CN109679729A - A kind of preparation process of high base number sulfurized alkylsalicylate - Google Patents
A kind of preparation process of high base number sulfurized alkylsalicylate Download PDFInfo
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- CN109679729A CN109679729A CN201910119354.0A CN201910119354A CN109679729A CN 109679729 A CN109679729 A CN 109679729A CN 201910119354 A CN201910119354 A CN 201910119354A CN 109679729 A CN109679729 A CN 109679729A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
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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
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/20—Thiols; Sulfides; Polysulfides
- C10M135/22—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M135/26—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives thereof
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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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/043—Sulfur; Selenenium; Tellurium
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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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
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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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
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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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/024—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
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- 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
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- 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
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- 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
- C10N2030/64—Environmental friendly compositions
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- 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
- C10N2030/66—Hydrolytic stability
Abstract
The invention discloses a kind of preparation processes of high base number sulfurized alkylsalicylate, first using salicylic acid and long-chain olefin as starting material, it is alkylated reaction under the action of polar catalyst, alkyl salicylate is made, alkyl salicylate is neutralized again, vulcanize, high base number (TBN > 350mgKOH/g) sulfurized alkylsalicylate product is prepared in high quaternization.For the present invention using being continuously synthesizing to technique, reaction condition is mild, and product has higher base number, is free of free phenol, and have excellent high temperature detergency, inoxidizability and wear resistence, be a kind of performance comprehensively, environmental protection, energy-saving product.
Description
Technical field
The present invention relates to a kind of preparation processes of high base number sulfurized alkylsalicylate.
Background technique
Alkylsalicylate has excellent high temperature detergency and hydrolysis stability, is widely used in I. C. engine oil and peculiar to vessel
In oil.With the fast development in lubricating oil field, the quality and performance of oil dope made higher requirement.
There are mainly two types of the preparation processes of sulfurized alkylsalicylate, is starting material one is alkyl phenol, passes through after curing
Kolbe-Schmitt reaction introduces carboxyl on the phenyl ring of alkyl phenol, obtains neutral alkylsalicylate, then through vulcanization and carbonic acid
Change reaction to obtain vulcanizing alkaline alkylsalicylate；Another kind is to live using alkyl salicylate as reaction raw materials on promotor, surface
Property agent etc. under the action of sulfurized alkylsalicylate obtained by curing, vulcanization and carbonation reaction.In view of Kolbe-Schmitt
The preparation of the problems such as harshness and reaction yield of technique is low, sulfurized alkylsalicylate more preferably uses second method.At present
The alkylated salicylamide acid product not circulated in the market, manufacturer mainly in a manner of self-produced personal based on, the conjunction of alkyl salicylate
Ingredient is Kolbe-Schmitt technique and Friedel-Crafts technique, the former is usually reaction with phenol and long-chain alpha-olefin
Raw material reacts to obtain alkyl salicylate through Kolbe-Schmitt after alkylated reaction, and the carboxylated of alkyl phenol needs in the technique
Higher reaction pressure, consersion unit are at high cost；It is low additionally, due to the reactivity of ortho alkyl phenol, cause to contain in reaction product
There are a large amount of free alkyl phenol, influences product quality.Friedel-Crafts technique is then directly with salicylic acid and long-chain alpha-olefin
Starting material, reaction under the action of polar catalyst obtain alkyl salicylate, and the technological operation is simple, reaction condition temperature
With catalyst is easily separated, therefore the preparation of alkyl salicylate mostly uses Friedel-Crafts technique.
Patent CN1035015C discloses a kind of preparation method of Acid Thiosalicylique compound, and alkyl phenol and alkaline-earth metal try
Agent carries out neutralization reaction under the facilitation of water and ethylene glycol, obtained alkyl phenol calcium and carbon dioxide under a certain pressure into
Row carboxylation reaction, carboxylated product are alkylsalicylate, and the product and sulphur and alkaline earth metal reagent are in nitrogen environment
Vulcanized and generates Acid Thiosalicylique salt, product sulfur content 2.3-3.9%, total base number 153-252mgKOH/g after base number.It should
Technique vulcanization, carboxylation reaction are incomplete, and reaction terminates to need free alkyl phenol removal, and energy consumption is larger, actual product
It is the mixture of sulfurized alkylsalicylate and alkyl monosulfide phenates.
Patent CN1043784C reports a kind of method for being firstly vulcanized rear calcification and preparing high base number alkyl monosulfide calcium salicylate,
After alkyl salicylate, alkyl phenol and calcium oxide carry out slaking reaction, vulcanization reaction is carried out in advanced alcoholic solution, then passes through height
Basicity reacts to obtain sulfur content to be 3.0% or so, and total base number is the alkyl monosulfide calcium salicylate of 200-300mgKOH/g.It should
Technique introduces alkyl phenol, unavoidably brings harm to environment.
There is alkyl phenol to participate in reaction in the above patent, the presence of free alkyl phenol will affect product service performance (as resisted
Oxidisability, detergency), serious harm can be also caused to environment.Alkyl phenol is not degradable in the environment, has endocrine poison
Property, genotoxicity, threaten the entire ecosystem." global chemicals homogeneous classification and labeling system " (GHS) was March 1 in 2018
The genotoxicity of alkyl phenol is changed to 1B class by original 2 classes (questionable person's class reproduction poisonous substance) and (speculates the possible mankind by day
Reproduction poisonous substance), alkyl phenol can not be ignored the influence of environment bring.High base number sulfurized alkylsalicylate has excellent acid
Neutralising capacity can effectively reduce its additive amount in lubricating oil, has positive effect for energy-saving and emission-reduction, is the following lubricating oil
The development trend of detersive.Product total base number in the patent of sulfurized alkylsalicylate is recorded at present is lower than 300mgKOH/g more,
And the patent about high base number (TBN > 350) sulfurized alkylsalicylate has not been reported.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provide a kind of performance comprehensively, environmental protection, energy-saving high base number sulphur
Change the preparation method of alkyl salicylate product salt.
The present invention provides a kind of preparation process of high base number sulfurized alkylsalicylate, including the following steps:
Step 1: alkylated salicylamide acid product is prepared
Salicylic acid, long-chain alpha-olefin and polar catalyst methanesulfonic acid are added in flask to be reacted, and is tied in reaction
Zonal centrifugation separation removal lower layer's polar catalyst methanesulfonic acid, obtains the alkylated salicylamide acid product for containing solvent in upper layer after beam；
Step 2: high base number sulfurized alkylsalicylate is prepared
Alkylated salicylamide acid product, dispersion aids, base oil, alkaline metal cpds, sulphur are sequentially added in flask, so
Ethylene glycol is added in backward flask and carries out vulcanization reaction, then puts into alkaline metal cpds and is passed through carbon dioxide and start to carry out height
Quaternization, filtering and removing slag after reaction, filtrate obtain high base number sulfurized alkylsalicylate product after being evaporated under reduced pressure.
Preferably, the step 1 specifically: salicylic acid, long-chain alpha-olefin and polar catalyst first are added in flask
System is heated to 110-150 DEG C by sulfonic acid, stirs and keep the temperature 8-20h, and alkane solvent oil is added after reaction, stands 10-
It is layered after 48h, centrifuge separation removal lower catalyst agent, obtaining upper layer is the alkylated salicylamide acid product containing solvent.
Preferably, the long-chain alpha-olefin is one of the alkene of carbon number between 10-30 or multiple combinations.
Preferably, the salicylic acid, long-chain alpha-olefin, polar catalyst methanesulfonic acid, the addition quality of alkane solvent oil are full
Foot: the molar ratio of the salicylic acid and long-chain alpha-olefin is 1:1-1.5:1, and polar catalyst methanesulfonic acid dosage is long-chain alpha-olefin
The 20-40% of quality, the alkane solvent oil account for salicylic acid, long-chain alpha-olefin, polar catalyst methanesulfonic acid, alkane solvent oil shape
At system gross mass 30-50%.
Preferably, the step 2 specifically: sequentially add the alkylated salicylamide acid product containing solvent in flask, help point
Powder, base oil, alkaline metal cpds, sulphur open heat temperature raising, and 1-4h is maintained neutralize instead at 130-160 DEG C
It answers, ethylene glycol is then added into flask and carries out vulcanization reaction, system then puts into alkalinity gold in 130-180 DEG C of heat preservation 3-6h
Belong to compound and be passed through carbon dioxide and start high quaternization, carbon dioxide duration of ventilation is maintained at 3-5h, drops after ventilation
Alkane solvent oil and filter aid slagging-off is added to 100 DEG C in temperature, and filtered filtrate removes ethylene glycol and molten through vacuum distillation
High base number sulfurized alkylsalicylate product is obtained after agent.
Preferably, the dispersion aids is polyisobutene succinimide, in polyisobutylene butanedioic anhydride, alkyl benzene sulphonate
It is one or more.
Preferably, the alkaline metal cpds be one of calcium oxide, calcium hydroxide, magnesia, magnesium hydroxide or
It is a variety of.
Preferably, alkylated salicylamide acid product, dispersion aids, base oil, alkaline metal cpds, the sulphur containing solvent
Mass ratio between sulphur, ethylene glycol meets: in terms of being 100 parts by weight by the additional amount of the alkyl salicylate containing solvent, helping dispersion
Agent 2-8 parts by weight, base oil 20-40 parts by weight, alkaline metal cpds 15-30 parts by weight, wherein alkalinity is golden when neutralization reaction
The additional amount 5-10 parts by weight for belonging to compound, the additional amount 5-25 parts by weight of alkaline metal cpds, sulphur when high quaternization
5-10 parts by weight, ethylene glycol 10-50 parts by weight.
Preferably, the additional amount of the alkane solvent oil is 50-100 parts by weight.
Present invention has the advantage that:
The present invention is using technique is continuously synthesizing to, and reaction condition is mild, and process is simple, easily operated, and product tool is higher
Base number, and free phenol is free of, it is small to environmental hazard.In addition, using the known prepared product of present invention preparation in addition to good
Outside good high temperature detergency and hydrolysis stability, also there is excellent inoxidizability, thermal stability and wear resistence, and and sulfonic acid
Product salt compatibility is good, and no alkyl phenol residual, the development of the product has a very important significance.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention,
Technical solution of the present invention is clearly and completely described, it is clear that described embodiment is that a part of the invention is implemented
Example, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creativeness
Every other embodiment obtained, shall fall within the protection scope of the present invention under the premise of labour.
The present invention provides a kind of preparation process of high base number sulfurized alkylsalicylate, specifically includes following steps:
Step 1: alkylated salicylamide acid product is prepared
Salicylic acid, long-chain alpha-olefin (carbon number 10-30) and polar catalyst methanesulfonic acid are added in flask, by system
It is heated to 110-150 DEG C, stirs and keeps the temperature 8-20h and be alkylated reaction, a certain amount of alkane is added after alkylated reaction
Solvent naphtha is layered after standing 10-48h, centrifuge separation removal catalyst (lower layer), and upper layer is that the alkyl salicylate containing solvent produces
Product.
The addition quality satisfaction of the salicylic acid, long-chain alpha-olefin, polar catalyst methanesulfonic acid, alkane solvent oil: described
The molar ratio of salicylic acid and long-chain alpha-olefin is 1:1-1.5:1, and polar catalyst methanesulfonic acid dosage is long-chain alpha-olefin quality
20-40%, the alkane solvent oil account for salicylic acid, long-chain alpha-olefin, polar catalyst methanesulfonic acid, alkane solvent oil and are formed
The 30-50% of system gross mass.
Long-chain alpha-olefin can be the mixture of one or more alkene, and being mutually mixed quality, there is no limit, it is only necessary to total
Amount is met the requirements.
Step 2: high base number sulfurized alkylsalicylate is prepared
Alkylated salicylamide acid product, dispersion aids (polyisobutene succinimide, polyisobutene fourth are sequentially added in flask
One of dicarboxylic anhydride, alkyl benzene sulphonate are a variety of, and when being selected as a variety of, there is no limit total amount meets mutual mass ratio
It is required that), base oil, (one of calcium oxide, calcium hydroxide, magnesia, magnesium hydroxide are more for alkaline metal cpds
Kind, when being selected as a variety of, mutual mass ratio there is no limit, total amount is met the requirements), sulphur, open heating slowly rise
Temperature maintains 1-4h to carry out neutralization reaction at 130-160 DEG C, and ethylene glycol (analysis is pure) is added after reaction into flask and carries out sulphur
Change reaction, system then puts into quantitative alkaline metal cpds (dividing 2-6 addition) and be passed through in 130-180 DEG C of heat preservation 3-6h
Carbon dioxide starts high quaternization, and carbon dioxide duration of ventilation is maintained at 3-5h, be cooled to after ventilation 60-110 DEG C it is (excellent
It is selected as 100 DEG C), a certain amount of alkane solvent oil and filter aid slagging-off is added, filtrate removes ethylene glycol and molten through vacuum distillation
High base number sulfurized alkylsalicylate product is obtained after agent.
The alkylated salicylamide acid product containing solvent, dispersion aids, base oil, alkaline metal cpds, sulphur, second two
The additional amount of alcohol, alkane solvent oil and filter aid meets: with the additional amount of the alkyl salicylate containing solvent for 100 parts by weight
Meter, dispersion aids 2-8 parts by weight, base oil 20-40 parts by weight, alkaline metal cpds 15-30 parts by weight, wherein neutralization reaction
When alkaline metal cpds additional amount 5-10 parts by weight, the additional amount 5-25 weight of alkaline metal cpds when high quaternization
Measure part, sulphur 5-10 parts by weight, ethylene glycol 10-50 parts by weight, alkane solvent oil 50-100 parts by weight.The additional amount of filter aid
The filter cake thickness formed after filtering of being subject to is 2-3mm, is selected according to the actual situation.
The base oil is a kind of, two classes or three classes hydrogenated base oil.
Embodiment 1:
The present embodiment 1 provides a kind of preparation process of alkylated salicylamide acid solution, specifically:
In flask be added salicylic acid 160g, n-hexadecene hydrocarbon, positive octadecylene hydrocarbon, positive icosa alkene hydrocarbon mixture 400g,
System is heated to 130 DEG C, stirs and keep the temperature 15h by polar catalyst methanesulfonic acid 80g, and 200# solvent naphtha is added after reaction
500g is layered after standing 48h, and the methanesulfonic acid of centrifuge separation removal lower layer, upper layer is solvent-laden alkyl salicylate, takes upper layer sample
Product do gas-chromatography, and the acid content for measuring alkylated salicylamide acid solution is 50%.
Embodiment 2:
Step 1: alkylated salicylamide acid product is prepared
Alkylated salicylamide acid product containing solvent is prepared using the sample and data of embodiment 1.
Step 2: high base number sulfurized alkylsalicylate is prepared
Alkylated salicylamide acid product 150g (acid content 50%) is added in flask, polyisobutene succinimide 10g adds hydrogen
Base oil 50g, calcium oxide 10g, sulphur 9g open heating slowly heating, maintain 3h at 130 DEG C.Second two is added into flask
Alcohol 30g carries out vulcanization reaction, and system keeps the temperature 6h at 155 DEG C, then puts into 25g calcium oxide (point 4 additions) and is passed through dioxy
Change carbon and start high quaternization, carbon dioxide duration of ventilation is maintained at 5h, 100 DEG C are cooled to after ventilation, is added 100g's
200# solvent naphtha is simultaneously removed the gred using filter aid, and filtrate obtains high base number vulcanization after vacuum distillation removes ethylene glycol and solvent
Alkyl calcium salicylate, product base number are 365.7mgKOH/g, 100 DEG C of viscosity 162.87mm2/s, sulfur content 2.85%.
Embodiment 3:
The present embodiment 3 provides a kind of preparation process of high base number sulfurized alkylsalicylate, specifically includes following step
It is rapid:
Step 1: alkylated salicylamide acid product is prepared
Alkylated salicylamide acid product containing solvent is prepared using the sample and data of embodiment 1.
Step 2: high base number sulfurized alkylsalicylate is prepared
Alkylated salicylamide acid product 150g (acid content 50%) is added in flask, polyisobutylene butanedioic anhydride 5g adds hydrogen-based
Plinth oil 50g, calcium oxide 10g, sulphur 9g open heating slowly heating, maintain 2h at 150 DEG C.Ethylene glycol is added into flask
30g carries out vulcanization reaction, and system keeps the temperature 6h at 160 DEG C, then puts into 25g calcium oxide (point 4 additions) and is passed through titanium dioxide
Carbon starts high quaternization, and carbon dioxide duration of ventilation is maintained at 5h, 100 DEG C are cooled to after ventilation, is added 100g's
200# solvent naphtha is simultaneously removed the gred using filter aid, and filtrate obtains high base number vulcanization after vacuum distillation removes ethylene glycol and solvent
Alkyl calcium salicylate, base number 380.4mgKOH/g, 100 DEG C of viscosity 234.60mm2/s, sulfur content 3.01%.
Embodiment 4
The present embodiment 4 provides a kind of preparation process of high base number sulfurized alkylsalicylate, specifically includes following step
It is rapid:
Step 1: alkylated salicylamide acid product is prepared
Alkylated salicylamide acid product containing solvent is prepared using the sample and data of embodiment 1.
Step 2: high base number sulfurized alkylsalicylate is prepared
Alkylated salicylamide acid product 150g (acid content 50%) is added in flask, polyisobutylene butanedioic anhydride 5g adds hydrogen-based
Plinth oil 60g, magnesia 8g, sulphur 10.5g open heating slowly heating, maintain 3h at 130 DEG C.Second two is added into flask
Alcohol 20g carries out vulcanization reaction, and system keeps the temperature 6h at 160 DEG C, then puts into 19g magnesia (point 4 additions) and is passed through dioxy
Change carbon and start high quaternization, carbon dioxide duration of ventilation is maintained at 5h, 100 DEG C are cooled to after ventilation, is added 100g's
200# solvent naphtha is simultaneously removed the gred using filter aid, and filtrate obtains high base number vulcanization after vacuum distillation removes ethylene glycol and solvent
Magnesium alkylsalicylate, base number 392.2mgKOH/g, 100 DEG C of viscosity 287.40mm2/s, sulfur content 3.23%.
Embodiment 5:
The present embodiment 5 provides a kind of preparation process of high base number sulfurized alkylsalicylate, specifically includes following step
It is rapid:
Step 1: alkylated salicylamide acid product is prepared
Alkylated salicylamide acid product containing solvent is prepared using the sample and data of embodiment 1.
Step 2: high base number sulfurized alkylsalicylate is prepared
The alkylated salicylamide acid product 150g (acid content 50%) containing solvent is added in flask, alkyl benzene sulphonate 10g adds
Hydrogen base oil 50g, calcium hydroxide 10g, sulphur 9g open heating slowly heating, maintain 2h at 150 DEG C.It is added into flask
Ethylene glycol 30g carries out vulcanization reaction, and system keeps the temperature 6h at 160 DEG C, then puts into 25g calcium hydroxide (point 4 additions) and leads to
Enter carbon dioxide and start high quaternization, carbon dioxide duration of ventilation is maintained at 5h, and 100 DEG C are cooled to after ventilation, is added
The 200# solvent naphtha of 100g is simultaneously removed the gred using filter aid, and filtrate obtains height after vacuum distillation removes ethylene glycol and solvent
Base number alkyl monosulfide calcium salicylate, base number 374.3mgKOH/g, 100 DEG C of viscosity 186.55mm2/s, sulfur content 2.98%.
Embodiment 6:
The present embodiment 6 provides a kind of preparation process of high base number sulfurized alkylsalicylate, specifically includes following step
It is rapid:
Step 1: alkylated salicylamide acid product is prepared
Alkylated salicylamide acid product containing solvent is prepared using the sample and data of embodiment 1.
Step 2: high base number sulfurized alkylsalicylate is prepared
The alkylated salicylamide acid product 150g (acid content 50%) containing solvent is added in flask, alkyl benzene sulphonate 10g adds
Hydrogen mineral oil 55g, magnesium hydroxide 8g, sulphur 9g open heating slowly heating, maintain 2h at 150 DEG C.It is added into flask
Ethylene glycol 20g carries out vulcanization reaction, and system keeps the temperature 6h at 160 DEG C, then puts into 19g magnesium hydroxide (point 4 additions) and leads to
Enter carbon dioxide and start high quaternization, carbon dioxide duration of ventilation is maintained at 5h, and 100 DEG C are cooled to after ventilation, is added
The 200# solvent naphtha of 100g is simultaneously removed the gred using filter aid, and filtrate obtains height after vacuum distillation removes ethylene glycol and solvent
Base number alkyl monosulfide magnesium salicylate, base number 405.1mgKOH/g, 100 DEG C of viscosity 262.68mm2/s, sulfur content 3.04%.
By evaluation physical and chemical index, anti-oxidative stability, free alkyl phenol etc., compare product produced by the invention with it is commercially available
The performance of product compares, as shown in table 1.Wherein,
Free phenol content: pass through liquid chromatographic detection.
Oxidation induction period: sample and 150N are mixed into mass fraction as 5% to test sample, using PDSC measurement sample one
Determine the oxidation induction period at temperature, evaluates oxidation stability.
High temperature detergency: sample and multistage base oil (by 150SN, 500SN and viscosity index improver are deployed) are mixed
Synthesizing mass fraction is 2% to test sample, and test method is referring to SH/T 0300-92.
Wear resistence: sample and multistage base oil (by 150SN, 500SN and viscosity index improver are deployed) are mixed into
Mass fraction is 2% to test sample, and experimental facilities is four-ball tester.
Compatibility: sample and TBN400 sulfonate product each 15% are diluted with 150N base oil, are stood and are placed observation oil sample
Appearance.
1 product physical and chemical index of table and performance indicator
By comparing above, it can be seen that product produced by the invention has the effect that
1. introducing sulphur bridge in alkyl salicylate molecules of salt, product sulfur content is 2.8-3.3%, is helped to improve anti-oxidant
Property and wear resistence, product have good high temperature detergency, inoxidizability, heat-resisting quantity and wear resistence, be that a kind of performance is comprehensive
Alkylsalicylate.
2. preparation process does not introduce alkyl phenol, the harm to environment is reduced.
3. it is steady to help to improve product using dispersion aids such as polyisobutene succinimide, alkyl benzene sulphonates in reaction
Qualitative and base number.
4. at present about in the report of sulfurized alkylsalicylate, product base number is generally lower than 300mgKOH/g, the present invention
Base number (TBN > 350mgKOH/ that there is superelevation by being firstly vulcanized the sulfurized alkylsalicylate that rear high-alkali value is reacted
g)。
5. reaction condition is mild, process is simple, easily operated, is conducive to large-scale industrial production.
These are only the preferred embodiment of the present invention, is not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of preparation process of high base number sulfurized alkylsalicylate, which is characterized in that including the following steps:
Step 1: alkylated salicylamide acid product is prepared
Salicylic acid, long-chain alpha-olefin and polar catalyst methanesulfonic acid are added in flask to be reacted, and after the completion of reaction
Zonal centrifugation separation removal lower layer's polar catalyst methanesulfonic acid, obtains the alkylated salicylamide acid product for containing solvent in upper layer；
Step 2: high base number sulfurized alkylsalicylate is prepared
Alkylated salicylamide acid product, dispersion aids, base oil, alkaline metal cpds, sulphur are sequentially added in flask, then to
Ethylene glycol is added in flask and carries out vulcanization reaction, then puts into alkaline metal cpds and is passed through carbon dioxide and start to carry out high alkalization
Reaction, filtering and removing slag after reaction, filtrate obtain high base number sulfurized alkylsalicylate product after being evaporated under reduced pressure.
2. the preparation process of high base number sulfurized alkylsalicylate according to claim 1, which is characterized in that the step
One specifically: salicylic acid, long-chain alpha-olefin and polar catalyst methanesulfonic acid are added in flask, system is heated to 110-
150 DEG C, 8-20h is stirred and kept the temperature, alkane solvent oil is added after reaction, is layered after standing 10-48h, centrifuge separation removal
Lower catalyst agent, obtaining upper layer is the alkylated salicylamide acid product containing solvent.
3. the preparation process of high base number sulfurized alkylsalicylate according to claim 1 or 2, which is characterized in that described
Long-chain alpha-olefin is one of the alkene of carbon number between 10-30 or multiple combinations.
4. the preparation process of high base number sulfurized alkylsalicylate according to claim 2, which is characterized in that the bigcatkin willow
The addition quality satisfaction of acid, long-chain alpha-olefin, polar catalyst methanesulfonic acid, alkane solvent oil: the salicylic acid and long-chain alpha-alkene
The molar ratio of hydrocarbon is 1:1-1.5:1, and polar catalyst methanesulfonic acid dosage is the 20-40% of long-chain alpha-olefin quality, the alkane
Solvent naphtha accounts for the 30- for the system gross mass that salicylic acid, long-chain alpha-olefin, polar catalyst methanesulfonic acid, alkane solvent oil are formed
50%.
5. the preparation process of high base number sulfurized alkylsalicylate according to claim 1, which is characterized in that the step
Two specifically: alkylated salicylamide acid product, dispersion aids, base oil, alkaline metal cpds, sulphur are sequentially added in flask,
Heat temperature raising is opened, maintains 1-4h to carry out neutralization reaction at 130-160 DEG C, ethylene glycol is then added into flask and is vulcanized
Reaction, system then put into alkaline metal cpds and are passed through carbon dioxide and start high alkalization instead in 130-180 DEG C of heat preservation 3-6h
It answers, carbon dioxide duration of ventilation is maintained at 3-5h, and 100 DEG C are cooled to after ventilation, and alkane solvent oil and filter aid mistake is added
Slag is filtered out, filtered filtrate obtains high base number sulfurized alkylsalicylate after vacuum distillation removes ethylene glycol and solvent and produces
Product.
6. the preparation process of high base number sulfurized alkylsalicylate according to claim 1 or 5, which is characterized in that described
Dispersion aids is one of polyisobutene succinimide, polyisobutylene butanedioic anhydride, alkyl benzene sulphonate or a variety of.
7. the preparation process of high base number sulfurized alkylsalicylate according to claim 1 or 5, which is characterized in that described
Alkaline metal cpds are one of calcium oxide, calcium hydroxide, magnesia, magnesium hydroxide or a variety of.
8. the preparation process of high base number sulfurized alkylsalicylate according to claim 5, which is characterized in that the alkyl
Bigcatkin willow acid product, dispersion aids, base oil, alkaline metal cpds, sulphur, the mass ratio between ethylene glycol meet: with alkyl
Salicylic additional amount is 100 parts by weight meters, dispersion aids 2-8 parts by weight, base oil 20-40 parts by weight, alkalinous metal chemical combination
Object 15-30 parts by weight, wherein when neutralization reaction alkaline metal cpds additional amount 5-10 parts by weight, alkalinity when high quaternization
The additional amount 5-25 parts by weight of metallic compound, sulphur 5-10 parts by weight, ethylene glycol 10-50 parts by weight.
9. the preparation process of high base number sulfurized alkylsalicylate according to claim 8, which is characterized in that the alkane
The additional amount of solvent naphtha is 50-100 parts by weight.
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| CN111170850A (en) * | 2019-12-26 | 2020-05-19 | 山东源根石油化工有限公司 | Additive, preparation method and lubricating oil using additive |
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