CN103725355A - Preparation method of low-base number lubricating oil clearing agent - Google Patents
Preparation method of low-base number lubricating oil clearing agent Download PDFInfo
- Publication number
- CN103725355A CN103725355A CN201210389973.XA CN201210389973A CN103725355A CN 103725355 A CN103725355 A CN 103725355A CN 201210389973 A CN201210389973 A CN 201210389973A CN 103725355 A CN103725355 A CN 103725355A
- Authority
- CN
- China
- Prior art keywords
- acid
- accordance
- alkylphenol
- oil
- organosulfur
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 *c1ccc(*)c(CC(C(*)=CC2)=CC2=O)c1 Chemical compound *c1ccc(*)c(CC(C(*)=CC2)=CC2=O)c1 0.000 description 1
Landscapes
- Lubricants (AREA)
Abstract
The invention provides a preparation method of a low-base number lubricating oil clearing agent. The method of the invention comprises the following steps: (1) mixing and stirring organic sulfur phosphonic acid, alkylphenol and/or sulfurized alkylphenol, particle activated carbon, and aqueous solution of low molecular alcohol, separating and recovering an oil-phase product; (2) adding oxides of alkaline earth metal, water, inorganic acid and/or aryl carboxylic acid promoters in the oil-phase product of step (1), performing a metallization reaction, and collecting the product. The clearing agent obtained by the method of the invention has good oxidation resistance, high-temperature clearing performance, less toxin, and less smell, and is a lubricating oil additive with comprehensive performance.
Description
Technical field
The present invention relates to a kind of detergent for lubricating oil, particularly a kind of preparation method of low alkali value detergent for lubricating oil.
Background technology
Polyisobutene phosphine sulfide salt additives is a class purification agent of developing early, and traditional phosphine sulfide hydrochlorate is take barium salt as metal, and product has good dispersiveness and certain detergency, but its thermostability has certain limitation.
Research report about polyisobutene phosphine sulfide acid barium is more, patent GB 1004401 and US 3377282 have introduced the preparation method of phosphine sulfide acid barium, its method is by mixing phosphine sulfide polyisobutene and alkylphenol or sulfenyl phenolate reaction, then react with oxide compound or the oxyhydroxide of divalent metal, the alkyl that wherein connects alkylphenol or sulfenyl phenolate is 5-20 carbon atom, and the molecular weight of polyisobutene is 500-3500.
US 3135729 has introduced in the product hydrolysis phosphine sulfide acid of reacting with thiophosphoric anhydride at polyisobutene and has added barium oxide again, passing into carbon dioxide reaction, to obtain barium content be 7% barium salt, but polyisobutene phosphine sulfide acid barium salt toxicity is larger, has greater environmental impacts, and therefore no longer produces.What substitute polyisobutene phosphine sulfide acid barium salt is polyisobutene phosphine sulfide acid calcium salt and magnesium salts, and the two also has good dispersiveness and certain detergency except toxicity is lower.
Research report about polyisobutene phosphine sulfide acid calcium salt and magnesium salts is more, for example at patent GB 910738, introduced the preparation method of sulphur phosphorus hydrocarbon derivative, with hydrolysis sulphur phosphorus hydrocarbon and alkaline-earth metal mixture, when formaldehyde or ketone promotor exist, react, its product can be tested by the detergency of CRC L-1.
GB 1039732 has introduced the preparation method of polyisobutene phosphine sulfide hydrochlorate purification agent, in acid sulfur-bearing alkyl, phenol and inert solvent, add and be less than stoichiometric basic metal or alkaline-earth metal, then in high temperature, pass into carbonic acid gas and form colloidal-carbon hydrochlorate, after needing to have water, carbonation reaction to finish in carbonation reaction, add sulphur to carry out vulcanization reaction.
GB 1177835 has introduced high alkalinity purification agent preparation method, and the method is to pass into carbonic acid gas after mixing with reactants such as sulfenyl phenolate, thiophosphoric anhydride, polyolefine, amine, calcium oxide, calcium hydroxide, alkoxide.
US 3321399 has introduced the preparation of oil-soluble metal carbonate, comprises take phosphine sulfide polyolefine, nonyl phenol, calcium hydroxide, urea, mineral oil, water as raw material reaction.
Patent GB 910738, US 313572, US 3706665 are take the polyisobutene of molecular weight 780-1100 as raw material, patent GB 103972, GB 1004401, US 3377282, GB 1177835, US 3135729 are take polyisobutene and a small amount of alkylphenol as raw material, although the product of preparation has certain detergency, still lower compared with alkyl benzene calcium sulfonate, calcium sulfenyl phenolate, alkyl sodium salicylate.
Summary of the invention
The invention provides a kind of preparation method of low alkali value detergent for lubricating oil.
The inventive method comprises:
(1) aqueous solution of organosulfur phosphonic acids, alkylphenol and/or sulfenyl phenolate, granulated active carbon and low mass molecule alcohol is stirred to Separation and Recovery oil-phase product;
(2) in the oil-phase product of step (1), add oxide compound, water, mineral acid and/or the aryl carboxylic acid promotor of alkaline-earth metal, carry out metallization reaction, collect product.
The structure of the organosulfur phosphonic acids described in step (1) is:
Wherein R
1for the alkyl of number-average molecular weight between 500-5000, preferably 700-3500, most preferably 850-2500; X is O atom or S atom, and wherein at least one X is S atom, the preferred S atom of X.
Organosulfur phosphonic acids described in step (1) is to be obtained by the reaction of polyolefine generation phosphine sulfideization, and polyolefine and thiophosphoric anhydride and/or sulphur phosphatase reaction obtain.Described polyolefine is by ethene, propylene, C
4-C
10the independent polymerization of alkene or copolymerization and the polyolefine that obtains, described C
4-C
10alkene can be selected one or more in n-butene, iso-butylene, positive amylene, n-hexylene, positive octene and positive decene, preferably polyisobutene.Described polyolefinic number-average molecular weight is 500-5000, preferably 700-3500, most preferably 850-2500.The temperature of described phosphine sulfideization reaction between 100-300 ℃, preferably 150-250 ℃, the reaction times is 5h～20h, preferably 12h～18h.
The preferred methylene-bridged alkylphenol of alkylphenol described in step (1), its structural formula is:
Wherein R
2for C
4-C
30alkyl, preferably C
6-C
20alkyl, most preferably C
8-C
15alkyl.
The preparation method of described methylene-bridged alkylphenol is: alkylphenol, aqueous sodium hydroxide solution are mixed, stir and heat up, in the time of 50 ℃, drip formaldehyde, after adding, be warmed up to 80-90 ℃ of isothermal reaction 3 hours, then be warmed up to 150 ℃, remove water and unreacted formaldehyde, obtain methylene-bridged alkylphenol.
Described in step (1), the structure of sulfenyl phenolate is:
Wherein R
2for C
4-C
30alkyl, preferably C
6-C
20alkyl, most preferably C
8-C
15alkyl; N is the integer between 1-10, preferably 1-7, most preferably 1-4.
Sulfenyl phenolate described in step (1) is normally reacted and obtains under promotor exists by vulcanizing agent and abovementioned alkyl phenol, described vulcanizing agent is one or more in sulphur, sulfur dichloride and sulfur subchloride normally, described promotor generally includes organo-peroxide and/or polysulphide polymer, for example benzoyl peroxide and/or 2-mercaptobenzothiazole.
Described in step (1), the preferred specific surface area of granulated active carbon is at 700-2000m
2the granulated active carbon of/g, most preferably specific surface area is at 900-1100m
2the granulated active carbon of/g.
Low mass molecule alcohol described in step (1) is selected from monohydroxy-alcohol or the polyvalent alcohol of carbonatoms between 1-8, adducible example includes but not limited to methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, octanol, enanthol, ethylene glycol, propylene glycol, the preferably monohydroxy-alcohol of carbonatoms between 1-4, one or more in most preferred ethanol, propyl alcohol and butanols.
Described in step (1), in the aqueous solution of low mass molecule alcohol, low mass molecule alcohol accounts for the 5%-50% of aqueous solution total mass, preferably 10%-40%, most preferably 15%-30%.
Mol ratio described in step (1) between organosulfur phosphonic acids and described alkylphenol and/or sulfenyl phenolate is 1:10～10:1, preferably 1:6～6:1, most preferably 1:4～4:1.
Granulated active carbon described in step (1) is the 5-50% of organosulfur phosphonic acids and described alkylphenol and/or sulfenyl phenolate quality sum, preferably 10-40%, most preferably 15-35%.
Mass ratio described in step (1) between granulated active carbon and low mass molecule alcohol solution is 1:15-1:50, preferably 1:20-1:40.
In step (1), can not add solvent, also can add solvent.Described solvent is the hydro carbons of boiling range between 80-200 ℃, can be simple substance hydrocarbon, can be also hydrocarbon mixture, and can select normal heptane, octane, No. 120 industrial napthas, No. 200 industrial napthas and boiling range is one or more in the sherwood oil of 90-120 ℃.The quality of described solvent is the 50-200% of organosulfur phosphonic acids and described alkylphenol and/or sulfenyl phenolate quality sum, preferably 60-150%, most preferably 70-120%.
In step (1), the temperature of mix and blend is between 10-50 ℃, preferably 30-40 ℃, and the time of mix and blend is 0.5-10 hour, preferably 1-5 hour.
One or more in oxide compound preferential oxidation magnesium, calcium oxide, strontium oxide and the barium oxide of the alkaline-earth metal described in step (2), most preferably calcium oxide and/or magnesium oxide.
The mole number of the oxide compound of alkaline-earth metal described in step (2) is the 1:10～10:1 of the mole number sum of organosulfur phosphonic acids described in step (1) and described alkylphenol and/or sulfenyl phenolate, preferably 1:5～5:1, most preferably 1:4～4:1.
In step (2), the mol ratio of the oxide compound of water and alkaline-earth metal is 1:4～6:1, preferably 1:2～4:1, most preferably 1:1～3:1.
Described in step (2), mineral acid can be selected one or more in sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, preferably sulfuric acid; Described aryl carboxylic acid comprises aryl monoprotic acid and/or aryl diprotic acid, described aryl is phenyl and/or naphthyl, aryl dicarboxylic acid comprise neighbour,, contraposition aryl dicarboxylic acid, described aryl carboxylic acid can be selected phenylformic acid, naphthoic acid, phthalic acid, m-phthalic acid, terephthalic acid, adjacent naphthalic acid, a naphthalic acid and to one or more in naphthalic acid.
Mineral acid and/or aryl carboxylic acid promotor described in step (2) are the 0.1-10% of organosulfur phosphonic acids described in step (1) and described alkylphenol and/or sulfenyl phenolate quality sum, preferably 0.5-6%, most preferably 1-3%.
In step (2), can not add thinning oil, also can add thinning oil.Described thinning oil is that 100 ℃ of kinematic viscosity are at 2-10mm
2the lubricating base oil of/s, can be solvent treatment lubricating base oil, can be also hydrofining lubricating base oil, can select one or more in I class, II class, III class and IV class lubricating base oil.Described thinning oil occupies the 30-150% of the acid of machine phosphine sulfide and described alkylphenol and/or sulfenyl phenolate quality sum, preferably 50-120%, most preferably 70-100%.
Described in step (2), the temperature of metallization reaction is 20～200 ℃, preferably 40～160 ℃, and most preferably 60～120 ℃.
The time of metallization reaction described in step (2) is 1～10 hour, preferably 2～8 hours, and most preferably 3～6 hours.
The product of step (2) metallization reaction is filtered, remove unreacted solid residue, then distillation is collected product after removing desolventizing or promotor.
Utilize the purification agent that the inventive method obtains to have good oxidation-resistance, high temperature detergency, and its toxicity being little, smell is little, is the comprehensive lubricating oil additive of a kind of performance.
Embodiment
Below by example, further describe the present invention, but the present invention is not limited to this.
The preparation of organosulfur phosphonic acids A
In the there-necked flask that electric stirring is installed, adding number-average molecular weight is 1000 grams of 750 polyisobutene, add P2S5168 gram, from room temperature, be warmed up to gradually 210 ℃, heat-up rate, at 30 ℃/h, is warmed up to rear constant temperature 12 hours, now material gradually becomes brown from colourless, after reaction, pass into 8.5 grams of water vapors and react, and carry out aftertreatment, the polyisobutene phosphine sulfide acid sulphur content obtaining is 5.2%, phosphorus content is 2.2%, is designated as organosulfur phosphonic acids A.
The preparation of organosulfur phosphonic acids B
1000 grams of polyisobutene that add number-average molecular weight 1300 in the there-necked flask that electric stirring is installed, add P
2s
5140 grams, from room temperature, be warmed up to gradually 223 ℃, 30 ℃/h of heat-up rates, are warmed up to rear constant temperature 11 hours, and now material gradually becomes brown from colourless, passes into 8 grams of water vapors and reacts, and carry out aftertreatment.The polyisobutene phosphine sulfide acid sulphur content obtaining is 4.8%, and phosphorus content is 1.7%, is designated as organosulfur phosphonic acids B.
Synthesizing of sulfenyl phenolate
Add 1710 grams of 4-dodecylphenols being provided with in the there-necked flask with hydrogen sulfide absorption device electric stirring, airtight, add 145 grams of SULPHUR POWDER, 3 grams of sulphurized catalyst 2-mercaptobenzothiazoles, 100 grams of ethylene glycol, be warmed up to 160 ℃ of reactions 12 hours, after reaction finishes, steam ethylene glycol, sedimentation, obtain vulcanizing 4-dodecylphenol FDDP, sulphur content is 5.3%.
Synthesizing of methylene-bridged alkylphenol
In the there-necked flask that electric stirring is installed, add 1000 grams of 4-dodecylphenols, 20 grams of 20% aqueous sodium hydroxide solutions, stir and heat up, add 352 grams, 37% formaldehyde, in the time of 50 ℃, drip formaldehyde, after adding, be warmed up to reflux temperature, be 80-90 ℃ of isothermal reaction 3 hours, then be warmed up to 150 ℃, remove water and unreacted formaldehyde, obtain the MDDP that contains methylene-bridged 4-dodecylphenol.
Adopt above synthetic raw material, synthetic purification agent of the present invention, specific embodiment is as follows:
Embodiment 1 (organosulfur phosphonic acids A is 1:3.1 with the mol ratio of sulfuration 4-dodecylphenol)
In the 3000ml there-necked flask that temperature control system and electric stirring are installed; add 40 grams of (molecular weight 1112 of organosulfur phosphonic acids A; 0.036mol); add again 60 grams of (molecular weight 554 of sulfuration 4-dodecylphenol; 0.11mol), 100 grams of 90-120 ℃ of sherwood oils, stir 15 minutes; (traditional Chinese medicines group produces, and specific surface area is 900-1100m to add 30 grams of grain active carbons again
2the aqueous ethanolic solution of/g) He 1000 gram 20%.The temperature of controlling there-necked flask is 20-30 ℃, and mix and blend stopped after 4 hours, separated the oil phase on upper strata, was about 194 grams, and water is the used ethanolic soln that contains grain active carbon.
194 grams of oil phases that separate are above incorporated with in the 500ml there-necked flask of temperature control system and electric stirring, then add 90 grams of 150SN neutral oils, add 4.4 grams of calcium oxide (0.079mol), 2.5 grams, water (0.139mol), 2.0 gram of 98% vitriol oil, controlling temperature of reaction is 100 ℃, react 5 hours, then steam water, material is cooled to 50 ℃, on the whizzer that is 2000rpm at rotating speed centrifugal 30 minutes, except distillation after removing slag, obtain low alkali value purification agent Ca-1, smell is less, its base number is 40.2mgKOH/g, sulphur content is 2.5%, phosphorus content is 0.43%.
Embodiment 2 (mol ratio of organosulfur phosphonic acids B and methylene-bridged 4-dodecylphenol is 1:2.9)
In the 3000ml there-necked flask that temperature control system and electric stirring are installed, (molecular weight is 2341 to add 60 grams of organosulfur phosphonic acids B, 0.026mol), (molecular weight is 536 to add 40 grams of methylene-bridged 4-dodecylphenols again, 0.075mol), 100 grams of octanes, stir 15 minutes, add again 25 grams of grain active carbons, 25% 1000 grams of aqueous ethanolic solutions, at 20-30 ℃ of mix and blend, controlling stirring velocity there is the interface of oil phase and water all the time, after mix and blend 4 hours, the oil phase on upper strata is separated, about 196 grams, water is the used aqueous ethanolic solution that contains grain active carbon.
196 grams of oil phases that separate are above incorporated with in the 500ml there-necked flask of temperature control system and electric stirring, then add 95 grams of 150SN neutral oils, add 4.5 grams of calcium oxide (0.080mol), 1.5 grams, water (0.083mol), 2.2 grams of phenylformic acid, controlling temperature of reaction is 100 ℃, react 5 hours, then steam water, material is cooled to 50 ℃, on the whizzer that is 2000rpm at rotating speed centrifugal 30 minutes, except distillation after removing slag, obtain low alkali value purification agent Ca-2, smell is less, its base number is 39.6mgKOH/g, and sulphur content is 1.45%; Phosphorus content is 0.51%.
Embodiment 3 (mole number of organosulfur phosphonic acids A is 1.1 with the ratio of sulfuration 4-dodecylphenol and methylene-bridged 4-dodecylphenol mole number sum)
In the 3000ml there-necked flask that temperature control system and electric stirring are installed, add A70 gram of (molecular weight 1112 of organosulfur phosphonic acids, 0.063mol), add again 15 grams of (molecular weight 554 of sulfuration 4-dodecylphenol, 0.027mol), 15 grams of (molecular weight 536 of methylene-bridged 4-dodecylphenol, 0.028mol), 90 grams of No. 200 industrial napthas, stir 15 minutes, add again 28 grams of grain active carbons, 30% 960 grams of aqueous ethanolic solutions, at 20-30 ℃ of mix and blend, now should control stirring velocity, the interface of oil phase and water is occurred all the time, after mix and blend 4 hours, the oil phase on upper strata is separated, about 187 grams, water is the used aqueous ethanolic solution that contains grain active carbon.
175 grams of oil-phase product that separate are above incorporated with in the 500ml there-necked flask of temperature control system and electric stirring, then add 70 grams of 150SN neutral oils, add 4.5 grams of calcium oxide (0.080mol), 2.2 grams of water (0.122mol), add 1.9 grams of phthalic acids, controlling temperature of reaction is 100 ℃, react 5 hours, then steam water, material is cooled to 50 ℃, on the whizzer that is 2000rpm at rotating speed centrifugal 30 minutes, except distillation after removing slag, obtain low alkali value purification agent Ca-3, smell is less, its base number is 39.2mgKOH/g, and sulphur 2.6 content are %; Phosphorus content is 0.85%.
Embodiment 4 (mol ratio of organosulfur phosphonic acids A and methylene-bridged 4-dodecylphenol is 2.6:1)
In the 3000ml there-necked flask that temperature control system and electric stirring are installed, add A80 gram of (molecular weight 1112 of organosulfur phosphonic acids, 0.072mol), add again 20 grams of (molecular weight 536 of methylene-bridged 4-dodecylphenol, 0.028mol), 90 grams of No. 200 industrial napthas, stir 15 minutes, add again 32 grams of grain active carbons, 22% 1050 grams of ethanolic solns, at 20-30 ℃ of mix and blend, now should control stirring velocity, the interface of oil phase and water is occurred all the time, after mix and blend 4 hours, the oil phase on upper strata is separated, about 187 grams, water is the used aqueous ethanolic solution that contains grain active carbon.
187 grams of oil phases that separate are above incorporated with in the 500ml there-necked flask of temperature control system and electric stirring, then add 90 grams of 150SN neutral oils, add 3.2 grams of magnesium oxide (0.08mol), 2.2 grams, water (0.12mol), 2.2 grams of vitriol oils (98%), controlling temperature of reaction is 100 ℃, react 5 hours, then steam water, material is cooled to 50 ℃, on the whizzer that is 2000rpm at rotating speed centrifugal 30 minutes, except distillation after removing slag, obtain low alkali value purification agent Mg-1, smell is less, its base number is 46.2mgKOH/g, sulphur content is 2.2%, phosphorus content is 0.92%.
Comparative example 1 (organosulfur phosphonic acids A is 1:3.1 with the mol ratio of sulfuration 4-dodecylphenol)
In the 500ml there-necked flask that temperature control system and electric stirring are installed, add 40 grams of (molecular weight 1112 of organosulfur phosphonic acids A, 0.036mol), add again 60 grams of (molecular weight 554 of sulfuration 4-dodecylphenol, 0.11mol), 100 grams of 90-120 ℃ of sherwood oils, stir 15 minutes, then add 90 grams of 150SN neutral oils, add 4.4 grams of calcium oxide (0.078mol), 2.5 grams, water (0.139mol), 2.0 gram of 98% vitriol oil, controlling temperature of reaction is 100 ℃, react 5 hours, then steam water, material is cooled to 50 ℃, on the whizzer that is 2000rpm at rotating speed centrifugal 30 minutes, except distillation after removing slag, obtain contrasting low alkali value purification agent DCa-1, smell is larger, its base number is 40.1mgKOH/g, sulphur content is 2.6%, phosphorus content is 0.44%.
Comparative example 2-4
Similar to embodiment 2-4 respectively, just in step (1), do not add gac and aqueous ethanolic solution, and there is no mixing process, other reaction conditions is identical, prepare respectively thus contrast low alkali value purification agent DCa-2, DCa-3, DCa-4.DCa-2 smell is larger, and its base number is 39.7mgKOH/g, and sulphur content is 1.45%, and phosphorus content is 0.52%; DCa-3 smell is large, and its base number is 39.2mgKOH/g, and sulphur content is 2.6%, and phosphorus content is 0.86%; DCa-4 smell is large, and its base number is 46.3mgKOH/g, and sulphur content is 2.3%, and phosphorus content is 0.92%.
The purification agent that embodiment 1-4 and comparative example 1-4 are prepared carries out the qualification test of high temperature detergency, anti-oxidative stability, and evaluation method is as follows:
Adopt lacquering and coking plate to test to evaluate high temperature detergency:
On L-1 plate-type coking device, carry out lacquering and the experiment of coking plate.Coke test condition is: plate temperature/oil temperature=320 ℃/100 ℃, time 2 h, stop/ETAD expected time of arrival and departure=45 second/15 seconds.Lacquering test conditions is: plate temperature/oil temperature=300 ℃/150 ℃, time 2 h, continuous operation.
On L-A type detergency tester, test, to investigate its high temperature detergency.Test conditions is: plate temperature/oil temperature=300 ℃/100 ℃, 1 hour time, stop/ETAD expected time of arrival and departure=40 second/20 seconds.Oil droplet speed is 1.0mL/min.
Anti-oxidative stability evaluation adopts PDSC (Pressure Differential Scanning Calorimeter pressure means of differential scanning calorimetry) method, and testing installation is TA5000 DSC2910 thermal analyzer.
By 150SN, 500SN, 150BS is modulated into lubricating base oil by the mass ratio of 14:5:1, purification agent in embodiment 1-4 and comparative example 1-4 is called in to the embodiment 5-8 and the comparative example 5-8 that in lubricating base oil, obtain lubricating composition with 2% add-on respectively, the various performances of these lubricating compositions being carried out above-mentioned qualification test and investigated purification agent, test-results is in Table 1.
As can be seen from Table 1, in High Temperature Detergent Experiment, coking amount, the lacquering amount of embodiment 5-8 are less, and coking amount and lacquering amount in comparative example 5-8 is larger.In PDSC test, the oxidation induction period of embodiment 5-8 is slightly long with respect to the oxidation induction period of comparative example 5-8, illustrates that its oxidation-resistance is better.The smell of embodiment 5-8 is significantly less than comparative example 5-8.
In sum, utilize the purification agent that the inventive method obtains to have good oxidation-resistance, high temperature detergency, and its toxicity being little, smell is little, is the comprehensive lubricating oil additive of a kind of performance.
Table 1 assessment of performance result
Claims (20)
1. a preparation method for low alkali value detergent for lubricating oil, comprising:
(1) aqueous solution of organosulfur phosphonic acids, alkylphenol and/or sulfenyl phenolate, granulated active carbon and low mass molecule alcohol is stirred to Separation and Recovery oil-phase product;
(2) in the oil-phase product of step (1), add oxide compound, water, mineral acid and/or the aryl carboxylic acid promotor of alkaline-earth metal, carry out metallization reaction, collect product.
2. in accordance with the method for claim 1, it is characterized in that, the structure of the organosulfur phosphonic acids described in step (1) is:
Wherein R
1for the alkyl of number-average molecular weight between 500-5000, X is O atom or S atom, and wherein at least one X is S atom.
3. in accordance with the method for claim 1, it is characterized in that, described in step (1), alkylphenol is methylene-bridged alkylphenol, and its structural formula is:
Wherein R
2for C
4-C
30alkyl.
4. in accordance with the method for claim 1, it is characterized in that, described in step (1), the structure of sulfenyl phenolate is:
Wherein R
2for C
4-C
30alkyl, n is the integer between 1-10.
5. in accordance with the method for claim 1, it is characterized in that, described in step (1), the specific surface area of granulated active carbon is 700-2000m
2/ g.
6. in accordance with the method for claim 1, it is characterized in that, low mass molecule alcohol described in step (1) is selected from monohydroxy-alcohol or the polyvalent alcohol of carbonatoms between 1-8.
7. in accordance with the method for claim 1, it is characterized in that, described in step (1), in the aqueous solution of low mass molecule alcohol, low mass molecule alcohol accounts for the 5%-50% of aqueous solution total mass.
8. in accordance with the method for claim 1, it is characterized in that, the mol ratio described in step (1) between organosulfur phosphonic acids and described alkylphenol and/or sulfenyl phenolate is 1:10～10:1.
9. in accordance with the method for claim 1, it is characterized in that, granulated active carbon described in step (1) is the 5-50% of organosulfur phosphonic acids and described alkylphenol and/or sulfenyl phenolate quality sum.
10. in accordance with the method for claim 1, it is characterized in that, the mass ratio described in step (1) between granulated active carbon and low mass molecule alcohol solution is 1:15-1:50.
11. in accordance with the method for claim 1, it is characterized in that, step adds solvent in (1), and described solvent is the hydro carbons of boiling range between 80-200 ℃, and the quality of described solvent is the 50-200% of organosulfur phosphonic acids and described alkylphenol and/or sulfenyl phenolate quality sum.
12. in accordance with the method for claim 1, it is characterized in that, in step (1), the temperature of mix and blend is between 10-50 ℃, and the time of mix and blend is 0.5-10 hour.
13. in accordance with the method for claim 1, it is characterized in that, the oxide compound of the alkaline-earth metal described in step (2) is one or more in magnesium oxide, calcium oxide, strontium oxide and barium oxide.
14. in accordance with the method for claim 1, it is characterized in that, the mole number of the oxide compound of alkaline-earth metal described in step (2) is the 1:10～10:1 of the mole number sum of organosulfur phosphonic acids described in step (1) and described alkylphenol and/or sulfenyl phenolate.
15. in accordance with the method for claim 1, it is characterized in that, in step (2), the mol ratio of the oxide compound of water and alkaline-earth metal is 1:4～6:1.
16. in accordance with the method for claim 1, it is characterized in that, mineral acid described in step (2) is one or more in sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid; Described aryl carboxylic acid comprises aryl monoprotic acid and/or aryl diprotic acid, and described aryl is phenyl and/or naphthyl.
17. in accordance with the method for claim 1, it is characterized in that, described aryl carboxylic acid can be selected phenylformic acid, naphthoic acid, phthalic acid, m-phthalic acid, terephthalic acid, adjacent naphthalic acid, a naphthalic acid and to one or more in naphthalic acid.
18. in accordance with the method for claim 1, it is characterized in that, mineral acid and/or aryl carboxylic acid promotor described in step (2) are the 0.1-10% of organosulfur phosphonic acids described in step (1) and described alkylphenol and/or sulfenyl phenolate quality sum.
19. in accordance with the method for claim 1, it is characterized in that, step adds thinning oil in (2).Described thinning oil is that 100 ℃ of kinematic viscosity are at 2-10mm
2the lubricating base oil of/s, described thinning oil occupies the 30-150% of the acid of machine phosphine sulfide and described alkylphenol and/or sulfenyl phenolate quality sum.
20. in accordance with the method for claim 1, it is characterized in that, described in step (2), the temperature of metallization reaction is 20～200 ℃, and the time of metallization reaction is 1～10 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210389973.XA CN103725355B (en) | 2012-10-15 | 2012-10-15 | Preparation method of low-base number lubricating oil clearing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210389973.XA CN103725355B (en) | 2012-10-15 | 2012-10-15 | Preparation method of low-base number lubricating oil clearing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103725355A true CN103725355A (en) | 2014-04-16 |
| CN103725355B CN103725355B (en) | 2015-07-01 |
Family
ID=50449655
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210389973.XA Active CN103725355B (en) | 2012-10-15 | 2012-10-15 | Preparation method of low-base number lubricating oil clearing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103725355B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107022398A (en) * | 2016-02-01 | 2017-08-08 | 江西福安路润滑材料有限公司 | A kind of alkyl phenate detersive and preparation method and application |
| CN116064188A (en) * | 2021-11-04 | 2023-05-05 | 中国石油化工股份有限公司 | Lubricating oil composition and method for producing the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3377282A (en) * | 1965-09-13 | 1968-04-09 | Monsanto Chemicals | Production of oil additives |
| CN101423483A (en) * | 2008-06-20 | 2009-05-06 | 辽宁天合精细化工股份有限公司 | High basic value (TBN400) sulfurized calcium alkyl and preparation method thereof |
| CN102071085A (en) * | 2009-11-19 | 2011-05-25 | 中国石油化工股份有限公司 | High-base number metal detergent and preparation method thereof |
-
2012
- 2012-10-15 CN CN201210389973.XA patent/CN103725355B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3377282A (en) * | 1965-09-13 | 1968-04-09 | Monsanto Chemicals | Production of oil additives |
| CN101423483A (en) * | 2008-06-20 | 2009-05-06 | 辽宁天合精细化工股份有限公司 | High basic value (TBN400) sulfurized calcium alkyl and preparation method thereof |
| CN102071085A (en) * | 2009-11-19 | 2011-05-25 | 中国石油化工股份有限公司 | High-base number metal detergent and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107022398A (en) * | 2016-02-01 | 2017-08-08 | 江西福安路润滑材料有限公司 | A kind of alkyl phenate detersive and preparation method and application |
| CN107022398B (en) * | 2016-02-01 | 2020-05-22 | 江西福安路润滑材料有限公司 | Alkyl phenate detergent and preparation method and application thereof |
| CN116064188A (en) * | 2021-11-04 | 2023-05-05 | 中国石油化工股份有限公司 | Lubricating oil composition and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103725355B (en) | 2015-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI383972B (en) | Alkylated heterocyclic reaction products useful as antioxidants | |
| CN100567335C (en) | Single site palladium catalyst complexes | |
| JP6695853B2 (en) | Lubricating composition for electric vehicle | |
| CN103725355B (en) | Preparation method of low-base number lubricating oil clearing agent | |
| EP3131932B1 (en) | Hydrogenated polymers with a radial structure having a core based on calixarenes and use thereof in lubricant compositions | |
| CN105503535B (en) | The preparation method and application of bis-phenol kind antioxidant based on mixed base catalyst | |
| TWI518061B (en) | Tritylated ethers | |
| CN101365777A (en) | Lubricant antioxidant compositions employing synergistic organotungstate component | |
| CN103725350B (en) | A kind of lubricant composition for internal combustion engines | |
| CN103725358B (en) | Preparation method for vulcanized alkylphenol | |
| US3873627A (en) | Carbon-to-carbon nuclear dimer coupling of p-alkylphenols with ferricyanide catalysis | |
| CN104560283A (en) | Sulfonate, preparation method thereof, lubricating grease containing sulfonate and preparation method of lubricating grease | |
| CN103725354B (en) | Preparation method of high-base number sulfurized alkylphenol salt | |
| CN104130822B (en) | A kind of terephthalic acid list lauryl alcohol ester calcium salt purification agent and synthetic method thereof | |
| EP4319916A1 (en) | Novel carbonylation catalysts and methods of making the same | |
| CN103725357B (en) | Low-alkali detergent, preparation method of detergent and lubricating oil composition containing detergent | |
| CN103725353B (en) | Low-base number lubricating oil additive, preparation method and lubricating oil composition | |
| CN102888262A (en) | Industrial gear oil composition | |
| CN103725372B (en) | Lubricant composition for internal combustion engines | |
| CN111072706B (en) | Silole derivative, preparation method and application thereof, and photoluminescent lubricating grease | |
| KR101278872B1 (en) | Norbornene dialkyl ester containing dialkyl dithiocarbamate compounds, antiwear additives and lubricant comprising the same | |
| JPH0425996B2 (en) | ||
| CN107986954A (en) | A kind of alkylsalicylate and preparation method thereof | |
| WO2010083303A1 (en) | Processes for production of macromolecular amine-phenolic antioxidant compositions containing low amounts of non-macromolecular byproducts | |
| CN102976884B (en) | Preparation method of alkyl biphenyl type lubricating base oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |