CN1323062C - Method for preparing alkyl salicylic acid - Google Patents
Method for preparing alkyl salicylic acid Download PDFInfo
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- CN1323062C CN1323062C CNB2004100711118A CN200410071111A CN1323062C CN 1323062 C CN1323062 C CN 1323062C CN B2004100711118 A CNB2004100711118 A CN B2004100711118A CN 200410071111 A CN200410071111 A CN 200410071111A CN 1323062 C CN1323062 C CN 1323062C
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Abstract
The present invention relates to a method for preparing alkyl salicylic acid, which comprises the following steps: olefin of C6 to C50 is mixed with salicylic acid in organic solution, and alkylation reaction is carried out at the temperature of 50 to 150 DEG C under the action of a carried heteropoly acid catalyst. The catalyst is composed of carried phosphotungstic acid and phosphomolybdic acid, and the carrier is cation acidic resin. The dosage of the carried heteropoly acid catalyst is 3 to 15 wt % of the weight of the salicylic acid. In the method of the present invention, the carried heteropoly acid is used as the catalyst, and simultaneously, the solvent is introduced; thus, better reaction yield can be achieved, and the products and the catalyst can be easily separated; the catalyst can be repeatedly used for many times, and no waste acid discharge problem exists, which is favorable for environmental protection.
Description
Technical field
The present invention relates to a kind of method for preparing alkyl salicylic acid.
Technical background
Patent UK586461, UK1146925, EP370555 have disclosed the traditional preparation method of alkyl salicylate.Be raw material with phenol exactly, make alkylphenol, and then by koble-schmitt reaction carrying out carboxylation reaction by alkylated reaction with alkene.This instead needs higher pressure and temperature of reaction.Simultaneously exist chain alkyl to be positioned at ortho position and two kinds of situations of contraposition in alkylphenol, its about ratio is 3: 1 to 1: 10.And the adjacent activity is lower in the koble-schmitt reaction, and therefore the productive rate that can cause productivity ratio to be estimated is low.
FR-A-2542732 has disclosed a kind of salicylic strand alkylation preparation method, is to make catalyzer with the vitriol oil, allows Whitfield's ointment and ether material react.Wherein the carbon number of R base is 1-4 in the ether.This method still is feasible for the production of short run, but the shortage and the costliness of the ether of longer carbochain make scale operation infeasible.
Two preparation methods of DD-A-269619 and DD-A-293108 are salicylic direct alkylations, and catalyzer mainly is acidic ion exchange resin and Tripyrophosphoric acid.This method requires Whitfield's ointment will at first become ester, and alkylating chain length is six below the carbon.
US-A-5415792 then is by the alkylsalicylate than short chain being carried out alkylation, preparing the chain alkyl Whitfield's ointment, is exactly to allow methyl salicylate be hydrolyzed earlier, obtains cresotinic acid, carries out alkylation then.But this preparation for later purification agent is a unnecessary step.
EP0771782 has disclosed with 80% sulfuric acid and has made catalyzer to the direct alkylating preparation method of Whitfield's ointment, and this method vitriolic amount ratio is bigger, makes that so the more intense liquid of this corrodibility of sulfuric acid is unfavorable for handling.This method has been selected to react under the condition that lacks solvent simultaneously, has increased the difficulty of reaction.
Summary of the invention
The invention provides a kind of method for preparing alkyl salicylate.
Method provided by the invention comprises: in the presence of organic solvent, be carbon number that the alkene of 6-50 mixes with Whitfield's ointment, carrying out alkylated reaction under the katalysis of carried heteropoly acid under 50 ℃-150 ℃.
Said solvent is to dissolve salicylic organic solvent, as n-butyl ether etc.
Said olefin carbon number is 6-50, and carbon number is 8-40 preferably, and best scope is 12-30.
Alkene and Whitfield's ointment can feed intake promptly 1: 1 according to the required mol ratio of complete reaction.
Said catalyzer is a carried heteropoly acid, and preferred load phosphotungstic acid, phospho-molybdic acid, carrier can be the acid resins of positively charged ion.Weight in carrier is 100%, and the charge capacity of heteropolyacid on carrier is the heavy % of 10-70, the heavy % of preferred 20-50.The consumption of carried heteropoly acid catalyst is the heavy % of the 3-15 of Whitfield's ointment weight, the heavy % of preferred 5-12.
Carried heteropoly acid can adopt the equi-volume impregnating preparation.Carrier is selected the macropore strong acid cation exchange resin for use, and functional group is SO
3H, elder generation's water is demarcated the incipient impregnation volume of carrier, take by weighing a certain amount of carrier then, loaded by heteropoly acid amount on demand adds the heteropolyacid aqueous solution of respective concentration again, make its incipient impregnation on the carrier of institute's weighing, dipping is 4-10 hour in 40-80 ℃ of water-bath, moves into 40-100 ℃ and finishes preparation after oven for drying 6-15 hour.
Temperature of reaction is 50 ℃-150 ℃, and optimum range is 80 ℃-120 ℃.
Reaction times is 0.5-10 hour, and the reaction times is 1-5 hour preferably.
The present invention adopts carried heteropoly acid as catalyzer, introduce solvent simultaneously, than general catalyzer, carried heteropoly acid has stronger acidity, can reach reaction yield preferably, and product is easy to separate with catalyzer, catalyzer can repeatedly use, no spent acid emission problem helps environmental protection.
Description of drawings
The salicylic mass spectrum of 12 thiazolinyls that Fig. 1 obtains for embodiment 2.
The salicylic mass spectrum of 16 thiazolinyls that Fig. 2 obtains for embodiment 3.
Embodiment
Comparative Examples 1
Add Whitfield's ointment 13.8g in the single necked round bottom flask of the 250ml that prolong is housed, the adding n-butyl ether is 20ml, adds positive 12 alkene of 16.8g again, then resin cation (R.C.) 1.5g.Stir with magnetic stirring apparatus, temperature of reaction is 80 ℃, and the reaction times is 4 hours.Layered filtration carries out vacuum distilling then, obtains the finished product at last.Reaction conversion ratio is 0%.
Embodiment 2
Add Whitfield's ointment 13.8g in the single necked round bottom flask of the 250ml that prolong is housed, the adding n-butyl ether is 20ml, adds positive 12 alkene of 16.8g again, and the charge capacity that adds 1.5g then is 30% phospho-wolframic acid.Stir with magnetic stirring apparatus, temperature of reaction is 80 ℃, and the reaction times is 4 hours.Layered filtration carries out vacuum distilling then, obtains the finished product at last.The olefine reaction transformation efficiency is 52.1%.
Embodiment 3
Add Whitfield's ointment 13.8g in the single necked round bottom flask of the 250ml that prolong is housed, the adding n-butyl ether is 20ml, adds positive 16 alkene of 22.4g again, and the charge capacity that adds 0.5g then is 20% phospho-wolframic acid.Stir with magnetic stirring apparatus, temperature of reaction is 90 ℃, and the reaction times is 3 hours.Layered filtration carries out vacuum distilling then, obtains the finished product at last.The olefine reaction transformation efficiency is 42.1%.
Embodiment 4
Add Whitfield's ointment 13.8g in the single necked round bottom flask of the 250ml that prolong is housed, the adding n-butyl ether is 20ml, and adding the 33.6g carbon number again is the positive alkene of mixing of 20-30, and the charge capacity that adds 1.0g then is 50% phospho-molybdic acid.Stir with magnetic stirring apparatus, temperature of reaction is 100 ℃, and the reaction times is 5 hours.Layered filtration carries out vacuum distilling then, obtains the finished product at last.Reaction conversion ratio is 31.4%.
Embodiment 5
Reaction conditions is with embodiment 1, and catalyst recirculation is used, and test-results is as shown in table 1.
The effect that table 1 catalyst recirculation is used
| The catalyst recirculation number of times | 0 | 1 | 2 | 3 | 4 |
| Transformation efficiency (%) | 52.1 | 52.2 | 52.0 | 52.4 | 52.2 |
As can be found from Table 1, after the catalyst recirculation 4 times, catalytic activity does not reduce, and still has catalytic activity preferably.
Claims (11)
1. method for preparing alkyl salicylic acid comprises: in the presence of organic solvent, be carbon number that the alkene of 6-50 mixes with Whitfield's ointment, carrying out alkylated reaction under the effect of carried heteropoly acid catalyst under 50 ℃-150 ℃.
2. according to the described preparation method of claim 1, it is characterized in that said olefin carbon number is 8-40.
3. according to the described preparation method of claim 1, it is characterized in that said olefin carbon number is 12-30.
4. according to the described preparation method of claim 1, it is characterized in that said catalyzer is load phosphotungstic acid, phospho-molybdic acid, carrier is the acid resin of positively charged ion.
5. according to the described preparation method of claim 1, it is characterized in that, is 100% in the weight of carrier, and the charge capacity of heteropolyacid on carrier is the heavy % of 10-70.
6. according to the described preparation method of claim 5, it is characterized in that, is 100% in the weight of carrier, and the charge capacity of heteropolyacid on carrier is the heavy % of 20-50.
7. according to the described preparation method of claim 1, it is characterized in that the consumption of carried heteropoly acid catalyst is the heavy % of the 3-15 of Whitfield's ointment weight.
8. according to the described preparation method of claim 1, it is characterized in that the consumption of carried heteropoly acid catalyst is the heavy % of the 5-12 of Whitfield's ointment weight
9. according to the described preparation method of claim 1, it is characterized in that temperature of reaction is 80 ℃-120 ℃.
10. according to the described preparation method of claim 1, it is characterized in that said organic solvent is a n-butyl ether.
11., it is characterized in that the reaction times is 0.5-10 hour according to the described preparation method of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100711118A CN1323062C (en) | 2004-07-29 | 2004-07-29 | Method for preparing alkyl salicylic acid |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100711118A CN1323062C (en) | 2004-07-29 | 2004-07-29 | Method for preparing alkyl salicylic acid |
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| CN1727323A CN1727323A (en) | 2006-02-01 |
| CN1323062C true CN1323062C (en) | 2007-06-27 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195785B (en) * | 2006-12-07 | 2010-05-19 | 中国石油天然气股份有限公司 | Preparation method of alkyl sodium salicylate metal detergent |
| CN104387238B (en) * | 2014-10-27 | 2016-05-11 | 新乡市瑞丰新材料股份有限公司 | A kind of preparation method of branched alkyl phenol |
| CN107497497A (en) * | 2017-09-26 | 2017-12-22 | 丹东明珠特种树脂有限公司 | A kind of resin catalyst and its method of modifying applied to Etherification of Light FCC Gasoline reaction |
| CN112574022A (en) * | 2020-11-23 | 2021-03-30 | 国家能源集团宁夏煤业有限责任公司 | Alkyl salicylic acid and alkyl salicylate type lubricating oil detergent and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87104109A (en) * | 1986-06-10 | 1988-01-20 | 住友化学工业株式会社 | Process for producing hydroxy group-containing alkyl aromatic compound |
| US5734078A (en) * | 1995-11-01 | 1998-03-31 | Bp Chemicals (Additives) Limited | Alkylation process |
| CN1277894A (en) * | 1999-06-16 | 2000-12-27 | 中国科学院大连化学物理研究所 | Loading type heteropoly acid catalyst used for prepn. of linear alkyl benzene by alkylation of straight chair olefin and benzene |
-
2004
- 2004-07-29 CN CNB2004100711118A patent/CN1323062C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87104109A (en) * | 1986-06-10 | 1988-01-20 | 住友化学工业株式会社 | Process for producing hydroxy group-containing alkyl aromatic compound |
| US5734078A (en) * | 1995-11-01 | 1998-03-31 | Bp Chemicals (Additives) Limited | Alkylation process |
| CN1277894A (en) * | 1999-06-16 | 2000-12-27 | 中国科学院大连化学物理研究所 | Loading type heteropoly acid catalyst used for prepn. of linear alkyl benzene by alkylation of straight chair olefin and benzene |
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