DE4317105A1 - Lubricant with improved low temperature properties - Google Patents

Description

Viscosity index improvers (viscosity index improvers; VI- improver) are used extensively in the lubricant industry especially in oils for automatic transmissions (ATF) and in crankcases formulations used. Changes in the structure of automatic transmissions have too new requirements in oils for automatic transmissions. To achieve one Optimal performance requires electronically controlled gear oils with better ones Low temperature properties. Accordingly, with the arrival of the DEXRON® IIE specifications in the spring of 1991 and the possible introduction the DEXRON® III specifications for automatic transmission oils at the end of 1992 a need - and significant efforts have been made - to develop Oils for automatic transmissions with excellent low temperature properties. To the To meet DEXRON® IIE specifications is a Brookfield viscosity of 20,000 cP or less required at -40 ° C. To meet the DEXRON® III specifications the Brookfield viscosity may be 15,000 cP or less -40 ° C.

In many cases, light starting materials (e.g. below 100 N) are used to obtain the To meet the requirements of the DEXRON® IIE specifications, since these are raw materials already contain less wax. However, this leads to increased values of the Treatment with agents to improve the viscosity index to the required value to achieve the kinematic viscosity at 100 ° C.

An important contribution to this area of technology would be an effective way of doing it enables mineral oil based materials in the range of 75 N to 200 N in Formulations with improved low temperature properties (e.g. -40 ° C) and lower requirements for polymeric agents to improve the viscosity index to use. The present invention is believed to make such a contribution represents.

In one embodiment, the present invention provides a lubricating oil formulation ready which includes:

• a) a larger amount of mineral oil in the range of 75 N to 200 N, preferably in Range from 85 N to 160 N and most preferably in the range from 90 N to 140 N, e.g. B. 100 N; and smaller quantities
• b) a poly-α-olefin oligomer formed by a process which involves the oligomerization of at least one 1-alkene having a number of carbon atoms in the molecule in the range from 6 to 20, preferably from 8 to 16, more preferably from 10 to 12, and most preferably 10, the oligomer having a kinematic viscosity at 100 ° C in the range of 2 to 7 mm ² / s, preferably in the range of 2 to 6 mm ² / s, more preferably in the range from 2 to 4 mm ² / s, and most preferably about 2 mm ² / s, and wherein the oligomer is preferably, but not necessarily, a hydrogenated oligomer; and
• c) an oil-soluble polymeric agent to improve the viscosity index based of acrylic acid;

the preparation being further characterized in that it is a Brookfield Viscosity at -40 ° C, which is equal to or less than 20,000 mPa · s, and preferably is equal to or less than 15,000 mPa · s.

Another embodiment relates to a lubricating oil preparation which comprises:

• a) a larger amount of a mineral oil in the range of 75 N to 200 N, preferably in the range of 85 N to 160 N and most preferably in the range of 90 N to 140 N, e.g. B. 100 N; and smaller quantities
• b) a poly-α-olefin oligomer formed by a process which involves the oligomerization of at least one 1-alkene having a number of carbon atoms in the molecule in the range from 6 to 20, preferably from 8 to 16, more preferably from 10 to 12, and most preferably 10, the oligomer having a kinematic viscosity at 100 ° C in the range of 2 to 7 mm ² / s, preferably in the range of 2 to 6 mm ² / s, more preferably in the range from 2 to 4 mm ² / s and most preferably from 2 mm ² / s, and wherein the oligomer is preferably, but not necessarily, a hydrogenated oligomer; and
• c) a solution of a polymeric agent for improving the viscosity index based on poly (alkyl methacrylate) in a hydrocarbon solvent, the solution having a viscosity in bulk (bulk viscosity) in the range from 600 to 1200 mm ² / s at 100 ° C. having;

the preparation being further characterized in that it is a Brookfield Viscosity at -40 ° C, which is equal to or less than 20,000 mPa · s, preferably is equal to or less than 15,000 mPa · s.

Among the advantages made possible by the present invention is that Achieve very good viscometric low temperature properties (e.g. at -40 ° C) in Mineral oil-based base materials that have better viscometric high temperatures have properties as mineral oils of the lower viscosity levels, d. H. less than 100 N. In addition, the present invention enables the production of a lubricant and functional lubricant preparations that have greater shear stability and better thermal properties and oxidation properties compared to, for example Lubricants for automatic transmissions based on output materials of the lighter naphthen type are formulated.

In addition, at least in some preparations of the invention, a highly effective one synergistic behavior in relation to the viscometric low temperature properties be achieved, and indeed has been achieved. This in turn makes it possible to Reduce amount of components (b) and / or (c) above while taking the maintains synergistic improvement in low temperature performance.

In a preferred embodiment, the polymeric viscosity index improver is a solution consisting of 30 to 45% by weight of an acrylic type viscosity index improver, e.g. B. a poly (alkyl methacrylate) polymer, which is dissolved in 70 to 55 wt .-% of a hydrocarbon solvent. This solution has a bulk viscosity of 600 to 800 mm ² / s at 100 ° C. An example of such an agent for improving the viscosity index is the oil additive Acryloid® 1263 from the Rohm & Haas Company, which is stated by the manufacturer to have a nominal bulk viscosity of 700 mm ² / s at 100 ° C and has a typical basic nitrogen content of 0.12%. With regard to the composition, the manufacturer states as of June 1990 that the product consists of 40 to 42% by weight of an acrylic polymer, 1.9% by weight (maximum) of residual monomer (s) and 58 to 60% by weight Naphthene hydrocarbons exist (CAS Reg. Nos. 64742-53-6 and 64741-97-5 are listed). Earlier editions of the product were identified in terms of composition so that they contained 34 to 39 weight percent acrylic polymer and 61 to 66 weight percent extracted naphthenic oil and solvent refined light naphthenic distillates. The agents for improving the viscosity index with the designations Acryloid® 1265 and Acryloid® 1267 can also be used. These are stated to have bulk viscosities of 700 mm ² / s at 100 ° C. Their basic nitrogen levels are given as 0.14% and 0.16%, respectively.

In a further preferred embodiment, the polymeric viscosity index improver is a solution composed of 20 to 65% by weight of an acrylic type viscosity index improver, e.g. B. a poly (alkyl methacrylate) copolymer, which is dissolved in 35 to 80 wt .-% of a hydrocarbon solvent. This solution has a bulk viscosity of 800 to 1200 mm ² / s at 100 ° C. An example of such an agent for improving the viscosity index is the Texaco® TLA-5010 oil additive from Texaco Chemical Company, which is stated by the manufacturer to have a nominal bulk viscosity of 1000 mm ² / s at 100 ° C and a typical specific gravity of 0.905 and from 4.00 to 10.99% polymerized n-butyl ester of methacrylic acid, 1.00 to 3.99% polymerized dimethylaminopropyl methacrylamide and 20.00 to 34.99% polymerized lauryl ester of methacrylic acid, which are dissolved in 35.00 to 49.99% highly solvent-refined, hydrotreated light naphthen petroleum distillates and 11.00 to 19.99% highly refined, hydrotreated heavy naphthenic petroleum distillates. The percentages for the components of the product are believed to be TLA-5010% by weight.

In a further preferred embodiment of the present invention, the agent for improving the viscosity index of the acrylic type is a solution of a viscosity index-improving agent of the polymethacrylate type in a highly refined mineral oil, wherein the mineral oil content is in the range from 40 to 45% by weight and where the solution has a bulk viscosity in the range of 600 to 800 mm ² / s at 100 ° C. The viscosity index improver, called Viscoplex® 0-800 from Rohm Tech Inc., is an example of such a viscosity index improver. According to the manufacturer, this product has a mineral oil content of about 42%, a specific weight at 15 ° C of 0.9 g / ml, a flash point of over 200 ° C (ASTM D 92) and a viscosity in the mass ( bulk viscosity) of 700 mm ² / s at 100 ° C.

In the preferred embodiments described above, it is particularly preferred to use a hydrogenated poly-α-olefin oligomer having a kinematic viscosity in the range of 2 to 4 mm ² / s at 100 ° C, and most preferably about 2 mm ² / s at 100 ° C.

Other embodiments and features of the present invention result obviously further from the following description and the appended claims.

Component (a)

The mineral oil base material used in the preparations of the present invention used falls in the specification category 75 N to 200 N and can be a single Mineral oil or a mixture of two or more mineral oils. Oils on Naphthene bases can be used, and these are preferably highly refined oils such as solvent-treated neutral oils. Preferred base materials for Paraffin oils such as, for example, are used in the context of the present invention solvent-refined paraffin-based base materials, hydrotreated base materials paraffin-based and hydrotreated and catalytically waxed base materials Paraffin base. Some aromatic oils may be suitable, although less preferred are. Mixtures, preferably those containing a larger amount of base materials Containing paraffin base are also suitable.  

The mineral oils can be refined from crude oil including any source Crude oils from the Gulf Coast, oils from the center of the continent, oils from Pennsylvania, oils from California, oils from Alaska, oils from the Middle East and oils from the North Sea. Standard refining processes can be used to treat the mineral oil. A large number of suitable mineral oils are from various companies that deal with the Refining petroleum deal, available.

Component (b)

As indicated, the lubricating oil preparations of the present invention comprise a minor amount (ie less than 50% by weight) of at least one poly-α-olefin oligomer liquid with a kinematic viscosity at 100 ° C. in the range from 2 to 7 mm ² / s, preferably in the range of 2 to 6 mm ² / s, more preferably in the range of 2 to 4 mm ² / s and most preferably of about 2 mm ² / s. Such liquids are formed by oligomerization of at least one 1-alkene hydrocarbon having a number of carbon atoms in the molecule in the range from 6 to 20, preferably in the range from 8 to 16, more preferably from 10 to 12 and most preferably from 10 . The oligomerization is usually carried out catalytically. The oligomer liquid can be a hydrogenated oligomer liquid or a non-hydrogenated oligomer liquid. Hydrogenated oligomers are preferred, and hydrogenated oligomers formed from 1-decene are particularly preferred.

Processes for the production of such liquid oligomeric 1-alkene hydrocarbons are known; they have been reported in the literature, for example, in U.S. Pat. 3,763,244; 3,780,128; 4,172,855; 4,218,330 and 4,950,822. In addition, hydrogenated 1- Alkene oligomers of this type are available as commercial products, for example under the Trade names for poly-α-olefin oils ETHYLFLO 162, ETHYLFLO 164 and ETHYLFLO 166 (Ethyl Corporation; Ethyl Canada Limited; Ethyl S. A.). In the table below technical details are listed, which are the typical The composition and properties of these products relate. In these tabular Statements are the typical compositions based on normalized  Percentage of area, determined by GC, expressed; "n. d." means "not determined (not determined) ".

• - ETHYLFLO 162-poly-α-olefin oil:
  Composition: monomer 0.4; Dimer 90.7; Trimer 8.3; Tetramer 0.6
  Properties: viscosity at 100 ° C 1.80 mm² / s; Viscosity at 40 ° C 5.54 mm² / s; Viscosity at -18 ° C nd; Viscosity at -40 ° C 306 mm² / s; Pour point -63 ° C; Flash point (ASTM D 92) 165 ° C; NOACK volatility 99%.
• - ETHYLFLO 164-poly-α-olefin oil:
  Composition: Trimer 82.7; Tetramer 14.6; Pentamer 2.7
  Properties: viscosity at 100 ° C 4.06 mm² / s; Viscosity at 40 ° C 17.4 mm² / s; Viscosity at -18 ° C nd; Viscosity at -40 ° C 2490 mm² / s; Pour point <-65 ° C; Flash point (ASTM D 92) 224 ° C; NOACK volatility 12.9%.
• - ETHYLFLO 166-poly-α-olefin oil:
  Composition: Trimer 32.0; Tetramer 43.4; Pentamer 21.6; Hexamer 3.0
  Properties: viscosity at 100 ° C 5.91 mm² / s; Viscosity at 40 ° C 31.4 mm² / s; Viscosity at -18 ° C nd; Viscosity at -40 ° C 7877 mm² / s; Pour point - 63 ° C; Flash point (ASTM D 92) 235 ° C; NOACK volatility 7.5%.

Suitable 1-alkene oligomers are also available from other suppliers. As is well known, hydrogenated oligomers of this type contain little, if any, residual ethylene-like unsaturated molecular regions, while non-hydrogenated oligomers contain residual unsaturation to some extent. Preferred oligomers are formed using a Friedel-Crafts catalyst, especially with water or a C _1-20 alkanol activated boron trifluoride, which is followed by catalytic hydrogenation of the oligomer so formed using procedures such as those set forth in the above-referenced U.S. patents are described.

Other catalyst systems used to form oligomers of 1-alkene hydrocarbons substances can be used, which after hydrogenation to suitable lubricating oil liquids lead, include Ziegler catalysts such as ethyl aluminum sesquichloride Titanium tetrachloride, aluminum alkyl catalysts, chromium oxide catalysts on silica or Alumina supports and a system in which to undergo oligomerization Use of boron trifluoride as a catalyst treatment with an organic Peroxide follows.

Mixtures or blends of 1-alkene oligomers can also be used in practice Implementation of the present invention can be used provided that the Overall mixture has the required viscosity properties as specified above are. Typical examples of suitable blends of hydrogenated 1-decene oligomers include the following blends, in which the typical components of the compositions are given as normalized area percentages in gas chromatography (GC) Determination, and wherein "n. D." means "not determined".

• - 75/25 blend of ETHYLFLO 162 and ETHYLFLO 164 poly-α-olefin oils:
  Composition: monomer 0.3; Dimer 66.8; Trimer 27.3; Tetramer 4.8; Pentamer 0.8
  Properties: viscosity at 100 ° C 2.19 mm² / s; Viscosity at 40 ° C 7.05 mm² / s; Viscosity at -18 ° C 84.4 mm² / s; Viscosity at -40 ° C 464 mm² / s; Pour point <-65 ° C; Flash point (ASTM D 92) 166 ° C; NOACK volatility 78.2%.
• - 50/50 blend of ETHYLFLO 162 and ETHYLFLO 164 poly-α-olefin oils:
  Composition: monomer 0.2; Dimer 44.7; Trimer 45.9; Tetramer 7.6; Pentamer 1.3; Hexamer 0.3
  Properties: viscosity at 100 ° C 2.59 mm² / s; Viscosity at 40 ° C 9.36 mm² / s; Viscosity at -18 ° C 133 mm² / s; Viscosity at -40 ° C 792 mm² / s; Pour point <-65 ° C; Flash point (ASTM D 92) 168 ° C; NOACK volatility 57.4%.
• - 25/75 blend of ETHYLFLO 162 and ETHYLFLO 164 poly-α-olefin oils:
  Composition: monomer 0.1; Dimer 23.1; Trimer 62.7; Tetramer 11.5; Pentamer 2.1; Hexamer 0.5
  Properties: viscosity at 100 ° C 3.23 mm² / s; Viscosity at 40 ° C 12.6 mm² / s; Viscosity at -18 ° C 214 mm² / s; Viscosity at -40 ° C 1410 mm² / s; Pour point <-65 ° C; Flash point (ASTM D 92) 190 ° C; NOACK volatility 30.8%.
• - 95/05 blend of ETHYLFLO 164 and ETHYLFLO 166 poly-α-olefin oils:
  Composition: Dimer 0.5; Trimer 78.4; Tetramer 15.6; Pentamer 3.7; Hexamer 1.8
  Properties: viscosity at 100 ° C 4.15 mm² / s; Viscosity at 40 ° C 17.9 mm² / s; Viscosity at -18 ° C nd; Viscosity at -40 ° C 2760 mm² / s; Pour point <-65 ° C; Flash point (ASTM D 92) 225 ° C; NOACK volatility 10.5%.
• - 90/10 blend of ETHYLFLO 164 and ETHYLFLO 166 poly-α-olefin oils:
  Composition: Dimer 0.3; Trimer 76.0; Tetramer 17.0; Pentamer 4.7; Hexamer 2.0
  Properties: viscosity at 100 ° C 4.23 mm² / s; Viscosity at 40 ° C 18.4 mm² / s; Viscosity at -18 ° C nd; Viscosity at -40 ° C 2980 mm² / s; Pour point <-65 ° C; Flash point (ASTM D 92) 228 ° C; NOACK volatility 11.4%.
• - 80/20 blend of ETHYLFLO 164 and ETHYLFLO 166 poly-α-olefin oils:
  Composition: Dimer 0.3; Trimer 71.5; Tetramer 19.4; Pentamer 6.5; Hexamer 2,3
  Properties: viscosity at 100 ° C 4.39 mm² / s; Viscosity at 40 ° C 19.9 mm² / s; Viscosity at -18 ° C nd; Viscosity at -40 ° C 3240 mm² / s; Pour point <-65 ° C; Flash point (ASTM D 92) 227 ° C; NOACK volatility 9.2%.
• - 75/25 blend of ETHYLFLO 164 and ETHYLFLO 166 poly-α-olefin oils:
  Composition: Dimer 0.7; Trimer 69.0; Tetramer 21.0; Pentamer 7.3; Hexamer 2.0
  Properties: viscosity at 100 ° C 4.39 mm² / s; Viscosity at 40 ° C 20.1 mm² / s; Viscosity at -18 ° C 436 mm² / s; Viscosity at -40 ° C 3380 mm² / s; Pour point <-65 ° C; Flash point (ASTM D 92) 226 ° C; NOACK volatility 14.2%.
• - 50/50 blend of ETHYLFLO 164 and ETHYLFLO 166 poly-α-olefin oils:
  Composition: Dimer 0.4; Trimer 57.3; Tetramer 27.4; Pentamer 11.8; Hexamer 3.1
  Properties: viscosity at 100 ° C 4.82 mm² / s; Viscosity at 40 ° C 23.0 mm² / s; Viscosity at -18 ° C 544 mm² / s; Viscosity at -40 ° C 4490 mm² / s; Pour point <-65 ° C; Flash point (ASTM D 92) 226 ° C; NOACK volatility 12.5%.
• - 25/75 blend of ETHYLFLO 164 and ETHYLFLO 166 poly-α-olefin oils:
  Composition: Dimer 0.3; Trimer 45.3; Tetramer 33.4; Pentamer 16.4; Hexamer 4.6
  Properties: viscosity at 100 ° C 5.38 mm² / s; Viscosity at 40 ° C 26.8 mm² / s; Viscosity at -18 ° C 690 mm² / s; Viscosity at -40 ° C 6020 mm² / s; Pour point <-65 ° C; Flash point (ASTM D 92) 250 ° C; NOACK volatility 9.2%.
• - 75/25 blend of ETHYLFLO 166 and ETHYLFLO 168 poly-α-olefin oils:
  Composition: Dimer 0.4; Trimer 28.4; Tetramer 42.0; Pentamer 22.9; Hexamer 6.3
  Properties: viscosity at 100 ° C 6.21 mm² / s; Viscosity at 40 ° C 33.7 mm² / s; Viscosity at -18 ° C 1070 mm² / s; Viscosity at -40 ° C 9570 mm² / s; Pour point <-65 ° C; Flash point (ASTM D 92) 242 ° C; NOACK volatility 6.8%.
• - 50/50 blend of ETHYLFLO 166 and ETHYLFLO 168 poly-α-olefin oils:
  Composition: Trimer 20.4; Tetramer 45.4; Pentamer 26.5; Hexamer 7.7
  Properties: viscosity at 100 ° C 6.79 mm² / s; Viscosity at 40 ° C 38.1 mm² / s; Viscosity at -18 ° C 1180 mm² / s; Viscosity at -40 ° C 12200 mm² / s; Pour point <-65 ° C; Flash point (ASTM D 92) 244 ° C; NOACK volatility 6.0%.

Component (c)

Oil-soluble polymeric agents for improving the viscosity index on an acrylic basis and Methods of making them are well known to those skilled in the art known. Reference is made to the publications "W. L. von Horne, Ind. Eng. Chem., 41, page 952 (1949) ";" F. J. Glavis, Ind. Eng. Chem., 42, page 2441 (1950) "; and the U.S. Patents No. 2,091,627; 2,100,993; 2,114,233; 3,052,648; 3,163,605; 3,506,574; 4,036,766; 4,496,691; 4,606,834; 4,968,444; 5,013,468 and 5,013,470.

As is well known, the function of an agent to improve viscosity is index is the viscosity of an oil at a relatively constant viscosity value above the Keep range of application temperatures. As in some of the above Documents addressed address acrylate or methacrylate ester polymers and copoly This function is very effective. Oil soluble polymeric agents have also been used Improvement of the viscosity index based on acrylic developed with effect for the Lubricants contribute other functions, such as dispersibility or Oxidation inhibition ability.

There are a number of means to improve the viscosity index based on acrylic available on the market. A number of such products have already been mentioned above.

The acrylic acid ester viscosity index improver is generally in the form a solution or mixture in a suitable light mineral oil, e.g. B. in a hydrotreated 40 N to 200 N paraffin oil or to a high degree refined 40 N to 200 N naphthen oil. If desired, however, this can be acrylic acid  ester viscosity index improver in the form of a solution in a poly-α-olefin oil are used, for example in a poly-α-olefin oil of the type used as a component (b) the preparations according to the present invention are used. In one In such a case, a suitable light mineral oil can also be present, or it can not be used as a diluent for the acrylic acid ester polymer. It is hence it can be seen that components (b) and (c) in combination with one another may be present, along with an additional light mineral oil diluent or solvent or without this, before the components (b) and (c) with the Component (a) mixes.

Components (a), (b) and (c) can be used simultaneously or in any order are mixed together and the mixture can be stirred or otherwise agitated to ensure homogeneity. The application of heat to the mixture during mixing may prove useful in that it Mixing process facilitated. Of course, the temperature should be well below the Temperature value are maintained, at which thermal degradation of one of the components would occur. During mixing, the temperatures are often in the range kept up to a maximum of around 60 ° C, although higher temperatures are usually permitted.

Quantities of components (a), (b) and (c)

As mentioned above, the poly-α-olefin oligomer and the polymeric agent are used Improvement of the viscosity index based on acrylic acid esters in quantities and proportions nissen in the special mineral oil used as component (a), that the resulting preparation has a Brookfield viscosity at -40 ° C of 20,000 mPa · s or less and preferably 15,000 mPa · s or less.

The particular amounts used are therefore subject to considerable fluctuations and depend on the characteristics and properties of each of the components (a), (b) and (c) which are used in any given individual case. In general, however, the preparation usually contains at least 1% by weight, preferably at least 3% by weight, more preferably at least 7% by weight and most preferably at least 9% by weight of component (b), ie the oligomer, and at least 0.01% by weight, preferably at least 0.02% by weight, more preferably at least 0.04% by weight and even more preferably at least 2% by weight and most preferably at least 3% by weight. % of component (c), ie the polymeric agent for improving the viscosity index. For very good results, the amount of component (b) used should be at least sufficient to not only achieve the viscometric values described above at low temperature (ie 20,000 mPa · s or less at -40 ° C), but also one finished preparation to lead, which has a kinematic viscosity of at least 6.5 mm ² / s at 100 ° C and preferably at least 6.8 mm ² / s at 100 ° C. In any case, the total amount of components (b) and (c) is below 50% by weight of the total preparation.

It should be noted that the above weight percent values for the component (c), d. H. the polymeric viscosity index improver, based on weight of the actual polymer and not on the weight of a solution or mixture of the Obtain polymers in a diluent or solvent, the latter Form is the form in which the agent to improve the viscosity index most often is used. In short, the concentrations of component (c) relate to how they were given above based on the weight of the active polymeric verb viscosity index and include the weight of any solvents or Diluents related to this.

As is evident from the measurement data given below, there is a particularly preferred aspect of the present invention in that components (b) and (c) to use in proportions and amounts such that a synergistic Brookfield viscosity improvement at -40 ° C is achieved.  

Other components and additives (A) Other oils

If desired, the preparations of the present invention may contain minor amounts, preferably no more than 30% by weight of other suitable oily base materials included to the product additional, as part of the special end use for which it is intended to use the finished lubricant or the functional liquid, to impart required and / or desired properties. The main requirements are that (1) any such additional base material has the low temperature viscosity characteristics should not adversely affect to the extent that the resulting preparation does not a Brookfield viscosity at -40 ° C of 20,000 mPa · s or less, and preferably of 15,000 mPa · s or less, and (2) each such additional base material is one suitable compatibility with the other components of the preparation in the manner should show that their stability, homogeneity or fitness for purpose are not significant is deteriorating.

Alkylene oxide polymers and interpolymers and their derivatives in which the terminal hydroxyl groups have been modified, e.g. By esterification or etherification, are a class of synthetic oils that can be contemplated for use in the preparations of the present invention. Examples of these are oils which are produced by polymerizing alkylene oxides such as, for example, ethylene oxide or propylene oxide, and the alkyl ethers and aryl ethers of these polyoxyalkylene polymers, e.g. B. methyl polyisopropylene glycol ether with an average molecular weight of 1000, diphenyl ether of polyethylene glycol with a molecular weight of 500 to 1000, diethyl ether of polypropylene glycol with a molecular weight of 1000 to 1500, or monocarboxylic acid esters and polycarboxylic acid esters of the compounds mentioned, for example the acetic acid esters, mixed C ₃ - to C ₆ fatty acid esters or the C ₁₃ oxo acid diesters of tetraethylene glycol.

Another class of synthetic oils that can be used include the esters of dicarboxylic acids, e.g. B. phthalic acid, succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid and the dimer of linoleic acid, with a variety of alcohols, e.g. B. butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol and ethylene glycol. Specific examples of these esters include dibutyl adipate, di (2-ethylhexyl) adipate, didodecyl adipate, di (iso-tridecyl) adipate (e.g. the product glissofluid A13 from BASF), di (2-ethylhexyl) ) sebacate, dilauryl sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, mixed C ₉ and C ₁₁ dialkyl phthalates (e.g. the product Emkarate 911P ester oil from the company ICI eicosyl-) sebacate, the 2-ethylhexyl diester of linoleic acid dimer and the complex esters which are prepared by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.

Synthetic esters that can also be used include those compounds made from C ₃ to C ₁₂ monocarboxylic acids and polyols and polyol ethers, such as neopentyl glycol, trimethylol propane, pentaerythritol and dipentaery thritol, trimethylol propane tripelargonate, trimethylol propane trioleate, pentaerythritol tetra tetra tetra tetra tetrate tetra pentaerythritol tetra tetra tetra toluene tetra pentaerythritol tetra toluene tetra pentaerythritol tetra toluene tetra tetra peptone tetra tetra tetrachol tetra tetra peptate, and pentaerythritol tetra tetra tetritol tetra tetra tetra tetritol tetra tetra toluene tetra tetra tetritol tetra tetra toluene serve as examples.

Oils based on silicon such as the polyalkyl, polyaryl, or polyalkoxy or Polyaryloxysiloxane oils and silicate oils are another class of synthetic lubricants that can be selected for use. Close these connections for example tetraethyl silicate, tetraisopropyl silicate, tetra (2-ethylhexyl) silicate, tetra (p- tert-butylphenyl) silicate, poly (methyl) siloxanes and poly (methylphenyl) siloxanes. Other synthetic lubricating oils include liquid esters of acids containing phosphorus, e.g. B. Tricresyl phosphate, trioctyl phosphate, triphenyl phosphite and diethyl ester from Decanphos phonic acid.

Among other oils that can be considered for use in appropriate amounts in the compositions of the present invention into consideration are homo- and interpolymers of C ₂ - to C ₁₂ olefins, polyglycols, alkylated aromatic compounds, carbonates, thiocarbonates, orthoformates, borates and halogenated hydrocarbons. Representative examples of such oils are homo- and interpolymers of C ₂ - to C ₁₂ hydrocarbons -Monoolefinkohlen, alkylated benzenes (e.g., dodecylbenzenes, Didodecylbenzole, Tetradecylben Zole, dinonylbenzenes and di- (2-ethylhexyl) benzenes.).

Exemplary other oils with lubricating viscosity that are in the blends of the present Invention that can be used include natural fatty oils and esters such as for example castor oil, olive oil, peanut oil, rapeseed oil, corn oil, sesame oil, cotton seed oil, soybean oil, sunflower oil, safflower oil, hemp oil, linseed oil, tung oil, Oiticika oil, jojoba oil and cuckoo flower oil. Such oils can be partially or be fully hydrated, if desired, provided, of course, that you are there retain their oily character.

(B) additives

The additives included in the preparations of the present invention can, and preferably also be included, to a large extent be varied, depending on such factors as use or application area in which the finished preparation is intended to be used, the severity of the Operating conditions that the preparation is likely to be exposed to which the special preparation should have and the specifications to which the special preparation should suffice. So the oil can with additives or Additive concentrates are formulated that are suitable for use as Lubricant in the crankcase, in spark ignition engines (Otto combustion engines) or diesel internal combustion engines, as lubricants for use as cylinder oils, as functional fluids for use as fluids (oils) for automatic transmissions and as Oils for use as lubricants in manual transmissions, as fluids in liquids operated brakes, as tractor oils, gear oils and as lubricants in Locking differential axles.

Those skilled in the art are familiar with the general composition of Additive packages are familiar as used for these different types of applications  will. The one who is not familiar with this technology only has to deal with the huge amount of patent literature in this area, especially with the U.S. patents granted over the past ten years. For an overview Additives to crankcase lubricating oils can be referred to Publication "R.L. Watson and McDonnel, Jr.; Additives - The Right Stuff for Automotive Engine oils; Society of Automotive Engineers Special Publication SP-603 (Fuels and Lubrication Technology); Pages 17 to 28 (1984) "and the publications cited therein. Particularly preferred oil additive preparations for crankcase lubricants are in the Examples I through XVIII of U.S. Patent No. 4,904,401, and particularly preferred Additive preparations for automatic transmission oils are in U.S. Patent No. 4,857,214 described.

Descriptive examples of some types of conventional additives are described below, which are used in conventional amounts in the preparations of the present invention can be. Any of a variety of ashless dispersants can be used can be used in the preparations of the present invention. These close the following types:

Type A - Ashless dispersant based on carboxylic acid

These compounds are reaction products of an acylating agent, e.g. B. one Monocarboxylic acid, dicarboxylic acid, polycarboxylic acid or derivatives thereof, with one or several polyamines and / or polyhydroxy compounds. These products that are in the referred to the present description as an ashless dispersant based on carboxylic acid are described in many patents, for example in the British patent 1,306,529 and in the following U.S. patents: 3,163,603; 3,184,474; 3,215,707; 3,219,666; 3,271,310; 3,272,746; 3,281,357; 3,306,908; 3,311,558; 3,316,177; 3,340,281; 3,341,542; 3,346,493; 3,381,022; 3,399,141; 3,415,750; 3,433,744; 3,444,170; 3,448,048; 3,448,049; 3,451,933; 3,454,607; 3,467,668; 3,522,179; 3,541,012; 3,542,678; 3,574,101; 3,576,743; 3,630,904; 3,632,510; 3,632,511; 3,697,428; 3,725,441; 3,868,330; 3,948,800; 4,234,435; and Re 26,433.  

There are a number of subcategories of ashless carboxylic acid dispersants. One such subcategory, which is a preferred type, is composed of the polyamine succinamides and more preferably the polyamine succinimides in which the succinic acid group contains a hydrocarbyl substituent containing at least 30 carbon atoms. The polyamine used to form such compounds contains at least one primary amino group capable of forming an imide group upon reaction with a hydrocarbon-substituted succinic acid or succinic acid derivative such as an anhydride, lower alkyl ester, acid halide or acid ester. Representative examples of such dispersants are described in U.S. Patent Nos. 3,172,892; 3,202,678; 3,216,936; 3,219,666; 3,254,025; 3,272,746 and 4,234,435. The alkenyl succinimides can be formed by conventional methods, for example by heating the alkenyl succinic anhydride, the acid, the acid ester, the acid halide, or the lower alkyl ester with a polyamine containing at least one primary amino group. The alkenyl succinic anhydride can be prepared simply by heating a mixture of an olefin and maleic anhydride at 180 to 220 ° C. The olefin is preferably a polymer or copolymer of a lower monoolefin such as ethylene, propylene, 1-butene or isobutene. The more preferred starting material for an alkenyl group is polyisobutene with a number average molecular weight of up to 100,000 or higher. In an even more preferred embodiment, the alkenyl group is a polyisobutylene group with a number average molecular weight (determined using the method described in detail below) from 500 to 5000, preferably from 700 to 2500, even more preferably from 700 to 1400 and especially from 800 to 1200. The isobutene used to prepare the polyisobutene is usually (but not necessarily) a mixture of isobutene and other C ₄ isomers of butene, for example 1-butene. More specifically, the acylating agent formed from maleic anhydride and "polyisobutene" made from mixtures of isobutene and other C ₄ isomers such as 1-butene can be referred to as "polybutenyl succinic anhydride" and a succinimide made therewith can be called "Polybutenyl succinimide" may be referred to. However, it is common practice to refer to such substances as "polyisobutenyl succinic anhydride" or "polyisobutenyl succinimide". As used in the present specification, the term "polyisobutenyl" is used to indicate the alkenyl moiety, whether it is made from high purity isobutene or a more contaminated mixture of isobutene and other C ₄ isomers, for example wise 1-butene.

Polyamines which can be used to form the ashless dispersant, include any polyamine that has at least one primary amino group contained in the Can react in such a way that it forms an imide group. A few representative examples include branched chain alkanes containing two or more primary amino groups, for example tetraaminoneopentane, polyaminoalkanols such as 2- (2-amino ethylamino-) ethanol and 2- (2- (2-aminoethylamino-) ethylamino-) ethanol, heterocyclic Compounds containing two or more amino groups, at least one of which is a primary amino group, e.g. B. 1- (β-aminoethyl-) 2-imidazolidone, 2- (2-aminoethyl-a mino-) 5-nitropyridine, 3-amino-N-ethylpiperidine, 2- (2-aminoethyl-) pyridine, 5-aminoindole, 3-amino-5-mercapto-1,2,4-triazole and 4- (aminomethyl) piperidine and the alkylene polyamines such as, for example, propylenediamine, dipropylenetriamine, di (1,2-butylene) triamine, N- (2- Aminoethyl-) 1,3-propanediamine, hexamethylenediamine and tetra- (1,2-propylene-) pentaxine.

The most preferred amines are the ethylene polyamines represented by the formula

H ₂ N (CH ₂ CH ₂ NH) _n H

can be reproduced, where n is an integer from 1 to 10. This ver Bonds include the following: ethylene diamine, diethylene triamine, triethylene tetramine, Tetraethylene pentamine and pentaethylene hexamine including mixtures of the above Links. In this case, n is the mean of the mixture. These ethylene polyamines have a primary amine group at each end of the molecule and so can Form monoalkenyl succinimides and bisalkenyl succinimides. Commercially available Ethylene polyamine blends usually contain smaller amounts of branched Molecular species and cyclic molecular species such as N-aminoethylpiperazine, N, N'-bis (aminoethyl) piperazine and N, N'-bis (piperazinyl) ethane. The preferred ones in Commercially available mixtures have approximate total compositions, which are in  fall within the range that corresponds to diethylenetriamine to pentaethylenehexamine, where Mixtures are most preferred, generally of an overall composition to correspond to tetraethylene pentamine. Process for the preparation of polyalkylene polyamines are known and are reported in the literature, see for example US patent No. 4,827,037 and the publications cited therein.

Especially preferred ashless dispersants for use in the The present invention is therefore the products of a reaction of a polyethylene polyamine, e.g. As triethylene tetramine or tetraethylene pentamine, with one with a hydrocarbon substituted carboxylic acid or an anhydride (or other suitable Acid derivative) by the reaction of a polyolefin, preferably polyisobutene, with a Number average molecular weight from 500 to 5000, preferably from 700 to 2500, even more preferably from 700 to 1400 and in particular from 800 to 1200, with a Unsaturated polycarboxylic acid or an anhydride can be prepared, e.g. B. Ma linseic anhydride, maleic acid or fumaric acid, including mixtures of two or several such substances.

The term "succinimide" as used in the present specification is so to understand that he has the finished reaction product from a reaction between the / the Amine reactant (s) and the hydrocarbon-substituted carboxylic acid or Carboxylic anhydride reactant (s) or a similar acid derivative. It is intends this term to include compounds in which the product Amide bonds, amidine bonds and / or salt bonds in addition to the imide bond of the type resulting from the reaction of a primary amino group and one Anhydride unit results.

If desired, parts of the molecule with residual unsaturation in the alkenyl group of the Alkenyl succinimides can be used as a site for further reactions. For example the alkenyl substituent can be hydrogenated to form an alkyl substituent. More like that Way, the olefinic bond (s) in the alkenyl substituent can be sulfurized, halogenated or hydrohalogenated. Usually it can be applied  such procedures do not achieve very much, and therefore the use of Alkenyl succinimides preferred.

Another subcategory of ashless dispersants based on carboxylic acids, which are described in Alke includes the preparations of the present invention nylsuccinic acid esters and diesters of alcohols containing 1 to 20 carbon atoms and Contain 1 to 6 hydroxyl groups. Representative examples of such compounds are in U.S. Patent Nos. 3,331,776; 3,381,022 and 3,522,179. The Alke nylsuccinic acid part of this ester corresponds to the alkenylsuccinic acid part of the above described succinimides, including the same preferred and most preferred subclass of compounds e.g. B. the alkenyl succinic acids and succinic anhydrides in which the alkenyl group has at least 30 carbon atoms contains, and in particular the polyisobutenyl succinic acids and succinic anhydrides, in which the polyisobutenyl group has a number average molecular weight of 500 to 5000, preferably from 700 to 2500, more preferably from 700 to 1400 and especially from 800 to 1200. As in the case of succinimides, the alkenyl group be hydrogenated or other reactions including the olefinic double bonds be subjected.

Alcohols useful in the preparation of the esters include methanol, ethanol, 2-methylpropanol, octadecanol, eicosanol, ethylene glycol, diethylene glycol, tetraethylene glycol, diethylene glycol monoethyl ether, propylene glycol, tripropylene glycol, glycerin, Sorbitol, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, 1,1,1-trimethylolbutane, Pentaerythritol and dipentaerythritol.

The succinic acid esters are prepared in a simple manner by simply heating a mixture of alkenyl succinic acid, anhydrides or lower alkyl esters (e.g. C ₁ to C ₄ alkyl esters) with the alcohol while distilling off water or lower alcohol. In the case of the acidic esters, less alcohol is used. In fact, acidic esters made from alkenyl succinic anhydrides do not release water. In a further process the alkenyl succinic acid or the alkenyl succinic anhydrides can simply be reacted with a suitable alkylene oxide such as ethylene oxide or propylene oxide including their mixtures.

Another subcategory of ashless dispersants based on carboxylic acid, which are used for Formation of the preparations of the present invention are useful comprises a mixture from an alkenylsuccinic acid ester and an amide. Such mixtures can be prepared by using the alkenylsuccinic acids, alkenylberbers described above succinic anhydrides or lower alkyl esters with either an alcohol and an amine implemented sequentially or in a mixture. The alcohols described above and Amines are also useful in this embodiment. Alternatively, you can Amino alcohols alone or with the alcohol and / or the amine to form the Esteramide mixtures can be used. The amino alcohol can have 1 to 20 carbon contain atoms, 1 to 6 hydroxyl groups and 1 to 4 amine nitrogen atoms. examples are Ethanolamine, diethanolamine, N-ethanol diethylenetriamine and trimethylolaminomethane.

Here too, the alkenyl group of succinic acid ester amide can be hydrogenated or others Reactions involving the olefinic double bonds are subjected.

Representative examples of suitable ester amide mixtures are described in the following US Patents called: 3,184,474; 3,576,743; 3,632,511; 3,804,763; 3,836,471; 3,862,981; 3,936,480; 3,948,800; 3,950,341; 3,957,854; 3,957,855; 3,991,098; 4,071,548; and 4,173,540.

Yet another subcategory of ashless carboxylic acid dispersants, the can be used includes derivatives of Mannich-based hydroxyarylsuccinimides. Such compounds can be prepared by using a polyalkenylber succinic anhydride with an aminophenol to produce an N- (hydroxyaryl) hydrocarbyl succinimide, which is then reacted with an alkylenediamine or polyalkylene polyamine and an aldehyde, e.g. B. formaldehyde in a Mannich base reaction becomes. Details of such a synthesis are described in U.S. Patent No. 4,354,950 described. As with the other ashless dispersants based on carboxylic acid, which has already been mentioned above is the alkenyl succinic anhydride or a  similar acylating agent derived from a polyolefin, preferably from one Polyisobutene, with a number average molecular weight of 500 to 5000, preferably from 700 to 2500, more preferably from 700 to 1400 and especially from 800 to 1200. In the same way, a remaining unsaturation in the Polyalkenyl substituent group can be used as the site for the reaction, for example by hydrogenation or sulfurization.

Type B - Mannich polyamine dispersant

This category of ashless dispersants used in the preparations of the present Invention can be used consists of reaction products of an alkylphenol with one or more aliphatic aldehydes containing 1 to 7 carbon atoms, especially with formaldehyde and its derivatives, and polyamines, in particular Polyalkylene polyamines of the type described above. Example of this Mannich polyamine Dispersants are described in the following U.S. patents: 2,459,112; 2,962,442; 2,984,550; 3,036,003; 3,166,516; 3,236,770; 3,368,972; 3,413,347; 3,442,808; 3,448,047; 3,454,497; 3,459,661; 3,493,520; 3,539,633; 3,558,743; 3,586,629; 3,591,598; 3,600,372; 3,634,515; 3,649,229; 3,697,574; 3,703,536; 3,704,308; 3,725,277; 3,725,480; 3,726,882; 3,736,357; 3,751,365; 3,756,953; 3,793,202; 3,798,165; 3,798,247; 3,803,039; 3,872,019; 3,980,569; and 4,011,380.

The polyamine group of the Mannich polyamine dispersants is derived from polyamine bonds which are characterized in that they form a group of the structure -NH- contain, in which the two remaining valences of nitrogen by hydrogen, Amino groups or organic residues are saturated, which are bonded to the nitrogen atom are. These compounds include aliphatic, aromatic, heterocyclic or carbocyclic polyamines. The source of the oil soluble hydrocarbyl group in the Mannich polyamine dispersant is one with a hydrocarbyl group (hydrocarbon rest) substituted hydroxyaromatic compound which the reaction product from a hydroxyaromatic compound made according to well known procedures with a hydrocarbyl radical or an  Includes hydrocarbon source. The hydrocarbyl substituent gives the hydroxyaromati compound has considerable oil solubility and is preferably substantially aliphatic in character. Usually the hydrocarbyl substituent is derived from one Polyolefin with at least about 40 carbon atoms. The source material for the Hydrocarbon residue should be essentially free of groups attached to it make the hydrocarbyl group insoluble in oil. Examples of acceptable substituent groups are the groups halide, hydroxy, ether, carboxy, ester, amide, nitro and cyano. However, these substituent groups preferably make up no more than 10% by weight of the Hydrocarbon feedstock.

The preferred hydrocarbon feedstocks for making the Mannich Polyamine dispersants are those materials that are substantially saturated Petroleum fractions and olefin polymers are derived, preferably from polymers of Monoolefins with 2 to 30 carbon atoms. The source of the hydrocarbon material can for example of polymers of olefins such as ethylene, propene, 1- Butene, isobutene, 1-octene, 1-methylcyclohexene, 2-butene and 3-pentene can be derived. Copolymers of such olefins with other polymerizable ones are also useful olefinic substances such as styrene. Generally, these copolymers should contain at least 80% and preferably about 95%, by weight, of units, which are derived from the aliphatic monoolefins to increase solubility in oil preserve. The source of the hydrocarbon material generally contains at least about 40 carbon atoms, and preferably at least about 50 carbon atoms, around the To impart a considerable oil solubility to dispersants. The olefin polymers with one Number average molecular weights between 600 and 5000 are for good reasons Reactivity and low cost preferred. However, polymers can also be higher Molecular weight can be used. Particularly suitable hydrocarbon output materials are isobutylene polymers.

The Mannich polyamine dispersants are generally prepared in that one with a hydrocarbyl radical (hydrocarbon radical) substituted hydroxyaromati reaction with an aldehyde and a polyamine. Typically the substituted hydroxyaromatic compound with 0.1 to 10 mol of polyamine and 0.1 to 10  Moles of aldehyde contacted per mole of substituted hydroxyaromatic compound. The reactants are mixed and brought to a temperature above about 80 ° C warmed to initiate the reaction. The reaction is preferably carried out at a Temperature carried out in the range of 100 to 250 ° C. The resulting Mannich Product primarily has a benzylamine bond between the aromatic compound and the polyamine. The reaction can be carried out in an inert diluent such as for example mineral oil, benzene, toluene, naphtha, ligroin or other inert Solvents are carried out to regulate viscosity, temperature and To facilitate reaction speed.

Suitable polyamines for use in the manufacture of Mannich polyamine Dispersants include, but are not limited to, the following polyamines: Methylene polyamines, ethylene polyamines, butylene polyamines, propylene polyamines, pentylene polyamines, hexylene polyamines and heptylene polyamines. The higher homologues like that Amines and related aminoalkyl substituted piperazines are also useful. Specific Examples of such polyamines include ethylenediamine, triethylenetetramine, tris- (2- aminoethyl-) amine, propylene diamine, pentamethylene diamine, hexamethylene diamine, Heptamethylene diamine, octamethylene diamine, decamethylene diamine, di (heptamethylene) triamine, pentaethylene hexamine, di (trimethylene) triamine, 2-heptyl-3- (2-aminopropyl) imidazoline, 1,3-bis (2-aminoethyl) imidazoline, 1- (2-aminopropyl) piperazine, 1,4-bis (2- aminoethyl-) piperazine and 2-methyl-1- (2-aminobutyl-) piperazine. Higher homologues that obtained by condensation of two or more of the above amines also useful, also the polyoxyalkylene polyamines.

The polyalkylene polyamines, examples of which have been mentioned above, are particular useful in the manufacture of Mannich polyamine dispersants for reasons of Cost and effectiveness. Such polyamines are under the keyword "Diamines and higher amines" described in "Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd edition, volume 7, pages 22 to 39 ". They are extremely simple prepared by reacting an ethyleneimine with a ring opening agent such as for example ammonia. To a certain extent, these implementations lead to production complex mixtures of polyalkylene polyamines, the cyclic condensation products  such as include piperazines. Because of their availability, these are Mixtures particularly useful in the manufacture of Mannich polyamine dispersants. However, it is understood that satisfactory dispersants can also be used pure polyalkylene polyamines can be obtained.

Alkylenediamines and polyalkylenepolyamines containing one or more hydroxyalkyl sub have substituents on the nitrogen atom are also useful in the preparation of the Mannich Polyamine dispersant. These materials are typically obtained from Reaction of the corresponding polyamide with an epoxy such as ethylene oxide or propylene oxide. Preferred hydroxyalkyl substituted diamines and polyamines are Compounds in which the hydroxyalkyl groups have less than about 10 carbon atoms exhibit. Examples of suitable hydroxyalkyl substituted diamines and polyamines include following connections, but are not limited to these connections: N- (2- Hydroxyethyl-) ethylenediamine, N, N'-bis- (2-hydroxyethyl-) ethylenediamine, mono- (hydroxy propyl-) diethylene triamine, di- (hydroxypropyl-) tetraethylene pentamine and N- (3-hydrobutyl) tetramethylene diamine. Higher homologues by condensation of the above hydroxyalkyl-substituted diamines and polyamines via amine groups or via Ether groups obtained can also be used.

Any conventional formaldehyde donor can be used with the Manufacture of Mannich polyamine dispersants. Examples of such formaldehyde releasing reagents are trioxane, paraformaldehyde, trioxymethylene, aqueous formalin and gaseous formaldehyde.

Type C - polymeric polyamine dispersant

Also suitable for use in the preparations of the present invention Polymers containing basic amine groups and oil solubilizing groups, for example wise alkyl groups of at least about 8 carbon atoms. Such polymers In the present description, dispersants are referred to as "polymeric polyamine Dispersant ". Such materials include interpolymers of decylmeth acrylate, vinyl decyl ether or from an olefin with a relatively high molecular weight  Amino alkyl acrylates and amino alkyl acrylamides, but are not on these materials limited. Examples of polymeric polyamine dispersants are in the following patents called: U.S. Patents No. 3,329,658; 3,449,250; 3,493,520; 3,519,565; 3,666,730; 3,687,849 and 3,702,300.

Type D - Aftertreated ashless dispersant

Any of the ashless dispersants mentioned above under types A to C can an aftertreatment with one or more suitable reagents such as, for example Urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, Anhydrides, dibasic acids with low molecular weight, nitriles, epoxides, Phosphoric acids and phosphoric acid esters are subjected. Such post-treated Ashless dispersants can be used in the formation of the preparations of the present Invention can be used. Examples of post-treatment procedures and examples post-treated ashless dispersants are mentioned in the following US patents: 3,036,003; 3,200,107; 3,216,936; 3,256,185; 3,278,550; 3,312,619; 3,366; 569; 3,367,943; 3,373,111; 3,403,102; 3,442,808; 3,455,831; 3,455,832; 3,493,520; 3,502,677; 3,513,093; 3,573,010; 3,579,450; 3,591,598; 3,600,372; 3,639,242; 3,649,229; 3,649,659; 3,702,757; and 3,708,522 and 4,971,598.

Mannich base derivatives of hydroxyarylsuccinimides which have been post-treated with C ₅ to C ₉ lactones such as ε-caprolactone and optionally with other post-treatment agents, as described, for example, in US Pat. No. 4,971,711, can also be used in practice Application of the present invention can be used. U.S. Patent No. 4,971,711 and related U.S. Patents No. 4,820,432; 4,828,742; 4,866,135; 4,866,139; 4,866,140; 4,866,141; 4,866,142; 4,906,394 and 4,913,830 disclose other suitable ashless dispersants that can be used.

Metal hydrocarbyl dithiophosphates can be used in the preparations of the invention whenever this is desired. As is well known, metal hydrocarbyl dithiophosphates usually produced by reacting phosphorus pentasulfide with  one or more alcohols or phenolic compounds or diols Preparation of a hydrocarbylditniophosphoric acid, followed by one or more Metal containing bases is neutralized. If a monohydric alcohol or a phenol used in this reaction, the end product is a metal dihydrocarbyl dithio phosphate. On the other hand, if a suitable diol, e.g. B. 2,4-pentanediol, in this Implementation is used, the end product is a metal salt of a cyclic hydrocarbyl dithiophosphoric acid. For example, see U.S. Patent No. 3,089,850 referred. Typical oil-soluble metal hydrocarbyl dithiophosphates can thus by the formula

are reproduced, wherein R ₁ and R _{2 are} independently hydrocarbyl groups (hydrocarbon groups) or taken together are a single hydrocarbyl group which forms a cyclic structure with the phosphorus atom and the two oxygen atoms, preferably a hydrocarbyl-substituted trimethylene group with sufficient content of carbon atoms to form the compound to make oil soluble. In the formula, M is also a metal and x is an integer that corresponds to the valence of M. The preferred compounds are those in which R ₁ and R _{2 are} separate hydrocarbyl groups, ie the metal dihydrocarbyl dithiophosphates. Typically, the hydrocarbyl groups of the metal dihydrocarbyl dithiophosphates contain no more than about 50 carbon atoms each, although even higher molecular weight hydrocarbyl groups may be present in the compound. The hydrocarbyl groups include cyclic and acyclic groups, both saturated and unsaturated groups such as alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, aryl groups, cycloalkylalkyl groups and aralkyl groups. It is understood that the hydrocarbyl groups may contain elements other than carbon and hydrogen, provided that such other elements do not affect the hydrocarbon-like nature of the hydrocarbyl group. Thus, the hydrocarbyl groups can contain ether oxygen atoms, thioether sulfur atoms, secondary or tertiary amino nitrogen atoms and / or inert functional groups such as, for example, esterified carboxyl groups, keto groups and thioketo groups.

Those in the oil-soluble metal dihydrocarbyl dithiophosphates and oil-soluble metal Hydrocarbyl dithiophosphates with cyclic hydrocarbyl radicals close metals present Metals such as lithium, sodium, potassium, copper, magnesium, calcium, zinc, strontium, Cadmium, barium, mercury, aluminum, tin, lead, chrome, molybdenum, tungsten, Manganese, iron, cobalt, nickel and ruthenium as well as combinations of two or several such metals. Of the above compounds are the Salts, Group II metals, aluminum, lead, tin, molybdenum, manganese, cobalt and / or contain nickel, preferred. The dihydrocarbyl dithiophosphates of zinc and Copper is particularly preferred, with the zinc salts being the most preferred type of Connections to the application is.

The phosphorodithioic acids from which the metal salts are formed can by Reaction of about 4 moles of one or more alcohols (cyclic or acyclic Alcohols) or one or more phenols or mixtures of one or more Alcohols and one or more phenols (or about two moles of one or more Diols) per mole of phosphorus pentasulfide. The reaction can be in one Temperature range of 50 to 200 ° C can be carried out. The reaction comes in 1 to 10 h at the end. Hydrogen sulfide is released during the reaction.

Another process for the preparation of the phosphorodithioic acids concludes the reaction one or more alcohols and / or one or more phenols with phosphorus sesquisul fid in the presence of sulfur, as described, for example, in the PCT (International) Publication No. WO 90/07512 is described. This reaction increases with Temperature, preferably in the range of 85 to 150 ° C, at a total atomic ratio P: S of about 2.5: 1 performed.  

The in the manufacture of phosphorodithioic acids according to one of the two above Alcohols used in the process are preferably primary alcohols or secondary alcohols Alcohols. Mixtures of these are also suitable. The primary alcohols close Propanol, butanol, isobutyl alcohol, pentanol, 2-ethyl-1-hexanol, isooctyl alcohol, nonanol, Decanol, undecanol, dodecanol, tridecanol, tetradecanol, octadecanol and eicosanol. The primary alcohols can have various substituent groups such as Contain halogen atoms and nitro groups that do not interfere with the desired reaction. At suitable secondary alcohols include 2-butanol, 2-pentanol, 3-pentanol, 2-hexanol and 5-methyl-2-hexanol. In some cases it is preferred to use mixtures to use different alcohols, for example mixtures of 2-propanol with a or more primary alcohols of higher molecular weight, especially primary Alcohols with 4 to 13 carbon atoms. Such mixtures preferably contain at least 10 mole% 2-propanol and usually contain 20 to 90 mole% 2-propanol. In a preferred embodiment, the alcohol comprises 30 to 50 mol% of 2-propanol, 30 to 50 mol% of isobutyl alcohol and 10 to 30 mol% of 2-ethyl-1-hexanol.

Other suitable mixtures of alcohols include 2-propanol / butanol, 2-propanol / 2- Butanol, 2-propanol / 2-ethyl-1-hexanol, butanol / 2-ethyl-1-hexanol, isobutyl alcohol / 2-ethyl 1-hexanol and 2-propanol / tridecanol.

Cycloaliphatic alcohols used in the manufacture of the phosphorodithio acids are suitable include cyclopentanol, cyclohexanol, methylcyclohexanol, Cyclooctanol and borneol. Such alcohols are preferably used in combination with one or more primary alkanols such as butanol and isobutyl alcohol used.

Illustrative examples of phenols used in the formation of phosphorodithioic acids include phenol, o-cresol, m-cresol, p-cresol, 4-ethylphenol and 2,4- Xylenol. It is desirable to use phenolic compounds in combination with primary ones To use alkanols such as propanol, butanol and hexanol.  

Other alcohols that can also be used include benzyl alcohol, Cyclohexenol and their ring alkylated analogs.

It is understood that when mixtures of two or more alcohols and / or Phenols can be used to prepare the phosphorodithioic acids, the resulting Usually a product of a mixture of three or more different dihydrocarbylphos phordithioic acids, usually in the form of a statistical distribution, based on the number and the proportions of the alcohols and / or phenols used.

Illustrative examples of diols used in the formation of phosphorodithioic acids include 2,4-pentanediol, 2,4-hexanediol, 3,5-heptanediol, 7-methyl-2,4- octanediol, neopentyl glycol, 2-butyl-1,3-propanediol and 2,2-diethyl-1,3-propanediol.

The production of the metal salts of the hydrocarbyldithiophosphoric acids or Cyclic hydrocarbyldithiophosphoric acids are usually effected by reaction the acidic product with a suitable metal compound such as a Metal carbonate, metal hydroxide, metal alkoxide, metal oxide or other suitable Metal salt. Simply mixing and heating the reactants mentioned is normal sufficient to effect the reaction and the resulting product is common of sufficient purity for use in the practical implementation of the present invention. Typically, the salts are in the presence of a dilution by means such as in the presence of an alcohol, water or one light mineral oil. Neutral salts are produced by one Equivalent of a metal oxide or hydroxide with one equivalent of the acid. Basic metal salts are made by adding an excess, i.e. H. one over an equivalent amount, the metal oxide or hydroxide an equivalent of Adds dihydrocarbylphosphorodithioic acid or cyclic hydrocarbylphosphorodithioic acid.

Illustrative examples of metal compounds used in such reactions include calcium oxide, calcium hydroxide, silver oxide, silver carbonate, Magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium ethoxide, zinc oxide, Zinc hydroxide, strontium oxide, strontium hydroxide, cadmium oxide, cadmium hydroxide,  Cadmium carbonate, barium oxide, aluminum oxide, aluminum propoxide, iron carbonate, Copper hydroxide, lead oxide, tin butoxide, cobalt oxide, nickel hydroxide and manganese oxide.

In some cases, the installation of certain components, such as smaller ones, facilitates Amounts of metal acetate or acetic acid together with the metal reactant and the reaction leads to an improved product. For example, the use of up to approx 5% zinc acetate in combination with the desired amount of zinc oxide causes the formation is facilitated by zinc dihydrocarbyl dithiophosphates.

Examples of useful metal salts of dihydrocarbyldithiophosphoric acids and methods for Preparation of such salts are found in prior art documents for example, in U.S. Patent Nos. 4,263,150; 4,289,635; 4,308,154; 4,322,479; 4,417,990 and 4,466,895.

Generally, the preferred types of metal salts are dihydrocarbyl dithiophosphorus acid the oil-soluble metal salts of dialkyldithiophosphoric acids. Such connections generally contain alkyl groups with at least 3 carbon atoms, and preferably the alkyl groups contain up to 10 carbon atoms, although as above noted - the use of even higher molecular weight alkyl groups is completely possible. A few illustrative examples of zinc dialkydithiophosphates include zinc diisopropyl dithiophosphate, zinc dibutyl dithiophosphate, zinc diisobutyl dithio phosphate, zinc di-sec-butyldithiophosphate, the zinc dipentyldithiophosphate, the zinc di hexyldithiophosphate, the zinc diheptyldithiophosphate, the zinc dioctyldithiophosphate, the Zinkdinonyldithiophospate, the Zinkdidecyldithiophosphate and their higher homologues. Mixtures of two or more such compounds are often used preferred, such as metal salts of dithiophosphoric acids, from mixtures of isopropyl alcohol and sec-butyl alcohol, isopropyl alcohol, isobutyl alcohol and 2- Ethyl hexyl alcohol, isopropyl alcohol, butyl alcohol and pentyl alcohol and isobutyl alcohol and octyl alcohol are formed.  

If desired, the metal dihydrocarbyl dithiophosphate additives of the above type described with an epoxy to form an adduct. in the in general, the most suitable metal dihydrocarbyl dithiophosphates used for Formation of such adducts can be used, the zinc dihydrocarbyl dithiophosphates. The Epoxies include alkylene oxides and arylalkylene oxides. Typical alkylene oxides that can include alkylene oxides having up to about 8 carbon atoms in the Molecule such as ethylene oxide, propylene oxide, 1,2-butene oxide, trimethylene oxide, Tetramethylene oxide, butadiene monoepoxide, 1,2-hexene oxide and epichlorohydrin. The Arylalkylene oxides are exemplified by styrene oxide. Other suitable epoxies For example, include butyl 9,10-epoxystearate, epoxidized soybean oil, epoxidized Tung oil and an epoxidized styrene-butadiene copolymer. Procedures for Manufacture of epoxy adducts are known and are used for example in the U.S. Patent No. 3,390,082 reports.

The adduct can be obtained by simply the metalphosphorodithioate and the epoxy mixes. The reaction is usually exothermic and can be at wide temperatures limits from 0 ° C to 300 ° C. Since the reaction is exothermic, it becomes best carried out in such a way that a reactant, usually the epoxide, in small aliquots to the other reactants for easy control of the To allow temperature of the reaction. The reaction can be carried out in a solvent such as For example, benzene, mineral oil, naphtha or n-hexene can be carried out.

The chemical structure of the adduct is unknown. The adducts caused by the reaction one mole of the phosphorodithioate with 0.25 moles to 5 moles, usually up to 0.75 moles or 0.5 moles of a lower alkylene oxide, especially ethylene oxide and propylene oxide are the preferred adducts.

Another type of metal dihydrocarbylphosphorodithioate additives used in the Preparations of the present invention can be used includes mixed acid Metal salts of a combination of (a) at least one phosphorodithioic acid of the formula (RO) (R′O) PSSH as described above by way of example (where R and R ′ are independent from each other are hydrocarbyl groups of a sufficient carbon content to the salt  solubilize in a lubricating oil, or R and R 'taken together, a single one Hydrocarbyl form a cyclic unit with the two oxygen atoms and the phosphorus atom), and (b) at least one aliphatic or alicyclic Carboxylic acid. The carboxylic acid can be a monocarboxylic acid or a polycarboxylic acid, which usually contains 1 to 3 carboxyl groups and preferably only one carboxyl group. It can have 2 to 40 carbon atoms, preferably 2 to 20 carbon atoms and advantageously contain 5 to 20 carbon atoms.

The preferred carboxylic acids are those having the formula R ³ COOH, wherein R ^{3 is} an aliphatic or alicyclic hydrocarbon based residue which is preferably free of acetylenic unsaturation. Suitable acids include butanoic acid, pentanoic acid, hexanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, octadecanoic acid and eicosanoic acid as well as olefinically unsaturated acids such as oleic acid, linoleic acid and linolenic acid and the linoleic acid dimer. Most often, R ^{3 is} a saturated aliphatic group and especially a branched alkyl group such as the isopropyl group or the 3-heptyl group. Illustrative examples of polycarboxylic acids are succinic acid, alkyl and alkenyl succinic acid, adipic acid, sebacic acid and citric acid.

The mixed acid metal salts can be prepared by using a metal salt a phosphorodithioic acid with a metal salt of a carboxylic acid in the desired one Ratio mixes. The ratio of the equivalents of phosphorodithioic acid salt to Carboxylic acid salt is between 0.5: 1 and 200: 1. Advantageously, the ratio in the range from 0.5: 1 to 100: 1, preferably from 0.5: 1 to 50: 1 and even more preferably from 0.5: 1 to 20: 1. In addition, the ratio can range from 0.5: 1 to 4.5: 1, preferably from 2.5: 1 to 4.25: 1. For this purpose it is Equivalent weight of a phosphorodithioic acid its molecular weight divided by the number of -PSSH groups in the molecule, and the equivalent weight of a carboxylic acid is hers Molecular weight divided by the number of carboxy groups in the molecule.  

A second and preferred procedure for the preparation of the mixed acid metal salts, which are useful in the context of the present invention is a mixture of the To produce acids in the desired ratio and the acid mixture with a to implement a suitable metal base. When using this manufacturing process, it is often possible to produce a salt that has an excess of metal based on the Number of equivalents of acid present. So mixed acid metal salts that as much as two equivalents and especially up to about 1.5 equivalents of metal per Equivalent to contain acid. The equivalent of a metal for this Purpose is its atomic weight divided by its value.

Modifications to the procedures described above can also be used to manufacture the mixed acid metal salts used in the context of the present invention are useful. For example, a metal salt can combine one of the two acids with the other Acid are mixed, and the resulting mixture is made with additional metal base implemented.

Suitable metal bases for the preparation of the mixed acid metal salts include the oxides, Hydroxides, alkoxides and other basic salts of the metals listed above. In some cases, the free metals themselves can also be used. Examples are sodium hy hydroxide, potassium hydroxide, magnesium oxide, calcium hydroxide, zinc oxide, lead oxide and Nickel oxide.

The temperature at which the mixed acid metal salts are produced is generally between 30 ° C and 150 ° C, preferably up to 125 ° C. If the mixed acid salts are produced by neutralizing a mixture of acids with a metal base, it is preferred to use temperatures above about 50 ° C., especially temperatures above about 75 ° C. It is often advantageous to carry out the reaction in the presence of an im essential inert, normally liquid organic diluents such as for example, naphtha, benzene, xylene or mineral oil. If that Thinner is mineral oil, it often does not need to be removed before that Mixed acid metal salt as an additive for lubricants or functional liquids is used.  

U.S. Patent Nos. 4,308,154 and 4,417,970 describe manufacturing procedures of these mixed acid metal salts and disclose a number of examples of such Mixed salts.

Metal hydrocarbyl dithocarbamates are another type of oil-soluble metal salts that can be used in the preparations of the present invention. These are salts one or more dithiocarbamic acids of the formula RR'N-CSSH, wherein R and R 'are each are independently hydrocarbyl groups in which the total number of carbon atoms in the radicals R and R 'is sufficient to make the metal salt oil-soluble. R and R 'can be taken together for a polymethylene group or alkyl substituted Polymethylene group stand and thereby a cyclic connection with the nitrogen atom form, d. H. a monocyclic hydrocarbyl dithiocarbamate. Generally contain the Hydrocarbyl groups each have at least two carbon atoms and can be 50 or more Contain carbon atoms. The metal component found in the dihydrocarbyl dithiocarbamate salts (or monocyclic hydrocarbyldithiocarbamate salts) may be present be monovalent metal or a multivalent metal, although multivalent metals are preferred because the salts of the polyvalent metals have a tendency to to have better solubility in oils with lubricating viscosity. So although the alkali metal hydrocarbyldithiocarbamate with monocyclic hydrocarbon structure or the Alkali metal dihydrocarbyl dithiocarbamates can be used if they are oil-soluble, the preferred salts include, for example, salts of one or more of the alkaline earth metals le, of zinc, cadmium, magnesium, tin, molybdenum, iron, copper, nickel, cobalt, Chrome and lead one. The metal dihydrocarbyldithiocarbamates with Group H metals are preferred.

When choosing a metal salt of a dithiocarbamic acid, which is in preparations of the The present invention is to be used, the radicals R and R 'and the metal be varied as long as the metal salt is sufficiently oil-soluble. The nature and type of Mineral raw material and the possible scope of the Treated lubricating oil should be considered when choosing the metal salt.  

The metal component of the metal dihydrocarbyldithiocarbamate is usually a simple metal ion. In the case of certain polyvalent metal derivatives, such as in the case of tin and lead compounds, however, the metal component itself can be hydrocarbyl-substituted, e.g. B. a group (RR'N-CSS) _x MR ₁ R ₂ , wherein M is a polyvalent metal, R, R ', R ₁ and R _{2 are} independently hydrocarbyl groups (and optionally R and R' taken together a single cyclic hydrocarbyl group in which the total number of carbon atoms is sufficient to render the compound oil-soluble and x is a sufficient integer for the remaining valence (s) of M to be saturated. Procedures such as those described in U.S. Patent No. 2,786,814 can be used to prepare such hydrocarbyl substituted metal dithiocarbamates.

Mixtures of metal salts of dithiocarbamic acids also come in useful Within the scope of the present invention. Such mixtures can are prepared by first preparing mixtures of dithiocarbamic acids and then the acid mixtures are converted into metal salts. Alternatively, metal salts various dithiocarbamic acids and then obtaining the desired Product to be mixed. The mixtures used in the preparations of the invention can be introduced, so the physical mixture of different Be metal dithiocarbamic acid compounds or be compounds that are various Contain dithiocarbamate groups bound to the same polyvalent metal atoms.

Examples of alkyl groups are the groups ethyl, propyl, butyl, amyl, hexyl, heptyl, Octyl, decyl, dodecyl, tridecyl, pentadecyl and hexadecyl including their isomeric ones To form. Examples of cycloalkyl groups include cyclohexyl groups and cycloheptyl groups, and examples of aralkyl groups include benzyl groups and phenethyl group. Examples of polymethylene groups include pentamethylene groups and Hexamethylene groups, and examples of alkyl substituted polymethylene groups include methyl pentamethylene groups and dimethyl pentamethylene groups.  

Specific examples of the metal dithiocarbamates used in the preparations of the invention usable include the following compounds: zinc dibutyldithiocarbamate, Zinc diamyl dithiocarbamate, zinc di (2-ethylhexyl) dithiocarbamate, cadmium dibutyl dithio carbamate, cadmium dioctyldithiocarbamate, cadmium octyldithiocarbamate, magnesium dibu tyldithiocarbamate, magnesium dioctyldithiocarbamate, cadmium dicetyldithiocarbamate, Copper diamyldithiocarbamate, sodium dioctadecyldithiocarbamate, lead dioctyldithiocarbamate, Nickel diheptyldithiocarbamate and calcium di-2-ethylhexyldithiocarbamate.

The various metal salts of dithiocarbamic acids used in the preparations of the Invention are usable, are well known in the art and can by known procedures are produced. For example, reference is made to "Ullmann Encyclopedia of Technical Chemistry, Volume 10, Verlag Chemie, Weinheim, Copyright 1975, pages 167 to 170 "(and references cited therein);" Thorn and Ludwig, The Dithiocarbamates and Related Compounds, Elsevier Publishing Company, 1962, pages 12 to 37 "(and references cited therein);" Delepine, Compt. Rend., 144, p. 1125 (1907) ";" Whitby et al., Proceedings and Transactions of the Royal Society of Canada, XVIII, pp. 111 to 114 (1924) "(and references cited therein); "Chabrier et al., Bulletin de la Societe Chimique De France, pages 43 ff. (1950)" (and references cited therein); and U.S. Patent Nos. 1,622,534; 1,921,091; 2,046,875; 2,046,876; 2,258,847; 2,406,960; 2,443,160; 2,450,633; 2,492,314; 2,580,274; 3,513,094; 3,630,897; 4,178,258 and 4,226,733.

Although boron is not a metallic element, boron tris (dihydrocarbyldithiocarbamate) in the preparations of the present invention either alone or in combination with one or more metal dihydrocarbyldithiocarbamates can be used. Procedure which are suitable for the production of such bordithiocarbamates are in the US U.S. Patent No. 4,879,071.

Derivatives of metal dihydrocarbyldithiocarbamates can be in addition to or instead of of the metal dihydrocarbyl dithiocarbamates. Such derivatives close phosphates derived from dithiocarbamate, as described, for example, in US Pat. 4,919,830 are described, reaction products of N, N-diorganodithiocarbamates with  Thionyl chloride as described in U.S. Patent No. 4,867,893, N, N-diorgano dithiocarbamate alkylthiosuifinyl halide reaction products, such as those in the U.S. Patent No. 4,859,356, reaction products of halogenated EPDM Terpolymers and alkali metal dialkyldithiocarbamate as described in U.S. Patent No. 4,502,972 and sulfurized metal dihydrocarbyl dithiocarbamates as described in U.S. Patent No. 4,360,438. These are just individual mentions below other. In addition, the metal dihydrocarbyldithiocarbamates in combination with other carbamate compounds such as a 1,2-dicarbethoxyethyl dialkyldithio carbamate as described in U.S. Patent No. 4,479,883 or a mercaptoal kanoic acid dithiocarbamate of the type used in U.S. Patent No. 3,890,363 is described.

Metal-containing surfactants (detergents) can be found in the preparations of the present invention can be used. Examples of these components are oil-soluble or oil-dispersible basic salts of alkali metals or alkaline earth metals with one or more of the following acidic substances (or mixtures thereof): (1) Sulfonic acids, (2) carboxylic acids, (3) salicylic acids, (4) alkylphenols, (5) sulfurized Alkylphenols, (6) organic phosphoric acids by at least one direct Carbon-phosphorus bond are marked. Such organic phosphoric acids include such compounds as are obtained by treating an olefin polymer (e.g. Polyisobutene with a molecular weight of 1000) with a phosphorizing agent such as phosphorus trichloride, phosphorheptasulfide, phosphorus pentasulfide, Phosphorus trichloride and sulfur, white phosphorus and sulfur halide or phosphorus thiochloride can be produced. The most widely used salts of such Acids are the salts of sodium, potassium, lithium, calcium, magnesium, strontium and bariums. The salts for use in this embodiment are preferred basic salts with a TBN value of at least 50, preferably of over 100 and am most preferably over 200. In this context, the TBN value is determined in accordance with ASTM D 2896-88.  

The term "basic salt" is used to refer to metal salts in which the Metal is present in stoichiometrically larger amounts than the rest of the organic acid. Close the commonly used procedures for the preparation of the basic salts heating a mineral oil solution of an acid with a stoichiometric excess a neutralizing agent containing a metal, such as a metal oxide, Metal hydroxides, metal carbonates, metal bicarbonates or metal sulfides at one temperature of about 50 ° C and filtering the resulting mass. The use of a "Promoters" in the neutralization step to support the installation of a large one Excess metal is known in the same way. Examples of compounds used as Promoters that can be used include phenolic substances such as phenol, Naphthol, alkylphenol, thiophenol, sulfurized alkylphenol and condensation products of formaldehyde with a phenolic substance, alcohols such as methanol, 2-propanol, octyl alcohol, cellosolve alcohol, carbitol alcohol, ethylene glycol, stearyl alcohol hol and cyclohexyl alcohol and amines such as aniline, phenylenediamine, Phenothiazine, phenyl-beta-naphthylamine and dodecylamine. A particularly effective one A process for making the basic salts involves mixing an acid with a Excess of a basic neutralizing agent containing alkaline earth metal and at least one alcohol promoter and the carbonation of the mixture an elevated temperature of, for example, 60 ° C to 200 ° C.

Examples of suitable metal-containing surfactants include the following Compounds, but are not limited to these compounds: basic or overbased salts of such substances as lithium phenates, sodium phenates, potassium phenates, Calcium phenates, magnesium phenates, sulfurized lithium phenates, sulfurized sodium phenates, sulfurized potassium phenates, sulfurized calcium phenates and sulfurized magnesium phenates, in which each aromatic group has one or more aliphatic groups in order to Imparting solubility in a hydrocarbon, lithium sulfonates, sodium sulfonates, Potassium sulfonates, calcium sulfonates and magnesium sulfonates, in which each is sulfonic acid unit is bound to an aromatic nucleus, which in turn usually contains one or contains several aliphatic substituents to increase solubility in a hydrocarbon to lend; Lithium salicylates, sodium salicylates, potassium salicylates, calcium salicylates and Magnesium salicylates, in which the aromatic unit is usually a substituent  or contains more aliphatic substituents to solubility in a hydrocarbon to rent; the lithium, sodium, potassium, calcium and magnesium salts are more hydrolyzed phosphosulfurized olefins with 10 to 2000 carbon atoms or from hydrolyzed phosphosulfurized alcohols and / or substituted with aliphatic groups Phenolic compounds having 10 to 2000 carbon atoms; the lithium, sodium, potassium, Calcium and magnesium salts of aliphatic carboxylic acids and with aliphatic groups substituted cycloaliphatic carboxylic acids and many other similar alkali metal and Alkaline earth metal salts of oil-soluble organic acids. Mixtures basic or over basic salts of two or more different alkali metals and / or alkaline earths Tallen can be used. Basic or overbased can also be used in the same way Salts of mixtures of two or more different acids or two or more different types of acids (e.g. one or more calcium phenates with one or several calcium sulfonates) can be used. Although salts of rubidium, Cesiums and strontiums are used; however, they make their cost for most Uses impractical to use. Although barium salts are effective, in equally the status of barium as a heavy metal from toxicolic barium salts View less preferred for an application taking place today.

As is well known, overbased metal surfactants are generally used as compounds viewed that contain excessive amounts of inorganic bases, probably in Form of microdispersions or colloidal suspensions. The terms "oil-soluble" and "Dispersible in oil" are applied to these metal-containing surfactants in such a way that these include metal detergents in which there are inorganic bases that are not are necessarily completely or really oil-soluble in the strict sense of the term, insofar as such detergents, when mixed with base oils, become in many points behave exactly as if they were completely or totally dissolved in the oil would be.

Common were the various basic or overbased detergents listed above have been described in detail, sometimes quite simply alkaline or called alkaline earth metal salts of organic acids.  

Process for the preparation of the oil-soluble basic or overbased aikalimetall- and alkaline earth metal detergents are experts in this field of technology well known. They are extensively reported in the patent literature. For example, it will to the disclosures of U.S. Patent No. 2,451,345; 2,451,346; 2,485,861; 2,501,731; 2,501,732; 2,585,520; 2,671,758; 2,616,904; 2,616,905; 2,616,906; 2,616,911; 2,616,924; 2,616,925; 2,617,049; 2,695,910; 3,178,368; 3,367,867; 3,496,105; 3,629,109; 3,865,737; 3,907,691; 4,100,085; 4,129,589; 4,137,184; 4,148,740; 4,212,752; 4,617,135; 4,647,387; 4,880,550; British published patent application 2,082,619 A and European Patent Publications No. 121,024 B1 and 259,974 A2.

For certain applications, the preparations can contain metal-free, sulfur-containing antiwear agents and / or agents for applications under extremely high pressure (extreme pressure agents; EP agents). Examples of such compounds are included in the categories dihydrocarbyl polysulfides, sulfurized olefins, sulfurized fatty acid esters of both natural and synthetic origin, trithiones, sulfurized thienyl derivatives, sulfurized terpenes, sulfurized oligomers of C ₂ to C ₈ monoolefins and sulfurized Diels-Alder adducts, for example, those disclosed in US Reissue Patent Re 27,331. Specific examples include Mn 1100 sulfurized polyisobutene, sulfurized isobutylene, sulfurized diisobutylene, sulfurized triisobutylene, dicyclohydyl polysulfide, diphenyl polysulfide, dibenzyl polysulfide, dinonyl polysulfide, and mixtures of di-tert-butyl polysulfide such as mixtures of di-tert-butyl-trisulfide, for example Di-tert-butyl pentasulfide (among others).

Kombin 30753 00070 552 001000280000000200012000285913064200040 0002004317105 00004 30634ations of such categories of sulfur-containing antiwear agents and / or agents for working at extremely high pressure (EP agents) can also can be used, for example a combination of sulfurized isobutylene and di-tert- butyl trisulfide, a combination of sulfurized isobutylene and dinonyl trisulfide, and one Combination of sulfurized tall oil and dibenzyl polysulfide.  

The most preferred oil-soluble, metal-free, sulfur-containing antiwear medium and / or high pressure additives (EP additives) - assessed from the perspective of cost efficiency - the sulfurized olefins containing at least 30% by weight sulfur are the dihydrocar byl polysulfides containing at least 25% by weight sulfur and mixtures thereof sulfurized olefins and polysulfides. Of these materials, sulfurized isobutylene is included a sulfur content of at least 40% by weight and a chlorine content of at least 0.2% by weight the most particularly preferred material. Manufacturing process sulfurized olefins are described in U.S. Patent Nos. 2,995,569; 3,673,090; 3,703,504; 3,703,505; 3,796,661 and 3,873,454. Sulfurized can also be used Oleic derivatives as described in U.S. Patent No. 4,654,156.

Other types of antiwear additives and / or high pressure additives (EP additives), that can be used in the preparations of the present invention for example esters of boric acid, esters of phosphoric acids, amine salts of phosphoric acid ren and acid esters, higher carboxylic acids and their derivatives and chlorine-containing Additives. Esters of boric acids that can be used include borate esters, Metaborate esters, pyroborate esters and Biborate esters of monovalent and / or multivalent Alcohols and / or phenols, for example trioctylborate, tridecylborate, 2- Ethyl hexyl pyroborate, isoamyl metaborate, trixylyl borate and butyl (2,4-hexanediyl) borate.

Typical esters of phosphoric acids used as antiwear additives and / or high pressure additives (EP additives) can be used, including trihydrocarbyl phosphite, -phos phonates and phosphates as well as dihydrocarbyl phosphites such as tricresyl phosphate, Tributyl phosphite, tris (2-chloroethyl) phosphate and phosphite, dibutyltrichloromethylphos phonate, di (n-butyl) phosphite, triphenyl phosphite and tolylphosphinic acid dipropyl ester.

Among the amine salts of phosphoric acids and phosphoric acid esters that are used can be amine salts of partially esterified phosphoric acid, the partially esterified phosphorous acids, the partially esterified phosphonic acid and the partially esterified Phosphinic acid and its partial and total thio analogs such as partial esterified monothiophosphoric acid, dithiophosphoric acid, trithiophosphoric acid and tetra thiophosphoric acid and amine salts of phosphonic acids and their thio analogues. Specific  Examples include the dihexylammonium salt of dodecylphosphoric acid, diethylhexyl ammonium salt of dioctyldithiophosphoric acid, the octadecylammonium salt of Dibutylthiophosphoric acid, the dilaurylammonium salt of 2-ethylhexylphosphoric acid, the Dioleylammonium salt of butanephosphonic acid and analogous compounds.

Higher carboxylic acids and derivatives used as an antiwear additive and / or high pressure additive (EP additive) can be used, are exemplified by fatty acids, dimerized and trimerized unsaturated natural acids, e.g. B. linoleic acid and ester, amine, Ammonia and metal salts of the compounds mentioned, in particular lead salts, and Amides and imidazoline salts and their condensation products, oxazolines and esters of Fatty acids such as ammonium di (linoleic acid), lard, oleic acid, animal glycerides and pencil stearate reproduced.

Suitable chlorine-containing additives include both paraffin-type chlorinated waxes as well as the microcrystalline type, multi-halogenated aromatic compounds such as for example dichlorobenzene and trichlorobenzene, trifluoromethylnaphthalenes, perchlorobenzene, Pentachlorophenol and dichlorodiphenyltrichloroethane. Chlorosulfurizers can also be used te olefins and olefinic waxes and sulfurized chlorophenylmethyl chlorides and Chlorxanthate. Specific examples include chlorodibenzyl disulfide, chlorosulfurized Polyisobutene with Mn 600, chlorosulfurized pinene and chlorosulfurized lard.

Seal performance improvers (elastomer compatibility additives) can be used in the formulations of the present invention. Known materials of this type include dialkyl diesters such as, for example, dioctyl sebacate, aromatic hydrocarbons of suitable viscosity, such as, for example, Panasol AN-3N, products such as, for example, Lubrizol 730, polyol esters such as, for example, the Emery 293, 2936 and 2939 esters from the Emery Group from Henkel Corporation and Hatcol 2352, 2962, 2925, 2938, 2939, 2970, 3178 and 4322 polyol ester products from Hatco Corporation. Generally speaking, the most suitable diesters include the adipates, azelates and sebacates of C ₈ to C ₁₃ alkanols or mixtures thereof and the phthalates of C ₄ to C ₁₃ alkanols or mixtures thereof. Mixtures of two or more different types of diesters, e.g. B. dialkyl adipates and dialkylacelates can also be used. Examples of such materials include the n-octyl, 2-ethylhexyl, isodecyl and tridecyl diesters of adipic acid, azelaic acid and sebacic acid and the n-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, Decyl, undecyl, dodecyl and tridecyl diesters of phthalic acid.

Oxidation inhibitors can be used, for example one or more phenolic oxidation inhibitors, aromatic amine-containing oxidation inhibitors, sulfurized phenol oxidation inhibitors and organic phosphites, among others Links. Examples include 2,6-di-tert-butylphenol, liquid mixtures of tertiary butylated phenols, 2,6-di-tert-butyl-4-methylphenol, 4,4'-methylenebis- (2,6-di-tert- butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), mixtures of methylene ver bridged polyalkylphenols, 4,4'-thiobis- (2-methyl-6-tert-butylphenol), N, N'-di-sec-butyl- p-phenylenediamine, 4-isopropylaminodiphenylamine, phenyl-α-naphthylamine and phenyl-β- naphthylamine.

Corrosion inhibitors comprise a further type of additives which may be present Use in the preparations of the present invention. So dimers and trimeric acids are used, for example compounds such as those obtained from tall oil Fatty acids, oleic acid or linoleic acid can be produced. Products of this type are currently available from various commercial sources. For example, the dimer and Trimer acids under the trademark HYSTRENE from Humco Chemical Division of Witco Chemical Corporation and under the trademark EMPOL from distributed by Emery Chemicals. Another type of corrosion inhibitor that can be used for use in practicing the present invention are US Pat Corrosion inhibitors based on alkenylsuccinic acid and alkenylsuccinic acid drid, for example tetrapropenyl succinic acid, tetrapropenyl succinic anhydride, Tetradecenylsuccinic acid, tetradecenylsuccinic anhydride, hexadecenylsuccinic acid and hexadecenyl succinic anhydride. The half esters from can also be used Alkenyl succinic acids with 8 to 24 carbon atoms in the alkenyl group with alcohols such as with the polyglycols. Close other suitable corrosion inhibitors Etheramines, acid phosphates, amines, polyethoxylated compounds such as, for example ethoxylated amines, ethoxylated phenols and ethoxylated alcohols, imidazolines and  Aminosuccinic acids or their derivatives. Materials of this type are specialists in are well known in the art and there are a number of such materials available as commercial products.

Foam inhibitors are used in the same way as possible components in the preparations of the present invention. Such inhibitors close Silicones, polyacrylates and surfactants. Various anti-foaming agents are in the Publication "Foam Control Agents by H. T. Kerner (Noyes Data Corporation, 1976, Pages 125 to 176) ". Mixtures of silicone-type antifoams such as for example the liquid dialkyl silicone polymers with various other substances are also effective. Typical of such mixtures are with an acrylate polymer mixed silicones, silicones mixed with one or more amines and with one or several amine carboxylates mixed silicones.

Copper corrosion inhibitors represent another class of additives that are used for Incorporation into the preparations of the present invention are suitable. Such Compounds include thiazoles, triazoles and thiadiazoles. Examples of such Compounds include benzotriazole, tolyltriazole, octyltriazole, decyltriazole, dodecyl triazole, 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-5-hydrocar bylthio-1,3,4-thiadiazole, 2-mercapto-5-hydrocarbyldithio-1,3,4-thiadiazole, 2,5-bis- (hydrocarbylthio-) 1,3,4-thiadiazoles and 2,5- (bis-hydrocarbyldithio-) 1,3,4-thiadiazoles. The preferred compounds are the 1,3,4-thiadiazoles, a number of which are considered Commercial products is available.

The formulations of the present invention can also include certain agents for Modifying the friction (friction modifiers) such as aliphatic amines or ethoxylated aliphatic amines, aliphatic fatty acid amides, aliphatic carboxylic acids, aliphatic carboxylic acid esters, aliphatic carboxylic acid ester amides, aliphatic phosphona te, aliphatic phosphates, aliphatic thiophosphonates and aliphatic thiophosphates contain in which the aliphatic group usually contains a number of carbon contains atoms above about 8 to suitably make the compound oil soluble. Are suitable also aliphatic substituted succinimides, which are obtained by reacting one or more  aliphatic succinic acids or succinic anhydrides are formed with ammonia.

Still other components in the preparations of the present invention usable are lubricants such as sulfurized fats, sulfurized Isobutylene, dialkyl polysulfides and sulfur-bridged phenols such as Nonylphenol polysulfide. Air separating agent, the pour point lowering agent, demulgato Ren and dyes can also in the preparations of the present invention be incorporated.

It is natural when choosing any of the possible additives mentioned above It is important to ensure that the selected component (s) are soluble in the oily liquid is / are, is / are and are compatible with the other components of the preparation significantly the desired low-temperature viscosity properties of the finished Total oil preparation impaired.

These additives can of course be used individually in the preparations of the present invention or mixed in different sub-combinations. However, it is common preferred, the additives in the preparation in the form of an additive package or concentrate (which is sometimes referred to differently as "ad-pack" or "DI-pack") since this minimizes errors when mixing in, simplifies the mixing process and one Benefit from the compatibility properties and mutual solubility properties of the additive concentrate.

Typical additive concentrates used in the preparations of the present invention can be used are in the examples listed below A to K listed. It is understood and can be seen that these additive concentrates are only for purposes the illustration of the invention and that it is not intended that they impose limitations on the scope of the present invention; they should therefore, it should not be construed as limiting the present invention.  

Example A

A concentrate ("DI-pack") was made from the following components:

Ashless dispersant containing 67.56% phosphorus and boron 1)
2.69% ethoxylated amines 2)
0.72% tolyltriazole (Cobratec TT-100)
1.06% silicone antifoam (4% solution in a hydrocarbon)
4.66% bis (p-nonylphenyl) amine (Naugalube 438L)
0.90% calcium phenate 3)
0.90% octanoic acid
8.60% Sulfurized Fat 4) and
12.91% mineral oil thinner

Remarks:
1) Prepared as in Example 1A of US Pat. No. 4,857,214; this component contains about 25% of a mineral oil diluent
2) A combination of 2.24% Ethomeen T-12 (Akzo Chemical, Inc.) and 0.45% Tomah PA-14 (Exxon Chemical Company)
3) OLOA 216C (Chevron Chemical Company)
4) Sulperm 10S (Keil Products Division of Ferro Corporation)

Example B

A concentrate was made from the following components:

Ashless dispersant containing 67.56% phosphorus and boron 1)
2.95% ethoxylated amine 2)
0.72% 2- (dodecyldithio-) 5-mercapto-1,3,4-thiadiazole
1.06% silicone antifoam (4% solution in a hydrocarbon)
4.66% bis (p-nonylphenyl) amine (Naugalube 438L)
1.80% tansid 3)
0.90% calcium phenate 4)
0.90% octanoic acid
19.45% mineral oil thinner

Remarks:
1) Prepared as in Example 1A of US Pat. No. 4,857,214; this component contains about 25% of a mineral oil diluent
2) Ethomeen T-12
3) Pluronic L-81
4) OLOA 225

Example C

A concentrate was made from the following components:

Ashless dispersant containing 67.56% phosphorus and boron 1)
2.69% ethoxylated amine 2)
0.72% benzotriazole (Cobratec 99)
1.06% silicone antifoam (4% solution in a hydrocarbon)
4.66% bis (p-nonylphenyl) amine (Naugalube 438L)
1.62% surfactants 3)
1.05% octanoic acid
4.45% Sulfurized Fat 4) and
16.19% mineral oil thinner

Remarks:
1) Prepared as in Example 1A of US Pat. No. 4,857,214; this component contains about 25% of a mineral oil diluent
2) Tomah PA-14
3) A combination of 1.14% PC 1244 and 0.48% Pluronic L-814
4) Sulperm 10S

Example D

A concentrate was made from the following components:

Ashless dispersant containing 67.56% phosphorus and boron 1)
3.44% ethoxylated amines 2)
0.72% 2,5-di- (methylthio-) 1,3,4-thiadiazole
1.06% silicone antifoam (4% solution in a hydrocarbon)
4.66% ethyl antioxidant 728 (Ethyl Corporation)
1.48% surfactant 3)
0.90% calcium phenate 4)
0.90% octanoic acid
2.75% Sulfurized Isobutylene and
16.53% mineral oil thinner

Remarks:
1) Prepared as in Example 1A of US Pat. No. 4,857,214; this component contains about 25% of a mineral oil diluent
2) A combination of 1.88% Ethomeen T-12 and 1.56% Tomah PA-14
3) Mazawet 77
4) OLOA 218A

Example E

A concentrate was made from the following components:

Ashless dispersant containing 67.56% phosphorus and boron 1)
2.69% ethoxylated amines 2)
0.72% 2- (dodecyldithio-) 5-mercapto-1,3,4-thiadiazole
1.06% silicone antifoam (4% solution in a hydrocarbon)
4.66% bis (p-nonylphenyl) amine (Naugalube 438L)
1.62% surfactants 3)
0.90% calcium phenate 4)
0.90% octanoic acid
8.60% Sulfurized Fat 5)
11.29% mineral oil thinner

Remarks:
1) Prepared as in Example 1A of US Pat. No. 4,857,214; this component contains about 25% of a mineral oil diluent
2) A combination of 1.79% Ethomeen T-12 and 0.90% Tomah PA-1
3) A combination of 0.54% PC 1244, 0.90% Mazawet 77 and 0.18% Pluronic L-814
4) OLOA 216C
5) Sulperm 10S

Example F

A concentrate was made from the following components:

Ashless dispersant containing 67.56% phosphorus and boron 1)
2.95% ethoxylated amines 2)
0.72% 2- (dodecyldithio-) 5-mercapto-1,3,4-thiadiazole
1.06% silicone antifoam (4% solution in a hydrocarbon)
4.66% bis (p-nonylphenyl) amine (Naugalube 438L)
1.85% surfactant 3)
0.90% calcium phenate 4)
0.90% octanoic acid
7.42% Sulfurized Fat 5)
11.98% mineral oil thinner

Remarks:
1) Prepared as in Example 1A of US Pat. No. 4,857,214; this component contains about 25% of a mineral oil diluent
2) A combination of 1.79% Ethomeen T-12 and 0.90% Tomah PA-1
3) PC 1244
4) OLOA 218A
5) Sulperm 60-93 (Keil Products Division from Ferro Corporation)

Example G

A concentrate was made from the following components:

Ashless dispersant containing 67.56% phosphorus and boron 1)
2.35% ethoxylated amines 2)
0.70% tolytriazole
1.06% silicone antifoam (4% solution in a hydrocarbon)
8.65% ethyl oxidation inhibitor 728 (Ethyl Corporation)
1.58% surfactants 3)
0.90% calcium phenate 4)
0.90% octanoic acid
4.42% Sulfurized Fat 5)
11.88% mineral oil thinner

Remarks:
1) Prepared as in Example 1A of US Pat. No. 4,857,214; this component contains about 25% of a mineral oil diluent
2) A combination of 1.40% Ethomeen T-12 and 0.95% Tomah PA-14
3) A combination of 0.95% PC 1244 and 0.63% Mazawet 77
4) OLOA 216C
5) Sulperm 60-93

Example H

A concentrate was made from the following components:

Ashless dispersant containing 67.56% phosphorus and boron 1)
1.79% ethoxylated amine 2)
0.72% 2- (dodecyldithio-) 5-mercapto-1,3,4-thiadiazole
1.08% silicone anti-foaming agent (4% solution in a hydrocarbon)
4.66% bis (p-nonylphenyl) amine (Naugalube 438L)
1.98% surfactants 3)
0.90% calcium phenate 4)
0.90% octanoic acid
0.54% M-544 (Monsanto Company)
8.60% Sulfurized Fat 5)
11.26% mineral oil thinner (45N)

Remarks:
1) Prepared as in Example 1A of US Pat. No. 4,857,214; this component contains about 25% of a mineral oil diluent
2) Ethomeen T-12
3) A combination of 0.90% Tomah PA-14, 0.90% Mazawet 77 and 0.18% Pluronic L-81
4) OLOA 216C
5) Sulperm 10S

Example I

A concentrate was made from the components used in the manufacture of the additive Paranox 445 (Exxon Chemical Company) were used, except that all (or essentially all) of the polymeric agent to improve the Viscosity index, which is not a polymeric agent to improve the viscosity index Acrylic acid base (and also the diluent associated with a  such acrylic acid viscosity index improver) used in the Additive Paranox 445 was used, if any of it was used, was omitted. Under "essentially all" in this and the following Examples are understood that the amount of viscosity index improver, that was not of the acrylic type that was present in the commercially available additive concentrate, if there was any of it at all, not the low-temperature viscometric Destroys properties provided by the present invention. More specifically the addition amount should be in a suitable treatment concentration for an additive concentrate occurred containing a non-acrylic type viscosity index improver an oil preparation of the present invention is not the oil preparation of an Oil preparation that has a Brookfield viscosity of 20,000 mPa · s or less at -40 ° C if it contains nothing of the concentrate, to an oil preparation that has a Brookfield viscosity above 20,000 mPa · s at -40 ° C, convert when the concentrate is dissolved therein has been.

Example J

A concentrate was made from the components used to make the additive Lubrizol® LZ-6715D (company The Lubrizol Corporation) were used with the Except that all (or essentially all) of the polymeric agent for Viscosity index improvement that is not a viscosity index improver of acrylic Type, if any, and all of the diluent contained in Combined with such a non-acrylic type viscosity index improver was used if such was used as that in the additive Lubrizol® LZ- 6715D was used, was eliminated.

Example K

Seven concentrates were made from the components used in the manufacture of the The following seven commercial products from The Lubrizol Corporation were used: Lubrizol® LZ-6704 additive; Lubrizol® LZ-7900 additive; Lubrizol® LZ-7901 additive; Lubrizol® LZ-7907 additive; Lubrizol® LZ-7925 additive; Lubrizol® Lz-7993 additive and  Lubrizol® LZ-7993A additive. In each case, the total (or essentially eliminates the total amount) of a polymeric viscosity index improver, that was not an acrylic type viscosity index improver, if any was used at all, and the total amount of diluent combined hung with such a viscosity index improver of the non-acrylic type was used, if any, was used at the particular Commercial product from the company Lubrizol was used.

Example L

Four concentrates were made from the components used in the manufacture of the the following four commercial products from Exxon Chemical Company were used: Paramins ECA 9172 additive, Paramins ECA 11998 additive, Paranox 440 additive and Paranox 442 additive. In each case, the total (or essentially the Total amount) of a polymeric agent to improve the viscosity index, that was not an acrylic type viscosity index improver, if any was used at all, and the total amount of diluent combined hung with such a viscosity index improver of the non-acrylic type was used, if any, was used at the particular Commercial product from Exxon Chemical Company was used.

Ratios of additives

In general, the additive components used in the preparations of the present Invention used, used in smaller amounts that are sufficient to the To improve functional parameters and properties of the basic liquid. The amounts so vary in accordance with such factors as the severity and type of Performance range in which the use of the preparation is intended, the in the Final preparation desired functional parameters, the composition of the special Base oil preparation, the nature of the additives used and other similar Considerations. Generally speaking, however, the following concentrations (in% by weight) to give the components (active components) in the basic liquids as examples:  

It should be noted that some additives perform multiple functions (multifunctional additives) that are capable of the mixture in which it is used to confer more than a single property. So if one multifunctional additive component in the preparations of the present invention is used, the amount used will of course be sufficient to the from the Using these components to achieve desired function (s) and result (s).

For some applications, the finished oil-like lubricant preparations or functional liquid preparations of the present invention in ashless or only provided small amounts of ash, d. H. contain the preparations in these cases either no added metal-containing additive (and then are "ash free"), or they contain a maximum of 100 ppm of a metal in the form of an or several additive (s) containing a metal. In this context, boron, Phosphorus and certain other non-metallic elements ash-like residues on parts form that are exposed to extremely high temperatures or combustion processes. However, such non-metal additives are classified as "ash-free" additives and can therefore be present in any suitable amounts without this leading to a Deviation from the characterization of the preparation as "ash-free" or "with low Ash content "leads.  

power

To illustrate the excellent performance achieved through the practical implementation of the In the present invention, low temperature viscosity tests have been carried out performed in which the Brookfield viscosities at -40 ° C in accordance with the ASTM test method D 2983 were determined. The preparations tested and the Results related to Brookfield viscosities at -40 ° C are as follows Tables compiled. In each case the additive concentrate used ("DI-Pack") that of Example H, and the viscosity measured at -40 ° C is the Brookfield viscosity when measuring after the preparations have remained in the bath at -40 ° C. for a period of 16 h.

Table I

It can be seen from Table I that Run 2, which is a preferred preparation according to of the present invention used a Brookfield viscosity below -40 ° C 20,000 mPa · s, while the comparative preparations in which the combination of Components (a), (b) and (c) had not been used, the required low temperature viscosity not reached.  

Table II

The values in Table II show that the preparation according to the present invention (Run 5) in which component (c) is another preferred type of agent for Improvement in the viscosity index of the acrylic type was a much better performance temperature at low temperature showed than either of the two comparative preparations. In addition, neither of the two comparative preparations reached a Brookfield viscosity, which was equal to or below the required value of 20,000 mPa · s at -40 ° C.  

Table III

The data given in Table III further show the synergistic results that have been made possible by the practice of the present invention. So had one preferred preparation according to the invention (run 6) a Brookfield viscosity that was far below the required value of 20,000 mPa · s at -40 ° C.

In fact, the Brookfield viscosity of this preparation was also clear at -40 ° C below the value of 15,000 mPa · s or less at -40 ° C, as it results from the Requirements of the upcoming DEXRON®-III specification. In contrast to achieved neither of the two comparative preparations as in runs 1 and 7 Brookfield viscosity used equal to or below 20,000 mPa · s -40 ° C.  

Table IV

Table IV shows that the synergistic results obtained through the practice of the present Invention are achievable if an amount as small as 1% (about 0.4% of active ingredient) of the viscosity index improver Acrylic type used.  

Table V

It can be seen from Table V that synergistic results have been achieved with a lot the agent to improve the viscosity index of the acrylic type, which is so small Value was like 0.5% (about 0.2% of active ingredient).

Table VI

The numbers in Table VI show that even with an amount as small as 0.1% (about 0.04% active ingredient) of the agent for improving the viscosity index of the acrylic Type the synergistic results that could be obtained through the practice of present invention have been made possible.

Similar synergistic results were obtained when 3% Acryloid 1263 VII and 5% Acryloid 1263 VII with 10% ETHYLFLO 162 oligomer in the same base oil and with used the same DI pack as used in the tests described above were. The Brookfield viscosities at -40 ° C were 13 625 and 13 900 mPa · s.

Another preparation according to the present invention was produced in that Exxon 1365 100 neutral oil (74.9%), ETHYLFLO 164 poly-α-olefin oligomer (15.0%), ACRYLOID® 1263 VI improver (4.5%) and the DI pack of Example H (5.6%) mixed. The resulting formulation had a Brookfield viscosity at -40 ° C of 17 280 mPa · s.

Claims (11)

1. Oil preparation, which includes:

• a) a larger amount of a mineral oil in the range from 75 N to 200 N; and smaller amounts
• b) a poly-α-olefin oligomer with a kinematic viscosity in the range of 2 to 7 mm ² / s at 100 ° C, which is prepared by a process which the oligomerization of at least one 1-alkene having 6 to 20 carbon atoms in the Molecule includes; and
• c) an oil-soluble polymeric agent to improve the viscosity index of the acrylic type;

with the proviso that the preparation has a Brookfield viscosity of 20,000 mPa · s at -40 ° C having. 2. Preparation according to claim 1 with a Brookfield viscosity 15,000 mPa · s at -40 ° C. 3. A preparation according to claim 1 or claim 2, wherein the poly-α-olefin oligomer is hydrogenated poly-α-olefin oligomer. 4. A preparation according to claim 3, wherein the poly-α-olefin oligomer is a hydrogenated poly-α- olefin oligomer from 1-decene.   5. A preparation according to any one of the preceding claims, wherein the polymeric viscosity index improver is incorporated into the preparation in the form of a solution of a polymeric acrylic viscosity improver in a hydrocarbon solvent, the solution having a bulk viscosity (bulk viscosity) in the range of 600 to 1200 mm ² / s at 100 ° C. 6. The preparation of claim 5, wherein the polymeric viscosity index improver is incorporated into the preparation in the form of a solution composed of 30 to 45% by weight of a polymeric viscosity index improver of the acrylic type described in US Pat 55 to 70 wt .-% of a hydrocarbon solvent is dissolved, the solution having a bulk viscosity at 100 ° C of 600 to 800 mm ² / s. 7. The preparation of claim 5, wherein the polymeric viscosity index improver is incorporated into the preparation in the form of a solution composed of 20 to 65% by weight of a polymeric viscosity index improver of the acrylic type described in US Pat 35 to 80 wt .-% of a hydrocarbon solvent is dissolved, the solution having a bulk viscosity at 100 ° C of 800 to 1200 mm ² / s. 8. Preparation according to one or more of claims 1 to 7, wherein the polymeric agent for improving the viscosity index is worked into the preparation in the form of a solution having a nominal bulk viscosity at 100 ° C of 1000 mm ² / s and has a specific gravity of about 0.905 and composed of 4 to 10.99% polymerized n-butyl methacrylate, 1 to 3.99% polymerized dimethylaminopropyl methacrylamide and 20 to 34.99% polymerized lauryl methacrylate, dissolved in 35 to 49.99% highly solvent-refined, hydrotreated, naphthenic light oil distillates and 11 to 19.99% highly refined, hydrotreated, naphthenic heavy oil distillates. 9. A preparation according to any one of claims 1 to 8, wherein the poly-α-olefin oligomer is a hydrogenated poly-α-olefin oligomer formed from 1-decene, the polymeric agent for improving the viscosity index in the preparation is incorporated in the form of a solution of a polymeric agent for improving the viscosity index of the acrylic type in a hydrocarbon solvent, the solution having a bulk viscosity at 100 ° C. in the range from 600 to 1200 mm ² / s and the preparation contains an additive package. 10. The preparation of claim 9, wherein the Brookfield viscosity of -40 ° C Preparation is 15 000 mPa · s.