Patent Publication Number: US-2006019842-A1

Title: Aluminum complex grease

Description:
CROSS REFERENCE TO RELATED APPLICATIONS  
      This application is a divisional of U.S. patent application Ser. No. 10/221,336 filed on Feb. 03, 2003, for Thickener Component and Aluminum Complex Grease, the disclosure of which is incorporated herein by reference. 
    
    
     BACKGROUND OF THE INVENTION  
      1. Field of the Invention  
      This invention relates to a thickener component based on an aluminium carboxylate compound and to an aluminium complex grease made therefrom with addition of a base liquid.  
      2. Description of the Prior Art  
      Aluminium complex greases have been known. They essentially comprise a mineral-oil base liquid and a thickener system containing one or more aluminium carboxylate compounds. The aluminium carboxylate compound is obtained by reacting a fatty acid and/or an aromatic carboxylic acid with an aluminium alcoholate derivative. The industrially used aluminium alcoholates comprise aluminium isopropoxylate and tri-oxy-aluminium-triisopropoxide. In theory, the reaction proceeds as shown hereinbelow:  
                 
 
      When using aluminium isopropoxylate, partial hydrolysis is performed with water before, during, or after reaction of the acids with aluminium alcoholate to produce the usually required free -OH group on the aluminium. Aluminium complex greases are distinguished by a high dropping point, good conveyance and water resistance, and low separation of oil.  
     SUMMARY OF THE INVENTION  
      It is an object of this invention to provide more effective aluminium complex greases, in particular more suitable thickener components for manufacturing thickeners for aluminium complex greases. The term ‘more effective’ shall mean that the grease exhibits better lubricating properties than conventional aluminium complex greases. Furthermore, it is desired that the thickener component employed for making said aluminium complex greases be storable and marketable as such, thus enabling the grease manufacturer to produce the thickener-containing grease himself.  
      According to this invention, the problem has been resolved by providing a thickener component comprising 
          (A) from 99.99 to 94 weight percent, preferably 99.9 to 97 weight percent of an aluminium compound which can be prepared by reacting a hydrolysable aluminium compound with one or more aliphatic monocarboxylic acid(s) or aliphatic derivatives thereof, optionally in the presence of water and/or a C 1 - to C 40 -alcohol, thereby forming one or more aluminium compound(s) having at least one aluminium carboxylate bond per aluminium atom and, in addition, one or more aluminium-, hydroxy-, aluminium alcoholate-, and/or aluminium-oxygen-aluminium bond(s) and     (B) from 0.01 to 6 weight percent, preferably 0.1 to 3 weight percent of an ester compound having from 6 to 60 carbon atoms, 
 
 each referring to the total of components (A) and (B).
       

    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENTS  
      The term ‘hydrolysable aluminium compounds’ as used herein refers to aluminium compounds that are capable of forming aluminium-oxygen bonds by the action of protondonating compounds, such as water or organic acids. Preferably, such hydrolysable aluminium compounds are aluminium alcoholate- or aluminium-oxo-alcoholate compounds with the alcoholate group preferably being a C 2 - to C 4 -alcohol, particularly isopropanolate. The carboxylic acids can be branched or unbranched aliphatic monocarboxylic acids of the type R 1 —COOH, wherein R 1  represents a C 10 - to C 40 -radical, preferably a C 14 - to C 24 -radical, or a C 16 - to C 24 -radical.  
      Carboxylic acid derivatives as used herein are defined as compounds which are capable of forming in combination with said aluminium compounds the aluminium-carboxylate bonds that would likewise be obtained when using the corresponding acids. Examples thereof include the anhydrides, acid chlorides, or amides of the aforesaid carboxylic acids.  
      Ester compounds as used herein particularly refer to compounds which may be formed by reaction of the alcohols/alcoholates present in the reaction mixture with the carboxylic acids/carboxylate residues.  
      The thickener component is prepared by reaction, preferably about equimolar reaction, i.e. about 1 mole of monocarboxylic acid per mole of aluminium atoms in the compound, of a hydrolysable aluminium compound with one or more of the abovementioned carboxylic acid(s) or carboxylic acid derivative(s) at a temperature not exceeding 145° C., most preferably 135° C., with a temperature profile most preferably increasing gradually by at least 20° C. during a period of at least 90 minutes being ensured. It is preferred that the hydrolysable aluminium compound be placed in the vessel first.  
      Moreover, it is preferred that the reaction be carried out in a base liquid and the volatile compound released during the reaction, e.g. alcohol, be withdrawn from the equilibrium.  
      The term ‘thickener’ as used herein is defined as a compound or mixture of compounds prepared from the thickener component, which thickener can be produced by reacting the thickener component with aromatic or cyclic monocarboxylic acids of the type R 2 —COOH, wherein R 2  represents a C 6 - to C 16 -radical, or with the derivatives thereof. Said (aromatic or cyclic) carboxylic acid derivatives are defined as described hereinabove.  
      The resultant aluminium compound preferably has more than 40 mole % of aliphatic monocarboxylic acid radicals, referring to the amount of carboxylate groups (100 mole %=all the carboxylate groups). The remainder is comprised of aromatic or cyclic monocarboxylic acid radicals. As used herein, the term ‘aromatic monocarboxylic acid’ is defined as a carboxylic acid which has at least one benzene ring or condensed benzene ring and, in addition, may comprise aliphatic hydrocarbon radicals as well. Hence, compounds such as C 6 H 5 —CH 2 —CH 2 —. COOH or CH 3 —CH 2 —C 6 H 4 —COOH are explicitly included herein.  
      The thickener as a constituent of the aluminium complex grease is produced by compounding the thickener component, optionally taken up in additional base liquid, with the aromatic or cyclic monocarboxylic acid.  
      The production process of the invention ‘yields a raw material (thickener component) with a low ester content for making the real thickener that keeps its low ester content even upon storage.  
      Besides the thickeners of the invention the aluminium complex greases of the invention also comprise a base liquid which is a hydrocarbon compound and/or a synthetic oil added to the overall composition in quantities of from 30 to 98 weight percent, preferably 60 to 95 weight percent.  
      The hydrocarbon compound can be a paraffin-base or naphthenic mineral oil, a polyalphaolefin, or a white oil. Further synthetic oils which are suitable as base liquid include fatty acid esters based on mono- or multifunctional fatty acids having a chain length of from 8 to 24 carbon atoms and mono- or polyhydric alcohols. Additional constituents of the aluminium complex greases of the invention may be typical additives. Table 1 presents examples of suitable additives.  
      The thickener components of the invention are useful as raw materials for producing thickeners included in aluminium complex greases exhibiting improved lubricating properties. They are preferably employed in high-temperature applications for which high dropping points are especially desirable, in central lubricators, and/or for lubricating machinery used for example for producing or processing foodstuffs.  
      The prior art thickeners based on aluminium carboxylate compounds or the aluminium complex greases made therefrom have significantly higher ester concentrations. Surprisingly, compositions with lower ester concentrations, preferably less than 6 % in the thickener component, and improved lubricating properties have now become accessible by the process.  
      It is preferred that the thickener components as well contain 20 to 80 weight percent, most preferably 30 to 70 weight percent of the base liquid described hereinabove.  
      Examples of Tests  
      Table 2 shows the rheometric values (Physica UDS 200, oscillating measurement, deformation=0.2%, frequency=0.1 Hz, temperature 20° C., plate/plate distance=1 mm) of aluminium complex greases of the invention. Example 4 presents a high ester concentration, whereas the ester concentration in Example 5 (comparative example) is too high. The measurements were made on a thickener component having an aluminium content of 4.1 weight percent. The solvent in the aluminium-containing thickener component is identical with the base oil. The starting material is aluminium isopropanolate. The aliphatic monocarboxylic acid employed herein is a technical-grade stearic acid mixture.  
      Exemplary Synthesis  
      Into a 5-litre agitated vessel equipped with a nitrogen supply line, a 30-cm column (metalized, packed with Raschig rings), and a reflux condenser there are placed 1.466 moles (299.5 g) of DOROX® D 10 (aluminium triisopropylate, liquid) and 500.0 g of Sera® 100 mineral oil (approx. 50 wt. % paraffin-base oil). The educts are heated to 97° C. (bottom temperature) while stirring. The stearic acid is heated to 75-80° C. to keep the product liquid upon feeding. 1.466 moles (393.5 g) of the liquid stearic acid (acid number=209 mg of KOH/g) and the mixture of water (1.372 moles=24.7 g) and 2-propanol (123.6 g) are charged steadily and simultaneously through separate submerged pipes during a period of 2.5 hours. The released 2-propanol is removed overhead (head temperature max. 85° C.). The bottom temperature is gradually increased to 127° C. during this period. Once the bottom temperature reaches 127° C., the pressure is reduced to 200 hPa during 20 minutes and the remainder of the low-boiling 2-propanol is drawn off. During the reaction a distillate comprised of 3.623 moles (217.7 g) of 2-propanol is removed from the reaction and the mixture (123.6 g). The product, oxo-aluminium-stearate, is obtained after purification and filtration. The total residence time of the product at 127° C. is 30 minutes (until end of vacuum phase). Filtration is performed at approx. 120° C. using a 60-μm sieve.  
      The material parameters of the thickener component have been compiled in Table 3.  
                           TABLE 1                                   Concentration               Range, wt. %                                                Extreme-pressure     2-10   dibenzyldisulfide with       additives       chlorinated paraffins;               sulphurized fatty oils               or terpenes       Additives for enhancing   0.1-5   diisopropyl- or dilauryl       film resistance       hydrogen phosphite       Rust-inhibiting additives   0.5-5   sodium petroleum sulfo-               nates or barium dinonyl               naphthalene sulfonate       Copper deactivators   0.05-1    2-mercaptobenzthiazol       Viscosity index improvers   0.1-1   polymethacrylates       Desludgers   0.001   silicone oils       Additives for producing   0.5-2   polymers       ropiness       Antiwear additives   0.1-2   tricresylic phosphate,               zinc dialkyl dithio-               phosphate       Additives for producing   0.1-2   oil- or other vegetable       water resistance       fatty acids       Deodorants    0.05-0.5   perfumes       Anticorrosion additives   0.5-3   nonylphenoxy vinegar,               ethylenediamine               sulfonate, lead               dinonylnaphthyl sul-               fonate, barium sulfo-               nates, lead- and zinc               naphthenates       Oxidation inhibitors       diphenylamine, phenyl-               α-naphthylamine, di-               octyldiphenylamine,               phenothiazine, poly-               meric trimethyldi-               hydroquinoline, 2,6-               di-tert-butyl-4-               methylphenol, lead               diamyldithiocarbamate,               dilaurylthiodipro-               pionate-1/citric acid,               ascorbic acid                  
 
     
       
         
           
               
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 2 
               
               
                   
               
               
                   
               
               
                   
                   
                   
                 Base Liquid 
                 Ester Concen- 
                 Base Liquid 
                 Thickener 
                   
                   
                   
               
               
                   
                   
                 Base Liquid 
                 Concentra- 
                 tration in 
                 Concentration 
                 Component 
                 Benzoic Acid 
               
               
                   
                   
                 Viscosity 
                 tion in 
                 Thickener 
                 in Thickener 
                 Concentration 
                 Concentration 
                 Modulus of 
                 Modulus of 
               
               
                   
                   
                 at 40° C. 
                 Grease 
                 Component 
                 Component 
                 in Grease 
                 in Grease 
                 Elasticity 
                 Viscosity 
               
               
                 No. 
                 Base Liquid 
                 mm 2 /s 
                 wt. % 
                 wt. % 
                 wt. % 
                 wt. % 
                 wt. % 
                 Pa 
                 Pa 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 1 
                 Paraffin- 
                 100 
                 91.3 
                 1.4 
                 60 
                 7.3 
                 1.4 
                 860 
                 330 
               
               
                   
                 based 
               
               
                   
                 mineral oil 
               
               
                 2 
                 Paraffin- 
                 100 
                 87.1 
                 1.4 
                 60 
                 10.9 
                 2.0 
                 5,720 
                 1,030 
               
               
                   
                 based 
               
               
                   
                 mineral oil 
               
               
                 3 
                 Paraffin- 
                 100 
                 82.8 
                 1.4 
                 60 
                 14.5 
                 2.7 
                 35,100 
                 5,400 
               
               
                   
                 based 
               
               
                   
                 mineral oil 
               
               
                 4 
                 Paraffin- 
                 100 
                 87.1 
                 3.9 
                 60 
                 10.9 
                 2.0 
                 1,100 
                 270 
               
               
                   
                 based 
               
               
                   
                 mineral oil 
               
               
                 5 
                 Paraffin- 
                 100 
                 87.1 
                 8.7 
                 60 
                 10.9 
                 2.0 
                 800 
                 170 
               
               
                   
                 based 
               
               
                   
                 mineral oil 
               
               
                 6 
                 Naphthene- 
                 100 
                 87.1 
                 1.2 
                 50 
                 10.9 
                 2.0 
                 5,820 
                 1,000 
               
               
                   
                 based 
               
               
                   
                 mineral oil 
               
               
                 7 
                 Naphthene- 
                 40 
                 87.1 
                 1.2 
                 50 
                 10.9 
                 2.0 
                 2,680 
                 450 
               
               
                   
                 based 
               
               
                   
                 mineral oil 
               
               
                 8 
                 Polyalpha- 
                 30 
                 91.3 
                 2.4 
                 60 
                 7.3 
                 1.4 
                 290 
                 60 
               
               
                   
                 olefin 
               
               
                 9 
                 Polyalpha- 
                 30 
                 87.1 
                 2.4 
                 60 
                 10.9 
                 2.0 
                 2,100 
                 290 
               
               
                   
                 olefin 
               
               
                 10 
                 Polyalpha- 
                 30 
                 82.8 
                 2.4 
                 60 
                 14.5 
                 2.7 
                 13,300 
                 1,100 
               
               
                   
                 olefin 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
             
               
                   
                 TABLE 3 
               
               
                   
                   
               
               
                   
                   
               
               
                   
                 Method 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 Al content 
                 4.1% 
                 M 635 
               
            
           
           
               
               
               
               
               
            
               
                   
                 Turbidity 
                 20 
                 FNU 
                 DIN 38404 T2 
               
               
                   
                 Viscosity(25° C.) 
                 1,500 
                 mPa · s 
                 DIN 53015 
               
               
                   
                 Viscosity (100° C.) 
                 100 
                 mPa · s 
                 Rotation (200s −1 ) 
               
               
                   
                 Pour point 
                 16° 
                 C. 
                 DIN ISO 3016 
               
            
           
           
               
               
               
               
            
               
                   
                 2-Propanol concentration 
                 3.5% 
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 Density (20° C.) 
                 0.94 
                 g/cm 3   
                 DIN 51757 
               
               
                   
                 Density (40° C.) 
                 0.93 
                 g/cm 3   
                 DIN 51757 
               
               
                   
                 Density (50° C.) 
                 0.93 
                 g/cm 3   
                 DIN 51757 
               
               
                   
                 Flash point 
                 190° 
                 C. 
                 DIN 51758 
               
            
           
           
               
               
               
               
            
               
                   
                 Colour number 
                 10 
                 DIN 6162