CN107986961B - Process for preparing alkyl salicylic acid and/or alkyl salicylate - Google Patents

Process for preparing alkyl salicylic acid and/or alkyl salicylate Download PDF

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CN107986961B
CN107986961B CN201610942309.1A CN201610942309A CN107986961B CN 107986961 B CN107986961 B CN 107986961B CN 201610942309 A CN201610942309 A CN 201610942309A CN 107986961 B CN107986961 B CN 107986961B
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salicylic acid
salicylate
olefin
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刘依农
段庆华
张耀
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Abstract

The invention provides a preparation method of alkyl salicylic acid and/or alkyl salicylate. The preparation method of alkyl salicylic acid and/or alkyl salicylate of the invention comprises the following steps: carrying out alkylation reaction on alpha-olefin, salicylic acid and/or salicylate under the action of a catalyst, and collecting a product; the catalyst is obtained by mixing ionic liquid, polyphosphoric acid and organic acid salt for 1-12 hours at 30-100 ℃. The method has the advantages of high conversion rate, good product selectivity, relatively mild reaction conditions, easy catalyst recovery and the like, and is a green and pollution-free preparation process.

Description

Process for preparing alkyl salicylic acid and/or alkyl salicylate
Technical Field
The invention relates to alkyl salicylic acid and alkyl salicylate, in particular to a preparation method of the alkyl salicylic acid and the alkyl salicylate.
Background
The calcium alkyl salicylate is one of the lubricating oil detergents appearing in the early 40 th of the 20 th century, has good high-temperature detergency, acid neutralization capacity, higher thermal stability, certain low-temperature dispersing capacity and oxidation and corrosion resistance, does not contain elements such as sulfur, phosphorus and the like, and is particularly suitable for being used as a detergent for internal combustion engine oil.
The traditional production process of the alkyl salicylate has more problems, wherein the more outstanding problems are that the preparation process of the alkyl salicylic acid follows Kolbe-Schmidt (Kolbe-Schmidt) reaction, the preparation of the calcium alkyl salicylate by using alkylphenol as an initial raw material has five or six steps of reaction, more than ten steps of process are very complicated, and overlong process causes potential safety hazard increase, overhigh production cost and serious environmental protection problem. Meanwhile, the use of strong acid and strong base causes severe corrosion to equipment. Therefore, it is necessary to develop a new process for alkyl salicylic acid.
CN 103508881 discloses a method for synthesizing alkyl salicylic acid, which comprises mixing C4-50 olefin with salicylic acid, and carrying out alkylation reaction at 50-160 ℃ under the catalysis of aryl sulfonic acid. The invention adopts aryl sulfonic acid as a catalyst, the conversion rate can reach 60-95%, but the method has long reaction time, and the catalyst is difficult to reuse after the reaction.
CN 103508882 discloses a method for preparing alkyl salicylic acid, which comprises the steps of mixing olefin with 6-50 carbon atoms with salicylic acid, and carrying out alkylation reaction at 80-150 ℃ under the catalysis of mixed acid of methanesulfonic acid and 98% concentrated sulfuric acid. The invention adopts mixed acid as catalyst, and the conversion rate can reach 60-80%. The disadvantages of this process are the long reaction times and the high costs of the post-treatment of the catalyst due to the incorporation of concentrated sulfuric acid.
CN 1708470 discloses a process for the preparation of alkyl salicylic acids by reacting salicylic acid with an olefin having at least four carbon atoms at elevated temperature in the presence of a perfluoroalkylsulfonic acid, an alkylsulfonic acid or an acidic clay.
US 7045654 discloses a process for the preparation of alkyl salicylic acids by reaction of an olefin having at least 4 carbon atoms with salicylic acid at elevated temperature using a catalyst which is a perfluorosulphonic acid or acid clay, which process is long lasting and difficult to recycle after reaction.
EP 0771782 discloses a process for preparing alkyl salicylic acid, wherein sulfuric acid is used as a catalyst, and olefin with at least 6 carbon atoms is used as a raw material to prepare the alkyl salicylic acid.
As can be seen from the above patents, when alkyl salicylic acid is directly synthesized from salicylic acid and olefin, the reaction conditions are relatively severe, and the catalyst post-treatment cost is high, so that the method for synthesizing alkyl salicylic acid needs to be further improved.
Disclosure of Invention
The invention provides a preparation method of alkyl salicylic acid and/or alkyl salicylate.
The preparation method of alkyl salicylic acid and/or alkyl salicylate of the invention comprises the following steps: carrying out alkylation reaction on alpha-olefin, salicylic acid and/or salicylate under the action of a catalyst, and collecting a product; the catalyst is obtained by mixing ionic liquid, polyphosphoric acid and organic acid salt for 1-12 hours at 30-100 ℃.
The α -olefin is C10-C30α -olefins, preferably C12-C24α -olefins of (I), most preferably C14-C20α -olefin of (1).
The salicylate is C1-C4Salicylic acid esters of (2), preferably C1-C2Most preferably methyl salicylate.
The molar ratio of the salicylic acid and/or the salicylate to the alpha-olefin is (1-2): 1, preferably 1 to 1.6: 1, most preferably 1.1 to 1.3: 1.
the cation of the ionic liquid is alkyl imidazole or alkyl pyridine, and the anion of the ionic liquid is one of tetrafluoroborate, trifluoromethyl sulfonate, hexafluorophosphate, p-toluenesulfonic acid, nitrate, perchlorate, methanesulfonate, oxalate and hydrosulfate.
The alkyl imidazole has the structure:
Figure BDA0001140280090000021
wherein R is1、R2Are each independently selected from C1-C6Alkyl of (3), preferably C1-C4Alkyl group of (1).
The alkylpyridine has the structure:
Figure BDA0001140280090000022
wherein R is C1-C6Alkyl of (3), preferably C1-C4Alkyl group of (1).
The structure of the tetrafluoroborate, the trifluoromethyl sulfonate, the hexafluorophosphate, the p-toluenesulfonate, the nitrate, the perchlorate, the methanesulfonate, the oxalate and the hydrogensulfate is as follows in sequence:
Figure BDA0001140280090000031
Figure BDA0001140280090000032
the ionic liquid can be one or more of alkyl imidazole tetrafluoroborate, alkyl imidazole trifluoromethyl sulfonate, alkyl imidazole hexafluorophosphate, alkyl imidazole hydrosulfate, alkyl pyridine tetrafluoroborate, alkyl pyridine trifluoromethyl sulfonate, alkyl pyridine hexafluorophosphate and alkyl pyridine hexahydroate. The structure of the polyphosphoric acid is as follows: hn+2PnO3n+1Wherein n is a positive integer of 1 or more, preferably 1 to 3.
The polyphosphoric acid can be phosphoric acid (H)3PO4) Pyrophosphoric acid (H)4P2O7) And tripolyphosphoric acid (H)5P3O10) One or more of (a).
The organic acid salt is preferably a metal salt of an organic carboxylic acid and/or a metal salt of an organic sulfonic acid. The organic carboxylic acid is preferably C2-C18Most preferably C3-C15The fatty acid of (2). The organic sulfonic acid is preferably C6-C18With sulfonic acid or with C6-C18Benzenesulfonic acids with alkyl radicals, most preferably with C8-C16Alkyl benzene sulfonic acid. The metal is an alkali metal and/or an alkaline earth metal, such as one or more of lithium, sodium, potassium, calcium, magnesium and barium, preferably sodium and/or calcium.
The catalyst is prepared by mixing ionic liquid, polyphosphoric acid and organic acid salt for 1-12h at 30-100 ℃, wherein the mass ratio of the ionic liquid to the polyphosphoric acid to the organic acid salt is 100: 5-30: 5-20, preferably 100: 10-25: 5 to 15. The catalyst is added in an amount of 1-100%, preferably 2-50%, most preferably 3-10% of the mass sum of the alpha-olefin, salicylic acid and/or salicylate. The temperature of the alkylation reaction is 50-250 ℃, preferably 80-200 ℃, and most preferably 100-160 ℃.
The alkylation reaction time is 1-16 hours, preferably 2-12 hours, and most preferably 3-8 hours.
The method has the advantages of high conversion rate, good product selectivity, relatively mild reaction conditions, easy catalyst recovery and the like, and is a green and pollution-free preparation process.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to be limiting.
Unless otherwise specified, the percentages mentioned below are percentages by mass.
The raw material sources are as follows:
n-methylimidazole, 1-N-bromo-butane, all of analytical purity, purchased from Acros corporation;
ethyl acetate, NaBF4Dichloromethane, pyrophosphoric acid, metaphosphoric acid, tripolyphosphoric acid, NaHSO4Pyridine, trifluoromethanesulfonic acid, petroleum ether, sodium dodecylbenzenesulfonate, sodium caprate, salicylic acid, C16α -alkene, methanesulfonic acid are analytically pure and purchased from Beijing chemical agents of national drug group;
calcium dodecylbenzene sulfonate is prepared through double decomposition reaction of sodium dodecylbenzene sulfonate.
Catalyst IL-1 preparation example 1
Synthesis of 1-methyl-3-butylimidazole boron tetrafluoride salt-metaphosphoric acid-sodium dodecylbenzenesulfonate catalyst IL-1
1mol of N-methylimidazole and 1.05mol of 1-N-bromo-butane are added into a three-neck flask, and N is introduced2After purging for 20 mm, starting stirring and heating to 85 ℃ for 30-36 h. After the reaction is finished, standing and cooling to room temperature, wherein the lower layer of the solution is light yellow, and the upper layer of the solution is unreacted raw materials. The upper layer liquid was decanted, 3 times the volume of ethyl acetate was added to the lower layer liquid to wash, and then ethyl acetate was separated to remove unreacted raw materials. After washing, drying at 70 ℃ for 24h to obtain a light yellow viscous 1-methyl-3-butylimidazolium bromide salt.
The obtained 1-methyl-3-butylimidazolium bromide was dissolved in methylene chloride, and NaBF was added thereto4Stirring and reacting 1mol of aqueous solution at normal temperature for 24 hours. After the reaction is finished, washing the dichloromethane phase for a plurality of times by using a small amount of water, removing the dichloromethane by using a rotary evaporator, drying in vacuum,obtaining the ionic liquid 1-methyl-3-butyl imidazole boron tetrafluoride salt.
Adding 100 g of the synthesized 1-methyl-3-butylimidazole boron tetrafluoride salt into a three-neck flask, adding 10 g of metaphosphoric acid and 7 g of sodium dodecyl benzene sulfonate, heating to 75 ℃, and stirring for 3 hours to form yellow viscous liquid, namely the catalyst of the 1-methyl-3-butylimidazole boron tetrafluoride salt-metaphosphoric acid-sodium dodecyl benzene sulfonate, which is marked as IL-1.
Catalyst IL-2 preparation example 2
Synthesis of 1-methyl-3-butylimidazole hydrosulfate-tripolyphosphate-sodium caprate catalyst IL-2
1mol of N-methylimidazole and 1.05mol of 1-N-bromo-butane are added into a three-neck flask, and N is introduced2After purging for 20 mm, starting stirring and heating to 85 ℃ for 30-36 h. After the reaction is finished, standing and cooling to room temperature, wherein the lower layer of the solution is light yellow, and the upper layer of the solution is unreacted raw materials. The upper layer liquid was decanted, 3 times the volume of ethyl acetate was added to the lower layer liquid to wash, and then ethyl acetate was separated to remove unreacted raw materials. After washing, drying at 70 ℃ for 24h to obtain the light yellow viscous 1-methyl-3-butylimidazole bromide salt.
Dissolving the obtained 1-methyl-3-butylimidazolium bromide in methanol, adding NaHSO4Stirring and reacting 1mol of aqueous solution at normal temperature for 24 hours. And then carrying out suction filtration, removing methanol from the filtered clear liquid, and then carrying out vacuum drying to obtain the ionic liquid 1-methyl-3-butyl imidazole hydrosulfate.
Taking 100 g of the synthesized 1-methyl-3-butylimidazole hydrosulfate, adding the 1-methyl-3-butylimidazole hydrosulfate into a three-neck flask, adding 12 g of tripolyphosphoric acid, 8 g of sodium caprate, heating to 80 ℃, stirring for 3 hours to form yellow viscous liquid, namely the catalyst of the 1-methyl-3-butylimidazole hydrosulfate-tripolyphosphoric acid-sodium caprate, and marking the yellow viscous liquid as IL-2.
Catalyst IL-3 preparation example 3
Synthesis of N-butylpyridine trifluoromethanesulfonate-calcium pyrophosphate-dodecylbenzene sulfonate catalyst IL-3
Into a three-necked flask, 1mol of pyridine and 1.05mol of 1-N-chloro-butane were charged, and N was introduced2After purging for 20 mm, starting stirring and heating to 75 ℃ for 30-36 h. After the reaction is finished, standing and cooling to room temperature, wherein the lower layer of the solution is light yellow, and the upper layer of the solution is unreacted raw materials. The upper layer liquid was decanted, 3 times the volume of ether was added to the lower layer liquid to wash, and then the ether was separated to remove unreacted raw materials. After washing, the mixture was dried at 70 ℃ for 24 hours to obtain a pale yellow viscous N-butylpyridinium chloride salt.
Mixing the obtained N-butylpyridinium chloride and 1mol of trifluoromethanesulfonic acid in a three-neck flask, stirring at 50 ℃ for 24 hours, extracting and purifying with diethyl ether, removing the diethyl ether by rotation, and drying in vacuum to obtain the ionic liquid N-butylpyridinium trifluoromethanesulfonate.
And adding 100 g of the synthesized N-butylpyridine trifluoromethanesulfonate into a three-neck flask, adding 12 g of pyrophosphoric acid and 8 g of calcium dodecylbenzene sulfonate, heating to 65 ℃, and stirring for 5 hours to form a reddish brown viscous liquid, namely the N-butylpyridine trifluoromethanesulfonate-calcium pyrophosphoric acid-dodecylbenzene sulfonate catalyst, which is marked as IL-3.
Catalyst DIL-1 preparation comparative example 1
Synthesis of 1-methyl-3-butylimidazole boron tetrafluoride salt-metaphosphoric acid catalyst DIL-1
1mol of N-methylimidazole and 1.05mol of 1-N-bromo-butane are added into a three-neck flask, and N is introduced2After purging for 20 mm, starting stirring and heating to 85 ℃ for 30-36 h. After the reaction is finished, standing and cooling to room temperature, wherein the lower layer of the solution is light yellow, and the upper layer of the solution is unreacted raw materials. The upper layer liquid was decanted, 3 times the volume of ethyl acetate was added to the lower layer liquid to wash, and then ethyl acetate was separated to remove unreacted raw materials. After washing, drying at 70 ℃ for 24h to obtain the light yellow viscous 1-methyl-3-butylimidazole bromide salt.
Dissolving the obtained 1-methyl-3-butylimidazolium bromide in dichloromethane, and adding NaBF to the solution4Stirring and reacting 1mol of aqueous solution at normal temperature for 24 hours. After the reaction is finished, washing the dichloromethane phase for a few times by using a small amount of water to remove ions, then distilling to remove dichloromethane, and then drying in vacuum to obtain the ionic liquid 1-methyl-3-butylimidazole tetrafluorideA boron salt.
Adding 100 g of the synthesized 1-methyl-3-butylimidazole boron tetrafluoride salt into a three-neck flask, adding 22 g of metaphosphoric acid, heating to 75 ℃, and stirring for 3 hours to form yellow viscous liquid, namely the 1-methyl-3-butylimidazole boron tetrafluoride salt-metaphosphoric acid catalyst, which is marked as DIL-1.
The conversion rate of the alkyl salicylic acid after the alkylation reaction is converted by the residual amount of the alpha-olefin in the product.
EXAMPLE 4 Ionic liquid IL-1 catalyzed salicylic acid alkylation
A500 mL three-necked flask with temperature control, heating and stirring was charged with 20 g of catalyst IL-1 and 100 g of C16α -olefin (Mn 224.4, 0.446 mol), 70.78 g salicylic acid (Mn 138.12, 0.512 mol), nitrogen purge, stirring and heating were started, the temperature in the three-neck flask was controlled between 140 ℃ and 142 ℃, and the reaction was carried out for 5 hours.
After the reaction is finished, when the temperature of the materials is reduced to be below 40 ℃, the stirring is stopped, and 150 g No. 120 solvent gasoline is added. Taking out the materials in the three-neck flask, placing the materials in a separating funnel for layering, collecting the oil phase on the upper layer, washing the oil phase for three times by using 300 g of distilled water, removing unreacted salicylic acid in the oil phase, and drying the oil phase by using anhydrous magnesium sulfate to finally obtain the dark brown alkyl salicylic acid.
Analyzing the content of the residual alpha-olefin in the oil phase by using a gas chromatography external standard method, determining the acid value of the alkyl salicylic acid product according to an SH/T0092 petroleum acid test method, wherein the analysis result shows that the conversion rate of the alkyl salicylic acid is 90.2 percent, and the acid value of the product is 63.2 mgKOH/g.
EXAMPLE 5 Ionic liquid IL-2 catalyzed salicylic acid alkylation
A500 mL three-necked flask with temperature control, heating and stirring was charged with 20 g of catalyst IL-2 and 100 g of C16α -olefin (Mn 224.4, 0.446 mol), 70.78 g salicylic acid (Mn 138.12, 0.512 mol), nitrogen purge, stirring and heating were started, the temperature in the three-neck flask was controlled between 140 ℃ and 142 ℃, and the reaction was carried out for 5 hours.
After the reaction is finished, when the temperature of the materials is reduced to be below 40 ℃, the stirring is stopped, and 150 g No. 120 solvent gasoline is added. Taking out the materials in the three-neck flask, placing the materials in a separating funnel for layering, collecting the oil phase on the upper layer, adding 300 g of distilled water for washing for three times, removing unreacted salicylic acid in the oil phase, and drying the oil phase by anhydrous magnesium sulfate to finally obtain the dark brown alkyl salicylic acid.
Analyzing the content of residual alpha-olefin in the oil phase by using a gas chromatography external standard method, determining the acid value of the alkyl salicylic acid product according to an SH/T0092 petroleum acid test method, wherein the analysis result shows that the conversion rate of the alkyl salicylic acid is 91.4 percent, and the acid value of the product is 62.9 mgKOH/g.
EXAMPLE 6 Ionic liquid IL-3 catalyzed salicylic acid alkylation reaction
A500 mL three-necked flask with temperature control, heating and stirring was charged with 28 g of catalyst IL-3 and 100 g of C16α -olefin (Mn 224.4, 0.446 mol), 70.78 g salicylic acid (Mn 138.12, 0.512 mol), nitrogen purge, stirring and heating were started, the temperature in the three-neck flask was controlled between 140 ℃ and 142 ℃, and the reaction was carried out for 5 hours.
After the reaction is finished, when the temperature of the materials is reduced to be below 40 ℃, the stirring is stopped, and 150 g No. 120 solvent gasoline is added. Taking out the materials in the three-neck flask, placing the materials in a separating funnel for layering, collecting the oil phase on the upper layer, adding 300 g of distilled water for washing for three times, removing unreacted salicylic acid in the oil phase, and drying the oil phase by anhydrous magnesium sulfate to finally obtain the dark brown alkyl salicylic acid.
Analyzing the content of residual alpha-olefin in the oil phase by using a gas chromatography external standard method, determining the acid value of the alkyl salicylic acid product according to an SH/T0092 petroleum acid test method, wherein the analysis result shows that the conversion rate of the alkyl salicylic acid is 94.2 percent, and the acid value of the product is 65.8 mgKOH/g.
EXAMPLE 7 Ionic liquid IL-2 catalyzed salicylate alkylation
A500 mL three-necked flask with temperature control, heating and stirring was charged with 26 g of catalyst IL-2 and 100 g of C14-C18α -olefin (average Mn 224.4, 0.446 mol), 65.61 g methyl salicylate (Mn 154.12, 0.535 mol), introducing nitrogen, stirring, heating, and controlling the temperature between 145 deg.C and 147 deg.CAnd reacting for 6 hours.
After the reaction is finished, cooling the three-neck flask, stopping stirring when the temperature of the materials is reduced to be below 40 ℃, and adding 140 g of petroleum ether with the temperature of 90-120 ℃. And taking out the materials in the three-neck flask, placing the materials in a separating funnel for layering, collecting the oil phase at the upper layer, and reusing the ionic liquid at the lower layer. And adding 300 g of distilled water into the oil phase, washing for three times, removing unreacted salicylic acid in the oil phase, and drying the oil phase by using anhydrous magnesium sulfate to obtain the dark brown alkyl salicylate B.
The content of the remaining alpha-olefin in the oil phase was analyzed by gas chromatography external standard method, and it was found that the conversion of the alkyl salicylate B was 93.1% and the hydroxyl value of the product alkyl salicylate B was 65.1mgKOH/g (GB/T7383 method).
Comparative example 2DIL-1 catalyzed salicylic acid alkylation reaction
20 g of ionic liquid DIL-1 (similar to IL-1, no organic acid salt is added in the synthesis process) and 100 g of C are added into a 500mL three-neck flask with temperature control, heating and stirring functions16α -olefin (Mn 224.4, 0.446 mol), 70.78 g salicylic acid (Mn 138.12, 0.512 mol), nitrogen purge, stirring and heating, controlling the temperature in the three-neck flask between 140 ℃ and 142 ℃, and reacting for 5 hours.
After the reaction is finished, when the temperature of the materials is reduced to be below 40 ℃, the stirring is stopped, and 150 g No. 120 solvent gasoline is added. Taking out the materials in the three-neck flask, placing the materials in a separating funnel for layering, collecting the oil phase on the upper layer, adding 300 g of distilled water for washing for three times, removing unreacted salicylic acid in the oil phase, and drying the oil phase by anhydrous magnesium sulfate to finally obtain the dark brown alkyl salicylic acid.
Analyzing the content of the residual alpha-olefin in the oil phase by using a gas chromatography external standard method, determining the acid value of the alkyl salicylic acid product according to an SH/T0092 petroleum acid test method, wherein the analysis result shows that the conversion rate of the alkyl salicylic acid is 81.3 percent, and the acid value of the product is 56.8 mgKOH/g.
Comparative example 3 methanesulfonic acid catalyzed salicylic acid alkylation reaction
A500 mL three-necked flask with temperature control, heating and stirring was charged with 20 g of methanesulfonic acid and 100 gC16α -olefin (Mn 224.4, 0.446 mol), 70.78 g salicylic acid (Mn 138.12, 0.512 mol), nitrogen purge, stirring, heating, controlling the temperature in the three-neck flask between 140 ℃ and 142 ℃, and reacting for 16 hours.
After the reaction is finished, when the temperature of the materials is reduced to be below 40 ℃, the stirring is stopped, and 150 g No. 120 solvent gasoline is added. Taking out the materials in the three-neck flask, placing the materials in a separating funnel for layering, collecting the oil phase on the upper layer, adding 300 g of distilled water for washing for three times, removing unreacted salicylic acid in the oil phase, and drying the oil phase by anhydrous magnesium sulfate to finally obtain the dark brown alkyl salicylic acid.
Analyzing the content of the residual alpha-olefin in the oil phase by using a gas chromatography external standard method, determining the acid value of the alkyl salicylic acid product according to an SH/T0092 petroleum acid test method, wherein the analysis result shows that the conversion rate of the alkyl salicylic acid is 75.6 percent, and the acid value of the product is 42.8 mgKOH/g.

Claims (11)

1. A method of preparing an alkyl salicylic acid and/or alkyl salicylate, comprising: carrying out alkylation reaction on alpha-olefin, salicylic acid and/or salicylate under the action of a catalyst, and collecting a product; the catalyst is obtained by mixing ionic liquid, polyphosphoric acid and organic acid salt for 1-12 hours at 30-100 ℃;
the cation of the ionic liquid is alkyl imidazole or alkyl pyridine, and the anion of the ionic liquid is one of tetrafluoroborate, trifluoromethyl sulfonate, hexafluorophosphate, p-toluenesulfonic acid, nitrate, perchlorate, methanesulfonate, oxalate and hydrosulfate;
the structure of the polyphosphoric acid is as follows: hn+2PnO3n+1Wherein n is a positive integer greater than or equal to 1;
the organic acid salt is a metal salt of organic carboxylic acid and/or a metal salt of organic sulfonic acid.
2. The process of claim 1 wherein said α -olefin is C10-C30α -olefin of (1).
3. The method of claim 1 wherein said salicylate is C1-C4The salicylic acid ester of (1).
4. The method according to claim 1, wherein the molar ratio of the salicylic acid and/or the salicylate to the α -olefin is 1 to 2: 1.
5. the method of claim 1, wherein the alkyl imidazole has the structure:
Figure FDA0002197899180000011
wherein R is1、R2Are each independently selected from C1-C6Alkyl groups of (a);
the alkylpyridine has the structure:
Figure FDA0002197899180000012
wherein R is C1-C6Alkyl group of (1).
6. The method of claim 1, wherein the ionic liquid is selected from one or more of the group consisting of alkyl imidazole tetrafluoroborate, alkyl imidazole trifluoromethylsulfonate, alkyl imidazole hexafluorophosphate, alkyl imidazole hydrosulfate, alkyl pyridine tetrafluoroborate, alkyl pyridine trifluoromethylsulfonate, alkyl pyridine hexafluorophosphate, and alkyl pyridine hydrosulfate.
7. The method of claim 1, wherein the polyphosphoric acid is selected from one or more of phosphoric acid, pyrophosphoric acid, and tripolyphosphoric acid.
8. The process of claim 1 wherein the organic carboxylic acid is C2-C18Of (2)Fatty acid, the organic sulfonic acid is C6-C18With sulfonic acid or with C6-C18Alkyl benzene sulfonic acid, the metal being alkali metal and/or alkaline earth metal.
9. The method according to claim 1, wherein the mass ratio of the ionic liquid, the polyphosphoric acid, and the organic acid salt is 100: 5 to 30: 5 to 20.
10. The process according to claim 1, wherein the catalyst is added in an amount of 1 to 100% by mass of the sum of the α -olefin, salicylic acid and/or salicylate.
11. The method according to claim 1, wherein the temperature of the alkylation reaction is 50 to 250 ℃ and the time of the alkylation reaction is 1 to 16 hours.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD293108A5 (en) * 1990-03-02 1991-08-22 Adw Zi Fuer Organische Chemie,De PROCESS FOR THE PREPARATION OF 5-ALKYL SALICYLSAEURES AND THEIR DERIVATIVES
CN102167692A (en) * 2011-03-03 2011-08-31 清华大学 Synthesis method of alkyl-substituted benzocrown ether
CN103508881A (en) * 2012-06-21 2014-01-15 中国石油天然气股份有限公司 Alkyl salicylic acid synthesis method
CN105523920A (en) * 2016-02-16 2016-04-27 辽宁石化职业技术学院 Preparation method of alkyl salicylate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD293108A5 (en) * 1990-03-02 1991-08-22 Adw Zi Fuer Organische Chemie,De PROCESS FOR THE PREPARATION OF 5-ALKYL SALICYLSAEURES AND THEIR DERIVATIVES
CN102167692A (en) * 2011-03-03 2011-08-31 清华大学 Synthesis method of alkyl-substituted benzocrown ether
CN103508881A (en) * 2012-06-21 2014-01-15 中国石油天然气股份有限公司 Alkyl salicylic acid synthesis method
CN105523920A (en) * 2016-02-16 2016-04-27 辽宁石化职业技术学院 Preparation method of alkyl salicylate

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