Abstract:
The present invention is directed to organo-silicone compound that have alkoxylated allyl alcohol groups of different degree of ethylene oxide and or propylene oxide present on two or more different groups. It is also directed to the use of that compound in personal care and other applications. These compounds by virtue of their unique structure provide outstanding emulsions including microemulsions.

Description:
RELATED APPLICATIONS 
     This application claims priority to and benefit of U.S. Provisional Application No. 61/128,798 filed May 27, 2008, the disclosure of which is incorporated herein for all purposes. 
    
    
     FIELD OF THE INVENTION 
     The present invention is directed to organo-silicone compound that have alkoxylated allyl alcohol groups of different degree of ethylene oxide and or propylene oxide present on two or more different groups. It is also directed to the use of that compound in personal care and other applications. These compounds by virtue of their unique structure provide outstanding emulsions including microemulsions. 
     BACKGROUND OF THE INVENTION 
     Organofunctional silicone compounds are one of two types, internal and terminal depending upon the location of the silicone group. 
     The so-called terminal group has the organic functional groups at the alpha and omega terminus of the molecule. Typical; of this class of compounds is the class of compounds currently called bis-dimethicone conforming to the following structure: 
                                
In the case where R is —(CH 2 ) 3 —O—(CH 2 CH 2 O) 8 H the compound is bis PEG-8 dimethicone.
 
     The other type of compound is referred to as comb structure in which the organofunctionality is located on non-terminal ends of the molecule. This type of compound is called a “comb” compound since the organofunctionality lies in the molecule much like the teeth of a comb. These compounds are shown in the following structure: 
                                
In the case where R is —(CH 2 ) 3 —O—(CH 2 CH 2 O) 8 H the compound is simply PEG-8 dimethicone.
 
     The present invention is directed to compounds in of the comb type having two different “R” groups. Such compounds have been disclosed in the so-called comb alkyl dimethicone copolyol class. 
                                
In the case where R 1  is —(CH 2 ) 3 —O—(CH 2 CH 2 O) 8 H and R 2  is —(CH 2 ) 11 —CH 3  the compound is lauryl PEG-8 dimethicone. Such compounds are known and U.S. Pat. No. 7,279,503 to O&#39;Lenick, incorporated herein by reference, is typical of patents related to such compounds. These compounds have two different types of compounds present on the molecule, in this case alkyl and alkoxylated.
 
     We have surprisingly found that when two different level of alkoxylation are placed on one molecule the surfactant properties of the resulting emulsifier can be improved. None of the prior art known to us disclose such a compound. 
     THE INVENTION 
     Object of the Invention 
     The object present invention a series of silicone polymers containing two different alkoxylated groups on the same molecule together. These materials have outstanding surfactant properties and are therefore useful in personal care applications. Other objects will become clear by reading the specification. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The compounds of the present invention conform to the following structure: 
                                
wherein;
     R 3  is —(CH 2 ) 3 —O—(CH 2 CH 2 O) x —(CH 2 CH(CH 3 )O) y —(CH 2 CH 2 O) z H;   R 4  is —(CH 2 ) 3 —O—(CH 2 CH 2 O) t —(CH 2 CH(CH 3 )O) u —(CH 2 CH 2 O) v H;   s is an integer ranging from 11 to 25;   x, y and z are independently integers ranging from 0 to 20;   t, u, and v are independently integers ranging from 0 to 20, with the proviso x does not equal t, and y does not equal u and z does not equal v (that is that the alkoxylate groups are not identical)   m is an integer ranging from 0 to 200;   n is an integer ranging from 1 to 20;   p is an integer ranging from 1 to 20;   q is an integer ranging from 0 to 20.   
     The compounds of the present invention are prepared by the reaction of a silanic hydrogen containing silicone polymer conforming to the following structure: 
                                
wherein:
     and an “q” moles of alpha olefinic containing polymer selected from the group consisting of:
 
CH 2 ═CH—(CH 2 ) s-2 —CH 3 ;
   “n” moles of the first alkoxylate conforming to the following structure:
 
CH 2 ═CH—CH 2 —O—(CH 2 CH 2 O) x —(CH 2 CH(CH 3 )—O) y —(CH 2 CH 2 O) z —H
 
and
   “p” moles of the first alkoxylate conforming to the following structure:
 
CH 2 ═CH—CH 2 —O—(CH 2 CH 2 O) t —(CH 2 CH(CH 3 )—O) u —(CH 2 CH 2 O) v —H
   s is an integer ranging from 11 to 25;   t, u and v are independently integers ranging from 0 to 20;   x, y, and z are independently integers ranging from 0 to 5, with the proviso x+y+z is less than or equal to 5 and t+u+v are greater than or equal to 10;   m is an integer ranging from 0 to 200;   n is an integer ranging from 1 to 20;   p is an integer ranging from 1 to 20;   q is an integer ranging from 0 to 20.   
     Preferred Embodiment 
     In a preferred embodiment x+y+z is zero and t+u+v is equal to or greater than 10. 
     In a preferred embodiment x+y+z are less than 5 and t+u+v is equal to or greater than 10. 
     In a preferred embodiment q is zero and x+y+z is zero and t+u+v is equal to or greater than 10. 
     In a preferred embodiment q is 1 or greater embodiment x+y+z are less than 5 and t+u+v is equal to or greater than 10. 
     In a preferred embodiment q is zero and x+y+z is zero and t+u+v is equal to or greater than 10 and s is less than or equal to 7. 
     In a preferred embodiment q is 1 or greater embodiment x+y+z are less than 5 and t+u+v is equal to or greater than 10 and s is less than or equal to 17. 
     In a preferred embodiment q is zero and x+y+z is zero and t+u+v is equal to or greater than 10 and s is greater than or equal to 19. 
     In a preferred embodiment q is 1 or greater embodiment x+y+z are less than 5 t+u+v is equal to or greater than 10 and s is greater than or equal to 19. 
     EXAMPLES 
     Silanic Hydrogen Compounds 
     Silanic hydrogen compounds conform to the following structure: 
                                
wherein;
     m is an integer ranging from 0 to 200;   n is an integer ranging from 1 to 20;   p is an integer ranging from 1 to 20;   q is an integer ranging from 0 to 20.   
     They are commercially available from Siltech LLC of Dacula, Ga. The specific values reported below for the molecule were determined by Si-29 nmr. 
     
       
         
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 Example 
                 m 
                 n 
                 p 
                 q 
                 n + p + q 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 1 
                 0 
                 1 
                 5 
                 1 
                 7 
               
               
                   
                 2 
                 4 
                 5 
                 1 
                 5 
                 11 
               
               
                   
                 3 
                 10 
                 4 
                 10 
                 0 
                 14 
               
               
                   
                 4 
                 20 
                 3 
                 10 
                 10 
                 23 
               
               
                   
                 5 
                 40 
                 10 
                 20 
                 10 
                 40 
               
               
                   
                 6 
                 50 
                 20 
                 5 
                 5 
                 30 
               
               
                   
                 7 
                 15 
                 5 
                 2 
                 20 
                 27 
               
               
                   
                 8 
                 20 
                 15 
                 15 
                 6 
                 36 
               
               
                   
                 9 
                 100 
                 20 
                 5 
                 1 
                 26 
               
               
                   
                 10 
                 200 
                 20 
                 20 
                 0 
                 40 
               
               
                   
                   
               
             
          
         
       
     
     Olefinic Compounds 
     Alpha olefins are commercially available form a variety of sources including Chevron. They conform to the following structure:
 
CH 2 ═CH—(CH 2 ) s-2 —CH 3 ;
 
     
       
         
               
               
               
             
               
               
               
             
           
               
                   
                   
               
               
                   
                 Example 
                 s 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 11 
                 9 
               
               
                   
                 12 
                 11 
               
               
                   
                 13 
                 23 
               
               
                   
                 14 
                 20 
               
               
                   
                 15 
                 25 
               
               
                   
                   
               
             
          
         
       
     
     Allyl Alcohol Alkoxylates 
     Class 1 
     Allyl alcohol alkoxylates are commercially available from several sources including Dow Chemical, Ethox Chemical, Siltech Corporation and KAO Chemical. They conform to the following structure:
 
CH 2 ═CH—CH 2 —O—(CH 2 CH 2 O) x —(CH 2 CH(CH 3 )—O) y —(CH 2 CH 2 O) z —H
 
x, y, and z are independently integers ranging from 0 to 5, with the proviso x+y+z is less than or equal to 5.
 
     
       
         
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 Example 
                 x 
                 y 
                 z 
               
               
                   
                   
               
             
             
               
                   
                 13 
                 0 
                 0 
                 0 
               
               
                   
                 14 
                 1 
                 1 
                 1 
               
               
                   
                 15 
                 0 
                 5 
                 0 
               
               
                   
                 16 
                 2 
                 0 
                 2 
               
               
                   
                 17 
                 0 
                 1 
                 4 
               
               
                   
                   
               
             
          
         
       
     
     Class2 
     Likewise the allyl alcohol alkoxylates of class 2 are commercially available from several sources including Dow Chemical, Ethox Chemical, Siltech Corporation and KAO Chemical. They conform to the following structure
 
CH 2 ═CH—CH 2 —O—(CH 2 CH 2 O) t —(CH 2 CH(CH 3 )—O) u —(CH 2 CH 2 O) v —H
 
t, u and v are independently integers ranging from 0 to 20 with the proviso t+u+v are than or equal to 10;
 
     
       
         
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 Example 
                 t 
                 u 
                 v 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 18 
                 20 
                 20 
                 20 
               
               
                   
                 19 
                 0 
                 10 
                 0 
               
               
                   
                 20 
                 10 
                 0 
                 0 
               
               
                   
                 21 
                 5 
                 3 
                 5 
               
               
                   
                 22 
                 20 
                 2 
                 5 
               
               
                   
                   
               
             
          
         
       
     
     PRODUCTS OF THE PRESENT INVENTION 
     General Procedure 
     The specified number of grams of allyl alcohol alkoxylates Class 1 (examples 13-17) and the specified number of grams of the specified allyl alcohol alkoxylate Class 2 (examples 18-20) are added to a vessel having agitation and cooling. Next the specified number of grams of silanic hydrogen (examples 1-10) and specified number of gram of alpha olefin (examples 11-16) is added, following by the specified number of grams of anhydrous isopropanol. The batch is then heated until the alpha olefin is liquid, or 80 C whichever is lower. Next 20 ppm Karnstedt catalyst (based upon the weight of all materials to be added) is added. Cooling is added to control the exotherm. It is not uncommon for the temperature to rise from 80 C to 90 C. Hold at 120 C for 4 hours, checking the Silanic hydrogen content until it becomes vanishing small. Distill off isopropanol using vacuum. 
     
       
         
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 Silanic Hydrogen 
                 Alkoxylate 1 
                 Alkoxylate 2 
                 Alpha Olefin 
                 Isopropanol 
               
             
          
           
               
                 Example 
                 Example 
                 Grams 
                 Example 
                 Grams 
                 Example 
                 Grams 
                 Example 
                 Grams 
                 Grams 
               
               
                   
               
             
          
           
               
                 23 
                 1 
                 58 
                 13 
                 6 
                 18 
                 1500 
                 11 
                 14 
                 20 
               
               
                 24 
                 2 
                 112 
                 14 
                 103 
                 19 
                 65 
                 12 
                 84 
                 88 
               
               
                 25 
                 3 
                 174 
                 15 
                 141 
                 20 
                 500 
                 13 
                 0 
                 163 
               
               
                 26 
                 4 
                 302 
                 16 
                 70 
                 21 
                 675 
                 14 
                 280 
                 265 
               
               
                 27 
                 5 
                 664 
                 17 
                 294 
                 22 
                 2556 
                 15 
                 364 
                 776 
               
               
                 28 
                 6 
                 566 
                 13 
                 118 
                 18 
                 1500 
                 11 
                 70 
                 460 
               
               
                 29 
                 7 
                 289 
                 14 
                 100 
                 19 
                 130 
                 12 
                 336 
                 200 
               
               
                 30 
                 8 
                 380 
                 15 
                 528 
                 21 
                 748 
                 13 
                 202 
                 400 
               
               
                 31 
                 9 
                 912 
                 16 
                 470 
                 22 
                 337 
                 14 
                 28 
                 450 
               
               
                 32 
                 10 
                 173 
                 17 
                 588 
                 18 
                 2556 
                 15 
                 0 
                 610 
               
               
                   
               
             
          
         
       
     
     Emulsion Formulation 
     The first set of experiments are conducted using all four emulsifiers, and allow the formulator not only the ability to evaluate emulsion stability, but also cosmetic aesthetics. 
     The formulation is: 
     
       
         
               
             
               
               
               
             
               
               
               
             
           
               
                   
               
               
                 Emulsifier Formula 
               
             
          
           
               
                   
                 Material 
                 % 
               
               
                   
                   
               
             
          
           
               
                   
                 Water 
                 47.25 
               
               
                   
                 Oil 
                 47.25 
               
               
                   
                 Emulsifier 
                 5.00 
               
               
                   
                 Salt 
                 0.5 
               
               
                   
                   
               
             
          
         
       
     
     Procedure: 
     1. Place emulsifier or emulsifier blend into the oil phase. 
     2. Mix well, noting clarity. 
     3. Add salt to water phase. 
     4. Heat both phases to 50° C. 
     5. Add water phase to oil phase and using mixer mix for 120 seconds. 
     6. Note appearance. 
     A comparison was made using the above formulation. The emulsions that were formed using the products containing a high and a low allyl allyl alcohol were more stable than those made with a molecule having the same number of moles of ethylene oxide and propylene oxide together in one allyl alcohol group. The presence of a high and a low amount of polyoxyalkylene in two different groups on the silicone polymer gives stability to emulsions made using the polymer over a silicone emulsifier in which there is one allyl alcohol alkoxylate with the same average number of moles of alkoxylate present. The conclusion is that two different allyl alcohol alkoxylates, one with a high amount of EO/PO and the other with a low amount of EO/PO will give surprisingly different surfactant properties than if the molecule made with the same average content on one molecule. While not wanting to be held to one reason for this it appears that the allyl alcohol portion with the low degree of alkoxylation (EO/PO) is a low HLB material and the portion with a high degree of alkoxylation (EO/PO) is a high HLB material and that putting the two in one molecule a particularly potent intra-molecular HLB pair emulsifier results. 
     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.