Patent Publication Number: US-2012046485-A1

Title: Novel Polyorganosiloxanes And Use Thereof

Description:
The invention relates to novel polyorganosiloxanes, methods for their preparation and their use, in particular as force and/or heat transmitting liquids, such as hydraulic liquids. 
     Apart from various aliphatic, aromatic or unsaturated hydrocarbons, such as alpha olefins, phosphoric acid esters, phenylethers, polyesters or polyethers, polyorganosiloxanes have long been known as synthetic hydraulic liquids (e.g. U.S. Pat. No. 2,398,187; U.S. Pat. No. 4,048,084; U.S. Pat. No. 4,116,847; U.S. Pat. No. 4,132,664; U.S. Pat. No. 4,175,049; U.S. Pat. No. 4,357,473; GB 1093555; GB 867167; U.S. Pat. No. 4,340,495 etc). Furthermore, U.S. Pat. No. 5,684,112 discloses branched polyorganosiloxanes as conditioners for use in cosmetic compositions. A compound of the formula (Me 3 SiO) 3 Si-phenyl is sold by Momentive Performance Materials under the brand name Baysilon PD5 as a damping liquid, among other things. In case of contact with silicone seals or membranes, however, the above compound, like many other polyorganosiloxanes with a low molar weight, leads to an increased swelling of the silicone seals or membranes or to a diffusion of the liquid through the silicone seal and thus to the liquid leaking out. Thus, the object of the present invention was to find a medium which is suitable as a force-transmitting liquid and does not exhibit the aforementioned drawbacks. The medium was to be capable, in particular, of being used for force transmission, as well as a medium for damping, i.e. delayed force distribution or force transmission. This requirement is evident particularly in a hydro-mount which is comprised of elastic rubber membranes as a spring system or of air cushions enclosed by membranes which separate another space with a viscous, damping force-transmitting liquid. Moreover, this liquid was supposed to have a suitable viscosity range at various temperatures, in particular at low temperatures, as well as be resistant to high temperatures and modify the enclosing membrane only to a small extent. Furthermore, the liquid medium was supposed to have a low compressibility and, during interaction with metals and sealing materials, such as, in particular, elastomers, such as silicone elastomers, should not change their properties if possible. 
     Though the glycols that are also used as damping liquids in the production of so-called hydro-mounts can be used in hydro-mounts with elastomeric spring elements based on natural rubber or EPDM, they prove to be largely unfit for use in the case of spring elements from silicone elastomers because, though they lead to an acceptable swelling, they cause an undesirably high degree of diffusion or permeability or permeation through these membranes, and furthermore do not have a sufficiently low viscosity in the low-temperature range. Other compounds, such as low-molecular synthetic media, have a boiling point that is too low, or they resinify in the presence of atmospheric oxygen or humidity in such a way that the viscosity at least increases or that the liquid actually solidifies. 
     Therefore, the invention had the object of finding a suitable liquid that avoids these problems that occur in the case of contact of glycols, hydrocarbons or linear polydimethylsiloxanes with polyorganosiloxane elastomer membranes or seals. 
     In the class of silylated siliconates and silicates, the inventors surprisingly found compounds with a low degree of polymerization that were capable of achieving these objects. 
     Hence, the present invention provides: 
     The use of polyorganosiloxanes of the formula (I): 
       M a D b T c Q d   (I)
         wherein:   a=2 to 6, preferably 3 or 4, particularly preferably 4,   b=0 to 10, preferably 0 to 2, still 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)&gt;2, preferably ≧3,   wherein   M, D, T, Q signify       

     
       
         
         
             
             
         
       
     
     and
 
R is selected from the group consisting of:
 
aliphatic and/or aromatic residues with up to 30 carbon atoms which can comprise one or more oxygen atoms, one or more halogen atoms as well as one or more cyano groups, provided that
         at least one of the residues R in M is bonded to silicon via a carbon atom and at least one of the residues R in M comprises at least 2, preferably at least 4, still more preferably at least 5 carbon atoms,
 
wherein they
   are used as force and/or heat transmitting liquid or as a constituent in cosmetic compositions.       

     A force-transmitting liquid is suitable for transmitting and/or distributing mechanical forces over a certain distance between the location of generation and the location of action. In particular, hydraulic, damping and gear liquids or oils count among force-transmitting liquids. Requirements that are met by the force-transmitting liquids according to the invention generally include:
         good lubrication properties   high resistance to ageing   high flash point,   low setting point or pour point,   compatibility with silicone elastomers,   in particular low permeability or permeation,   freedom from resins or acids,   low influence of temperature on viscosity (both dynamic as well as kinematic viscosity)   low compressibility.       

     Thus, the polyorganosiloxanes of the formula (I) preferably have a pour point (DIN ISO 3016, ASTM D5985) of less than −28° C. or a setting point (DIN ISO 3016, ASTM E 537-76 D of less than −30° C. 
     The polyorganosiloxanes of the formula (I) preferably have a boiling point of greater than 180° C., preferably of greater than 190° C. 
     The polyorganosiloxanes of the formula (I) preferably have a permeation on polydimethylsiloxane elastomers, determined as so-called fuel permeability FP in accordance with DIN 53532, of less than 70 [g/m 2 /d] at 140° C., preferably less than 40 [g/m 2 /d], particularly preferably an FP value of less than 20 [g/m 2 /d] for a sample having a thickness of 2 mm. 
     In formula (I), groups R both include groups R which are bonded via carbon atoms to silicon atoms as well as groups R which are bonded via oxygen atoms to silicon atoms, i.e., they are in this case alkoxy groups (hereinafter sometimes referred to as R′). 
     Polyorganosiloxanes according to the invention with groups M that comprise alkoxy groups R′ are, however, less preferred, or, in other words: Si—C-bonded groups R (hereinafter sometimes referred to as R″) in M are preferred according to the invention. 
     The requirement according to which at least one of the residues R in M is bonded to silicon via a carbon atom and at least one of the residues R in M comprises at least two carbon atoms also includes the case that there is a residue R present in M which is Si—C-bonded and at the same time comprises at least two carbon atoms, preferably at least four carbon atoms, still more preferably at least five carbon atoms. This case, in which M comprises an Si—C-bonded residue R with at least two carbon atoms, preferably at least four carbon atoms, still more preferably at least five carbon atoms, is the case preferred in the invention. 
     In a preferred embodiment, at least one of the residues R in M in the polyorganosiloxanes according to the invention represents a group which comprises 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, at least one of the residues R in M in the polyorganosiloxanes according to the invention represents a group of the formula R* which is 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 ,   wherein   R 2  has the same meaning as R, and   R 3  has the same meaning as R or is hydrogen.       

     Preferred groups M include:
         —SiR″ 3 ;       

     wherein preferably at least one, more preferably exactly one group R″ is a group R*, as mentioned above; particularly preferably, M is a group
         SiMe 2 R*;
 
or
   —SiR″ 2 R′;   wherein at least one of the residues R″ or R′ comprises at least two carbon atoms, preferably at least four carbon atoms, still more preferably at least five carbon atoms; particularly preferably, M is   SiMe 2 R′.       

     The polyorganosiloxanes according to the invention can comprise the same or different groups M. That means that, apart from the obligatory groups M as defined above, there may also be groups M present that neither comprise residues R with at least two carbon atoms, nor SiC-bonded residues, such as —SiMe 3  and —Si(OMe) 3 . 
     Preferably, however, all groups M in the polyorganosiloxanes according to the invention comprise residues R with at least two carbon atoms, in particular SiC-bonded residues R with at least two carbon atoms. 
     In another preferred embodiment, the present invention relates to the use of polyorganosiloxanes of the formula (I), wherein the polyorganosiloxanes have the formula (Ia) or (Ib): 
       M 2-6 Q 1-2   (Ia),
 
       M 2-6 D 0-3 T 1-2   (Ib),
 
     wherein M, D, T and Q are as defined above. 
     Preferably, the polyorganosiloxanes of the formulae (Ia) or (Ib) have the following structures: 
       M 4 Q, 
       M 3 T. 
     In another preferred embodiment, the present invention relates to the use of polyorganosiloxanes of the formula (I), wherein all residues M comprise at least one, preferably exactly one group of the formula R*. 
     In another preferred embodiment, the present invention relates to the use of polyorganosiloxanes of the formula (I), wherein all residues R in M are bonded via carbon atoms to silicon. 
     Most preferably, the polyorganosiloxanes according to the invention comprise identical groups M comprising SiC-bonded residues R with at least two carbon atoms, in particular R*. 
     Examples include: 
       QM 4 , 
       such as, for example: 
       SiO—SiR″ 3-z —R* z ] 4   z= 1-2
 
       SiO—SiR″ 3-z —R′ z ] 4   z= 1-2
 
     preferred are the formulae 
     
       
         
         
             
             
         
       
     
     or compounds of the type TM 3 ,
 
such as, for example:
 
       R 5 Si—O—SiR″ 3-z —R* z ] 3   z= 1-2
 
       R 5 Si—O—SiR″ 3-z —R′ z ] 3   z= 1-2
 
     preferred are the formulae: 
     
       
         
         
             
             
         
       
     
     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), wherein the ratio of the siloxane units is M:Q=4 to 1:1, preferably 4 to 3:1, or M:T=3 to 1:1, preferably 3 to 2:1. 
     In another preferred embodiment, the present invention relates to the use of polyorganosiloxanes of the following formulae: 
     
       
         
         
             
             
         
       
     
     In another preferred embodiment, the present invention relates to the use of polyorganosiloxanes of the formula (I), which have a viscosity of less than 100 mPa·s at 25° C. and a shear rate gradient of D=1 s −1 . I.e., the polyorganosiloxanes of the formula (I) are generally liquid at room temperature. Preferably, the polyorganosiloxanes according to the invention are still liquid even at −40° C., and at −40° C. in particular have a viscosity of less than 20,000 mPa·s, preferably measured at a shear rate D of 1 s −1 . 
     Preferably, the polyorganosiloxanes used according to the invention have a molecular weight (determined by gel permeation chromatography against polystyrene as standard) with a number average M n  of 360 to 2,000 g/mol. 
     The use according to the invention in particular includes the use as a force-transmitting liquid in hydro-mounts. Hydro-mounts are damping elements comprising a spring body and a damping unit. The damping unit comprises the cavities and flow channels filled with the force-transmitting liquid (see e.g. EP 0 547 287). Accordingly, the present invention also relates to hydro-mounts comprising polyorganosiloxanes of the formula (I). 
     Moreover, the polyorganosiloxanes of the formula (I) surprisingly can also be used as a constituent of cosmetic compositions, because siloxane compounds with a solubility behavior suitable for cosmetic ingredients can be provided therewith. Furthermore, they have a desired low spreading or migration behavior, low stickiness with regard to, for example, sand and dust, and a high refractive index n 25   D  of more than 1.50, in particular higher than 1.51. A refractive index of more than 1.51 was found in particular in compounds of the formula (Ia) and (Ib) and R═ arylalkyl. Special glossy effects can be accomplished therewith. In addition, the low migration behavior is desired in particular in coloring cosmetic formulations in order to prevent these components from entering the eye or mouth. There, they act in particular as film-forming agents, glossing additives, enhancers for making the constituents compatible, carrier material for sun blocking products, in particular in water-resistant sun-blocking products that have a low sand adhesion (‘anti-sanding’), as glossing constitutents, in particular of decorative skin-care products, such as lipsticks, make-up by means of the properties of the polyorganosiloxanes of the formula (I), which in contrast to fats, oils, such as in particular polydimethylsiloxanes, spread to a lesser extent. Thus, cosmetic compositions such as mascaras and ‘lip gloss’, other coloring skin-care products as well as hair care products such as shampoos, conditioners and in particular hair tonics, oils and fluids for enhancing the gloss of skin, nail and hair surfaces can advantageously be produced with the compounds according to the invention. Due to the high refractive index of more than 1.5, the substances according to the invention are also eminently suitable to contribute to reducing the whitening of pigmented or solid-containing or wax-containing cosmetic products (antitranspirants) on the skin (‘anti-whitening’). 
     Accordingly, the present invention also relates to cosmetic compositions comprising polyorganosiloxanes of the formula (I). 
     The polyorganosiloxanes according to the invention also include novel compounds of the formula (I′): 
       M a D b T c Q d   (I′)
         wherein:   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)&gt;2   wherein   M, D, T, Q signify       

     
       
         
         
             
             
         
       
     
     and wherein
         R is selected from the group consisting of:   aliphatic and/or aromatic residues with up to 30 carbon atoms which can comprise one or more oxygen atoms, one or more halogen atoms as well as one or more cyano groups,   provided that at least one of the residues R in M is bonded to silicon via a carbon atom and at least one of the residues is arylalkyl or arylalkenyl. With regard to the preferred polyorganosiloxanes of the formula (I′), reference can be made to the comments regarding the polyorganosiloxanes of the formula (I).       

     Finally, the present invention also relates to a method for preparing polyorganosiloxanes of the formula (I′) 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 H , D, T, Q signify           

     
       
         
         
             
             
         
       
         
         
           
             
               
                 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 with 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, during which reaction a R—O—Si group is formed in M with hydrogen evolution,   or       iii. hydrolysis or alcoholysis of several halogen and/or alkoxysilanes which correspond to precursors of the units M, D, T, Q as in claim  1 , and which comprise at least one group R, wherein R is as defined above.       

     The invention is illustrated in more detail by the following examples. 
    
    
     EXAMPLES 
     Example 1 
     Preparation of Si[OSiMe 2 H] 4  and its Oligomers 
     2,010 g tetramethyldisiloxane (30 mol), 1,200 g water, 60 g 37% hydrochloric acid and 1,000 g toluene are received under nitrogen blanketing in a 61 flat flange vessel with a heating or cooling jacket equipped with a stirrer, thermometer, reflux condenser and dosing device. 1,248 g tetraethoxysilane (6 mol) is metered in under vigorous stirring. Due to the reaction, the mixture heats up to 47° C. during metering. 
     After the metering process is completed, this is followed by stirring for one hour; after the stirrer has been switched off, 2 phases form rapidly; the lower aqueous phase is separated and discarded, the top organic phase is washed with 100 ml water. After the aqueous phase has been removed, the excess tetramethyldisiloxane is separated in a fractioned manner by single-stage distillation with a column. The distillation process is stopped as soon as an overhead temperature of 110° C. has been reached. 
     Analysis of the remaining bottom by gas chromatography yielded a composition of 71% by wt. QM H   4 , 3.3% Q 2 M H   6  1% Q 3 M H   8  and 24.7% Toluene with an SiH content of 9.15 mmol/g. This fraction was added without further purification to the 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[OSiMe 2 R*] 4  tetrakis(dimethylphenylpropylsiloxy)silane 
     3,835 g α-methylstyrene CH 2 ═CHCH 3 —C 6 H 5  (32.5 mol), 710 g product from Example 1 (6.5 mol M H ) are received under nitrogen blanketing in a 6 l flat flange vessel with a heating or cooling jacket equipped with a stirrer, thermometer, reflux condenser and dosing device, and heated to 90° C. with stirring. 0.44 g Pt of a platinum catalyst consisting of a Pt 0  complex in tetramethyltetravinylcyclotetrasiloxane (Silopren catalyst Pt/S) with a Pt content of 15% by wt. is added to the mixture. 
     The mixture heats up to 120° C. due to the released reaction heat. The rest of the amount of 2,022 g reaction mixture from Example 1 (18.5 mol M H -groups) is metered in within approximately one hour. The temperature of the reaction mixture is kept between 140 and 150° C. by controlling the metering rate or by controlling the temperature of the heating means. 
     After the metering process was completed, this was followed by stirring for 3 hours at 140° C. The subsequent measurement of the SiH content yields 0.03 mmol/g. This corresponds to a conversion relative to SiH of 99.2%. The excess methylstyrene is removed by baking out at 150° C. bottom temperature and a vacuum of &lt;5 mbar. After cooling off to below 100° C., the platinum catalyst is removed by adding 25 g activated carbon Prekolit BKT 3 and 5 g water, followed by stirring for one hour, and removing the water under vacuum at 60° C. and a pressure of &lt;30 mbar. After the further addition of 30 g diatomaceous earth Celite 499, the product is filtered through a Seitz pressure nutsche covered with a filter layer of Supra 300. 
     Yield: 5,114 g of a slightly yellow-colored product=90% relative to the SiH siloxane used. 
     Characteristic Data of the Product: 
     Formula: 
     
       
         
         
             
             
         
       
     
     Viscosity at 25° C. in a Happier falling-ball viscometer: 40 mPa·s at 25° C., 4,117 mPa·s at −40° C., 
     Refractive index n 25   D =1.5020, density: 25° C. by aerometer 1.015 g/ml. 
     Evaporable contents determined with the Mettler HR 73 halogen dryer, 1 g weighed portion after 30 min 120° C. of 1.6% by wt. 
     Example 3 
     Preparation of the Precursor T Ph M H   3    
     2,010 g tetramethyldisiloxane (30 mol), 1,200 g water, 60 g 37% hydrochloric acid and 1,000 g toluene are received in a 61 flat flange vessel with a heating/cooling jacket equipped with a stirrer, thermometer, reflux condenser, dosing device and nitrogen blanketing. 1,586 g phenyltrimethoxysilane (8 mol) are metered in with vigorous stirring. Due to the reaction, the reaction mixture heats up to 47° C. during metering. 
     After the metering process is completed, this is followed by stirring for one hour; after the stirrer has been switched off, 2 phases form rapidly. The lower aqueous phase is separated and discarded. The top organic phase is washed with 100 ml water. After the aqueous phase has been removed, the excess tetramethyldisiloxane is separated in a fractioned manner by distillation. The distillation process is stopped as soon as an overhead temperature of 110° C. has been reached. 
     Analysis of the remaining bottom by gas chromatography yielded a composition of 45% by wt. 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 added without further purification to the subsequent reaction of Example 4. 
     Example 4 
     Preparation of the methylstyrene Derivative PheSi[OSiMe 2 R*] 3    
     3,068 g α-methylstyrene (26 mol), 806.5 g product from Example 1 (5 mol M H ) are received in a 6 l flat flange vessel with a heating/cooling jacket equipped with a stirrer, thermometer, reflux condenser, dosing device and nitrogen blanketing, and heated to 90° C. with stirring. 0.42 g of a platinum catalyst consisting of a Pt 0  complex in tetramethyltetravinylcyclotetrasiloxane with a Pt content of 15% by wt. is metered into the mixture. The reaction mixture heats up to 120° C. due to the released reaction heat. The rest of the amount of 2,419 g reaction mixture from Example 3 (15 mol M H ) is metered in within approximately one hour. The temperature of the reaction mixture is kept between 140 and 150° C. by controlling the metering rate or by controlling the temperature of the heating means. 
     After the metering process was completed, this was followed by stirring for three hours at 140° C. The measurement of the SiH content yields 0.05 mmol/g. This corresponds to a conversion relative to SiH of 98.4%. The excess methylstyrene is removed by evaporation at 150° C. bottom temperature and a vacuum of &lt;5 mbar. After cooling off to below 100° C., the platinum catalyst is removed by adding 25 g activated carbon Prekolit BKT 3 and 5 g water, followed by stirring for one hour, and evaporating the water under vacuum at 60° C. and a pressure of &lt;30 mbar. After the further addition of 30 g diatomaceous earth Celite 499, the product is filtered through a Seitz pressure nutsche covered with a filter layer of Supra 300. 
     Yield: 4,328 g of a slightly yellow-colored product=91.5% relative to the SiH siloxane used. 
     Characteristic Data: 
     Viscosity at 25° C. in a Höppler falling-ball viscometer: 42 mPa·s, 
     Viscosity at −40° C. in a Höppler falling-ball viscometer: 11,300 mPa·s, 
     Refractive index n 25   D =1.5210, evaporable contents, Mettler HR 73 halogen dryer 1.6% by wt. at 1 g weighed portion after 30 min 120° C., density: 25° C. by aerometer spindle 1.000 g/ml 
     Formula: 
     
       
         
         
             
             
         
       
     
     Example 5 
     Measurement of Weight Swelling and Permeabilities on Cross-Linked Silicone Elastomers 
     In order to test the suitability of the force or heat transmitting liquid according to the invention in contact with silicone elastomers, the degree of swelling and the permeability was investigated in comparison to a standard elastomer of a peroxidically cross-linked highly viscous polydimethylsiloxane rubber, Silopren HV 3/601 by Momentive Performance Materials GmbH 
     For this purpose, this rubber was cross-linked under pressure for 10 min at 175° C. with 0.6% by wt. Varox. 100%, i.e. 2,5-dimethylhexane-2,5-di-tert.-butylperoxide and was post-crosslinked or tempered for 4 h at 200° C. The following data were determined on a 2 mm testing plate with a surface area of 3.2 10 −3  m 2 : 
     Measurement of Swelling: 
     Three testing bodies (triple testing) with a diameter of 36.6 mm are respectively cut out with a punching iron from a 2 mm testing plate of the cross-linked silicone elastomer, and markings for differentiating the samples 1-3 are applied by punching additional small holes. 
     The weight of each test object is determined on an analytical scale and its density is determined by measuring buoyancy in water with a scale for determining the density. The testing bodies are covered with a liquid level of 10-20 mm. The liquid volume is about 80 times that of the entire testing body volume. 
     After the contact time with the liquid testing media and defined temperature, the testing bodies are removed and left to cool off to room temperature (25° C.) for about 10 minutes on a cellulose pad. The weight and density are determined again before an hour after removal has passed. 
     In the process, the weight swelling was calculated according to the following formula. 
       Weight swelling is calculated in % by: (wt. before −wt. after )*100/wt. before  
 
     A compound of the composition T phe M 3  (PD5) was additionally provided for the measurements. It had the following characteristics: 
     Viscosity eta kin =4 cSt or [mm 2 /s] (20° C.); settling point −102° C., boiling point 110° C. at 1 mm Hg (Torr), density 0.924 g/ml (20° C.), n D   20 =1.437. 
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 1 
               
               
                   
                   
               
               
                   
                 Contact medium 
                 Swelling [% by wt.] 
                 Time [h] 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 diethyleneglycol 
                 2 
                 96 
               
               
                   
                 T phe M 3   
                 101 
                 96 
               
               
                   
                 MD alc  M ) 1   
                 12 
                 46 
               
               
                   
                 Mineral oil ) 2   
                 91 
                 46 
               
               
                   
                 Example 4 
                 9 
                 72 
               
               
                   
                 Example 2 
                 11 
                 96 
               
               
                   
                   
               
               
                   
                 ) 1  Alc = C 8 -alkyl residue (such as Silsoft 034 INCI: caprylyl methicone) 
               
               
                   
                 ) 2  Sigma Aldrich order number 33.077-9 n 20   D  = 1.4680 D = 0.838 [g/ml]. The experiment shows that the polyorganosiloxanes used according to the invention exhibit a slightly increased weight swelling compared with glycol. However, swelling is less than that of mineral oil or a compound such as T phe M 3 . 
               
            
           
         
       
     
     Determination of Permeability: 
     Permeability was determined as a FP value according to the formula in DIN 53532 with aluminum testers by Rycobel, hereinafter referred to as “vapometer”. The testing surface of the respective individual samples of the cross-linked silicone elastomer was 31.7 cm 2 , thickness was about 2 mm, the duration of the experiment was 42 days. 
     Following a defined preconditioning of the testing bodies from silicone elastomer in a climate chamber at 23° C. and 50% air humidity over 12 h, the testing body plates with the above-mentioned dimensions were attached to one vapometer, respectively, and the latter were placed for the measurement in a circulating drying cabinet at the specified temperatures—in this case 140° C.—and storage times. After the measurement, the vapometer was removed from the circulating cabinet heated to 140° C. The testing bodies of silicone elastomer were left to cool off for 1 h in a climate chamber at 23° C. and 50% air humidity, and the weight change of the testing bodies was determined. 
     The calculation was carried out in accordance with the formula specified in DIN 53532, with no additional corrections being made. 
     FP=k.10 4 /A in [g(m 2 /d] 
     with simplified k=(m 0 −m t )/(t−t 0 ), i.e. k corresponds to the gradient of a straight line in the mass-time diagram. 
     A=surface area in [cm 2 ], m 0 =initial mass in [g] at starting time t 0 , 
     m=mass after contact after testing time t in [days] or [d] 
     
       
         
           
               
               
             
               
                   
                 TABLE 2 
               
               
                   
                   
               
               
                   
                 Permeability FP at 140° C. 
               
               
                   
                 [g/m 2 /d] 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                   
                 glycol 
                 152 ) 3   
               
               
                   
                 Example 4 
                 14.8 
               
               
                   
                 Example 2 
                 13.4 
               
               
                   
                 MD alk  M ) 1   
                 &gt;1500 ) 4    
               
               
                   
                   
               
               
                   
                 ) 1  Silsoft ® 034 by Momentive 
               
               
                   
                 ) 3  the vapometer did not contain any more liquid after 14 days, i.e. diffusion was too high for determining a quantity flow. 
               
               
                   
                 ) 4  the vapometer did not contain any more liquid after 2 days, i.e. diffusion was too high for determining a quantity flow. 
               
            
           
         
       
     
     The experiments show that permeability, measured as FP value at 140° C., is smaller with the polyorganosiloxanes used according to the invention than in contact with glycol or a siloxane of the formula T phe M 3 , which has a similar structure as Example 4, in which, however, M signifies Me 3 SiO 1/2 —. This is surprising because the person skilled in the art, due to the higher swelling as compared to glycol, would have expected a higher permeability value FP also for the compounds according to the invention, such as it can typically measured, for example, in the case of 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 with the following compositions: 
     Water-Resistant Mascara Composition with a polymethyl siloxane Resin of the MQ type, such as SR 1000 
     
       
         
           
               
               
               
               
             
               
                   
               
               
                   
                   
                 Brand name 
                   
               
               
                   
                   
                 by Momentive 
               
               
                 wt-% 
                 INCI 
                 or Example 
                 Function 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                 5.0 
                 Cyclopentasiloxane (and) 
                 SF 1540 
                 emulsifier 
               
               
                   
                 PEG/PPG-20/15 dimethicone 
               
               
                 7.5 
                 Dimethicone (and) 
                 TP 3784 
                 film-forming 
               
               
                   
                 isododecane 
                   
                 agent 
               
               
                 1.6 
                 Cetyl Alcohol 
               
               
                 1.6 
                   
                 Example 2 
                 film-forming 
               
               
                   
                   
                   
                 agent 
               
               
                 1.6 
                 Trimethylsiloxysilicate 
                 SR 1000 
                 adhesion 
               
               
                   
                   
                   
                 extender 
               
               
                 4.6 
                 Carnauba wax 
                   
                 wax 
               
               
                 4.65 
                 Bees wax 
                   
                 wax 
               
               
                 3.0 
                 Stearic acid 
               
               
                 2.0 
                 Polymethylsilsesquioxane 
                 Tospearl ® 
                 skin-feeling 
               
               
                   
                   
                 2000 B* 
                 enhancer 
               
               
                 1.2 
                 Triethanolamine 
                   
                 pH regulator 
               
               
                 57.0 
                 Aqua 
                   
                 liquid carrier 
               
               
                 0.75 
                 Hydroxyethylcellulose 
                   
                 thickening 
               
               
                   
                   
                   
                 agent 
               
               
                 9.5 
                 Pigments 
                   
                 pigments 
               
               
                   
               
            
           
         
       
     
     Example 7 
     Cosmetic Formulation: Mascara Containing a So-Called “fluorosilicate” (INCI) with Extended Adhesion Time 
     
       
         
           
               
               
               
               
             
               
                   
               
               
                   
                   
                 Brand name 
                   
               
               
                 % by 
                   
                 by Momentive 
               
               
                 wt. 
                 INCI 
                 or Example 
                 Function 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
            
               
                 component A 
               
            
           
           
               
               
               
               
            
               
                 1.5 
                 Cetyl alcohol 
                   
                 wax 
               
               
                 2.0 
                 Stearic acid 
                   
                 wax 
               
               
                 4.0 
                 Carnauba wax 
                   
                 wax 
               
               
                 5.5 
                 C 30 -C 45 -alkyl dimethicone 
                 SF 1642 
                 wax 
               
               
                 2.0 
                 Trifluoropropyldimethylsiloxy- 
                 XS66 B8226 
                 adhesion 
               
               
                   
                 trimethylsiloxysilicate 
                   
                 extender 
               
               
                 6.0 
                 Cyclopentasiloxane 
                 SF 1202 
                 solvent 
               
               
                 2.0 
                   
                 Example 4 
                 film-forming 
               
               
                   
                   
                   
                 agent 
               
            
           
           
               
            
               
                 component B 
               
            
           
           
               
               
               
               
            
               
                 63.55 
                 Aqua 
                   
                 solvent 
               
               
                 0.25 
                 Hydroxyethylcellulose 
                   
                 thickening 
               
               
                   
                   
                   
                 agent 
               
               
                 2.0 
                 Polyvinylpyrrolidone 
                   
                 film-forming 
               
               
                   
                   
                   
                 agent 
               
               
                 1.2 
                 Triethanolamine 
                   
                 pH regulator 
               
            
           
           
               
            
               
                 component C 
               
            
           
           
               
               
               
               
            
               
                 10.0 
                 Pigments 
                   
                 pigments 
               
               
                   
               
            
           
         
       
     
     Example 8 
     Cosmetic Formulation: “Cream-To-Powder” Make-Up 
     
       
         
           
               
               
               
               
             
               
                   
               
               
                   
                   
                 Brand name 
                   
               
               
                 % by 
                   
                 by Momentive 
               
               
                 wt. 
                 INCI 
                 or Example 
                 Function 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                 44.5 
                 Cyclopentasiloxane (and) 
                 Velvesil ® 125 
                 Skin-feeling- 
               
               
                   
                 C 30 -C 45 -alkyl cetearyl 
                   
                 enhancer/matting 
               
               
                   
                 dimethicone crosspolymer 
                   
                 agent 
               
               
                 30.5 
                 Cyclopentasiloxane 
                 SF 1202 
                 solvent 
               
               
                 3.0 
                   
                 Example 2 
                 compatibility 
               
               
                   
                   
                   
                 enhancer 
               
               
                 6.5 
                 Cyclopentasiloxane (and) 
                 SF 1214 
                 liquid carrier - 
               
               
                   
                 dimethicone 
                   
                 solvent 
               
               
                 12.0 
                 Polymethyl- 
                 Tospearl ® 
                 soft-feel additive 
               
               
                   
                 silsesquioxane 
                 2000 B 
               
               
                 3.5 
                   
                 pigments 
                 pigment 
               
               
                   
               
            
           
         
       
     
     Example 9 
     Cosmetic Formulation: Wax-Like Lip-Gloss Formulation 
     
       
         
           
               
               
               
               
             
               
                   
               
               
                   
                   
                 Brand name 
                   
               
               
                 % by 
                   
                 by Momentive 
               
               
                 wt. 
                 INCI 
                 or Example 
                 Function 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
            
               
                 component A 
               
            
           
           
               
               
               
               
            
               
                 75.0 
                 Caprylic/capric 
                   
                   
               
               
                   
                 triglyceride 
               
               
                 20.0 
                 PEG bees wax 
                   
                 wax 
               
               
                 2.0 
                   
                 Example 4 
                 glossing additive 
               
            
           
           
               
            
               
                 component B 
               
            
           
           
               
               
               
               
            
               
                 3.0 
                 Cyclopentasiloxane 
                 SF 1202 
                 evaporable liquid 
               
               
                   
                   
                   
                 carrier 
               
               
                   
               
            
           
         
       
     
     Example 10 
     Cosmetic Formulation: Liquid Color Lipstick 
     
       
         
           
               
               
               
               
             
               
                   
               
               
                   
                   
                 Brand name 
                   
               
               
                 % by 
                   
                 by Momentive 
               
               
                 wt. 
                 INCI 
                 or Example 
                 Function 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                 12.0 
                 Dimethicone (and) 
                 TP 3784 
                 liquid carrier - 
               
               
                   
                 isododecane 
                   
                 solvent 
               
               
                 9.5 
                 Isododecane (&amp;) disteardi- 
                 Bentone gel 
               
               
                   
                 monium hectorite (&amp;) 
               
               
                   
                 propylene carbonate 
               
               
                 23.0 
                   
                   
                 pigments 
               
               
                 12.5 
                 Trimethylsiloxysilicate 
                 SR 1000 
                 adhesion extender 
               
               
                 26.0 
                 Ethyltrisiloxane 
                 Silsoft ® ETS 
                 evaporable liquid 
               
               
                   
                   
                   
                 carrier 
               
               
                 10.0 
                 C 30 -C 45 -alkyl dimethicone 
                 SF 1642 
                 wax 
               
               
                 4.5 
                   
                 Ceralution H 
               
               
                 2.5 
                   
                 Example 4 
                 film-forming 
               
               
                   
                   
                   
                 agent 
               
               
                   
               
            
           
         
       
     
     Example 11 
     Cosmetic Formulation: Liquid Lipstick 
     
       
         
           
               
               
               
               
             
               
                   
               
               
                   
                   
                 Brand name 
                   
               
               
                 % by 
                   
                 by Momentive 
               
               
                 wt. 
                 INCI 
                 or Example 
                 Function 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                 10.0 
                 Dimethicone (and) isododecane 
                 Baysilone ® 
                 liquid carrier - 
               
               
                   
                   
                 TP 3784 
                 solvent 
               
               
                 9.5 
                 Isododecane (and) 
               
               
                   
                 disteardimonium hectorite 
               
               
                   
                 (and) propylene carbonate 
               
               
                 12.0 
                 C 30 -C 45 -alkyl dimethicone 
                 SF 1642 
                 wax 
               
               
                 12.0 
                 Trimethoxysiloxysilicate (and) 
                 TP 3744 
                 adhesion 
               
               
                   
                 isododecane 
                   
                 extender 
               
               
                 4.5 
                 Behenyl alcohol &amp; glyceryl 
               
               
                   
                 stearate &amp; glyceryl stearate 
               
               
                   
                 citrate &amp; sodium dicocoylethyl- 
               
               
                   
                 enediamine PEG-15 sulfate 
               
               
                 2.5 
                   
                 Example 2 
                 film-forming 
               
               
                   
                   
                   
                 agent 
               
               
                 25.5 
                 Isododecane 
                   
                 liquid carrier 
               
               
                 24.0 
                 pigments 
                   
                 pigment 
               
               
                   
               
            
           
         
       
     
     Example 12 
     Lipstick Composition with Pigments 
     
       
         
           
               
               
               
               
             
               
                   
               
               
                   
                   
                 Brand name 
                   
               
               
                 % by 
                   
                 by Momentive 
               
               
                 wt. 
                 INCI 
                 or Example 
                 Function 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                 12 
                 Dimethicone (and) isododecane 
                 TP 3784 
                 liquid carrier - 
               
               
                   
                   
                   
                 solvent 
               
               
                 9 
                 Bentone gel ISDV 
               
               
                 12 
                 Trimethoxysiloxysilicate (and) 
                 TP 3744 
                 adhesion 
               
               
                   
                 isododecane 
                   
                 extender 
               
               
                 11 
                 C30-C45-alkyl dimethicone 
                 SF 1642 
                 wax 
               
               
                 5 
                 Ceralution H 
                 Ceralution H 
               
               
                 2.4 
                   
                 Example 2 
                 film-forming 
               
               
                   
                   
                   
                 agent 
               
               
                 10 
                 Carnauba wax LT 314 
                 carnauba 
                 wax 
               
               
                   
                   
                 wax LT 314 
               
               
                 — 
                   
                 SF 1632 
               
               
                 15.6 
                 Isododecane 
                 isododecane 
                 solvent 
               
               
                 14.86 
                 Corona Bordeaux 
                   
                 pigment 
               
               
                 8.14 
                 Timiron Sun Gold Sparkle 
                   
                 pigment 
               
               
                   
                 MP-29 
               
               
                   
               
            
           
         
       
     
     Examples 6 to 12 show that compounds such as those of Examples 2 and 4 can replace cosmetic ingredients, such as the compound Silshine® 151 listed under the INCI name phenylpropyldimethylsiloxysilicate, with regard to miscibility with cosmetic ingredients without having to accept evident drawbacks with respect to the cosmetic properties. The high refractive index of the compound from Example 4 leads to particularly advantageous glossy effects.