CN1164560C - Process for preparing hydroxyphenyl carboxylic ester - Google Patents
Process for preparing hydroxyphenyl carboxylic ester Download PDFInfo
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- CN1164560C CN1164560C CNB011022396A CN01102239A CN1164560C CN 1164560 C CN1164560 C CN 1164560C CN B011022396 A CNB011022396 A CN B011022396A CN 01102239 A CN01102239 A CN 01102239A CN 1164560 C CN1164560 C CN 1164560C
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Abstract
The present invention relates to a method for preparing hydroxyphenyl carboxylic acid ester with a structural formula (I). The method comprises that hydroxyphenyl carboxylic ester and alcohol react at 120 to 200 DEG C in the presence of a zinc salt catalyst, and organic acid is added for breaking the catalyst after the reaction is over. The method of the present invention can effectively solve the problem of turbid product appearance and can avoid color change because of the oxidation of residual catalyst, and the method has the advantage of few byproduct and can omit filtration procedures.
Description
The invention relates to the preparation method of hydroxyphenyl carboxylic acid esters.
Hydroxyphenyl carboxylic acid esters is the oil product oxidation inhibitor that a class has industrial application value, and this kind antioxidant has higher thermal stability, and good oil soluble and characteristics such as ashless are used widely in oil product.
Hydroxyphenyl carboxylic acid esters generally can prepare by transesterification, for example: US 5081280 and US 4536593, with organo-tin compound as catalyzer, reaction is easy to carry out, transformation efficiency is higher, but catalyzer is difficult to remove from reaction product, in case consume, then must not inconsiderate loaded down with trivial details method destroy, and remaining stannide can cause the product appearance muddiness in the final product.US 5563291 is a catalyzer with the magnesium acetate, and it is difficult for dissolving in reaction raw materials liquid, speed and conversion of raw material that the influence reaction is carried out.As catalyzer, reaction excessive velocities in early stage is difficult to control with potassium tert.-butoxide for US 4529809, and late phase reaction is difficult to carry out thoroughly, and the reaction product appearance color is darker, and by product is more and be difficult to separation.
Zinc acetate is known transesterification catalyzer, for example US 4716244 discloses a kind of method for preparing hydroxyphenyl carboxylic acid esters, is under reduced pressure, is catalyzer with inorganic zinc salt or organic zinc salt, temperature of reaction is controlled at 140～190 ℃, and pressure range is at 250～3mbar.Because of not taking any post-treating method to destroy catalyzer, cause the product appearance muddiness, after long-term the placement, there is precipitation to produce.
The objective of the invention is to aftertreatment technology, a kind of method for preparing hydroxyphenyl carboxylic acid esters is provided, hydroxyphenyl carboxylic acid esters purity height, productive rate height that this method makes, appearance transparent, but long-term storage and do not have precipitation and produce by means of compliance with environmental protection requirements.
The preparation method of the hydroxyphenyl carboxylic acid esters that structural formula provided by the invention (I) is represented comprises: with the represented compound of structural formula (II), with the represented compound of structural formula (III) in the presence of the zinc salt catalyzer, react in 120～200 ℃, after reaction finishes, add organic acid and destroy catalyzer.
R
3OH (III)
R wherein
1And R
2Be C independent of each other
1～C
8Alkyl, preferred C
1～C
4Alkyl, the more preferably tertiary butyl; M is 0,1,2 or 3, preferred 2; R
3Be C
4～C
20Alkyl or C
5～C
12Cycloalkyl, preferred C
4～C
20Alkyl, more preferably C
4～C
12Alkyl is as normal-butyl, isobutyl-, iso-octyl, n-octyl etc.
Specifically, the present invention prepares the method for hydroxyphenyl carboxylic acid esters, and can adopt there-necked flask is reaction vessel, reacts under normal pressure.Reactant preferably earlier that structural formula II, III is represented before adding catalyzer is at 40～80 ℃ of solution that dissolve into homogeneous.Carry out to the direction that helps generating product for making reaction, the represented pure common side of ester that structural formula (II) is represented and structural formula (III) is excessive, because the boiling point of ester is higher than alcohol, remove unreacted raw material for ease of reacting the back distillation, be advisable so that alcohol is excessive, the ratio of general reactant II and III is 1: 1.1～1: 1.7, be preferably 1: 1.3～and 1.5.Said zinc salt catalyzer can be zinc acetate, zinc chloride, zinc sulfate, Zinc Stearate, zinc acetate preferably, and catalyst consumption is 0.2～1% of reactant (II) weight, is preferably 0.3～0.7%.Temperature of reaction is 120～200 ℃, is preferably 160～180 ℃.In 4～15 hours reaction times, depend on the pressure and temperature of reaction.After reaction is finished,, organic acid is joined in the reaction product under preferred 85～100 ℃, stirred 5～30 minutes, can destroy catalyzer in 80～110 ℃.Suitable acid is mainly acid or glacial acetic acid, and its consumption is more than 1 times of catalyzer mole number, preferably 2～3 times.For the ease of metering organic acid add-on, can be with its wiring solution-forming, general concentration is 5～50%.
The preparation method of hydroxyphenyl carboxylic acid esters provided by the invention can effectively solve the muddy problem of product appearance, the discoloration problem of also having avoided the oxidation of remainder catalyst to cause, and by product is few, can save the filtration operation.The hydroxyphenyl carboxylic acid esters oxidation inhibitor that this method obtains has good antioxidant effect in oil product, particularly still have good behaviour under higher service temperature.
The invention will be further described below by embodiment.
Embodiment 1
With 58.4 gram (0.2mol) β-(3,5-di-t-butyl-4-hydroxyphenyl) methyl propionates, 39 gram (0.3mol) 2-ethyl-hexanols and 0.292 gram (0.0013mol) zinc acetate dihydrate add in the 250ml there-necked flask.Mechanical stirring, thermometer, water trap, prolong, nitrogen inlet are housed in the flask, under nitrogen protection, heat and dissolve, be warming up to 175 ℃ gradually to 60 ℃; reacted 5 hours, the methyl alcohol that generates is extracted in decompression out, is cooled to 90 ℃; adding concentration is 10% aqueous acetic acid 2ml, stirs 10 minutes, adds an amount of industrial naptha extraction; be washed to PH ≈ 7 again; normal decompression steams gasoline and excessive 2-ethyl-hexanol, obtains yellow transparent liquid, is product; productive rate 95%, product purity 99.13%.The content of unreacted β-(3,5-di-t-butyl-4-hydroxyphenyl) methyl propionate is 0.12%.
Embodiment 2
In embodiment 1 described reactor; add 58.4 gram (0.2mol) β-(3,5-di-t-butyl-4-hydroxyphenyl) methyl propionate and 28.6 gram 2-ethyl-hexanols; under nitrogen protection; heating is dissolved to 60 ℃; add 0.292 gram (0.0013mol) zinc acetate dihydrate catalyzer; be warming up to 160 ℃ gradually, reacted 10 hours, have methyl alcohol to deviate from therebetween.The methyl alcohol that generates is extracted in decompression out then, is cooled to 90 ℃, and adding concentration is 10% aqueous acetic acid 2ml, stirs after 10 minutes, according to method extraction, washing, the distillation of embodiment 1, obtains the yellow transparent liquid product again.Productive rate 93%, purity 98.76%, the content of unreacted β-(3,5-di-t-butyl-4-hydroxyphenyl) methyl propionate is 0.64%.
Embodiment 3
In embodiment 1 described reactor; add 58.4 gram (0.2mol) β-(3,5-di-t-butyl-4-hydroxyphenyl) methyl propionate; 39 gram (0.3mol) 2-ethyl-hexanols and 0.292 gram (0.0013mol) zinc acetate dihydrate; under nitrogen protection, heat and dissolve to 60 ℃; be warming up to 180 ℃ gradually; reacted 5 hours, methyl alcohol is extracted in decompression out, is cooled to 100 ℃.Adding concentration is 10% aqueous formic acid 1.5ml, stirs after 10 minutes, and method extraction, washing, distillation according to embodiment 1 obtain the yellow transparent liquid product.Productive rate 95%, product purity 99.24%.The content of unreacted β-(3, the 5--tertiary butyl-4-hydroxyphenyl) methyl propionate is 0.26%.
Embodiment 4
In embodiment 1 described reactor; add 58.4 gram (0.2mol) β-(3,5-di-t-butyl-4-hydroxyphenyl) methyl propionate; 39 gram (0.3mol) 2-ethyl-hexanols and 0.292 gram (0.0021mol) zinc chloride; under nitrogen protection, heat and dissolve to 60 ℃; be warming up to 180 ℃ gradually, have methyl alcohol to deviate from therebetween, react after 10 hours; methyl alcohol is extracted in decompression out, is cooled to 80 ℃.Adding concentration is 10% aqueous acetic acid 4ml, stirs after 10 minutes, according to method extraction, washing, the distillation of embodiment 1, obtains the yellow transparent liquid product again.Productive rate 95%, purity 98.46%, the content of unreacted β-(3,5-di-t-butyl-4-hydroxyphenyl) methyl propionate is 0.76%.
Embodiment 5
Present embodiment is that stability in storage is investigated.The product of embodiment 1 preparation was placed 30 days under-15 ℃ and 60 ℃ of conditions respectively, and product appearance is still transparent, and does not have the precipitation generation.And after placing the identical time under the same conditions according to the product of US4716244 method preparation, begin to have precipitation to produce.The results are shown in Table 1.
Table 1
| Sample | 30 days/-15 ℃ | 30 days/60 ℃ |
| Embodiment 1 | Yellow transparent | Yellow transparent |
| Press the product of US4716244 preparation | Yellow muddy | Yellow muddy |
Embodiment 6
Present embodiment is assessment of performance.Adopt ASTMD-2272 rotary oxygen bomb method, the embodiment product is carried out oxidation test, investigate inductive phase.Base oil is the HVIS150SN of Dalian Petrochemical Industry Company, and the dosage with 0.5% adds the product of embodiment 4, and compares with external similar sample L-135, the results are shown in Table 2.
Table 2
| Additive | Add dosage, % | Oxidation induction period, min |
| Embodiment 4 | 0.5 | 126 |
| L-135 | 0.5 | 106 |
Table 2 explanation, the product of the inventive method preparation has better antioxygen property with external like product.
Claims (9)
1. the preparation method of the hydroxyphenyl carboxylic acid esters of structural formula (I) expression, comprise: the compound of structural formula (II) expression and the compound of structural formula (III) expression are reacted in 120～200 ℃ in the presence of the zinc salt catalyzer, after reaction finishes, add organic acid, stir and destroyed catalyzer in 5～30 minutes, the organic acid consumption is 1～3 times of catalyzer mole number
R
3OH (III)
R wherein
1And R
2Be C independent of each other
1～C
8Alkyl, m are 0,1,2 or 3, and R
3Be C
4～C
20Alkyl or C
5～C
12Cycloalkyl, A is OR
3
2. according to the described preparation method of claim 1, it is characterized in that m is 2.
3. according to the described preparation method of claim 1, it is characterized in that R
1And R
2Be C
1～C
4Alkyl.
4. according to the described preparation method of claim 1, it is characterized in that R
3Be C
4～C
20Alkyl.
5. according to the described preparation method of claim 1, it is characterized in that R
1And R
2Be the tertiary butyl, R
3Be C
4～C
12Alkyl.
6. according to the described preparation method of claim 1, it is characterized in that said zinc salt catalyzer is selected from zinc acetate, zinc chloride, zinc sulfate and Zinc Stearate.
7. according to claim 1 or 6 described preparation methods, it is characterized in that said zinc salt catalyzer is a zinc acetate.
8. according to the described preparation method of claim 1, it is characterized in that catalyst consumption is 0.2～1% of reactant (II) weight.
9. according to the described preparation method of claim 1, it is characterized in that, after reaction finishes, add organic acid down, destroy catalyzer at 80～110 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011022396A CN1164560C (en) | 2001-01-18 | 2001-01-18 | Process for preparing hydroxyphenyl carboxylic ester |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011022396A CN1164560C (en) | 2001-01-18 | 2001-01-18 | Process for preparing hydroxyphenyl carboxylic ester |
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| Publication Number | Publication Date |
|---|---|
| CN1364753A CN1364753A (en) | 2002-08-21 |
| CN1164560C true CN1164560C (en) | 2004-09-01 |
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|---|---|---|---|
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| CN107954863A (en) * | 2017-12-13 | 2018-04-24 | 新乡市瑞丰新材料股份有限公司 | The preparation method of phenolic ester type antioxidant |
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2001
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