CN1043784C - Prepn of lubricating-oil additive - Google Patents
Prepn of lubricating-oil additive Download PDFInfo
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- CN1043784C CN1043784C CN95115487A CN95115487A CN1043784C CN 1043784 C CN1043784 C CN 1043784C CN 95115487 A CN95115487 A CN 95115487A CN 95115487 A CN95115487 A CN 95115487A CN 1043784 C CN1043784 C CN 1043784C
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Abstract
The present invention relates to a method for preparing lubricating oil additives, particularly to a method for preparing sulfurized calcium alkyl salicylate with high base number. In the method, alkyl salicylate, alkyl phenol and calcium oxide are used as raw materials, and sulfurized alkyl calcium salicylate with high base number is synthesized according to definite mixture ratio under the condition that ethylene glycol is used as an accelerant. The synthesis process has the advantages of simple application and convenient operation. Besides the favorable property of purification, the synthetic product of the present invention also has excellent properties of extreme-pressure wear resistance and high temperature service, and is a lubricating oil detergent with excellent properties.
Description
The present invention relates to preparation process lubricant oil additive, especially a kind of preparation method of high base number Acid Thiosalicylique calcium, belonging to lubricating oil additive field international Patent classificating number is C10M.
As everyone knows, alkylsalicylate (calcium, magnesium) series product have the good high-temperature cleansing performance, but its antioxygen erosion resistance is relatively poor.The resistance of oxidation of certain free alkyl phenol content influence product in the alkylsalicylate.In recent years, along with the fast development of engine oil, must be more comprehensive to the performance requriements of additive.Particularly, more and more harsher to the high-temperature behavior requirement of oil product along with engine develops to little, the high-power direction of volume.The alkyl monosulfide salicylate is except that having preferably outside the high temperature detergent performance, and its resistance to elevated temperatures is also more excellent, also has more excellent antioxygen erosion resistance, will be widely used in top-grade lubricating oil (as CF
4Or SH) in.It is more that relevant Acid Thiosalicylique salt prepares patent, and the EP168 of Shell company is arranged, and 110, EP168,880, the FR.2 of Orogils company, 625,220, and the Sekiyu cakkaishi34 of Japan National Oil Corporation, (6).They adopt first calcification, postcure prepared Acid Thiosalicylique product salt, or overbasic calcium salicylate product directly vulcanized.
The method of the alkyl monosulfide calcium salicylate of the preparation high base number of calcification provides a kind of good new lubricant purification agent thereby can be lubricating oil after the objective of the invention is to provide a kind of elder generation to vulcanize.
The preparation method of high base number alkyl monosulfide calcium salicylate of the present invention is as follows: will have electronic stirring, the there-necked flask of condensation water trap installs, drop into the alkyl salicylate of metering, alkylphenol, be warming up to 40-50 ℃, add metered calcium oxide, stirred 10 minutes, add the water of metering, carried out slaking reaction 30 minutes; After being warming up to 80-90 ℃, add the sulphur powder, higher alcohols (decyl alcohol) is warming up to 120 ℃, adds ethylene glycol, feeds the N2 protection simultaneously, is warming up to 170-190 ℃ and carries out vulcanization reaction 2-4 hour; After vulcanization reaction finishes, feed carbonic acid gas, carry out high basicity reaction 2-3 hour.Lower the temperature then, dilution, centrifugally remove slag, solvent distillation gets product.
A kind of preparation method of high base number alkyl monosulfide calcium salicylate is characterized in that: the alkyl salicylate and the alkylphenol of metering are put in the reactor, and stirring is warming up to 40～60 ℃ of input metering calcium oxide and water carries out slaking reaction; Add higher alcohols and sulphur powder then, be warming up to more than 120 ℃, add ethylene glycol and carry out vulcanization reaction, feed carbonic acid gas then, carry out the high basicity reaction.After reaction finishes, solvent cut, centrifugally remove slag, steam desolventizing and get product.This preparation method characteristic is that certain proportion scale is arranged between each feed composition: alkyl salicylate and alkylphenol are in 100 parts (weights), and the ratio of alkyl salicylate and alkylphenol can be: 10: 0～5: 5; The add-on of calcium oxide is 17～30 parts, and the water yield is 6.0～16.0 parts, and the sulphur powder is 10.0～16.0 parts, and higher alcohols is 100～300 parts, and ethylene glycol is 10～60 parts, and carbonic acid gas is 20～50 parts, and diluting solvent is 100～500 parts.Reactions steps divided for three steps: the first step is a slaking reaction.The slaking reaction Controllable Temperature between 20～60 ℃, add water cure after, will heat up automatically 40～60 ℃.The reaction of second step is vulcanization reaction.The vulcanization reaction temperature is 160 ℃～190 ℃, 24 hours time.Three-step reaction is the high basicity reaction.Temperature of reaction is that 130～170 ℃ of Ventilation Rates are 100～300ml/min, time 2-3 hour.Reaction can be a benzene,toluene,xylene with solvent, also can be 60～150 ℃ of gasoline.Higher alcohols can be the alcohols (straight or branched) of purity greater than 95%C7～C12; Calcium oxide is that purity all can greater than 93.0% industrial goods; Ethylene glycol can be that purity is greater than 98% industrial goods.The structure of alkyl salicylate is:
The structure of alkylphenol is: R-＜O 〉-OH, R are C
8～30Alkyl chain.
Specifically be exactly: a kind of preparation method of high base number alkyl monosulfide calcium salicylate, it is characterized in that: alkyl salicylate, alkylphenol, the calcium oxide of metering are dropped in the reaction flask, be warming up to 40-60 ℃, add water cure, reaction 30min, heat up then in 100 ℃, add the sulphur powder, decyl alcohol is warming up to 120 ℃, add ethylene glycol, logical simultaneously N
2Protection, be warming up to 160-190 ℃ of sulfuration, reaction 2-4h, after vulcanization reaction finishes, feed carbonic acid gas and carry out a high basicity reaction, also calcium oxide can be added at twice, carry out the high basicity reaction of secondary, temperature of reaction is 130-170 ℃, and the reaction times is 2-3h, and Ventilation Rate is 100-300ml/min; Ethylene glycol must divide for two steps added, and when leading to carbonic acid gas, added remainder; Calcium oxide also can add at twice, is added in for the second time that ethylene glycol adds for the second time, carries out before the logical carbonic acid gas.Sulfuration and high basicity promotor are used the ethylene glycol of industrial extensive application, ethylene glycol adds at twice, add 5.0～6.0g (to 100.0g Whitfield's ointment and alkylphenol) during vulcanization reaction, add 25.0～35.0g during high quaternization, in addition, the ratio of components of each component has a specified proportion: if Whitfield's ointment and alkylphenol are in 100.0, the calcium oxide add-on is that 17～30.0g (can add at twice, must not add greater than 20.0g for the first time, remaining adding for the second time), the water yield is 6.0～16.0g, and the sulphur powder is 10.0～15.0g, higher alcohols (decyl alcohol) is 100-300g, and carbonic acid gas is 20-50g.This reaction is divided into slaking reaction, the reaction of vulcanization reaction and high basicity, during slaking reaction Controllable Temperature between 20-60 ℃, time 15～60min; The vulcanization reaction temperature is 160-190 ℃, and the time is 2-4h; The high basicity temperature of reaction is 130-170 ℃, and the reaction times is 2-3h, and Ventilation Rate is 100-300ml/min.The preparation sulphur content is greater than 2.5%, and base number is greater than the Acid Thiosalicylique calcium product of 270mgKOH/g, available single stage method (i.e. step sulfuration, a step calcification method), and also available two step method (promptly a step vulcanizes, and two go on foot the calcification methods) is prepared.This reaction system can be used the alkyl salicylate and the alkylphenol of different molecular weight, and its structure is as follows respectively:
Alkyl salicylate:
Wherein R is C
3-30Alkyl chain;
Alkylphenol:
Wherein R is C
8～80Alkyl chain;
Alkyl salicylate can be 40%～100% oil solution.Ethylene glycol can be industrial goods, also can be the SILVER REAGENT chemical, and purity must be greater than 98%.Calcium oxide must be a purity greater than 93% commercial grade product, reagent product.The sulphur powder must be a purity greater than 95% technical grade or chemical reagent product.Ethylene glycol is as sulfuration and high basicity promotor, and its consumption is 30.0～40.0g/100.0g Whitfield's ointment and alkylphenol: with 5.0～6.0g, all the other add when high basicity reacts during vulcanization reaction.The add-on of water should be 0.3～0.5 times in calcium oxide: water can be service water, also can be fresh water, and higher alcohols can be C
3-C
12The straight or branched alcohols, decyl alcohol (C preferably
10Alcohol).
High base number alkyl monosulfide calcium salicylate has high temperature detergent performance preferably.Antioxygen resistance to corrosion, fabulous resistance to compression fastness to wear, it relatively sees Table 1 with equal base number calcium salicylate performance.
As can be seen from Table 1, Acid Thiosalicylique salt has more excellent extreme pressure and antiwear behavior and antioxygen erosion resistance than salicylate.
Table 1 alkyl monosulfide calcium salicylate and calcium salicylate performance are relatively
Annotate: add the single agent of 2m% in the thermal oxidation stability experiment in the 300ZN oil.
| Sample | High base number Acid Thiosalicylique calcium | Commodity high base number calcium salicylate |
| C m,m％ | 10.50 | 10 |
| TBN,mgKOH/g | 292 | 280 |
| S,％ | 2.58 | 0.1 |
| 100 ℃ of kinematic viscosity .mm 2/s | 218 | 22.7 |
| Form: tensio-active agent and carbonate (m%) | 54.5 | 53.1 |
| Oil | 45.0 | 44.7 |
| Free alkyl phenol | 0.5 | 2.2 |
| (165 ℃ * 6h), divide of thermal oxidation stabilities | 1.13 | 33.98 |
| Tappet weightlessness, mg | 22.3 | 60.0 |
| PB＇N | 931 | 637 |
P
BAnd contain the above-mentioned single agent of 1.5m% in the tappet weightless test oil.The high base number alkyl monosulfide calcium salicylate additive of the present invention's preparation, the product base number has extremely strong acid neutralization capacity greater than 270mgKOH/g, has guaranteed the performance of this other performance of agent; The product sulphur content has fabulous extreme pressure and abrasion resistance greater than 2.5%.Product is after sulfuration, and molecular weight increases, after free alkyl phenol also cures, and calcification again, the product thermostability is improved, and shows high-temperature stability preferably.Alkyl monosulfide calcium salicylate additive adopts sulfuration back Calcific technology earlier, has solved the corrosion problems of first calcification postcure product, and copper corrosion is brought up to 1 grade from 4 grades, and is anticorrosive with the alkyl monosulfide phenates, oxidation susceptibility is suitable.This product is formed rationally, alkylphenol calcium, calcium sulfenyl phenolate, calcium salicylate, Acid Thiosalicylique calcium etc. is arranged, and performance is comprehensive; Base number is also higher, can guarantee the more comprehensive performance of oil product to have certain economic benefits under less consumption condition; The synthesis technique of this product is simpler, and behind the slaking reaction, a step calcify reaction can be finished.
The following examples and comparative example are to further specify of the present invention, rather than limit the invention, and spirit of the present invention and protection domain are listed in claims.
Embodiment 1: add the 70.0g alkyl salicylate in the 500ml there-necked flask that has electric mixer and condensation water trap; 30.0g alkylphenol stirs and to be warming up to 35 ℃, adds calcium oxide 23.0g and water 7.4g carries out slaking reaction, temperature is warming up to 8u ℃ automatically, is warming up to 100 ℃ then, adds sulphur powder 12.0g and higher alcohols (decyl alcohol) 100ml; Dehydration is warming up to 130 ℃, adds ethylene glycol 5.0g, continues to be warming up to 170 ℃, during vulcanizing ingredient, feeds nitrogen 200ml/min, reaction 4.0h; Be cooled to 160 ℃ then, add ethylene glycol 27.0g, feed carbonic acid gas, Ventilation Rate is 250ml/min, ventilation 3.0h, and reaction finishes.With product dilute, centrifugal removing slag, steam down to 170 ℃ in decompression, desolventizing, product.Product calcium contents 10.07%, base number 282mgKOH/g, sulphur content 2.61%.
Embodiment 2: by implementing 1 operation, the alkyl salicylate consumption is 80.0g, alkylphenol is 20.0g, the calcium oxide consumption is 25.0g, and the water yield is that 8.0g ethylene glycol adds 5.0g for the first time, and when carbonic acid gas (logical) adds 27.0g during high basicity, the sulphur powder is 12.0g, the sulphur content of sintetics is 2.58%, and calcium contents is 10.50, and base number is 292mgKOH/g.
Comparative example 1: with base number is 280mgKOH/g, and calcium contents is that 10% calcium alkyl salicylate with high base number 100.0g drops into and is with electronic stirring, in the there-necked flask of condensation water trap, is warming up to 100 ℃, adds sulphur powder 6.0g, and ethylene glycol 6.0g is warming up to 180 ℃, logical N
2(200ml/min) protection, vulcanization reaction 4.0 hours, solvent cut is centrifugal to remove slag, and gets product behind the steaming desolventizing.The product sulphur content is 1.76%, and base number is 275mgKOH/g.The product copper corrosion is the 3b level.And the copper corrosion of embodiment 1,2 (D * 130) is the 1b level.
Comparative example 2 is pressed comparative example 1 operation, the ethylene glycol consumption is reduced to 4.0g after, the product sulphur content is 2.78%, base number is 275mgKOH/g.After product is placed for some time, precipitation occurs, copper corrosion is the 4C level.
Comparative example 3: with alkyl salicylate with SCl
2, S
2Cl
2Get Acid Thiosalicylique after the sulfuration, its acid number is 90.1mgKOH/g, and sulphur content is 4.05.Acid Thiosalicylique, calcium oxide, methyl alcohol and water have synthesized the Acid Thiosalicylique calcium of high base number together, and the product base number is 293mgKOH/g, and calcium contents is 10.20%, and sulphur content is 2.61%.The copper corrosion of product is the 3b level.
Embodiment 3: press embodiment 1 operation, the input Whitfield's ointment is 240.0g, and alkylphenol is 60.0g.For the first time adding calcium oxide is 30.0g, and the water yield is 9.6g, and the sulphur powder is 32.0g, and ethylene glycol is 16.0g, sulfuration 4.0h; Add 20.0g ethylene glycol then, feed carbonic acid gas, Ventilation Rate is 350ml/min, 2.0h; Add calcium oxide 30.0g then, ethylene glycol 55.0g feeds carbonic acid gas, 350ml/min * 2.0h.After reaction finishes, centrifugal distill product, the sulphur content of product is 2.40%, base number is 314mgKOH/g, calcium contents is that 11.6%, 100 ℃ of kinematic viscosity is 235.0mm
2/ s.
Embodiment 4: press embodiment 1 operation, select Whitfield's ointment, alkylphenol, calcium oxide, water, the ethylene glycol equivalent of different amounts, consider the influence of each factor to product base number and calcium contents, sulphur content.Test-results sees Table 2.
By table 2 as seen, suitable preparation sulphur content is greater than 2.5%, and base number greater than the ratio of components of 270mgKOH/g is: Whitfield's ointment, and the alkylphenol ratio was greater than 7: 3; The calcium oxide consumption is greater than 21.0g, and consumption is between 5.0～6.0g for the first time for ethylene glycol, and total amount is between 30.0～40.0g.
Table 2 raw material consumption is to the influence of product property
| Reaction raw materials * | The product physico-chemical analysis | ||||||||||||
| The water thiamines | Alkyl powder | Calcium oxide | Water | Higher alcohols ml | The Hai powder | Ethylene glycol (once) | Ma, ml/mln×h | Ethylene glycol (secondary) | CO m ml/min×h | S m％ | C 4M％ | TRN mgKOH/g | |
| 1 | 60 | 20 | 19 | 6.1 | 100 | 13 | 5.0 | 200×4 | 27.0 | 250×3 | 3.0 | 8.57 | 236 |
| 2 | 70 | 30 | 19 | 6.1 | 100 | 11 | 1.0 | 200×4 | 28.0 | 250×3 | 2.92 | 7.03 | 226 |
| 3 | 60 | 40 | 19 | 6.1 | 100 | 12 | 6.0 | 200×4 | 28.0 | 250×3 | 3.23 | 5.46 | 262 |
| 4 | 60 | 20 | 21.0 | 6.7 | 100 | 12 | 4.0 | 200×4 | 20.0 | 250×3 | 2.98 | 9.35 | 232 |
| 5 | 70 | 30 | 21.0 | 6.7 | 100 | 13 | 6.0 | 200×4 | 26.0 | 250×3 | 2.78 | 8.68 | 232 |
| 6 | 60 | 40 | 21.0 | 6.7 | 100 | 11 | 5.0 | 200×4 | 27.0 | 250×3 | 2.89 | 8.53 | 232 |
| 7 | 80 | 20 | 23.0 | 7.4 | 100 | 11 | 6.0 | 200×4 | 26.0 | 250×3 | 2.05 | 10.32 | 283 |
| 8 | 70 | 30 | 23.0 | 7.4 | 100 | 12 | 5.0 | 200×4 | 27.0 | 250×3 | 2.61 | 18.07 | 262 |
| 9 | 60 | 40 | 23.0 | 7.4 | 100 | 13 | 4.0 | 200×4 | 29.0 | 250×3 | 3.50 | 7.16 | 198 |
| 10 | 70 | 30 | 25.0 | 8.0 | 100 | 13 | 6.0 | 200×4 | 26.0 | 250×3 | 2.76 | 8.68 | 231 |
| 11 | 70 | 30 | 25.0 | 8.0 | 100 | 13 | 6.0 | 200×4 | 26.0 | 250×3 | 2.76 | 8.68 | 236 |
| 12 | 80 | 20 | 25.0 | 8.0 | 100 | 12 | 5.0 | 200×4 | 27.0 | 250×3 | 2.50 | 10.50 | 292 |
| 13 | 60 | 40 | 25.0 | 8.0 | 100 | 11 | 4.0 | 200×4 | 28.0 | 250×3 | 3.02 | 8.50 | 233 |
| 14 | 80 | 20 | 25.0 | 8.0 | 100 | 13 | 5.0 | 200×4 | 27.0 | 250×3 | 2.46 | 9.52 | 264 |
| 15 | 70 | 30 | 25.0 | 8.0 | 100 | 11 | 4.0 | 200×4 | 20.0 | 250×3 | 2.72 | 8.62 | 243 |
| 16 | |||||||||||||
Embodiment 5: according to the operation of embodiment 1, add the 75.0g Whitfield's ointment, the 25.0g alkylphenol adds the 20.0g calcium oxide for the first time, and sulphur powder consumption is 13.0g, and adding the ethylene glycol consumption for the first time is 5.0g; After vulcanization reaction finishes, add 5.0,7.0 and 10.0g calcium oxide and 27.0g ethylene glycol again, feed carbonic acid gas, carry out the high basicity reaction.The base number of product is followed successively by 275,278,320mgKOH/g, and calcium contents is respectively 9.82,9.95,11.5%, and sulphur content is respectively: 2.91,2.90,2.71%.
Embodiment 6: according to the operation of embodiment 1, add the 75.0g Whitfield's ointment, 20.0g alkylphenol and 5.0g sulfonic acid (acid number 113mgkOH/g, sulphur content 3.58%), add calcium oxide 20.0g, sulphur powder 13.0g for the first time, add for the first time ethanol 5.0g, (logical carbonic acid gas before) adds that calcium oxide is respectively 3.0,5.0g for the second time, and ethylene glycol 27.0g is after reaction finishes, the product base number is respectively 252,268mgKOH/g, calcium contents is 9.0,9.6%, and sulphur content is 3.09,3.03%.
Claims (10)
1. the preparation method of a high base number alkyl monosulfide calcium salicylate, it is characterized in that: alkyl salicylate, alkylphenol, the calcium oxide of metering are dropped in the reaction flask, be warming up to 40-60 ℃, add water cure, reacted 30 minutes, heat up then in 100 ℃, add the sulphur powder, decyl alcohol is warming up to 120 ℃, add ethylene glycol, logical simultaneously N
2Protection, be warming up to 160-190 ℃ of sulfuration, reacted 2-4 hour, after vulcanization reaction finishes, feed carbonic acid gas and carry out a high basicity reaction, also calcium oxide can be added at twice, carry out the high basicity reaction of secondary, temperature of reaction is 130-170 ℃, and the reaction times is 2-3 hour, and ventilation rate is the 100-300 ml/min; Ethylene glycol must divide for two steps added, and when leading to carbonic acid gas, added remainder; Calcium oxide also can add at twice, is added in for the second time that ethylene glycol adds for the second time, carries out before the logical carbonic acid gas.
2. method according to claim 1, it is characterized in that: sulfuration and high basicity promotor are used the ethylene glycol of industrial extensive application, ethylene glycol adds at twice, vulcanization reaction adds the 5.0-6.0 gram to 100.0 gram Whitfield's ointments and alkylphenol, add the 25.0-35.0 gram during high quaternization, in addition, the ratio of components of each component has a specified proportion; If Whitfield's ointment and alkylphenol are in 100.0, the calcium oxide add-on is the 17-30.0 gram, can add at twice, must not add for the first time greater than 20.0 grams, remaining adding for the second time,, the water yield is the 6.0-16.0 gram, the sulphur powder is the 10.0-15.0 gram, and decyl alcohol is the 100-300 gram, and carbonic acid gas is the 20-50 gram.
3. method according to claim 1 is characterized in that: this reaction is divided into slaking reaction, the reaction of vulcanization reaction and high basicity, during slaking reaction Controllable Temperature between 20-60 ℃, time 15-60 minute; The vulcanization reaction temperature is 160-190 ℃, and the time is 2-4 hour; The high basicity temperature of reaction is 130-170 ℃, and the reaction times is 2-3 hour, and Ventilation Rate is the 100-300 ml/min.
4. method according to claim 1 is characterized in that: the preparation sulphur content is greater than 2.5%, and base number is greater than the Acid Thiosalicylique calcium product of 270mgKOH/g, available single stage method, and also available two step method is prepared.
5. method according to claim 1 is characterized in that; This reaction system can be used the alkyl salicylate and the alkylphenol of different molecular weight, and its structure is as follows respectively:
Alkyl salicylate:
Wherein R is C
3-30Alkyl chain;
Alkylphenol:
, wherein R is C
3-30Alkyl chain;
Alkyl salicylate can be the oil solution of 40%-100%.
6. method according to claim 1 is characterized in that: ethylene glycol can be industrial goods, also can be the SILVER REAGENT chemical, and purity must be greater than 98%.
7. method according to claim 1 is characterized in that: calcium oxide must be a purity greater than 93% commercial grade product, reagent product.
8. method according to claim 1 is characterized in that: the sulphur powder must be a purity greater than 95% technical grade or chemical reagent product.
9. method according to claim 1 is characterized in that: ethylene glycol is as sulfuration and high basicity promotor, and its consumption is 30.0-40.0 gram/100.0 gram Whitfield's ointment and alkylphenols; Restrain with 5.06.0 during vulcanization reaction, all the other add when high basicity reacts.
10. method according to claim 1 is characterized in that: the add-on of water should be calcium oxide 0.3-0.5 doubly; Water can be service water, also can be fresh water.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95115487A CN1043784C (en) | 1995-09-18 | 1995-09-18 | Prepn of lubricating-oil additive |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95115487A CN1043784C (en) | 1995-09-18 | 1995-09-18 | Prepn of lubricating-oil additive |
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| CN1145944A CN1145944A (en) | 1997-03-26 |
| CN1043784C true CN1043784C (en) | 1999-06-23 |
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| CN95115487A Expired - Lifetime CN1043784C (en) | 1995-09-18 | 1995-09-18 | Prepn of lubricating-oil additive |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| ES2945907T3 (en) | 2015-02-13 | 2023-07-10 | Xinxiang Richful Lube Additive Co Ltd | Calcium alkylphenate sulfide and method of preparation thereof, and lubricating oil comprising the same |
| CN105462652B (en) * | 2015-02-13 | 2018-05-11 | 新乡市瑞丰新材料股份有限公司 | A kind of metal detergent and preparation method thereof and the lubricating oil containing the metal detergent |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987005045A1 (en) * | 1986-02-21 | 1987-08-27 | The Lubrizol Corporation | Novel carbamate additives for functional fluids |
| US5205947A (en) * | 1988-11-07 | 1993-04-27 | Exxon Chemical Patents Inc. | Dispersant additives comprising amine adducts of dicarboxylic acid monoepoxy thiol reaction products |
| US5308518A (en) * | 1993-02-22 | 1994-05-03 | Exxon Research And Engineering Company | Lubricant composition containing alkoxylated amine salt of a dihydrocarbyldithiobenzoic acid |
| US5340487A (en) * | 1988-11-07 | 1994-08-23 | Exxon Chemical Patents Inc. | Dispersant adducts comprising alcohol adducts of dicarboxylic acid monoepoxy thiol reaction products |
| CN1094085A (en) * | 1993-04-23 | 1994-10-26 | 中国石油化工总公司 | Antioxygen, anti-rotten, antiwear compound additive composition |
-
1995
- 1995-09-18 CN CN95115487A patent/CN1043784C/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987005045A1 (en) * | 1986-02-21 | 1987-08-27 | The Lubrizol Corporation | Novel carbamate additives for functional fluids |
| US5205947A (en) * | 1988-11-07 | 1993-04-27 | Exxon Chemical Patents Inc. | Dispersant additives comprising amine adducts of dicarboxylic acid monoepoxy thiol reaction products |
| US5340487A (en) * | 1988-11-07 | 1994-08-23 | Exxon Chemical Patents Inc. | Dispersant adducts comprising alcohol adducts of dicarboxylic acid monoepoxy thiol reaction products |
| US5308518A (en) * | 1993-02-22 | 1994-05-03 | Exxon Research And Engineering Company | Lubricant composition containing alkoxylated amine salt of a dihydrocarbyldithiobenzoic acid |
| CN1094085A (en) * | 1993-04-23 | 1994-10-26 | 中国石油化工总公司 | Antioxygen, anti-rotten, antiwear compound additive composition |
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| CN1145944A (en) | 1997-03-26 |
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