CN105237392B - The preparation method of aralkyl salicylic acid and its derivative - Google Patents
The preparation method of aralkyl salicylic acid and its derivative Download PDFInfo
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- CN105237392B CN105237392B CN201510828994.0A CN201510828994A CN105237392B CN 105237392 B CN105237392 B CN 105237392B CN 201510828994 A CN201510828994 A CN 201510828994A CN 105237392 B CN105237392 B CN 105237392B
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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
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
- C07C65/105—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups polycyclic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/94—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of polycyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of six-membered aromatic rings
Abstract
The invention provides the preparation method of a kind of aralkyl salicylic acid and its derivative, methods described includes：In the presence of a catalyst, salicylic acid or derivatives thereof, styrene or derivatives thereof and alhpa olefin derivative is made to react, wherein, one or more of the catalyst in organic sulfonic acid, inorganic acid or Emathlite.In methods described, styrene derivative provides necessary oil-soluble with the long-chain aralkyl that alhpa olefin derivative is collectively forming for product.Compared with alkylated salicylamide acid derivative of the aromatic olefin for alkylating reagent is used alone, under the conditions of identical oil-soluble is ensured, its molecular weight is smaller, and acid number is higher, it is easier to the product of the more high-alkali value of synthesis.The method of the present invention is easy to operate, and step is clear and definite, favorable reproducibility, and reaction yield is high, and the bromine number of products therefrom is low.
Description
Technical field
The present invention relates to chemical field, in particular to the preparation method of a kind of aralkyl salicylic acid and its derivative.
Background technology
Alkyl salicylate salt compound due to preferable high temperature detergency and certain antioxygen, resistance to corrosion,
It is widely used in lube oil additive field.The long-chain olefin that alkyl is typically made up of 4~30 carbon atoms provides, or by benzene
Ethene derivatives provide.The alkali reserve (being represented with total base number TNB) of alkylsalicylate is higher, and what it can be neutralized adds added with this
Add the amount of caused acidic combustion products in the oil of agent bigger, its peace and quiet effect is better.
Patent US2004097750 and US2004127743 are reported in perfluoro alkyl sulfonic acid, alkyl sulfonic acid or acid viscosity
In the presence of, the salicylic method of olefin alkylation synthesis of alkyl of salicylic acid and at least four carbon atom.Particularly with C14 and
Above linear alpha-alkene and salicylism reaction, then neutralized carbonating form high alkaline compound.The alkyl obtained by the method
Calcium salicylate detersive is tested through panel coker shows compared with overbased sulfonate, there is more preferable high-temperature cleaning
Energy.
Patent US20040138076 reports a kind of machine containing the salicylic high alkaline salicylate of styrene-based base
Oil.Wherein, styryl salicylic acid presses >=8 by styrene and salicylic acid:Prepared by 1 molar ratio reaction, multiple styrene chains provide
Necessary oil-soluble, resulting high alkaline salicylate have the spatter property and antioxygen better than conventional salicylate detergent
The property changed.But because styrene and salicylism reaction feed intake mole bigger, obtained alkyl salicylate molecular weight is big, product
Acid number is low, it is difficult to synthesis more high base number product, therefore limit its use.
In view of this, it is special to propose the present invention.
The content of the invention
It is an object of the invention to provide the preparation method of a kind of aralkyl salicylic acid and its derivative, methods described energy gram
The deficiency of existing styryl salicylic acid synthetic technology is taken, by salicyclic acid derivatives and styrene derivative and alpha-olefin derived
Thing reaction prepares a kind of new long-chain aralkyl salicyclic acid derivatives.What styrene derivative was collectively forming with alpha-olefin derived thing
Long-chain aralkyl provides necessary oil-soluble for product.Spread out with aromatic olefin is used alone for the alkyl salicylate of alkylating reagent
Biofacies ratio, under the conditions of identical oil-soluble is ensured, its molecular weight is smaller, and acid number is higher, it is easier to the more high-alkali value of synthesis
Product, the preparation available for environment-protective lubricant oil additive.Long-chain can be obtained with outstanding yield using the method for the present invention
Aralkyl salicylic acid, target product can be controlled by feeding intake, and meet the high oil-soluble of HMW or low molecule amount peracid
The different demands of value.In addition, the present invention can be carried out on the basis of inventory is more saved, its extend to it is fairly large
When, can be significantly cost-effective.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
The present invention relates to the preparation method of a kind of aralkyl salicylic acid and its derivative, methods described includes：In catalyst
In the presence of, salicylic acid or derivatives thereof, styrene or derivatives thereof and alpha-olefin derived thing is reacted, wherein, it is described to urge
One or more of the agent in organic sulfonic acid, inorganic acid or Emathlite.
The raw material and catalyst of the present invention is that this area is common and be readily obtained, and styrene derivative spreads out with alpha-olefin
The long-chain aralkyl that biology is collectively forming provides necessary oil-soluble for product.It is alkylating reagent with aromatic olefin is used alone
Alkylated salicylamide acid derivative compare, under the conditions of identical oil-soluble is ensured, its molecular weight is smaller, and acid number is higher, it is easier to
The product of the more high-alkali value of synthesis.
Preferably, shown in the structural formula of described salicylic acid or derivatives thereof such as formula (1)：
Wherein X1、X2It is separately matter for hydrogen atom or the direct-connected or branched paraffin containing 1 to 10 carbon atom, M
Son, metal, alkali metal ion or the straight or branched alkyl containing 1 to 10 carbon atom；It is highly preferred that X1、X2Separately
Direct-connected or branched paraffin for hydrogen atom or containing 1 to 4 carbon atom, M are proton, metal, alkali metal ion or contain 1 to 4
The straight or branched alkyl of individual carbon atom.
Preferably, shown in the structural formula of described 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 R3Carbon number sum 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 scope of its substituent is quite varied, in theory for, it is any
The substituent not had an impact to reaction is optionally substituted base.
Preferably, shown in the structural formula such as formula (3) of the alpha-olefin derived thing：
Wherein, R4、R5It is separately hydrogen atom or straight chained alkyl or branched alkyl containing 1 to 28 carbon atom, and
And R4And R5Carbon number sum be not less than 4, it is highly preferred that R4、R5It is separately hydrogen atom or contains 1 to 28 carbon
The straight chained alkyl or branched alkyl of atom, and R4And R5Carbon number sum be not less than 6.
R4、R5Selection be directly connected to the property of product, its containing carbon number it is smaller when can make it that product has relatively large
Acid number, so as to beneficial to preparing the product of base number, and correspondingly, its oil-soluble can be affected.In contrast, when its is carbon containing
When number is higher, its oil-soluble is preferable, but because the increase of its molecular weight, its product acid number are relatively low.
Preferably, the organic sulfonic acid is one kind in p-methyl benzenesulfonic acid or methanesulfonic acid；The inorganic acid is Bronsted acid, more
One or more in preferably sulfuric acid, hydrochloric acid, phosphoric acid.
In order to obtain the aralkyl salicylic acid and its derivative that molecular weight is smaller, acid number is higher, it is preferable that the salicylic acid
Or derivatives thereof, the mol ratio of styrene or derivatives thereof and alpha-olefin derived thing be 1：(1-5)：(1-5), more preferably 1：
1.3：1.2.
Preferably, methods described comprises the following steps that：
1) organic sulfonic acid, inorganic acid or Emathlite catalyst and salicylic acid or derivatives thereof are placed in reactor
In；
2) stir, and styrene or derivatives thereof is added dropwise into reactor；
3) stir, add the alpha-olefin derived thing and reacted.
From above step as can be seen that in the method for the invention, the reaction carried out can be in the absence of a solvent
Carry out.When reaction uses laboratory scale, the reactor of step 1) should be selected equipped with condenser, thermometer, constant pressure addition leakage
Bucket and churned mechanically four-hole bottle, ensure that reaction system can carry out temperature control and realize backflow in a heated condition.In addition, step
2) constant pressure funnel can be used to be added dropwise in, and the alpha-olefin derived thing in step 3) can disposably add system
In.The step of the present invention is the step of being easily achieved, and requires very not harsh to operation, and can be amplified to industrial rule
Mould.
Preferably, in the step 2), styrene or derivatives thereof is added dropwise and is carried out under the conditions of 120-160 DEG C, it is more excellent
Elect 140 DEG C as.
Preferably, in the step 3), the temperature of the reaction is 140-180 DEG C, is more preferably heated to 160 DEG C.
Preferably, the dropwise operation in the step 2) continues 0.5-12 hours, more preferably lasting 8-12 hours；The step
It is rapid 3) in, add after alpha-olefin derived thing and continue stirring 0.5 to 24 hour, more preferably continue to stir 10-12 hours.
The method of the present invention, heating, the time of stirring reaction in its step are optimized by many experiments.Optimization
Reaction afterwards can be carried out under room temperature to the conventional reaction temperature in this area.
Compared with prior art, beneficial effects of the present invention are：
(1) it is molten with long-chain aralkyl that alpha-olefin derived thing is collectively forming to provide necessary oil for product for styrene derivative
Property.Compared with alkylated salicylamide acid derivative of the aromatic olefin for alkylating reagent is used alone, ensureing identical oil-soluble bar
Under part, its molecular weight is smaller, and acid number is higher, it is easier to the product of the more high-alkali value of synthesis.
(2) method of the invention is easy to operate, and step is clear and definite, favorable reproducibility, and reaction yield is high, the bromine number of products therefrom
It is low.
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 present invention.It is unreceipted specific in embodiment
Condition person, the condition suggested according to normal condition or manufacturer are carried out.Agents useful for same or the unreceipted production firm person of instrument, it is
The conventional products of commercially available acquisition can be passed through.
Reactive chemistry formula in embodiment 1-5 is as follows：
Embodiment 1
In equipped with condenser, thermometer, constant pressure funnel and churned mechanically 500ml four-hole bottles, methyl sulphur is added
Salicyclic acid derivatives 69.1g (0.5mol) shown in sour 9.6g, formula (1), weighs the 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.Weigh again containing 14
Alkene 117.8g (0.6mol) shown in the formula (3) of individual carbon, disposably adds reaction bulb, is warming up to 160 DEG C, stirring reaction 12 is small
When, stop reaction.Cooling, 200ml 120# solvent naphthas are added, material are poured into separatory funnel, static layering, liquid separation removes
Lower catalyst agent, removal of solvent under reduced pressure oil, obtains amber transparent long-chain aralkyl bigcatkin willow acid product 239.6g, yield 94.1%.
Bromine number：1.7gBr/100g, acid number：115.8mgKOH/g.
In 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 the alkyl of straight chain C 12.
Embodiment 2
In equipped with condenser, thermometer, constant pressure funnel and churned mechanically 500ml four-hole bottles, methyl sulphur is added
Salicyclic acid derivatives 83.1g (0.5mol) shown in sour 9.6g, formula (1), weighs the 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) is weighed again
Shown alkene 67.3g (0.6mol), disposably adds reaction bulb, is warming up to 140 DEG C, stirring reaction 10 hours, stops reaction.
Cooling, 200ml 120# solvent naphthas are added, material are poured into separatory funnel, static layering, 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 number：1.3mgKOH/g.
In above reaction raw materials, M is methyl in formula (1), X1For 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.
Experimental example 3
In equipped with condenser, thermometer, constant pressure funnel and churned mechanically 500ml four-hole bottles, methyl sulphur is added
Salicyclic acid derivatives 136.1g (0.5mol) shown in sour 9.6g, formula (1), weighs the 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) is weighed again
Shown alkene 67.3g (0.6mol), disposably adds reaction bulb, is warming up to 180 DEG C, stirring reaction 24 hours, stops reaction.
Cooling, 200ml 120# solvent naphthas are added, material are poured into separatory funnel, static layering, 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 number：1.2mgKOH/g.
In above reaction raw materials, M is Na in formula (1)+, X1It is methyl, X2It is side chain 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
In equipped with condenser, thermometer, constant pressure funnel and churned mechanically 500ml four-hole bottles, methyl sulphur is added
Salicyclic acid derivatives 104.1g (0.5mol) shown in sour 9.6g, formula (1), weighs the 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.Weigh again containing 30
Alkene 252.0g (0.6mol) shown in the formula (3) of individual carbon, disposably adds reaction bulb, is warming up to 180 DEG C, stirring reaction 0.5
Hour, stop reaction.Cooling, 200ml 120# solvent naphthas are added, material are poured into separatory funnel, static layering, liquid separation removes
Sub-cloud catalyst, removal of solvent under reduced pressure oil, obtains amber transparent long-chain aralkyl bigcatkin willow acid product 396.9g, yield
91.7%.Bromine number：1.7gBr/100g, acid number：70.2mgKOH/g.
In above reaction raw materials, M is normal-butyl in formula (1), X1For 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 side chain C28 alkyl.
Embodiment 5
In equipped with condenser, thermometer, constant pressure funnel and churned mechanically 500ml four-hole bottles, add acid white
Salicyclic acid derivatives 75.6g (0.5mol) shown in native 10.0g, formula (1), weighs the 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.Weigh again containing 30
Alkene 252.0g (0.6mol) shown in the formula (3) of individual carbon, disposably adds reaction bulb, is warming up to 180 DEG C, stirring reaction 0.5
Hour, stop reaction.Cooling, 200ml 120# solvent naphthas are added, material are poured into separatory funnel, static layering, liquid separation removes
Sub-cloud catalyst, removal of solvent under reduced pressure oil, obtains amber transparent long-chain aralkyl bigcatkin willow acid product 376.8g, yield
93.2%.Bromine number：1.5gBr/100g.Acid number：73.8mgKOH/g：
In 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 side chain C28 alkyl.
Embodiment 6
In equipped with condenser, thermometer, constant pressure funnel and churned mechanically 5000ml four-hole bottles, methyl sulphur is added
Salicyclic acid derivatives 691.0g (5mol) shown in sour 96.0g, formula (1), weighs the 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.Weigh again containing 14
Alkene 1178.0g (6.0mol) shown in the formula (3) of carbon, disposably adds reaction bulb, is warming up to 160 DEG C, stirring reaction 12 is small
When, stop reaction.Cooling, 2000ml 120# solvent naphthas are added, material are poured into separatory funnel, static layering, liquid separation removes
Lower catalyst agent, removal of solvent under reduced pressure oil, obtains amber transparent long-chain aralkyl bigcatkin willow acid product 2412.0g, yield 94.7%.
Bromine number：1.8gBr/100g, acid number：114.3mgKOH/g.
In 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 the alkyl of straight chain C 12.
Embodiment 7
In equipped with condenser, thermometer, constant pressure funnel and churned mechanically 1000ml four-hole bottles, add acid white
Salicyclic acid derivatives 209.2g (0.5mol) shown in native 10.0g, formula (1), weighs the 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.Weigh again
Alkene 252.0g (0.6mol) shown in formula (3) containing 30 carbon, disposably adds reaction bulb, is warming up to 180 DEG C, stirring is anti-
Answer 0.5 hour, stop reaction.Cooling, 200ml 120# solvent naphthas are added, material are poured into separatory funnel, static layering, point
Liquid removes lower catalyst agent, removal of solvent under reduced pressure oil, obtains amber transparent long-chain aralkyl bigcatkin willow acid product 566.0g, yield
91.3%.Bromine number：1.2gBr/100g.Acid number：49.5mgKOH/g：
In above reaction raw materials, M is H, X in formula (1)1, X2It is C10 straight chained alkyls；R in formula (2)1, R2、R3、X3For H, X4
For C10 branched alkyls；R in formula (3)4It is H, R5It is side chain C28 alkyl.
Embodiment 8
In equipped with condenser, thermometer, constant pressure funnel and churned mechanically 1500ml four-hole bottles, add acid white
Salicyclic acid derivatives 209.4g (0.5mol) shown in native 10.0g, formula (1), weighs the 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.Weigh again
Alkene 252.0g (0.6mol) shown in formula (3) containing 30 carbon, disposably adds reaction bulb, is warming up to 180 DEG C, stirring is anti-
Answer 0.5 hour, stop reaction.Cooling, 200ml 120# solvent naphthas are added, material are poured into separatory funnel, static layering, point
Liquid removes lower catalyst agent, removal of solvent under reduced pressure oil, obtains amber transparent long-chain aralkyl bigcatkin willow acid product 836.7g, yield
93.4%.Bromine number：1.3gBr/100g.Acid number：0.8mgKOH/g.In 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 side chain C28 alkyl, R5It is
H。
Embodiment 9
In equipped with condenser, thermometer, constant pressure funnel and churned mechanically 1000ml four-hole bottles, add acid white
Salicyclic acid derivatives 279.3g (0.5mol) shown in native 10.0g, formula (1), weighs the 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.Weigh again
Alkene 252.0g (0.6mol) shown in formula (3) containing 30 carbon, disposably adds reaction bulb, is warming up to 180 DEG C, stirring is anti-
Answer 0.5 hour, stop reaction.Cooling, 200ml 120# solvent naphthas are added, material are poured into separatory funnel, static layering, point
Liquid removes lower catalyst agent, removal of solvent under reduced pressure oil, obtains amber transparent long-chain aralkyl bigcatkin willow acid product 573.9g, yield
94.4%.Bromine number：1.4gBr/100g.Acid number：0.5mgKOH/g.In above reaction raw materials, M, X in formula (1)1For C10 branched alkanes
Base, X2It is C10 straight chained alkyls；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 side chain C28 alkyl.
From above example and comparative example it is apparent that with aromatic olefin is used alone as alkylating reagent
Alkylated salicylamide acid derivative is compared, and method of the invention is under the conditions of identical oil-soluble is ensured, its molecular weight is smaller, and acid number is more
It is high, it is easier to the product of the more high-alkali value of synthesis.In addition, the method for the present invention is easy to operate, step is clear and definite, favorable reproducibility, and
Reaction yield is high, and the bromine number of products therefrom is low.
Although illustrate and describing the present invention with specific embodiment, but will be appreciated that without departing substantially from the present invention's
Many other change and modification can be made in the case of 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 (17)
1. the preparation method of a kind of long-chain aralkyl salicylic acid and its derivative, it is characterised in that methods described includes：It is being catalyzed
In the presence of agent, salicylic acid or derivatives thereof, styrene or derivatives thereof and alpha-olefin derived thing is set to react, wherein, it is described
One or more of the catalyst in organic sulfonic acid, inorganic acid or Emathlite；
Methods described comprises the following steps that：
1) organic sulfonic acid, inorganic acid or Emathlite catalyst and salicylic acid or derivatives thereof are placed in reactor；
2) stir, and styrene or derivatives thereof is added dropwise into reactor under the conditions of 120-160 DEG C；
3) stir, add the alpha-olefin derived thing and reacted.
2. according to the method for claim 1, it is characterised in that the structural formula of described salicylic acid or derivatives thereof such as formula (1)
It is shown：
Wherein X1、X2It is separately hydrogen atom or the direct-connected or branched paraffin containing 1 to 10 carbon atom, M is proton, gold
Belong to ion or the straight or branched alkyl containing 1 to 10 carbon atom.
3. according to the method for claim 2, it is characterised in that X1、X2It is separately hydrogen atom or contains 1 to 4 carbon
The direct-connected or branched paraffin of atom, M are proton, alkali metal ion or the straight or branched alkyl containing 1 to 4 carbon atom.
4. according to the method for claim 1, it is characterised in that the structural formula of described styrene or derivatives thereof such as formula (2)
It is shown：
Wherein R1、R2、R3、X3、X4It is separately hydrogen atom or the direct-connected or branched paraffin containing 1 to 10 carbon atom.
5. according to the method for claim 4, it is characterised in that R1、R2、R3、X3、X4Separately hydrogen atom or to contain
The direct-connected or branched paraffin of 1 to 4 carbon atom, and meet R2And R3Carbon number sum be not more than 4.
6. according to the method for claim 5, it is characterised in that R1、R2、R3、X3、X4It is hydrogen atom.
7. according to the method for claim 1, it is characterised in that shown in the structural formula such as formula (3) of the alpha-olefin derived thing：
Wherein, R4、R5It is separately hydrogen atom or straight chained alkyl or branched alkyl containing 1 to 30 carbon atom, and R4
And R5Carbon number sum be not less than 4.
8. according to the method for claim 7, it is characterised in that R4、R5Separately for hydrogen atom or contain 1 to 28
The straight chained alkyl or branched alkyl of carbon atom, and R4And R5Carbon number sum be not less than 6.
9. according to the method for claim 1, it is characterised in that the organic sulfonic acid is in p-methyl benzenesulfonic acid or methanesulfonic acid
It is a kind of；The inorganic acid is Bronsted acid.
10. according to the method for claim 9, it is characterised in that the inorganic acid is one kind in sulfuric acid, hydrochloric acid, phosphoric acid
It is or a variety of.
11. according to the method for claim 1, it is characterised in that described salicylic acid or derivatives thereof, styrene or its derivative
The mol ratio of thing and alpha-olefin derived thing is 1：(1-5)：(1-5).
12. according to the method for claim 11, it is characterised in that described salicylic acid or derivatives thereof, styrene or its spread out
The mol ratio 1 of biology and alpha-olefin derived thing：1.3：1.2.
13. according to the method for claim 1, it is characterised in that styrene or derivatives thereof is added dropwise and enters under the conditions of 140 DEG C
OK.
14. according to the method for claim 1, it is characterised in that in the step 3), the temperature of the reaction is 140-
180℃。
15. according to the method for claim 14, it is characterised in that the temperature of the reaction is 160 DEG C.
16. according to the preparation method described in right 1, it is characterised in that it is small that the dropwise operation in the step 2) continues 0.5-12
When；In the step 3), continue stirring 0.5 to 24 hour after adding alpha-olefin derived thing.
17. according to the method for claim 16, it is characterised in that add after alpha-olefin derived thing continue to stir 10-12 it is small
When.
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