WO2010103103A1

WO2010103103A1 - Novel polyorganosiloxanes and use thereof

Info

Publication number: WO2010103103A1
Application number: PCT/EP2010/053180
Authority: WO
Inventors: Dieter Wrobel; Hubertus Eversheim; Julien Richeton
Original assignee: Momentive Performance Materials Gmbh
Priority date: 2009-03-13
Filing date: 2010-03-12
Publication date: 2010-09-16
Also published as: CN102395620B; KR20110131267A; DE102009012665A1; EP2406303A1; CN102395620A; JP2012520367A

Abstract

The invention relates to novel polyorganosiloxanes, to methods for the production thereof, and to the use thereof, in particular as force- and/or heat-transfer fluids such as hydraulic fluids and in cosmetic compositions.

Description

New polyorganosilioxanes and their use

The invention relates to novel Polyorganosiioxane, processes for their preparation and their use, in particular as power and / or Wärmeübertragungsflüssi- opportunities, such as hydraulic fluids.

Synthetic hydraulic fluids are known in addition to various aliphatic, aromatic or unsaturated hydrocarbons, such as alpha-olefins, phosphoric esters, phenyl ethers, polyesters or polyethers, and also polyorganosiloxanes for a long time (eg US 2398187, US 4048084, US 4116847, US 4132664, US 4175049, US 4357473, GB 1093555, GB 867167, US 4340495, etc.). Further, US 5684112 discloses branched polyorganosilioxanes as conditioning agents for use in cosmetic compositions. A compound of the formula (Me ₃ Si0) ₃ Si-phenyl is sold under the trade name Baysilon PD5 by Momentive Performance Materials inter alia as a damping fluid. However, said compound, as well as many other low molecular weight polyorganosioxanes, when contacted with silicone gaskets or membranes, result in increased swelling of the silicone gaskets or membranes or diffusion of the liquid through the silicone gasket, resulting in leakage of the liquid. The object of the present invention was therefore to find a suitable as a power transmission fluid medium, which does not have the disadvantages mentioned. The medium should be used in particular for power transmission as well as a medium for damping so time-delayed force distribution or power transmission. This requirement arises in particular in a hydraulic bearing, which consists of elastic see rubber membranes as a spring system, or enclosed by membranes air cushion, which separate another room with a viscous, damping power transmission fluid. This liquid should continue to have a suitable viscosity range at different temperatures, in particular at low temperature, and be resistant to high temperatures and change the enclosing membrane only slightly. Furthermore, the liquid medium should have a low compressibility and in interaction with metals and sealing materials such as in particular elastomers, such as silicone elastomers they should not change their properties as possible. The glycols also used as damping fluid for the production of so-called hydraulic bearings, although they are used in hydraulic bearings with elastomeric spring elements based on natural rubber or EPDM, but prove to be largely unusable in spring elements made of silicone elastomers, since they are an acceptable swelling, but lead to an undesirably high diffusion or permeability through these membranes, and further do not have a sufficiently low viscosity in the low temperature range. Other compounds, such as low molecular weight synthetic media, have too low a boiling point or they will harden in the presence of atmospheric oxygen or moisture in such a way that the viscosity at least increases or even the liquid solidifies.

The invention thus had the task to find a suitable liquid, the

Avoids problems arising from contact of glycols, hydrocarbons or linear polydimethylsiloxanes with polyorganosiloxane elastomer membranes or

Seals occur.

The inventors surprisingly found in the class of silylated siliconates and

Silicates Compounds with a low degree of polymerization that could solve these problems.

The present invention thus provides:

The use of polyorganosiloxanes of the formula (I):

MaDbT ₀ Qd (I)

in which: a = 2 to 6, preferably 3 or 4, particularly preferably 4, b = 0 to 10, preferably 0 to 2, more preferably 0, c = 0 to 3, preferably 0 to 2, more preferably 0 or 1, d = 0 to 2, preferably 0 or 1, c + d = 1 to 2, preferably 1, a / (c + d)> 2, preferably> 3, in which

M ₁ D ₁ T ₁ Q

R R - Si-O- M

1.2

R

-Si- O- D

R

Q -l / 2

-O-Si-O- T

R

0 1/2

^ O-Si-O-Q

O 1/2

mean, and

R is selected from the group consisting of:

Aliphatic and / or aromatic radicals having up to 30 carbon atoms, which may have one or more oxygen atoms, one or more halogen atoms and one or more cyano groups, with the proviso that at least one of the radicals R is bound in M via a carbon atom to silicon, and at least one of the radicals R in M has at least two, more preferably at least 4, even more preferably at least 5 carbon atoms, these being used as a force and / or heat transfer fluid or constituent in cosmetic compositions. A power transmission fluid is suitable for transmitting and / or distributing mechanical forces over a certain distance between the place of generation and action. The power transmission fluids include, in particular, hydraulic, damping and transmission fluids or oils. Requirements that meet the power transmission fluids of the present invention generally include:

• good lubricating properties

«High resistance to aging

High flash point, low pour point or pour point,

Compatibility with silicone elastomers,

Especially low permeability or permeation,

• Resin and acid freedom

• low temperature influence on viscosity (both dynamic and kinematic viscosity)

• low compressibility.

To assign the polyorganosiloxanes of formula (I) preferably has a pour point (DIN ISO 3016, ASTM D5985) of less than -28 ⁰ C and a pour point (DIN ISO 3016, ASTM E 537-76 D of less than -30 ⁰ C. The polyorganosiloxanes of the formula (I) preferably have a boiling point greater than 180 ^° C., more preferably greater than 190 ^° C.

The polyorganosiloxanes of formula (I) preferably at polydimethylsiloxane elastomers have a permeation determined as so-called fuel permeability KD according to DIN 53532 of less than 70 [g / m ² / d] at 140 ⁰ C, preferably less than 40 [g / m ² / d], more preferably a KD value of less than 20 [g / m ² / d] for a sample having the thickness of 2 mm.

In the formula (I), the groups R include both R groups which are over

Carbon atoms are bonded to silicon atoms, as well as groups R, which are bonded via oxygen atoms to silicon atoms, i. it is in this

Case of alkoxy groups (hereinafter sometimes referred to as R '). However, polyorganosiloxanes having groups M having alkoxy groups R 'according to the invention are less preferred, or in other words: Si-C bonded groups R (hereinafter sometimes referred to as R ") in M are preferred in the invention.

The proviso according to which at least one of the radicals R in M is bonded to silicon via a carbon atom and at least one of the radicals R in M has at least two carbon atoms also includes the case that a radical R is present in M, the Si-C having at least two carbon atoms, more preferably at least four carbon atoms, more preferably at least five carbon atoms. This case, wherein M has a Si-C bonded radical R having at least two carbon atoms, more preferably at least four carbon atoms, more preferably at least five carbon atoms, is the preferred case of the present invention.

In a preferred embodiment, in the polyorganosiloxanes according to the invention at least one of the radicals R in M represents a group which has an aromatic group, in particular a phenyl group, preferably a phenylethyl or phenylpropyl group, in particular a (2-phenyl-2-methyl) ethane-1-yl group.

In a preferred embodiment, in the polyorganosiloxanes according to the invention at least one of the radicals R in M represents a group of the formula R * which is selected from the group consisting of: - aryl,

-CH ₂ -CHR ¹ -R ² , in which

R ^{1 is} hydrogen or C ₁ to C ₃ alkyl, and

R ^{2 has} the same meaning as R,

-CR ³ = CH-R ² , - in which

R ^{2 has} the same meaning as R, and

R ^{3 has} the same meaning as R or is hydrogen. Preferred groups M include:

-SiFT ₃ ; wherein preferably at least one, more preferably exactly one group R "is a group R ^* , as mentioned above, more preferably M is a group -SiMe ₂ R ^* ;

-SiR " ₂ R 'is;

wherein at least one of R "or R 'has at least two carbon atoms, more preferably at least four carbon atoms, more preferably at least five carbon atoms, more preferably M is

-SiMe ₂ R '.

The polyorganosiloxanes according to the invention may have the same or different groups M. That is, in addition to the obligatory groups M, as defined above, there may also be groups M which have neither radicals R with at least two carbon atoms nor SiC-bonded radicals, such as -SiMe ₃ and -Si (OMe) ₃ .

However, all groups M in the polyorganosiloxanes according to the invention are preferably radicals R having at least two carbon atoms, in particular SiC-bonded radicals R having at least two carbon atoms.

In a further preferred embodiment, the present invention relates to the use of polyorganosiloxanes of the formula (I) in which the polyorganosiloxanes have the formula (Ia) or (Ib):

wherein M, D, T and Q are as defined above.

The polyorganosiloxanes of the formulas (Ia) or (Ib) preferably have the following structures: M ₄ QM ₃ T

In a further preferred embodiment, the present invention relates to the use of polyorganosiloxanes of the formula (I) in which all radicals M have at least one, preferably exactly one group of the formula R ^* .

In a further preferred embodiment, the present invention relates to the use of polyorganosiloxanes of the formula (I) in which all R radicals in M are bonded to silicon via carbon atoms.

Most preferably, the polyorganosiloxanes according to the invention have identical groups M, the SiC-bonded radicals R with at least two

Carbon atoms, in particular R *, have.

Examples include:

QM ₄ , such as:

Si - [O-SiRVz-R ^* J ₄ z = 1-2 Si J O-SiR V _z -R ' ₂ ] ₄ z = 1-2

preferred are the formulas

or TM3 type compounds, such as:

preferred are the formulas:

n = 0 to 8, preferably 1 to 5. In a preferred embodiment, the present invention relates to the use of polyorganosiloxanes of the formula (I) in which the ratio of the siloxane units M: Q = 4 to 1: 1, preferably 4 to 3: 1, or M: T = 3 to 1: 1 , preferably 3 to 2: 1.

In a further preferred embodiment, the present invention relates to the use of polyorganosiloxanes of the following formulas:

In a further preferred embodiment, the present invention relates to the use of polyorganosiloxanes of formula (I) which have a viscosity of less than 100 mPa.s at 25 ⁰ C and a Schergeschwingkeitsgefälle D = 1 ^'1. That is, the polyorganosiloxanes of formula ( I) at room temperature is generally liquid. polyorganosiloxanes the invention are preferably also at -40 ⁰ C still liquid, and exhibit at -40 ⁰ C. in particular a viscosity of less than 20,000 mPa.s, preferably measured at a shear rate D of 1 ¹ s.

The polyorganosiloxanes used according to the invention preferably have a molecular weight (determined by gel permeation chromatography against polystyrene as standard) with a number average M _n of 360 to 2000 g / mol.

The use according to the invention also includes in particular the use as a power transmission fluid in hydraulic bearings. Hydraulic bearings are damping elements which comprise a spring body and a damping unit. The damping unit comprises the cavities and flow channels filled with the power transmission fluid (see, for example, EP 0 547 287). Accordingly, the present invention also relates to hydraulic bearings containing polyorganosiloxanes of the formula

(I) -

Furthermore, the polyorganosiloxanes of the formula (I) can also surprisingly be used as a constituent of cosmetic compositions, since in this way siloxane compounds having a solubility behavior suitable for cosmetic ingredients can be provided. In addition, they have a desired low spreading or migration behavior, low tack compared to, for example, sand and dust and a high refractive index n ₂ 5 ^D above 1, 50, in particular higher than 1, 51. A refractive index of more than 1.51 was found especially for compounds of formula (Ia) and (Ib) and R = arylalkyl. This can be achieved special gloss effects. In addition, the low migration behavior is particularly desirable in color cosmetic formulations to prevent penetration of these components into the eye or mouth. They act there in particular as a film former, gloss additive, compatibilizer for components, support material for sunscreen products, in particular in waterproof sunscreen products, which have a low sand adhesion ( ^' anti-sanding ^' ), as gloss-imparting ingredients, especially of decorative skin products, such as lipsticks, make -up- By virtue of the properties of the polyorganosiloxanes of the formula (I) which, in contrast to fats, oils, and in particular the polydimethylsiloxanes, spread less. With the inventive compounds can therefore be advantageous cosmetic compositions such as mascaras and ^'LJP ^Gloss', other coloring skin care products and hair care products such as shampoos, hair conditioners and, in particular hair treatments, oils and -fluids produce to increase the gloss of skin nail and hair surfaces. Due to the high refractive index of more than 1, 5, the inventive substances are also excellently suitable for containing a decrease in the whitening of pigmented or solids or waxes cosmetic products (antiperspirants) on the skin contribute (anti-Weissel effect, ^{'Anti-whitening} ^' ).

Accordingly, the present invention also relates to cosmetic compositions containing polyorganosiloxanes of the formula (I).

Among the polyorganosiloxanes used according to the invention are also novel compounds of the formula (I '):

M _a D _b T _c Q _d (I ')

in which: a = 2 to 6, preferably 2 to 4 b = 0 to 2, preferably 0 c = 0 to 2, preferably 0 or 1, d = 0 to 2, preferably 0 or 1, c + d = 1 to 2, a / (c + d)> 2 where

M ₁ D ₁ T ₁ Q

R

Si-O- D

R

Q 1/2 l _fl O-SI-0-Q

O 1/2 mean, and where

R is selected from the group consisting of:

Aliphatic and / or aromatic radicals having up to 30 carbon atoms, which may have one or more oxygen atoms, one or more halogen atoms and one or more cyano groups, with the proviso that at least one of the radicals R in M on a

Carbon atom is bonded to silicon and at least one of the radicals

Arylalkyl or arylalkenyl. With regard to the preferred polyorganosiloxanes of the formula (I '), the statements for the polyorganosiloxanes of the

Refer to formula (I).

Finally, the present invention also relates to a process for the preparation of the polyorganosiloxanes of the formula (T), comprising:

i. To implement a compound of the formula:

M ^H _a D _b T _c Q d (H) wherein, a, b, c, d are as defined above, wherein M is ^H , D, T, Q

R

H - Si-O - wr

1.2

R

-Si-O - D

R

and R is as defined above with a compound

CH ₂ = CHR ¹ -R ² , wherein R ¹ and R ^{2 are} as defined above, or a compound

CR ³ ≡CR ² , wherein R ² and R ^{3 are} as defined above, in the presence of a hydrosilylation catalyst, or

To implement a compound of the formula:

M ^H aD _b T _c Q _d (II) which is as defined above with a compound of the formula HO-R, wherein R is as defined above, in the presence of a catalyst, in which reaction with hydrogen evolution an RO-Si group is formed in M,

or

iii. Hydrolysis or alcoholysis of a plurality of halogen and / or alkoxysilanes which correspond to precursors of the units M, D, T, Q as defined in claim 1 and which have at least one group R in which R is as defined above. The invention is illustrated by the following examples.

Examples

example 1

Preparation of Si [OSϊMe ₂ H] ₄ and its Oligomers.

In a 6 L flat-section vessel with heating or cooling jacket, which is equipped with stirrer, thermometer, reflux condenser, metering device, 2010 g of tetramethyldisiloxane (30 mol), 1200 g of water, 60 g of 37% hydrochloric acid and 1000 g Submitted toluene. With vigorous stirring to metered 1248 g of tetraethoxysilane (6 mol). As a result of the reaction, the mixture heats up to 47 ^° C. during the metering.

After completion of the metering is stirred for one hour, after switching off the stirrer rapidly form 2 phases, the lower aqueous phase is separated and discarded, the upper organic phase is washed with 100 ml of water. After the aqueous phase has been separated off, the excess tetramethyldisiloxane is fractionated by single-stage distillation with a column. The distillation is stopped when a head temperature of 110 ⁰ C is reached. Gas chromatographic analysis of the remaining bottoms showed a composition of 71 wt% QM ^H ₄ , 3.3% Q ₂ M ^H ₆ 1% QsM ^H ₈ and 24.7% toluene with an SiH content of 9.15 mmol / g , This fraction was used without further purification described subsequent reaction of Example 2, in which the olefin was attached to the SiH bond.

Example 2

Preparation of a polyorganosiloxane of the formula Si [OSiMO 2 R *] ₄ tetrakis (dimethylphenylpropylsiloxy) silane

In a 6 L flat-section vessel with heating or cooling jacket, which is equipped with stirrer, thermometer, reflux condenser, metering device, under nitrogen blanketing 3835 g of α-methylstyrene CH ₂ = CHCH ₃ -C ₆ H ₅ (32.5 mol) 710 g of product from Example 1 (6.5 mol M ^H ) and heated to 90 ^° C. with stirring. To the mixture are added 0.44 g Pt of a platinum catalyst from a Pt ° complex in tetramethyltetravinylcyclotetrasiloxane (Silopren catalyst Pt / S) having a Pt content of 15% by weight.

Due to the liberated heat of reaction, the mixture heats up to 120 ⁰ C. The remaining amount of 2022 g of reaction mixture from Example 1 (18.5 mol M ^H groups) are added within about one hour. The temperature of the reaction mixture is maintained by controlling the metering or by controlling the heating medium temperature between 140 and 150 ⁰ C. After completion of the metering is stirred at 140 ⁰ C for 3 hours. The subsequent measurement of the SiH content gives 0.03 mmol / g. This corresponds to a conversion based on SiH of 99.2%. The excess methylstyrene is removed by heating at 150 ⁰ C bottom temperature and a vacuum of <5 mbar. After cooling below 100 ⁰ C is removed, the platinum catalyst in which 25 g of activated carbon Prekolit BKT 3 and 5 g of water added, stirred for one hour and the water in vacuo at 60 ⁰ C and a pressure of <30 mbar. After further addition of 30 g of diatomaceous earth Celite 499, the product is filtered through a Seitz pressure filter, which is covered with a Supra 300 filter layer. Yield: 51 14 g of slightly yellow-colored product = 90%, based on the SiH-siloxane used.

Characteristics of the product: Formula:

Viscosity at 25 ⁰ C in Höppler falling ball viscometer: 40 mPa.s at 25 ⁰ C, 41 17 mPa.s at -40 ° C,

Refractive index n ₂₅ ^D = 1, 5020, density: 25 ⁰ C per aerometers 1, 015 g / ml, vaporizable proportions determined by weight with the halogen dryer Mettler HR 73, 1 g of sample weight after 30 min 120 ⁰ C of 1, 6.%.

Example 3 Preparation of the precursor T ^Ph M ^H ₃ 2010 g of tetramethyldisiloxane (30 mol), 1200 g of water, 60 g of 37% hydrochloric acid and 1000 g of toluene are placed in a 6 L flat-section vessel with heating / cooling jacket equipped with stirrer, thermometer, reflux condenser, metering device and nitrogen blanketing. With vigorous stirring 1586 g of phenyltrimethoxysilane (8 mol) are added. As a result of the reaction, the reaction mixture heats up to 47 ^° C. during the metering. After the end of the metering, stirring is continued for one hour; after switching off the stirrer, two phases rapidly form. The lower aqueous phase is separated and discarded. The upper organic phase is washed with 100 ml of water. After the aqueous phase has been separated, the excess tetramethyldisiloxane is fractionally separated by distillation. The distillation is stopped when a head temperature of 1 10 ⁰ C is reached. Gas chromatographic analysis of the remaining bottoms showed a composition of 45% by weight T ^Ph M ^H ₄ , 21% T ^Ph ₂ M ^H ₆ , 7.5% T ^Ph ₃ M ^H ₈ and 26.5% toluene (SiH content 6 , 2 mmol / g) and is used without further purification in the subsequent reaction of Example 4.

Example 4 Preparation of the Methylstyrene Derivative PheSi [OSiMO 2 R *] 3

Into a 6 L flat-section vessel with heating / cooling jacket, equipped with stirrer, thermometer, reflux condenser, metering device and nitrogen blanketing, 3068 g of α-methylstyrene (26 mol), 806.5 g of product from Example 1 (5 mol M ^H ) are initially charged and placed under Stirred to 90 ⁰ C heated. 0.42 g of a platinum catalyst consisting of a Pt ° complex in tetramethyltetravinylcyclotetrasiloxane having a Pt content of 15% by weight are metered into the mixture. Due to the liberated heat of reaction, the reaction mixture heats up to 120 ⁰ C. The remaining amount of 2419 g of reaction mixture from Example 3 (15 mol (M ^H ) is added in the course of about one hour. The temperature of the reaction mixture is maintained between 140 and 150 ^° C. by controlling the metering rate or by regulating the temperature of the heating medium.

After completion of the metering is stirred at 140 ⁰ C for three hours. The measurement of the SiH content gives 0.05 mmol / g. This corresponds to a conversion based on SiH of 98.4%. The excess methylstyrene is removed by Evaporation at 150 ⁰ C bottom temperature and a vacuum of <5 mbar. After cooling below 100 ° C, the platinum catalyst is removed by adding 25 g of activated carbon Prekolit BKT 3 and 5 g of water, stirred for one hour and the water evaporated in vacuo at 60 ⁰ C and a pressure of <30mbar. After further addition of 30 g of diatomaceous earth Celite 499, the product is filtered through a Seitz pressure filter, which is covered with a Supra 300 filter layer. Yield: 4328 g of a slightly yellow-colored product = 91.5%, based on the SiH siloxane used. Characteristics: viscosity at 25 ⁰ C in Höppler falling ball viscometer: 42 mPa.s,

Viscosity at -40 ⁰ C in Höppler falling ball viscometer: 11,300 mPa · s, refractive index n ₂₅ ^D = 1, 5210, vaporisable portion, Halogen dryer Mettler HR 73 1, 6 wt% at 1 g test sample, 30 min 120 ⁰ C, density. : 25 ⁰ C per aerometer spindle 1, 000 g / ml formula:

Example 5

Measurement of weight swellings and cross-linked permeabilities

silicone elastomers

In order to test the suitability of the force or heat transfer fluid according to the invention in contact with silicone elastomers, the degree of swelling and the permeability to a standard elastomer of a peroxidically crosslinked high-viscosity polydimethylsiloxane rubber, Silopren HV 3/601 from Momentive Performance Materials GmbH was investigated. The purpose of this rubber was mixed with 0.6.% Varox.100% dh2,5-dimethyl-hexane-2,5-di-tert-butyl peroxide 10 min 175 ⁰ C and crosslinked under pressure for 4 hours at 200 ⁰ C postcrosslinked or tempered. The following data were determined on a 2 mm test plate with an area of 3.2 × 10 ^-3 m ² :

Measurement of swelling:

With a punching iron you cut from a 2 mm test plate of the networked

Silicone elastomers 3 test specimens (triple determination) with a diameter of 36.6 mm and brings by punching further smaller holes markings to distinguish sample 1-3. From each test specimen, the weight is determined on an analytical balance and its density by buoyancy measurement in water with a balance for density determination. The specimens are covered with a liquid level of 10 - 20 mm. The liquid volume is about 80 times the total specimen volume.

After contact time with the liquid test media and defined temperature, the specimens are removed and allowed to cool for about 10 minutes to room temperature (25 ⁰ C) on a pulp base. Again, weight and density are determined within one hour of removal. The weight swelling was calculated according to the following formula.

Weight _{swelling is} calculated in% to: (wt. _NaHg- weight. _VO r) ^* 100 / wt. _VO r

For the measurements, a compound of composition T ^phe M ₃ (PD5) was additionally provided. It had the following characteristics:

Viscosity eta _kin = 4 cSt or [mm ² / s] (20 ^° C.); Pour point -102 ⁰ C, bp. 110 ⁰ C at 1 mm Hg (Torr), density 0.924 g / ml (20 ⁰ C), n _D ²⁰ = 1, 437,. Tab. 1

) 'AIk = Cs-alkyl radical (such as Silsoft 034 INCI: Caprylyl Methicone) f Sigma Aldrich order no. 33.077-9 n ₂₀ ^D = 1, 4680 D = 0.838 [g / ml].

The experiment shows that the polyorganosiloxanes according to the invention have a slightly increased weight swelling compared to glycol. However, the swelling is below that of mineral oil or a compound such as T ^phe M ₃ .

Determination of permeability:

The permeability was determined as KD value according to formula in DIN 53532 with aluminum test equipment from Rycobel, hereinafter referred to as 'Vapometer ^' . The test area of each individual sample of the crosslinked silicone elastomer had a value of 31, 7 cm ² , a thickness of about 2 mm, the test duration was 42 days.

After defined preconditioning of the samples of silicone elastomer in a climatic chamber at 23 ⁰ C and 50% humidity for 12 h attached to the test specimens with the above dimensions to each one of the vapometers and put them for measurement in a convection oven with the specified temperatures - here 140 ⁰ C and storage times. After the measurement, the vapometer was removed from the convection oven, which was heated to 140 ° C. The test specimens of silicone elastomer were allowed to cool for 1 h in a climate chamber at 23 ⁰ C and 50% humidity and determined the weight change of the specimens. The calculation was carried out according to the formula given in DIN 53532, with no additional corrections being made.

KD = k.10 ⁴ / A in [g (m ² / d] with simplified k = (mo-m _t ) / (t-to), ie k corresponds to the slope value of one

Straight lines in the chart Measured over time.

A = area in [cm ² ], rrio = initial mass in [g] at initial time to, m = mass after contact after test period t in [days] or [d]

Table 2

) ¹ Silsoft® 034 from Momentive

) ³ the vapometer contained no liquid after 14 days, ie the diffusion was too high to determine a mass flow.

) ⁴ the vapometer contained no liquid after 2 days, ie the diffusion was too high to determine a mass flow.

The experiments show that the permeability measured as KD value at 140 ^° C. with the polyorganosiloxanes used according to the invention is smaller than in contact with glycol or a siloxane of the formula T ^phe M ₃ , which has a structure similar to Example 4, in which M but a group Mβ ₃ SiOi / 2 means. This is surprising because the skilled ^person would have expected a higher transmission ^value KD for the compounds ^according to the invention because of the higher swelling compared to glycol, as can be measured, for example, typically with the compound T ^phe M ₃ . Example 6

The use of the compounds according to the invention and their suitability in cosmetic formulations is illustrated by the following compositions:

Waterproof mascara composition with an MQ type polymethyl siloxane resin such as SR 1000

Example 7

Cosmetics Formulation: Mascara containing a so-called 'fluorosilicates ^' (INCI) with extended duration of adhesion

Example 8

Cosmetic formulation: ^' Cream-to-Powder ^' - make-up

Example θ

Cosmetic formulation: waxy lip gloss formulation

Example 10

Cosmetic formulation: Liquid colored lipstick

Example 11

Cosmetic formulation: liquid lipstick

Example 12

Lipstick composition with pigments

Examples 6 to 12 show that compounds such as those of Examples 2 and 4 cosmetic ingredients such as the mentioned under the INCI name Phenylpropyldimethylsiloxysilicate Silshine® 151 with regard to miscibility with cosmetic ingredients, without accepting obvious disadvantages with cosmetic properties. The high refractive index of the compound of Example 4 leads to particularly advantageous gloss effects.

Claims

claims:

1. Use of polyorganosiloxanes of the formula (I):

M _a D _b T _c Q _d (I) wherein a = 2 to 6, b = 0 to 10, c = 0 to 3, d = 0 to 2, c + d ^■ = 1 to 2, a / (c + d)> 2 where M, D ₁ T, Q

R

R - Si-O-M

I 1/2

R

-Si-O- D

R

mean, and

R is selected from the group consisting of: Aliphatic and / or aromatic radicals having up to 30 carbon atoms, which may have one or more oxygen atoms, one or more halogen atoms and one or more cyano groups, with the proviso that at least one of the radicals R in M on a

Carbon atom is bonded to silicon and at least one of the radicals R in M has at least two carbon atoms, as a force and / or heat transfer fluid.

2. Use according to claim 1, wherein at least one of R in M represents a group of formula R * selected from the group consisting of:

aryl,

-CH ₂ -CHR ¹ -R ² , wherein R ^{1 is} hydrogen or C ₁ to C ₃ alkyl, and

R ^{2 has} the same meaning as R,

-CR ³ = CH-R ² , in which

R ^{2 has} the same meaning as R, and

R ^{3 has} the same meaning as R or is hydrogen.

3. Use according to claim 1 or 2, wherein the polyorganosiloxanes have the formula (Ia) or (Ib):

M _2-6 Qi _-2 (Ia)

wherein M, D, T and Q are as defined above.

4. Use according to any one of the preceding claims, wherein the ratio of the siloxane units M: Q = 4 to 1: 1 or M: T = 3 to 1: 1.

5. Use according to claim 3 or 4, wherein the Polyorganosiioxane of the formulas (Ia) and (Ib) have the following structure:

M ₄ Q (Ia), M ₃ T (Ib).

6. Use according to any one of claims 2 to 5, wherein all radicals f have at least one group of the formula R *.

7. Use according to one of the preceding claims, wherein all radicals M have exactly one group of the formula R *.

Use according to any one of the preceding claims, wherein all R's in M are bonded to silicon via carbon atoms.

Use according to any one of the preceding claims, wherein the

Polyorganosilioxanes are selected from the group consisting of:

10. Use according to any of the preceding claims, wherein the polyorganosiloxanes have a viscosity of less than 100 mPa.s at 25 ⁰ C.

11. Use according to any one of the preceding claims, wherein the polyorganosiloxanes have a molecular weight (determined by gel permeation chromatography against polystyrene as standard) having a number average M _n of 360 to 2000 g / mol.

12. Use of the polyorganosiloxanes according to any one of claims 1 to 1 1 as a power transmission fluid in Hydrolagem.

13. Use of the polyorganosiloxanes of the formula (I) as defined in any one of claims 1 to 1 1, as an ingredient of cosmetic compositions.

14. Hydro bearing, containing polyorganosiloxanes, as defined in any one of claims 1 to 1 1 defined.

A cosmetic composition containing polyorganosiloxanes of the formula (I) as defined in any one of claims 1 to 11.

16. polyorganosiloxanes of the formula (I):

M _a D _b T _c Q _d (I ¹ )

wherein: a = 2 to 6, b = 0 to 2, c = 0 to 2, d = 0 to 2, c + d = 1 to 2, a / (c + d)> 2 where

M ₁ D ₁ T ₁ Q

R

R - Si-O-M

I 1/2

R

-Si-O- D

R

Q 1/2 w O-Si-O-Q

O 1/2, and R is selected from the group consisting of:

Aliphatic and / or aromatic residues of up to 30

Carbon atoms, which may have one or more oxygen atoms, one or more halogen atoms and one or more cyano groups, with the proviso that at least one of the radicals R in M on a

Carbon atom is bonded to silicon and at least one of

Radicals arylalkyl or arylalkenyl.

17. A process for preparing the polyorganosiloxanes of 16, comprising:

i) Reacting a compound of the formula:

M ^H _a D _b T _c Q _d (II)

wherein, a, b, c, d are as defined above, wherein M is ^H , D, T, Q

R

H - Si-O- M ^H

I 1/2

R

- Si - O - D

R

Q 1/2

- 1/2 O-Si-O-1/2

O 1/2

and R is as defined above, with a compound CH ₂ = CHR ¹ -R ² , wherein R ¹ and R ^{2 are} as defined above, or a compound

CR ³ ≡CR ² , wherein R ² and R ^{3 are} as defined above, in the presence of a hydrosilylation catalyst, or ii) reacting a compound of the formula:

M ^H _a D _b T _c Q _d (II)

which is as defined above, with a compound of the formula HO-R, wherein R is as defined above, in the presence of a catalyst, in which reaction with hydrogen evolution an R-O-Si group is formed in M,

or

iii) hydrolysis or alcoholysis of a plurality of halogen and / or alkoxysilanes, the precursors of the units M, D, T, Q, as claimed in claim 1, and having at least one group R, wherein R is as defined above.