Patent Abstract:
The present invention is directed to a series of polyesters that are made by the reaction of a diacid with a pre-formed mono-hydroxy, di-hydroxy and optionally a tri-hydroxy ester of polyols selected from pentaerythritol, dipentearythritol trimethylolpropane and mixtures thereof. When reacted in the sequence shown, that is pre-formation of the mono-ester, di-ester and tri-ester, selection of the proper ratio of one to the other and then and only then reacted with the diacid, do these polyesters remain free of a gel and form cosmetically elegant oil phases.

Full Description:
RELATED APPLICATIONS 
       [0001]    This application is a continuation in part of Ser. No. 13/986,523, which is in turn a continuation in part of co-pending application Ser. No. 12/930,515, which in turn claims priority to and benefit of U.S. Provisional Application Nos. 61/459,348, filed Dec. 13, 2010, the disclosures of each of which are incorporated herein for all purposes. 
     
    
     FIELD OF THE INVENTION 
       [0002]    The present invention is directed to a series of polyesters made by the reaction of a mono-hydroxy ester, a di-hydroxy ester and a tri-hydroxy ester with diacids. The mono-hydroxy acid is a chain terminator, the di-hydroxy acid is a chain extender and the tri-hydroxy acid is a crosslinker. We have determined that one must make the individual components before reaction with the diacids, to avoid a gel and a useless product. 
       BACKGROUND OF THE INVENTION 
       [0003]    Cosmetic formulations applied to the skin and must have four key functions, (1) providing the cosmetic benefit sought (emmoliency, humectancy, smoothing, sun protection and the like; (2) provide cosmetic elegance when so applied; (3) be free of undesired reactive species like free vinyl monomer; and (4) be cost effective. The cosmetic chemist has long sought after this combination of properties. 
         [0004]    Historically, the selection of materials that provide the oil phase for emulsions, serums and lotions have been made from mineral oil, petrolatum, naturally occurring oils and fatty esters. These materials while well used lack the ability to modify the feel, flow and film forming properties on the skin. 
         [0005]    In making polyesters, one can either add all reactants, or pre-esterify the individual reactants followed by the reaction with diacids. We have learned that the pre-esterification of the intermediates followed by the reaction with diacids results in highly desirable polyesters, while reacting all raw materials together results in a gel. 
       OBJECTIVE OF THE INVENTION 
       [0006]    The present invention is aimed at providing a series of polyesters that are made in a sequential way by first making mono hydroxyl esters of polyol compounds selected from the group consisting of pentaerythritol, dipentaerythritol and trimethylol propane which have been made using fatty acids, next in a separate reactor making di hydroxyl esters of polyol compounds selected from the group consisting of pentaerythritol, dipentaerythritol and trimethylol propane, followed by crosslinking the mono and di hydroxyl, one having the high melting point and the other the low melting point acids esterified thereon, with a diacids to make a polyester. This is because the di hydroxyl functional compound can polymerize with the diacids to form a chain and the mono-functional compound can only terminate the reaction. 
         [0007]    Other objectives of the invention will become clear as one reads the specification. All patents cited herein are incorporated herein by reference. All percentages are percentages by weight, all temperatures are degrees centigrade, unless specifically stated otherwise. 
       SUMMARY OF THE INVENTION 
       [0008]    The present invention is directed to a series of polyesters made by reacting a mono-hydroxy polyol ester, a di-hydroxy poloyl ester and optionally a tri-hydroxy polyester with a diacid to make polyesters. 
         [0009]    The polymers of the present invention are not made using free radical chemistry, which can have residual and very undesirable vinyl monomers left after the reaction. These polymers are made by esterification chemistry, using fatty acids, diacids and polyols. The resulting polymers contain well-known reactants that are well known, and have a molecular weight above 1500 Daltons, which minimizes their ability to penetrate the skin. 
         [0010]    This combination of properties result in what we refer to as epigenomic friendly compounds, staying on the skin and providing benefits to the skin without penetration and causing irritation and inflammation. 
     
    
     DETAILED DESCRIPTION OF THE INVENTION 
       [0011]    The polyesters of the present invention have the following structure; 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    wherein;
 
R 2  is selected from the group consisting of
 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    with the proviso that R 2  is not mixtures there of;
 
R 1  is selected from the group consisting of;
       (1) alkyl and alkylene derived from a fatty acid having a melting point below 30° C.,   (2) alkyl or alkylene derived from a fatty acid having a melting point above 40° C. with the proviso that R′ is not mixtures thereof;
 
R 3  is selected from the group consisting of;
 
(1) —(CH 2 ) n —
   n is an integer from 2 to 10;
 
(2) a cyclic unsaturated having the structure
       
 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    and
 
(3) a saturated cyclic having the following structure;
 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    n is an integer ranging from 5 to 20;
 
a is an integer ranging from to 0 to 20
 
b is an integer ranging from 0 to 20,
 
c is an integer ranging from 0 to 20
 
d is an integer ranging from 0 to 20 with the proviso that a+b+c+d=n.
 
         [0015]    Another aspect of the present invention is a series if esters that are used as intermediates in the preparation of the compounds of the present invention selected from the group consisting of; 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    wherein;
 
R 1  is selected from the group consisting of
 
(1) alkyl and alkylene derived from a fatty acid having a melting point below 30° C. and
 
(2) alkyl or alkylene derived from a fatty acid having a melting point above 40° C. with the proviso that R 4  is not mixtures thereof.
 
         [0016]    Still another aspect of the present invention is esters that are used as intermediates in the preparation of the compounds of the present invention selected from; 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    wherein;
 
R 1  is selected from:
 
(1) alkyl and alkylene derived from a fatty acid having a melting point below 30° C. and
 
(2) alkyl or alkylene derived from a fatty acid having a melting point above 40° C. with the proviso that R 5  is not mixtures thereof.
 
         [0017]    Another aspect of the present invention is a polyester made by the reaction of:
   (a) a mono-hydroxy substituted complex ester selected from the group consisting of:
       (i) a pentaerythritol tri-ester having the structure:   
       
 
         [0000]      (R—C(O)—O—CH 2 ) 3 —C—CH 2 OH
       (ii) a dipentaerythritol penta-ester having the structure:       
 
         [0000]    
       
                 
         
             
             
         
       
       
         
           
             (iii) a trimethylol propane di-ester having the structure: 
           
         
       
     
         [0000]    
       
                 
         
             
             
         
       
       
         
           
              wherein R is alkyl having 17 to 21 carbon atoms and mixtures thereof; 
             (iv) and mixtures thereof; 
           
         
         (b) a di-hydroxy substituted complex ester selected from the group consisting of:
       (i) a pentaerythritol di-ester having the structure:   
     
       
     
         [0000]      (R—C(O)—O—CH 2 ) 2 —C—(CH 2 OH) 2  
       (ii) a dipentaerythritol tetra-ester having the structure:       
 
         [0000]    
       
                 
         
             
             
         
       
       
         
           
             (iii) a trimethylol propane di-ester having the structure: 
           
         
       
     
         [0000]    
       
                 
         
             
             
         
       
       
         
           
              wherein R is alkyl having 17 to 21 carbon atoms and mixtures thereof; 
             (iv) and mixtures thereof;
 
and optionally;
 
           
         
         (c) a tri-hydroxy substituted complex ester selected from the group consisting of:
       (i) a pentaerythritol mono-ester having the structure:   
     
       
     
         [0000]      (R—C(O)—O—CH 2 ) 3 —C—CH 2 OH
       (ii) a dipentaerythritol tri-ester having the structure:       
 
         [0000]    
       
                 
         
             
             
         
       
       
         
           
              wherein R is alkyl having 17 to 21 carbon atoms and mixtures thereof;
 
and
 
           
         
         (d) a diacid selected from the group consisting of
       (i) dimer acid having the following structure:   
     
       
     
         [0000]    
       
                 
         
             
             
         
       
       
         
           
             (ii) hydrogenated dimer acid having to the following structure: 
           
         
       
     
         [0000]    
       
                 
         
             
             
         
       
       
         
           
             (iii) a dicarboxylic acid having following structure; 
           
         
       
     
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    wherein;
 
c is an integer ranging from 1 to 10.
 
R is alkyl having 7 to 21 carbon atoms and mixtures thereof.
 
         [0035]    Another aspect of the present invention is a process for conditioning skin, which comprises contacting the skin with an effective conditioning concentration of a polyester made by the reaction of:
   (a) a mono-hydroxy substituted complex ester selected from the group consisting of:
       (i) a pentaerythritol tri-ester having the structure:   
       
 
         [0000]      (R—C(O)—O—CH 2 ) 3 —C—CH 2 OH
       (ii) a dipentaerythritol penta-ester having the structure:       
 
         [0000]    
       
                 
         
             
             
         
       
       
         
           
             (iii) a trimethylol propane di-ester having the structure: 
           
         
       
     
         [0000]    
       
                 
         
             
             
         
       
       
         
           
              wherein R is alkyl having 17 to 21 carbon atoms and mixtures thereof; 
             (iv) and mixtures thereof; 
           
         
         (b) a di-hydroxy substituted complex ester selected from the group consisting of:
       (i) a pentaerythritol di-ester having the structure:   
     
       
     
         [0000]      (R—C(O)—O—CH 2 ) 2 —C—(CH 2 OH) 2  
       (ii) a dipentaerythritol tetra-ester having the structure:       
 
         [0000]    
       
                 
         
             
             
         
       
       
         
           
             (iii) a trimethylol propane di-ester having the structure: 
           
         
       
     
         [0000]    
       
                 
         
             
             
         
       
       
         
           
              wherein R is alkyl having 17 to 21 carbon atoms and mixtures thereof; 
             (iv) and mixtures thereof;
 
and optionally
 
           
         
         (c) a tri-hydroxy substituted complex ester selected from the group consisting of:
       (i) a pentaerythritol monoester having the structure:   
     
       
     
         [0000]      R—C(O)—O—CH 2 —C—(CH 2 OH) 3  
       (ii) a dipentaerythritol tri-ester having the structure:       
 
         [0000]    
       
                 
         
             
             
         
       
       
         
           
              wherein R is alkyl having 17 to 21 carbon atoms and mixtures thereof;
 
and
 
           
         
         (d) a diacid selected from the group consisting of
       (i) dimer acid having the following structure:   
     
       
     
         [0000]    
       
                 
         
             
             
         
       
       
         
           
             (ii) hydrogenated dimer acid having to the following structure: 
           
         
       
     
         [0000]    
       
                 
         
             
             
         
       
       
         
           
             (iii) a dicarboxylic acid having following structure; 
           
         
       
     
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    wherein;
 
c is an integer ranging from 1 to 10;
 
and
   (iv) mixtures thereof.   
 
         [0054]    In the present invention, the mono hydroxyl containing and the di hydroxyl containing ester intermediate are reacted with the proper amount of diacids and linked together to form the polymer of the present invention. 
       Preferred Embodiment 
       [0055]    In a preferred embodiment said mono hydroxy substituted complex ester is a pentaerythritol tri-ester, said dihydroxy substituted complex ester is a dipentaerythritol tetra-ester. 
         [0056]    In a preferred embodiment said mono hydroxy substituted complex ester is a dipentaerythritol penta-ester, said dihydroxy substituted complex ester is a pentaerythritol di-ester and said trihydroxy substituted complex ester is a a pentaerythritol monoester. 
         [0057]    In a preferred embodiment said mono hydroxy substituted complex ester is a dipentaerythritol penta-ester, said di-hydroxy substituted complex ester is a pentaerythritol di-ester. 
         [0058]    In a preferred embodiment said effective conditioning concentration ranges from 0.1% to 15.0% by weight. 
         [0059]    Raw Materials 
         [0060]    Pentaerythritol 
         [0061]    Pentaerythritol is a useful raw material in the synthesis of the compounds of the present invention. They are commercially available from a variety of sources including Sigma Aldrich online at http://www.sigmaaldrich.com. It has the following structure; 
         [0000]    
       
                 
         
             
             
         
       
     
         [0062]    Dipentaerythritol 
         [0063]    Dipentaerythritol is a useful raw material in the synthesis of the compounds of the present invention. They are commercially available from a variety of sources including Sigma Aldrich online at http://www.sigmaaldrich.com. It has the following structure: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0064]    Trimethylol Propane 
         [0065]    Trimethylol propane is a useful raw material in the synthesis of the compounds of the present invention. They are commercially available from a variety of sources including Sigma Aldrich online. It has the following structure: 
         [0000]    
       
                 
         
             
             
         
       
     
       Example 1 
     Dimer Acid 
       [0066]    Dimer acid is an item of commerce available commercially from Cognis Corporation. It has the following structure: 
         [0000]    
       
                 
         
             
             
         
       
     
       Example 2 
     Hydrogenated Dimer Acid 
       [0067]    Hydrogenated dimer acid is an item of commerce available commercially from Henkel Corporation. It conforms to the following structure: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0068]    Dicarboxylic Acid 
         [0069]    Dicarboxylic acid useful as raw materials in the synthesis of the compounds of the present invention are commercially available from a variety of sources including Cognis. They have following structure; 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    wherein;
 
c is an integer ranging from 1 to 10.
 
       Saturated Dicarboxylic Acids 
       [0070]      
         [0000]    
       
         
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                 Common  
                   
                 Molecular  
               
               
                   
                 Example 
                 Name 
                 c 
                 Weight 
               
               
                   
                   
               
             
             
               
                   
                  3 
                 Malonic 
                  1 
                 104 
               
               
                   
                  4 
                 Succinic 
                  2 
                 118 
               
               
                   
                  5 
                 Glutaric 
                  3 
                 132 
               
               
                   
                  6 
                 Adipic 
                  4 
                 146 
               
               
                   
                  7 
                 Pimelic 
                  5 
                 160 
               
               
                   
                  8 
                 Subric 
                  6 
                 174 
               
               
                   
                  9 
                 Azelaic 
                  7 
                 188 
               
               
                   
                 10 
                 Sebacic 
                  8 
                 202 
               
               
                   
                 11 
                 Undecanedioic  
                  9 
                 216 
               
               
                   
                 12 
                 Dodecanedioic  
                 10 
                 230 
               
               
                   
                   
               
             
          
         
       
     
         [0071]    Fatty Acids 
         [0072]    Fatty acids useful in the practice of the present invention are items of commerce commercially available from Cognis. 
         [0073]    Fatty Acid Names 
         [0074]    Fatty acids useful as raw materials in the preparation of compounds of the present invention are commercially available from a variety of sources including Procter and Gamble of Cincinnati Ohio. The structures are well known to those skilled in the art. 
         [0000]      R—C(O)—OH
 
       Saturated 
       [0075]      
         [0000]    
       
         
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                   
                 Common  
                 Molecular  
               
               
                   
                 Example 
                 R Formula 
                 Name 
                 Weight 
               
               
                   
                   
               
             
             
               
                   
                 13 
                 C 7 H 5   
                 Caprylic 
                 144 
               
               
                   
                 14 
                 C 9 H 19   
                 Capric 
                 172 
               
               
                   
                 15 
                 C 11 H 23   
                 Lauric 
                 200 
               
               
                   
                 16 
                 C 13 H 27   
                 Myristic 
                 228 
               
               
                   
                 17 
                 C 14 H 29   
                 Pentadecanoic 
                 242 
               
               
                   
                 18 
                 C 15 H 31   
                 Palmitic 
                 256 
               
               
                   
                 19 
                 C 17 H 35   
                 Stearic 
                 284 
               
               
                   
                 20 
                 C 17 H 35   
                 Isosteric 
                 284 
               
               
                   
                 21 
                 C 19 H 39   
                 Arachidinic 
                 312 
               
               
                   
                 22 
                 C 21 H 43   
                 Behenic 
                 340 
               
               
                   
                 23 
                 C 26 H 53   
                 cetrotic 
                 396 
               
               
                   
                 24 
                 C 33 H 67   
                 geddic acid 
                 508 
               
               
                   
                   
               
             
          
         
       
     
       Unsaturated 
       [0076]      
         [0000]    
       
         
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                   
                 Common  
                 Molecular  
               
               
                   
                 Example 
                 R Formula 
                 Name 
                 Weight 
               
               
                   
                   
               
             
             
               
                   
                 25 
                 C 17 H 33   
                 Oleic 
                 282 
               
               
                   
                 26 
                 C 17 H 31   
                 Linoleic 
                 280 
               
               
                   
                 27 
                 C 17 H 29   
                 Linolenic 
                 278 
               
               
                   
                 28 
                 C 15 H 29   
                 Palmitoleic 
                 254 
               
               
                   
                 29 
                 C 13 H 25   
                 Myristicoleic 
                 226 
               
               
                   
                 30 
                 C 21 H 41   
                 Erucic 
                 338 
               
               
                   
                   
               
             
          
         
       
     
         [0077]    Chain Terminators 
         [0078]    Chain terminators are mono-functional molecules, meaning that they only have one reactive hydroxyl site (the others are esterified). The fact that they have only one reactive site means that they cannot be incorporated into the polymer backbone. The moment a chain terminator reacts in a polymerization, the polymer chain is terminated. Since these mono-functional molecules terminate polymer chains, they are employed in polymer chemistry to control molecular weight and functionalize chain ends. 
         [0079]    General Procedure 
         [0080]    To the specified number of grams of the specified polyol (pentaerythritol, dipentaerythritol or TMP) is added the specified number of grams of the specified fatty acid (examples 13-30). The reaction mixture is heated to 180° C. and held until the acid value fails to drop any further. Product is analyzed and used in the subsequent polymerization step, by reacting it with diacids. 
         [0000]    
       
         
               
               
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 Pentaerythritol  
                 Fatty Acid 
               
             
          
           
               
                   
                 Example 
                 Grams 
                 Example 
                 Grams 
               
               
                   
                   
               
             
          
           
               
                   
                 31 
                 18.5 
                 13 
                 81.5 
               
               
                   
                 32 
                 16.6 
                 14 
                 83.4 
               
               
                   
                 33 
                 15.0 
                 26 
                 85.0 
               
               
                   
                 34 
                 13.8 
                 17 
                 86.2 
               
               
                   
                 35 
                 11.8 
                 20 
                 88.2 
               
               
                   
                 36 
                 8.6 
                 22 
                 91.4 
               
               
                   
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                 Pentaerythritol 
                 Fatty Acid 
               
             
          
           
               
                   
                 Example 
                 Grams 
                 Example 
                 Grams 
               
               
                   
                   
               
               
                   
                 37 
                 59.8 
                 11 
                 190.3 
               
               
                   
                 38 
                 52.3 
                 12 
                 197.8 
               
               
                   
                 39 
                 34.5 
                 18 
                 215.5 
               
               
                   
                 40 
                 34.5 
                 23 
                 215.5 
               
               
                   
                 41 
                 35.0 
                 24 
                 215.0 
               
               
                   
                 42 
                 32.5 
                 19 
                 217.5 
               
               
                   
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                 Dipentaerythritol 
                 Fatty Acid 
               
             
          
           
               
                   
                 Example 
                 Grams 
                 Example 
                 Grams 
               
               
                   
                   
               
               
                   
                 43 
                 65.3 
                 11 
                 184.7 
               
               
                   
                 44 
                 57.0 
                 12 
                 193.0 
               
               
                   
                 45 
                 38.0 
                 18 
                 212.0 
               
               
                   
                 46 
                 38.3 
                 23 
                 211.7 
               
               
                   
                 47 
                 38.8 
                 24 
                 211.2 
               
               
                   
                 48 
                 35.8 
                 19 
                 214.2 
               
               
                   
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                 Dipentaerythritol 
                 Fatty Acid 
               
             
          
           
               
                   
                 Example 
                 Grams 
                 Example 
                 Grams 
               
               
                   
                   
               
               
                   
                 49 
                 50.8 
                 13 
                 199.2 
               
               
                   
                 50 
                 45.5 
                 14 
                 204.5 
               
               
                   
                 51 
                 41.5 
                 26 
                 208.5 
               
               
                   
                 52 
                 38.0 
                 17 
                 212.0 
               
               
                   
                 53 
                 32.5 
                 20 
                 217.5 
               
               
                   
                 54 
                 24.0 
                 22 
                 226.0 
               
               
                   
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                 TMP 
                 Fatty Acid 
               
             
          
           
               
                   
                 Example 
                 Grams 
                 Example 
                 Grams 
               
               
                   
                   
               
               
                   
                 55 
                 62.8 
                 13 
                 187.3 
               
               
                   
                 56 
                 56.8 
                 14 
                 193.3 
               
               
                   
                 57 
                 51.8 
                 26 
                 198.2 
               
               
                   
                 58 
                 47.8 
                 17 
                 202.2 
               
               
                   
                 59 
                 41.3 
                 20 
                 208.7 
               
               
                   
                 60 
                 30.5 
                 22 
                 219.5 
               
               
                   
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                 TMP 
                 Fatty Acid 
               
             
          
           
               
                   
                 Example  
                 Grams 
                 Example 
                 Grams 
               
               
                   
                   
               
               
                   
                 61 
                 79.5 
                 11 
                 170.5 
               
               
                   
                 62 
                 70.0 
                 12 
                 180.0 
               
               
                   
                 63 
                 47.8 
                 18 
                 202.3 
               
               
                   
                 64 
                 48.0 
                 23 
                 202.0 
               
               
                   
                 65 
                 48.5 
                 24 
                 201.5 
               
               
                   
                 66 
                 45.3 
                 19 
                 204.8 
               
               
                   
                   
               
             
          
         
       
     
         [0081]    Monomers 
         [0082]    Monomers are molecules that have two reactive hydroxyl sites (all others are esterified on the molecule). They can be easily polymerized by a diacid. These molecules make up the polymer back-bone and control physical properties of the polymer chain. 
         [0083]    General Procedure 
         [0084]    To the specified number of grams of the specified polyol (pentaerythritol, dipentaerythritol or TMP) is added the specified number of grams of the specified fatty acid (examples 13-30). The reaction mixture is heated to 180° C. and held until the acid value fails to drop any further. Product is analyzed and used in the subsequent polymerization step, by reacting it with diacids. 
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                 Pentaerythritol 
                 Fatty Acid 
               
             
          
           
               
                   
                 Example 
                 Grams 
                 Example 
                 Grams 
               
               
                   
                   
               
               
                   
                 67 
                 25.4 
                 13 
                 74.6 
               
               
                   
                 68 
                 23.0 
                 14 
                 77.0 
               
               
                   
                 69 
                 21.0 
                 26 
                 79.0 
               
               
                   
                 70 
                 19.3 
                 17 
                 80.7 
               
               
                   
                 71 
                 16.7 
                 20 
                 83.3 
               
               
                   
                 72 
                 12.4 
                 22 
                 87.6 
               
               
                   
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                 Pentaerythritol 
                 Fatty Acid 
               
             
          
           
               
                   
                 Example 
                 Grams 
                 Example 
                 Grams 
               
               
                   
                   
               
               
                   
                 73 
                 32.1 
                 11 
                 67.9 
               
               
                   
                 74 
                 28.3 
                 12 
                 71.7 
               
               
                   
                 75 
                 19.3 
                 18 
                 80.7 
               
               
                   
                 76 
                 19.4 
                 23 
                 80.6 
               
               
                   
                 77 
                 19.7 
                 24 
                 80.3 
               
               
                   
                 78 
                 18.3 
                 19 
                 81.7 
               
               
                   
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                 Dipentaerythritol 
                 Fatty Acid 
               
             
          
           
               
                   
                 Example 
                 Grams 
                 Example 
                 Grams 
               
               
                   
                   
               
               
                   
                 79 
                 60.2 
                 13 
                 189.8 
               
               
                   
                 80 
                 54.5 
                 14 
                 195.5 
               
               
                   
                 81 
                 49.7 
                 26 
                 200.3 
               
               
                   
                 82 
                 45.6 
                 17 
                 204.4 
               
               
                   
                 83 
                 39.3 
                 20 
                 210.7 
               
               
                   
                 84 
                 29.2 
                 22 
                 220.8 
               
               
                   
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                 Dipentaerythritol 
                 Fatty Acid 
               
             
          
           
               
                   
                 Example 
                 Grams 
                 Example 
                 Grams 
               
               
                   
                   
               
               
                   
                 85 
                 76.5 
                 11 
                 173.5 
               
               
                   
                 86 
                 67.4 
                 12 
                 182.6 
               
               
                   
                 87 
                 45.6 
                 18 
                 204.4 
               
               
                   
                 88 
                 26.9 
                 23 
                 223.1 
               
               
                   
                 89 
                 46.2 
                 24 
                 203.8 
               
               
                   
                 90 
                 43.2 
                 19 
                 206.8 
               
               
                   
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                 TMP 
                 Fatty Acid 
               
             
          
           
               
                   
                 Example 
                 Grams 
                 Example 
                 Grams 
               
               
                   
                   
               
               
                   
                 91 
                 40.1 
                 13 
                 59.9 
               
               
                   
                 92 
                 37.0 
                 14 
                 63.0 
               
               
                   
                 93 
                 34.4 
                 26 
                 65.6 
               
               
                   
                 94 
                 32.1 
                 17 
                 67.9 
               
               
                   
                 95 
                 28.3 
                 20 
                 71.7 
               
               
                   
                 96 
                 21.8 
                 22 
                 78.2 
               
               
                   
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                 TMP 
                 Fatty Acid 
               
             
          
           
               
                   
                 Example 
                 Grams 
                 Example 
                 Grams 
               
               
                   
                   
               
             
          
           
               
                   
                 97 
                 48.2 
                 11 
                 51.8 
               
               
                   
                 98 
                 43.8 
                 12 
                 56.2 
               
               
                   
                 99 
                 32.1 
                 18 
                 67.9 
               
               
                   
                 100 
                 32.2 
                 23 
                 67.8 
               
               
                   
                 101 
                 32.4 
                 24 
                 67.6 
               
               
                   
                 102 
                 30.6 
                 19 
                 69.4 
               
               
                   
                   
               
             
          
         
       
     
         [0085]    Cross-Linker 
         [0086]    Cross-linkers are molecules that have three or more hydroxyl reactive sites (all other hydroxyl groups are esterified). The molecules can link two or more polymer chains together. Thus the term “cross-link”. These cross-links are bridges linking two polymer chains together. The physical and thermo-properties of the polymer are drastically changed by cross-linking process. As the cross-linking is increased, the polymer chains become less mobile. This loss of mobility causes the polymer to become brittle and decreases solubility. 
         [0087]    General Procedure 
         [0088]    To the specified number of grams of the specified polyol (pentaerythritol, dipentaerythritol or TMP) is added the specified number of grams of the specified fatty acid (examples 13-30). The reaction mixture is heated to 180° C. and held until the acid value fails to drop any further. Product is analyzed and used in the subsequent polymerization step, by reacting it with diacids. 
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                 Pentaerythritol 
                 Fatty Acid 
               
             
          
           
               
                   
                 Example 
                 Grams 
                 Example  
                 Grams 
               
               
                   
                   
               
             
          
           
               
                   
                 103 
                 101.2 
                 13 
                 148.8 
               
               
                   
                 104 
                 93.4 
                 14 
                 156.6 
               
               
                   
                 105 
                 86.7 
                 26 
                 163.3 
               
               
                   
                 106 
                 80.9 
                 17 
                 169.1 
               
               
                   
                 107 
                 71.4 
                 20 
                 178.6 
               
               
                   
                 108 
                 55.2 
                 22 
                 194.8 
               
               
                   
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                 Pentaerythritol 
                 Fatty Acid 
               
             
          
           
               
                   
                 Example 
                 Grams 
                 Example 
                 Grams 
               
               
                   
                   
               
             
          
           
               
                   
                 109 
                 121.4 
                 11 
                 128.6 
               
               
                   
                 110 
                 110.4 
                 12 
                 139.6 
               
               
                   
                 111 
                 80.9 
                 18 
                 169.1 
               
               
                   
                 112 
                 81.3 
                 23 
                 168.7 
               
               
                   
                 113 
                 81.7 
                 24 
                 168.3 
               
               
                   
                 114 
                 77.3 
                 19 
                 172.7 
               
               
                   
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                 Dipentaerythritol 
                 Fatty Acid 
               
             
          
           
               
                   
                 Example 
                 Grams 
                 Example  
                 Grams 
               
               
                   
                   
               
               
                   
                 115 
                 74.4 
                 13 
                 175.6 
               
               
                   
                 116 
                 67.7 
                 14 
                 182.3 
               
               
                   
                 117 
                 62.1 
                 26 
                 187.9 
               
               
                   
                 118 
                 57.3 
                 17 
                 192.7 
               
               
                   
                 119 
                 49.8 
                 20 
                 200.2 
               
               
                   
                 120 
                 37.5 
                 22 
                 212.5 
               
               
                   
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                 Dipentaerythritol 
                 Fatty Acid 
               
             
          
           
               
                   
                 Example 
                 Grams 
                 Example 
                 Grams 
               
               
                   
                   
               
               
                   
                 121 
                 92.6 
                 11 
                 157.4 
               
               
                   
                 122 
                 82.5 
                 12 
                 167.5 
               
               
                   
                 123 
                 57.3 
                 18 
                 192.7 
               
               
                   
                 124 
                 34.6 
                 23 
                 215.4 
               
               
                   
                 125 
                 58.0 
                 24 
                 192.0 
               
               
                   
                 126 
                 54.5 
                 19 
                 195.5 
               
               
                   
                   
               
             
          
         
       
     
         [0089]    Linear Polymers 
         [0090]    General Procedure 
         [0091]    A specified number of grams of monomer (examples 67-102), diacid (examples 3-12), and chain terminator (example 31-66) are added into a reaction flask. The reaction mixture is heated to 180° C. and held until the acid value and molecular weight reach a desired value. The polymer is analyzed and used with out further purification. 
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
               
               
                   
                 Monomer 
                 Diacid 
                 Chain Terminator 
               
             
          
           
               
                 Example 
                 Example 
                 Grams 
                 Example 
                 Grams 
                 Example 
                 Grams 
               
               
                   
               
             
          
           
               
                 127 
                 67 
                 126.3 
                 4 
                 30.5 
                 34 
                 93.1 
               
               
                 128 
                 68 
                 174.7 
                 6 
                 45.2 
                 35 
                 30.1 
               
               
                 129 
                 77 
                 151.1 
                 9 
                 49.3 
                 37 
                 49.6 
               
               
                 130 
                 78 
                 177.0 
                 12 
                 57.5 
                 38 
                 15.5 
               
               
                 131 
                 81 
                 127.8 
                 1 
                 72.0 
                 49 
                 50.2 
               
               
                 132 
                 82 
                 153.8 
                 2 
                 69.9 
                 54 
                 26.3 
               
               
                 133 
                 85 
                 127.8 
                 4 
                 19.9 
                 45 
                 102.7 
               
               
                 134 
                 86 
                 186.7 
                 6 
                 30.4 
                 46 
                 33.0 
               
               
                 135 
                 95 
                 126.7 
                 9 
                 60.3 
                 56 
                 63.1 
               
               
                 136 
                 96 
                 166.8 
                 12 
                 65.6 
                 57 
                 17.6 
               
               
                 137 
                 99 
                 73.9 
                 1 
                 127.3 
                 65 
                 48.8 
               
               
                 138 
                 100 
                 92.7 
                 2 
                 140.8 
                 66 
                 16.5 
               
               
                   
               
             
          
         
       
     
         [0092]    Cross-Linked Polymer General Procedure 
         [0093]    A specified number of grams of monomer (examples 67-102), diacid (examples 3-12), chain terminator (example 31-66), and cross-linker (examples 103-126) are added into a reaction flask. The reaction mixture is heated to 180° C. and held until the acid value and molecular weight reach a desired value. The polymer is analyzed and used with out further purification. 
         [0000]    
       
         
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
             
           
               
                   
               
               
                   
                 Monomer 
                 Diacid 
                 Cross-linker 
                 Chain Terminator 
               
             
          
           
               
                 Example 
                 Example 
                 Grams 
                 Example 
                 Grams 
                 Example 
                 Grams 
                 Example 
                 Grams 
               
               
                   
               
             
          
           
               
                 139 
                 67 
                 102.8 
                 4 
                 36.3 
                 103 
                 94.8 
                 34 
                 16.1 
               
               
                 140 
                 68 
                 166.7 
                 6 
                 47.6 
                 104 
                 30.2 
                 35 
                 5.4 
               
               
                 141 
                 77 
                 122.8 
                 9 
                 58.4 
                 113 
                 50.4 
                 37 
                 18.5 
               
               
                 142 
                 78 
                 135.1 
                 12 
                 72.4 
                 114 
                 15.8 
                 38 
                 26.6 
               
               
                 143 
                 81 
                 99.5 
                 1 
                 81.8 
                 117 
                 48.8 
                 49 
                 19.9 
               
               
                 144 
                 82 
                 145.0 
                 2 
                 72.7 
                 118 
                 26.1 
                 54 
                 6.1 
               
               
                 145 
                 85 
                 98.7 
                 4 
                 22.5 
                 124 
                 99.6 
                 45 
                 29.2 
               
               
                 146 
                 86 
                 176.3 
                 6 
                 30.2 
                 125 
                 10.8 
                 46 
                 32.8 
               
               
                 147 
                 95 
                 99.1 
                 9 
                 68.8 
                 105 
                 61.7 
                 56 
                 20.5 
               
               
                 148 
                 96 
                 127.8 
                 12 
                 83.0 
                 110 
                 17.9 
                 57 
                 21.4 
               
               
                 149 
                 99 
                 49.0 
                 1 
                 123.2 
                 119 
                 40.5 
                 65 
                 37.4 
               
               
                 150 
                 100 
                 83.0 
                 2 
                 139.1 
                 126 
                 15.6 
                 66 
                 12.2 
               
               
                   
               
             
          
         
       
     
         [0094]    Co-Polymer General Procedure 
         [0095]    A specified number of grams of monomer 1 (examples 67-102), monomer 2 (examples 67-102), diacid (examples 3-12), and chain terminator (example 31-66) are added into a reaction flask. The reaction mixture is heated to 180° C. and held until the acid value and molecular weight reach a desired value. The polymer is analyzed and used with out further purification. 
         [0000]    
       
         
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                   
               
               
                   
                   
                   
                   
                   
                 Chain 
               
               
                   
                 Monomer 1 
                 Monomer 2 
                 Diacid 
                 Cross-Link 
                 Terminator 
               
             
          
           
               
                 Example 
                 Example 
                 Grams 
                 Example 
                 Grams 
                 Example 
                 Grams 
                 Example 
                 Grams 
                 Example 
                 Grams 
               
               
                   
               
             
          
           
               
                 151 
                 67 
                 101.3 
                 100 
                 35.7 
                 4 
                 19.7 
                 103 
                 0.0 
                 34 
                 93.3 
               
               
                 152 
                 68 
                 159.1 
                 99 
                 12.5 
                 6 
                 48.0 
                 104 
                 0.0 
                 35 
                 30.5 
               
               
                 153 
                 77 
                 75.7 
                 96 
                 67.1 
                 9 
                 57.5 
                 113 
                 0.0 
                 37 
                 49.7 
               
               
                 154 
                 78 
                 95.6 
                 95 
                 60.9 
                 12 
                 76.8 
                 114 
                 0.0 
                 38 
                 16.7 
               
               
                 155 
                 81 
                 27.2 
                 86 
                 80.1 
                 1 
                 89.3 
                 117 
                 0.0 
                 49 
                 53.3 
               
               
                 156 
                 82 
                 132.1 
                 85 
                 78.9 
                 2 
                 125.9  
                 118 
                 0.0 
                 54 
                 45.2 
               
               
                 157 
                 85 
                 69.4 
                 82 
                 38.8 
                 4 
                 21.1 
                 124 
                 27.4 
                 45 
                 93.4 
               
               
                 158 
                 86 
                 153.6 
                 81 
                 29.4 
                 6 
                 24.5 
                 125 
                 10.5 
                 46 
                 31.9 
               
               
                 159 
                 95 
                 44.5 
                 78 
                 61.8 
                 9 
                 69.9 
                 105 
                 18.4 
                 56 
                 55.4 
               
               
                 160 
                 96 
                 13.6 
                 77 
                 138.4 
                 12 
                 66.5 
                 110 
                 17.1 
                 57 
                 14.4 
               
               
                 161 
                 99 
                 11.5 
                 68 
                 49.1 
                 1 
                 116.0 
                 119 
                 35.2 
                 65 
                 38.1 
               
               
                 162 
                 100 
                 8.3 
                 67 
                 95.7 
                 2 
                 131.3 
                 126 
                 0.0 
                 66 
                 14.7 
               
               
                   
               
             
          
         
       
     
         [0096]    Applications 
         [0097]    The ability to regulate the structure of compounds allows for the preparation of products that have unique properties in skin and sun care. The compounds of the present invention are used to provide a water-resistant film that holds actives on the skin. 
         [0098]    The ability to regulate the location of the oil soluble groups in the polymer allows for the alteration of the Partition Coefficient, which determines the solubility of the various actives in the polymer. This ability to alter the partition coefficient of the polymer allows for the ability to engineer a polymer for the specific active that one decides to place on the skin. We refer to these polymers are partition coefficient technology polymers. 
         [0099]    Additionally, the ability to place different polyol types in the terminal or internal groups positions of the polymer allows unique products for a slower release of actives. The more “internal” the liquid polymer portion the more “shielded” the active dissolved therein. 
         [0100]    The understanding that the monomers need to be premade then reacted with the diacid is absolutely critical in avoiding a gel, which renders the product non-usable. Specifically the mono-hydroxy monomer (chain terminator), di-hydroxy monomer (chain extender) and the tri-hydroxy monomer (crosslinker) will make the products of the present invention unique in both the functional and aesthetics provided on the skin. 
         [0101]    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 herein above 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.

Technology Classification (CPC): 2