CN1012074B - Sulphurized alkaline earth metal hydrocarby phenates, their production and use thereof - Google Patents
Sulphurized alkaline earth metal hydrocarby phenates, their production and use thereofInfo
- Publication number
- CN1012074B CN1012074B CN87108344A CN87108344A CN1012074B CN 1012074 B CN1012074 B CN 1012074B CN 87108344 A CN87108344 A CN 87108344A CN 87108344 A CN87108344 A CN 87108344A CN 1012074 B CN1012074 B CN 1012074B
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- Prior art keywords
- acid
- alkaline earth
- earth metal
- product
- weight
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
Abstract
An additive concentrate suitable for incorporation into a finished lubricating oil composition is disclosed. The additive concentrate comprises (a) a lubricating oil; (b) a lubricating oil soluble sulphurized alkaline earth metal hydrocarbyl phenate modified by incorporation of from greater than 2 to 35% by weight based on the weight of the composition of either (i) at least one carboxylic acid having formula (I), wherein R is C10 to C24 alkyl or alkenyl group and R' is either hydrogen, a C1 to C4 alkyl group or a -CH2-COOH group, or an anhydride acid, chloride or ester thereof or (ii) a di- or polycarboxylic acid containing from 36 to 100 carbon atoms or an anhydride acid, chloride or ester thereof, the composition having a TBN greater than 300.
Description
The present invention relates generally to sulphurized alkaline earth metal hydrocarby phenates, and the preparation method of this salt and they application as lubricating oil additive.The present invention be more particularly directed to have the composition that contains sulphurized alkaline earth metal hydrocarby phenates of high total basicnumber (TBN) and suitable viscosity, and prepare this method for compositions with the sulfurizing hydrocarbyl phenol alkali earth metals of low total basicnumber (TBN).
In oil engine, usually there is by product from the slit of fuel chambers and piston, to spill and admixes with lubricating oil.Many this by products form acidic substance in lubricating oil.Particularly in the diesel engine of the low-grade fuel that burns high sulfur content, owing to burning has produced caustic acid, the acid of this and lubricating oil blending has the sulfuric acid that is obtained by the sulphur oxidation, by the plumbous scavenging agent institute's deutero-haloid acid of halogen in the fuel with by the nitrogen acid that oxidation produced of atmospheric nitrogen in the combustion chamber.These acid have caused the deposition of sludge, the corrosion of bearing, thereby and make the quick wearing and tearing of engine component cause breaking in early days of engine.
Be generally used for neutralizing these acidic substance and to be used to disperse a compounds of lubricated sludge in oil be the sulfenyl phenolate metal-salt, metal wherein is a kind of alkaline-earth metal, for example calcium, magnesium or barium.At present not only the sulfenyl phenolate alkaline earth salt of " generally " is used, and " high alkalinity " sulfenyl phenolate alkaline earth salt also is used, term " high alkalinity " is generally used for describing following sulfenyl phenolate alkaline earth salt, promptly in this salt the ratio of the equivalent value of alkaline-earth metal part and the equivalent value of phenol moieties greater than 1, usually greater than 1.2, also can equal 4.5 or higher.On the contrary, in the alkylphenol alkaline earth salt of " generally ", the alkaline-earth metal part is 1 with the equivalence ratio of phenol moieties.Therefore, " high alkalinity " material contains than the corresponding high excess base earth metals more than 20% of " generally " material.Therefore, " high alkalinity " sulfenyl phenolate alkaline earth salt has the more ability of senior middle school and acidic substance than corresponding " generally " alkylphenol alkaline earth salt.
Existing technology has been lectured the method for many preparations " generally " or " high alkalinity " sulfenyl phenolate metal-salt." the one step lime addition method " technology that wherein has the method for a kind of preparation " high alkalinity " alkyl monosulfide phenates to be referred to as usually, this technology comprises alkylphenol reacting down at lubricating oil, sulphur, oxy-compound and excessive alkaline earth metal hydroxides (in being and the required above-mentioned stoichiometric ratio of alkylphenol), generate a kind of intermediate product, carbonating is pulled out head distillation (to remove unreacted oxy-compound) and filtration then.The generation of intermediate product is accompanied by the obvious increase of viscosity, follow-up carbonating then is reduced to viscosity one than low value, the viscosity increase of following intermediate product to generate and occurring is undesirable, and is unfavorable to subsequent reactions because this will make reaction mixture become to be difficult to stir.Yet the increase of this viscosity can control to a suitable value by mix a small amount of alkaline earth metal hydroxides in reaction, and high alkaline alkyl phenol salt product must have lowered neutralising capacity.For the product that obtains senior middle school and ability and the viscosity of controlling intermediate product simultaneously in the acceptable value scope, alkaline earth metal hydroxides can be in two steps, (being referred to as " two step lime addition method " technology usually) or three independent reactions steps, the carbonation step that is thereafter continues.Yet this method has comprised the quite long intermittent time.Another method is to use viscosity depressant in the preparation of intermediate product, for example tridecyl alcohol, 2-Ethylhexyl Alcohol, or the hydroxylic solvent of similar boiling range, but a kind of like this way has increased the material cost in the technology.Although generally the total basicnumber scope of existing technology is 200-300, but can obtain and be suitable for viscosity the highest corresponding to total basicnumber (TBN) (to make measure unit by existing processing method usually with mgKOH/g, be 300, know that very the ideal target is to produce the sulfenyl phenolate alkaline-earth metal salt composition with high total basicnumber (TBN), said high total basicnumber (TBN) is that TBN is greater than 300, more preferably greater than 350.Also having an ideal target is to prepare above-mentioned composition from the sulfenyl phenolate alkaline earth salt with low total basicnumber (TBN).Up to the present, also find no the product that the people can obtain high like this total basicnumber.This is because the alkaline-earth metal alkali concn that uses is too high, has caused the high viscosity of product, makes this high-viscosity products become insolubles, and this high-viscosity products is attempted with the excess carbon dioxide carbonating also not " thinning " that continues.But we have reached these purposes, and obtained total basicnumber (TBN) and surpass 300(and surpass 350 sometimes) composition, kept simultaneously desirable viscosity again, viscosity less than 1000 centistokes (cst), by will having at least one carboxylic acid or its acid derivant of at least 10 carbon atoms to mix in the reaction mixture that contains the sulfenyl phenolate alkaline earth salt in the molecule, thereby have avoided insoluble.
Using carboxylic acid when producing the sulfenyl phenolate alkaline earth salt has not been new technology, referring to U.S. Pat-A-4049560 number and European patent EP-A-0094814 number.
U.S. Pat-A-4049560 has narrated the method production high alkalinity magnesium washing composition that carbonic acid gas is fed reaction mixture, and said reaction mixture comprises:
(a) 15-40%(is heavy) phenol red that contains one or more hydrocarbyl substituents or thiophenol, or contain the phenol or the thiophenol of one or more hydrocarbyl substituents, or contain one or more said phenol or thiophenols with sulphur hydrocarbyl substituent together,
(b) organic sulfonic acid 5-15%(weight), organic sulfonate or organic sulfate,
(c) glycol 5-15%(weight), C
1-C
5Monobasic alkanol or C
2-C
4Alkoxy chain triacontanol,
(d) 2-15%(weight) magnesium hydroxide or activated magnesia,
(e) it is heavy to be at least 0.1%() C
1-C
18Carboxylic acid, and acid anhydrides, or its ammonium salt or amine salt, said C
1-C
18The I family metal-salt of carboxylic acid or II family metal-salt and
(f) 10%(is heavy at least) thinning oil [comprise be present in (a) and (b) in the component].
It is heavy that the amount of carboxylic acid [component (e)] is preferably 0.5-2.0%(), it is said that with the product of this prepared in reaction total basicnumber (TBN) is about 200-250, for example about 225.
European patent EP-A-0094814 has disclosed the multifunctional additive for lubricating oils that mixes lubricating oil composition, this enriched material contains lubricating oil, with heavy from 10%() heavy to 90%() or the high alkalinity process or the high alkalinity sulphurized alkaline earth metal hydrocarby phenates of in height alkalization process subsequent step, handling, and 0.1%(is heavy) heavy to 10%(), it is heavy to be preferably 2-6%() the following formula acid of (based on additive concentration):
R-CH-COOH????（Ⅰ）
R
1
(R is C in the formula
10-C
24Unbranched alkyl or alkenyl, and R
1Be hydrogen, C
1-C
4Alkyl or-CH
2-COOH yl) or basic acid anhydrides or its salt.The goal of the invention of European patent EP-A-0094814 is to solve the problem that many multifunctional additive for lubricating oils ran into that contains high alkalinity additive, promptly causes deposition and foaming problem deficient in stability.The problem of EP-A-0094814 is not that preparation has TBN greater than 300 phenates with really with the method preparation and the phenates (although having overcome stability and foaming problem) of this invention, and its total basicnumber (TBN) also is lower than 300.
Can conclude, use carboxylic acid to prepare total basicnumber greater than 300 and there is the overbased sulfurized alkylphenols as active phenol alkaline earth salt of suitable viscosity not have what problem in the existing technology.
Therefore, an object of the present invention is to provide a kind of suitable multifunctional additive for lubricating oils that mixes the finished lube composition, this multifunctional additive for lubricating oils comprises:
(a) lubricating oil
(b) lubricating oil can be improved sulphurized alkaline earth metal hydrocarby phenates by dissolved, its incorporation (with following (ⅰ) or composition (ⅱ) be benchmark) heavy greater than 2%() heavy to 35%(), (ⅰ) be carboxylic acid a: R-CH-COOH (I) who has following formula at least
R
1
In the formula, R is C
10-C
24Alkyl or alkenyl, and R
1Or hydrogen, C
1-C
4Alkyl or-CH
2-COOH base, or its acid anhydrides, chloride of acid or ester.(ⅱ) be two or the poly carboxylic acid that contains the 36-100 carbon atom, or its acid anhydrides, chloride of acid or ester.The total basicnumber of above-mentioned composition is greater than 300.
The component of composition (a) is a lubricating oil.Suitable lubricating oil can be animal oil, vegetables oil or mineral oil.Suitable lubricating oil can be the lubricating oil by petroleum derivation, for example naphthene base crude oil, paraffinic based oil or mixing base oil.Solvent neutral oil preferably.In addition, lubricating oil can also be ucon oil, and suitable ucon oil comprises ester oil, and this class oil has for example Octyl adipate of diester oil, certain herbaceous plants with big flowers two dioctyl phthalates and hexanodioic acid 13 esters, or polymeric hydrocarbon lubricating oil (for example liquid polyisobutene and poly-alpha olefins.Based on the weight of composition, suitable lubricating oil content can be 10-90%, is preferably 10-70%.
Component (b) be lubricating oil can dissolved the improvement sulphurized alkaline earth metal hydrocarby phenates, its incorporation (based on or (ⅰ) or (ⅱ) weight of composition) be greater than 2% to 35%.Suitable alkaline-earth metal can be strontium, calcium, magnesium or barium, preferably calcium, barium or magnesium, particularly calcium.
The alkyl phenol moieties of sulphurized alkaline earth metal hydrocarby phenates is preferably derived by at least one alkylphenol.The alkyl of alkylphenol can be that side chain or unbranched is arranged.Suitable alkyl contains 4-50, preferably 9-28 carbon atom.Optimum alkylphenol is the C that obtains with the tetrapropylene alkylated phenol
12-alkylphenol.
Sulphurized alkaline earth metal hydrocarby phenates is by mixing or (ⅰ) or (ⅱ) obtaining improveing.About (ⅰ), this is one at least chemical formula I or its acid anhydrides, the carboxylic acid of chloride of acid or ester.Preferably unbranched alkyl of R or alkenyl in the chemistry formula I.The preferred acid of chemistry formula I is that wherein R is C
10-C
24, be preferably C
18-C
24Straight chained alkyl, and R
1Be those acid of hydrogen.The example of suitable chemical formula I saturated carboxylic acid has capric acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, eicosanoic acid, docosoic and Lignoceric acid.The example of the suitable unsaturated acid of chemistry formula I has: lauroleic acid, Oleomyristic acid, Zoomeric acid, oleic acid, cis 9-eicosenoic acid, erucic acid, ricinolic acid, linoleic acid plus linolenic acid.Can also use the mixture of acid, rape seed oil (rapetop) lipid acid for example, optimum mixing acid is those acid of commercial grade that contain a series of acid, comprises two kinds of saturated acid and unsaturated acid.These mixtures can be obtained by synthesis method, or obtain for example cotton oil, peanut oil, Oleum Cocois, Toenol 1140, palm-kernel oil, sweet oil, Semen Maydis oil, plam oil, Viscotrol C, soya-bean oil, sunflower oil, menhaden fish oil, sardine fat and tallow oil by natural product.The mixture of sulfurized acid and acid also can use, and except carboxylic acid, can also use acid anhydrides, the ester derivative of chloride of acid or acid, but acid anhydrides the best.Yet preferably use the mixture of carboxylic acid or carboxylic acid.The carboxylic acid of preferred chemical formula I is a stearic acid.
Except (ⅰ), sulphurized alkaline earth metal hydrocarby phenates also can mix (ⅱ) and improve.Said (ⅱ) is two or poly carboxylic acid or the basic acid anhydrides that contains 36-100 carbon atom, chloride of acid or ester derivative, preferably its acid anhydrides.Preferably (ⅱ) is polyisobutene Succinic Acid or polyisobutylene butanedioic anhydride.
The carboxylic acid of chemistry formula I, and two or poly carboxylic acid, or acid anhydrides, the preferred incorporation of chloride of acid or ester is greater than 10% to 35% based on the weight of composition, is preferably about 12%-20%, for example about 16%.Normally the viscosity of enriched material is lower greater than 10% advantage for the incorporation of carboxylic acid or derivatives thereof.
Suitable alkaline-earth metal is present in the amount in the composition, can be that 10%(is heavy based on the weight of composition)-20%(is heavy).
Suitable sulphur is present in the amount in the composition, can be heavy for 10%(based on the weight of composition)-6%(is heavy), it is heavy to be preferably 1.5%()-3%(is heavy).
Suitable carbonic acid gas is present in the amount in the composition, can be that 5%(is heavy based on the weight of composition)-20%(is heavy), it is heavy to be preferably 9%()-15%(is heavy).
The preferred total basicnumber (TBN) of composition is greater than 350, more preferably greater than 400.
The viscosity that suitable compositions had is measured in the time of 100 ℃ should be less than 1000 centistokes, preferably less than 750 centistokes, especially less than 500 centistokes.
Another object of the present invention provides a kind of multifunctional additive for lubricating oils that is suitable for mixing finished lube, and this enriched material can be obtained by the reaction under the high temperature.(A) total basicnumber that sulphurized alkaline earth metal hydrocarby phenates had (TBN) is less than the total basicnumber of final multifunctional additive for lubricating oils, (B) in the middle of reaction process constantly with alkaline earth metal alkali or once add or add several times, (C) or add the polyvalent alcohol with 2-4 carbon atom, two or three (C
2-C
4) ethylene glycol, alkylidene group ethylene glycol alkyl oxide or polyglycol alkyl oxide; (D) add lubricating oil; (E) component of every adding (B) back feeds a carbonic acid gas; (F) be enough to provide from heavy greater than 2%() heavy to 35%() (based on or (ⅰ) or (ⅱ) enriched material weight) by or (ⅰ) or (ⅱ) enriched material of formation; (ⅰ) be carboxylic acid or its acid anhydrides with chemical formula I; chloride of acid or ester; (ⅱ) be two or the poly carboxylic acid that contains 36-100 carbon atom; or its acid anhydrides, chloride of acid or ester.Component (A) is a preparation total basicnumber (TBN) greater than the weight ratio of 300 enriched material to the weight ratio of (F).
The 3rd purpose of the present invention provides a kind of preparation method who mixes multifunctional additive for lubricating oils in the finished lube, this method comprises the reaction of at high temperature carrying out said components (A) to (F), and component (A) is that preparation has the weight ratio of total basicnumber (TBN) greater than 300 enriched materials to the weight ratio of (F).
Method of the present invention is excellent, because it provides a kind of method that improves low TBN product quality in the existing technology, the product that maybe will not meet quality becomes high total basicnumber (TBN) product with suitable viscosity.In addition, owing to do not emit hydrogen sulfide in the operating period of technology of the present invention, on the contrary, in the technology of preparation sulphur alkylphenol alkaline earth salt, comprising the reaction of alkylphenol and sulphur, by prevailing route, the emission problem of hydrogen sulfide can be avoided, therefore, and the regional process for processing of environment sensitive and need not to use senior meticulous factory around.
The component of response composite (A) is to have the sulphurized alkaline earth metal hydrocarby phenates that total basicnumber is lower than final product (promptly being usually less than 300).Any sulphurized alkaline earth metal hydrocarby phenates can use.Sulphurized alkaline earth metal hydrocarby phenates can carbonating or non-carbonated.The alkaline-earth metal of sulphurized alkaline earth metal hydrocarby phenates part and alkyl acid moieties can with aforesaid those.The method for preparing sulphurized alkaline earth metal hydrocarby phenates is known in affiliated field.In addition, the predecessor of sulphurized alkaline earth metal hydrocarby phenates, promptly unvulcanised alkaline earth metal hydrocarby phenates and sulphur also can use.
Suitable alkaline earth metal alkali (component B) can be alkaline earth metal oxide or oxyhydroxide, oxyhydroxide preferably, and for example the form that calcium hydroxide can white lime adds.Preferred alkaline-earth metal is calcium, magnesium and barium, preferably calcium.For component (A), the add-on of alkaline earth metal alkali must be to be enough to prepare total basicnumber to surpass 300, preferably surpasses 350 product.This add-on depends on multiple factor, comprises the performance of sulphurized alkaline earth metal hydrocarby phenates.Component (B) is generally 0.1-50 with the suitable weight ratio of component (A), is preferably 0.2-5.Alkaline earth metal alkali (B) can all join in the initial reactant, or partly joins in the initial reactant, and remainder can join in the subsequent step in the technology one or more times.Component (B) preferably once joins in the initial reactant.
Component (C) or the polyvalent alcohol of 2-4 carbon atom is arranged, two or three (C
2-C
4) ethylene glycol, alkylidene group ethylene glycol alkyl oxide, or polyglycol alkyl oxide.Suitable polyvalent alcohol can be a dibasic alcohol, for example ethylene glycol or propylene glycol.Also can be trivalent alcohol, for example glycerol.Two or three suitable (C
2-C
4) ethylene glycol can be or glycol ether or triglycol.Suitable alkylidene group ethylene glycol alkyl oxide or polyglycol alkyl oxide have following chemical formula: R(OR
1) XOR
2(II)
R is C in the formula
1-C
6Alkyl, R
1Be alkylidene group, R
2Be hydrogen or C
1-C
6Alkyl, and X is the integer of a 1-6.Suitable solvent with chemical formula II comprises: the monomethyl ether of ethylene glycol or dimethyl ether, glycol ether, triglycol or Tetraglycol 99.Optimum solvent is methyl digol alcohol (CH
3OCH
2CH
2OCH
2CH
2OH.The mixture of ethylene glycol and chemical formula II alcohol ether also can use.The alcohol ether that makes spent glycol or chemical formula II during as solvent best incorporated use relevant therewith inorganic halides (for example ammonium chloride) and rudimentary (C
1-C
4) carboxylic acid (as acetate).Preferred ingredients (C) or ethylene glycol or methyl digol alcohol, the latter uses in conjunction with ammonium chloride and acetate.
Component (D) is the aforesaid lubricating oil relevant with concentrate composition.
Component (E) is a carbonic acid gas, and it can add with gaseous state or solid-state form, and the most handy gaseous form adds, and is blown in the reaction mixture with gaseous form is suitable.We have found that the incorporation of common carbonic acid gas increases along with the increase of component (F) concentration.Carbonic acid gas be preferably in component (A), (B), (C), (D) and (F) between reaction finish after, and feed adding component (B) back each time.
The component relevant with concentrate composition (F) or the carboxylic acid of chemical formula I contain two or poly carboxylic acid of 36-100 carbon atom or its acid anhydrides, chloride of acid or ester.For providing heavy greater than 2%() heavy to 35%() (based on the weight of enriched material) required above-mentioned (F) group component will be the first approximation by the enriched material derivation.For example when this amount of calculating, should take into account the dehydration in the carboxylic acid.
This reaction can be carried out in the presence of thinner.Suitable thinner is to have and the corresponding to volatile liquid of technological operation, promptly when reaction can easy stripping goes out from reaction mixture when finishing volatile liquid.The example of suitable diluents has 2-Ethylhexyl Alcohol, isooctyl alcohol, iso-heptanol and tridecanol.Extra sulphur also can join in the reaction mixture, and this additional sulphur exists as component (A).The advantage that adds extra sulphur is to have increased the content of sulphur in the enriched material, and this uses some is desirable.Add sulphur on the other hand and caused the discharging of hydrogen sulfide, thereby impair aforesaid those advantages of the present invention to a certain extent.
Preferably be reflected under the existence of annexing ingredient and carry out, said annexing ingredient is to be used for catalyst for reaction, operable catalyzer is an inorganic halides, suitable inorganic halides or hydrogen halide, ammonium halide or metal halide, the halid metal part of suitable metal can be zinc, aluminium or alkaline-earth metal, calcium preferably.Said halogenide is muriate preferably.Suitable catalyzer has hydrogenchloride, calcium chloride, ammonium chloride, aluminum chloride and zinc chloride, preferably calcium chloride.It is heavy that the suitable usage quantity of catalyzer can reach 2.0%()/(weight).
The reaction of corresponding component (A)-(F) and carbonation reaction can be at 120-200 ℃, be preferably under about 130-165 ℃ the high temperature to carry out, but the reaction of component (A)-(F) and the selected actual temperature of carbonation reaction also are on demand and different.Pressure can be normal pressure, low pressure or superatmospheric pressure.
Enriched material can reclaim with conventional method, for example distillation stripping of component (C) and dilution (if the words that have).
At last, preferably filter resulting enriched material.Usually, technology of the present invention can prepare the enriched material of appropriate viscosity, and promptly its viscosity and can be prepared the enriched material that has less than 750 or 500 centistoke viscosity less than 1000 centistokes in the time of 100 ℃ in the time of 100 ℃.In addition, enriched material generally has desired viscosity index character.Because enriched material is processed (comprising filtration) easily, so this viscometric properties is useful.Yet, usually when higher total basicnumber, also might prepare and have high viscosity more (as 100 ℃ viscosity greater than 1000 centistokes, enriched material, can go wrong when filtering this enriched material, but can before filtration, overcome, and after filtration, thinner be obliterated with vaporizing extract process with the method that adds thinner.In addition, enriched material can and still keep TBN to surpass 300 with lubricating oil dilution, and is especially all the more so when the total basicnumber of prepared enriched material is higher than 400.
Last purpose of the present invention provides a kind of finished lube composition, and said composition includes the above-mentioned multifunctional additive for lubricating oils of lubricating oil and q.s, is the scope of 0.5-120 so that a TBN to be provided.
Preferred finished lube composition contains the concentrate composition of capacity, is the scope of 0.5-100 so that a TBN to be provided.
The amount that is present in concentrate composition in the finished lube will depend on the character of final use.Therefore, for marine lubricant, the suitable amount of concentrate composition should be enough to provide total basicnumber (TBN) to be the scope of 9-100, and for automobile engine lubricating oil, the suitable amount of enriched material should be enough to provide total basicnumber (TBN) to be the scope of 4-20.
The lubricating oil additive commonly used that can also contain one or more other types of significant quantity in the finished lube, viscosity index improver for example, anti-wear agent, oxidation inhibitor, dispersion agent, rust-preventive agent, pour point depressant or the like.These additives can directly be incorporated in the finished lube composition, also can add as intermediary by concentrate composition.
Additive finds that also concentrate composition of the present invention also can make fuel dope and use except the application of mixing lubricating oil composition.
To further specify the present invention with embodiment below.
All used term " TBN " in all embodiment, TBN is total basicnumber (Total Base Nomber), measure with the ASTMD2896 method, and be measure unit with mgKOH/g.
In all embodiment, except as otherwise noted outside, employed be bought on the market by C
12The prepared calcium sulfenyl phenolate of-alkylphenol.This phenates provides with the lubricant oil solution form, its 36-40%W/W the most in composition.The TBN of composition is 250, and said composition is made up of following component: calcium (9.25%W/W), sulphur (3.25%W/W) and carbonic acid gas (4.6%W/W).Here be the supplementary component that has been present in the phenates composition for " charging " the included lubricating oil among any embodiment.
Method with ASTMD445 is measured viscosity.
Embodiment 1:
Improve the quality of calcium sulfenyl phenolate
Charging:
Lubricating oil (57 gram)
Calcium sulfenyl phenolate (206 gram)
Lime (49 gram)
Stearic acid (70 gram)
Calcium chloride (4 gram)
α-ethylhexanol (112 gram)
This charging is heated to 145-165 ℃/700mmHg adds 36 gram ethylene glycol simultaneously.Keep it then at 165 ℃/700mmHg1 hour, fed carbonic acid gas (50 gram) down at 165 ℃ in more than 1 hour.This product is cooled to 125 ℃/700mmHg.Add lime (33 gram).Temperature is raised to 165 ℃/700mmHg and this temperature was kept 1 hour.More than 1 hour at 165 ℃ of feeding carbonic acid gas (25 gram).Then with this product stripping under 200 ℃/10mmHg.At last product is filtered.Can see that filtration velocity is very fast.Obtain 437 gram products and 167 gram overhead products.
This product is carried out the analysis of calcium, sulphur and carbonic acid gas.Record its TBN, BPHVISO and viscosity in the time of 100 ℃.The BPHVISO assay method is a solubility test.The result of this test with scale 1(than high resolution, by) the 2(line of delimitation) and 3(by) expression.
The result:
Calcium :=13.9%W/W(is equivalent to 96% the calcium charging in the product of being retained in)
Sulphur :=1.5%W/W(is equivalent to 100% the sulphur charging in the product of being retained in)
Carbonic acid gas :=12.3%W/W(is equivalent to 62% the CO in the product of being retained in
2Charging)
TBN＝395
V100=228 centistoke (cst)
BPHVISO＝1A
Stearic acid=16%W/W
This embodiment has illustrated that low TBN product can change into high TBN product and an acceptable viscosity is arranged by method of the present invention.
Embodiment 2:
Charging:
Calcium sulfenyl phenolate: 230 grams
Lubricating oil: 26 grams
Calcium chloride: 3 grams
Method:
(a) charging is heated to 100 ℃/700mmHg.Add stearic acid (63 gram) and mixture was stirred 15 minutes;
(b) when 100-110 ℃/700mmHg, add 2-Ethylhexyl Alcohol (190 gram);
(c) when 110 ℃/700mmHg, add lime 66 grams;
(d) said mixture is joined 165 ℃/700mmHg and quick (1 minute) ethylene glycol (32 gram) that adds;
(e) this mixture was kept under 165 ℃/700mmHg 5 minutes;
(f) when 165 ℃/1bar, add carbonic acid gas (66 gram) then;
(g) when 200 ℃/10mmHg, reclaim solvent and
(h) steam stripped product is filtered.
Product weight:
Crude product: 398 grams
Overhead product: 236 grams
Product after the filtration is formed: filtering speed is very fast.
Calcium 14.1%W/W
Sulphur 2.0%W/W
CO
212.9%W/W
TBN????399
V100 825 centistokes (cst)
Stearic acid 15.8%W/W
Embodiment 3
Charging: identical with embodiment 2.
Method:
Except in step (d), (e) with the temperature (f) replaces 165 ℃ with 145 ℃, all the other are identical with embodiment 2.
Product weight:
Crude product 402 grams
Overhead product: 239 grams
Crossing filtered product forms:
Calcium 13.9%W/W
Sulphur 1.9%W/W
CO
213.9%W/W
TBN????392
V100 206 centistokes (cst)
Stearic acid 15.7%W/W
Embodiment 4
Charging: identical with embodiment 2.
Method:
Except in step (d), (e) with the temperature (f) replaces 165 ℃ with 130 ℃, all the other steps are identical with embodiment 2.
Product weight:
Crude product 377 grams
Overhead product: 236 grams
Crossing filtered product forms:
Calcium 13.7%W/W
Sulphur 2.1%W/W
CO
213.2%W/W
TBN????380
V100 99 centistokes (cst)
Stearic acid 16.7%W/W
Embodiment 5
Charging: except removing calcium chloride, all the other are identical with embodiment 3.
Method: with embodiment 3
Product weight:
Crude product 388 grams
Overhead product: 239 grams
Crossing filtered product forms:
Calcium 11.9%W/W
Sulphur 2.1%W/W
CO
29.0%W/W
TBN????331
V100????98cst
VI????148
Stearic acid 16.2%W/W
Filtration step (h) is very difficult.
This embodiment that compares with embodiment 3 has illustrated that in technology of the present invention it is desirable using catalyzer.Do not having under the situation of catalyzer, although obtained lower V100, this result obtains under by the cost that reduces calcium and carbon dioxide mixture, filters in addition and has become difficulty.
Embodiment 6
Charging:
Calcium sulfenyl phenolate: 253 grams
Lubricating oil (100SN) 26 grams
Calcium chloride 4 grams
2-Ethylhexyl Alcohol 190 grams
Stearic acid 40 grams
Method:
(a) charging is heated to 120 ℃/700mmHg, adds lime (36 gram) then
(b) this mixture heating up is arrived 145-165 ℃, add ethylene glycol (32 gram) simultaneously;
(c) this mixture was kept under 165/700mmHg 1 hour;
(d) under 165 ℃/1bar, add carbonic acid gas (44 gram);
(e) mixture is cooled to 120 ℃ and adds lime (25 gram);
(f) this mixture was kept under 165 ℃/700mmHg 1 hour;
(g) under 165 ℃/1bar, add carbonic acid gas (22 gram);
(h) under 200 ℃/10mmHg stripping go out solvent and
(i) filtration product, filtration velocity are very fast.
Product weight:
Crude product: 401 grams
Overhead product: 239 grams
Crossing filtered product forms:
Calcium 14.3%W/W
Sulphur 2.1%W/W
CO
211.3%W/W
TBN????405
V100????1483cst
Stearic acid 10%W/W
This embodiment has illustrated the enriched material that can prepare high total basicnumber, yet owing to mix the stearic acid of 10%W/W, it is high that its viscosity is wanted relatively.
Embodiment 7
Charging: except phenates is increased to 268 grams from 250 grams, stearic acid is outside 40 grams are increased to 51 grams, and all the other are with embodiment 6.
Method: with embodiment 6.
Product weight:
Crude product: 396g
Overhead product: 234g
Crossing filtered product forms:
Calcium 14.5%W/W
Sulphur 2.2%W/W
CO
213.1%W/W
TBN????399
V100????706cst
Stearic acid 12.9%W/W
This embodiment shows, when stearic acid content is the 12.9%W/W of enriched material, can make the enriched material of the low viscous high TBN that compares with embodiment 6.
Embodiment 8
Charging:
Calcium sulfenyl phenolate: 230g
Lubricating oil (SN100) 0g
Calcium chloride: 3g
Method:
(a) charging is heated to 100 ℃, adds stearic acid (99g) then, this mixture stirred 15 minutes.
(b) add 2-Ethylhexyl Alcohol (190g) at 100-110 ℃,
(c) 110 ℃/2 " under the Hg vacuum condition, add lime (66g),
(d) with this mixture heating up to 145 ℃/10 " Hg added ethylene glycol (32g) in 20 minutes,
(e) this mixture is 145 ℃/10 " left standstill under the Hg condition 5 minutes,
(f) add carbonic acid gas (66g) at 145 ℃,
(g) 200 ℃/30 " under the Hg condition, product is carried out stripping,
(h) filtering product, its filtration velocity is slow.
Product weight:
Crude product: 398g
Overhead product: 209g
Crossing filtered product forms:
Calcium 11.95%W/W
Sulphur 1.65%W/W
CO
211.6%W/W
TBN????349
V100????100cst
V40????947cst
Stearic acid 24.9%W/W
This embodiment shows, when stearic acid content is 24.9%W/W, makes that to have low viscous high TBN enriched material be possible.
Comparison test 1
Charging: as embodiment 3
Method:
Identical with embodiment 3, just in step (d), add one step of ethylene glycol and omit.
Product weight:
Crude product: 382g
Overhead product: 200g
Crossing filtered product forms:
Calcium 8.4%W/W
Sulphur 2.3%W/W
CO
24.4%W/W
TBN????239
V100????41cst
Filtration velocity is slow in step (h).
This is not embodiments of the invention, but is used for illustrating that the existence of component (c) is absolutely necessary for carrying out process of the present invention.
Embodiment 9
Charging: as embodiment 3
Method:
Identical with embodiment 3, just the ethylene glycol that adds in step (d) is reduced to 16g from 32g.
Product weight:
Crude product: 399g
Overhead product: 225g
Crossing filtered product forms:
Calcium 13.7%W/W
Sulphur 2.0%W/W
CO
213.5%W/W
TBN????395
V100????182cst
Stearic acid 15.8%W/W
Filtration velocity in the step (h) is slow.
This embodiment shows that the addition of comparing the second triol with embodiment 3 can reduce 50%.
Embodiment 10
Charging:
Phenol red alkyl calcium 230g
Lubricating oil (100SN) 26g
Ammonium chloride 4g
Acetate 2g
Method:
Identical with embodiment 3, just in step (b) without 2-Ethylhexyl Alcohol (190g), replace methyl glycol ether (130g), and add one step of ethylene glycol in the step (d) and omit.
Product weight:
Crude product: 390g
Overhead product: 166g
Crossing filtered product forms:
Calcium 14.1%W/W
Sulphur 2.0%W/W
CO
214.2%W/W
TBN????398
V100????210cst
V40????3821cst
VI????170
Stearic acid 16.2%W/W
Filtration velocity in the step (h) is fast.
This embodiment shows that the methyl glycol ether is effective as component (c).
Embodiment 11
Charging: as embodiment 3
Method:
Identical with embodiment 3, just pressure is 270mmHg in step (d).
Product weight:
Crude product: 402g
Overhead product: 238g
Crossing filtered product forms:
Calcium 14.9%W/W
Sulphur 1.9%W/W
CO
214.4%W/W
TBN????392
V100????288cst
Stearic acid 15.7%W/W
Embodiment 12
Charging: as embodiment 3
Method:
Identical with embodiment 3, just the 190g2-ethylhexanol is used 40g instead.
Product quality:
Crude product: 399g
Overhead product: 90g
Crossing filtered product forms:
Calcium 13.9%W/W
Sulphur 1.9%W/W
CO
212.1%W/W
TBN????408
V100????387cst
V40????7980cst
VI????193
Stearic acid 15.8%W/W
Embodiment 13
Charging:
Calcium sulfenyl phenolate 230g
Stearic acid 63g
Calcium chloride 4g
C
18Straight chain alpha-olefins 26g
2-ethyl hexanol 90g
Method:
(a) mixture heating up is arrived 145-165 ℃/700mmHg, adds ethylene glycol (32g) simultaneously,
(b) when 165 ℃/700mmHg, this mixture left standstill 30 minutes,
(c) under 165 ℃/1bar, add carbonic acid gas (38g),
(d) this mixture is cooled to 122 ℃, adds 2-ethyl hexanol (100g),
(e) add lime (66g),
(f) this mixture left standstill 5 minutes at 165 ℃/700mmHg,
(g) add carbonic acid gas (66g),
(h) stripping reclaims solvent under 200 ℃/10mmHg,
(i) product is filtered.
Product weight:
Crude product: 385g
Overhead product: 256g
Crossing filtered product forms:
Calcium 14.8%W/W
Sulphur 1.9%W/W
CO
213.4%W/W
TBN????424
V100????583cst
V40????13，080cst
VI????209
Stearic acid 16.4%W/W
Filtration velocity in the step (ⅰ) is fast.
This embodiment shows that lubricating oil can (be C here with long carbochain alpha-olefins
18) replace.
Embodiment 14
Charging:
From C
12/ C
22/ C
24The calcium sulfenyl phenolate of alkylphenol mixture (250TBN) 233.5g
Lubricating oil (SN100) 26g
Calcium chloride 3g
Method:
(a) with mixture heating up to 100 ℃, add stearic acid, this mixture stirred 15 minutes.
(b) add 2-Ethylhexyl Alcohol at 100-110 ℃,
(c) 110 ℃/2 " under the Hg vacuum, add lime (66g),
(d) with mixture heating up to 145 ℃/10 " Hg added ethylene glycol (32g) in 20 minutes,
(e) 145 ℃/10 " under the Hg, this mixture left standstill 5 minutes,
(f) add carbonic acid gas (66g),
(g) 200 ℃/30 " under the Hg, product is carried out stripping,
(h) filtration product.
Product weight:
Crude product: 385g
Overhead product: 250g
Crossing filtered product forms:
Calcium 14.0%W/W
Sulphur 1.84%W/W
CO
212.9%W/W
TBN????401
V100????381cst
V40????8385cst
VI????186
Stearic acid 16.4%W/W
This embodiment shows from C
12/ C
22/ C
24The calcium sulfenyl phenolate that obtains in the alkylphenol mixture can be improved.
Embodiment 15
Charging:
Calcium sulfenyl phenolate 181g
Lubricating oil (SN100) 50g
Calcium chloride 4g
Rape oil fatty acid 62g
2-Ethylhexyl Alcohol 190g
Method:
(a) with mixture heating up to 120 ℃,
(b) 120 ℃/2 " under the Hg vacuum, add lime (43g),
(c) 145-165 ℃/2 " under the Hg, add ethylene glycol (32g),
(d) mixture is 165 ℃/2 " left standstill under the Hg 1 hour,
(e) add carbonic acid gas (44g),
(f) mixture is cooled to 130 ℃, 130 ℃/2 and " adds lime (29g) during Hg.
(g) mixture is 165 ℃/2 " left standstill under the Hg 1 hour,
(h) in the time of 165 ℃, add lime (22g),
(i) 200 ℃/30 " under the Hg, product is carried out stripping,
(j) filtration product.
Product quality:
Crude product: 382g
Overhead product: 230g
Crossing filtered product forms:
Calcium 14.0%W/W
Sulphur 1.8%W/W
CO
212.3%W/W
TBN????374
V100????176cst
V40????2826cst
VI????172
Carboxylic acid content 16.2%W/W
This embodiment shows that the present invention can use rape oil fatty acid.
Embodiment 16
Charging:
Calcium sulfenyl phenolate 230g
Lubricating oil (SH100) 26g
Calcium chloride 3g
Method:
Identical with embodiment 2, just in the step (a) without stearic acid (63g), and replace ready denier oil acid (63g).
Product weight:
Crude product 380g
Overhead product 223g
Crossing filtered product forms:
Calcium 14.0%W/W
Sulphur 2.09%W/W
CO
29.7%W/W
TBN????380
V100????263cst
Carboxylic acid content 16.6%W/W(is a product weight)
This embodiment shows in process of the present invention can use ready denier oil acid.
Embodiment 17
Charging: as embodiment 16
Method:
Identical with embodiment 16, just in the mixture of SN100 lubricating oil (TBN=60mgKOH/g) and stearic acid (47g), replace ready denier oil acid (63g) with 52g polyisobutylene succinic anhydride (PIBSA).
Product quality:
Crude product: 390g
Overhead product: 219g
Crossing filtered product forms:
Calcium 13.1%W/W
Sulphur 1.8%W/W
CO
212.5%W/W
TBN????360
V100????416cst
V40????12，690cst
VI????164
Carboxylic acid content 12.1%W/W is with product weight
Anhydride content 7.2%W/W is the basis
This embodiment shows that in process of the present invention, carboxylic acid can part be replaced by PIBSA.
Embodiment 18
Charging: as embodiment 16
Method:
Identical with embodiment 16, just Yong docosoic (16g) replaces ready denier oil acid (63g).
Product quality:
Crude product: 402g
Overhead product: 247g
Crossing filtered product forms:
Calcium 12.4%W/W
Sulphur 1.9%W/W
CO
211.4%W/W
TBN????354
V100????141cst
Mountain acid 15.7%W/W
This embodiment shows that in process of the present invention, available docosoic is as carboxylic acid.
Embodiment 19
Charging: identical with embodiment 15, just replace rape oil fatty acid (62g) with palmitinic acid (56.2g).
Method:
Identical with embodiment 15, just step (f), (g) and (h) omission.
Product weight:
Crude product: 312g
Overhead product: 222g
Crossing filtered product forms:
Calcium 11.7%W/W
Sulphur 1.9%W/W
CO
28.2%W/W
TBN????332
V100????70cst
V40????831cst
VI????156
Palmitinic acid 18.0%W/W
This embodiment shows, can use palmitinic acid in the process of the present invention.
Embodiment 20
Charging: as embodiment 15,
Method:
Identical with embodiment 15, just omit step (f), (g) and (h).
Product weight
Crude product: 334g
Overhead product: 234g
Crossing filtered product forms
Calcium 11.8%W/W
Sulphur 1.8%W/W
CO
210.9%W/W
TBN????321
V100????168cst
V40????1009cst
VI????286
Carboxylic acid content accounts for 18.6% of product weight
Simultaneous test 2
Charging:
Calcium sulfenyl phenolate: 230g
Lubricating oil: 26g
Calcium chloride: 3g
Method:
(a) with mixture heating up to 100 ℃, add 2-Ethylhexyl Alcohol (190g),
(b) add acetate (14g),
(c) mixture retrogradation, inhomogeneous, and the green of imagination occurs, to stir inoperatively, reaction is discrete.
This test is not embodiments of the invention, just is used for illustrating can not using the low-grade carboxylic acid in process of the present invention, refers to acetate here.
Embodiment 21
Charging: identical with embodiment 16, just with non-carbonated, commercially available sulfuration C
12-alkylphenol calcium (145TBN) replaces commercially available calcium sulfenyl phenolate.
Method:
Identical with embodiment 16, just amount of lime is increased to 83g from 6g in the step (c), and the amount of carbonic acid gas is increased to 83g from 66g in the step (f).
Product weight
Crude product: 421g
Overhead product: 246g
Crossing filtered product forms
Calcium 13.7%W/W
Sulphur 1.9%W/W
CO
210.3%W/W
TBN????383
V100????137cst
V40????2119cst
VI????163
Carboxylic acid 15.0%W/W
This embodiment shows that process of the present invention can be used the calcium sulfenyl phenolate of the low TBN of non-carbonic acid.
Embodiment 22
Charging
The calcium sulfenyl phenolate of carbonating (150TBN) 253g
Stearic acid 40g
2-Ethylhexyl Alcohol 90g
Calcium chloride 4g
Method:
(a) mixture is heated to 165 ℃/700mmHg from 145 ℃, adds ethylene glycol (32g) simultaneously,
(b) mixture left standstill 30 minutes when 165 ℃/700mmHg,
(c) under 165 ℃/1bar, add carbonic acid gas (38g),
(d) mixture is cooled to 120 ℃, adds 2-Ethylhexyl Alcohol (100g) and lime (76g),
(e) when 165 ℃/700mmHg, mixture left standstill 60 minutes,
(f) when 165 ℃/1bar, add carbonic acid gas (82g),
(g) at 200 ℃/10mmHg, reclaim solvent,
(h) filtering product.
Product quality
Product weight: 390g
Crossing filtered product forms
Calcium 14.4%W/W
Sulphur 2.3%W/W
CO
211.6%W/W
TBN????402
V100????674cst
Stearic acid 10.3%W/W
This embodiment shows that the calcium sulfenyl phenolate of low TBN can be improved to the product of high TBN.
Embodiment 23
Charging: identical with embodiment 14, just do not use the calcium sulfenyl phenolate that obtains from alkylphenol mixture, and replace from C
12The calcium sulfenyl phenolate that-alkylphenol (250TBN) obtains (the commercial acquisition).
Method:
Identical with embodiment 14, just step (b) uses iso-heptanol (190g) to replace 2-Ethylhexyl Alcohol (194g), adds ethylene glycol (in 1 minute) in the step (d) fast.
Product weight:
Crude product: 402g
Overhead product: 239g
Crossing filtered product forms:
Calcium 13.9%W/W
Sulphur 1.9%W/W
CO
212.0%W/W
TBN????391
V100????313cst
V40????6700cst
VI????177
Stearic acid 15.7%W/W
Filtration velocity is fast.
This embodiment shows, in process of the present invention, iso-heptanol can be used as solvent.
Claims (26)
1, a kind of production method of mixing the multifunctional additive for lubricating oils in the finished lube composition that is applicable to, the TBN value of said enriched material are greater than 300, and less than 1000cst, this method comprises at high temperature makes following material react 100 ℃ of following viscosity:
(A) have sulfuration alkaline earth metal hydrocarbyl phenates less than the TBN value of final multifunctional additive for lubricating oils,
(B) alkaline earth metal alkali joins it in reagent in the method or once, and perhaps partly join in the reagent, and remainder is added in follow-up phase with a part or many parts,
(C) have polyvalent alcohol, two or three (second is to fourth) glycol, aklylene glycol alkyl oxide or the polyalkylene glycol alkyl oxide of 2-4 carbon atom,
(D) lubricating oil,
(E) carbonic acid gas, with the adding of (B) component or each add that the back is added and
(F) provide at least a carboxylic acid or its acid anhydride or ester with following logical formula I greater than 2-35% (weight) (is base with enriched material weight) (i),
R
1
Wherein R is C
10-C
24Alkyl or alkenyl, R
1Be hydrogen, C
1-C
4Alkyl or-CH
2COOH group or (ii) have binary or polycarboxylic acid or its acid anhydride or the ester of 36-100 carbon atom,
(G) inorganic halides
Component (A) will make the enriched material of generation have TBN value greater than 300 to the weight ratio of (F).
2, according to the process of claim 1 wherein that lubricating oil accounts for the 10-90%(weight of composition).
3, according to the oxide compound or the oxyhydroxide of calcium, magnesium or the barium of the alkaline earth metal alkali that the process of claim 1 wherein.
4, according to the method for claim 3, alkaline earth metal alkali wherein is the oxide compound or the oxyhydroxide of calcium.
5, according to the process of claim 1 wherein that sulfuration alkaline earth metal hydrocarbyl phenates is derived from least one alkylphenol, alkyl or alkylphenol group or contain the ester of 9-28 carbon atom.
6, according to the method for claim 5, the C that sulfuration alkaline earth metal hydrocarbyl phenates wherein obtains derived from phenol and tetrapropylene alkylation
12-alkylphenol.
7, according to the process of claim 1 wherein that R is unbranched alkyl or alkenyl.
8, according to the method for claim 7, wherein R is C
10-C
24Straight chained alkyl, R
1Be H.
9, according to the process of claim 1 wherein (F) mixture for the carboxylic acid of logical formula I, this mixture is a commercial grade, contains a series of saturated and undersaturated acid.
10, according to the process of claim 1 wherein that (F) is stearic acid.
11, according to the process of claim 1 wherein that (F) is di-carboxylic acid or poly carboxylic acid or its acid anhydrides that contains 36-100 carbon atom.
12, according to the method for claim 11, wherein (F) is polyisobutylene succinic acid or polyisobutylene succinic anhydride.
13, according to the process of claim 1 wherein that (F) is enough to provide greater than 10-35%(weight) (ⅰ) or (ⅱ) (is base with enriched material weight).
14, according to the process of claim 1 wherein that (F) is enough to provide 12-20%(weight) (ⅰ) or (ⅱ) (is base with enriched material weight).
15, according to the process of claim 1 wherein that the TBN value of said enriched material is greater than 350.
16, according to the process of claim 1 wherein that the TBN value of said enriched material is greater than 400.
17, according to the process of claim 1 wherein 100 ℃ of viscosity of descending said enriched materials less than 500cst.
18, according to the process of claim 1 wherein that (B) is lime.
19, according to the process of claim 1 wherein that (B) and weight ratio (A) are 0.2-5.
20, according to the process of claim 1 wherein that (C) is ethylene glycol.
21, according to the process of claim 1 wherein that (C) is methyl digol.
22, basis the process of claim 1 wherein when (A)-(D) and the end of the reaction (F), adds carbonic acid gas (E) after adding (B) separately.
23, there is thinner according to the process of claim 1 wherein.
24, according to the process of claim 1 wherein that the additional sulphur that will be stored in wherein by adding (A) joins in the reaction mixture.
25, according to the process of claim 1 wherein that the said catalyzer that is reflected at carries out under existing.
26, according to the method for claim 25, wherein said catalyzer is a calcium chloride.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB868628609A GB8628609D0 (en) | 1986-11-29 | 1986-11-29 | Lubricating oil additives |
| GB8628609 | 1986-11-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87108344A CN87108344A (en) | 1988-06-22 |
| CN1012074B true CN1012074B (en) | 1991-03-20 |
Family
ID=10608200
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87108239A Expired CN1015642B (en) | 1986-11-29 | 1987-11-29 | Alkaline earth metal hydrocarbyl phenates, their sulphurised derivates, their production and use thereof |
| CN87108344A Expired CN1012074B (en) | 1986-11-29 | 1987-11-29 | Sulphurized alkaline earth metal hydrocarby phenates, their production and use thereof |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87108239A Expired CN1015642B (en) | 1986-11-29 | 1987-11-29 | Alkaline earth metal hydrocarbyl phenates, their sulphurised derivates, their production and use thereof |
Country Status (20)
| Country | Link |
|---|---|
| EP (2) | EP0273588B2 (en) |
| JP (2) | JPH0631383B2 (en) |
| KR (2) | KR960010992B1 (en) |
| CN (2) | CN1015642B (en) |
| AT (2) | ATE79396T1 (en) |
| AU (2) | AU609075B2 (en) |
| BR (2) | BR8707551A (en) |
| CA (2) | CA1305696C (en) |
| DE (2) | DE3781126T3 (en) |
| DK (2) | DK419788D0 (en) |
| ES (2) | ES2051751T3 (en) |
| FI (2) | FI93654C (en) |
| GB (1) | GB8628609D0 (en) |
| GR (2) | GR3006075T3 (en) |
| IN (2) | IN172581B (en) |
| MX (2) | MX169106B (en) |
| NO (2) | NO176147C (en) |
| SG (2) | SG101192G (en) |
| WO (2) | WO1988003944A1 (en) |
| ZA (2) | ZA878939B (en) |
Families Citing this family (43)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8628609D0 (en) * | 1986-11-29 | 1987-01-07 | Bp Chemicals Additives | Lubricating oil additives |
| GB8814012D0 (en) * | 1988-06-14 | 1988-07-20 | Bp Chemicals Additives | Chemical process |
| GB8814010D0 (en) * | 1988-06-14 | 1988-07-20 | Bp Chemicals Addivites Ltd | Lubricating oil additives |
| GB8814009D0 (en) * | 1988-06-14 | 1988-07-20 | Bp Chemicals Additives | Lubricating oil additives |
| GB8814013D0 (en) * | 1988-06-14 | 1988-07-20 | Bp Chemicals Additives | Chemical process |
| GB8814008D0 (en) * | 1988-06-14 | 1988-07-20 | Bp Chemicals Additives | Lubricating oil additives |
| DK0385616T3 (en) * | 1989-02-25 | 1994-10-10 | Bp Chemicals Additives | Process for preparing a lubricating oil additive concentrate |
| GB8917094D0 (en) * | 1989-07-26 | 1989-09-13 | Bp Chemicals Additives | Chemical process |
| US5366648A (en) * | 1990-02-23 | 1994-11-22 | The Lubrizol Corporation | Functional fluids useful at high temperatures |
| GB9213723D0 (en) * | 1992-06-27 | 1992-08-12 | Bp Chemicals Additives | Process for the production of lubricating oil additives |
| JP2737096B2 (en) * | 1993-08-25 | 1998-04-08 | 株式会社コスモ総合研究所 | Method for producing overbased sulfurized alkaline earth metal phenates |
| TW277057B (en) * | 1993-08-25 | 1996-06-01 | Cosmo Sogo Kenkyusho Kk | |
| GB9318810D0 (en) * | 1993-09-10 | 1993-10-27 | Bp Chem Int Ltd | Lubricating oil additives |
| GB9325132D0 (en) * | 1993-12-08 | 1994-02-09 | Bp Chemicals Additives | Lubricating oil additives |
| GB9400415D0 (en) * | 1994-01-11 | 1994-03-09 | Bp Chemicals Additives | Detergent compositions |
| GB9400417D0 (en) * | 1994-01-11 | 1994-03-09 | Bp Chemicals Additives | Lubricating oil composition |
| US6008166A (en) * | 1994-01-11 | 1999-12-28 | Lubrizol Adibis Holdings Limited | Detergent compositions |
| GB9411093D0 (en) | 1994-06-03 | 1994-07-27 | Bp Chemicals Additives | Detergent additives for lubricating oils, their preparation and use |
| US5529705A (en) * | 1995-03-17 | 1996-06-25 | Chevron Chemical Company | Methods for preparing normal and overbased phenates |
| CA2183906A1 (en) * | 1995-08-23 | 1997-02-24 | Christopher S. Fridia | Production of low fine sediment high tbn phenate stearate |
| EP0778336A1 (en) * | 1995-12-08 | 1997-06-11 | Cosmo Research Institute | Petroleum additive having excellent storage stability and heat stability comprising an alkaline earth metal salt of aromatic hydroxycarboxylic acid or a sulfurized mixture thereof. |
| GB9611424D0 (en) * | 1996-05-31 | 1996-08-07 | Exxon Chemical Patents Inc | Overbased metal-containing detergents |
| GB9611317D0 (en) * | 1996-05-31 | 1996-08-07 | Exxon Chemical Patents Inc | Overbased metal-containing detergents |
| GB9611316D0 (en) * | 1996-05-31 | 1996-08-07 | Exxon Chemical Patents Inc | Overbased metal-containing detergents |
| US5728657A (en) * | 1996-08-20 | 1998-03-17 | Chevron Chemical Company | Production of low fine sediment high TBN phenate stearate |
| WO1998050500A1 (en) * | 1997-05-07 | 1998-11-12 | Cosmo Research Institute | Lube oil composition, overbased alkaline earth metal sulfide pheneate concentrate used for preparing the same, and process for preparing the concentrate |
| US5942476A (en) * | 1998-06-03 | 1999-08-24 | Chevron Chemical Company | Low-viscosity highly overbased phenate-carboxylate |
| US6348438B1 (en) | 1999-06-03 | 2002-02-19 | Chevron Oronite S.A. | Production of high BN alkaline earth metal single-aromatic ring hydrocarbyl salicylate-carboxylate |
| EP1710294B1 (en) | 2005-04-06 | 2013-03-06 | Infineum International Limited | A method of improving the stability or compatibility of a detergent |
| EP1743933B1 (en) | 2005-07-14 | 2019-10-09 | Infineum International Limited | A use to improve the compatibility of an overbased detergent with friction modifiers in a lubricating oil composition |
| US20080153723A1 (en) | 2006-12-20 | 2008-06-26 | Chevron Oronite Company Llc | Diesel cylinder lubricant oil composition |
| JP5823392B2 (en) | 2009-08-06 | 2015-11-25 | ザ ルブリゾル コーポレイションＴｈｅ Ｌｕｂｒｉｚｏｌ Ｃｏｒｐｏｒａｔｉｏｎ | Lubricating composition containing asphaltene dispersant |
| BR112012012892A2 (en) | 2009-11-30 | 2017-06-20 | Lubrizol Corp | stabilized mixtures containing friction modifiers. |
| EP2507347A1 (en) | 2009-11-30 | 2012-10-10 | The Lubrizol Corporation | Methods of controlling sulfur trioxide levels in internal combustion engines |
| US9528067B2 (en) | 2009-11-30 | 2016-12-27 | The Lubrizol Corporation | Stabilized blends containing friction modifiers |
| SG191274A1 (en) | 2010-12-21 | 2013-07-31 | Lubrizol Corp | Lubricating composition containing a detergent |
| SG191974A1 (en) | 2011-02-09 | 2013-08-30 | Lubrizol Corp | Asphaltene dispersant containing lubricating compositions |
| SG192724A1 (en) | 2011-02-17 | 2013-09-30 | Lubrizol Corp | Lubricants with good tbn retention |
| DK2607462T3 (en) | 2011-12-20 | 2014-03-31 | Infineum Int Ltd | Ship engine lubrication |
| CN104540842B (en) * | 2012-02-08 | 2017-09-22 | 路博润公司 | The method for preparing vulcanization alkaline-earth metal dodecylphenol salt |
| EP2674474B1 (en) * | 2012-06-13 | 2015-09-09 | Infineum International Limited | Phenate detergent preparation |
| WO2014172125A1 (en) | 2013-04-17 | 2014-10-23 | The Lubrizol Corporation | 2-stroke internal combustion engine cylinder liner lubricating composition |
| NZ725495A (en) | 2014-04-02 | 2020-05-29 | Franck Natali | Doped rare earth nitride materials and devices comprising same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4328111A (en) * | 1978-11-20 | 1982-05-04 | Standard Oil Company (Indiana) | Modified overbased sulfonates and phenates |
| DE3379663D1 (en) * | 1982-05-14 | 1989-05-24 | Exxon Research Engineering Co | Lubricating oil additives |
| CA1246615A (en) * | 1982-05-22 | 1988-12-13 | Charles Cane | Process for the production of alkaline earth metal alkyl phenates |
| ZA833532B (en) * | 1982-05-22 | 1984-12-24 | Orobis Ltd | Process for the production of either an alkaline earth metal alkyl phenate or a sulphurised alkaline earth metal alkyl phenate |
| FR2549080B1 (en) * | 1983-07-11 | 1986-04-04 | Orogil | PROCESS FOR THE PREPARATION OF VERY HIGH ALKALINITY DETERGENT-DISPERSANT ADDITIVES BASED ON CALCIUM AND DETERGENT-DISPERSANT ADDITIVES FOR LUBRICATING OILS THUS OBTAINED |
| GB8628609D0 (en) * | 1986-11-29 | 1987-01-07 | Bp Chemicals Additives | Lubricating oil additives |
-
1986
- 1986-11-29 GB GB868628609A patent/GB8628609D0/en active Pending
-
1987
- 1987-11-26 EP EP87310461A patent/EP0273588B2/en not_active Expired - Lifetime
- 1987-11-26 ES ES87310460T patent/ES2051751T3/en not_active Expired - Lifetime
- 1987-11-26 AU AU82372/87A patent/AU609075B2/en not_active Ceased
- 1987-11-26 BR BR8707551A patent/BR8707551A/en not_active IP Right Cessation
- 1987-11-26 AT AT87310461T patent/ATE79396T1/en not_active IP Right Cessation
- 1987-11-26 AT AT87310460T patent/ATE79395T1/en not_active IP Right Cessation
- 1987-11-26 BR BR8707550A patent/BR8707550A/en not_active IP Right Cessation
- 1987-11-26 ES ES87310461T patent/ES2051752T3/en not_active Expired - Lifetime
- 1987-11-26 KR KR1019880700896A patent/KR960010992B1/en not_active IP Right Cessation
- 1987-11-26 DE DE3781126T patent/DE3781126T3/en not_active Expired - Fee Related
- 1987-11-26 WO PCT/GB1987/000847 patent/WO1988003944A1/en active IP Right Grant
- 1987-11-26 JP JP62507102A patent/JPH0631383B2/en not_active Expired - Fee Related
- 1987-11-26 KR KR1019880700889A patent/KR960010991B1/en not_active IP Right Cessation
- 1987-11-26 WO PCT/GB1987/000848 patent/WO1988003945A1/en active IP Right Grant
- 1987-11-26 DE DE3781118T patent/DE3781118T3/en not_active Expired - Lifetime
- 1987-11-26 EP EP87310460A patent/EP0271262B2/en not_active Expired - Lifetime
- 1987-11-26 AU AU82380/87A patent/AU608792B2/en not_active Ceased
- 1987-11-26 JP JP62507103A patent/JPH0631384B2/en not_active Expired - Fee Related
- 1987-11-27 CA CA000552952A patent/CA1305696C/en not_active Expired - Lifetime
- 1987-11-27 ZA ZA878939A patent/ZA878939B/en unknown
- 1987-11-27 CA CA000552953A patent/CA1305697C/en not_active Expired - Lifetime
- 1987-11-27 ZA ZA878938A patent/ZA878938B/en unknown
- 1987-11-29 CN CN87108239A patent/CN1015642B/en not_active Expired
- 1987-11-29 CN CN87108344A patent/CN1012074B/en not_active Expired
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- 1987-11-30 IN IN1019DE1987 patent/IN172581B/en unknown
- 1987-11-30 IN IN1018/DEL/87A patent/IN169547B/en unknown
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1988
- 1988-07-25 FI FI883503A patent/FI93654C/en not_active IP Right Cessation
- 1988-07-25 FI FI883502A patent/FI93653C/en not_active IP Right Cessation
- 1988-07-27 DK DK419788A patent/DK419788D0/en not_active Application Discontinuation
- 1988-07-27 DK DK198804198A patent/DK175287B1/en not_active IP Right Cessation
- 1988-07-28 NO NO883349A patent/NO176147C/en unknown
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1992
- 1992-10-05 SG SG1011/92A patent/SG101192G/en unknown
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- 1992-10-26 GR GR920402404T patent/GR3006075T3/el unknown
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