JPH01501400A - Method for producing additive concentrate containing sulfurized alkaline earth metal hydrocarbyl phenolate - 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] Sulfurized alkaline earth metal hydrocarbyl phenolates, their production and use The present invention generally relates to sulfurized alkaline earth metal hydrocarbyl phenolics (sulp). hurized alkaline earth metat hydroca rbyl phenate), their production and their lubricating oil additives Regarding the use of.

Specifically, the present invention provides sulfur with high total base number (TBN) and acceptable viscosity. alkaline earth metal hydrocarbyl phenolate-containing compositions and low TBN. For their preparation from sulfurized alkaline earth metal hydrocarbyl phenolates with related.

In internal combustion engines, byproducts from the combustion chamber are often pumped out by the piston and Mixed with lubricating oil. Many of these by-products form acidic substances within the lubricating oil. child This is especially true for diesel engines operated on low-grade fuels with high sulfur content, which produce corrosive acids on combustion. This is noticeable in diesel engines. As a result, the acid mixed into the lubricating oil contains sulfur. Sulfuric acid produced by oxidation, halogens derived from halogen lead scavengers in fuel Contains hydrohydric acids and nitrogen acids produced by the oxidation of atmospheric nitrogen in the combustion chamber. be able to. Such acids cause sludge deposits and damage to bearings and engines. corrosion of engine parts, resulting in rapid engine wear and early failure.

A type of compound commonly used for neutralizing acidic substances and dispersing sludge in lubricating oils The substance is an alkali metal alkyl phenolate sulfide, and the metal is an alkaline earth metal. genus such as calcium, magnesium or barium. “Normal” and “Excessive” Both sulfurized alkaline earth metal alkyl phenolates were used. "Past The term ``basification'' refers to the number of equivalents of the alkaline earth metal moiety and the number of equivalents of the phenol moiety. The ratio of Used to describe sulfurized alkaline earth metal alkali phenolates that can be done. In contrast, the alkali in "normal" alkaline earth metal alkyl phenolates The equivalent ratio of the lithium metal moiety to the phenolic moiety is 1. Therefore, “overbasing” The substance has an excess of more than 20% of the alkaline earth metal present in the corresponding "normal" substance. For this reason, "overbased" sulfurized alkaline earth metal alkyl phenolates are larger acidic substances than the corresponding “normal” alkaline earth metal alkyl phenolates. It has the ability to neutralize.

Both "normal" and "overbased" sulfurized metal alkyl phenolates in the prior art A method of producing poly(single lime) is taught; commonly referred to as the "single lime addition" method. One method of producing such "overbased" sulfurized alkyl phenolates is Lukylphenol in the presence of lubricating oil contains sulfur, hydroxyl compounds and excess Alkaline earth metal hydroxides (more than the stoichiometric ratio required for neutralizing alkylphenols) ) to form an intermediate product, followed by carbonation and heading distillation ( to remove unreacted hydroxyl compounds) and filtration. intermediate The product is accompanied by a significant increase in viscosity, and subsequent carbonation reduces the viscosity to a relatively low level. Ru.

The increase in viscosity associated with the formation of intermediate products makes stirring of the reaction mixture difficult; This is undesirable as it will be harmful to the next reaction. This increase in viscosity is less Although it can be controlled to an acceptable level by mixing a certain amount of alkaline earth metal hydroxide, Also, overbased alkylphenolate products necessarily have low neutralization capacity. high Achieve a neutralized capacity product and at the same time control the viscosity of the intermediate product within acceptable limits In order to ) or in three separate reaction stages, it can be added in a continuous carbonation stage . However, this method involves relatively long batch times. Other methods are intermediate Viscosity reducing agents such as tridecanol, 2-ethylhexanol, or by using hydroxyl solvents in the boiling point range, but the Such measures increase the raw material costs of the process. Traditionally measured in mgKOH/g The highest total base number (T B N) is approximately 300, but the TBN of the conventional technology is within the range of 200 to 300. It is in. Sulfur having a high TBN of 300 or more, preferably 350 or more TBN. Desirable objects for producing alkaline earth metal alkyl phenolate compositions It is obvious that. Alkali sulfide with low TBN such materials Production from earth metal alkyl phenolates is also a desirable target. now Until today, achieving such high TBN products was possible only with large concentrations of alkaline earths. The use of metal bases results in a highly viscous product, which can be used next to using excess carbon dioxide. This is possible because attempts at carbonation render it insoluble rather than "diluting" it. It was not recognized that

We introduce the molecule into the reaction mixture containing the sulfurized alkaline earth metal alkyl phenolate. at least one carboxylic acid or its acid derivative having at least 10 carbon atoms in These objectives were achieved by mixing conductors, thereby making more than 300, young Acceptable materials having a TBN of 350 or more when dry and a viscosity of 1 ooocsT or less. A composition has been achieved that maintains a viscosity that is acceptable and avoids insolubility.

The use of carboxylic acids in the production of sulfurized alkaline earth metal alkyl phenolates is Not new, e.g. US-A-4,049,560 and B-P- See A-0,094,814.

US-A-4,049,560 provides (a) one or more hydrocarbons; Sulfurized phenols or thiophenols containing carbyl substituents, or one or more is a phenol or thiophenol containing more hydrocarbyl substituents; or the aforementioned phenols containing one or more hydrocarbyl substituents; Thiophenol and sulfur, 15-40% by weight, ~) Organic sulfonic acid, organic sulfonate or organic sulfate, 5-15 amount%, (C) Glycol, C3-C,-valent alkanol or 02-C4 alkoxy Alkanol, 5-15% by weight, [d) Magnesium hydroxide or activated magnesium oxide Gnesium, 2-15% by weight, (e) C+"C+*carboxylic acids, their acid anhydrides, or ammonium, Amine salt, Group Ⅰ metal or Group Ⅰ metal salt of the above Cl-01, carboxylic acid, at least 0.1% by weight of both, and (fl) present in the diluent oil (components (a) and ), at least 10% by weight, overbased magnesium washing by introducing carbon dioxide into the reaction mixture containing The preparation of the agent is described.

The amount of carboxylic acid (component (e)) is preferably in the range 0.5 to 2.0% by weight. Ru. The product produced by this reaction is approximately 200-250, e.g. 225 TB It is said to have N.

EP-A-0,094,814 includes lubricants and during the overbasing step or Then 0.1-10% by weight, preferably 2-6% by weight (additive concentrate) Weight basis) formula: (wherein R is a C1° to C0 unbranched alkyl or alkenyl group, and R1 is Hydrogen, C1-C4 alkyl group or -co! -coon group) an overbased alkaline earth metal hydride treated with an acid or its anhydride or salt. Mixed into a lubricating oil composition containing 10-90% by weight of locarbyl sulfurized phenolate An additive concentrate is disclosed.

The object of the invention of EP-A-0,094,814 is to problems encountered with additive concentrates, namely settling and foaming. The goal is to overcome the lack of stability.

The problem in EP-A-0,094,814 is that The aim is not to produce phenolates, but in fact to produce phenates produced by the method of the invention. Although Nolate overcomes stability and foaming issues, TBN values below 300 has.

Prior art techniques using carboxylic acids include overbased sulfurized alkalis having TBN of 300 or more It deals with the production and acceptable viscosity of lithium metal alkyl phenolates. It can be concluded that there is no.

Accordingly, in one aspect, the present invention provides additive compositions suitable for incorporation in finished lubricating oil compositions. the additive concentrate: Ta) Lubricating oil, (i) Formula: (wherein R is C3 ゜~CZa is an alkyl or alkenyl group, R1 is hydrogen, C3-C4 alkyl ) or -CH and -CODH groups) at least one carboxylic acid having is an ester, or (ii) a di- or polyester containing from 36 to 100 carbon atoms. - by mixtures of carboxylic acids or their acid anhydrides, acid chlorides or esters; modified lubricating oil soluble alkaline earth metal sulfide hydrocarbyl phenolates, Generally, the composition has a TBN of 300 or more.

Component (a) of the composition is a lubricating oil. Lubricating oil can be animal oil, vegetable oil or mineral oil. can be. Suitably the lubricating oil is a petroleum derived lubricating oil such as a naphthenic, para-based lubricating oil. It can be a fin-based or mixed base oil. Solvent neutral oil is especially Appropriate. Alternatively, the lubricating oil can be a synthetic lubricating oil. suitable synthetic lubrication Synthetic ester lubricating oils (these oils include diesters such as adipic acid dioxin) dioctyl, dioctyl sebacate and tridecyl adipate) or heavy Synthetic hydrocarbon lubricating oils include liquid polyisobutynes and polyalpha-olefins. be caught. The lubricating oil suitably accounts for 10-90% of the weight of the composition, preferably 10-7%. 0% can be included.

Composition (b) contains from 2 to 35 percent by weight, based on the weight of the composition, of (i) or Lubricating oil soluble alkaline earth metal sulfide modified by mixing the compound of (ii) Drocarbyl phenolate. Suitably alkaline earth metal is strontium , calcium, magnesium or barium, preferably calcium, barium Or it can be magnesium, more preferably calcium.

Hydrocarbyl Phenol of Sulfurized Alkaline Earth Metal Hydrocarbyl Phenolate The moiety is preferably derived from at least one alkylphenol. Archi The alkyl group of phenol can be branched or unbranched. Appropriate Alkyl groups contain from 4 to 50 carbon atoms, preferably from 9 to 28 carbon atoms, especially through Alkylphenol can be obtained by alkylating phenol with propylene tetramer. CI obtained by! - It is an alkylphenol.

The sulfurized alkaline earth metal hydrocarbyl phenolate is (i) or (ii) Modified by mixing compounds. Regarding (i), this means that the small number with equation (1) At least one carboxylic acid or its acid anhydride, acid chloride or ester.

Preferably, R in formula (1) is an unbranched alkyl or alkenyl group. Preferred acids of 1) are those in which R is C0° to czi, more preferably CI8 to CZa linear chain atom. a suitable saturated carboxyl group of formula (1), which is a rukyl group and R1 is hydrogen. Examples of acids include capric acid, lauric acid, myristic acid, palmitic acid, and stearic acid. Acid, suitable for formula 9 (1) including arachidonic acid, behenic acid and lignoceric acid Examples of unsaturated acids include lauroleic acid, myristoleic acid, palmitoleic acid, Oleic acid, gadoleic acid, erucic acid, ricinoleic acid, linoleic acid and linoleic acid Contains acid. Mixtures of acids, such as rapeseed top and rape fatty acids Can also be used. Particularly suitable mixtures of acids include both saturated and unsaturated acids. It is a commercial grade containing a range of acids. Such mixtures can be obtained synthetically or natural products such as cotton oil, peanut oil, coconut oil, linseed oil, palm kernel oil, olive oil, corn oil, palm oil, castor oil, soybean oil, sunflower oil, It can be derived from coconut oil, sardine oil and beef tallow. Sulfuric acids and acid mixtures can also be used. Acid anhydrides, acid chlorides instead of or in addition to carboxylic acids Alternatively, ester derivatives of acids, preferably acid anhydrides, can be used. but Preferably, a carboxylic acid or a mixture of carboxylic acids is used. The preferred carboxylic acid is stearic acid.

Alkaline earth metal hydrocarbyl phenol sulfide instead of or in addition to (+) A di- or poly-carboxylic acid containing 36 to 100 carbon atoms or are their acid anhydrides, acid chlorides or ester derivatives, preferably acid anhydrides. can be modified by mixing (ii). Preferably (ii) is It is lyisobutinsuccinic acid or polyisobutinsuccinic anhydride.

Preferred carboxylic acid(s), di- or polycarboxylic acids having the formula are their acid anhydrides, acid chlorides or esters, based on the weight of the composition. 35%, more preferably 12-20%, such as about 16%, by weight. Ru. The benefits of mixing more than 105 carboxylic acids or derivatives thereof are generally relatively low. Concentrate viscosity.

Suitably, the alkaline earth metal ranges from 10 to 20% by weight based on the weight of the composition. can be present in the composition in an amount within.

Suitably the sulfur is 1 to 6%, preferably 1.5 to 3%, based on the weight of the composition; can be present in the composition in an amount within the range of .

Suitably carbon dioxide is present in an amount of 5 to 20%, preferably 9 to 1%, based on the weight of the composition. It can be present in the composition in an amount within the range of 5%, by weight.

Preferably, the TBN of the composition is 350 or higher, more preferably 400 or higher.

Suitably, the composition has a temperature of 1. OO0cSt or less, preferably 7 Can have a viscosity of 50 cSt or less, more preferably 500 cSt or less .

In another aspect, the invention provides an additive outlet suitable for incorporation into a finished lubricant. (A) T of the final additive concentrate; sulfurized alkaline earth metal hydrocarbyl phenolates having a TBN of less than BN; (B) Alkali added in single or multiple additions at intermediate points during the reaction. earth metal base, (C) polyhydric alcohol having 2 to 4 carbon atoms, di- or tri(CZ~C,) glycol, alkylene glycol alkyl ether Polyalkylene glycol alkyl ether, (D) lubricating oil, (E) component ( B) carbon dioxide added after the or each addition, as well as CF) concentration Sufficient (i) carbonate having formula (1) to give 2 to 35% by weight based on the weight of the carbonate. Rubonic acid or its acid anhydride, acid chloride or ester, or (ii) 3 Di- or poly-carboxylic acids or anhydrides containing 6 to 100 carbon atoms Component (A) ~ The weight ratio of (F) is the ratio at which a concentrate having a TBN of 300 or more is produced. It is.

In yet another aspect, the present invention provides an additive concentrate for mixing into a finished lubricating oil. Provided is a method for producing a nitrate, the method comprising reacting the above components (A) to (F) at high temperature. and the weight ratio of components (A) to (F) has a TBN of 300 or more. is the ratio at which the concentrate is produced.

The process of the present invention shows that it cannot tolerate the low TBN or off-spec products of the prior art. This is advantageous because it provides a way to upgrade high TBN products with viscosity that can be reduced.

Additionally, sulfidation involves the reaction of alkylphenols and sulfur by more conventional routes. In contrast to the process for producing alkaline earth metal alkyl phenolates, the present invention Since no hydrogen sulfide is generated during operation of the process, the problem of disposal of hydrogen sulfide is avoided and This allows production in environmentally sensitive areas and the use of less complex equipment. Make it.

Component (A) of the reaction mixture has a TBN lower than that of the final product, i.e. generally 300 is a sulfurized alkaline earth metal hydrocarbyl phenolate having a TBN of less than Ru. Any sulfurized alkaline earth metal hydrocarbyl phenolate can be used. Wear. Sulfurized alkaline earth metal hydrocarbyl phenolates can be carbonated or non-carbonated. It can be a monster. of sulfurized alkaline earth metal hydrocarbyl phenolates The alkaline earth metal moiety and the hydrocarbyl phenolate moiety are suitably as described above. It can be a cage. of sulfurized alkaline earth metal hydrocarbyl phenolates The manufacturing method is well known (or known). Precursor of sulfurized alkaline earth metal hydrocarbyl phenolates in phenolate form and sulfur can be used.

The alkaline earth metal base (component B) is suitably an alkaline earth metal oxide or water. It can be an oxide, preferably a hydroxide. For example, quench calcium hydroxide. It can be added in the form of lime. Preferred alkaline earth metals include calcium, minerals, Gnesium and barium, with calcium being more preferred. alkaline earth gold Genus bases are useful for producing products with a TBN of 300 or higher, preferably 350 or higher. A sufficient amount of component (A) should be added.

This amount includes many properties including the nature of the sulfurized alkaline earth metal hydrocarbyl phenolate Depends on the factors. Typically, the weight ratio of component (B) to component (A) is suitably 0. ．． It can be in the range of 1 to 50, preferably 0.2 to 5. alkaline earth The metal base (B) can be added in its entirety to the initial reactants or in a portion to the initial reactants and The remainder is added in one or more parts at the next one or more steps in the process. You can get it. Preferably component (B) is added to the initial reactants in a single addition. .

Component (C) is a polyhydric alcohol having 2 to 4 carbon atoms, di or tri( 01~Ca) Glycol, alkylene glycol alkyl ether, or polymer It is realkylene glycol alkyl ether. Polyhydric alcohol is appropriately Dihydric alcohols such as ethylene glycol or propylene glycol, or can be a trihydric alcohol such as glycerin. Gee or Tory (C 2-Ca) Glycol is suitably diethylene glycol or triethylene glycol. Could be a recall. Alkylene glycol alkyl ether or polymer Realkylene glycol alkyl ether has the appropriate formula: % formula % () (In the formula, R is 01 to C, an alkyl group, R1 is an alkylene group, and R1 is hydrogen or C3-C&alkyl, and X is an integer within the range of 1-6) Suitable solvents with formula (If) which can be diethylene glycol, triethylene glycol or tetraethylene glycol Recalls include monomethyl or dimethyl ether. Particularly suitable solvents are methyldigol (CHsOCHiCLOCLCHz Mixtures of glycols and glycol ethers of formula (II) which are Using a glycol or glycol ether of formula (n), which can be used as a solvent, When combined with inorganic halides such as ammonium chloride, (C8-C4) carboxylic acids, such as acetic acid, are preferred. Preferably, component (C) is ethylene glycol or methyldigol, the latter being A combination with ammonium chloride and acetic acid.

Component (D) is the lubricating oil described above with respect to the concentrate composition.

Component (E) is carbon dioxide, which is in gaseous or solid form, preferably gaseous. Can be added in body form. In gaseous form it is suitably added to the reaction mixture. Infused. We generally know that the amount of carbon dioxide taken in increases the concentration of component (F) found that it increases with After the single addition of component (B), carbon dioxide It is added at the end of the reaction between (A), (B), (C), (D) and (F).

Component CF) comprises a carboxylic acid of formula (I) as previously described in the concentrate composition. di- or poly-carboxylic acids containing from 36 to 100 carbon atoms, or their acid anhydrides, acid chlorides or esters. weight of concentrate The above amounts required to give 2-35% by weight on a first approximation is the amount induced during the rate. In calculating this amount, e.g. Water loss should be taken into account.

The reaction can be carried out in the presence of a diluent. Appropriate diluent is inconsistent with process operation has no volatility, i.e. is easily stripped from the reaction mixture at the end of the reaction. It is a liquid with such volatility that it can be poured. Examples of suitable diluents include 2-ethyl ethyl Contains xanol, isooctatool, isoheptatool and tridecanol It will be done.

Adding sulfur, which is additional sulfur to that already present as component (A), to the reaction mixture can be added to. The advantage of adding more sulfur is that it is concentrated during It can be desirable for certain applications to increase the amount of sulfur. on the other hand Addition of sulfur results in the generation of hydrogen sulfide, thereby reducing the advantages of the invention to some extent. It will be lowered.

Preferably the reaction is carried out in the presence of other components that are catalysts for the reaction. touch Inorganic halides can be used as the medium, suitably halogenated water. It can be an ammonium halide, an ammonium halide or a metal halide. suitable The metal part of the metallogenide is zinc, aluminum or alkaline earth. It can be a metal, preferably calcium. Chloride is preferred among halides. Delicious. Suitable catalysts include hydrogen chloride, calcium chloride, ammonium chloride, and ammonium chloride. Includes luminium and zinc chloride, preferably calcium chloride. Appropriately, The amount of catalyst used can be up to 2.0% w/w.

Suitably, the reaction of components (A) to (F) and also the carbonation reaction is carried out at 120-200°C. can be carried out at elevated temperatures, preferably in the range of about 130-165°C, but only The actual temperatures chosen for the reaction and carbonation of components (Δ) to (F) are determined by the desired Then you can do something different. Pressure is atmospheric, below atmospheric, or above atmospheric be able to.

Concentrates are prepared in a conventional manner, for example by adding component (C), t5 and a diluent (if present). (b) can be recovered by distillative stripping.

Finally, it is preferable to filter the concentrate obtained.

In general, the method of the invention has an acceptable viscosity, i.e. 1,000 cS at 100°C. 750 or 50 at 100°C. Concentrates with viscosities below 0 cSt can be produced. moreover, Concentrates generally have desirable viscosity index properties. Such viscometer characteristics nature is advantageous because it facilitates processing (including filtration) of the concentrate. . However, at 100℃ 1. Concentrate with viscosity higher than OO0cSt It is also possible to manufacture sheets generally at high TBN levels. such a power outlet Trate filtration presents a problem, it is adding diluent before filtration and adding diluent after filtration. Can be overcome by stripping. alternatively or in addition In particular, if the resulting concentrate has a high TBN, e.g. In some cases, it is possible to maintain a TBN of 300 or more even after diluting with lubricating oil.

In a final aspect, the present invention provides a lubricating oil and a TBN in the range of 0.5 to 120. providing a finished lubricating oil composition containing sufficient of said additive concentrate to give .

Preferably the finished lubricant composition is sufficient to give a TBN within the range of 0.5 to 100. Contains a concentrated composition.

The amount of concentrate composition present in the finished lubricant depends on the nature of the end use. . Therefore, the amount of concentrate composition present for marine lubricating oils should be suitably The amount can be sufficient to give a TBN in the range of 9 to 100, and It is sufficient to provide the amount for the lubricating oil, suitably within the range of 4 to 20 TBN. be able to.

The finished lubricant also contains an effective amount of one or more other types of conventional lubricant additives. , such as viscosity index improvers, anti-wear agents, antioxidants, dispersants, rust inhibitors, pour point depressants, etc., which may be added directly or condensed into the finished lubricant composition. Mixing can be achieved through the mediation of a centrate composition.

In addition to its use as an additive in lubricating oil compositions, the concentrate of the present invention The compositions may also find use as fuel additives.

The invention will now be further illustrated by reference to the following examples.

The term rTBNJ is used throughout all examples. TBN is ^STMD2896 Total base number, mgKOH/g, measured by the method.

In all Examples, except as explicitly stated, CI! -Alkylphenol? A commercially available calcium sulfide alkylphenolate derived from phenolate is supplied as a solution in lubricating oil forming 36-40% w/w of the composition . The composition has a TBN of 250 and the following composition: Calcium (9,25 %W/W), sulfur (3,25%w/W) and carbon dioxide (4,6 %w/w), if the "charge" for the examples includes lubricating oil, this is phenolic It is an addition to what is already present in the composition.

Viscosity was measured by the ASTM D445 method.

Example I P　0 vertical head top charge of calcium alkyl phenolate: Lubricating oil 57g Calcium sulfide alkyl phenolate 206g lime 49g Stearic acid 70g Calcium chloride 4g 2-ethylhexanol 112g Charge 145~b 36 g of ethylene glycol was added. Then it was heated at 165℃/700wHg for 1 Time was maintained. Carbon dioxide (50g) was added over 1 hour at 165°C. Living The product was cooled to 125° C./700 mHg and added with lime (33 g). temperature was raised to 7700 ml (g) at 165°C and held at this temperature for 1 hour. Carbon dioxide ( 25g) was added over 1 hour at 165°C and then the product was heated to 200°C/10 Stripped with mHg. Finally the product was filtered. Filtration speed is very fast was recognized. 437 g of product and 167 g of distillate were obtained.

The product was analyzed for calcium, sulfur and carbon dioxide.

Its TBN, BPHVI viscosity at 50 and 100°C were measured. BPH The VI50 measurement is a solubility test. The test result is scale 1 (high solubility; passed) , 2 (borderline) and 3 (fail).

boar fruit Calcium - 13.9% W/W (equivalent to 96% retention of charged calcium in the product) ) Sulfur - 1,5% w/w (equivalent to 100% retention of charged sulfur in the product) Carbon dioxide - 12.3% W/W (equivalent to 62% retention in the product of the initial CO) TBN -395 V + ** -228cSt BPHVI50-IA Stearic acid #16%w/w This example demonstrates how high TBN products with acceptable viscosity can be produced by the process of the present invention. It shows that it can be converted to BN product.

Example 2 Loading vehicle: Calcium sulfide alkylphenol)? 230g lubricating oil = 26g Calcium chloride 3g way - direction +a+ The charge was heated to 100°C/700n+Hg. Stearic acid (6 3g) was added, the mixture was stirred for 15 minutes, and (bl　2-ethylhexanol (190g) was added with 100~b700 Tsuru H, (Add C1 lime (66g) at 110℃/700TsuruHg, fd) Add the mixture to 16g Heat to 5℃/700sgHg and immediately add ethylene glycol (32g). (1 minute), hold the mixture at 165℃/700wmHg for 5 minutes, ( f) Carbon dioxide (66g) was then added at 165°C/1 bar (to remove the phantom solvent) The stripped product was collected at 200°C/10+uHg and filtered.

Ikusokouri Crude product: 398g Distillate = 236g Pa''s Filtration speed was fast.

Calcium: 14.1%w/w Sulfur = 2.0%w/w cow: 12.9%w/w TBN: 399 V+oo: 825cSt Stearic acid: 15.8% w/w Example 3 Charging vehicle: As in Example 2 Man-nuki As in Example 2, but the temperatures were changed in steps (d), (e) and (f). The temperature was changed from 165°C to 145°C.

generation success Crude product: 402g Distillate: 239g T aim 11 coarse Calcium: 13.9%w/w Sulfur: 1.9%w/W Cot: 13.9%w/w TBN: 392 V+ao: 206 C3t Stearic acid: 15.7% w/w Example 4 Charging vehicle: As in Example 2 1-floor As in Example 2, but with temperatures in steps (d), (6) and (f); The temperature was changed from 165°C to 130°C.

Genso 11 Crude product: 377g Distillate: 236g J″ Calcium: 13.7%w/w Sulfur = 2.1%w/w Cot: 13.2%w/w TBN: 380 V+eo: 99cSt Stearic acid: 16.7% w/w Example 5 As in Example 3 product weight Crude product: 388g Distillate: 239g Product composition after filtration Calcium: 11.9% w/w Sulfur・2.1% w/w Co2゛゛　9.0%w/w 'I'BN: 331 V+oo: 98cSt V4+1: t49ocst VI: 148 Stearic acid: 16.2% w/w The filtration step (h) was very difficult.

This example is Example 3. ! : Desired use of the catalyst in the two methods of the present invention to compare Show something good. Low V, when no catalyst is present. . However, This is achieved at the cost of low uptake of calcium and carbon dioxide, and also Filtering was difficult.

Example 6 Charge: Calcium sulfide alkyl phenol): 253g Lubricating oil (100SN): 26g Calcium chloride 4g 2-Ethylhexanol: 190g Stearin H: 40g Ho-ri (Al　Heat the charge at 120℃/700+mdi, then add lime (36g) In addition, ~) Heat the mixture to 145-165°C, while adding ethylene glycol (32g ) and (C) Hold the mixture at 165°C/700 mmog for 1 hour, (d) Diacid (e) Cool the mixture to 120°C. Cool, add lime (25g), and (f) heat the mixture to 165℃/700mmWg Carbon dioxide (22 g) was added at 165°C and 71 bar. b) Strip the solvent at 200°C/10 mmHg, and (1) filter the product. did. Filtration speed was fast.

Generation and village! Crude product: 401g Distillate: 239g 'of Calcium: 14.3%w/w Sulfur: 2.1%w 7w Cot: 11.3%w/w TBN: 405 V+oo: 1483cSt Stearic acid = 10%w/w This example has a relatively high viscosity due to the mixture of 10% w/w stearic acid. However, it is shown that it is possible to produce high TBN concentrates.

Example 7 Charging vehicle: As in Example 6, but with 250 g of phenolate to 26 Stearic acid was increased from 40g to 51g.

direction - floor As in Example 6 Generation 11 Crude product: 396g Distillate: 234g ゝ゛′ Calcium: 14.5% w/w Sulfur = 2.2%w/w Cot: 13.1%w/w TBN: 399 VIO@: 706 cst Stearic acid: 12.9% w/w This example is a high TBN concentrate with lower viscosity compared to Example 6. containing 12.9% w/w stearic acid based on the weight of the concentrate. Indicates that it can be manufactured in quantity.

Example 8 Charging 1: Calcium sulfide alkyl phenolate: 230g Lubricant (SN100): 0 g Calcium chloride: 3g 1-ta ta) Heat the charge to 100°C, then add stearic acid (99g) and mix. Stir the mixture for 15 minutes, add (bl) 2-ethylhexanol (190 g) to 1 Add at 00-110℃・ (e) Add lime (66g) at 110°C/2’Hg vacuum and mix (tll) Heat to 145℃/10'H, add ethylene glycol (32g) for 20 minutes. Add the tel mixture and hold the mixture at 145℃/10''H for 5 minutes, Carbon oxide (66 g) was added at 145°C, and the phantom product was added at 200°C/30'H. Stripped and filtered the product. The filtration rate was slow.

Criticize generation! Crude product 7 398g Distillate: 209g Pa''s Calcium: 11.95%w/w Sulfur: 1.65%w/w co, = 11.6%w/w TBN: 349 Vies: 100cSt Va. :974cSt Stearic acid: 24.9% w/w This example contains 24.9% w/w stearic acid. The ability to produce high TBN concentrates with low viscosity and low viscosity with stearic acid content show.

Comparison test 1 Charging standing 2 As in Example 3 1-ta As in Example 3, but with the addition of ethylene glycol in step (d). Addition was omitted.

Generated vehicle weight 1 Crude product: 3g2g Distillate: 200g 11 Japanese jobs per month Calcium: 8.4% w/w Sulfur: 2.3%w/w cot: 4.4%w/w TBN: 239 Vies H41cSt The filtration rate in stage (h) was slow.

This is not an example according to the invention and the presence of component (C) does not affect the performance of the method of the invention. Included to indicate that it is required.

Example 9 Meji (thing) - as in Example 3 1-ta As in Example 3, but with the addition of ethylene glycol in step (d). The weight was reduced from 32g to 16g.

Generation ship ll Crude product: 399g Distillate: 225g 1 ■ Round edge 4I Calcium = 13.7%w/w Sulfur: 2.05w/w cot: 13.5%w/w TBN: 395 VI60 = 182cst Stearic acid: tS, S%w/w The filtration rate in stage (h) was slow.

This example shows that the addition of ethylene glycol can be reduced by 50% compared to Example 3. and

Example 10 Charging room: Calcium sulfide alkyl phenol): 230g Lubricating oil (100SN): 2 6g Ammonium chloride: 4g Vinegar acid + 2g 1-excluded As in Example 3, but in step (b) 2-ethylhexanol Add methyl diglycol (130 g) instead of 190 g, and proceed to step i (d). The addition of ethylene glycol in was omitted.

Generation valuable ■ Crude product: 390g Distillate?　166g Jl (1) Note■ Calcium: 14.1% w/w Sulfur: 2.0% w/w Cot: 14.2%w/w TBN: 398 Vies: 210cSt V4o: 3821cSt Vl: 170 Stearic acid: 16.2% w/w The filtration rate at stage (h) was fast .

This example shows that methyl diglycol is effective as component (C).

Example 11 Charging chamber: As in Example 3 1-floor As in Example 3, but the pressure in step (d) is 270 mdg Met.

Lesson.

Crude product: 402g Distillate = 238g t1μl1 Calcium: 14.05w/w Sulfur; 1.9%w/w cot: 14.4%w/w TBN: 392 View: 288 cst Stearic acid: 15.7% w/w Example 12 Charging chamber: As in Example 3 1-bottom As in Example 3, but using 2-ethylhexanol instead of 190 g. 40g was used.

Generation Seal U Crude product: 399g Distillate; 90g I surplus 1■ Calcium: 13.9% w/w Sulfur: 1.9% w/w Cot: 12.1%w/w TBN: 408 V+oo: 3B7cSt V4 @ Near 980cSt Vl: 193 Stearic acid: 15.8% w/w Example 13 Kasairi: Calcium sulfide alkyl phenolate: 230g stearic acid = 63g Calcium chloride: 48 C1l linear α-olefin: 26g 2-ethylhexanol: 90g up to 1- (111 mixture to 145-b Add ethylene glycol (32g) and heat the mixture to 165℃/700a lm) Hold in Ig for 30 minutes, (c) Cot (38g) at 165℃/1 bar. (d) Cool the mixture to 120°C and add 2-ethylhexanol (10 0g) and (8) Add lime (66g), (f) The mixture was held at 165°C/700 mmHg for 5 minutes and (phantom dioxide Add carbon (66g), (hl The solvent was recovered by stripping at 200°C/10 mmHg. , 1i1 The product was filtered.

generation soll Crude product = 385g Distillate: 256g t shadow (1) pride of place Calcium: 14.8% w/w Sulfur: 1.9% w/w Cot　’　13.4%w　/　w TBN: 424 VIO@: 583cSt Vaa: 13.080 cSt Vl: 209 Stearic acid: 16.4% w/w The filtration rate in stage (i) was fast .

This example shows that the lubricating oil can be replaced by a long carbon chain α-olefin (C, in this case). Show that you can do it.

Mottled top soil Charged beans: Derived from a mixture of CIz/Czt/Ct-alkylphenols Calcium sulfide alkyl phenolate (250TBN): 233.5g Lubricating oil (SN100) = 26g Calcium chloride: 3g 1-Year (Al　Heat the mixture to 100℃, add stearic acid (63g), and add the mixture to Stir for 15 minutes, ~) Add 2-ethylhexanol (194g) at 100-110°C. (Add C1 lime (66g) at 110°C/2″H, vacuum, add (dl) mixture to 14 Heat to 5°C/10'Hg and add ethylene glycol (32g) for 20 minutes. (e) Hold the mixture at 145°C/10'Hg for 5 minutes and add (fl diacid Add carbon dioxide (66 g) and strip the phantom product at 200°C/30'Hg. , (hl) The product was filtered.

Generate precious l Crude product: 385g Distillate = 250g Pa''s Calcium: 14.0%w/w Sulfur: 1.84%w/w cot: 12.9%w/w TBN: 401 V+oo: 81cSt Vas:8385cSt Vl: 186 Stearic acid: 16.4% w/w This example is C+t/Ctt/C Calcium sulfide alkylphenol derived from a mixture of alkylphenols This shows that it is possible to improve the quality of latkes.

Example 15 Criticism of Kasairi: Calcium sulfide alkyl phenolate = 181g Lubricating oil (SN100): 5 0g Calcium chloride = 4g Rapeseed top fatty acids = 62g 2-ethylhexanol = 190g 1-5 [a) Heating the mixture to 120°C, Add (bl lime (43g) at 120℃/2"Hg vacuum, (C1 ethylene glycol) Add cole (32g) at 145~b, (d) Hold the mixture at 165°C/2″Hg for 1 hour and add tel carbon dioxide (4 (f) Cool the mixture to 130°C, add lime (29g) to 130°C. /2”Hg added, (d) Hold the mixture at 165°C/2'Hg for 1 hour, add 1 hour of lime (22g) Add at 65°C and remove product by stripping at 200°C/30”Hg. Filtered things.

Generation precious 1 Crude product: 382g Distillate = 230g 1 Indulgences” - Criticism Calcium: 14.0% w/w Sulfur: 1.8% w/w Cot: 12.3%w/w TBN: 374 V+e*: 176cSt Vat: 2826cSt Vl: 172 Carboxylic acid content: 16.2% w/w This example does not demonstrate that rapeseed top fatty acids can be used in the method of the invention.

Example 16 Charge: Calcium sulfide alkyl phenol): 230g Lubricating oil (SN100): 2 6g Calcium chloride = 3g Method As in Example 2, but stearic acid (63 g) in step (a) ) was used instead of tall oil fatty acid (63g).

product weight Crude product: 380g Distillate: 223g Product composition after filtration Calcium: L4.0%w/w Sulfur +2.09%w/w Go2: 9.7% w/w 'rBN: 380 VIOe: 263 cSt Carboxylic acid content: 16.6% w/w Product weight basis This example shows that tall oil fatty acids can be used in the method of the invention.

Example 17 way - direction As in Example 16, but 5N instead of tall oil fatty acid (63g) Polyisobutyne succinic acid free in 100 lubricating oil (TBN=60 B KOH/g) Water (PIBSA) 52g and stearin TL! 47 g of the mixture was used.

Maso ILJiL Crude product: 390g Distillate: 219g 11-7 Calcium: 13.1% w/w Sulfur: 1.8% w/w CO2・12.5%w/w TBN: 360 VIOe: 416cSt V4゜: 12,690 cSt This example shows that the carboxylic acid can be partially replaced by PIBSA in the method of the invention. to show that

Example 18 Belly loading: As in Example 16 Ho-Kei As in Example 16, but instead of tall oil fatty acids (63g), behen Acid (63g) was used.

generation l1l Crude product: 402g Distillate: 247g Product composition after filtration Calcium: 12.4% w/w Sulfur: 1.9% w/w CO,: 11.4%w/w TBN: 354 VIao: 141cSt Behenic acid: 15.7% w/w This example shows that behenic acid can be used as the carboxylic acid in the method of the invention. Show that you can do it.

Example 19 Charge: As in Example 15, but with rapeseed top fatty acids (62g) Valmitic acid (56.2 g) was used instead.

Method As in Example 15, but omitting steps (''), (g) and (h) did.

product weight Crude product: 312g Distillate: 222g Product composition after filtration Calcium: 11.7%w/w Sulfur = 1.9% w/w co,: 8.2%w/w TBN: 232 ■1°. Near 0cSt V4@:83tcSt Vl: 156 Valmitic acid: 18.0%w/w This example shows that valmitic acid can be used in the method of the invention.

Example 20 Charge: As in Example 15 Method As in Example 15, but omitting steps (f), (g) and (h) did.

product weight Crude product: 334g Distillate: 234g Product composition after tightening Calcium: 11.8% w/w Sulfur・1.8% w/w COa: 10.9% w/w TBN: 321 VIOe: 168 cSt V411:1009 cSt Vl: 286 Carboxylic acid content: 18.6% w/w, product weight comparison test 2 Charge: Calcium sulfide alkyl phenolate: 230g lubricating oil = 26g Calcium chloride 3g (a) Heat the mixture to 1000°C and add 2-ethylhexanol (1,90g) Add (b) Add acetic acid (14g), (C) The mixture became thick and heterogeneous and took on a green color. Stirring is not effective It was. The reaction was interrupted.

This test is not an example according to the invention, but simply a lower carboxylic acid, in this case acetic acid, is included to indicate wood that cannot be used in the method of the invention.

Example 21 Charge: As in Example I6, but commercially available calcium sulfide alkyl Non-carbonated commercially available calcium sulfide CI2-alkylphenolate in place of phenolate (145 TBN> was used.

Method: As in Example 16, but in step (C) 66 g of lime worms and in step (f) the amount of carbon dioxide was increased from 66 g to 83 g. added.

product weight Crude product: 421g Distillate: 246g Product composition after filtration Calcium: 13.7% w/w Sulfur: 1.9% w/w Cot: 10.3%w/w TBN: 383 ■1゜a: 137cst V411:2119cSt Vl: 163 Carboxylic acid: 15.0%w/w This example uses a low initial TBN non-carbonated calcium sulfide alkyl phenolate. This shows that it can be used in the method of the present invention.

Example 22 Charged beans: Carbonated Calcium Sulfide Alkyl Pheno (150TBN) I253g Stearic acid: 40g 2-ethylhexanol: 90g Calcium chloride = 4g way - direction (Al Mixture 145-b Add ethylene glycol (32g) and heat the mixture to 165℃/700℃. mmHg for 30 min, (C1 carbon dioxide (38 g) at 165 °C/l bar (dl) The mixture was cooled to 120°C and 2-ethylhexanol (100 g) and lime (76g) and heated the mixture to 165℃/700+u +ltg for 60 minutes, then (fl　carbon dioxide (82g) at 165℃/1 bar (h) Filter the product. passed.

Generated vehicle weight 1 Product weight = 390g ′−゛. ' raw Calcium: 14.4%W/w Sulfur I2.3%w/w COt: 11.6%w/w TBN: 402 V+oo: 674 cst Stearic acid: 10.3% w/w This example combines a low (150) TBN calcium sulfide alkyl phenolate with a high TBN This shows that it is possible to improve the N product.

Example 23 Charge: As in Example 14, but with a mixture of alkylphenols C12-alkyl phenolate instead of calcium sulfide alkyl phenolate derived from A commercially available calcium alkylphenolate derived from phenolate was used.

Method: As in Example 14, but in step (b), 2-ethylhexano in step (d) using isoheptator (190 g) instead of tool (194 g). ethylene glycol was added quickly (within 1 minute).

product weight Crude product: 402g Distillate: 239g Product composition after filtration Calcium: 1.3.9% w/w Sulfur: 1.9% w/w Cot: 12.0%w/w TBN: 391 V+**: 313cSt Vl@: 6700 cSt Vl: 177 Stearic acid: 15.7% w/w Filtration rate was slow.

This example demonstrates that isoheptator can be used as a solvent in the method of the invention. and

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Claims (32)

[Claims] 1. An additive concentrate suitable for incorporation into a finished lubricating oil composition, the additive concentrate comprising: (a) Lubricating oil (b) 2 to 35% by weight based on the weight of the composition, (i) Formula ▲ Numerical formula, chemical formula, table etc. ▼(I) (wherein R is a C10-C24 alkyl or alkenyl group and R1 is hydrogen, C1-C4 alkyl group or -CH2-COOH group ) at least one carboxylic acid or its acid anhydride, acid chloride or is an ester, or (ii) a di- or polyester containing from 36 to 100 carbon atoms. - mixing carboxylic acids or their acid anhydrides, acid chlorides or esters; A lubricating oil soluble alkaline earth metal sulfide hydrocarbyl phenol modified with to, an additive concentrate having a TBN of 300 or more. 2. The additive composition according to claim 1, wherein the lubricating oil is contained in an amount of 10 to 90% by weight of the composition. centrate. 3. Alkali of lubricating oil soluble sulfurized alkaline earth metal hydrocarbyl phenolates Claim 1 or wherein the earth metal is calcium, magnesium or barium. is the additive concentrate described in 2. 4. The additive condenser according to claim 3, wherein the alkaline earth metal is calcium. Trait. 5. Hydrocarbyl of oil-soluble sulfurized alkaline earth metal hydrocarbyl phenolates the phenolate moiety is derived from at least one alkylphenol; 9 to 28 alkyl groups or alkyl groups of phenol or phenols Additive outlet according to any one of claims 1 to 4, comprising carbon atoms of rate. 6. The hydrocarbyl phenolate moiety binds phenol with propylene tetramer. derived from C12-alkylphenol obtained by alkylation, The additive concentrate according to claim 5. 7. At least one of the formula (I) in which R is an unbranched alkyl or alkenyl group Addition according to any one of claims 1 to 6, in which one carboxylic acid is mixed. drug concentrate. 8. In the carboxylic acid of formula (I), R is a C10 to C24 straight chain alkyl group; , R1 is hydrogen. 9. A mixture of carboxylic acids of formula (I) is mixed, the mixture comprising saturated and unsaturated acids. According to any one of claims 1 to 6, which is a commercial grade containing a series of acids including both Additive concentrate as described. 10. The additive according to any one of claims 1 to 6, in which stearic acid is mixed. Added concentrate. 11. Di- or poly-carboxylic acids containing from 36 to 100 carbon atoms or their The additive concept according to any one of claims 1 to 6, in which an acid anhydride is mixed. rate. 12. Polyisobutenesuccinic acid or polyisobutenesuccinic anhydride is mixed and an additive concentrate according to claim 11. 13. Component (b)(i) or component (b)(ii) increases the weight of the concentrate. Any one of claims 1 to 12 mixed in an amount of 10 to 35% by weight based on Additive concentrates as described in Section. 14. Component (b)(i) or (b)(ii) is based on the weight of the concentrate. The additive according to claim 13, mixed in an amount within the range of 12 to 20% by weight. Concentrate. 15. Any one of claims 1 to 14, wherein the composition has a TBN of 350 or more. Additive concentrates as described in . 16. The additive concept according to claim 15, wherein the TBN of the composition is 400 or more. rate. 17. Claims 1-- having a viscosity of 1.000 cSt or less at 100°C 17. The additive concentrate according to claim 16. 18. The viscosity at 100°C is 500 cSt or less, according to claim 17. Additive concentrate. 19. An additive concentrate suitable for incorporation into finished lubricating oils, the additive concentrate comprising (A ) alkaline earth sulfide with a TBN less than the TBN of the final additive concentrate. metal hydrocarbyl phenolate, (B) single addition or multiple additions at intermediate points during the reaction; an alkaline earth metal added as an additive, (C) a polyvalent atom having 2 to 4 carbon atoms; alcohol, di- or tri-(C2-C4) glycol, alkylene glycol Alkyl ether or polyalkylene glycol alkyl ether, (D) Jun lubricating oil, (E) carbon dioxide added after the addition or each addition of component (B), and and (F) sufficient (i) to give 2-35% by weight based on the weight of the concentrate. ) Carboxylic acid having formula (I) or its acid anhydride, acid chloride or ester or (ii) a di- or poly-carbon containing 36 to 100 carbon atoms. By reacting acids or their acid anhydrides, acid chlorides or esters at high temperatures. electrical outlet, which has a TBN in which the weight ratio of components (A) to (F) is 300 or more. Concentrate, which produces torate. 20. A method for producing an additive concentrate according to claims 1 to 18, comprising: (A) Alkali sulfide having a TBN less than the TBN of the final additive concentrate. earth metal hydrocarbyl phenolate, (B) a single addition at an intermediate point during the reaction or Alkaline earth metal added in multiple additions, (C) polycarbonate having 2 to 4 carbon atoms; alcohols, di- or tri-(C2-C4) glycols, alkylene glycos polyalkylene glycol alkyl ether or polyalkylene glycol alkyl ether, (D ) lubricating oil, (E) carbon dioxide added after the addition or each addition of component (B); and (F) sufficient to provide 2 to 35% by weight based on the weight of the concentrate. (i) Carboxylic acid having formula (I) or its acid anhydride, acid chloride or ester or (ii) a di- or poly-carboxylic acid containing from 36 to 100 carbon atoms. Reacting bonic acids or their acid anhydrides, acid chlorides, or esters at high temperatures. and has a TBN in which the molar ratio of components (A) to (F) is 300 or more The method that causes the rate to be generated. 21. 21. The method of claim 20, wherein component (B) is lime. 22. The weight ratio of component (B) to component (A) is within the range of 0.2 to 5. The method according to range 20 or 21. 23. Any of claims 20 to 22, wherein component (C) is ethylene glycol. The method described in paragraph (1). 24. Any one of claims 20 to 22, wherein component (C) is methyl digol. The method described in section. 25. Carbon dioxide (component E) is added to components (A) to (D) after a single addition of component (B). and (F), added at the end of the reaction between The method described in section. 26. 26. A method according to any one of claims 20 to 25, wherein a diluent is present. 27. Sulfur other than that already present as component (A) is added to the reaction mixture , a method according to any one of claims 20 to 26. 28. 28. Any one of claims 20 to 27, wherein the reaction is carried out in the presence of a catalyst. The method described in. 29. 29. The method of claim 28, wherein the catalyst is calcium chloride. 30. The composition has sufficient lubricating oil and a TBN within the range of 0.5 to 120. A finish comprising an additive concentrate according to any one of claims 1 to 18. lubricating oil composition. 31. If the lubricating oil is a marine lubricating oil and has a TBN in the range of 9 to 100, The finished lubricating oil composition of claim 30, wherein an additive concentrate is present. . 32. The lubricating oil is an automotive engine lubricating oil and has a TBN in the range of 4 to 20. A finished lubricant set according to claim 30, wherein a sufficient additive concentrate is present. A product.