JPH03505884A - Overbased phenate detergent for lubricants with improved water tolerance - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] [Name of invention] Overbased phenate detergent for lubricants with improved water tolerance [Field of invention] The field of the invention is compositions comprising overbased detergent lubricant additives, and A method for preparing the above-mentioned overbased detergent additive useful as a lubricating oil additive is provided. . More specifically, the present invention provides a superfluid with improved water tolerance in finished lubricating oils. A method for producing overbased detergent additives.

One object of the present invention is to provide improved high temperature storage and modification, especially in the presence of moisture. Improved water tolerance and improved miscibility of phenate sulfonate mixtures The present invention provides a method for producing an overbased phenate as shown.

It is also an object of the present invention to provide improved miscibility as an additive in lubricating oil compositions. A lubricant composition containing an overbased detergent with high temperature stability and good storage stability at high temperatures. It's about providing things.

It is also an object of the present invention to provide a wear inhibitor containing zinc dithiophosphate. Including overbased detergents for improved stability in lubricating oil compositions The present invention provides a lubricant composition.

It is also an object of the present invention to provide an overbased phenol with improved water tolerance. The present invention provides a lubricant composition comprising a detergent.

These and other purposes will become apparent from the description provided below.

[Background of the invention]

Basic calcium sulfide alkyl phenates neutralize harmful acids in internal combustion engines, Corrosion and rubber formation caused by oxidation of lubricating oils and oxidative polymerization of engine fuel residues , and as a compounding agent or additive in lubricating oil to suppress piston ring adhesion. used. Metal sulfonates are commonly used as additives and rust inhibitors in lubricating oil compositions. , and used as detergents. Such phenates and sulfonates are against acids formed during engine combustion, without too rapid loss of potassium It is highly desirable to provide neutralizing capabilities. In some cases, these combinations or Additives should be added in molar excess over the amount needed to neutralize the phenolic material or sulfonic acid. Contains excess base and is overbased.

of overbased additive compounds! llI! One issue related to the final generation Immiscibility of mixtures of alkaline earth metal phenates and sulfonates as substances This is a problem. Overbased materials are typically alkaline earth metal compounds, commonly is a carbonate which is dispersed in an alkaline earth metal dispersant and is an alkali to be dispersed. The amount of lithium metal is known as the amount of overbasing.If the basicity of the material is high, The larger the amount, the less material is used in the lubricant for a given effect. Therefore, a higher basicity is better, so a higher excess basicity is highly desirable. , but to increase basicity, dispersed alkaline earth metals in carbonate complexes are generally used. It is necessary to increase the content of

A highly desirable purpose of overbased additives is in lubricants containing overbased additives. finely dispersed so that the composition is stable, does not cloud or gel, and does not undergo significant thickening is to obtain an overbased additive in the form of very fine particles of colloidal type. .

The process of the present invention involves the production of alkaline earth metal phenols in the presence of a low base sulfonate promoter. The immiscibility of phenate and sulfonate is improved by increasing the degree of both carbonation and sulfidation of phenate. By overcoming compatibility, it is possible to obtain products with improved water tolerance. .

Overbased phenate necks, including sulfurized phenates, are generally ethylene glycol must be removed from the product. , the presence of glycol in the overbased phenate is Phenotes are generally combined with phenols or substituted phenols, resulting in ker formation. It is a reaction product with metal or ammonium bases. Often the metal base is the 11th Group metal compounds. Substituted phenols are generally mono-, di-, or trihydric. locarbyl, such as alkyl, alkenyl, aryl, aralkyl, or alkyl It has been replaced by Reel. Monoalkyl substitution is preferred.

Hydrocarbyls include methyl, ethyl, propyl, butyl, pentyl, and hexyl. Low molecular weight groups such as isomers such as heptyl, octyl, nonyl, decyl, etc. It can also include high molecular weight materials having a number average molecular weight of 10,000 or more.

These hydrocarbyl substituents are C3-C,. . Ethylene or propylene or butylene It can be medium molecular weight polymeric olefins such as ten polymers. chlorine, Substitution with groups such as bromine, hydroxy, nitro, or sulfonic acid groups may The hydrocarbyl can be substituted with such substituents so long as they do not interfere with the utility. No. Group 11 metal compounds include metal oxides, hydroxides, alcoholates, acetates, etc. Can be included. Common metals include calcium, barium, strontium, and magnetism. It is Sium. Often the metal compound is calcium oxide or hydroxide. Fe The nerates can contain sulfur, which can be substituted with elemental sulfur or 5CI2 with phenol or By reaction with phenol or by reaction of elemental sulfur or SC+2 with metal phenate. It can be introduced.

These various phenates and sulfur-containing phenates are made and overbased. The method is described in U.S. Patent No. 2,680°096; No. 178,368; No. 3,336,224; No. 3,437,595; No. 3; No. 464,970; No. 3,761,414; No. 3゜801, 507; No. 3 , No. 810,837; No. 3,923,670; No. 3,932,289; No. 3 , No. 3,966.621 and No. 3,969,235. You can bring it out.

As is well known, calcium phenates with a TON of 80-250 are When combined with link case oil, it interacts with low base and high base sulfonates. It tends to cause clouding and precipitation. Immiscibility of this phenate sulfonate can be influenced by the components in the finished oil. For example, dialkyldithio The simultaneous presence of zinc phosphate (ZnDTP) and water leads to the phenate sulfonate interaction. may worsen. Many finished oils contain ZnDTP. Cargo handling This phenomenon occurs when the finished oil contains a small amount of moisture, as occurs during storage. The immiscibility of nathosulfonate worsens.

U.S. Patent Nos. 4,293,431; 4,302,342 and 4,412 ．． No. 927, alkaline earth metal sulfide alkylphenols alkaline earth metal alkylbenzene sulfonates, alkaline earth metal compounds By carbonating the diluent, alkylene glycol, and diluting oil, It has long been known that basicized metal detergent-dispersants can be prepared. but , these methods require a significant amount (based on phenate) for the phenate overbasing reaction. Then >201% by weight) of sulfonate is utilized.

This clearly reduces the reactor volume available for the phenate reaction and the resulting product loses flexibility in its application.

In this method, alkaline earth metal phenates are prepared in the presence of alkylene glycol and diluent oil. As a promoter for the reaction, a small amount (<10% by weight, and preferably 5% by weight) of We have discovered that only the lowest base sulfonate is required.

These phenates promoted with sulfonates in an overbased state are particularly A stable colloidal product with improved solubility in lubricating oils in the presence of small amounts of water. It is a dispersion, does not cloud, does not gel, is non-viscous, and does not significantly thicken. We also believe that optimization of sulfidation and carbonation has been improved in lubricating oil additives. It was also discovered that it provides water tolerance.

[Summary of the invention]

Overbased and sulfided calcium with improved water tolerance and excellent storage stability. The manufacturing method for ciumphenate has been revealed. Completed containing this additive The lubricating oil has continued brightness and transparency despite water content up to 0.620% by weight. 0gA additive, which shows brightness, indicates the presence of alkaline earth metal alkylbenzene sulfonate. A mixture of alkaline earth metal compounds, sulfur and polyhydroxy compounds is It is prepared by reacting with kylphenol, and the reaction mixture is charcoalized with carbon dioxide gas. It is acidified. High carbonation levels and high sulfidation levels aid stability in the presence of water becomes.

[Detailed description of the invention]

Overbased and sulfurized calcium alkyl phenates as lubricating oil additives The effectiveness of sulfidation is shown in the presence of low base calcium sulfonates as accelerators. It has now been discovered that it can be enhanced by preparing umfuenate. So In the case of sulfur/calcium/glycol/carbon dioxide alkylphenol reaction The molar ratios of the molecules and the parameters of the reaction are critically adjusted. The resulting invention When the product is incorporated into a lubricating oil composition, the excess salt prepared in conventional manner improved performance over that obtained with base-based and sulfurized calcium alkyl phenates. Indicates the amount of water allowed.

Overbased phenates with improved lubricant properties can be Calcium compounds, alkylphenols and glycols in the presence of lucium sulfonate React the recall intermediate and then react the above compounds with sulfur to generate a sulfidation force. It can be prepared by forming sium phenate. This pre-reaction stage consists of 1 No. 754,647, filed July 12, 1985, filed in Kyodo As described, it reduces the formation of neutral calcium compounds and is useful as a lubricating oil additive. Enhances the effectiveness of calcium sulfide alkyl phenates. Next, add additional grids. Add cole and carbonate the mixture. Filter the emitted product to remove solids. Ru.

The above method involves mixing the first four compounds above and heating the mixture at about 300'F to about 350'F. carried out by heating the mixture for a period of 10 seconds to 60 seconds at a temperature within the range It can be done. If the mixture is heated for longer than 60 seconds, the mixture will become less fluid and heavy. Forms a paste-like material. If the mixture is heated for less than 10 seconds, the reaction may not proceed properly. Interbody is not formed. Next, sulfur is added to the reaction mixture and Heat at 3700F for 1 to 2 hours. Then add additional glycol and carbonate the mixture for 1 to 2 hours at a temperature of about 300'F to about 3600F. carbonate in a bath. Next, excess glycol and unreacted alkylphenol are removed from approx. Incubate for 0.5 to 1 hour at a temperature ranging from 4700F to about 490'F. Burge the reaction mixture with nitrogen. Filter the diffused product to remove solids .

The above method steps can be carried out either batchwise or in a continuous process. However, the method parameters It has been found to be advantageous to use a continuous processing system for controlling the data. shown above Pretreatment of glycol/calcium compounds for more than 60 seconds results in Product becomes difficult to pump.

Pretreatment in less than 10 seconds removes the necessary chemical intermediates to obtain the desired final product. cannot be formed. Batch processing of alkylphenols/glycols/calcium compounds Processes tend to produce products that are extremely viscous and difficult to handle.

The above process steps can be carried out in either continuous or batch processes; For our purposes, the following discussion is about the continuous method. The flowchart of the continuous method is shown in Figure 1. vinegar.

A mixture of alkylphenols and lime is added in a low salt preheating area prior to the introduction of sulfur. Pretreatment with glycol in the presence of base calcium sulfonate. First reaction with sulfur When introduced into the vessel, water vapor and hydrogen sulfide gas are generated. Due to the carbonation reaction, the first Introduce carbon dioxide gas and additional glycol to the two reactors. Reaction products during process steps After the reaction, it is preferable to prepare a reaction diluent for easy handling of the glycol. The crude product was sparged to remove the phenol and unreacted alkylphenol, and then the solid Filter to remove.

Alkylphenols useful in the present invention are of the formula R(C6H4)OH; where R has 8-40 carbon atoms and preferably 10-30 carbon atoms. is a straight-chain or branched alkyl group, and the (C6H4) moiety is a benzene ring. suitable Examples of suitable alkyl groups are octyl, decyl, dodecyl, tetradecyl, hexadecy from tricontyl, triacontyl, etc. to tetracontyl.

The glycols used in this invention can contain up to 6 carbon atoms. suitable group Recalls include ethylene glycol; propylene glycol; butanediol- 2,3: Pentanediol-2,3; and 2-methylbutanediol 3°4 Contains. Ethylene glycol is the preferred glycol due to its higher reaction yield. Ru.

The calcium compound can be calcium oxide or calcium hydroxide. hydrated lime Calcium hydroxide is preferred for continuous charging. Other alkaline earth golds oxides or hydroxides of barium, magnesium, strontium, etc. compounds can also be used alone or in mixtures. However, alkaline earth metal compounds It should be understood that the types are not equivalent for the purposes of this invention. That is, ah This is because some are more effective than others under certain conditions.

Among the low base alkylbenzene sulfonates that can be used are petroleum distillate sulfonates. Preferably a natural sulfone 1 with a molecular weight of 400 or more obtained by phonation [or From olefins or polymers of C2-C4 olefins with a chain length of Cl5-C80 Synthetic salts obtained by sulfonation of derived alkylbenzenes and carbon There are alkaline earth metals such as lucium, barium, magnesium, etc. chain length Preferred are low base calcium sulfonates prepared from commercial C-60 polypropene. Yes.

The reactive diluent can be any lubricant used in the final lubricant formulation. this These lubricating oils are naphthenic based oils, paraffinic based oils, mixed mineral oil based oils, and synthetic lubricating oils. Includes other hydrocarbon lubricants such as lubricants derived from oil and coal products .

The reactant molar ratio is critical. The molar ratio of glycol to calcium varies slightly. However, the molar ratio of glycol in the reactant mixture is approximately that of calcium hydroxide. There is no maximum amount of sulfur and carbon dioxide to be used, which should preferably be equal; In practice, up to 2 moles each of sulfur and carbon dioxide per mole of alkylphenol is appropriate. Reaction diluents, including hydrocarbons such as petroleum oil , the stoichiometry of the reaction is:

lime mol/alkylphenol mol) 0.7-1.7 0.9-1.2 sulfur (mol/alkylphenol mol) 1.1-2.0 1.3-1.6 glycol (mol/alkylphenol mol) 0.7-1.7 0.9-1.3 Low base sulfur calcium phonate (lb/lb-mol alkylphenol) 2.5-30 5-15 carbon dioxide gas (mol/alkylphenol mol) 0.5-2.0 0.5-1.55W Ile (lb/lb-mol alkylphenol) +00-500 150-300 In the pre-reaction between glycol and lime in the presence of alkylphenols, the reactants react The temperature at which the reaction takes place depends on the nature of the reactants. ethylene glycol, dodecyl The pre-reaction mixture of phenol and lime was heated between 300'F and 350'F at atmospheric pressure. When reacted, the reaction intermediate and sulfur yield the appropriate reaction intermediate at a high voltage, 330' Closed for 1-2 hours nominal residence at F to 370'F and renewed at 3000F to 360'F. Allow to react for 1-2 hours, during which time glycol is added to carbonate the mixture.

The reaction occurs at atmospheric pressure, although pressures above or below atmospheric pressure can also be used.

An essential element of the present invention is the total alkalinity number (to tal base nuwber, TON) and sulfur as determined by X-ray fluorescence analysis. Yellow to Calcium Weight Ratio (as compared to total TBN (ASTM D-2896)) be. In the Coulomb titration method, an excess amount of hydrochloric acid is added to the sample to remove carbon dioxide gas from the sample. Next, the released carbon dioxide gas is titrated potentiometrically. This method exists Measure the amount of inorganic carbonate present.

The ASTM D-2896 test method is highly overbased by titration with perchloric acid. It was developed to measure the basicity of oil additives. The basicity caused by such components is measured.

The chemistry of the reactions involved in the method of the invention is highly ambiguous. Improved at higher temperatures To create a complete detergent with reduced storage capacity and improved water capacity, Preparation of overbased and sulfurized alkaline earth metal phenate detergents of the present invention I don't want to be tied to any particular theory or hypothesis about what happens in However, in the presence of underbased sulfonate promoters, the increase in the degree of carbonation and sulfidation was modified. Provides improved overbased and sulfurized alkaline earth metal phenate detergents If this is unexpectedly discovered, the above phenate detergent can be tested by Coulombic titration. D-2896 method and X-ray fluorescence gravimetry for sulfur and calcium abundance and has measurable characteristics.

Using the appropriate analytical techniques above, the data presented in Example 5 below and represented in FIG. data was obtained. As is clear in FIG. 2, the water The tolerance is improved when the sulfur to calcium weight ratio is at least 0.52. Sometimes, the nitrogen-emitting products of the present invention have at least 0.35 Coulombic titrations of carbonic acid. The ratio of salt TON to total 7 [IN (ASTMD-289fl), and the above Coulombic titration as described above when the weight ratio of sulfur to calcium is at least 0.38. The ratio of carbonate TBN to gold TON (ASTM D-2876) is at least This is also the case when 0.57.

The overbasing power lucium phenate made above is about 1600F to about 275 Temperatures in the range above °F, pressures of 0.5 to 100 atmospheres, under nitrogen for 1 to 24 hours. During this time, it is combined with other additives to form a so-called additive package. Ji Wear inhibitors such as zinc thiophosphate can be incorporated at 1600F for about 3 hours.

Of particular significance according to the invention is the overbased detergent-dispersant and mineral oil or synthetic Ability to improve the storage properties of compositions with oil-based materials, such as lubricating media comprising oil. It is.

Generally, paraffinic, naphthenic and mixtures of mineral oils have a 5 SSU from 100'F 0005SUf and preferably 210'F lubricant viscosities ranging from about 40 to about 250 SSU. these The oil can have a viscosity index ranging up to about 100 or more. Viscosity of about 70 to about 95 The average molecular weight of these oils, with a preferred index, ranges from about 250 to about 800. I can do it.

In some cases, synthetic oils are desirable over mineral oils or in combination with mineral oils. In this case, there are 1llllllll of different compounds of this type! It is used for l. typical Synthetic vehicles include polyisobutylene, polybutenes, and hydrogenated polyolefins. , polypropylene glycol, polyethylene glycol, trimethylol propane esters, neopentyl and pentaerythritol esters, di(2-ethyl tylhexyl) sebacate, di(2-ethylhexyl) adipate, dibutylph Talates, fluorocarbons, silicate esters, silanes, phosphorous acid esters Stells, liquid urea, ferrocene derivatives, hydrogenated mineral oils, chain polyphenyls siloxanes, silicones (polysiloxanes), butyl-substituted bis Alkyl-substituted diphenyl esters typically represented by (p-phenoxyphenol) esters Includes esters and phenoxyphenyl ethers.

The term lubricating oil composition as used herein refers to lubricating oil compositions for lubricating case motors. Fully formulated compositions for applications such as lubricants. of some conventionally used base oils and typical amounts that provide the usual ancillary functions. additives, especially ash-forming or ash-forming detergents and dispersants, antioxidants, rust inhibitors, Viscosity index improvers such as olefin copolymers, pour point depressants, and metal-containing detergents Additives such as neutral and basic metal phenates, sulfurized phenates, Sulfonates with sium and magnesium, such as highly basic magnesium sulfonates. phonates, and zinc dialkyldithiophosphates as antioxidant and wear inhibitor additives Contains.

Therefore, it is possible that the lubricating oil compositions contemplated in this application may contain other materials. be understood. For example, corrosion inhibitors, rust inhibitors like magnesium sulfonate agent, nitrogen-containing dispersant, extreme pressure agent, viscosity index improver, co-oxidant, dialkyldithi Anti-wear agents such as zinc phosphate can be used. These materials are suitable for the composition of the present invention. not to diminish the value of the species, but rather to the individual compositions in which they are mixed. plays the role of imparting properties.

Generally, the overbased detergents of the present invention exhibit the desired degree of improved storage at room or elevated temperatures. It can be used in any amount effective to impart storage properties. However, in many applications, excessive The basic detergent is about 0.5% to about 15% by weight of the total weight of the composition, and preferably about 0.5% by weight of the total composition. Effectively used in amounts of ~5%.

In summary, the method of the present invention provides improved high temperature storage stability and improved water tolerance. Improved overbased and sulfurized alkaline earth metal phenate detergent moisturizer with This manufacturing method includes (a) a polyhydroxy compound and an aliphatic oil additive; in the presence of alkali earth metal alkylbenzene sulfonate from about 300'F to Carry out a chemical reaction to produce a reaction intermediate at a temperature within the range of about 350'F reacting the alkaline earth metal compound with the alkylphenol for a time sufficient to (b) adding elemental sulfur to the reaction mixture of (a); (c) reducing the reaction mixture of (b) to about sulfur as described above and (b) as described above at a temperature within the range of 3300F to about 370°F. The reaction mixture is heated for a sufficient time to cause the reaction between (d) and (c). adding an additional amount of the polyhydroxy compound described above to the product to form a reaction mixture; (e) The reaction mixture of (d) above is heated within the range of about 300'F to about 360'F. for a time sufficient to obtain a high carbonation level of the reaction mixture of (d) above at a temperature of (f) the reaction mixture of (e) above; The compound is nitrogen sparged at a temperature within the range of about 470'F to about 490'F to produce (g ) filtering the nitrogen-emitting product of (f), thereby The nitrogen-emitting product described above has a sulfur/calcium weight ratio of at least 0.52. The carbonate total base number (TBN) by Coulometric titration of at least 0.35 and the total TON (ASTMD-2896) and the above sulfur/calcium weight. Carbonate TON and gold by Coulomb titration as described above when the quantitative ratio is at least 0.38. TON (ASTM D-2896) is at least 0.57.

In summary, the compositions of the present invention contain improved excess bases made by the inventive method described above. and sulfurized alkaline earth metal phenate detergent lubricant additive compositions and lubricant oil and an effective amount of the above improved overbased sulfided alkaline earth gold A lubricating oil composition containing a phenate detergent lubricant additive.

The following examples illustrate typical compositions of the invention and methods of making them. Ru. Unless otherwise noted, percentages are by weight.

Example 1 This example illustrates the batch preparation of an overbased detergent dispersant of the present invention. 1ri Tuturu resin pot, dodecylphenol 210.0 g, lime 41.4 g, Glycol 30. Og, C6°-calcium sulfonate 10.0 g, and 5 I charged 184゜0g of enemy oil. Store the mixture and heat to 300'F. held for seconds. At this point, add 33.5 g of sulfur and stir the mixture. Heat to 60'F and hold for 60 minutes. Next, reduce the temperature to 340'F and Le 20. Next, add Og and 204 g of lime to the pot, then heat the mixture to 3400F. Hold for 120 minutes, during which time the mixture is carbonated with 0.2 liters of carbon dioxide per minute. Ta. The temperature was raised to 480'F. The mixture was then placed under a vacuum of 75 torr each time. Closed diffusion treatment was performed for 60 minutes with 0.3 liters of nitrogen. Add 40% of 5-carbonate oil to the reaction mixture. ．． After adding 0 g, the product was filtered in a Buchner funnel with 40.0 g did. The sample number was 9745-149-1.

The product inspection is summarized below.

Analysis 9745-149-1 Calcium, weight % 6.5 Sulfur, weight% 3.0 Gri Cole, weight% 0.2D-28967BN, 0 in B 87g 1? + Carbonate 7BH (11, Qin g KOH/g 85PM Flash, 'F (Penske-Martin) 372 viscosity , cst, 100℃ 65 residual reaction solids, volume % (0.05 color, double dilution (ASTM D-1500) 　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　 8 cloud - (1) Curro Titration groove Example 2 The following example illustrates a continuous process for making overbased detergent compositions of the present invention.

Two stirred 4 liter resin kettles in series were used. Product dissipation and filtration are It was batchwise similar to that described in Example 1. The reaction conditions are summarized below. .

Doquesylphenol Lime 1.00 Sulfur 1.43 Glycol-th reactor 0,5 1 Second reactor 0.63 Total 1.14 Carbon dioxide gas 1.27Coo-calcium sulfonate, 1bs1 mol 12.55 Enemy oil, I bs 1 mol 242 Preheater First reactor Second reactor Residence time, min 0.5 90 90 Temperature, 'F' The inspection of 330, 360, and 340 products is summarized below.

Analysis 922 Loli Calcium, weight% 6,6 sulfur, weight% 3.1 glycol Le, weight% 0.3D-28967BN, 0 to Ilg ) 1/g 173 carbonate TBN (11, OH/g to mg 82PM Flash, QF (Pensuf: Martin) 365 viscosity , C5t, 100℃ 70 Residual reaction solid content, volume % <0.05 color, double dilution (ASTM D-1500) 3.0 specific gravity, lbs/gal 8.6 (1 ) per coulomb titration Example 3 The products of Examples I and 2 were formulated into a heavy duty lubricating oil composition. Formulated with nitrogen-containing dispersion agent, zinc dialkyldithiophosphate wear inhibitor, high base magnesium sulfonate, Contains a moving point depressant and base oil. The control was an overbased filter prepared using conventional procedures. Contains henato. Some commercial overbased phenate samples, e.g. Oroa obtained from Bron Chemical Co., Sun Francisco, California. -2+8A, Oroar 219, and Oroar 229, also Labrisil Corpore The LZ-6499 and LZ-650 were hand-built by the 0, as well as from Exxon Chemical Co., Hughston, Texas. Varanox-52 is also a powerful lubricant formulation based on their calcium content. It was blended into. Formulated transport water capacity 0.2% by weight, 70'F and 13 Tested at 00F for 30 days. The results are as follows.

Control N-6% > N-71 sample 9745-149-I A-OX A-OX sample 9226-38 A-O X A-OX O [117-2+8A >N-5% K-6 % lower 219 >N-281>N-+9χ o a y -229 J-20% N-281LZ-6499>N-10% 1-11! LZ -6500M-8X N-7! Hara/　　　Su-52＞N-1!　　　 D-20! (+) Cloudy rating: 8- clear, BN- increased cloudy. Sedimentation amount is volume %.

Example 4 Since it is a definitive reaction chemistry theory, it is preferable to monitor the reaction process by appropriate methods. Yes. This example shows that adjusting the sulfidation and carbonation of the phenate improves the water capacity. It is an example of what will be done.

Thirty-one samples with different degrees of sulfidation and carbonation were processed using the batch method (9745 series shown in Table 1). ) or by a continuous method (9226 series shown in Table 1). 2.5x each sample A 0-strength lubricating oil mixed with 0.20% water and then mixed with 0.20% water. The composition contains a nitrogen-containing dispersant, a zinc dialkyldithiophosphate wear inhibitor, and a high base sulfonate. It contained magnesium chloride, a pour point depressant, and a base oil. Bring the sample to room temperature (70’F) and stored at 130'F for 30 days. The water allowance results are summarized in Table 1.

As the table above shows, increasing levels of sulfidation and carbonation improve water capacity. this Their effect is clearly illustrated by FIG.

9745-92-2 0.48 0.27 >N-41>N-4% -93-20,440,451-2/$　　　-3z-94-20,460, 46K-1m K-IX-96-20,470,4400 -97-10,450,44E-1! G-21-97-20,430,5 700 -98-10,520,4600 -98-20,520,4600 -99-10,410,5500 -99-20,450,440-IX F-+$-100-1 0.51 0.51 0 0L# in TBN (1) Cloudy and settling 1 Li 100-20,510,4700 -1oil 0.4+ 0.52 0 0 0-1012 0.38 0.51 ＞N -5$　　　　＞N-6l-102-10,470,4800 102-20,440,42C-0X　　　　　F-I! -103-10,4 50,458-OX F-1χ-103-20゜45 0 ．． 32　　　　　　)N-6　　　＞N-5χ-104-10,380, 58>N-21>) I-4%-104-20,390,55>N-3% >N-1%-! 2B-20,480,5200 -129-20,390,5200 -130-20,510,4300 -13120,430,5300 -139-20,470,5000 -146・I O,430,5200-146-20,410,5500 -147-10,410,5400 -147-20,410,5400 9226-35-20,490,5200-35-30,500,39>N-l 5>N-5% (per ASTM D-664 per coulomb titration.

(2) Per ASTM D-2896 titration with perchloric acid.

(3) ○ indicates that the mixture generated from the ingredients used is transparent and free of sediment. vinegar.

Cloudiness evaluation: A-Clear, B-N-Cloudy increase sedimentation amount is % by volume.

FIG. 2 Right hand pawn - TtI Luciube 171. international search report

Claims (1)

[Claims] 1. Improved overbasing with improved high temperature storage and improved water tolerance A method for producing a calcium tuunato detergent lubricant additive, the method comprising: (3) Presence of polyhydroxy compound and calcium alkylbenzene sulfonate below, producing a chemical reaction intermediate at a temperature within the range of about 300°F to about 350°F. The calcium compound is reacted with the alkylphenol for a sufficient time to In this case, the molar ratio of calcium compound to alkylphenol is about 0.7-1.7 :1, and the amount of calcium alkylbenzene sulfonate is about 2.5-301 b per mole of nor; (b) About 1.1-2.0% per mole of alkylphenol is added to the reaction mixture of (a). adding 0 moles of elemental sulfur; (c) a temperature within the range of about 330°F to about 370°F; at a temperature sufficient to effect the reaction between the sulfur described above and the reaction mixture of (b) above. heating the reaction mixture of (b) for a time; (d) adding an amount above the reaction product of (c); Add the following polyhydroxy compound to form a reaction mixture: (e) at about 300°F. Heating the reaction mixture of (d) to a temperature within the range of about 360° F. carbonation with about 0.5 to 2.0 moles of carbon dioxide per mole of nor; (f) The reaction product of (e) is treated with nitrogen at a temperature within the range of about 470°F to about 490°F. dissipate; and (g) filtering the nitrogen depletion product of (f), but first of all steps (a) and (b); The molar ratio of the polyhydroxy compound to the alkylphenol added in is about 0. ．． 7-1.7:1; Second, the ratio of carbonate TBN to total TBN. , and controlling the weight ratio of sulfur to calcium to reduce the above ratio in the nitrogen depletion product. Ensure that the measured value satisfies the equation y≧−1.5(x)+1.14, where y represents the ratio of carbonate TBN to total TBN, and x represents the weight of sulfur and calcium. A lubricant package in which the product contains 0.2% by weight of water. When present at 130°F for 30 days in the Thirdly, the ratio of carbonate TBN to total TBN is small. has a value of at least 0.42 and the above ratio of sulfur to calcium is at least A hair method comprising the above steps. 2. The above polyhydroxy compounds are ethylene glycol, propylene glycol , butanediol-2,3, bentanediol-2,3, and 2-methylbutane 2. The method of claim 1, wherein the diol is selected from the group consisting of -3,4. 3. Claims in which the above polyhydroxy compound is ethylene glycol Method of Section 1. 4. The alkylphenol mentioned above is of formula R(C6H4)OH, where R is a straight-chain or branched alkyl group having 8-40 carbon atoms. Method of scope 1. 5. The above alkylphenols are octylphenol, decylphenol, dode Cylphenol, tetradecylphenol, hexadecylphenol, triaco selected from the group consisting of methylphenol and tetracontylphenol. , the method of claim 1. 6. Claim 1, wherein the alkylphenol is dodecylphenol. Method in section 1. 7. The above calcium is selected from the group consisting of calcium oxide and calcium hydroxide. The method of claim 1, wherein: 8. Claims wherein the alkaline earth metal compound is calcium hydroxide. Method of Section 1. 9. The above calcium alkylbenzene sulfonates contain about 60 carbon atoms. The claimed invention is a low base calcium sulfonate made from polypropene. Method of scope 1. 10. The molar ratio of the above polyhydroxy compound and the above alkylphenol is approximately The method of claim 1, wherein the ratio is in the range 0.9-1.3:1. 11. The molar ratio of the above sulfur to the above alkylphenol is about 1.3-1.6: 1. The method of claim 1 within the scope of claim 1. 12. The above calcium compound is lime, and the ratio of lime to alkylphenol is 1. The method of claim 1, wherein: is in the range of about 0.9-1.2:1. 13. The molar ratio of the carbon dioxide gas and the alkylphenol is about 0.5-1. 5:1. 14. The above calcium alkylbenzene sulfonate is an alkylphenol. 2. The method of claim 1, wherein the hydroxide is present in a ratio of about 5 to 15 hydrides per mole of hydride. 15. The reaction diluent in step (a) is about 100% per mole of alkylphenol. 5. The method of claim 1, wherein about 500 lbs. 16. The method of claim 1, wherein said method is a batch method. 17. The method of claim 1, wherein said method is a continuous method. 18. The above polyhydroxy compound is ethylene glycol, and the above alkali The lithium metal compound is calcium hydroxide, and the above alkylphenol is silphenols, and sulfur is the sulfur element, and the above alkaline earth metals Alkylbenzene sulfonates are made from polypropenes with a chain length of approximately C-60. The patent claims are low base calcium sulfonate and the above method is continuous. The method described in item 1 of the scope of the request.