Patent Publication Number: US-2001000524-A1

Title: Carboxylated polymers complexes

Description:
RELATED APPLICATION  
     1. This application is a divisional patent application of co-pending Ser. No. 09/425,896 filed Oct. 25, 1999.  
    
    
     
       BACKGROUND OF THE INVENTION  
       2. 1. Field of the Invention  
       3. The present invention deals with the composition, and application of novel carboxylated polymers, and complexes thereof. The complexes useful as softening, anti-tangle, and conditioning agents for use in personal care applications due to their outstanding mildness. The properties of these novel compounds that makes them well suited for these applications is the fact that they are substantive to fibers, hair and skin and also very mild to the skin and eyes and provide protection from environmental factors like acid rain and other pollutions which come in contact with hair and skin. The use of the complex results in several additional desirable properties heretofore unattainable. This includes overcoming the problem of eye and skin irritation using traditional cationic conditioning agents.  
       4. 2. Arts and Practices  
       5. U.S. Pat. No. 5,162,472 to O&#39;Lenick discloses free radical polymers which incorporate silicone into the backbone. While these materials have desirable properties, they do not form monolayers on the hair nor do they provide protection to the hair.  
       6. The formation of a high molecular weight polymeric complex results in less penetration of the skin by the compounds of the present invention and a very effective conditioner that remains on the surfact of the hair or skin where the conditioning agent is most effective.  
       7. The references cited herein are incorporated by reference to the extent applicable. Ratios and percentages are by weight and temperatures are Celsius unless otherwise stated.  
       THE INVENTION  
       Object of the Invention  
       8. It is the object of the current invention to provide a novel series of anionic free radical polymers and complexes thereof with cationic compounds. The formation of a high molecular weight polymeric complex results in less penetration of the skin by the compounds of the present invention and a very effective conditioner that remains on the surfact of the hair or skin where the conditioning agent is most effective.  
       9. It is another object of the current invention to provide a novel allyl alkoxy carboxylate used as an intermediate in the preparation of the compounds of the present invention.  
       10. It is still another objective of the current invention to provide personal care compositions which contain an effective conditioning amount of the compounds of the current invention. That effective conditioning concentration will vary from 0.1 to 20% of the composition. The compounds of the present invention have outstanding conditioning properties when applied to hair and skin.  
       SUMMARY OF THE INVENTION  
       11. The present invention is directed to free radical polymers which contain a carboxyl group as one of the functional groups polymerized. The compounds of the invention are prepared by the free radical polymerization of a novel allyl carboxy monomer.  
       12. The carboxy functional allyl monomer is polymerized and subsequently complexed with a variety of quaternary compounds to form the conditioning quats of the present invention.  
       13. The allyl alkoxy carboxylate used to make the compounds of the present invention conform to the following structure:  
       CH 2 ═CH—CH 2 —O—(CH 2 CH 2 O) a —(CH 2 CH(CH 3 )O) b —(CH 2 CH 2 O) c —R 1    
       14. wherein:  
       15. a, b and c are integers each independently ranging from 0 to 20;  
       16. R 1  is selected from the group consisting of;  
                 
 
       17. The compounds are made by the reaction of allyl alcohol alkoxylates, which are commercially available with succinic anhydride, maleic anhydride and phthalic anhydride.  
                 
 
       18. wherein R 1  is —C(O)—CH 2 —CH 2 —C(O)—OH.  
       19. The same reaction is conducted with maleic anhydride and phthalic anhydride to give the other compounds.  
                 
 
       20. wherein R 1  is —C(O)—CH 2 ═CH 2 —C(O)—OH.  
                 
 
                 
 
       21. These allyl alkoxy carboxylates are key materials to synthesise the carboxy polymers that are used to make the ultimate complex. The carboxy polymers conform to the following structure;  
                 
 
       22. wherein;  
       23. R 2  is CH 2 CH 2 —CH 2 —O—(CH 2 CH 2 O) a —(CH 2 CH(CH 3 )O) b —(CH 2 CH 2 O) c —R 1    
       24. e is an integer from 10 to 2,000.  
       25. The compounds of the current invention are prepared by the free radical reaction of the allyl alkoxy carboxylate containing monomer.  
       COMPLEX  
       26. The complex compound of the present invention conform to the following structure;  
                 
 
       27. wherein;  
       28. R 2  is CH 2 CH 2 —CH 2 —O—(CH 2 CH 2 O) a —(CH 2 CH(CH 3 )O) b —(CH 2 CH 2 O) c —R 3    
       29. R 3  is selected from the group consisting of;  
                 
 
       30. and  
                 
 
       31. e is an integer from 10 to 2,000.  
       PREFERRED EMBODIMENTS  
       32. In a preferred embodiment of the allyl alkoxy carboxylate R 1  is —C(O)—CH 2 —CH 2 —C(O)—OH.  
       33. In a preferred embodiment of the allyl alkoxy carboxylate R 1  is —C(O)—CH═CH—C(O)—OH.  
       34. In a preferred embodiment of the allyl alkoxy carboxylate  
                 
 
       35. In a preferred embodiment of the allyl alkoxy carboxylate x, y, and z are each 0.  
       36. In a preferred embodiment of the allyl alkoxy carboxylate x ranges from 7 to 15 y is 0 and z is 0.  
       37. In a preferred embodiment of the carboxy polymer R 1  is —C(O)—CH 2 —CH 2 —C(O)—OH.  
       38. In a preferred embodiment of the carboxy polymer R 1  is —C(O)—CH═CH—C(O)—OH.  
       39. In a preferred embodiment of the carboxy polymer  
                 
 
       40. In a preferred embodiment of the carboxy polymer x, y, and z are each 0.  
       41. In a preferred embodiment of the carboxy polymer x ranges from 7 to 15 y is 0 and z is 0.  
       42. In a preferred embodiment of the complex R 3  is  
                 
 
       43. In a preferred embodiment of the complex R 3  is  
                 
 
       44. In a preferred embodiment of the complex R 3  is  
                 
 
       45. In a preferred embodiment of the complex R 4  is CH 3 .  
       46. In a preferred embodiment of the complex R 4  is CH 3 .  
     
    
    
     EXAMPLES   
     47.                              Raw Materials       Allyl Alcohol Alkoxylates       These compounds conform to the following structure:       CH 2 ═CH—CH 2 —O—(CH 2 CH 2 —O) x —(CH 2 CH(CH 3 )CH 2 —O) y —(CH 2 CH 2 —O) z —H                                     Example Number   x   y   z                                                 1   0   0   0           2   0   1   0           3   4   0   0           4   7   0   0           5   10   0   0           6   20   0   0           7   4   7   10           8   7   4   20           9   10   20   4           10   20   10   7           11   20   20   20           12   7   7   7                        
     48. These materials are items of commerce available commercially from Siltech Corporation Toronto Ontario Canada, and Pelron Corporation Chicago Ill.  
     Preparation of Allyl Alkoxy Carboxylates  
     49. General Procedure  
     50. Carboxy allyl alkoxylates are prepared by the reaction of the allyl alcohol alkoxylates example 1-12 with one mole of anhydride. The reaction mass is heated to 80 to 100° C. and the theoretical amount of water is stripped off.  
     Succinic Anhydride Examples  
     51. To 103.0 grams of succinic anhydride is added to a clean glass vessel equipped with agitation and a thermometer. Next, the specified amount of the specified allyl alkoxylate Examples 1-12 is added. The reaction mass is heated to 80 to 100 C. and the theoretical amount of water distills off. The allyl carboxylic ester is used without additional purification.  
     Examples 13-32   
     52.                                                              Allyl Alkoxylate                   Grams   Example Number                       Example 13   58.0   1           Example 14   102.0   2           Example 15   234.0   3                           Allyl alkoxylate   Allyl alkoxylate               Grams   Example Number                       Example 16   366.0   4           Example 17   498.0   5           Example 18   938.0   6           Example 19   1087.0   7           Example 20   1718.0   8           Example 21   1912.1   9           Example 22   1836.2   10           Example 23   2998.3   11           Example 24   1087.0   12                        
     Maleic Anhydride Examples  
     53. To 101.0 grams of maleic anhydride is added to a clean glass vessel equipped with agitation and a thermometer. Next, the specified amount of the specified intermediate Examples 1-12 is added. The reaction mass is heated to 80 to 100 C. and the theoretical amount of water distills off. The allyl carboxylic ester is used without additional purification.  
     Examples 25-36   
     54.                                                   Allyl Alkoxylate   Allyl Alkoxylate           Grams   Example Number                                                        Example 25   58.0   1           Example 26   102.0   2           Example 27   234.0   3           Example 28   366.0   4           Example 29   498.0   5           Example 30   938.0   6           Example 31   1087.0   7           Example 32   1718.0   8           Example 33   1912.1   9           Example 34   1836.2   10           Example 35   2998.3   11           Example 36   1087.0   12                        
     Examples 37-48  
     Phthalic Anhydride Examples  
     55. To 146.0 grams of phthalic anhydride is added to a clean glass vessel equipped with agitation and a thermometer. Next, the specified amount of the specified intermediate Examples 1-12 is added. The reaction mass is heated to 80 to 100 C. and the theoretical amount of water distills off. The allyl carboxylic ester is used without additional purification.  
                                                   Allyl alkoxylate   Allyl alkoxylate           Grams   Example Number                                                        Example 37   58.0   1           Example 38   102.0   2           Example 39   234.0   3           Example 40   366.0   4           Example 41   498.0   5           Example 42   938.0   6           Example 43   1087.0   7           Example 44   1718.0   8           Example 45   1912.1   9           Example 46   1836.2   10           Example 47   2998.3   11           Example 48   1087.0   12                      
 
     Preparation of Carboxy Polymers  
     Examples 49-84  
     56. General Polymerization Procedure  
     57. The polymerization of the allyl carboxy compound is achieved by utilizing free radical catalyst in a low oxygen containing solvent, most commonly water. The water is deionized and sparged with nitrogen to remove dissolved oxygen contained therein immediately prior to use. Then, the specified amount of the treated de-ionized water is added to a suitable glass vessel. Most commonly, 50 to 80% of the total weight of the batch is water. The specified amount of the specified monomers are then added under agitation. Nitrogen is continuously sparged and the temperature is raised to about 50 C. Once the temperature has reached 50 and the nitrogen has been bubbled through the reaction mass for thirty minutes, a free radical initiator is added. Many peracids, like t-butyl-perbenzoate, t-butyl-hydroperoxide and inorganic free radical initiators like stannic chloride can be used. The preferred initiator is azobisisobutylnitrile. The reaction is exothermic and cooling is used to keep the temperature below 90 C.  
     58. The molecular weight is monitored by viscosity and both increase as the reaction continues.  
     Example 49  
     59. To the 5,000 grams of deionized water, which has just been spargred with nitrogen for 30 minutes, is added the specified amount 5,000 grams of the specified allyl carboxy monomer Ex # 13 under good agitation and nitrogen sparge. The temperature is raised to about 50 C. Once the temperature has reached 50 and the nitrogen has been bubbled through the reaction mass for thirty minutes, 0.05% by weight of batch of azobisisobutylnitrile. The catalyst may be optimally added in smaller increments of one quarter of the total needed waiting 30 minutes between additions. The viscosity will raise as the polymerization occurs. The temperature raises to about 90 C. and is cooled with cooling water as needed to prevent the temperature from reaching 90 C. The molecular weight is controlled by viscosity. When the desired visocity is achieved, air is bubbled through the vessel to quench the polymer. The desired polymer is used as prepared.  
     Examples 50-84  
     60. Example 49 is repeated only substituting the allyl carboxy monomer for example 13 used in example 49.  
                                               Final Viscosity       Example   Allyl Carboxy Example   (centipose)                                            50   14   100       51   15   500       52   16   1000       53   17   2000       54   18   500       55   19   700       56   20   1200       57   21   5000       58   22   500       59   23   50       60   24   1250       61   25   1375       62   26   5000       63   27   8250       64   28   1000       65   29   500       66   30   800       67   31   2500       68   32   5000       69   33   7000       70   34   9000       71   35   100       72   36   500       73   37   900       74   38   1250       75   39   1450       76   40   780       77   41   6000       78   42   8000       79   43   7500       80   44   1500       81   45   280       82   46   1350       83   47   4000       84   48   1000                  
 
     Polymeric Complexes  
     61. Cationic Component  
     Stearalkonium Chloride  
     62. Stearalkonium Chloride is an item of commerce available from a variety of sources. One such source is Henkel Corporation in Hoboken N.J..  
     63. Stearylalkonium chloride is also known as n,n-dimethyl, n-stearyl, n benzyl ammonium chloride and conforms to the following structure:  
                 
 
     64. Stearyl trimethyl ammonium chloride  
     65. Stearyl trimethyl ammonium chloride is an item of commerce available from a variety of sources. One such source is Henkel Corporation in Hoboken N.J..  
     66. Stearyl trimethyl ammonium chloride is also known as n,n, n-trimethyl,n-stearyl ammonium chloride and conforms to the following structure:  
                 
 
     Preparation of Complex  
     Example 85  
     67. The polymers of the present invention (examples 51-84) are typically prepared solutions ranging in concentrations of between 10 and 55% solids. The examples given use a 50% solid product.  
     68. To 410.0 grams of the 50% solution of polymer example 50 is added 500 grams of water. The resulting solution is heated to 80 C. In a separate container the quaternary compound is heated to 80 C. The molten quat is added to the hot polymer solution under good agitation. The pH is adjusted to 7.0 using NaOH 50%. The result is a clear homogenous complex of quaternary and carboxy polymer.  
     Examples 86-119  
     69. Example 85 is repeated, only this time the specified number of grams of the specified polymer example replaces the polymer used in example 85. 500 grams of water is added. The resulting solution is heated to 80 C. In a separate container the quaternary compound is heated to 80 C. The molten quat is added to the hot polymer solution under good agitation. The pH is adjusted to 7.0 using NaOH 50%. The result is a clear homogenous complex of quaternary and carboxy polymer.  
                                                  Carboxy Polymer   Quaternary Compound                                 Example   Grams   Example   type   Grams                                         86   674.0   51   stearalkonium   424.0                   chloride       87   572.0   52   stearalkonium   424.0                   chloride       88   704.0   53   stearalkonium   424.0                   chloride       89   2082.0   54   stearalkonium   424.0                   chloride       90   1293.0   55   stearalkonium   424.0                   chloride       91   3642.0   56   stearalkonium   424.0                   chloride       92   2118.0   57   stearalkonium   424.0                   chloride       93   3878.0   58   stearalkonium   424.0                   chloride       94   6202.6   59   stearalkonium   424.0                   chloride       95   2380.0   60   stearalkonium   424.0                   chloride       96   318.0   61   stearalkonium   424.0                   chloride       97   406.0   62   stearalkonium   424.0                   chloride       98   670.0   63   stearalkonium   424.0                   chloride       99   934.0   64   stearalkonium   424.0                   chloride       100   1198.0   65   stearalkonium   424.0                   chloride       101   2978.0   66   stearalkonium   424.0                   chloride       102   2376.0   67   stearyltrimethyl   348.0                   ammonium chloride       103   1920.0   68   stearyltrimethyl   348.0                   ammonium chloride       104   4026.0   69   stearyltrimethyl   348.0                   ammonium chloride       105   3874.0   70   stearyltrimethyl   348.0                   ammonium chloride       106   6198.0   71   stearyltrimethyl   348.0                   ammonium chloride       107   2466.0   72   stearyltrimethyl   348.0                   ammonium chloride       108   408.0   73   stearyltrimethyl   348.0                   ammonium chloride       109   496.0   74   stearyltrimethyl   348.0                   ammonium chloride       110   760.0   75   stearyltrimethyl   348.0                   ammonium chloride       111   1024.0   76   stearyltrimethyl   348.0                   ammonium chloride       112   1288.0   77   stearyltrimethyl   348.0                   ammonium chloride       113   2168.0   78   stearyltrimethyl   348.0                   ammonium chloride       114   2466.0   79   stearyltrimethyl   348.0                   ammonium chloride       115   3728.0   80   stearyltrimethyl   348.0                   ammonium chloride       116   4116.0   81   stearyltrimethyl   348.0                   ammonium chloride       117   3965.0   82   stearyltrimethyl   348.0                   ammonium chloride       118   3144.3   83   stearyltrimethyl   348.0                   ammonium chloride       119   1233.0   84   stearyltrimethyl   348.0                   ammonium chloride                  
 
     Applications Examples  
     70. The polymers of the present invention are very substantive conditioners to the hair and are surprisingly mild to the skin and eyes. Eye irritation is a major concern in the formulation of personal care products, particularly when working with quats. Primary eye irritation was tested using the protocol outlined in FHSLA 16 CFR 1500.42. The products were tested at 25% actives. The results were as follows:  
                                                       Compound   Score   Description                                                        Stearyl trimethyl   106.0   Severely Irritating           ammonium chloride           Example 102   8.3   Minimally Irritating           Example 115   6.2   Minimally Irritating           Stearalkonium Chloride   116.5   Severely Irritating           Example 87   11.3   Minimally                   Irritating           Example 89   6.0   Minimally                   Irritating                      
 
     71. As the data clearly shows, the irritation potential of the complex is dramatically reduced, when compared to the starting quat.