Patent Publication Number: US-6342527-B1

Title: Polymeric castor polyesters

Description:
RELATED APPLICATIONS 
     This application is a continuation of Ser. No. 09/655,142 filed 09/05/2000. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention deals with the use of certain novel polyesters which are prepared by the sequential reaction of castor oil with isostearic acid to provide an intermediate that is subsequently esterified with a diacid to provide a polyester. In addition, the present invention describes a process for providing gloss to the skin which comprises application of an effective glossing concentration of this polyester. 
     2. Description of the Art Practices 
     There is a desire to develop an ester that gives gloss to the skin when applied from oils or applied from emulsions. An added aspect of the present invention is the fact that the compounds are polymeric. This has two very important implications on the use of the materials of the present invention. The polymeric nature means the compounds do not penetrate the skin. The fact that these molecules remain on the skin, increases gloss and provides a less irritation to the skin. They also provide a gloss that is more long lasting. 
     U.S. Pat. No. 5,786,389 issued Jul. 1998 to O&#39;Lenick, incorporated herein by reference, describes the use of a guerbet ester of castor for gloss. The compounds are a simple ester made by the reaction of castor and a specific mono functional alcohol to produce an ester. The products of this patent are neither polymeric, nor do they involve reaction of the hydroxyl group in the castor molecule. We have discovered that higher gloss, lower irritation and better durability of gloss results when one makes the polymers of the present invention. 
     Until the compounds of the present invention polyesters did not give a sufficient gloss when applied to the skin. None of the prior esters possess the critical combination of branching and the polymeric composition unique to castor. 
     THE INVENTION 
     This invention relates to a series of polyester compounds derived from castor oil. Castor oil, a hydroxy containing oil, can be esterified with a fatty acid to produce an intermediate having both an ester and triglyceride functionality. By selecting the ratios of reactants, the castor can be a partially substituted with fatty acid leaving some unreacted hydroxyl groups. The number of remaining hydroxyl groups, and the type and concentration of diacid used to react with the unreacted hydroxyl groups, results in a controllable polyester. The control of molecular weight and degree of polymerization is critical to functionality of the product. 
     The unique structure of castor oil coupled with the proper selection of the fatty acid and diacid chosen to make the polyester results in a product that has unique gloss when applied to skin. One of the unique aspects of the present invention is the fact that the reaction to make an ester is conducted on the castor hydroxyl group, not the triglyceride group. Another unique aspect of the present reaction is the selection of a proper mole ratio to leave unreacted hydroxyl groups present in each triglyceride to crosslink the product, providing a polyester. 
     Specifically, the present invention discloses novel polyesters and a process for providing gloss to the skin which comprises application of an effective glossing concentration of an polyester conforming to the following structure: 
     
       
         A—(B)x-A 
       
     
     wherein 
     A is:                                      
     wherein; 
     the linking group between all of the O— are succinyl groups conforming to the following structure —C(O)—CH 2 CH 2 —C(O)—; 
     R is selected from alkyl and alkylene having 5 to 33 carbon atoms; 
     x is an integer ranging from 1 to 50. 
     In a simple case where x is 1 the following polymer results:                    
     By varying the ratio of fatty acid more of the hydroxyl group is left. In the case of the “A” unit, two of the three hydroxyl groups on the castor oil are reacted, leaving only one group left to react. In the case of the “B” units two hydroxyl groups are left to react. In making a one pot synthesis, the total number of acid groups is calculated any reacted in the first step with the castor oil, followed by the reaction of the remaining hydroxyl groups with diacid. In some instances it is desirable to leave some unreacted hydroxyl groups in the polymer. 
     PREFERRED EMBODIMENTS 
     In a preferred embodiment x is an integer ranging from 3 to 5. 
     In a preferred embodiment x is an integer ranging from 5 to 10. 
     In a preferred embodiment R is alkylene having 11 to 21 carbon atoms. 
     In a preferred embodiment R is alkyl having 7 to 10 carbon atoms. 
     In a preferred embodiment R is alkylene having 17 carbon atoms. 
    
    
     EXAMPLES 
     Raw Materials 
     Castor Oil 
     Castor oil is a unique triglyceride. It is derived from Ricinus Communis L. The castor plant grows wild in many subtropical and tropical areas. Today Brazil, China and India provide over 90% of the oil. Castor oil contains a large content of hydroxy containing compounds that are unsaturated. The common name for the predominant species in castor is ricinoleic acid. More correctly it is called 12-hydroxy-9 octadecenoic acid or d-12-hydroxyoleic acid. The acid conforms to the following structure: 
     
       
         CH 3 —(CH 2 ) 5 —CH(OH)—CH 2 —CH═CH—(CH 2 ) 7 —C(O)—OH 
       
     
     Castor Oil is a clear, viscous, light colored fluid that is nondrying and quite stable. The Purity of Castor Oil occurs with remarkable uniformity. Regardless of country of origin, or season it is grown, the composition and chemical properties remain within a very narrow range. Castor Oil has a CAS Number of 8001-79-4 and an EINECS Number of 232-293-8. 
     Castor oil has a unique carbon distribution, which has 18 carbon atoms and one double bond. The concentration of that species is about 90% by weight. It is this ricinoleic moiety that when linked to a guerbet alcohol in an ester gives unique gloss when applied to the skin. 
     Ricinoleic acid has the unusual property of having both a double bond, that results in a specific conformation of the “kinked carbon chain” placing the hydroxyl group in a locked position. While not professing only one mechanism of action, it is believed that the introduction of the polar guerbet branched portion of the molecule results in an ester that has a great deal of branching. The molecule takes on a conformation having the minimum free energy. That conformation places the polar hydroxyl groups from different molecules into an associative complex. This complex is delivered to the skin either neat or in emulsions giving a great deal of gloss that is durable. There are many cosmetic applications in which gloss is desirable. 
     Fatty Acids 
     Fatty Acids are items of commerce, available in pure form and in mixtures. one of manufacturer offering a very wide range of products of high quality is Cognis, formerly Henkel Corporation. Fatty acids have common names. They also have a commonly used shorthand used to describe them. The designation is a letter “C” and a number indicating the number of carbon atoms in the molecule. If no additional information is offered the product is saturated. If a “:” follows and a number after it the product has the specified number of double bonds in the molecule. Consequently, C6 is a saturated six carbon fatty acid. C12:1 is a 12 carbon fatty acid having one double bond. 
     
       
         
           
               
               
               
               
             
               
                   
                   
               
               
                   
                 Example 
                 Designation and Name 
                 Formula 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                  1 
                 C6 
                 Caproic acid 
                 C 6 H 12 O 2   
               
               
                   
                  2 
                 C8 
                 Caprylic acid 
                 C 8 H 16 O 2   
               
               
                   
                  3 
                 C10 
                 Capric acid 
                 C 10 H 20 O 2   
               
               
                   
                  4 
                 C12 
                 Lauric acid 
                 C 12 H 24 O 2   
               
               
                   
                  5 
                 C12:1 
                 Lauroleic acid 
                 C 12 H 22 O 2   
               
               
                   
                  6 
                 C14 
                 Myristic acid 
                 C 14 H 28 O 2   
               
               
                   
                  7 
                 C14:1 
                 Myristoleic acid 
                 C 14 H 26 O 2   
               
               
                   
                  8 
                 C16 
                 Palmitic acid 
                 C 16 H 32 O 2   
               
               
                   
                  9 
                 C16:1 
                 Palmitoleic acid 
                 C 16 H 30 O 2   
               
               
                   
                 10 
                 C18 
                 Stearic acid 
                 C 18 H 36 O 2   
               
               
                   
                 11 
                 C18:1 
                 Oleic acid 
                 C 18 H 34 O 2   
               
               
                   
                 12 
                 C18:2 
                 Linoleic acid 
                 C 18 H 32 O 2   
               
               
                   
                 13 
                 C18:3 
                 Linolenic acid 
                 C 18 H 30 O 2   
               
               
                   
                 14 
                 C20 
                 Arachidic acid 
                 C 20 H 40 O 2   
               
               
                   
                 15 
                 C20:1 
                 Gadoleic acid 
                 C 20 H 38 O 2   
               
               
                   
                 16 
                 C22 
                 Behenic acid 
                 C 22 H 44 O 2   
               
               
                   
                 17 
                 C22:1 
                 Erucic acid 
                 C 22 H 42 O 2   
               
               
                   
                 18 
                 C22:2 
                 Clupanodinic acid 
                 C 22 H 40 O 2   
               
               
                   
                 19 
                 C24 
                 Lignoceric acid 
                 C 24 H 48 O 2   
               
               
                   
                 20 
                 C26 
                 Cerotic acid 
                 C 26 H 52 O 2   
               
               
                   
                 21 
                 C28 
                 Montanic acid 
                 C 28 H 56 O 2   
               
               
                   
                 22 
                 C30 
                 Myricic acid 
                 C 30 H 60 O 2   
               
               
                   
                 23 
                 C32 
                 Lacceroic acid 
                 C 32 H 64 O 2   
               
               
                   
                 24 
                 C34 
                 Geddic acid 
                 C 34 H 68 O 2   
               
               
                   
                   
               
            
           
         
       
     
     Succinic Acid 
     Succinic acid is an item of commerce and conforms the following structure: 
     
       
         HO—C (O)—(CH 2 ) 2 —C(O)—OH 
       
     
     Ester Synthesis 
     The esterification reaction is carried out using the proper amount of fatty acid to castor oil. The esterification reaction can be carried out with or without catalyst, however when no catalyst is used the reaction times are protracted. Catalysts like benzene sulfonic acid, tin, sulfuric acid, tin salts and the like can be used. The most satisfactory catalyst is stannous oxylate. 
     General Procedure 
     To 846.0 grams of castor oil is added the specified amount of the specified fatty acid (examples 1-24). Next add 0.1 % stannous oxylate based upon the total weight of the batch after all ingredients have been charged, under agitation. The temperature of the mass is raised to 195-200 C off. The reaction mass is held at this temperature for between 4 and 15 hours, until the acid value drops to vanishingly small values. 
     Next the specified amount of succinic acid is added. The reaction mass is kept between 195 and 200 C for an additional 4 to 15 hours until the acid value ceases to fall further. The resulting product is a cleat oil that is used without additional purification. 
     EXAMPLES 25-48 
     
       
         
           
               
               
               
            
               
                   
                   
               
               
                   
                 Fatty Acid 
                 Succinic Acid 
               
            
           
           
               
               
               
               
               
            
               
                 Example 
                 “x” Value 
                 Example 
                 Grams 
                 Grams 
               
               
                   
               
               
                 25 
                 1 
                  1 
                  64.4 
                  50.0 
               
               
                 26 
                 1 
                  2 
                  80.0 
                  50.0 
               
               
                 27 
                 3 
                  3 
                  80.3 
                 150.0 
               
               
                 28 
                 5 
                  4 
                  85.7 
                 250.0 
               
               
                 29 
                 4 
                  5 
                  88.0 
                 200.0 
               
               
                 30 
                 10  
                  6 
                  88.7 
                 500.0 
               
               
                 31 
                 50  
                  7 
                  78.2 
                 2500.0  
               
               
                 32 
                 1 
                  8 
                 142.2 
                  50.0 
               
               
                 33 
                 3 
                  9 
                 118.5 
                 150.0 
               
               
                 34 
                 3 
                 10 
                 132.5 
                 150.0 
               
               
                 35 
                 4 
                 11 
                 125.3 
                 200.0 
               
               
                 36 
                 5 
                 12 
                 120.0 
                 250.0 
               
               
                 37 
                 6 
                 13 
                 115.8 
                 300.0 
               
               
                 38 
                 3 
                 14 
                 145.6 
                 150.0 
               
               
                 39 
                 4 
                 15 
                 137.8 
                 200.0 
               
               
                 40 
                 5 
                 16 
                 145.7 
                 250.0 
               
               
                 41 
                 2 
                 17 
                 169.0 
                 100.0 
               
               
                 42 
                 1 
                 18 
                 186.7 
                  50.0 
               
               
                 43 
                 4 
                 19 
                  46.2 
                 200.0 
               
               
                 44 
                 5 
                 20 
                 169.7 
                 250.0 
               
               
                 45 
                 6 
                 21 
                 176.7 
                 300.0 
               
               
                 46 
                 7 
                 22 
                 184.1 
                 350.0 
               
               
                 47 
                 1 
                 23 
                 266.7 
                  50.0 
               
               
                 48 
                 5 
                 24 
                 217.7 
                 250.0 
               
               
                   
               
            
           
         
       
     
     APPLICATIONS EXAMPLES 
     The effective glossing concentration of the products of the present invention range from 0.05% to 30% by weight. The preferred concentration ranges from 1 to 10. 
     The compounds of the present invention are formulated into lipsticks and color cosmetics where they provide a high gloss to the skin. 
     The compounds can be emulsified and applied from aqueous systems using emulsification techniques known to those skilled in the art. 
     The compounds of the present invention can be applied to the hair to provide outstanding gloss.