KR100790434B1 - Anti-foaming compositions - Google Patents

Abstract

The present invention relates to (A) R _a (R ¹ O) _b R ² _c SiO _{(4-abc) / 2} (I), where the sum of a + b + c is 3 or less, and all units of formula I per molecule At least 1 to 100% of c is not 0 and at least 50% of all units of the formula (I) in the organosilicon compound are at least one organosilicon compound having units of: (B) At least one additive selected from (B1) filler particles and / or (B2) organopolysiloxane resins consisting of units of formula (II); And optionally (C) an organosilicon compound having a unit of formula III.

Description

Antifoam composition {ANTI-FOAMING COMPOSITIONS}

The present invention relates to compositions comprising organic compounds having aromatic radicals directly attached to silicon atoms and their use as antifoaming agents.

In many liquid systems, especially water systems, which contain a surface-active compound as a desired or unwanted component, if these systems are in rather intensive contact with the gaseous material, for example during gas treatment of wastewater, during intensive agitation of the liquid, distillation Problems may arise due to foaming during the cleaning or coloring operation or during the dispensing process.

Such bubbles can be controlled by mechanical means or by adding antifoaming agents. Siloxane defoamers have proved to be particularly suitable.

Siloxane defoamers are prepared, for example, according to DE-B 15 19 987 by heating hydrophilic silica in polydimethylsiloxane. The use of a basic catalyst can improve the effect of such defoamers, for example as disclosed in DE-A 17 69 940. Alternatively it is to disperse the calcined silica in polydimethylsiloxane according to DE-A 29 25 722, for example. Nevertheless, the effect of the resulting antifoaming agent still needs to be improved. Thus, for example, US Pat. No. 4,145,308 discloses an antifoam formulation which further comprises a copolymer comprising (CH ₃ ) ₃ SiO _1/2 and SiO ₂ units in addition to polydiorganosiloxane and silica. Copolymers comprising (CH ₃ ) ₃ SiO _1/2 and SiO ₂ units are also said to be advantageous in combination with siloxanes having long chain alkyl end groups as disclosed, for example, in EP-A 301 531. In some cases the use of partially crosslinked polydimethylsiloxanes which are already rubbery is advantageous for increasing the antifoam effect. In this respect reference may be made, for example, to US Pat. No. 2,632,736, EP-A 273 448 and EP-A 434 060. However, these products are generally very high in viscosity and difficult to handle or further process.

It is generally preferred to use polysiloxanes having methyl groups, such as polydimethylsiloxanes. Polymers having a series of other aliphatic or aromatic hydrocarbon groups on silicon are known and have been proposed in a number of patents on the production of antifoams, but little suggests that the defoaming effect can be substantially improved by selecting substituents on silicon. Often the purpose of introducing long chain alkyl groups or polyether substituents is to improve compatibility with mineral oils that may be present in, for example, antifoam compositions or to prevent silicone defects during coating. Accordingly, EP-A 121 210 recommends the use of polysiloxanes having C _6-30 alkyl groups in combination with mineral oil such that the fraction of carbon in the form of CH ₂ groups is 30-70%. In the examples, polysiloxanes having octadecyl groups are mentioned in particular. JP-A 60173068 recommends siloxanes having octyl groups and polyether groups as antifoaming agents in aqueous printing inks. According to US Pat. No. 4,584,125, siloxanes having _more than C ₃₀ alkyl groups in combination with aminosiloxanes are particularly advantageous for the antifoaming effect when the fraction of siloxane units containing these components is about 5%.

However, in surfactant-rich systems with strong foaming, antifoam formulations prepared according to the prior art are difficult to handle because they do not always have a sufficiently long lasting effect or are high in viscosity due to some degree of branching or crosslinking.

The present invention

(A) at least one organosilicon compound having units of formula

(B) at least one additive selected from organopolysiloxane resins comprising (B1) filler particles and / or (B2) units of formula (II): And optionally

(C) an organosilicon compound having a unit of formula III

It provides a composition comprising:

R _a (R ¹ O) _b R ² _c SiO _{(4-abc) / 2}

R ³ _d (R ⁴ O) _e SiO _{(4-de) / 2}

R ⁵ _g (R ⁶ O) _h SiO _{(4-gh) / 2}

Where

R may be the same or different and is a hydrogen atom, a monovalent optionally substituted SiC-bonded aliphatic hydrocarbon radical or an aromatic hydrocarbon radical bonded to silicon via an aliphatic group,

R ¹ may be the same or different and is a monovalent optionally substituted hydrocarbon radical attached to a silicon atom via a hydrogen atom or a carbon ring atom,

R ² may be the same or different and is a monovalent optionally substituted aromatic hydrocarbon radical bonded to a silicon atom via a carbon ring atom,

R ³ may be the same or different and is a hydrogen atom or a monovalent optionally substituted SiC-bonded hydrocarbon radical,

R ⁴ may be the same or different and is a hydrogen atom or a monovalent optionally substituted hydrocarbon radical,

R ⁵ may be the same or different and has the meanings disclosed for R,

R ⁶ may be the same or different and has the meanings disclosed for R ¹ ,

a is 0, 1, 2 or 3,

b is 0, 1, 2 or 3,

c is 0, 1, 2 or 3,

d is 0, 1, 2 or 3,

e is 0, 1, 2 or 3,

g is 0, 1, 2 or 3,

h is 0, 1, 2 or 3,

Provided that the sum of a + b + c is 3 or less and c is not 0 at 1-100%, preferably 10-60%, more preferably 20-40% of all units of formula I per molecule, In at least 50% of all units of formula I in the organosilicon compound the sum of a + b + c is 2,

The sum of d + e is 3 or less, and the sum of d + e is 2 in less than 50% of all units of formula II in the organopolysiloxane resin,

The sum of g + h is 3 or less, and the sum of g + h is 2 in 50% or more of all units of the formula (III) in the organosilicon compound.

In the present invention, component (A) comprises substantially aromatic radicals directly attached to silicon atoms. This means that there is a covalent bond between the silicon atom in the unit of formula (I) and the carbon atom belonging to the aromatic ring.

Examples of radicals R are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl radicals, hexyl radicals (eg n-hexyl Radicals), heptyl radicals (eg n-heptyl radicals), octyl radicals (eg n-octyl radicals) and isooctyl radicals (eg 2,2,4-trimethylpentyl radicals), nonyl radicals (eg n-nonyls) Alkyl radicals such as radicals), decyl radicals (eg, n-decyl radicals), dodecyl radicals (eg, n-dodecyl radicals); Alkenyl radicals such as vinyl and allyl radicals; Cycloalkyl radicals such as cyclopentyl, cyclohexyl, cycloheptyl radicals and methylcyclohexyl radicals, and aromatic groups attached to silicon atoms via aliphatic groups such as benzyl radicals, phenylethyl radicals or 2-phenylpropyl radicals.

Examples of substituted radicals R include 3,3,3-trifluoro-n-propyl radicals, cyanoethyl, glycidyloxy-n-propyl, polyalkylene glycol-n-propyl, amino-n-propyl, Aminoethylamino-n-propyl and methacryloyloxy-n-propyl radicals.

The radical R is preferably a hydrogen atom or an optionally substituted C _1-30 aliphatic hydrocarbon radical, more preferably a C _1-4 aliphatic hydrocarbon radical, in particular a methyl radical.

Examples of radicals R ¹ are hydrogen atoms and radicals disclosed for the radicals R and R ² .

The radical R ¹ is preferably a hydrogen atom or an optionally substituted C _1-30 hydrocarbon radical, more preferably a hydrogen atom or a C _1-4 hydrocarbon radical, in particular a methyl or ethyl radical.

Examples of radicals R ² are aryl radicals such as the phenyl, tolyl, xylyl, cumyl, naphthyl and anthracyl radicals.

The radical R ² is preferably a phenyl radical.

The radical R ² is preferably 10 to 100%, more preferably 15 to 50% of the SiC-bonded radicals in component (A).

b is preferably 0 or 1, more preferably 0.

c is preferably 0, 1 or 2.

Preferably less than 5%, in particular less than 1% of the radicals R are hydrogen atoms.

The organosilicon compounds containing units of formula (I) used as component (A) are preferably linear or branched organopolysiloxanes, which more preferably comprise units of formula (I).

In the context of the present invention, the term "organopolysiloxane" is intended to include polymers, oligomers and dimer siloxanes.

Examples of component (A) of the invention include units Ph ₃ SiO _1/2- , Ph ₂ MeSiO _1/2- , PhMe ₂ SiO _1/2- , Ph ₂ SiO ₂ /2-, PhMeSiO _2/2 -and PhSiO ₃ /2-, wherein Me is a methyl radical and Ph is a phenyl radical, such as the formula Me ₃ SiO (Ph ₂ SiO) _x (Me ₂ SiO) _z SiMe ₃ , Me ₃ SiO (PhMeSiO) _y (Me ₂ SiO) _z SiMe ₃ , Me ₃ SiO (Ph ₂ SiO) _x (PhMeSiO) _y (Me ₂ SiO) _z SiMe ₃ and Me ₃ SiO (Ph ₂ SiO) _x (Me ₂ SiO) _z SiMe ₃ Linear polysiloxanes and the formulas MeSi [O (Ph ₂ SiO) _x (Me ₂ SiO) _z SiMe ₃ ] ₃ , PhSi [O (PhMeSiO) _y (Me ₂ SiO) _z SiMe ₃ ] ₃ and Me ₃ SiO (Me ₂ SiO ) _z [PhSiO (OMe ₂ SiO) _z SiMe ₃ ] _v (Me ₂ SiO) _z SiMe ₃ (where the coefficients v, x and y are each independently 1 or more, z is 0 or 1 or more, v, x , the sum of y and z determines the degree of polymerization and v is the branched polysiloxane of branch number, thus determining the viscosity.

In each case, the viscosity of the organosilicon compound (A) of the present invention measured at 25 ° C is preferably 10 to 1,000,000 mPas, more preferably 100 to 50,000 mPas, particularly 500 to 5,000 mPas.

The organosilicon compound (A) of the present invention is a commercially available product or can be prepared by any method known to date in the organosilicon chemistry, such as by cohydrolysis of the silane.

The composition of the present invention comprises additive (B) in an amount of preferably from 0.1 to 30 parts by weight, more preferably from 1 to 15 parts by weight, based on 100 parts by weight of component (A) in each case.

The additive (B) used according to the invention may exclusively comprise component (B1), exclusively component (B2), or a mixture of components (B1) and (B2), with the latter being preferred.

Component (B1) preferably comprises a powdered filler, more preferably a powdered hydrophobic filler.

Component (B1) preferably has a BET surface area of 20 to 1000 m ² / g, a particle size of less than 10 μm, and an aggregate size of less than 100 μm.

 Examples of component (B1) are silicon dioxide (silica), titanium dioxide, aluminum oxide, metal soap, quartz powder, PTFE powder, fatty acid amides such as ethylenebisstearamide and finely divided hydrophobic polyurethane.

As component (B1), preference is given to using silicon dioxide (silica), titanium dioxide or aluminum oxide having a BET surface area of 20 to 1000 m ² / g, a particle size of less than 10 μm and an aggregate size of less than 100 μm.

Silica, in particular, having a BET surface area of 50 to 800 m ² / g is particularly preferred as component (B1). These silicas may be pyrogenic or precipitated silicas. As component (B1), both pretreated silica, that is, commercially available hydrophobic silica and hydrophilic silica, can be used.

Examples of hydrophobic silicas that can be used according to the invention are pyrogenic hexamethyldisilane-treated silica HDK® H2000 with a BET surface area of 140 m ² / g (commercially available from Wacker-Chemie GmbH, Germany) and a BET surface area of 90 m ² Precipitated polydimethylsiloxane-treated silica with / g (available under the trade designation "Sipernat® D10" by Degussa AG, Germany).

 When using hydrophobic silica as component (B1), the hydrophilic silica can be calcined in situ for the desired effect of the antifoam formulation (if this is advantageous). Many methods for calcining silica are known. Hydrophilic silica can be calcined in situ by heating the silica in a dispersion in component (A) or a mixture of (A) and (B2) and / or (C), for example, at a temperature of 100-200 ° C. for several hours. This reaction can be aided by the addition of a catalyst such as KOH and a calcining agent such as short chain OH-terminated polydimethylsiloxane, silane or silazane. This treatment is also possible with commercially available hydrophobic silica and can help to improve the effect.

It is also possible to use silica fired in situ in combination with commercially available hydrophobic silica.

Examples of radicals R ³ are hydrogen atoms and radicals disclosed for the radicals R and R ² .

R ³ preferably comprises an optionally substituted C _1-30 hydrocarbon radical, more preferably a C _1-6 hydrocarbon radical, in particular a methyl radical.

Examples of radicals R ⁴ are the radicals disclosed for the radical R ¹ .

R ⁴ preferably comprises a hydrogen atom or a C _1-4 hydrocarbon radical, in particular a hydrogen atom, a methyl radical or an ethyl radical.

The value of d is preferably 3 or 0.

Component (B2) optionally used according to the invention preferably comprises a silicone resin comprising units of formula II (the sum of d + e is 2) of less than 30%, preferably less than 5% of the units in the resin do.

Particularly preferably component (B2) is an organopolysiloxane resin (MQ resin) comprising mainly R ³ ₃ SiO _1/2 (M) and SiO _4/2 (Q) units, where R ³ is as defined above Also called). The molar ratio of M to Q units is preferably 0.5 to 2.0, more preferably 0.6 to 1.0. These silicone resins may further contain up to 10% by weight of free hydroxyl or alkoxy groups.

Preferably, these organopolysiloxanes (B2) have a viscosity at 25 ° C. of greater than 1000 mPas or solid. The weight-average molecular weight of these resins, determined by gel permeation chromatography (relative to polystyrene standards), is preferably from 200 to 200,000 g / mol, in particular from 1,000 to 20,000 g / mol.

Component (B2) comprises a commercially available product or may be prepared by methods customary in the field of silicon chemistry, for example according to EP-A 927 733.

When the additive (B) used according to the invention comprises a mixture of components (B1) and (B2), the weight ratio of component (B1) to (B2) in the mixture is preferably 0.01 to 50, more preferably 0.1-7.

Examples of the radical R ⁵ are the examples disclosed for the radical R.

R ⁵ preferably comprises a hydrogen atom or an optionally substituted aliphatic C _1-30 hydrocarbon radical, more preferably a C _1-4 aliphatic hydrocarbon radical, in particular a methyl radical.

Examples of radicals R ⁶ are hydrogen atoms and radicals disclosed for the radicals R and R ² .

R ⁶ preferably comprises a hydrogen atom or an optionally substituted C _1-30 hydrocarbon radical, more preferably a hydrogen atom or a C _1-4 hydrocarbon radical, in particular a methyl radical or an ethyl radical.

The value of g is preferably 1, 2 or 3.

The value of h is preferably 0 or 1.

The viscosity of the organopolysiloxane (C) optionally used is preferably 10 to 1,000,000 mm ² / s at 25 ° C.

Examples of component (C) optionally used according to the invention are the examples disclosed for component (A), for example organosilicon compounds which do not have an aromatic radical (R ² ) attached directly to silicon, such as polydimethylsiloxane. It has a viscosity of 100 to 1,000,000 mPas at ℃. These polydimethylsiloxanes can be resulting branched, including, for example, up to 5% of the total units of R ⁵ SiO _3/2 and SiO _4/2 units. These branched or partially crosslinked siloxanes then have viscoelastic properties.

Component (C), optionally used, may preferably have a linear organopolysiloxane containing units of formula III, more preferably a siloxane having a polyether group or a silanol group and / or an alkoxy group and / or trimethylsiloxy group at the terminal. It mainly contains polydimethylsiloxane. Polyether-modified polysiloxanes of this kind are known and are disclosed, for example, in EP-A 1076073.

Particularly preferably component (C) is of formula III wherein R ⁵ is a methyl radical, R ⁶ is a linear and / or branched hydrocarbon radical of at least C ₆ , the average value of h is from 0.005 to 0.5, and (g + h The average value of the sum of the above) includes an organosilicon compound containing a unit of 1.9 to 2.1. Products of this kind are, for example, silanol-terminated polydimethylsiloxanes having a viscosity of 50 to 50,000 mPas at 25 ° C. and C ₆ or more aliphatic alcohols (eg isotridecyl alcohol, n-octanol, stearyl alcohol, 4-ethyl By alkali-catalyzed condensation of hexadecanol or eicosanol).

When the composition of the present invention comprises component (C), the amount included is preferably 1 to 900 parts by weight, more preferably 2 to 100 parts by weight, in particular 2 to 1, based on 100 parts by weight of component (A) in each case. 10 parts by weight.

Component (C) may comprise a commercially available product or may be prepared by conventional methods in the silicon chemistry art.

In addition to components (A), (B) and (C) (when used), the compositions of the invention may comprise all further substances which have been used so far in antifoam formulations, such as for example water insoluble organic compounds (D).

The term "water insoluble" should be understood for the purpose of the present invention to mean that the solubility in water at 25 ° C under a pressure of 1013.25 hPa is 2% by weight or less.

Component (D) optionally used is preferably a water-insoluble organic compound having a boiling point above 100 ° C. under ambient atmospheric pressure, ie, a pressure of 900 to 1100 hPa, and in particular mineral oil, natural oil, isoparaffin, polyisobutylene, oxo From residues obtained from the synthesis of alcohols by the process, esters of low molecular weight synthetic carboxylic acids, fatty acid esters such as octyl stearate and dodecyl palmitate, fatty acid alcohols, ethers of low molecular weight alcohols, phthalates, esters of phosphoric acid and waxes It includes the compound selected.

The composition of the invention is in each case preferably 0 to 1000 parts by weight, more preferably 0 to 100 parts by weight, based on 100 parts by weight of the total weight of components (A), (B) and (C) (if used) It contains a water-insoluble organic compound (D).

The components used in the process of the invention may in each case comprise a mixture of one or two or more of these individual components.

The composition of the invention is preferably

(A) 100 parts by weight of an organosilicon compound comprising a unit of formula (I);

(B) 0.1 to 30 parts by weight of an additive selected from organopolysiloxane resins comprising (B1) filler particles and / or (B2) units of formula II;

Randomly

(C) 1 to 900 parts by weight of an organosilicon compound having a unit of formula III, and

Randomly

(D) 0 to 10,000 parts by weight of the water-insoluble organic compound

It is a composition comprising a.

The composition of the present invention more preferably

(A) 100 parts by weight of an organosilicon compound comprising a unit of formula (I);

(B) 0.1 to 30 parts by weight of an additive selected from organopolysiloxane resins comprising (B1) filler particles and / or (B2) units of formula II;

Randomly

(C) 1 to 900 parts by weight of an organosilicon compound comprising a unit of formula III, and

Randomly

(D) 0-1000 weight part water insoluble organic compound

It is a composition comprising a.

The composition of the present invention is preferably a viscous transparent to opaque colorless to brown liquid.

The viscosity of the composition of the invention is preferably 10 to 2,000,000 mPas, in particular 2,000 to 50,000 mPas, in each case at 25 ° C.

The composition of the present invention may be a solution, dispersion or powder.

The compositions of the present invention can be prepared by known methods such as, for example, mixing all components using high shear forces in a colloid mill, dissolver or rotor-stator homogenizer. This mixing operation can be carried out under reduced pressure, for example, to prevent the incorporation of air present in the highly dispersed filler. The filler can then be calcined in situ if necessary.

When the composition of the invention is an emulsion, all emulsifiers known to those skilled in the art can be used in the preparation of silicone emulsions, such as, for example, anionic, cationic or nonionic emulsifiers. Preference is given to using emulsifier mixtures, in which case such as, for example, sorbitan fatty acid esters, ethoxylated sorbitan fatty acid esters, ethoxylated fatty acids, ethoxylated linear or branched C _10-20 alcohols and / or glycerol esters At least one nonionic emulsifier should be present. In addition, compounds and preservatives known as extenders such as polyacrylic acid, polyacrylates, cellulose ethers (e.g. carboxymethylcellulose and hydroxyethylcellulose), natural rubbers (e.g. Known conventional auxiliaries can be added.

The continuous phase of the emulsion of the invention is preferably water. However, it is also possible to prepare the compositions of the invention in the form of emulsions in which the continuous phase is formed by components (A), (B) and (C) (if used) or component (D). The system involved may be a multiphase emulsion.

Processes for preparing silicone emulsions are known. It is usually prepared by simply stirring all the components together and then homogenizing the system using a jet disperser, rotor-stator homogenizer, colloid mill or high pressure homogenizer as appropriate.

When the composition of the present invention comprises an emulsion, an oil-in-water emulsion containing 5 to 50% by weight of components (A) to (D), 1 to 20% by weight of emulsifiers and extenders, and 30 to 94% by weight of water desirable.

The composition of the present invention may be prepared as a free-flowing powder. For example, it is preferable to apply to powder detergent. The preparation of these powders, starting from mixtures of components (A), (B), (C) (if used) and (D) (if used), is of skill in the art according to methods known to those skilled in the art, such as spray drying or flocculation granulation. It is carried out using an adjuvant known in the art.

The powder of the invention preferably contains 2 to 20% by weight of components (A) to (D). Examples of carriers used include zeolites, sodium sulfate, cellulose derivatives, urea and sugars. Further possible constituents of the powders of the invention include, for example, waxes or organic polymers as disclosed, for example, in EP-A 887097 and EP-A 1060778.

The invention also provides detergents and cleaning products comprising the composition of the invention.

The composition of the present invention can be used where the organosilicon compound composition has been used. In particular the composition of the present invention can be used as an antifoaming agent.

The present invention also provides a method for defoaming a medium and / or a method for preventing foaming in a medium comprising adding the present composition to the medium.

The composition of the present invention can be added directly to the foaming medium, either as a powder or as an emulsion, diluted directly with a suitable solvent such as toluene, xylene, methyl ether ketone or t-butanol. The amount necessary to achieve the desired antifoam effect is various and depends, for example, on the nature of the medium, the temperature and the air flow generated.

The composition of the invention is preferably added to the foaming medium in an amount of 0.1 to 1% by weight, in particular 1 to 100 ppm by weight, based on the weight of the foaming medium.

The process of the invention is carried out at ambient atmospheric pressure, i.e. at a pressure of about 900 to 1100 hPa, preferably at a temperature of -10 to + 150 ° C, more preferably 5 to 100 ° C. The process of the invention may also be carried out at higher or lower pressures, for example 3000 to 4000 hPa or 1 to 10 hPa.

The antifoam composition of the present invention can be used or the method of the present invention can be carried out where it is desired to prevent or break the destructive foaming. This is the case, for example, in non-aqueous media such as tar distillation or petroleum processing, and in aqueous media. The antifoam composition of the present invention and the method of the present invention are suitable for controlling foaming in aqueous media such as aqueous surfactant systems, such as their use in detergents and cleaning products, wastewater plants, textile dyeing processes, scrubbing of natural gas, foam control in polymer dispersions. Or in particular in the vesicles of an aqueous medium obtained in the production of cellulose.

The compositions of the present invention have the advantage of being easy to handle as antifoaming agents and distinguished by long lasting high effects in a wide variety of different media with low amounts of addition. This is very advantageous from an economic and environmental point of view.

The method of the present invention has the advantage of being easy to implement and very economical.

All parts and percentages in the following examples are by weight unless otherwise indicated. Unless otherwise specified, the following examples are carried out at ambient atmospheric pressure, ie a pressure of about 1000 hPa and room temperature, ie about 20 ° C. or at a temperature which occurs when the reactants are combined at room temperature without further heating or cooling. All viscosity values cited in the examples are intended to relate to a temperature of 25 ° C.

Below, the structure of the phenylsiloxane used for ²⁹ Si-NMR data (mol%) is elucidated.

In the following, Me is used for the methyl radical and Ph is abbreviated for the phenyl radical.

Antifoam effect test

1. Foam protection index AFI

In a device according to DE-A 25 51 260, 200 ml of a 4 weight percent strength aqueous solution of sodium alkylsulfonate (Mersolat) containing 10 mg of the antifoam to be irradiated (in a solution of 10 times the amount of methyl ethyl ketone) was added. Foam for 1 minute using two stirrers. Next, the collapse of the bubble is recorded. The antifoam index is calculated using the area plotted bubble height versus time. The lower this index, the more effective the antifoam.

2. Stirring Test

A 300 ml solution containing 1% by weight of the antifoam free cleaning powder was foamed for 5 minutes with a stirrer at 1000 revolutions per minute. Then 100 μl of an antifoam solution in methyl ethyl ketone of 10 wt% strength was added and stirring continued for another 25 minutes. The foam height was recorded throughout.

As a measure of the effect, the average foam height relative to the foam height in the absence of the antifoaming agent after 2-3 minutes is calculated. The lower the result, the more effective the antifoam.

3. Washing machine test with powder detergent

0.1 g of antifoam was added to 100 g of antifoam free cleaning powder. The cleaning powder was then introduced into a drum type washing machine (Miele Novotronic W918 without purge logic) with 3500 g of clean cotton detergent. The wash program is then started (at 30 ° C.) and the foam height is recorded over 55 minutes. Foaming average scores are determined using the foaming scores [0 (non-foamable) to 6 (excessive foaming)] measured during the period. The lower the score, the greater the effect of the antifoam agent over the period as a whole.

4. Washing machine test with liquid detergent

0.03 g of antifoam was added to 180 g of antifoam free liquid detergent. The detergent was then introduced into a drum type washing machine (Miele Novotronic W918 without purge logic) with 3500 g of clean cotton detergent. The wash program is then started (at 40 ° C.) and the foam height is recorded over 55 minutes. Foaming average scores are determined using the foaming scores [0 (non-foamable) to 6 (excessive foaming)] measured during the period. The lower the score, the greater the effect of the antifoam agent over the period as a whole.

Comparative Example 1 (C1)

Silicone comprising 2.5 parts of a condensation product of viscosity 180 mPas prepared from polydimethylsiloxane and octyldodecanol with a viscosity of 40 mPas and terminated with silanol groups and 40 mol% of trimethylsiloxy groups and 60 mol% of SiO _4/2 An antifoam base is prepared by mixing 5 parts of a 50% strength toluene-based solution of the resin and then removing the volatile components.

89.3 parts by weight of trimethylsiloxy-terminated polydimethylsiloxane (available from Wacker-Chemie GmbH, Germany, trade name "Siliconol AK 5000") at 25 ° C., 5 parts by weight of the above-mentioned defoamer base, BET surface area A mixture of 5 parts by weight of hydrophilic pyrogenic silica (available from Wacker-Chemie GmbH, trade name HDK® T30) of 300 m ² / g and 0.7 parts by weight of methanolic KOH is heated at 150 ° C. for 2 hours. This obtained the foam prevention body whose viscosity is 25600 mPas. This antifoam was investigated for antifoam index AFI in agitation test and washing machine test. The results of these tests are summarized in Table 1.

Comparative Example 2 (C2)

378 g of trimethylsiloxy-terminated polydimethylsiloxane (available from Wacker-Chemie GmbH, Germany, trade name "Siliconol AK 1000") having a viscosity of 1000 mPas at 25 ° C by heating at 140 ° C in the presence of 0.3 g of KOH , 180 g of polydimethylsiloxane having a viscosity of 10000 mPas at 25 ° C. and terminated with silanol groups (available from Wacker-Chemie GmbH, Germany, trade name “Polymer FD 10”), and ethyl silicate (from Wacker-Chemie GmbH, Germany) Yes, the brand name "SILIKAT TES 40") to produce a branched polyorganosiloxane by reaction of 18 g. Subsequently, 30 g of hydrophilic pyrogenic silica having a BET surface area of 200 m ² / g (available from Wacker-Chemie GmbH, Germany, tradename HDK® T20) and 30 g of polydimethylsiloxane terminated with silanol groups with a viscosity of 40 mPas Add and heat the mixture at 180 ° C. for a further 4 hours and liberate the volatile components at 50 hPa. This obtained the viscous colorless antifoamer formulation whose viscosity is 68640 mPas.

This antifoam was investigated for antifoam index AFI in agitation test and washing machine test. The results of these tests are summarized in Table 1.

Comparative Example 3 (C3)

90 parts trimethylsiloxy having a viscosity of 1000 mPas and containing 20 mol% of 2-phenylpropenylmethylsiloxane units and 80 mol% of dodecylmethylsiloxane units (ie, containing only aromatic groups in indirectly attached form) Terminated diorganopolysiloxane, 5 parts pyrogenic silica having a BET surface area of 300 m ² / g, 3 parts polydimethylsiloxane with C ₂₀ terminal alkoxy groups, solid at room temperature (according to ²⁹ Si-NMR and IR analysis) 40 2 parts comprising mole% CH ₃ SiO _1/2- , 50 mole% SiO ₄ / _2- , 8 mole% C ₂ H ₅ OSiO ₃ /2-and 2 mole% HOSiO ₃ / ₂ -units. Silicone resin. The weight-average molar mass of this resin was 7900 g / mol (based on polystyrene standard), 0.7 parts of 20% by weight strength methanol-based KOH mixed with a dissolver and heated at 150 ° C. for 4 hours. This obtained the viscous defoaming agent whose viscosity is 8000 mPas.

The composition thus obtained was then examined for antifoam index AFI in agitation test and washer test. The results of these tests are summarized in Table 1.

Example 1

Phenylsiloxane 1 is a silicone oil having a viscosity of 500 mm ² / s according to NMR comprising the following units:

Me ₃ SiO _(1/2) 9.7%

Me ₂ Si 0 _(2/2) 64.1%

Ph ₂ Si0 _(2/2) 19.6%

PhSiO _(3/2) 6.6%

90 parts Phenylsiloxane 1, 5 parts pyrogenic silica with a BET surface area of 300 m ² / g (available from Wacker-Chemie GmbH, Germany, tradename HDK® T30), solid at room temperature ( ²⁹ Si-NMR and IR analysis) According)) comprising 40 mol% CH ₃ SiO _1/2- , 50 mol% SiO ₄ / _2- , 8 mol% C ₂ H ₅ OSiO ₃ /2-and 2 mol% HOSiO ₃ / ₂ -units 5 parts of silicone resin to say. The weight-average molar mass of this resin was 7900 g / mol (based on polystyrene standard) and a viscosity of 1000 mPas and a dispersion in polydimethylsiloxane having trimethylsiloxy group end groups, mixed with 1.5 parts of 10 wt% strength methanolic KOH as a dissolver. And heated at 150 ° C. for 4 h. This obtained the viscous defoaming agent whose viscosity is 28,800 mPas.

The composition thus obtained was then examined for antifoam index AFI in agitation test and washer test. The results of these tests are summarized in Table 1.

Example 2

Phenylsiloxane 2 is a silicone oil having a viscosity of 200 mm ² / s according to NMR comprising the following units:

Me₃SiO_(1/2) 10.2%

Me₂Si0_(2/2) 62.2%

Ph ₂ Si (OH) O _(1/2) 0.7%

PhSi (Me) O _(2/2) 7.2%

Ph₂SiO_(2/2) 13.8%

PhSi (OH) 0 _(2/2) 1.1%

PhSiO_(3/2) 4.8%

90 parts phenylsiloxane 2, 5 parts pyrogenic silica with a BET surface area of 300 m ² / g (available from Wacker-Chemie GmbH, Germany, tradename HDK® T30), 5 parts solid silicone resin disclosed in Example 1, and viscosity 1.5 parts of 10% by weight strength methanol-based KOH as a dispersion in polydimethylsiloxane having 1000 mPas and having a trimethylsiloxy group end group was mixed with a dissolver and heated at 150 ° C. for 4 hours. This obtained the antifoamer with a viscosity of 15,200 mPas.

The composition thus obtained was then examined for antifoam index AFI in agitation test and washer test. The results of these tests are summarized in Table 1.

Example 3

Phenylsiloxane 3 is a silicone oil having a viscosity of 1250 mm ² / s according to NMR comprising the following units:

Me₃SiO_(1/2) 2.9%

Me₂Si0_(2/2) 34.7%

Me ₂ Si (OH) O _(1/2) 0.4%

PhSi (Me) O _(2/2) 61.0%

PhSiO_(3/2) 1.0%

87 parts phenylsiloxane 3, 5 parts pyrogenic silica with a BET surface area of 400 m ² / g (available from Wacker-Chemie GmbH, Germany, trade name HDK® T40), 3 with a viscosity of 100 mPas and containing a terminal C ₂₀ alkoxy group Part of polydimethylsiloxane, 5 parts of the solid silicone resin disclosed in Example 1, and 0.7 parts of 20% by weight strength methanol-based KOH were mixed with a dissolver and heated at 150 ° C. for 4 hours. This obtained the antifoamer with a viscosity of 6400 mPas.

The composition thus obtained was then examined for antifoam index AFI in agitation test and washer test. The results of these tests are summarized in Table 1.

Example 4

Phenylsiloxane 4 is a silicone oil having a viscosity of 1000 mm ² / s according to NMR comprising the following units:

Me₃SiO_(1/2) 8.8%

Me₂Si0_(2/2) 65.3%

Me ₂ Si (OH) O _(1/2) 0.5%

MeSiO_(3/2) 1.5%

PhSiO_(3/2) 23.9%

88 parts phenylsiloxane 4, 5 parts pyrogenic silica with a BET surface area of 200 m ² / g (available from Wacker-Chemie GmbH, Germany, trade name HDK® N20), 3.6 with viscosity of 100 mPas and containing terminal C ₂₀ alkoxy groups Part of polydimethylsiloxane, 2.4 parts of the solid silicone resin disclosed in Example 1, and 0.7 parts of 20% by weight strength methanol-based KOH were mixed with a dissolver and heated at 150 ° C. for 4 hours. Four parts of pretreated precipitated silica (available from Degussa AG, Germany, trade name SIPERNAT® D10), having a BET surface area of 90 m ² / g and being water repellent with polydimethylsiloxane, are then dispersed and incorporated using a dissolvers. This obtained the antifoamer with a viscosity of 4000 mPas.

The composition thus obtained was then examined for antifoam index AFI in agitation test and washer test. The results of these tests are summarized in Table 1.

Example 5

Phenylsiloxane 5 is a silicone oil with a viscosity of 1000 mm ² / s according to NMR comprising the following units:

Me₃SiO_(1/2) 7.6%

Me₂Si0_(2/2) 62.4%

Ph₂SiO_(2/2) 22.9%

PhSi (OH) O _(2/2) 0.3%

PhSiO_(3/2) 6.8%

90 parts phenylsiloxane 5, 2 parts precipitated silica with a BET surface area of 170 m ² / g (available from Degussa AG, Germany, trade name Sipernat 383 DS), 3 parts pyrogenic silica with a BET surface area of 300 m ² / g (Germany Available from Wacker-Chemie GmbH, tradename HDK® T30), 3 parts polydimethylsiloxane having a viscosity of 100 mPas and containing a terminal C ₂₀ alkoxy group, 2 parts solid silicone resin disclosed in Example 1, and 20 parts by weight 20 parts by weight Strength methanol-based KOH was mixed with a dissolver and heated at 150 ° C. for 4 hours. This obtained the antifoamer with a viscosity of 62000 mPas.

The composition thus obtained was then examined for antifoam index AFI in agitation test and washer test. The results of these tests are summarized in Table 1.

Example 6

90 parts of phenylsiloxane 3 of the structure disclosed in Example 3, 2 parts of precipitated silica (140K 2 Hg, available from Wacker-Chemie GmbH, Germany, trade name HDK® H2000) having a BET surface area of 140 m ² / g and water repellency, The disclosed 8 parts solid silicone resin, and 1.5 parts 10 wt% strength KOH, were mixed with a dissolver in a dispersion in polydimethylsiloxane having a viscosity of 1000 mPas and heated at 150 ° C. for 4 hours. This obtained the antifoamer with a viscosity of 3200 mPas.

The composition thus obtained was then examined for antifoam index AFI in agitation test and washer test. The results of these tests are summarized in Table 1.

Example 7

90 parts of phenylsiloxane 3 of the structure disclosed in Example 3, 8 parts of precipitated silica (available from Wacker-Chemie GmbH, Germany, trade name HDK® H2000) having a BET surface area of 140 m ² / g and water repellency, The disclosed two parts solid silicone resin, and 1.5 parts 10% by weight strength KOH were mixed with a dissolver in a dispersion in polydimethylsiloxane having a viscosity of 1000 mPas and containing trimethylsiloxy end groups and heated at 150 ° C. for 4 hours. This obtained the defoaming agent whose viscosity is 25600 mPas.

The composition thus obtained was then examined for antifoam index AFI in agitation test and washer test. The results of these tests are summarized in Table 1.

Example Antifoam Index AFI Stirring Test Average Edible Height (%) Washing machine test average firing score C1 682 58 3.3 ¹⁾ 4.9 ²⁾ C2 1612 75 4.4 ¹⁾ C3 2137 91 3.2 ¹⁾ Example 1 82 41 1.9 ¹⁾ Example 2 152 52 2.7 ¹⁾ Example 3 122 50 1.0 ¹⁾ 0.7 ²⁾ Example 4 135 45 3.0 ¹⁾ Example 5 62 21 0.4 ¹⁾ Example 6 212 43 0.7 ¹⁾ Example 7 337 55 2.9 ¹⁾

^{1) Use} powder detergent

²⁾ use liquid detergent

Example 8

Black liquor test:

This test was carried out in an emulsion containing the antifoaming agents disclosed in Examples 1 to 7 and Comparative Examples 1 to 3 as main components. These emulsions each contain 20 weight percent silicone antifoam, 10 weight percent soybean oil, ethoxylated isotridecyl alcohol (HLB 11.2), ethoxylated stearyl alcohol (HLB 9.7), pentaerythritol distearate and poly as emulsifiers. It contains 0.3 wt% formaldehyde as a mixture of ethersiloxanes and as a preservative.

400 ml of black liquor (hardwood from the treatment of birch) was conditioned at 80 ° C. using a thermometer in a 1 liter measuring cylinder with a washing bottle for 15 minutes. After adding 20 [mu] l of each antifoam emulsion, the black liquor was circulated and pumped at a rate of 2.3 l / min. The time (t) between the start of the test and the time the foam rose to 75 mm was measured. The longer this time t, the more effective the antifoam.

Example Black liquor test time t (s) C1 110 C2 80 C3 95 Example 1 165 Example 2 130 Example 3 195 Example 4 135 Example 5 205 Example 6 180 Example 7 170

Example 9

90 parts phenylsiloxane 3 prepared as disclosed in Example 3, 5 parts pyrogenic silica with a BET surface area of 400 m ² / g (available from Wacker-Chemie GmbH, Germany, tradename HDK® T40), solid at room temperature 40 mol% CH ₃ SiO _1/2 , 50 mol% SiO _4/2 , 8 mol% C ₂ H ₅ OSiO _3/2 and 2 mol% HOSiO ₃ (according to ²⁹ Si-NMR and IR analysis) Five parts of silicone resin having a weight-average molar mass of 7900 g / mol comprising _1/2 units are heated at 150 ° C. for 4 hours in the presence of 1500 ppm KOH.

This obtained 100 parts of antifoamer formulations. 30 parts of sorbitan monostearate (available under the trade name "Span 60" from Uniqema) and 60 parts polyoxyethylene (20) sorbitan monostearate (available under the trade name "Tween 60" from Uniqema) at 60 ° C. ) And gradually dilute with 500 parts of water. To this mixture is added 2 parts of polyacrylic acid (available under the trade name "Carbopol 934" from BF Goodrich) and further mixed with 345 parts of water and 3 parts of isothiazolinone-based preservative (trade name "Acticide from Thor-Chemie Speyer, Germany) MV "available). The emulsion is then homogenized at 100 bar using a high pressure homogenizer and adjusted to pH 6-7 with 10% NaOH.

The antifoam emulsion obtained was very suitable for defoaming the polymer aqueous dispersion.

Example 10

90 parts phenylsiloxane 3 prepared as disclosed in Example 3, 5 parts pyrogenic silica with a BET surface area of 400 m ² / g (available from Wacker-Chemie GmbH, Germany, tradename HDK® T40), solid at room temperature 40 mol% CH ₃ SiO _1/2 , 50 mol% SiO _4/2 , 8 mol% C ₂ H ₅ OSiO _3/2 and 2 mol% HOSiO ₃ (according to ²⁹ Si-NMR and IR analysis) Five parts of silicone resin having a weight-average molar mass of 7900 g / mol comprising _1/2 units are heated at 150 ° C. for 4 hours in the presence of 1500 ppm KOH.

35 ml of a 2% solution of a high molecular weight copolymer of acrylic acid, methacryloyl stearate and pentaerythritol diallyl ether (molar ratio 100: 2: 0.3) (when neutralized at a viscosity of 17500 mm ² / s) was placed in a glass beaker 10 g of the above-mentioned antifoam formulation was slowly added while filling and mixing in a load using a paddle stirrer, and after stirring for 10 minutes, an emulsion of the antifoam formulation was formed in the polymer solution. 88.5 g of light soda was added to this emulsion with continued stirring followed by removal of water under vacuum with continued mixing. 0.5 g of hydrophilic silica (trade name HDK® N20, available from Wacker-Chemie GmbH, Germany) was then mixed with a BET surface area of 200 m ² / g.

This gave a white free-flowing powder. This powder has been successfully used to prevent foaming in protective detergents of powdered detergents or powdered crops.

Claims (12)

(A) at least one organosilicon compound having units of formula (I) (B) A composition comprising (B1) filler particles and (B2) at least one additive selected from the group consisting of organopolysiloxane resins comprising units of formula II: Formula I R _a (R ¹ O) _b R ² _c SiO _{(4-abc) / 2} Formula II R ³ _d (R ⁴ O) _e SiO _{(4-de) / 2} Where R may be the same or different and is a hydrogen atom, a monovalent substituted or unsubstituted SiC-bonded aliphatic hydrocarbon radical or an aromatic hydrocarbon radical bonded to silicon via an aliphatic group, R ¹ may be the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon radical, R ² may be the same or different and is a monovalent substituted or unsubstituted aromatic hydrocarbon radical attached to a silicon atom via a carbon ring atom, R ³ may be the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted SiC-bonded hydrocarbon radical, R ⁴ may be the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon radical, a is 0, 1, 2 or 3, b is 0, 1, 2 or 3, c is 0, 1, 2 or 3, d is 0, 1, 2 or 3, e is 0, 1, 2 or 3, Provided that the sum of a + b + c is 3 or less, c is not 0 in 1-100% of all units of formula (I) per molecule, and a + b in 50% or more of all units of formula (I) in organosilicon compounds the sum of + c is 2, 10-100% of the SiC-bonded radicals in component (A) are radicals R ² , The sum of d + e is 3 or less, and the sum of d + e is 2 in less than 50% of all units of formula II in the organopolysiloxane resin. The composition of claim 1, wherein R ² comprises a phenyl radical. The composition of claim 1 or 2, wherein the organosilicon compound (A) has a viscosity of 10 to 1,000,000 mPas at 25 ° C. A composition according to claim 1 or 2, wherein R is a methyl radical. The composition of claim 1 or 2, wherein component (B1) comprises a powdered filler. The composition according to claim 1 or 2, wherein component (B2) comprises a silicone resin comprising units of formula II (the sum of d + e in less than 30% of the units in the resin is 2). . The method according to claim 1 or 2, (A) 100 parts by weight of an organosilicon compound comprising a unit of formula (I): and (B) 0.1 to 30 parts by weight of at least one additive selected from the group consisting of (B1) filler particles and (B2) organopolysiloxane resins comprising units of formula (II). A detergent comprising the composition of claim 1. Method of defoaming a medium, characterized in that the composition of claim 1 or 2 is added to the medium. 10. The method of claim 9, wherein the composition is added to the foamed medium in an amount of 0.1 wt% to 1 wt% based on the weight of the foamed medium. A method of preventing foaming in a medium, wherein the composition of claim 1 or 2 is added to the medium. 12. The method of claim 11, wherein the composition is added to the foamed medium in an amount of 0.1 wt% to 1 wt% based on the weight of the foamed medium.