Patent Publication Number: US-4220581-A

Title: Castor based quaternaries

Description:
BACKGROUND OF THE INVENTION 
     The cationic quaternary type of fatty derivation based on coconut, soybean or tallow fats has been the basis for the development of textile softening agents and/or cosmetic ingredients and other industrial uses. A typical tallow derived softening agent is the distearyl dimethyl quaternary ammonium chloride structure as indicated: 
     
         [(CH.sub.3).sub.2 --N--(C.sub.18 H.sub.37).sub.2 ].sup.+ Cl.sup.- 
    
     This is usually offered as a paste form at 75% solids in isopropanol or in lower dilutions in a mixture of isopropanol and water. This product has a very limited degree of water solubility, and exhibits irritation properties. Alternate methods employ an amide route including ethoxylation to develop other tallow based derivatives of higher polarity for improved water solubility, see U.S. Pat. No. 2,459,088. This is illustrated for another stearyl type quaternary: ##STR1## Compounds of this type have improved water solubility and softening properties. However, they are also fairly irritating. One recent development is the utilization of Lanolin fatty acids as a route for improving the irritation properties but this occurs at the expense of water solubility. A typical quaternary of this technology is illustrated: ##STR2## where Lan is defined as the mixed higher molecular weight fatty acids derived from Lanolin or wool fat. 
     In contrast to the prior art, the instant invention is directed to quaternized castor fatty acid based amido-amines prepared by (1) condensing a castor fatty acid with the amido protons of a diamine containing a tertiary amino group at one end to form a fatty amido-amine intermediate and then (2) quaternizing this intermediate with a quaternizing agent, and to these compounds used as softeners and fixatives. This invention takes advantage of the unique emollient and lubricating properties of the castor fatty acids which contain hydroxy groups capable of imparting extra softening, e.g. in textiles, and fixative properties so that the compounds do not easily wash out. Additionally the compounds have a high degree of water solubility and are not irritating. These properties are particularly useful in textile and cosmetic formulations such as fabric softeners, hair shampoos, etc. Unique cosmetic properties are also associated with compounds based upon castor based fattty acids which do not contain the hydroxy group and these compounds are included in this disclosure. 
     The castor based fatty acids preferably employed in the instant invention are ricinoleic acid, 12-hydroxystearic acid, and ethoxylated or propoxylated derivatives of ricinoleic acid or 12-hydroxystearic acid. Undecylenic acid, heptanoic acid and DCO fatty acids also can be used to produce compounds of this invention. 
     The general formula for the amido-amine intermediate condensation product derived from the fatty acid is illustrated by the following typical reaction: ##STR3## 
     In general, amines having the formula: ##STR4## where 
     n=1 to 10; 
     R 1  =H, saturated alkyl groups of CH 3  through C 10  H 21 , or alkenyl groups of C 2  H 4  through C 10  H 20  ; and, R 2  and R 3  can be the same as R 1  ·R 1 , R 2  and R 3  do not have to be the same but are independently selected. Substituted aminopropylamines where n is three, particularly alkyl substituted, e.g. dialkyl substituted aminopropylamines are a preferred class of amines. N,N-dimethylaminopropylamine having the formula: ##STR5## is typical. 
     The quaternizing agents which can be used in this invention include benzyl chloride or alkyl chlorides, bromides, phosphates and sulfates, such as dimethyl sulfate, dimethyl bromide and diethylsulfate. 
     The quaternary compounds of this invention can be represented by the formula: ##STR6## where: n, R 1 , R 2  and R 3  have the meanings described above; R 4  =12-hydroxystearyl, ricinoleyl, 12-(2-hydroxypropyloxy) stearyl, 12-(2-hydroxyethyloxy) stearyl, 12-(2-hydroxyethyloxy)oleyl 12-(2-hydroxypropyloxy) oleyl, undecylenyl, heptanoyl, or 9, 11-linoleyl; R 5  =benzyl or alkyl of 1 to 3 carbon atoms; and M=chloride, bromide, phosphate or sulfate. The 12-hydroxystearic acid and ricinoleyl acid derivatives are used to produce preferred water-soluble quaternary compounds in accordance with this invention. 
     It is preferred to carry out the reaction in the presence of a solvent such as, for example, propylene glycol or isopropanol. Although various amounts of solvent can be employed, it has been found that about 70-75% by weight is preferred. The reactions can be carried out without a solvent, however, gelatinous end products may result which is generally undesirable. 
     The reactions can be carried out at various temperatures; however, temperatures from about 50° to 90° C. are most satisfactory. The following general reaction illustrating the quaternization of the amido-amine intermediate with benzyl chloride, a preferred agent, is typical: ##STR7## 
     In order to describe the instant invention more thoroughly, the following examples are presented: 
    
    
     EXAMPLE 1 
     Production of γ-Ricinoleamidopropyl-dimethyl-benzyl ammonium chloride: 
     (a) Stage 1: Preparation of γ-Ricinoleamidopropyldimethylamine. 
     383 g (3.75 moles) of N,N-dimethylaminopropylamine were mixed with 1,043 g of commercial ricinoleic acid (3.5 moles) and heated to 180°-185° C. in a 5 liter reactor. The water of reaction is removed and the reaction is continued until a minimum acid value is attained. The product was then vacuum dried at 100°-105° C. at 50 mm vacuum. The amido-amide intermediate, γ-Ricinoleamidopropyldimethylamine, had the following properties: 
     
         ______________________________________                                    
Amine Value         146                                                   
Acid Value          4.5                                                   
Neutralization Equiv.                                                     
                    383 (theory 382)                                      
Appearance          Amber Clear Liquid                                    
Yield g.            1274                                                  
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     (b) Stage 2: Preparation of γ-Ricinoleamidopropyl-dimethylbenzyl ammonium chloride. 
     1,266 g (3.305 moles) of the amido-amine intermediate, γ-Ricinoleamidopropyl-dimethylamine, were mixed with 430 g of benzyl chloride (3.386 moles), 712 g propylene glycol and 48 g sodium bicarbonate. The mixture contained 72% solids. The mixture was heated to 70°-80° C. and allowed to react for 3 hours. Samples were removed periodically to determine the percentages of free amine and amine hydrochloride. When the minimum amounts were obtained, the batch was cooled to 25° C. and filtered to remove the inorganic salts. The product had the following properties: 
     
         ______________________________________                                    
Free Amine, %       2.99                                                  
Amine Hydrochloride, %                                                    
                    0.13                                                  
Spec. Grav., 25° C.                                                
                    1.022                                                 
Density, lbs./gal.  8.48                                                  
Ash, %              0                                                     
Viscosity, Strokes, 25° C.                                         
                    15.3                                                  
Appearance          Amber Clear Liquid                                    
Yield g             2,333                                                 
pH, 10% Aqueous Soln.                                                     
                    6.9-7.1                                               
______________________________________                                    
 
    
     γ-Ricinoleamidopropyl-dimethyl-benzyl ammonium chloride (Compound 1) is utilized in hair use products and textile softening agents to impart extra softening and fixative properties. The following formulations are typical: 
     
         ______________________________________                                    
Creme Rinse:                                                              
 Lauryl dimethyl amine oxide                                              
                      1-3 parts                                           
Compound 1, 70% active cationic                                           
                      3-4 parts                                           
Lanolin alcohol ethoxylates                                               
                      2-4 parts                                           
Water                 q.s.                                                
Shampoo:                                                                  
 Sodium lauryl ether sulfate,                                             
                      25-30 parts                                         
  40% active                                                              
Coco diethanol amide  3.5-5 parts                                         
Compound 1, 70% active cationic                                           
                      2-4.0 parts                                         
Wilson&#39;s Protein WSP X-250                                                
                      2-4.0 parts                                         
Preservative          0.1-0.2 parts                                       
EDTA                  0.1-0.25 parts                                      
Water                 q.s. to 100                                         
______________________________________                                    
 
    
     EXAMPLE 2 
     Production of γ-12-Hydroxystearamidopropyl-dimethylbenzyl ammonium chloride: 
     (a) Stage 1: Preparation of γ-12-Hydroxystearamidopropyl-dimethylamine. 
     655 g (6.42 moles) of N,N-dimethylaminopropylamine were mixed with 1800 g (6 moles) of 12-hydroxystearic acid and heated to 180°-185° C. in a 5 liter reactor. The water of reaction is removed and the reaction is continued until a minimum acid value is obtained. The product was then vacuum dried at 100°-105° C. at 50 mm vacuum. The amido-amide intermediate product, γ-12-Hydroxystearamidopropyl-dimethylamine, had the following properties: 
     
         ______________________________________                                    
Amine Value          144                                                  
Acid Value           5.1                                                  
Neutralization Equiv.                                                     
                     389 (theory 384)                                     
Appearance           Light Tan Wax                                        
Yield g              2248                                                 
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     (b) Stage 2: Preparation of γ-12-Hydroxystearamidopropyldimethyl-benzyl ammonium chloride. 
     1751 g (4.5 moles) of this intermediate product, γ-12-Hydroxystearamidopropyl-dimethylamine, were mixed with 587 g of benzyl chloride (4.62 moles), 981 g propylene glycol and 66 g sodium bicarbonate. The mixture contained 72% solids. The mixture was heated to 70°-80° C. and allowed to react for 5 hours. Samples were removed periodically to determine the percentages of free amine and amine hydrochloride. When the minimum amounts were obtained, the warmed product was filtered to remove the inorganic salts. The product has the following properties: 
     
         ______________________________________                                    
Free Amine, %         2.61                                                
Amine Hydrochloride, %                                                    
                      0.16                                                
Spec. Grav., 25° C.                                                
                      1.012                                               
Density, lbs./gal.    8.43                                                
Melting Point, °C.                                                 
                      66                                                  
Ash, %                0                                                   
Viscosity, Stokes, 100° C.                                         
                      0.4                                                 
Appearance            Soft White Wax                                      
Yield g               3,291                                               
pH, 10% Aqueous Soln. 7.4-7.5                                             
______________________________________                                    
 
    
     γ-12-Hydroxystearamidopropyl-dimethyl-benzyl ammonium chloride (Compound 2) is utilized in hair care products, having the formulations of Example 1, and textile softening agents. The following textile formulation is typical: 
     
         ______________________________________                                    
 Fabric Softener:                                                         
______________________________________                                    
  Compound 2, 70% active cationic                                         
                      3-5 parts                                           
  EDTA                0.1-0.25 parts                                      
  Water               q.s. to 100 parts                                   
______________________________________                                    
 
    
     EXAMPLE 3 
     Production of γ-10-Undecylenamidopropyl-dimethyl-benzyl ammonium chloride: 
     (a) Stage 1: Preparation of γ-10-Undecylenamidopropyl-dimethylamine. 
     956 g (9.37 moles) of N,N-dimethylaminopropylamine were mixed with 1,610 g (8.75 moles) of undecylenic acid and heated to 180°-185° C. in a 5 liter reactor. The water of reaction is removed and the reaction is continued until a minimum acid value is obtained. The product was then vaccum dried at 100°-105° C. at 50 mm vacuum. The amido-amine intermediate product, γ-10-undecylenamidopropyl-dimethylamine, had the following properties: 
     
         ______________________________________                                    
Amine Value         202                                                   
Acid Value          5.39                                                  
Neutralization Equiv.                                                     
                    273 (theory 268)                                      
Appearance          Amber Clear Liquid                                    
Yield g             2,316                                                 
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     (b) Stage 2: Preparation of γ-10-Undecylenamidopropyl-dimethyl-benzyl ammonium chloride. 
     1706 g (6.25 moles) of γ-10 -Undecylenamidopropyl-dimethylamine were mixed with 813 g. benzyl chloride (6.4 moles), 1,052 g propylene glycol, and 71 g sodium bicarbonate. The mixture contained 72% solids. The mixture was heated to 60°-80° C. and allowed to react for 2 hours. Samples were removed periodically to determine the percentages of free amine and amine hydrochloride. When the minimum amounts were obtained, the product was cooled to room temperature and filtered to remove the inorganic salts. The product had the following properties: 
     
         ______________________________________                                    
Free Amine, %       3.86                                                  
Amine Hydrochloride, %                                                    
                    0.18                                                  
Spec. Grav., 25° C.                                                
                    1.033                                                 
Density, lbs./gal.  8.6                                                   
Ash, %              0                                                     
Viscosity, Stokes, 25° C.                                          
                    12.9                                                  
Appearance          Amber Clear Liquid                                    
Yield g             3,468                                                 
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     γ-10-Undecylenamidopropyl-dimethyl-benzyl ammonium chloride (Compound 3) is useful in the area of hair care products and laundry detergents. A typical formulation is: 
     
         ______________________________________                                    
 Laundry Detergent:                                                       
______________________________________                                    
  Sodium Lauryl Sulfate, 30%                                              
                       20-25 parts                                        
  Active                                                                  
  Sodium Lauryl Ether Sulfate,                                            
                       20-25 parts                                        
  30% Active                                                              
  Alkylamido Sulfosuccinate,                                              
                       3-5 parts                                          
  Sodium Salt, 30% Active                                                 
  Compound 3, 70% Active Cationic                                         
                       2-3 parts                                          
  Nonionic Surfactant  5-7 parts                                          
  EDTA, Disodium Salt  1-2 parts                                          
  Calcofluor White SD  0.1-0.2 parts                                      
  Water                q.s. to 100 parts                                  
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     EXAMPLE 4 
     Production of γ9,11-Linoleamidopropyl-dimethyl-benzyl ammonium chloride. 
     (a) Stage 1: Preparation of γ-9,11-Linoleamidopropyldimethylamine. 
     383 g (3.75 moles) of N,N-dimethylaminopropylamine were mixed with 980 g (3.5 moles of DCO fatty acids and heated to 180°-185° C. in a 3 liter reactor. The water of reaction is removed, and the reaction is continued until a minimum acid value is obtained. The product was then vaccum dried at 100°-105° C. at 50 mm vacuum. The amido-amine intermediate product, γ-9,11-Linoleamidopropyl-dimethylamine, had the following properties: 
     
         ______________________________________                                    
Amine Value         162                                                   
Acid Value          5.93                                                  
Neutralization Equiv.                                                     
                    346 (theory 364)                                      
Appearance          Amber Clear Liquid                                    
Yield g             1,248                                                 
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     (b) Stage 2: Preparation of γ-9,11-Linoleamidopropyl-dimethyl-benzyl ammonium chloride. 
     537 g (1.552 moles) of γ-9,11-Linoleamidopropyl-dimethylamine were mixed with 202 g benzyl chloride (1.591 moles), 310 g propylene glycol, and 21 g. sodium bicarbonate. The mixture contained 72% solids. The mixture was heated to 70°-80° C. and allowed to react for 21/2 hours. Samples were removed periodically to determine the percentages of free amine and amine hydrochloride. When the minimum amounts were obtained, the product was cooled to room temperature (25° C.) and filtered to remove the inorganic salts. The product had the following properties: 
     
         ______________________________________                                    
Free Amine, %       2.95                                                  
Amine Hydrochloride, %                                                    
                    0.37                                                  
Spec. Gravity, 25° C.                                              
                    1.014                                                 
Density, lbs./gal.  8.41                                                  
Ash, %              0.01                                                  
Viscosity, Stokes, 25° C.                                          
                    11.14                                                 
Appearance          Amber Clear Liquid                                    
Yield g             1,023                                                 
pH, 10% Aqueous     6.1-6.2                                               
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     γ-9,11-Linoleamidopropyl-dimethyl-benzyl ammonium chloride (Compound 4) is useful in the area of hair care products. A typical formulation is given: 
     
         ______________________________________                                    
 Wave Set, or Setting Lotion:                                             
______________________________________                                    
 Resyn 28-2930       1.75-2.25 parts                                      
AMP                  0.18-0.25 parts                                      
Compound 4, 70% Active                                                    
                     2.0-4.0 parts                                        
  Cationic                                                                
Nonionic Surfactant  0.1-0.2 parts                                        
Water                q.s. to 100 parts                                    
______________________________________                                    
 
    
     EXAMPLE 5 
     Production of γ-Heptanoamidopropyl-dimethyl-benzyl ammonium chloride. 
     (a) Stage 1: Preparation of γ-Heptanoamidopropyl-dimethylamine. 
     383 g (3.75 moles) of N,N-dimethylaminopropylamine were mixed with 445 g (3.5 moles) of heptanoic acid and heated to 180°-185° C. in a 2 liter reactor. The water of reaction is removed, and the reaction is continued until a minimum acid value is obtained. The product was then vacuum dried at 100°-105° C. at 50 mm vacuum. The amido-amine intermediate product, γ-Heptanoamidopropyl-dimethylamine, had the following properties: 
     
         ______________________________________                                    
Amine Value         256 (theory 262)                                      
Acid Value          6.3                                                   
Neutralization Equiv.                                                     
                    219 (theory 214)                                      
Appearance          Amber Clear Liquid                                    
Yield g             678                                                   
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     (b) Stage 2: Preparation of γ-Heptanoamidopropyldimethyl-benzyl ammonium chloride. 
     438 (2.0 moles) of γ-Heptanoamidopropyl dimethylamine were mixed with 260 g benzyl chloride (2.05 moles), 291 g propylene glycol, and 10 g sodium bicarbonate. The mixture contained 72% solids. The mixture was heated to 60°-65° C. and allowed to react for 1 hour. Samples were removed periodically to determine the percentages of free amine and amine hydrochloride. When the minimum amounts were obtained, the product was cooled to 40° C. and filtered to remove the inorganic salts. The product had the following properties: 
     
         ______________________________________                                    
Free Amine, %       1.75                                                  
Amine Hydrochloride, %                                                    
                    0.38                                                  
Ash, %              .02                                                   
Gardner Holdt Viscosity,                                                  
                    Y + 1/4                                               
25° C.                                                             
Appearance          Amber Clear Liquid                                    
Yield g             944                                                   
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     EXAMPLES 6-14 
     The following quaternary compounds are produced by the procedure described in the preceeding examples using the described amines and acids. 
     
         __________________________________________________________________________
EXAMPLE                                                                   
       COMPOUND              AMINE        ACID                            
__________________________________________________________________________
6      γ(N-methyl-12-hydroxystearamido)propyl-                      
                             γ(N-methylamino)                       
                                          12-hydroxystearic               
       dimethyl-benzyl-ammonium chloride                                  
                             propyl-dimethyl-amine                        
                                          acid (Acid No. 1)               
7      4(N-methyl-ricinoleylamido)butyl-diethyl-                          
                             4(N-methylamino) butyl-                      
                                          ricinoleic acid                 
       benzyl-ammonium chloride                                           
                             diethyl-amine                                
                                          (Acid No. 2)                    
8      γ(N-methyl-ricinoleylamido)propyl-                           
                             γ(N-methylamino)propyl-                
                                          No. 2                           
       didecyl-benzyl-ammonium chloride                                   
                             didecyl-amine                                
9      2-ricinoleylamidoethyl-dioctyl-benzyl-                             
                             2-aminoethyl-dioctyl                         
                                          No. 2                           
       ammonium chloride     amine                                        
10     γ(N-hexyl-ricinoleylamido)propyl-propyl-                     
                             γ(N-hexylamino)propyl-                 
                                          No. 2                           
       methyl-benzyl-ammonium chloride                                    
                             propyl-methyl-amine                          
11     9(12-(2-hydroxyethyloxy)stearamido)                                
                             9-aminononyl-dimethyl                        
                                          12-(2-hydroxy                   
       nonyl-dimethyl-benzyl-ammonium chloride                            
                             amine        ethyloxy) stearic               
                                          acid                            
12     γ-12-(2-hydroxypropyloxy)stearamido)                         
                             N,N-dimethylamino                            
                                          12-(2-hydroxy                   
       propyl-dimethyl-benzyl-ammonium chloride                           
                             propylamine  propyloxy)-                     
                                          stearic acid                    
13     γ-(12-hydroxystearamido)propyl-dipropenyl-                   
                             N,N-dipropenylamino                          
                                          12-hydroxy                      
       benzyl-ammonium chloride                                           
                             propylamine  stearic acid                    
14     γ(N-methyl-ricinoleamido)propyl-diethenyl-                   
                             N,N-diethenylamino                           
                                          ricinoleic acid                 
       benzyl-ammonium chloride                                           
                             propylamine                                  
__________________________________________________________________________
 
    
     EXAMPLE 15 
     Compounds wherein R 5  is methyl are produced by substituting methyl chloride for benzyl chloride in the process of Examples 1 to 5. Similarly compounds where R 5  is ethyl and M is sulfate are produced substituting diethyl sulfate for benzyl chloride. 
     EXAMPLE 16 
     The quaternary compounds produced in accordance with Examples 6 through 15 are substituted for compounds 1, 2, 3 and 4 to produce fabric softeners, laundry detergents, cream rinses and hair shampoos of the formulae set forth in Examples 1 through 4.