CN105646187B - A kind of preparation method of super basicity alkyl aryl salicylic acid calcium salt - Google Patents
A kind of preparation method of super basicity alkyl aryl salicylic acid calcium salt Download PDFInfo
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- CN105646187B CN105646187B CN201610119411.1A CN201610119411A CN105646187B CN 105646187 B CN105646187 B CN 105646187B CN 201610119411 A CN201610119411 A CN 201610119411A CN 105646187 B CN105646187 B CN 105646187B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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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
- 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
- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
- C10M129/54—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic acid salts
- C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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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
- C10N2030/04—Detergent property or dispersant property
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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
- C10N2030/52—Base number [TBN]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Abstract
The present invention provides a kind of preparation methods of super basicity alkyl aryl salicylic acid calcium salt, include the following steps: the mixture that solvent naphtha, base oil, lime, kicker are mixed by (1), add surfactant and alkylaryl salicylic acid, it is stirred to react 50-60min at 85-88 DEG C, generates neutral alkylaryl salicylic acid calcium salt；(2) cooling and addition promotor and calcium hydroxide in the neutral alkylaryl salicylic acid calcium salt, are passed through carbon dioxide to get super basicity alkyl aryl salicylic acid calcium salt.The super basicity alkyl aryl salicylic acid calcium salt of the embodiment of the present invention is with oil-soluble is good, thermal stability is good, base number can reach 400-450mgKOH/g, belong to overbased product, compensates for the technological gap of the super super base number product of base number oil-soluble salicylic acid detersive preparation field in the prior art.
Description
Technical field
The present invention relates to Speciality Petrochemicals scope lube oil additive preparation fields, in particular to a kind of super alkali
It is worth the preparation method of alkylaryl salicylic acid calcium salt.
Background technique
Calcium alkyl salicylate with high base number is one of common detergent for lubricating oil, and alkyl salicylate salt compound is due to tool
There are preferable high temperature detergency and certain antioxygen, resistance to corrosion, is widely used in lube oil additive field.Alkyl is general
It is provided by benzene or is provided by the long-chain olefin that 15-30 carbon atom forms, is also described using benzene second both at home and abroad in the recent period
The relevant report of ene derivative preparation.
The most important index of Calcium Alkylsalicylate first is that the total base number of product, commonly using TBN indicates (Total Base
The abbreviation of Number).Total base number is by laying in base number RBN (abbreviation of Reserve Base Number) and direct alkali in product
Value DBN (abbreviation of Direct Base Number) composition.Base number unit is indicated with mgKOH/g, i.e. contains phase in every gram of product
When in the milligram number of potassium hydroxide.
Calcium Alkylsalicylate product classification is distinguished by the height of total base number (TBN)；In general TBN is 150mgKOH/g
Left and right is known as middle base number product, and TBN 300mgKOH/g or so is known as high base number product, and TBN is greater than 400mgKOH/g and is known as super alkali
It is worth product, the base number of product is higher, and the acidity that can be neutralized in oil product (can be oxidized, be condensed, is rancid) object in oil product use process
Matter is more, and neutralising capacity and peace and quiet effect will be better, thus base number it is high alkyl salicylate calcium product it is more joyous by user
It meets, but the base number of corresponding product is higher, production technology difficulty is bigger.
In the prior art, the patent of Publication No. CN1144216A discloses a kind of preparation of calcium alkyl salicylate with high base number
Method, using dodecyl salicylic acid and calcium oxide as raw material, with certain material proportion and defined charging sequence, synthesis
The dodecyl calcium salicylate of total base number 250mgKOH/g or so discloses a kind of alkylsalicylate in CN1199086A patent
Lube oil additive synthesizes have favorable compatibility with calcium sulfonate with high base number ten using the dosage of adjustment surfactant
Dialkylsalicylic acids calcium.
Using dodecyl salicylic acid and lime as raw material in CN1202479A patent, with different charge ratios, pass through control
The pH value of the reaction solution of carbonating can be respectively synthesized out the dodecyl calcium salicylate of different base numbers.
Using dodecyl salicylic acid and lime as raw material in CN1504451A patent, different basicity alkyls can be respectively synthesized out
Calcium salicylate, the pH value control of the reaction end reaction solution of carbonating.
Disclosed in CN1708471A patent it is a kind of using alkyl side chain be greater than 14 carbon alkyl salicylate be raw material,
In the presence of the promotors such as methanol and surfactant, carbonation reaction is occurred by carbon dioxide and lime and generates alkaline alkyl water
Poplar acid calcium, which, which further simultaneously discloses, generates alkaline alkyl salicylic acid using alkyl salicylate and sulfonate with high base number reactant salt
Salt.
Patent US20040138076, it was recently reported that a kind of containing the salicylic high alkaline salicylate of styrene-based base
Machine oil.Wherein, for styryl salicylic acid by styrene and salicylic acid by >=8:1 molar ratio reaction preparation, obtained is high-alkali
Property salicylate have better than previous salicylate detergent spatter property and inoxidizability.But since styrene is anti-with salicylic acid
What should be fed intake is mole bigger, and obtained alkyl salicylate molecular weight is big, and product acid value is low, it is difficult to which synthesis more high base number produces
Product to cause the molten difference of product oil, therefore limit it simultaneously because styrene polymerization segment polarity contained in product is larger
It uses.
The universal technological deficiency of the prior art is using many and diverse traditional mode of production dodecyl salicylic acid technique, i.e., with
Phenol is that raw material passes through and laurylene is alkylated the obtained dodecylphenol of reaction, then by Koble-Schmitt react into
Row carboxylation reaction obtains dodecyl salicylic acid.Raw material phenol used in such technique has serious dirt to environment and water quality
Dye, and there is also the lower ortho position dodecylphenols of 10-25% activity in product, and residual cannot degrade in the product, this
There is adverse effect to environmental and biological materials.
In addition, the carbon myristyl salicylic acid technique and polystyrene-based salicylic acid technique of external recent development, although
There is larger improvement in environmental protection and energy saving, but product stability and oil-soluble are poor, and the product base number for carbonating technique synthesis is general
All over lower, total base number using cost high metathesis process product base number mostly in 200mgKOH/g hereinafter, surpass only
300mgKOH/g。
In view of this, the present invention is specifically proposed.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of super basicity alkyl aryl salicylic acid calcium salt, the method energy
Overcome all defect of existing synthetic technology, easy to operate, step is clear, favorable reproducibility, by being with alkylaryl salicylic acid
Raw material, obtained alkylaryl salicylic acid calcium salt oil-soluble is good, thermal stability is good, base number can reach 400-450mgKOH/g,
Belong to overbased product, compensates for the super super base number product of base number oil-soluble salicylic acid detersive preparation field in the prior art
Technological gap.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
The present invention relates to a kind of preparation methods of super basicity alkyl aryl salicylic acid calcium salt, and the method includes walking as follows
It is rapid:
(1) mixture for being mixed and made into solvent naphtha, base oil, lime, kicker, adds surfactant and alkane
Base aryl salicylic acid is stirred to react 50-60min at 85-88 DEG C, generates neutral alkylaryl salicylic acid calcium salt；
(2) cooling and addition promotor and calcium hydroxide in the neutral alkylaryl salicylic acid calcium salt, and be passed through
Carbon dioxide is to get super basicity alkyl aryl salicylic acid calcium salt；
Wherein, the salicylic chemical structural formula of the alkylaryl are as follows:
R1、R2、R3、X1、X2、X3、X4It is separately hydrogen atom, alkoxy or the straight chain containing 1 to 10 carbon atom
Or branched alkyl, R4、R5It is separately hydrogen atom or straight chained alkyl or branched alkyl containing 1 to 30 carbon atom, and
R4And R5The sum of carbon atom number be not less than 4.
Raw material alkylaryl salicylic acid used in the present invention belongs to belongs to a kind of new compound in itself, in the prior art still
It finds no pass to record, does not find any record for preparing super basicity alkyl aryl salicylic acid calcium salt as raw material using it,
Inventor has finally synthesized the substance by largely practice, and it is used to implement as primary raw material in strict accordance with the solution of the present invention
The super basicity alkyl aryl calcium salicylate product salt of good quality is prepared.
Wherein, alkylaryl is salicylic the preparation method is as follows: in the presence of a catalyst, make salicylic acid or derivatives thereof,
Styrene or derivatives thereof and alpha-olefin derived object react, and raw material and catalyst are that this field is common and be easy to get
, the long-chain aralkyl that styrene derivative and alpha-olefin derived object are collectively formed provides necessary oil-soluble for product.With list
It is solely compared using the alkylated salicylamide acid derivative that aromatic olefin is alkylating reagent, oil-soluble is more preferable, and acid value is higher, it is easier to close
At the product of more high-alkali value.
Shown in the structural formula of the salicylic acid or derivatives thereof such as formula (1):
X1、X2Separately be hydrogen atom or the direct-connected or branched paraffin containing 1 to 10 carbon atom, M be hydrogen atom or
Linear or branched alkyl group containing 1 to 10 carbon atom；It is highly preferred that X1、X2Separately for hydrogen atom or contain 1 to 4
The direct-connected or branched paraffin of carbon atom.
Shown in the structural formula of the styrene or derivatives thereof such as formula (2):
Wherein R1、R2、R3、X3、X4It is separately hydrogen atom or the direct-connected or branched alkane containing 1 to 10 carbon atom
Hydrocarbon, preferably R1、R2、R3、X3、X4It is separately hydrogen atom or the direct-connected or branched paraffin containing 1 to 4 carbon atom, and
Meet R2And R3The sum of carbon atom number be not more than 4, particularly preferably, R1、R2、R3、X3、X4It is H atom.
Two kinds of raw materials of above formula (1) and formula (2), the optional range of substituent group is very extensive, theoretically for, it is any
The substituent group not having an impact to reaction is optionally substituted base.
Shown in the structural formula such as formula (3) of the alpha-olefin derived object:
Wherein, R4、R5It is separately hydrogen atom or straight chained alkyl or branched alkyl containing 1 to 28 carbon atom, and
And R4And R5The sum of carbon atom number be not less than 4, it is highly preferred that R4、R5Separately for hydrogen atom or contain 1 to 28 carbon
The straight chained alkyl or branched alkyl of atom, and R4And R5The sum of carbon atom number be not less than 12.
R4、R5Selection be directly related to the property of product, when smaller containing carbon number can so that product have it is relatively large
Acid value, be conducive to improve product neutral salt content；More Speleothems can be formed alkalinity by the neutral salt of high-content
Compared with group, thus be conducive to prepare the product of high base number, and correspondingly, oil-soluble will receive certain influence.In addition carbochain is too short
Colloid in product is not easy to stablize, reserve alkali CaCO3It is easy to be precipitated out, therefore the suitable carbochain of selection and structure are to prepare height
One of key technology of quality products.The total for example following chemical reaction equation of synthesis route of specific alkylaryl salicylic acid
Formula:
It synthesizes obtained alkylaryl salicylic acid and super basicity alkyl aryl salicylic acid is prepared by a series of step
Calcium salt, in step (1), alkylaryl salicylic acid is under the action of kicker and solvent naphtha, base oil and surfactant
Neutralization reaction is carried out with lime, generates neutral alkylaryl salicylate, lime therein is the mixing of quick lime and white lime
Object.Preferably, the molar ratio of quick lime and white lime is 1:(0.5-4 in lime), more preferably 1:(1-3), because of mistake herein
The water content of strict control system is needed in journey, therefore cannot add too many white lime, needs to control dosage appropriate.
In the step, solvent naphtha be may be selected to be: any one or more in naphtha, light aromatic hydrocarbons and pseudocumene is mixed
It closes, additional amount is the 210-250% of alkylaryl salicylic acid quality, and dosage is salicylic 2 times of alkylaryl or so.
Preferably, low-viscosity mineral oil neutral oil, II class of low-viscosity oil, any one or more of mixing of III class oil,
Additional amount is the 35-45% of the alkylaryl salicylic acid quality.
Preferably, surfactant is the mixture of stearic acid, any one or two kinds in aphthenic acids, and additional amount is
The 5-10% of the alkylaryl salicylic acid quality.
Preferably, kicker C1-C4Organic carboxyl acid or binary acid, additional amount be the alkylaryl salicylic acid
The 5-6% of additional amount.
The present invention selects above-mentioned efficient kicker, being capable of simplified control process, the high alkalization reaction process of acceleration, raising
The quality of product.
In step (2), after cooling down, be added in the neutral alkylaryl salicylic acid calcium salt of generation promotor and
Calcium hydroxide is passed through carbon dioxide gas, forms stable colloidal dispersion system, to obtain the super basicity alkyl virtue of purpose product
Base salicylic acid calcium salt is added in remaining lime or step (2) in the carbon dioxide being passed through and step (1) in this step
Calcium hydroxide carry out carbonation reaction together, obtain basic carbonate calcium salt, it is noted herein that be added be hydroxide
Calcium, rather than calcium oxide because calcium hydroxide is more conducive to the progress of carbonation reaction, and provide certain micro-moisture.It is dissolved in
The colloid micella of oil wraps up newborn calcium carbonate, forms water-in-oil system, the more voluminous object total alkali of calcium carbonate wrapped up in system
Value (TBN) is higher, and most of calcium carbonate is wrapped up by micella in carbonation, wherein having a small amount of calcium carbonate and calcium hydroxide not
It by micella package but remains stuck to colloid surface nor can be filtered, the base number that this moieties provides is known as direct alkali
It is worth (DBN).Product total base number (TBN) means the summation that base number and direct base number are laid in product.
Preferably, in step (2), promotor is the mixture of ammonium hydroxide and ethyleneamines, and additional amount is the alkylaryl
The molar ratio of the 1-10% of salicylic acid quality, ammonium hydroxide and ethyleneamines is preferably controlled in 1:(0.1-0.8) between, more excellent is 1:
Between (0.1-0.3), ethyleneamines refer to the acyclic polymer class product of ethylenediamine, and carbon number cannot be too high, otherwise will affect rush
Into the activity of agent, therefore the mixture for one or more of being preferably selected as ethylenediamine, diethylenetriamine, triethylene tetramine.
In step (2), preferably it is cooled to 45 DEG C or less and promotion is added in the neutral alkylaryl salicylic acid calcium salt again
Promotor and calcium hydroxide is added in agent, is preferably cooled between 35-39 DEG C.
Preferably, carbon dioxide intake is the 40-55% for the lime gross mass being added, and the carbon dioxide is passed through speed
Degree is 145-150mL/min.More preferably, the carbon dioxide intake is the 50-55% of the gross mass for the lime being wherein added.
Preferably, during being passed through carbon dioxide, at 35-39 DEG C, the reaction time is controlled in 2-3h for reaction temperature control.
Reaction temperature and reaction time are preferably controlled in suitable range, enable to the calcium salt properties of product prepared so more
It is excellent, obtain the product for meeting base number requirement.
Finally, the step of obtained super basicity alkyl aryl salicylic acid calcium salt is by distilling, centrifugation is with purification.Its
In, in distillation process, eliminate solvent, promotor and the water in system, obtain containing unreacted lime, crystal form calcium carbonate and
The crude product of the alkylaryl calcium salicylate of the super base number of polar object impurity, the temperature of distillation are preferably controlled in 160-170 DEG C.From
Heart process uses high temperature and high speed centrifugation technique, the super basicity alkyl aryl calcium salicylate product salt refined after centrifugation.
It is emphasized that if not otherwise indicated, the present invention is the numerical value of total base number (TBN) about the data of base number.
Compared with prior art, the invention has the benefit that
(1) preparation method of the invention can produce different size alkali according to user demand by adjusting material proportion
The alkylaryl calcium salicylate product of value, product total base number can reach 450mgKOH/g, compared with the prior art in alkyl water
The total base number 250mgKOH/g of poplar acid calcium product, there is huge promotion；
(2) method of the invention is easy to operate, radically simplifies processing step, and step is clear, favorable reproducibility, obtained production
Object alkylaryl salicylic acid calcium salt is able to achieve natural biology degradation, environmentally protective, does not pollute the environment, it is dissolved when concrete application
Performance is good, and purity is high, stability is good, and quality and yield are relatively high；
(3) the raw material alkylaryl salicylic acid used in the present invention belongs to a kind of new structural chemical substance, at present not yet
Related record is found, it is many about the research of alkyl salicylate and report in the prior art, but alkyl salicylate itself
Dissolubility is bad, acid value is low, it is difficult to which synthesis more high base number product, these defects limit its further application, the present invention
Product exactly solve puzzlement those skilled in the art technical problem for a long time, meet the urgency of domestic and international high-end oil product user
It needs.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products of commercially available acquisition can be passed through.
Embodiment 1: the salicylic method of alkylaryl is prepared
Equipped in condenser, thermometer, constant pressure funnel and churned mechanically 500ml four-hole bottle, methyl sulphur is added
Salicyclic acid derivatives 69.1g (0.5mol) shown in sour 9.6g, formula (1), weighs styrene derivative 67.7g shown in formula (2)
(0.65mol) is fitted into constant pressure funnel, is warming up to 140 DEG C, and styrene derivative is added dropwise, and 8h is dripped off.It is weighed again containing 14
Alkene 117.8g (0.6mol) shown in the formula (3) of a carbon, is added at one time reaction flask, is warming up to 160 DEG C, it is small to be stirred to react 12
When, stop reaction.Cooling is added 200ml 120# solvent naphtha, material is poured into separatory funnel, static layering, and liquid separation removes
Lower catalyst agent, is removed under reduced pressure solvent naphtha, obtains amber transparent long-chain aralkyl bigcatkin willow acid product 239.6g, yield 94.1%.
Bromine number: 1.7gBr/100g, acid value: 115.8mgKOH/g.Acid value does not decline after storage at normal temperature 30 days, and occurs without precipitating.
In the above reaction raw materials, M, X in formula (1)1And X2It is H；R in formula (2)1、R2、R3、X3、X4It is H；R in formula (3)4
For H, R5For straight chain C12Alkyl.
Embodiment 2: the salicylic method of alkylaryl is prepared
Equipped in condenser, thermometer, constant pressure funnel and churned mechanically 500ml four-hole bottle, methyl sulphur is added
Salicyclic acid derivatives 83.1g (0.5mol) shown in sour 9.6g, formula (1), weighs styrene derivative 76.7g shown in formula (2)
(0.65mol) is fitted into constant pressure funnel, is warming up to 120 DEG C, and styrene derivative is added dropwise, and 0.5h is dripped off.Formula (3) are weighed again
Shown in alkene 67.3g (0.6mol), be added at one time reaction flask, be warming up to 140 DEG C, be stirred to react 10 hours, stop reaction.
Cooling is added 200ml 120# solvent naphtha, material is poured into separatory funnel, static layering, and liquid separation removes lower catalyst agent, subtracts
Pressure removes solvent naphtha, obtains amber transparent long-chain aralkyl salicylate product 213.7g, yield 94.1%.Bromine number: 1.7gBr/
100g, acid value: 1.3mgKOH/g.
In the above reaction raw materials, M is methyl, X in formula (1)1For H, X2For 4- methyl；R in formula (2)1For methyl, R2、R3、
X3、X4For H；R4 is H, R in formula (3)5It is C6 alkyl.
Embodiment 3: the salicylic method of alkylaryl is prepared
Equipped in condenser, thermometer, constant pressure funnel and churned mechanically 500ml four-hole bottle, methyl sulphur is added
Salicyclic acid derivatives 136.1g (0.5mol) shown in sour 9.6g, formula (1), weighs styrene derivative 76.7g shown in formula (2)
(0.65mol) is fitted into constant pressure funnel, is warming up to 160 DEG C, and styrene derivative is added dropwise, and 12h is dripped off.Formula (3) are weighed again
Shown in alkene 67.3g (0.6mol), be added at one time reaction flask, be warming up to 180 DEG C, be stirred to react 24 hours, stop reaction.
Cooling is added 200ml 120# solvent naphtha, material is poured into separatory funnel, static layering, and liquid separation removes lower catalyst agent, subtracts
Pressure removes solvent naphtha, obtains amber transparent long-chain aralkyl bigcatkin willow acid product 266.9g, yield 95.3%.Bromine number: 1.8gBr/
100g, acid value: 1.2mgKOH/g.
In the above reaction raw materials, M is Na in formula (1)+, X1It is methyl, X2It is branch C8 alkyl；R in formula (2)1, R2、R3、X3
For H, X4For 4- methyl；R in formula (3)4It is H, R5It is C6 alkyl.
Embodiment 4: the salicylic method of alkylaryl is prepared
Equipped in condenser, thermometer, constant pressure funnel and churned mechanically 500ml four-hole bottle, methyl sulphur is added
Salicyclic acid derivatives 104.1g (0.5mol) shown in sour 9.6g, formula (1), weighs styrene derivative 76.7g shown in formula (2)
(0.65mol) is fitted into constant pressure funnel, is warming up to 140 DEG C, and styrene derivative is added dropwise, and 12h is dripped off.It is weighed again containing 30
Alkene 252.0g (0.6mol) shown in the formula (3) of a carbon, is added at one time reaction flask, is warming up to 180 DEG C, is stirred to react 0.5
Hour, stop reaction.Cooling is added 200ml 120# solvent naphtha, material is poured into separatory funnel, static layering, liquid separation removes
Sub-cloud catalyst, is removed under reduced pressure solvent naphtha, obtains amber transparent long-chain aralkyl bigcatkin willow acid product 396.9g, yield
91.7%.Bromine number: 1.7gBr/100g, acid value: 70.2mgKOH/g.
In the above reaction raw materials, M is normal-butyl, X in formula (1)1For H, X2It is 4- methyl；R in formula (2)1For methyl, R2、R3、
X3、X4For H；R in formula (3)4It is H, R5It is branch C28 alkyl.
Embodiment 5: the salicylic method of alkylaryl is prepared
Acid white equipped with being added in condenser, thermometer, constant pressure funnel and churned mechanically 500ml four-hole bottle
Salicyclic acid derivatives 75.6g (0.5mol) shown in native 10.0g, formula (1), weighs styrene derivative 76.7g shown in formula (2)
(0.65mol) is fitted into constant pressure funnel, is warming up to 140 DEG C, and styrene derivative is added dropwise, and 12h is dripped off.It is weighed again containing 30
Alkene 252.0g (0.6mol) shown in the formula (3) of a carbon, is added at one time reaction flask, is warming up to 180 DEG C, is stirred to react 0.5
Hour, stop reaction.Cooling is added 200ml 120# solvent naphtha, material is poured into separatory funnel, static layering, liquid separation removes
Sub-cloud catalyst, is removed under reduced pressure solvent naphtha, obtains amber transparent long-chain aralkyl bigcatkin willow acid product 376.8g, yield
93.2%.Bromine number: 1.5gBr/100g.Acid value: 73.8mgKOH/g:
In the above reaction raw materials, M, X in formula (1)1For H, X2It is 4- methyl；R in formula (2)1, R2、R3、X3For H, X4For 4- first
Base；R in formula (3)4It is H, R5It is branch C28 alkyl.
Embodiment 6: the salicylic method of alkylaryl is prepared
Equipped in condenser, thermometer, constant pressure funnel and churned mechanically 5000ml four-hole bottle, methyl sulphur is added
Salicyclic acid derivatives 691.0g (5mol) shown in sour 96.0g, formula (1), weighs styrene derivative 677.0g shown in formula (2)
(6.5mol) is fitted into constant pressure funnel, is warming up to 140 DEG C, and styrene derivative is added dropwise, and 8h is dripped off.It is weighed again containing 14
Alkene 1178.0g (6.0mol) shown in the formula (3) of carbon, is added at one time reaction flask, is warming up to 160 DEG C, it is small to be stirred to react 12
When, stop reaction.Cooling is added 2000ml 120# solvent naphtha, material is poured into separatory funnel, static layering, and liquid separation removes
Lower catalyst agent, is removed under reduced pressure solvent naphtha, obtains amber transparent long-chain aralkyl bigcatkin willow acid product 2412.0g, yield 94.7%.
Bromine number: 1.8gBr/100g, acid value: 114.3mgKOH/g.
In the above reaction raw materials, M, X in formula (1)1And X2It is H；R in formula (2)1、R2、R3、X3、X4It is H；R in formula (3)4
For H, R5For straight chain C12Alkyl.
Embodiment 7: the salicylic method of alkylaryl is prepared
Acid white equipped with being added in condenser, thermometer, constant pressure funnel and churned mechanically 1000ml four-hole bottle
Salicyclic acid derivatives 209.2g (0.5mol) shown in native 10.0g, formula (1), weighs styrene derivative shown in formula (2)
158.9g (0.65mol) is fitted into constant pressure funnel, is warming up to 140 DEG C, and styrene derivative is added dropwise, and 12h is dripped off.It weighs again
Alkene 252.0g (0.6mol) shown in formula (3) containing 30 carbon, is added at one time reaction flask, is warming up to 180 DEG C, stirring is anti-
It answers 0.5 hour, stops reaction.Cooling is added 200ml 120# solvent naphtha, material is poured into separatory funnel, static layering, point
Liquid removes lower catalyst agent, and solvent naphtha is removed under reduced pressure, obtains amber transparent long-chain aralkyl bigcatkin willow acid product 566.0g, yield
91.3%.Bromine number: 1.2gBr/100g.Acid value: 49.5mgKOH/g:
In the above reaction raw materials, M is H, X in formula (1)1, X2It is C10 straight chained alkyl；R in formula (2)1, R2、R3、X3For H, X4
For C10 branched alkyl；R in formula (3)4It is H, R5It is branch C28 alkyl.
Embodiment 8: the salicylic method of alkylaryl is prepared
Acid white equipped with being added in condenser, thermometer, constant pressure funnel and churned mechanically 1500ml four-hole bottle
Salicyclic acid derivatives 209.4g (0.5mol) shown in native 10.0g, formula (1), weighs styrene derivative shown in formula (2)
434.4g (0.65mol) is fitted into constant pressure funnel, is warming up to 140 DEG C, and styrene derivative is added dropwise, and 12h is dripped off.It weighs again
Alkene 252.0g (0.6mol) shown in formula (3) containing 30 carbon, is added at one time reaction flask, is warming up to 180 DEG C, stirring is anti-
It answers 0.5 hour, stops reaction.Cooling is added 200ml 120# solvent naphtha, material is poured into separatory funnel, static layering, point
Liquid removes lower catalyst agent, and solvent naphtha is removed under reduced pressure, obtains amber transparent long-chain aralkyl bigcatkin willow acid product 836.7g, yield
93.4%.Bromine number: 1.3gBr/100g.Acid value: 0.8mgKOH/g.In the above reaction raw materials, M, X in formula (1)1For C10 alkyl, X2
It is H；R in formula (2)1It is H, R2It is C4 alkyl, R3It is H, X3For C10 alkyl, X4For H；R in formula (3)4It is branch C28 alkyl, R5It is
H。
Embodiment 9: the salicylic method of alkylaryl is prepared
Acid white equipped with being added in condenser, thermometer, constant pressure funnel and churned mechanically 1000ml four-hole bottle
Salicyclic acid derivatives 279.3g (0.5mol) shown in native 10.0g, formula (1), weighs styrene derivative shown in formula (2)
76.7g (0.65mol) is fitted into constant pressure funnel, is warming up to 140 DEG C, and styrene derivative is added dropwise, and 12h is dripped off.It weighs again
Alkene 252.0g (0.6mol) shown in formula (3) containing 30 carbon, is added at one time reaction flask, is warming up to 180 DEG C, stirring is anti-
It answers 0.5 hour, stops reaction.Cooling is added 200ml 120# solvent naphtha, material is poured into separatory funnel, static layering, point
Liquid removes lower catalyst agent, and solvent naphtha is removed under reduced pressure, obtains amber transparent long-chain aralkyl bigcatkin willow acid product 573.9g, yield
94.4%.Bromine number: 1.4gBr/100g.Acid value: 0.5mgKOH/g.In the above reaction raw materials, M, X in formula (1)1For C10 branched alkane
Base, X2It is C10 straight chained alkyl；R in formula (2)1It is C4 alkyl, R2It is ethyl, R3It is ethyl, X3For H, X4For methyl；R in formula (3)4
It is H, R5It is branch C28 alkyl.
Embodiment 10: the synthesis of super basicity alkyl aryl salicylic acid calcium salt detersive
Room temperature is added pseudocumene 210g into 1000mL flask, 2 centistokes(cst) II class hydrogenated oil 45g, calcium hydroxide 4.8g and
Calcium oxide 6g, succinic acid 6g, aphthenic acids 3g, stearic acid 2g are stirred evenly and are warming up to 60 DEG C, and the alkane in embodiment 1 is then added dropwise
Base aryl salicylic acid 100g maintains 85-88 DEG C of reaction 50min of temperature.System cools to 45 DEG C hereinafter, promotor (ammonium hydroxide is added
With the mixture of ethylenediamine, matched according to molar ratio 1:0.1) 1g.24g calcium hydroxide (or being added before neutralizing) is added to system,
Temperature is adjusted between 35-39 DEG C, carbon dioxide is passed through with 145m L/min speed, carbon dioxide intake is the lime being added
The 40% of gross mass controls carbonation temperature at 37-38 DEG C, and distillation removes promotor, water and solvent.While hot by super basicity alkyl
Aryl salicylic acid calcium salt crude product is centrifuged with supercentrifuge, isolates a small amount of unreacted lime and solid carbonic acid calcium
Equal impurity, the base number for obtaining product is 450mgKOH/g, viscosity (100 DEG C) 65.04mm2/ s, flash-point are open >=190 DEG C, turbidity
19.2JTU.Crankcase simulation test: 0.5 grade；Plastic weight gain 12mg.
Embodiment 11: the synthesis of super basicity alkyl aryl salicylic acid calcium salt detersive
Solvent naphtha 250g, 5 centistokes(cst) II class hydrogenated oil 35g, calcium hydroxide 4.9g are added into 1000mL flask for room temperature
It stirs evenly with calcium oxide 6.1g, stearic acid 10g and is warming up to 60 DEG C, the alkylaryl salicylic acid in embodiment 2 is then added dropwise
100g maintains 85-88 DEG C of reaction 60min of temperature.System cools to 45 DEG C hereinafter, promotor (ammonium hydroxide and diethylenetriamine is added
Mixture, according to molar ratio 1:0.3 match) 10g.24g calcium hydroxide (or being added before neutralizing) is added to system, adjusts temperature
Between 38-39 DEG C, carbon dioxide is passed through with 150m L/min speed, carbon dioxide intake is the lime gross mass being added
50%, control carbonation temperature is at 35-39 DEG C, 160-170 DEG C of distillation methanol removal, water and solvent.While hot by super basicity alkyl
Aryl salicylic acid calcium salt crude product is centrifuged with supercentrifuge, isolates a small amount of unreacted lime and solid carbonic acid calcium
Equal impurity, the base number for obtaining product is 446mgKOH/g, viscosity (100 DEG C) 125.02mm2/ s, flash-point are open >=195 DEG C, turbidity
23.4JTU.Crankcase simulation test: 1.0 grades；Plastic weight gain 15mg.
Embodiment 12: the synthesis of super basicity alkyl aryl salicylic acid calcium salt detersive
Light aromatic hydrocarbons 210g, paraffinic base low-viscosity neutral oil 40g, calcium hydroxide 5g and oxygen are added into 1000mL flask for room temperature
Change calcium 5.8g, formic acid 5.5g, stearic acid 7g are stirred evenly and be warming up to 60 DEG C, and the alkylaryl bigcatkin willow in embodiment 3 is then added dropwise
Sour 100g maintains 85-88 DEG C of reaction 55min of temperature.System cools to 40 DEG C, be added promotor (ammonium hydroxide and diethylenetriamine
Mixture is matched according to molar ratio 1:0.8) 8g.24g calcium hydroxide (or being added before neutralizing) is added to system, adjusts temperature and exists
Between 38-39 DEG C, carbon dioxide is passed through with 148m L/min speed, carbon dioxide intake is the lime gross mass being added
55%, at 35-39 DEG C, the reaction time controls in 2-3h control carbonation temperature.In 160-170 DEG C of removed under reduced pressure promotor, water
With solvent.Super basicity alkyl aryl salicylic acid calcium salt crude product is centrifuged with supercentrifuge at 150-155 DEG C, point
The impurity such as a small amount of unreacted lime and solid carbonic acid calcium are separated out, the base number for obtaining product is 452mgKOH/g, viscosity (100 DEG C)
171.41mm2/ s, flash-point are open >=200 DEG C, turbidity 44.1JTU, crankcase simulated experiment: 1.5 grades；Plastic weight gain 20mg.
The total base number of alkylaryl calcium salicylate in the embodiment of the present invention can from the 250mgKOH/g or so of the prior art
It directly is increased to 450mgKOH/g, provides high quality master for China's lubricating oil and the upgrading of additive integral product level
Agent.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention
Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (9)
1. a kind of preparation method of super basicity alkyl aryl salicylic acid calcium salt, which comprises the steps of:
(1) mixture for being mixed and made into solvent naphtha, base oil, lime, kicker adds surfactant and alkyl virtue
Base salicylic acid is stirred to react 50-60min at 85-88 DEG C, generates neutral alkylaryl salicylic acid calcium salt；
(2) cooling and addition promotor and calcium hydroxide in the neutral alkylaryl salicylic acid calcium salt, are passed through titanium dioxide
Carbon is to get super basicity alkyl aryl salicylic acid calcium salt；
Wherein, the salicylic chemical structural formula of the alkylaryl are as follows:
R1、R2、R3、X1、X2、X3、X4It is separately hydrogen atom, alkoxy or the linear chain or branched chain containing 1 to 10 carbon atom
Alkyl, R4、R5It is separately hydrogen atom or straight chained alkyl or branched alkyl containing 1 to 30 carbon atom, and R4And R5
The sum of carbon atom number be not less than 4；
Wherein, the solvent naphtha are as follows: any one or more mixing in naphtha, light aromatic hydrocarbons and pseudocumene, additional amount
For the 210-250% of alkylaryl salicylic acid quality；
The base oil is that low-viscosity mineral oil neutral oil, II class of low-viscosity oil and III class oil are any one or more of mixed
It closes, additional amount is the 35-45% of the alkylaryl salicylic acid quality；
The surfactant is the mixture of stearic acid, any one or two kinds in aphthenic acids, and additional amount is the alkane
The 5-10% of base aryl salicylic acid quality；
The kicker is C1-C4Organic carboxyl acid, additional amount be the alkylaryl salicylic acid quality 5-6%；
The promotor is the mixture of ammonium hydroxide and ethyleneamines, and additional amount is the 1- of the alkylaryl salicylic acid quality
10%.
2. the preparation method of super basicity alkyl aryl salicylic acid calcium salt according to claim 1, which is characterized in that the step
Suddenly in (1), the molar ratio of quick lime and white lime is 1:(0.5-4 in the lime).
3. the preparation method of super basicity alkyl aryl salicylic acid calcium salt according to claim 1, which is characterized in that the rush
Into in agent, the molar ratio of ammonium hydroxide and ethyleneamines is controlled in 1:(0.1-0.8) between.
4. the preparation method of super basicity alkyl aryl salicylic acid calcium salt according to claim 3, which is characterized in that ethyleneamines
Mixture including one or more of ethylenediamine, diethylenetriamine, triethylene tetramine.
5. the preparation method of super basicity alkyl aryl salicylic acid calcium salt according to claim 1, which is characterized in that the step
Suddenly in (2), promotor and hydroxide is added in the neutral alkylaryl salicylic acid calcium salt again when being cooled to 45 DEG C or less
Calcium.
6. the preparation method of super basicity alkyl aryl salicylic acid calcium salt according to claim 5, which is characterized in that the step
Suddenly it in (2), is cooled between 35-39 DEG C.
7. the preparation method of super basicity alkyl aryl salicylic acid calcium salt according to claim 1, which is characterized in that the step
Suddenly in (2), the speed that is passed through of the carbon dioxide is 145-150mL/min.
8. the preparation method of super basicity alkyl aryl salicylic acid calcium salt according to claim 1, which is characterized in that the step
Suddenly in (2), during being passed through carbon dioxide, at 35-39 DEG C, the reaction time is controlled in 2-3h for reaction temperature control.
9. the preparation method of super basicity alkyl aryl salicylic acid calcium salt according to claim 1, which is characterized in that the step
Suddenly in (2), obtained super basicity alkyl aryl salicylic acid calcium salt passes through the step of distilling, being centrifuged with purification.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1504451A (en) * | 2002-11-29 | 2004-06-16 | 中国石油天然气股份有限公司 | Novel preparing process for alkalinous alkyl salicylate |
| CN1673208A (en) * | 2004-03-24 | 2005-09-28 | 中国石油天然气股份有限公司 | Prepn process of calcium alkyl salicylate |
| CN1300287C (en) * | 2002-07-23 | 2007-02-14 | 克朗普顿公司 | Engine oil comprising overbased salicylates based on styrenated salicylic acid |
| EP2832831A1 (en) * | 2012-03-26 | 2015-02-04 | JX Nippon Oil & Energy Corporation | Lubricating oil composition for internal combustion engine |
| CN104387267A (en) * | 2014-11-21 | 2015-03-04 | 锦州康泰润滑油添加剂股份有限公司 | Preparation method of high-base-number hydrocarbyl calcium salicylate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300287C (en) * | 2002-07-23 | 2007-02-14 | 克朗普顿公司 | Engine oil comprising overbased salicylates based on styrenated salicylic acid |
| CN1504451A (en) * | 2002-11-29 | 2004-06-16 | 中国石油天然气股份有限公司 | Novel preparing process for alkalinous alkyl salicylate |
| CN1673208A (en) * | 2004-03-24 | 2005-09-28 | 中国石油天然气股份有限公司 | Prepn process of calcium alkyl salicylate |
| EP2832831A1 (en) * | 2012-03-26 | 2015-02-04 | JX Nippon Oil & Energy Corporation | Lubricating oil composition for internal combustion engine |
| CN104387267A (en) * | 2014-11-21 | 2015-03-04 | 锦州康泰润滑油添加剂股份有限公司 | Preparation method of high-base-number hydrocarbyl calcium salicylate |
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