CN107022398A - A kind of alkyl phenate detersive and preparation method and application - Google Patents

A kind of alkyl phenate detersive and preparation method and application Download PDF

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CN107022398A
CN107022398A CN201610068967.2A CN201610068967A CN107022398A CN 107022398 A CN107022398 A CN 107022398A CN 201610068967 A CN201610068967 A CN 201610068967A CN 107022398 A CN107022398 A CN 107022398A
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acid
alkyl
preparation
reaction
consumption
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CN107022398B (en
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刘烨
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Fu'an Jiangxi Road Lubricating Material Co Ltd
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Fu'an Jiangxi Road Lubricating Material Co Ltd
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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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
    • 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
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/26—Compounds containing silicon or boron, e.g. silica, sand
    • C10M125/30—Clay
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04—Hydroxy compounds
    • C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
    • 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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/02—Sulfurised compounds
    • 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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/02—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic oxygen-containing compound
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/027—Neutral salts thereof
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of alkyl phenate detersive and preparation method and application, the preparation method includes：a）By alkyl phenol, alkali compounds, coupling reagent and solid acid with may be selected addition or without diluent and/or accelerator mix occur coupling reaction；b）Alkali compounds is added, and is passed through carbon dioxide and carries out carbonation reaction；C) separation obtains target product.The porous structure material of organic acid for activating is used during can preparing alkyl phenate detersive using the method for the present invention, particularly add the Emathlite of alkyl sulfonic acid activation, not only improve the split-phase problem of course of reaction, and solid acid can be used as filter aid in last handling process, efficiency of post treatment is improved.The alkyl phenate detersive synthesized by the present invention not only has preferable acid neutralization capacity, high temperature detergency and antioxygenic property in addition, and imparts its good rust-preventing characteristic, corrosion resistance, dispersive property and characteristic of solubilizing.

Description

A kind of alkyl phenate detersive and preparation method and application
Technical field
The present invention relates to detergent for lubricating oil field, more particularly to alkyl phenate detersive, its preparation method and application.
Background technology
Detergent for lubricating oil is as one of main dose of kind of lube oil additive, and its consumption is only second to the scattered of consumption maximum Agent.It not only has solubilising, the scattered effect such as greasy filth and cleaning, and the particularly detersive of high base number also has neutral lubrication simultaneously The effect for the acidic materials that oil is produced in use, can significantly reduce corrosion and damage of such acidic materials to device Evil, thus it is widely used in modulation marine cylinder oil, motor benzine machine oil and diesel engine oil, I. C. engine oil and air-cooled engine Oil etc..
Current detergent for lubricating oil mainly has sulfonate, alkyl phenate, salicylate, naphthenate, oleate etc. multiple Kind.Wherein, sulfonate, the alkyl of alkyl phenate and salicylate these three detersives are alkyl phenyl, account for lubricating oil clear More than the 90% of net agent total amount.
Compared with other detersives, the raw material sources of phenate detergents extensively, be easy to get, synthesis technique is simple, with low cost, And the alkyl phenate of high base number has splendid acid neutralization capacity and high temperature detergency, while also having good inoxidizability Energy.But, the rust-preventing characteristic of alkyl phenate detersive, corrosion resistance, dispersive property and characteristic of solubilizing are poor, therefore need to improve alkyl These performances of phenates, to improve its combination property.
At present, improving the method for rust-preventing characteristic, corrosion resistance, dispersive property and the characteristic of solubilizing of alkyl phenate has two kinds：The One kind is added in formulated oil during alkyl phenate while a certain amount of sulfonate need to be added, but this method When application is the product such as lubricant oil composite, between need to considering the problem of compatibility, in addition it is also necessary to coordinate complicated formula Allocating technology, operating difficulties, cost is high；Second method is that a certain amount of sulfonic acid is added in the preparation process of alkyl phenate Salt, can improve rust-preventing characteristic, corrosion resistance, dispersive property and the characteristic of solubilizing of alkyl phenate, reduce again and preparing lubricating oil Complicated allocating technology during composition.
For example, US4865754, US4614602, US4104180 disclose few in the presence of having ethylene glycol and flux oil The low alkalinity alkylbenzenesulfonate of amount prepares alkyl phenate detersive, and the main function of wherein low alkali value alkylbenzenesulfonate is can To improve solubility of the phenates in oil, stable dispersion that is not solidifying, not muddy, not gluing is become, while it is deposited Anticorrosive property in it can also improve final products.
But, in patent disclosed above, adding a small amount of low alkalinity alkylbenzenesulfonate improves the antirust of final products Property effect it is limited, still needed to when preparing lubricant oil composite add sulfonate detergent.
The content of the invention
In view of the shortcomings of the prior art, it is a primary object of the present invention to provide a kind of alkyl phenate detersive, its preparation Method and application, the detersive not only have preferable acid neutralization capacity, high temperature detergency and antioxygenic property, and impart Its good rust-preventing characteristic, corrosion resistance, dispersive property and characteristic of solubilizing.
To achieve the above object, the technical scheme that the present invention is provided includes：
The embodiment of the invention discloses a kind of preparation method of alkyl phenate detersive, including：
A) by alkyl phenol, alkali compounds, coupling reagent and solid acid with may be selected addition or without diluent and/or rush Enter agent mixing and occur coupling reaction；
B) alkali compounds is added, and is passed through carbon dioxide and carries out carbonation reaction；
C) separation obtains target product.
It is preferred that, in the preparation method of above-mentioned alkyl phenate detersive, the solid acid includes containing free acid Emathlite, activation Emathlite, solid super-strong acid, neutral clay, silica gel, powdered molecular sieve, montmorillonite, diatomite, Any one in activated carbon, zeolite, molecular sieve, porous ceramics, aluminum oxide, zirconium oxide, silicon nitride, carborundum, graphite or two Plant the combination of the above；
It is preferred that, in the preparation method of above-mentioned alkyl phenate detersive, the solid acid is selected from the acidity containing free acid Carclazyte, with any of the Emathlite for the acid activation that dissociates or two or more combinations, particularly preferably from organic acid for activating Emathlite, the organic acid include formic acid, oxalic acid, acetic acid, propionic acid, trifluoroacetic acid, benzoic acid, methanesulfonic acid, trimethylacetic acid, alkane Any of base benzene sulfonic acid or two or more combinations, the alkyl of the alkyl benzene sulphonate are selected from C1~C28Straight chained alkyl or Alkyl with side chain, wherein alkyl are distributed in contraposition, meta or ortho position.
It is preferred that, in the preparation method of above-mentioned alkyl phenate detersive, the Emathlite with the acid activation that dissociates Preparation method include：Carclazyte is subjected to acid treatment with free acid, treatment temperature is 20 ~ 70 DEG C, and the time is 1 ~ 7h, wherein free The mass ratio of acid and carclazyte is 0.5 ~ 10：1, dry afterwards, then 2 ~ 5h of roasting at 100 ~ 300 DEG C.
The embodiment of the invention also discloses the alkyl phenate detersive prepared by the above method.
The embodiment of the invention also discloses a kind of lubricant oil composite, including above-mentioned alkyl phenate detersive.
Compared with prior art, advantages of the present invention includes：
（1）The detersive of lubricant compositions is suitable for use as according to the alkyl phenate prepared by the inventive method, it is particularly following Lubricant, for example：Bus engine lubricating oil, heavy duty diesel engine lubricating oil, railway lubricating oil, natural gas engine lubrication Oil, turbine lube oil, rust preventive lubricating oil, oxidation lubricant, slip lubricating oil, hydraulic oil, automatic gear lubricant, automatic biography Hydrodynamic and manual transmission liquid, tractor liquid, all-purpose tractor liquid and hydraulic fluid, power steering gear liquid, gear lubricant, industry Lubricating oil, pump work oil and its mixture, the product that they are prepared using the present invention can be in detergency, inoxidizability, antirust Property, corrosion resistance and dispersiveness aspect produce good result.
（2）The method of the present invention can prepare alkyl phenate detersive, white with the acidity of organic acid for activating in preparation process Soil, particularly adds the Emathlite of alkyl sulfonic acid activation, not only improves the split-phase problem of course of reaction, and in post processing During solid acid can be used as filter aid, improve efficiency of post treatment.
（3）Synthesized alkyl phenate detersive of the invention, due to adding alkyl sulfonic acid during the course of the reaction, it can be effective Improve rust-preventing characteristic, corrosion resistance, dispersive property and the characteristic of solubilizing of final products and the additional proportion by adjusting solid acid The ratio of alkyl phenate and sulfonate can be regulated and controled.
Embodiment
The embodiment of the invention discloses a kind of preparation method of alkyl phenate detersive, including：
a）By alkyl phenol, alkali compounds, coupling reagent and solid acid with may be selected addition or without diluent and/or Coupling reaction occurs for accelerator mixing；
b）Alkali compounds is added, and is passed through carbon dioxide and carries out carbonation reaction；
c）Separation obtains target product.
In above-mentioned preparation method, the alkyl phenol is to include monomer by hydroxy aromatic compound one or more C8-C45The olefin alkylation of oligomer is obtained, and the monomer is selected from propylene, butylene or their mixture.
In above-mentioned preparation method, the alkali compounds can preferably be selected from but be not limited to alkali metal oxide, alkali metal Hydroxide, alkali metal carbon acid compound, alkaline earth oxide, alkaline earth metal hydroxide, alkaline-earth metal carbonate compound Or their mixture.Especially preferred, the alkali compounds may be selected from but be not limited to lithium hydroxide, sodium hydroxide, hydrogen-oxygen Change potassium, calcium oxide, calcium hydroxide, magnesia, magnesium hydroxide, calcium carbonate, magnesium carbonate or their mixture.
In above-mentioned preparation method, the coupling reagent can select but be not limited to sulfur-containing compound and/or fatty aldehyde.Especially It is preferred that, the coupling reagent can select but be not limited to elemental sulfur, vulcanized sodium, formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, hexanal, enanthaldehyde Or their mixture.
In above-mentioned preparation method, the solid acid includes the Emathlite containing free acid, the Emathlite of activation, consolidated Body super acids, neutral clay, silica gel, powdered molecular sieve, montmorillonite, diatomite, activated carbon, zeolite, molecular sieve, porous pottery Any one in porcelain, aluminum oxide, zirconium oxide, silicon nitride, carborundum, graphite or two or more combinations.
It is further preferred that in above-mentioned preparation method, the solid acid includes the Emathlite containing free acid, with trip Any of Emathlite from acid activation or two or more combinations, particularly preferably from white with the acidity of organic acid for activating Soil, the organic acid includes formic acid, oxalic acid, acetic acid, propionic acid, trifluoroacetic acid, benzoic acid, methanesulfonic acid, trimethylacetic acid, alkyl benzene sulphonate Any of or two or more combinations, the alkyl of the alkyl benzene sulphonate is selected from C1~C28Straight chained alkyl or with side chain Alkyl, wherein alkyl is distributed in contraposition, meta or ortho position.
It is further preferred that in above-mentioned preparation method, the preparation method bag of the Emathlite with the acid activation that dissociates Include：Carclazyte is subjected to acid treatment with free acid, treatment temperature is 20 ~ 70 DEG C, and the time is 1 ~ 7h, wherein free acid and carclazyte matter Amount is than being 0.5 ~ 10：1, dry afterwards, then 2 ~ 5h of roasting at 100 ~ 300 DEG C.
In the preparation process in accordance with the present invention, it can may be selected to use or without using diluent according to needs.Wherein, add dilute Release agent can prevent reaction solution too it is viscous so that be difficult to reaction and prevented also from filtration difficulty.
Wherein, the diluent can select but be not limited to the materials such as hydrocarbon solvent, alcoholic solvent, lube base oil, many cerebrols.
For example, the hydrocarbon solvent can select but be not limited to toluene, dimethylbenzene, pentane, n-hexane, hexamethylene, normal heptane, Any one in the materials such as normal octane, isooctane, n-decane or two or more combinations.
For example, the alcoholic solvent may be selected from but be not limited to C1-C13Monohydric alcohol or the material, example such as polyalcohol and its derivative Such as isobutanol, decyl alcohol.
More preferred, the diluent at least can select but be not limited to pentane, n-hexane, hexamethylene, normal heptane, just Octane, isooctane, n-decane, toluene, dimethylbenzene, lube base oil, many cerebrols or their mixture.
More preferred, the consumption of diluent is about 0.5wt%~1000.0wt% of the total consumption of alkyl phenol.It is more highly preferred to , the consumption of diluent is about 50 wt%~500.0wt% of the total consumption of alkyl phenol.
In the preparation process in accordance with the present invention, it can may be selected to use or without using accelerator according to needs.It is usually added into rush Reaction speed can be accelerated, improves reaction conversion ratio and reduce undesirable impurity in product by entering agent.
Wherein, the accelerator can select but be not limited at least one C1-C13Monohydric alcohol or polyalcohol and its derivative, Dialkyl sulphoxide, dialkylformamide, dialkyl ether, dimethyl acetamide, N, N- dialkyl acetamides, N- alkyl-pyrrolidines Ketone, methyl ethyl ketone, methyl butyl ketone, consisting of phase-transferring agent, crown ether, tetrahydrofuran or their mixture.It is more preferred , accelerator can select but be not limited to methanol, isobutanol, ethylene glycol, ethanol, propyl alcohol, isooctanol, cyclohexanol, cyclopentanol, tertiary fourth Alcohol, sec-amyl alcohol or their mixture.
Further, the amount of accelerator can change in the range of non-constant width, for example, the consumption of accelerator is preferably About 0.5mol%~5000.0mol% of the total consumption of alkyl phenol.
More preferred, in above-mentioned preparation method, compared with alkyl phenol, the consumption of the coupling reagent is about 0.01 to rub The molar equivalent of your equivalent~about 20, the consumption of the alkali compounds is the molar equivalent of about 0.01 molar equivalent~about 20, described The consumption of solid acid is the 0.1% ~ 60% of alkyl phenol weight.It is more highly preferred to, the consumption of the solid acid is the weight of alkyl phenol 0.5% ~ 50%.
In above-mentioned preparation method, the reaction condition that step a~step b is used includes：Reaction temperature is 5 DEG C~300 DEG C, Reaction time is 10min~16h.
Particularly preferably, the reaction temperature that step a~step b is used for 30 DEG C~250 DEG C, the reaction time be 20min~ 8h。
It is further preferred that the reaction temperature that step a~step b is used is 50 DEG C~220 DEG C, the reaction time is 20min ~6h.
It is further preferred that the reaction condition that step a is used includes：Range of reaction temperature is 60 DEG C~150 DEG C, during reaction Between be 20min~2h.
It is further preferred that the reaction condition that step b is used includes：Reaction temperature is 60 DEG C~200 DEG C, and the reaction time is 30min~6h.
In above-mentioned preparation method, step c can include：By step b finally obtained reaction product be heated above it is described The vapo(u)rizing temperature of water generated in diluent and step a~b, so that the diluent and the water of generation are distilled out from product Go.
In above-mentioned preparation method, after step b reactions terminate, unreacted raw material need to be removed, typically conventional side Method includes but is not limited to：The methods such as filtering, centrifugal filtration, decantation are by unreacted solid material and impurity and required production Thing is separated.Filter aid such as diatomite (Celite) can be used, to improve separative efficiency.Obtained solution is passed through into normal pressure again Distillation or vacuum distillation remove solvent and the water of generation.
Another aspect of the present invention is provided using alkyl phenate detersive made from aforementioned preparation process, is not only had Excellent peace and quiet peptizaiton, but also with good rust-preventing characteristic and corrosion resistance.
Further, the base number scope of alkyl phenate detersive of the invention is about 30mgKOH/g~350mgKOH/g.
Another aspect of the invention provides the purposes of the alkyl phenate detersive, for example, being added as lubricating oil The purposes of agent.
For example, the invention provides a kind of lubricant oil composite, it includes the alkyl phenate detersive.
Further, the lubricant oil composite can also include generally in cleaning agent composition and lubricating oil and detersive The other components of the convention amount occurred in the mixture of composition.For example, viscosity index improver, pour-point depressant, foam inhibitor, Dispersant, antioxidant, corrosion inhibitor, extreme pressure agent and antiwear additive, the lexical or textual analysis and its selection of these components are all this area skills Art personnel can be easy to what is known and determine according to this specification and common sense in the field.
Therefore, some embodiments of the present invention additionally provide a kind of composition, and it contains alkyl phenate as described above, and Following at least one compound can be added：Lube base oil, detergent-dispersant additive, antiwear additive（Such as dialkyl dithiophosphoric acid Zinc, but not limited to this）, antioxidant（Such as alkylated diphenylamine, but not limited to this）, viscosity index improver, pour point decline Agent, corrosion inhibitor, anti-foaming agent, friction improver or its mixture.
Technical scheme will be described in detail with reference to some embodiments as follows, but these embodiments are to pass through Expand invention rather than limit what the mode invented was proposed.
The preparation technology of some alkyl phenol calcium detersives is relate among following examples, it is various anti-employed in it It is more typical example that thing and process conditions, which should be participated in, but by the checking of inventor's lot of experiments, in listed above The other types of reaction partner gone out and other process conditions are also applicable, and also equal attainable cost invents what is claimed Technique effect.
Embodiment 1：
Under an argon atmosphere by dodecylphenol（49.5 g）, base oil（37.5g）, the carclazyte of p-methyl benzenesulfonic acid activation （24.75 g）And isooctanol（30mL）Successively add in reactor, logical bubbling argon under stirring, and heat the mixture to 60oC Afterwards, sulphur is added（11g）And calcium hydroxide（54.7g）.It is mixed to be warming up to 150oC, add ethylene glycol（10g）.Further heat up 175oC, and stirring reaction 3h at this temperature.Stop drum argon gas, the drum carbon dioxide into reaction solution（40 mL/min）5h.So Afterwards by mixed liquor under 150oC, high vacuum vacuum distillation steams solvent and water in 1 hour.Stop vacuum distillation, and add basis Oil（22g）.Mixture stirs 15min, and heat filtering obtains vulcanizing the total base number TBN of dodecylphenol calcium salt detersive：294 mg KOH/g。
Embodiment 2：
Under an argon atmosphere by dodecylphenol（Key component is p- dodecylphenol）（30g）, base oil（36.5g）, 12 The carclazyte of benzene sulfonamide acid activation（18 g）And isooctanol（50mL）Successively add in reactor, logical bubbling argon under stirring, and Heat the mixture to after 60oC, add formaldehyde（11g）And calcium hydroxide（34.2g）.It is mixed to be warming up to 160oC, add ethylene glycol （10g）.Further heat up 180oC, and stirring reaction 3h at this temperature.Stop drum argon gas, the drum titanium dioxide into reaction solution Carbon（40 mL/min）6 h.Then by mixed liquor under 150oC, high vacuum vacuum distillation 1h steams solvent and water.Stopping subtracts Pressure distillation, and add base oil（18g）.Mixture stirs 15min, and heat filtering obtains the total alkali of dodecylphenol calcium salt detersive Value TBN：239 mg KOH/g.
Embodiment 3：
Under an argon atmosphere by dodecylphenol（Key component is p- dodecylphenol）（30g）, base oil（36.5g）, C20- C24The carclazyte of benzene sulfonamide acid activation（1.5 g）And isooctanol（60mL）Successively add in reactor, logical bubbling argon under stirring, And heat the mixture to after 50oC, add formaldehyde（11g）And calcium hydroxide（32.9g）.It is mixed to be warming up to 120oC, add second two Alcohol（24g）.Further heat up 200oC, and the h of stirring reaction 5 at this temperature.Stop drum argon gas, the drum dioxy into reaction solution Change carbon（40 mL/min）8h.Then by mixed liquor under 150oC, high vacuum vacuum distillation 1h steams solvent and water.Stopping subtracts Pressure distillation, and add base oil（16 g）.Mixture stirs 15min, and heat filtering obtains the total of dodecylphenol calcium salt detersive Base number TBN：175 mg KOH/g.
Comparative example：
Under an argon atmosphere by dodecylphenol（34.5 g）, base oil（27.5g）, alkaline sulfonate detersive（4.9 g）, and Isooctanol (30mL) is successively added in reactor, logical bubbling argon under stirring, and is heated the mixture to after 60oC, adds sulphur Sulphur（7.9g）And calcium hydroxide（24.7g）.Mixture further heats up 150oC, by ethylene glycol in 30min（10g）It is added dropwise Finish.Reactant mixture further heats up 175oC, and stirring reaction 3h at this temperature.Stop drum argon gas, into reaction solution Drum carbon dioxide（40 mL/min）3h.Then by mixed liquor under 150oC, high vacuum vacuum distillation steams solvent and water in 1 hour Go out.Stop vacuum distillation, and add base oil（16g）.Mixture stirs 15min, adds diatomite（500 mg）Heat filtering is obtained To the total base number TBN of vulcanization dodecylphenol calcium salt detersive：273 mg KOH/g.
The performance of the following alkyl phenate detersive obtained to embodiment 1-3 and comparative example is tested, wherein using Experiment oil sample for the additive sample of certain mass is dissolved in base oil 150N, additive level is 3.0wt% oil sample. Inoxidizability（SH/T 0719-2002）, corrosion resistance（GB 5096-85）, rust-preventing characteristic（GB/T 11143-2008）Test result Refer to table 1.
The embodiment 1-3 of table 1 and comparative example product test result
It should be noted that in this manual, term " comprising ", "comprising" or its any other variant are intended to non-row His property is included, so that process, method, article or equipment including a series of key elements not only include those key elements, and And also including other key elements being not expressly set out, or also include for this process, method, article or equipment institute inherently Key element.In the absence of more restrictions, the key element limited by sentence " including one ... ", it is not excluded that including described Also there is other identical element in process, method, article or the equipment of key element.
It should be appreciated that for the person of ordinary skill of the art, can be according to technical solution of the present invention and technology structure Think of makes other various corresponding changes and deformation, and these change and deformation should all belong to the protection model of the claims in the present invention Enclose.

Claims (10)

1. a kind of preparation method of alkyl phenate detersive, it is characterised in that including：
Step a：By alkyl phenol, alkali compounds, coupling reagent and solid acid with may be selected addition or without diluent and/ Or coupling reaction occurs for accelerator mixing；
Step b：Alkali compounds is added, and is passed through carbon dioxide and carries out carbonation reaction；
Step c：Separation obtains target product.
2. the preparation method of alkyl phenate detersive according to claim 1, it is characterised in that：
The solid acid includes the Emathlite containing free acid, the Emathlite of activation, solid super-strong acid, neutral clay, silicon Glue, powdered molecular sieve, montmorillonite, diatomite, activated carbon, zeolite, molecular sieve, porous ceramics, aluminum oxide, zirconium oxide, nitridation Any one in silicon, carborundum, graphite or two or more combinations；
It is preferred that, the solid acid is selected from the Emathlite containing free acid, with any in the Emathlite for the acid activation that dissociates Kind or two or more combinations, particularly preferably from the Emathlite of organic acid for activating, the organic acid include formic acid, oxalic acid, Any of acetic acid, propionic acid, trifluoroacetic acid, benzoic acid, methanesulfonic acid, trimethylacetic acid, alkyl benzene sulphonate or two or more combinations, The alkyl of the alkyl benzene sulphonate is selected from C1~C28Straight chained alkyl or the alkyl with side chain, wherein alkyl be distributed in contraposition, Meta or ortho position;
It is further preferred that the preparation method of the Emathlite with the acid activation that dissociates includes：Carclazyte is carried out with free acid Acid treatment, treatment temperature is 20 ~ 70 DEG C, and the time is 1 ~ 7h, and wherein the mass ratio of free acid and carclazyte is 0.5 ~ 10：1, Zhi Hougan It is dry, then 2 ~ 5h of roasting at 100 ~ 300 DEG C;
Especially preferred, compared with alkyl phenol, the consumption of the solid acid is the 0.1% ~ 60% of alkyl phenol weight;
It is more highly preferred to, the consumption of the solid acid is the 0.5% ~ 50% of the weight of alkyl phenol.
3. the preparation method of alkyl phenate detersive according to claim 1, it is characterised in that：
The alkyl phenol is the C for including monomer by hydroxy aromatic compound one or more8-C45The olefin alkylation of oligomer Change is obtained, and the monomer is selected from propylene, butylene or their mixture.
4. the preparation method of alkyl phenate detersive according to claim 1, it is characterised in that：
The alkali compounds can preferably be selected from but be not limited to alkali metal oxide, the acidifying of alkali metal hydroxide, alkali metal carbon Compound, alkaline earth oxide, alkaline earth metal hydroxide, alkaline-earth metal carbonate compound or their mixture;
It is further preferred that the alkali compounds may be selected from but be not limited to lithium hydroxide, sodium hydroxide, potassium hydroxide, oxidation Calcium, calcium hydroxide, magnesia, magnesium hydroxide, calcium carbonate, magnesium carbonate or their mixture;
Especially preferred, the consumption of the alkali compounds is the molar equivalent of about 0.01 molar equivalent~about 20.
5. the preparation method of alkyl phenate detersive according to claim 1, it is characterised in that：
The coupling reagent can select but be not limited to sulfur-containing compound and/or fatty aldehyde;
It is further preferred that the coupling reagent can select but be not limited to elemental sulfur, vulcanized sodium, formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, Hexanal, enanthaldehyde or their mixture;
Especially preferred, the consumption of the coupling reagent is the molar equivalent of about 0.01 molar equivalent~about 20.
6. the preparation method of alkyl phenate detersive according to claim 1, it is characterised in that：
The diluent can select but be not limited to the materials such as hydrocarbon solvent, alcoholic solvent, lube base oil, many cerebrols;
It is further preferred that the hydrocarbon solvent can select but be not limited to toluene, dimethylbenzene, pentane, n-hexane, hexamethylene, just Any one in the materials such as heptane, normal octane, isooctane, n-decane or two or more combinations;
It is further preferred that the alcoholic solvent may be selected from but be not limited to C1-C13Monohydric alcohol or the thing such as polyalcohol and its derivative Matter, such as isobutanol, decyl alcohol;
Especially preferred, the diluent at least can select but be not limited to pentane, n-hexane, hexamethylene, normal heptane, just pungent Alkane, isooctane, n-decane, toluene, dimethylbenzene, lube base oil, many cerebrols or their mixture;
It is more highly preferred to, the consumption of diluent is about 0.5wt%~1000.0wt% of the total consumption of alkyl phenol；
It is more highly preferred to, the consumption of diluent is about 50 wt%~500.0wt% of the total consumption of alkyl phenol.
7. the preparation method of alkyl phenate detersive according to claim 1, it is characterised in that：
The accelerator can select but be not limited at least one C1-C13Monohydric alcohol or polyalcohol and its derivative, dialkyl group it is sub- Sulfone, dialkylformamide, dialkyl ether, dimethyl acetamide, N, N- dialkyl acetamides, N- alkyl-pyrrolidones, methyl second Base ketone, methyl butyl ketone, consisting of phase-transferring agent, crown ether, tetrahydrofuran or their mixture;
It is further preferred that the accelerator can select but be not limited to methanol, isobutanol, ethylene glycol, ethanol, propyl alcohol, isooctanol, Cyclohexanol, cyclopentanol, the tert-butyl alcohol, sec-amyl alcohol or their mixture;
Especially preferred, the consumption of the accelerator is preferably about 0.5mol%~5000.0mol% of the total consumption of alkyl phenol.
8. the preparation method of alkyl phenate detersive according to claim 1, it is characterised in that：
The reaction condition that step a~step b is used includes：Reaction temperature is 5 DEG C~300 DEG C, and the reaction time is 10min~16h;
It is further preferred that the reaction temperature that step a~step b is used is 30 DEG C~250 DEG C, the reaction time is 20min~8h;
Particularly preferably, the reaction temperature that step a~step b is used is 50 DEG C~220 DEG C, and the reaction time is 20min~6h;
It is further preferred that the reaction condition that step a is used includes：Range of reaction temperature is 60 DEG C~150 DEG C, and the reaction time is 20min~2h;
It is further preferred that the reaction condition that step b is used includes：Reaction temperature is 60 DEG C~200 DEG C, and the reaction time is 30min~6h.
9. alkyl phenate detersive prepared by the method as any one of claim 1-8.
10. a kind of lubricant oil composite, including the alkyl phenate detersive described in claim 9.
CN201610068967.2A 2016-02-01 2016-02-01 Alkyl phenate detergent and preparation method and application thereof Active CN107022398B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4865754A (en) * 1986-01-14 1989-09-12 Amoco Corporation Lubricant overbased phenate detergent with improved water tolerance
CN103725355A (en) * 2012-10-15 2014-04-16 中国石油化工股份有限公司 Preparation method of low-base number lubricating oil clearing agent
CN103725354A (en) * 2012-10-15 2014-04-16 中国石油化工股份有限公司 Preparation method of high-base number sulfurized alkylphenol salt

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4865754A (en) * 1986-01-14 1989-09-12 Amoco Corporation Lubricant overbased phenate detergent with improved water tolerance
CN103725355A (en) * 2012-10-15 2014-04-16 中国石油化工股份有限公司 Preparation method of low-base number lubricating oil clearing agent
CN103725354A (en) * 2012-10-15 2014-04-16 中国石油化工股份有限公司 Preparation method of high-base number sulfurized alkylphenol salt

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