CN101225307A - Preparation method of anti-oxidizing agent - Google Patents
Preparation method of anti-oxidizing agent Download PDFInfo
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- CN101225307A CN101225307A CNA2008100522326A CN200810052232A CN101225307A CN 101225307 A CN101225307 A CN 101225307A CN A2008100522326 A CNA2008100522326 A CN A2008100522326A CN 200810052232 A CN200810052232 A CN 200810052232A CN 101225307 A CN101225307 A CN 101225307A
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- butyl
- tert
- propionic acid
- hydroxy phenyl
- stearyl alcohol
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Abstract
The invention relates to a preparation method for an antioxidant of 3-(3,5-Di-tertbutyl-4-hydroxyphenyl) propionic octadecyl alcohol ester, which comprises following steps: adding 3-(3,5-Di-tert-butyl-4-hydroxyphenyl) propionic acid, octadecyl alcohol and butylhydroxyoxo-stannane; dewatering through azeotropic esterification reaction; decolorizing using active carbon and active bentonite; filtrating to removing solvent, then melt solution with antioxidant is obtained; adding crystallizing solvent in the melt; crystallizing and filtering to obtain antioxidant; recovering crystallizing solvent in filtrate to obtain distillation residue; adding sodium hydroxide in the distillation residue for reaction; adding extractant to extract octadecyl alcohol; adding sulfate in aqueous phase for acidification reaction; recovering raw material of 3-(3,5-Di-tert-butyl-4-hydroxyphenyl) propionic acid through crystallization and filtration. The antioxidant of 3-(3,5-Di-tertbutyl-4-hydroxyphenyl) propionic octadecyl alcohol ester has the advantages of fully recovering and utilizing raw material of 3-(3,5-Di-tert-butyl-4-hydroxyphenyl) propionic acid and improving yield of product.
Description
Technical field
The present invention relates to a kind of preparation method of antioxidant, exactly relate to the preparation method of a kind of 3-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive stearyl alcohol ester of propionic acid antioxidant, belong to the technology of preparing of antioxidant.
Background technology
Antioxidant 3-(3, the 5-di-tert-butyl-hydroxy phenyl) preparation method of the positive stearyl alcohol ester of propionic acid antioxidant, existing technology is to adopt 3-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate and positive stearyl alcohol are raw material, carry out transesterification reaction and obtain the purpose product in the presence of catalyzer, reaction formula is as follows:
R
1，R
2＝C(CH
3)
3
In existing technology, one of method is: adopt 3-(3, the 5-di-tert-butyl-hydroxy phenyl) the mole number ratio of methyl propionate and positive stearyl alcohol is greater than 1.0, temperature of reaction is at 150-200 ℃, the catalyzer that uses has Dibutyltin oxide, dioctyl tin oxide, decompression (1.0-20.0mmHg) separating methanol, generate product 3-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive stearyl alcohol ester of propionic acid, resultant of reaction crystallization in solvent obtains product 3-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive stearyl alcohol ester of propionic acid, the crystallization yield 88-92% of product.Reaction raw materials no longer reclaims.So situation can increase raw-material consumption and unnecessary waste, also can cause environmental pollution.Two of method is: adopt 3-(3 in the reactant, the 5-di-tert-butyl-hydroxy phenyl) the excessive more positive stearyl alcohol complete reaction that makes of methyl propionate, after finishing, reaction carries out the rectifying separation operation, 3-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate reclaims as front-end volatiles, leftover materials are the positive stearyl alcohol ester of 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid of content 97-98%.US 4594444 (Ciba-Geigy A.G) adopts as this method.But problem is owing to temperature higher (temperature of charge is more than 200 ℃) in the rectifying, be easy to generate purpose product 3-(3, the 5-di-tert-butyl-hydroxy phenyl) positive stearyl alcohol ester of propionic acid and raw material 3-(3, the 5-di-tert-butyl-hydroxy phenyl) tertiary butyl that takes off of methyl propionate reacts, cause the product quality to descend, raw materials quality reduces; And the production equipment requirement is high, and energy consumption is big, and industrializing implementation has certain degree of difficulty.
Summary of the invention
The present invention the object of the present invention is to provide a kind of preparation method of antioxidant, a kind of 3-(3 promptly is provided, the 5-di-tert-butyl-hydroxy phenyl) preparation method of the positive stearyl alcohol ester of propionic acid antioxidant, prepare 3-(3 with this method, the 5-di-tert-butyl-hydroxy phenyl) the positive stearyl alcohol ester of propionic acid antioxidant, productive rate height, cost are low.
The present invention is realized that by the following technical programs the preparation method of a kind of 3-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive stearyl alcohol ester of propionic acid antioxidant is characterized in that comprising following process:
1. with 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid is 1.0-1.25 with positive stearyl alcohol in molar ratio: 1.00 add in the solvent of dimethylbenzene or toluene, press catalyzer and 3-(3, the 5-di-tert-butyl-hydroxy phenyl) mass percent of propionic acid is that 0.40-2.00% adds the Monobutyltin acid catalyst again in solution, carry out the azeotropic esterification of anhydrating at temperature 120-180 ℃ then, obtain containing the reaction solution of 3-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive stearyl alcohol ester of propionic acid;
2. adding gac or atlapulgite in the reaction solution of step 1, is 120-130 ℃ in temperature, decolours 0.5-1.0 hour, filteringly obtains the filtrate of decolouring at temperature 80-100 ℃ then;
3. the decolouring filtrate that step 2 is obtained is under normal pressure or decompression, remove solvent xylene or toluene in temperature 160-180 ℃, obtain containing 3-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive stearyl alcohol ester of propionic acid fused solution, add methyl alcohol at 50-70 ℃ to this fused solution, ethanol, Virahol or butanol crystal solvent, go out 3-(3 in a temperature 20-40 ℃ crystallization, the 5-di-tert-butyl-hydroxy phenyl) the positive stearyl alcohol ester of propionic acid, obtain 3-(3 after filtration, the 5-di-tert-butyl-hydroxy phenyl) the positive stearyl alcohol ester products of propionic acid, filtrate (mother liquor) is at temperature 70-120 ℃ of distillation recovery methyl alcohol wherein, ethanol, Virahol or butanol crystal solvent, and obtain vinasse;
4. the mass ratio by vinasse and sodium hydroxide is 1.0: 0.10-0.30, adding mass concentration to vinasse is the aqueous sodium hydroxide solution of 2.0-5.0%, be 100-110 ℃ in temperature and carry out basic hydrolysis, 3-5 by the vinasse quality extraordinarily goes into dimethylbenzene in hydrolysis reaction liquid again, the extraction solvent of toluene or sherwood oil, extract positive stearyl alcohol at temperature 60-80 ℃, tell the solvent phase that contains stearyl alcohol, by sodium hydroxide and vitriolic mol ratio is 1.0: 0.5-0.6 adds sulfuric acid to aqueous phase, be 50-80 ℃ in temperature and carry out the acidification hydrolization reaction, cool the temperature to 20-50 ℃ after the acidifying, through crystallization, filtered and recycled 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid raw material.
The invention has the advantages that, in preparation process, raw material 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid has obtained sufficient recovery and utilization, and this had not only saved raw material consumption, but also has reduced the cost of product, the yield of purpose product is improved, calculate with 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid, the yield of purpose product reaches more than 98%, and this procedure is simple, and is workable.
Embodiment
Embodiment 1
Be equipped with to 250ml and add dimethylbenzene 50ml in the four-hole bottle of agitator, thermometer, nitrogen conduit, water trap and condenser, start stirring, add positive stearyl alcohol 27.0g (0.10mol), 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid 33.4g (0.12mol), monobutyl stannic acid 0.2g (0.001mol), feed nitrogen, be warming up to backflow, keep reacting liquid temperature about 160 ℃, back flow reaction was dewatered about 4.0 hours, and dehydration is near theoretical value.Be cooled to 100 ℃, add the 1.0g gac, stir maintenance 30 minutes, be cooled to 80-100 ℃, filter at 120-130 ℃.By reaction solution is reclaimed dimethylbenzene in 180 ℃ of normal pressures, decompression (20-50mmHg), be cooled to 60 ℃, add Virahol 150ml, 25 ℃ of crystallizations,, obtain 3-(3 by the filtration of cloth formula funnel, Virahol flushing, 40 ℃ of dryings, the 5-di-tert-butyl-hydroxy phenyl) the positive stearyl alcohol ester of propionic acid 46.0g, fusing point 50-53 ℃ is 98.5% through HPLC test purity, yield 86.79% (by positive stearyl alcohol).The mother liquor that crystallization obtains after filtering reclaims Virahol 80-120 ℃ of distillation, finally obtains thick liquid 12.5g.Be cooled to 70 ℃ to wherein adding entry 40ml, NaOH 1.3g, stirring is warming up to and refluxes about 103 ℃, kept 2.0 hours, cool to 70 ℃, add dimethylbenzene 40ml, stop to stir standing demix after stirring 15min., top solvent layer contains the positive stearyl alcohol that extraction obtains, the following water that the separatory processing obtains is 50% sulfuric acid 60 ℃ of adding 3.3g mass concentrations, carried out acidifying 1.0 hours at 70 ℃, be cooled to room temperature, the filtration of cloth formula funnel, water washing, 100 ℃ of dryings, obtain 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid 8.8g.Final 3-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive stearyl alcohol ester products of propionic acid yield can reach 98.08%[by 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid meter].
Embodiment 2
Repeat technology and the condition of embodiment 1, it is toluene that dimethylbenzene is substituted, and the consumption of toluene is 35ml, and it is atlapulgite that discoloring agent changes gac.Obtain 3-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive stearyl alcohol ester of propionic acid 45.4g, fusing point 50-53 ℃, purity 98.8%, yield 85.85% (by positive stearyl alcohol).Obtain 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid 8.9g.Ultimate yield 97.20%[presses 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid meter].
Embodiment 3
Repeat technology and the condition of embodiment 1, it is ethanol that Virahol is substituted, monobutyl stannic acid 0.4g.Obtain 3-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive stearyl alcohol ester of propionic acid 47.4g, fusing point 50-53 ℃, purity 98.3%, yield 89.43% (by positive stearyl alcohol).Obtain 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid 8.2g.Ultimate yield 98.66%[presses 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid meter].
Embodiment 4
Repeat technology and the condition of embodiment 1, the usage quantity of dimethylbenzene is 100ml, and temperature of reaction reaches 140 ℃, and it is atlapulgite that monobutyl stannic acid 0.65g, discoloring agent change gac.Obtain 3-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive stearyl alcohol ester of propionic acid 46.4g, fusing point 50-53 ℃, purity 98.6%, yield 87.55% (by positive stearyl alcohol).Use NaOH1.6g, toluene 50ml, 50% sulfuric acid 4.9g.Obtain 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid 8.4g.Ultimate yield 97.36%[presses 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid meter].
Embodiment 5
Repeat technology and the condition of embodiment 1, the usage quantity of toluene is 100ml, and temperature of reaction reaches 123 ℃, monobutyl stannic acid 0.13g.Obtain 3-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive stearyl alcohol ester of propionic acid 36.4g, fusing point 50-53 ℃, purity 98.2%, yield 68.68% (by positive stearyl alcohol).Use NaOH 3.0g, toluene 50ml, 50% sulfuric acid 8.0g.Obtain 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid 13.7g.Ultimate yield 96.91%[presses 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid meter].
Embodiment 6
Repeat technology and the condition of embodiment 1, the usage quantity of dimethylbenzene is 40ml, and temperature of reaction reaches 180 ℃, monobutyl stannic acid 0.3g.Obtain 3-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive stearyl alcohol ester of propionic acid 46.9g, fusing point 50-53 ℃, purity 98.1%, yield 88.49% (by positive stearyl alcohol).Obtain 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid 8.3g.Ultimate yield 98.01%[presses 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid meter].
Embodiment 7
Repeat technology and the condition of embodiment 1, positive stearyl alcohol 27.0g (0.10mol), 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid 27.8g (0.10mol).Obtain 3-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive stearyl alcohol ester of propionic acid 42.5g, fusing point 50-53 ℃, purity 98.2%, yield 80.19% (by positive stearyl alcohol).Obtain 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid 4.9g.Ultimate yield 97.34%[presses 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid meter].
Embodiment 8
Repeat technology and the condition of embodiment 1, positive stearyl alcohol 27.0g (0.10mol), 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid 30.6g (0.11mol).Obtain 3-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive stearyl alcohol ester of propionic acid 45.5g, fusing point 50-53 ℃, purity 98.7%, yield 85.85% (by positive stearyl alcohol).Obtain 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid 6.3g.Ultimate yield 98.21%[presses 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid meter].
Embodiment 9
Repeat technology and the condition of embodiment 1, positive stearyl alcohol 27.0g (0.10mol), 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid 34.8g (0.125mol), monobutyl stannic acid 0.5g.Obtain 3-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive stearyl alcohol ester of propionic acid 47.5g, fusing point 50-53 ℃, purity 98.6%, yield 89.62% (by positive stearyl alcohol).Obtain 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid 9.2g.Ultimate yield 97.32%[presses 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid meter].
Claims (1)
1. the preparation method of an antioxidant, described antioxidant is the positive stearyl alcohol ester of 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid, it is characterized in that comprising following process:
1) with 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid is 1.0-1.25 with positive stearyl alcohol in molar ratio: 1.00 add in the solvent of dimethylbenzene or toluene, press catalyzer and 3-(3, the 5-di-tert-butyl-hydroxy phenyl) mass percent of propionic acid is that 0.40-2.00% adds the Monobutyltin acid catalyst again in solution, carry out the azeotropic esterification of anhydrating at temperature 120-180 ℃ then, obtain containing the reaction solution of 3-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive stearyl alcohol ester of propionic acid;
2) adding gac or atlapulgite in the reaction solution of step 1), is 120-130 ℃ in temperature, decolours 0.5-1.0 hour, filteringly obtains the filtrate of decolouring at temperature 80-100 ℃ then;
3) with step 2) the decolouring filtrate that obtains is under normal pressure or decompression, remove solvent xylene or toluene in temperature 160-180 ℃, obtain containing 3-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive stearyl alcohol ester of propionic acid fused solution, add methyl alcohol at 50-70 ℃ to this fused solution, ethanol, Virahol or butanol crystal solvent, go out 3-(3 in a temperature 20-40 ℃ crystallization, the 5-di-tert-butyl-hydroxy phenyl) the positive stearyl alcohol ester of propionic acid, obtain 3-(3 after filtration, the 5-di-tert-butyl-hydroxy phenyl) the positive stearyl alcohol ester products of propionic acid, filtrate is at temperature 70-120 ℃ of distillation recovery methyl alcohol wherein, ethanol, Virahol or butanol crystal solvent, and obtain vinasse;
4) mass ratio by vinasse and sodium hydroxide is 1.0: 0.10-0.30, adding mass concentration to vinasse is the aqueous sodium hydroxide solution of 2.0-5.0%, be 100-110 ℃ in temperature and carry out basic hydrolysis, 3-5 by the vinasse quality extraordinarily goes into dimethylbenzene in hydrolysis reaction liquid again, the extraction solvent of toluene or sherwood oil, extract positive stearyl alcohol at temperature 60-80 ℃, tell the solvent phase that contains stearyl alcohol, by sodium hydroxide and vitriolic mol ratio is 1.0: 0.5-0.6 adds sulfuric acid to aqueous phase, be 50-80 ℃ in temperature and carry out the acidification hydrolization reaction, cool the temperature to 20-50 ℃ after the acidifying, through crystallization, filtered and recycled 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid raw material.
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| CNA2008100522326A CN101225307A (en) | 2008-02-01 | 2008-02-01 | Preparation method of anti-oxidizing agent |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153497A (en) * | 2011-02-22 | 2011-08-17 | 利安隆（天津）化工有限公司 | Method for recycling pentaerythritol (3-dodecyl sulfo-propionate) from pentaerythritol (3-dodecyl sulfo-propionate) crystallization raffinate |
| CN101955430B (en) * | 2009-11-26 | 2012-08-22 | 营口市风光化工有限公司 | Method for producing antioxygen 1076 through noncrystalline method |
| CN108409930A (en) * | 2018-03-07 | 2018-08-17 | 中国铁道科学研究院铁道建筑研究所 | One kind is in supercritical CO2The polyalcohol of middle grafting antioxygen agent molecule |
-
2008
- 2008-02-01 CN CNA2008100522326A patent/CN101225307A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955430B (en) * | 2009-11-26 | 2012-08-22 | 营口市风光化工有限公司 | Method for producing antioxygen 1076 through noncrystalline method |
| CN102153497A (en) * | 2011-02-22 | 2011-08-17 | 利安隆（天津）化工有限公司 | Method for recycling pentaerythritol (3-dodecyl sulfo-propionate) from pentaerythritol (3-dodecyl sulfo-propionate) crystallization raffinate |
| CN108409930A (en) * | 2018-03-07 | 2018-08-17 | 中国铁道科学研究院铁道建筑研究所 | One kind is in supercritical CO2The polyalcohol of middle grafting antioxygen agent molecule |
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