Abstract:
The present invention relates to a series of crosslinked silicone polymers that by virtue of the nature of the dimol alcohol undecylenic acid ester based crosslinker, have unique solubility and properties. These include improved tolerance for oily materials and improved skin feel. These polymers find use in personal care applications like pigmented products. In the personal care arena, solid products that do not experience syneresis are important. Syneresis is a condition that exists in a solid product that causes a liquid that is incompatible to ooze out, which is cosmetically unacceptable.

Description:
FEDERAL SPONSORSHIP 
     None 
     FIELD OF THE INVENTION 
     The present invention relates to a series of crosslinked silicone polymers that by virtue of the nature of the crosslinker have unique solubility and properties. These include improved tolerance for oily materials and water soluble materials. These polymers find use in personal care applications like pigmented products. In the personal care arena, solid products that do not experience syneresis are important. Syneresis is a condition that exists in a solid product that causes a liquid that is incompatible to ooze out, which is cosmetically unacceptable. 
     BACKGROUND OF THE INVENTION 
     The term silicone resin has been applied both to and misapplied to a variety of materials over time. Silicone resins as used herein refer to a series of products which include at least two silicone backbones that are joined by a “crosslinking group”. The number of crosslinking groups that are present as a percentage of the total molecular weight will determine the properties of the resulting polymer. 
     If there are no crosslinking groups; the polymer can freely rotate and consequently is an oily liquid. If a few crosslinking groups are introduced, the ability to rotate is slightly restricted and the oily material becomes “rubbery”. The rubbery material should be referred to as an elastomer. The properties are morel like a rubber band than plastic. As the percentage of crosslinking increases still the molecule becomes rigid. This class of compounds are resins. If you hit the film with a hammer and it shatters it is a resin, if it bounces it is an elastomer and if it squirts out is a silicone fluid. 
     The difficulty in determining if a product is a fluid an elastomer or resin occurs for products that lie between the classifications. Specifically, when does an elastomer become a resin? While this exact point is of academic interest it does not have any practical significance to the present invention. 
     There are a number of classes of resin compounds differing in the nature of the crosslinker. One class is the so called “Q resins”. 
     
       
                 
         
             
             
         
      
     
     The oxygen that needs another bond connects to another polymer as shown: 
     
       
                 
         
             
             
         
      
     
     The crosslinking group is —O—. This type of resin is disclosed in U.S. Pat. No. 6,139,823, incorporated herein by reference. This type of material has a group, the so called “Q” group in which a Si has four oxygen atoms attached. In the above case it is the group that is within the “a” subscript. This type of resin is very powdery and is rarely used without a plasticizer. This class of compounds can also dry the skin. 
     The next class of resin contain alkyl connecting groups. 
     
       
                 
         
             
             
         
      
     
     In the case where n=1 acetylene is used as a crosslinking reactant. It is reacted with a silanic hydrogen polymer. As n is increased the reactant is an alpha omega divinyl compound. 
     
       
                 
         
             
             
         
      
     
     
       
                 
         
             
             
         
      
     
     The reaction is called hydrosilylation and provides the linking groups between the molecules. The reaction is generally run in solvent like cyclomethicone (D4 or D5 or hexamethyl disiloxane) or in volatile organic like isododecane. A catalyst generally a platinum one is used to effect the reaction. Chloroplatinic acid or Karnsteadt catalyst are preferred. The resulting material is a viscous liquid that when the solvent evaporates provides a film. 
     The present invention makes use of novel crosslinking reagents that provide groups that significantly alter the solubility of the resin. This is done by introducing fatty ester linkages, water soluble groups linked with fatty esters and glyceryl esters. Not only does the solubility change, the ability to formulate solid products free from syneresis also occurs. Another unexpected benefit is that the ester moiety provides improved biodegradation of the resin making the resin “more green” and improving consumer acceptability. None of these advantageous are present in the compounds known heretofore. 
     THE INVENTION 
     Object of the Invention 
     It is the object of the present invention to provide a series of silicone polymers that make use of a unique crosslink compound. This compound is very efficient in reacting with a variety of silanic hydrogen containing polymers to provide a crosslinked product. The crosslinker is an undecylenic ester of dimer diol. 
     Another object of the present invention is to provide a series of products suitable for formulation into personal care products providing improved skin feel (i.e. not drying like Q resins) and having improved solubility over alkyl linked polymers. 
     Other objects of the invention will become clear as one reads the specification attached hereto. 
     All % given herein are % by weight, all temperatures are ° C., all patents and publications referred to herein are incorporated herein by reference in their entirety as appropriate. 
     SUMMARY OF THE INVENTION 
     The present invention relates to a series of silicone resins that (a) provide improved oil solubility and film forming properties when reacted into resin systems. 
     The compounds of the present invention are made by reacting specific vinyl diester compounds with silicone compounds that contain multiple silanic hydrogen (Si—H) groups. The reaction is conducted in a suitable solvent selected from the group consisting of cyclomethicone (D-4 and D-5 and mixtures thereof) and isoalkanes (iso-dodecane). 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     Resins of the present invention are a class of silicone compounds which are prepared by the reaction of a poly-vinyl compound reacted with a silanic hydrogen containing compound. 
                                
wherein;
 
R 1  is a mixture of:
 
     
       
                 
         
             
             
         
      
     
     
       
                 
         
             
             
         
      
     
                                
wherein:
 
R 2  is alkyl having 8 to 36 carbon atoms;
 
x is an integer ranging from 0 to 2000;
 
y is an integer ranging from 2 to 200;
 
z is an integer ranging from 0 to 200;
 
e is an integer ranging from 6 to 35;
 
f is an integer ranging from 0 to 20;
 
g is an integer ranging from 0 to 20;
 
h is an integer ranging from 0 to 20.
 
     The reactions are typically carried out in a solvent, either volatile silicone (cyclomethicone (D4 or D5 or mixtures thereof) or hydrocarbon solvent like isododecane. A suitable hydrosilylation catalyst like chloroplatinic acid or Karnstedt catalyst are used. 
     The value of “y” determines the degree of crosslinking and consequently if the product is resinous or elastomeric. Elastomeric materials are compounds that are crosslinked to a lesser extent than resins. They are “rubbery” producing films that are rubber band like. Resins in contrast are not rubbery, but are hard and because of their higher crosslink density form powders when struck by a hammer. 
     We have also found that reaction of an undecylenate ester will allow for the incorporation of the “R” moiety onto the molecule thereby increasing oil solubility and compatibility with oily materials present in the personal care application. 
     Crosslinker 
     We have surprisingly and unexpectently found that the undecylenate di-ester of dimol alcohol is a surprisingly good crosslinker when making silicone resins. 
     Dimol alcohol is a commercially available di-alcohol. It is available from a variety of sources including Jarchem located in Newark, N.J. It is a mixture of products conforming to the following structures: 
     
       
                 
         
             
             
         
      
     
     
       
                 
         
             
             
         
      
     
     This crosslinker is made by the reaction of two moles of undecylenic acid to form a mixed alpha-omega di vinyl crosslinker. Undecylenic acid is an item of commerce. The crosslinker conforms to the following structure: 
     
       
                 
         
             
             
         
      
     
     
       
                 
         
             
             
         
      
     
     The undecylenic acid esters are one aspect of the present invention. The product is made by an esterification reaction which is carried out at temperatures of between 150° C. and 220° C. Esterification catalysts can be added as required. 
     The second reactant is a silanic hydrogen containing compound, which is an item of commerce commercially available from Siltech LLC, Dacula, Ga., conforming to the following structure: 
     
       
                 
         
             
             
         
      
     
     An optional material (when “z” is not zero), is a fatty ester of undecylenic acid. This reactant is made by the reaction of a fatty alcohol with undecylenic acid. 
     The reaction is as follows:
 
R 2 —OH+CH 2 ═CH—(CH 2 ) 8 —C(O)OH-&gt;R 2 O—C(O)—(CH 2 ) 8 —CH═CH 2 +H 2 O
 
     The reaction is carried out using commercially available raw materials including undecylenic acid and fatty alcohols at temperatures of between 150° C. and 220° C. Esterification catalysts can be added as required 
     The addition of this material to the reaction mixture results in increased ester groups and increases compatibility with organics used in the formulation of pigmented products. 
     Resins with improved compatibility with organic components has been a long felt unsatisfied need in the personal care area. 
     The present invention relates to a series of compounds made by the hydrosilylation reaction of a silanic hydrogen containing silicone conforming to the following structure: 
     
       
                 
         
             
             
         
      
     
     wherein; 
     x is an integer ranging from 0 to 2000; 
     y is an integer ranging from 2 to 200; 
     z is an integer ranging from 0 to 200; 
     e is an integer ranging from 6 to 35; 
     f is an integer ranging from 0 to 20; 
     g is an integer ranging from 0 to 20; 
     h is an integer ranging from 0 to 20; 
     with an alpha-omega diol compound which is a mixture conforming to the following structures; 
     
       
                 
         
             
             
         
      
     
                                
and
 
                                
and optionally a mono substituted undecylenic compound conforming to the following structure:
 R 2 O—C(O)—(CH 2 ) 8 —CH═CH 2    
wherein;
 
R 2  is alkyl having 8 to 36 carbon atoms;
 
in the presence of a suitable hydrosilylation catalyst;
     in a suitable volatile solvent selected from the group consisting of cyclomethicone, hexamethyldisiloxane and isoparaffin.   
     Another aspect of the present invention relates to a series of compounds made by the hydrosilylation reaction conforming to the following structure: 
                                
wherein;
 
R 1  is a mixture of:
 
                                
and
 
                                
wherein:
 
R 2  is alkyl having 8 to 36 carbon atoms;
 
x is an integer ranging from 0 to 2000;
 
y is an integer ranging from 2 to 200;
 
z is an integer ranging from 0 to 200;
 
e is an integer ranging from 6 to 35;
 
f is an integer ranging from 0 to 20;
 
g is an integer ranging from 0 to 20;
 
h is an integer ranging from 0 to 20.
 
     PREFERRED EMBODIMENTS 
     In a preferred embodiment z is 0. 
     In a preferred embodiment z ranges from 1 to 20. 
     In a preferred embodiment R 2  is alkyl having 12 carbon atoms. 
     In a preferred embodiment R 2  is alkyl having 14 carbon atoms. 
     In a preferred embodiment R 2  is alkyl having 16 carbon atoms. 
     In a preferred embodiment R 2  is alkyl having 18 carbon atoms 
     In a preferred embodiment R 2  is alkyl having 20 carbon atoms 
     In a preferred embodiment R 2  is alkyl having 22 carbon atoms. 
     In a preferred embodiment R 2  is alkyl having 24 carbon atoms 
     In a preferred embodiment R 2  is alkyl having 36 carbon atoms. 
     EXAMPLES 
     Raw Materials 
     Example 1 
     Undecylenic Acid 
     Undecylenic acid is an item of commerce available from a variety of sources. It conforms to the following structure:
 
CH 2 ═CH—(CH 2 ) 8 —C(O)OH
 
     Example 2 
     Dimol Alcohol 
     Dimol alcohol is a commercially available di-alcohol. It is available from a variety of sources including Jarchem located in Newark, N.J. It is a mixture of products conforming to the following structures: 
                                
and
 
     
       
                 
         
             
             
         
      
     
     Examples 3-14 
     Fatty Alcohols 
     Fatty Alcohols are items of commerce. They conform to the following structure:
 
R 2 OH
 
     
       
         
               
               
             
               
               
             
           
               
                   
               
               
                 Example 
                 R 2  Formula 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 3 
                 C 8 H 17   
               
               
                 4 
                 C 10 H 21   
               
               
                 5 
                 C 12 H 25   
               
               
                 6 
                 C 14 H 29   
               
               
                 7 
                 C 16 H 33   
               
               
                 8 
                 C 18 H 37   
               
               
                 9 
                 C 20 H 41   
               
               
                 10 
                 C 22 H 45   
               
               
                 11 
                 C 24 H 49   
               
               
                 12 
                 C 36 H 73   
               
               
                 13 
                 C 26 h 53   
               
               
                 14 
                 C 30 H 61   
               
               
                   
               
             
          
         
       
     
     Silanic Hydrogen Silicone Compounds 
     Examples 15-25 
     Silanic Hydrogen compounds are items of commerce made by a variety of suppliers, including Siltech Corporation in Toronto Canada. They conform to the following structure: 
     
       
                 
         
             
             
         
      
     
     wherein; 
     x is an integer ranging from 0 to 2000; 
     y is an integer ranging from 2 to 200; 
     z is an integer ranging from 0 to 200; 
     e is an integer ranging from 6 to 35; 
     f is an integer ranging from 0 to 20; 
     g is an integer ranging from 0 to 20; 
     h is an integer ranging from 0 to 20. 
     
       
         
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 Example 
                 x 
                 y 
                 z 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 15 
                 0 
                 2 
                 0 
               
               
                   
                 16 
                 10 
                 5 
                 20 
               
               
                   
                 17 
                 15 
                 20 
                 15 
               
               
                   
                 18 
                 25 
                 50 
                 9 
               
               
                   
                 19 
                 50 
                 25 
                 50 
               
               
                   
                 20 
                 75 
                 15 
                 0 
               
               
                   
                 21 
                 100 
                 28 
                 5 
               
               
                   
                 22 
                 5 
                 5 
                 15 
               
               
                   
                 23 
                 10 
                 150 
                 10 
               
               
                   
                 24 
                 6 
                 100 
                 200 
               
               
                   
                 25 
                 2000 
                 200 
                 0 
               
               
                   
                   
               
             
          
         
       
     
     Crosslinker Preparation 
     General Procedure 
     The crosslinkers are made by the esterification reaction of undecylenic acid and a variety of hydroxy containing compounds. 
     To 184.0 grams of undecylenic acid (Example 1) is added the specified number of grams of the specified hydroxy containing compound (Examples 2-14). A catalyst is recommended, although the reaction can be run without one. Preferred catalyst is stannous oxylate. The reaction mixture is heated to 150-200° C. Water will distill off as reaction proceeds. The amount of water distilled off is measured and used to monitor the reaction. The reaction is also monitored by acid value reduction. 
     
       
         
               
               
               
             
               
               
               
             
               
               
               
             
           
               
                   
                   
               
               
                   
                 Hydroxy Compound 
                   
               
             
          
           
               
                 Example 
                 Example 
                 Grams 
               
               
                   
               
             
          
           
               
                 26 
                 2 
                 268 
               
               
                 27 
                 3 
                 130 
               
               
                 28 
                 4 
                 158 
               
               
                 29 
                 5 
                 186 
               
               
                 30 
                 6 
                 214 
               
               
                 31 
                 7 
                 242 
               
               
                 32 
                 8 
                 270 
               
               
                 33 
                 9 
                 298 
               
               
                 34 
                 10 
                 326 
               
               
                 35 
                 11 
                 354 
               
               
                 36 
                 12 
                 522 
               
               
                 37 
                 13 
                 382 
               
               
                 38 
                 14 
                 438 
               
               
                   
               
             
          
         
       
     
     Hydrosilylation Compounds of the Present Invention 
     Hydrosilylation Solvents 
     Examples 39-42 
     The hydrosilylation reactions are advantageously run in a volatile solvent, which can later be distilled off is desired. It is also a practice to sell the products in solvent. 
     
       
         
               
               
             
           
               
                   
               
               
                 Example 
                 Description 
               
               
                   
               
             
             
               
                 39 
                 isododecane 
               
               
                 40 
                 cyclomethicone 
               
               
                 41 
                 isodecane 
               
               
                   
               
             
          
         
       
     
     Hydrosilylation 
     Hydrosilylation is a process that reacts terminal vinyl compounds with silanic hydrogen to obtain a Si—C bond. References to this reaction, incorporated herein by reference, include: 
     U.S. Pat. Nos. 3,715,334 and 3,775,452 to Karstedt, shows the use of Pt(O) complex with vinylsilicon siloxane ligands as an active hydrosilylation catalyst. 
     Additional platinum complexes, such as complexes with platinum halides are shown by, U.S. Pat. No. 3,159,601 Ashby and, U.S. Pat. No. 3,220,972, to Lamoreaux. 
     Another hydrosilylation catalyst is shown by Fish, U.S. Pat. No. 3,576,027. Fish prepares a platinum(IV) catalyst by reacting crystalline platinum(IV) chloroplatinic acid and organic silane or siloxane to form a stable reactive platinum hydrosilylation catalyst. 
     General Procedure 
     To the specified number of grams of the specified solvent (Examples 39-41) is added the specified number of grams of the specified silanic hydrogen compound (Example 15-25). The mass is mixed well. To that mixture is added the specified number of grams of the specified dimol undecylenate (Example 26) compound and the specified number of grams of the monosubstituted undecylenate esters (Examples 27-38). The reaction mass is mixed well until homogeneous. To that mixture is added 0.01% Karstedt catalyst, which is commercially available from Geleste. The agitation is stopped and the reaction begins with an exotherm. The reaction mass will thicken over 4 hours, but most rapidly in the first twenty minutes. Once the maximum viscosity is reached the reaction is considered complete. The solvent may be distilled off or the product may be sold as prepared without additional purification. 
     Polymers  
     Examples 42-67 
     
       
         
               
             
               
               
               
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                   
               
               
                 Example 26 
               
             
          
           
               
                 Diol Ester 
                 Silanic Hydrogen 
                 Mono-Vinyl 
                 Solvent 
               
             
          
           
               
                 Example 
                 Grams 
                 Example 
                 Grams 
                 Example 
                 Grams 
                 Example 
                 Grams 
               
               
                   
               
             
          
           
               
                 42 
                 867 
                 15 
                 284 
                 — 
                 0 
                 39 
                 11510 
               
               
                 43 
                 216 
                 16 
                 240 
                 26 
                 53 
                 39 
                 5107 
               
               
                 44 
                 867 
                 17 
                 337 
                 27 
                 195 
                 39 
                 13994 
               
               
                 45 
                 2167 
                 18 
                 555 
                 28 
                 142 
                 39 
                 9141 
               
               
                 46 
                 1083 
                 19 
                 836 
                 29 
                 930 
                 39 
                 2849 
               
               
                 47 
                 650 
                 20 
                 661 
                 — 
                 0 
                 39 
                 6508 
               
               
                 48 
                 1213 
                 21 
                 64 
                 31 
                 121 
                 39 
                 13994 
               
               
                 49 
                 2168 
                 22 
                 1734 
                 32 
                 4050 
                 39 
                 7500 
               
               
                 50 
                 650 
                 23 
                 105 
                 33 
                 29 
                 39 
                 1354 
               
               
                 51 
                 4335 
                 24 
                 1860 
                 35 
                 708 
                 39 
                 69038 
               
               
                 52 
                 867 
                 25 
                 1601 
                 — 
                 0 
                 39 
                 24686 
               
               
                 53 
                 216 
                 16 
                 240 
                 37 
                 764 
                 39 
                 24436 
               
               
                 54 
                 867 
                 17 
                 337 
                 38 
                 657 
                 39 
                 23267 
               
               
                 55 
                 867 
                 15 
                 284 
                 — 
                 0 
                 40 
                 11510 
               
               
                 56 
                 216 
                 16 
                 240 
                 26 
                 536 
                 41 
                 9932 
               
               
                 57 
                 867 
                 17 
                 337 
                 27 
                 1950 
                 40 
                 31540 
               
               
                 58 
                 216 
                 18 
                 55 
                 28 
                 14 
                 40 
                 2865 
               
               
                 59 
                 108 
                 19 
                 83 
                 29 
                 93 
                 40 
                 34380 
               
               
                 60 
                 65 
                 20 
                 66 
                 — 
                 0 
                 41 
                 1310 
               
               
                 61 
                 121 
                 21 
                 6 
                 30 
                 10 
                 41 
                 1360 
               
               
                 62 
                 216 
                 22 
                 173 
                 32 
                 405 
                 40 
                 7952 
               
               
                 63 
                 650 
                 23 
                 105 
                 33 
                 29 
                 40 
                 7840 
               
               
                 64 
                 433 
                 24 
                 186 
                 35 
                 708 
                 41 
                 13275 
               
               
                 65 
                 867 
                 25 
                 1601 
                 — 
                 0 
                 41 
                 6404 
               
               
                 66 
                 216 
                 16 
                 240 
                 37 
                 764 
                 41 
                 12000 
               
               
                 67 
                 86 
                 17 
                 33 
                 38 
                 65 
                 40 
                 1861 
               
               
                   
               
             
          
         
       
     
     The key to understanding the functionality of the resin of the present invention is an appreciation that silicone and oil are mutually immiscible groups. This lack of solubility is the cause of the syneresis (or separation) seen in pigmented products that contain oil, and silicone. If the molecule has these groups properly connected the molecule will orientate itself into the lowest free energy. In this configuration the oil loving and silicone portions of the resin and of the formulation will all associate in a matrix. The parts of this linking group that connect to the silicone group are oil soluble. The length of that group is fairly long and symmetrical. The internal group is water loving (polar). Resins with this configuration allows for the incorporation of both oil loving (non-polar non-silicone) and silicone loving components in the formulation. This produces an emollient property to the skin in a film forming matrix. The presence of the ester group helps biodegradability. 
     While the illustrative embodiments of the invention have been described with particularity, it will be understood that various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the examples and descriptions set forth hereinabove but rather that the claims be construed as encompassing all the features of patentable novelty which reside in the present invention, including all features which would be treated as equivalents thereof by those skilled in the art to which the invention pertains.