples that fail

Viceroy 8th 0 DüvoI 8th 0 Shag (raw cloth) 8th 0 5 cm thick Dyed carpet *) 4th 4th

·) For comparison. This carpet was finished after of the dyeing process not rinsed with cold water. It is believed that the cold water after dyeing causes the Antifoam agent is removed from the carpet while ensuring that the silicone reduces the fire hazard of the Carpet does not increase and so enables it to pass the pill test

. true! of the entire dyeing cycle. On the textile

Example ζ materials were not stained with dye or silicone

A composition was observed as described in Example 1 60. These tests were carried out, produced, with the exception that it was made from 70%, with burgundy, black and light component (1), 15% component (2) and 15% Ingredient yellowing colored, three of the most difficult coloring types. (3) existed. This agent was under operating Using one of the commercially available conditions as antifoam agents in a Jetfärbetextilver- silicone Ar tischaummittel that were particularly used for the Jetfärfahren The composition was Bever drive in four 65 determined, sine ¹ tei these various Jetfärbevorrichtungen at concen - Shades 2.27 kg of antifoam prc device used by 0.91 kg / device In each case required to regulate the foam at the critical one reached an excellent foam control vent level.

709525/385

Test report
Pill test

ίο

• Type of carpet

Number of for number of for ok not found ok tried found try

Number of for number of for ϊη order not in found order in experiments found in experiments

Number of for number of for okay not okay found found tests tests

Viceroy 8th 0 8th 0 0 8th Duvol 8th 0 8th 0 0 8th Shag (5 cm thick) 8th 0 8th 0 0 8th Colored after sexton 4th 4th 8th 0 0 8th carpet

A - Foam-inhibiting agent according to the invention (Example II B - Polysiloxaneoxyalkylene copolymers, according to column 8, table I. Lines 3 and 4 from the bottom of US-PS 34 02 192, C - Antifoam according to claim 2 of U.S. Patent 3,455,839. Remarks: The pill test is generally used to determine the combustibility of colored carpets.

; The materials (A) and (C) had practically the same anti-foam properties. however, the Materia! (C) the Did not pass the crease test. Although the material (B) survived this pill test, it did not develop any anti-foaming properties in the dyebath, so that it was ruled out for this reason.

Claims (1)

Patent claims: 1. Antifoam agent based on liquid polydimethylsiloxane, siloxane heart made of (CHa) ₃ SiOiZ ₂ - and SiOr units and silicon dioxide, characterized in that äsSessss (1) 30 to 90% by weight of a siloxane-glycol copolymer of the general formulas