CN103724202A - Refining method of antioxidant 1076 - Google Patents
Refining method of antioxidant 1076 Download PDFInfo
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- CN103724202A CN103724202A CN201410011068.XA CN201410011068A CN103724202A CN 103724202 A CN103724202 A CN 103724202A CN 201410011068 A CN201410011068 A CN 201410011068A CN 103724202 A CN103724202 A CN 103724202A
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- antioxidant
- purification
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- ethyl acetate
- crude product
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/60—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
Abstract
The invention provides a refining method of an antioxidant 1076. The refining method comprises the following steps of: dissolving a crude antioxidant 1076 to a certain amount of organic solvent; preparing an aqueous solution at a certain concentration through a reducing agent of the antioxidant 1076; performing reduction reaction with the antioxidant 1076; neutralizing the reducing agent with olefine acid after the reaction is finished; processing an organic phase by water washing and liquid separation; distilling to recover the solvent to obtain a pre-treated crude antioxidant 1076; and recrystallizing and purifying the pre-treated crude antioxidant 1076 with the solvent once more to obtain the qualified antioxidant 1076 of which the light transmittance meets the industrial standard. The finished antioxidant 1076 has the advantages that the light transmittance is more than 97% under 425nm and more than 98% under 500nm; in addition, the yield is more than 85%. With the adoption of the method, colorful impurities in the crude antioxidant 1076 can be effectively removed, and thus the dosage of 15 to 50% of solvent for recrystallizing is decreased, the operation difficulty is lowered, and the cost is low.
Description
Technical field
The present invention relates to a kind of process for purification of antioxidant 1076.
Background technology
Antioxidant 1076, chemical name is 3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester, is a kind of Hinered phenols antioxidant of excellent property, can suppress oxidative degradation and the thermal destruction of many organic compound and polymkeric substance.
The use range of antioxidant 1076 comprises polyolefine, as polyethylene, polypropylene, polybutene, also recommend the superpolymer for other types, as engineering plastics, as aldehyde resin, urethane, vinylbenzene homopolymerization or multipolymer, elastomerics, tackiness agent and other organic materialss.
Simultaneously antioxidant 1076 can be used with other additives such as BA simultaneously, as auxiliary stabilizer (thioether, phosphorous acid ester), photostabilizer and other functional additives, binary compound system (IRGANOX B batch mixing) and ternary built system IRGANOX GX(IRGANOX1010 that itself and IRGAF0S168 combine, IRGAF0S168, HP-136) have a significant synergistic function.Have consistency good, antioxygen usefulness is high, not painted, do not pollute, and wash resistant, extraction, heat-resisting, the feature such as volatility is little.The supply requirement that average annual growth rate to Chinese antioxidant 1076 in 2012 in 2009 is 22.3%, 2013 year Chinese market antioxidant 1076 will reach 14400 tons.
Antioxidant 1076 crude product is with 2,6-DI-tert-butylphenol compounds, methyl acrylate and the 18 alcohol product of purifying without recrystallization that to be raw material obtain through addition reaction and transesterification reaction, wherein antioxidant 1076 content is 90～95%, 2,6-DI-tert-butylphenol compounds content is 0～2.0%, 18 alcohol content are 0～2.0, and quinones substance content is 1.0～5.0%.The raw material of antioxidant 1076 and synthetic antioxidant 1076--β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester all belongs to aldehydes matter, in the process of transesterification reaction, be subject to the impact of oxygen in high temperature and system, very easily be oxidized to dark quinones substance, and that this class material has boiling point is high, be insoluble in the shortcoming of antioxidant 1076 recrystallization solvent, purify to follow-up antioxidant 1076 and brought great difficulty.
Summary of the invention
The object of the present invention is to provide a kind of process for purification of antioxidant 1076, can reduce recrystallization solvent usage quantity, effectively reduce purification difficulty and cost.
For achieving the above object, the present invention mainly adopts following technical scheme:
A process for purification for antioxidant 1076, comprises the steps:
1) pre-treatment of antioxidant 1076 crude product
Antioxidant 1076 crude product is dissolved in and in organic solvent, forms mixed solution, the aqueous solution that reductive agent is configured to 5～60wt% joins in described mixed solution, stirs, and reacts 0.5～3h(and be white in color or rice white to organic phase color at 20～70 ℃), in reaction solution, add the diluted acid of 5～35wt% to be neutralized to slightly acidic or neutrality, separatory, washing, then separatory, dry, filter, Distillation recovery organic solvent, obtains pretreated antioxidant 1076;
2) refining antioxidant 1076
Pretreated antioxidant 1076 is added in recrystallization solvent and carries out recrystallization, obtain refining antioxidant 1076.
Further, step 2) in described recrystallization process, Tc is-5～15 ℃, and crystallization time is 3～5h, and crystalline product obtains refining antioxidant 1076 after 35～45 ℃ of vacuum-drying.
Separately, described organic solvent is ethyl acetate or toluene.
And the mass volume ratio of the consumption of the crude product consumption of antioxidant 1076 described in step 1) and organic solvent is 1:2～4, g/ml.In the consumption of recrystallization solvent step 2) and step 1), the mass ratio of antioxidant 1076 crude product consumption is 4～6:1, g/g.
Again, described reductive agent is selected from a kind of in following material: Sulfothiorine, S-WAT, ferrous sulfate, sodium borohydride or POTASSIUM BOROHYDRIDE.Described reductive agent consumption is 5mol%～15mol%.
Again, described diluted acid is selected from a kind of in following material: dilute hydrochloric acid, dilute sulphuric acid or dilute acetic acid.
Separately, described recrystallization solvent is selected from a kind of in following material: ethyl acetate/methanol mixed solution, ethyl acetate/alcohol mixeding liquid, ethyl acetate/Virahol mixed solution, dehydrated alcohol or Virahol.
Wherein, in ethyl acetate/methanol mixed solution, the volume ratio of ethyl acetate and methyl alcohol is 1:2; In ethyl acetate/alcohol mixeding liquid, the volume ratio of ethyl acetate and ethanol is 1:2; In ethyl acetate/Virahol mixed solution, the volume ratio of ethyl acetate and ethanol is 1:2.
Compared with prior art, beneficial effect of the present invention is:
The present invention is dissolved in antioxidant 1076 crude product in organic solvent, the reductive agent of antioxidant 1076 is made into the finite concentration aqueous solution, carry out reduction reaction with antioxidant 1076, after having reacted, utilize in diluted acid and reductive agent, organic phase is through washing, separatory, distillating recovering solvent, obtain pretreated antioxidant 1076 crude product, through solvent recrystallization, purify and can obtain the qualified product that transmittance reaches industry standard again, in finished product antioxidant 1076, transmittance: 425nm > 97%, 500nm > 98%, and yield is higher than 85%.The method utilizes reductive agent that the foreign pigment producing in antioxidant 1076 building-up process (being mainly the quinones substance that aldehydes matter oxidation produces) is reduced to colourless aldehydes matter, effectively reduce the color of antioxidant 1076 crude product, and then reduce in follow-up antioxidant 1076 purification process, 15～50% recrystallization solvent usage quantitys, improve transmittance, and can reduce operation easier, with low cost.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.
Embodiment 1
In with heating, stirring, thermometer reactor, add respectively 200ml ethyl acetate, (HPLC detects 53.1g (0.1mol) antioxidant 1076 crude product: quinones substance content 3.4%), 0.007mol Sulfothiorine is mixed with to the 10wt% aqueous solution to be joined in reactor, control 45 ℃ of temperature of reaction, stirring reaction 2.0h.With 20wt% dilute acetic acid neutralization reaction liquid to pH value ≈ 7, separatory, water washing once again, separatory, anhydrous sodium sulfate drying, filter, Distillation recovery ethyl acetate, (HPLC detects: quinones substance content 0.8%) to obtain pretreated antioxidant 1076, then use 319 dehydrated alcohol recrystallizations, 5 ℃ of Tcs, crystallization time is 4.0h, 40 ℃ of vacuum-dryings, obtain 46.5g solid, i.e. refining antioxidant 1076, yield: 87.6%, antioxidant 1076 content 99.8%, quinones substance content < 0.1%, 18 alcohol content 0.1%, transmittance: 425nm98.5%, 500nm100.2%.
Embodiment 2
In with heating, stirring, thermometer reactor, add respectively 4000ml ethyl acetate, (HPLC detects 1062g (2.0mol) antioxidant 1076 crude product: quinones substance content 2.9%), 0.12mol Sulfothiorine is mixed with to the 25wt% aqueous solution to be joined in reactor, control 50 ℃ of temperature of reaction, stirring reaction 1.5h.With 20wt% dilute acetic acid neutralization reaction liquid to pH value ≈ 7, separatory, water washing once again, separatory, anhydrous sodium sulfate drying, filter, Distillation recovery ethyl acetate, (HPLC detects: quinones substance content 0.7%) to obtain pretreated antioxidant 1076, then use 5310g dehydrated alcohol recrystallization, 10 ℃ of Tcs, crystallization time is 3.5h, 40 ℃ of vacuum-dryings obtain 922.9g solid, i.e. refining antioxidant 1076, antioxidant 1076 content 99.7%, quinones substance content < 0.1%, 18 alcohol content 0.2%, yield: 86.9%, transmittance: 425nm99.1%, 500nm101.0%.
Embodiment 3
In with heating, stirring, thermometer reactor, add respectively 400ml toluene, (HPLC detects 106.2g (0.2mol) antioxidant 1076 crude product: quinones substance content 3.3%), 0.01mol sodium borohydride is mixed with to the 10wt% aqueous solution to be joined in reactor, control 45 ℃ of temperature of reaction, stirring reaction 0.5h.With 15wt% dilute hydrochloric acid neutralization reaction liquid to pH value ≈ 7, separatory, water washing once again, separatory, anhydrous sodium sulfate drying, filter, Distillation recovery toluene, (HPLC detects: quinones substance content 0.5%) to obtain pretreated antioxidant 1076, then use 425g ethyl acetate/alcohol mixed solution (volume ratio of ethyl acetate and methyl alcohol is 1:2) recrystallization, Tc-5 ℃, crystallization time is 4.5h, 35 ℃ of vacuum-dryings obtain 95.9g solid, i.e. refining antioxidant 1076, antioxidant 1076 content 99.9%, quinones substance content < 0.1%, yield: 90.3%, transmittance: 425nm99.5%, 500nm103.2%.
Embodiment 4
In with heating, stirring, thermometer reactor, add respectively 400ml toluene, (HPLC detects 106.2g (0.2mol) antioxidant 1076 crude product: quinones substance content 3.3%), 0.01mol POTASSIUM BOROHYDRIDE is mixed with to the 10wt% aqueous solution to be joined in reactor, control 45 ℃ of temperature of reaction, stirring reaction 1.0h.With 15wt% dilute hydrochloric acid neutralization reaction liquid to pH value ≈ 7, separatory, water washing once again, separatory, anhydrous sodium sulfate drying, filter, Distillation recovery toluene, (HPLC detects: quinones substance content 0.6%) to obtain pretreated antioxidant 1076, then use 531g ethyl acetate/alcohol mixed solution (volume ratio of ethyl acetate and methyl alcohol is 1:2) recrystallization, 5 ℃ of Tcs, crystallization time is 4.0h, 40 ℃ of vacuum-dryings obtain 94.1g solid, i.e. refining antioxidant 1076, antioxidant 1076 content 99.8%, quinones substance content < 0.1%, 18 alcohol content 0.1%, yield: 88.6%, transmittance: 425nm99.2%, 500nm101.8%.
Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (9)
1. a process for purification for antioxidant 1076, is characterized in that, comprises the steps:
1) pre-treatment of antioxidant 1076 crude product
Antioxidant 1076 crude product is dissolved in and in organic solvent, forms mixed solution, the aqueous solution that reductive agent is configured to 5～60wt% joins in described mixed solution, stirs, and at 20～70 ℃, reacts 0.5～3h, to the diluted acid that adds 5～35wt% in reaction solution, being neutralized to pH value is 6～7, separatory, washing, then separatory, dry, filter, Distillation recovery organic solvent, obtains pretreated antioxidant 1076;
2) refining antioxidant 1076
Pretreated antioxidant 1076 is added in recrystallization solvent and carries out recrystallization, obtain refining antioxidant 1076.
2. the process for purification of a kind of antioxidant 1076 according to claim 1, it is characterized in that step 2) in described recrystallization process, Tc is-5～15 ℃, crystallization time is 3～5h, and crystalline product obtains refining antioxidant 1076 after 35～45 ℃ of vacuum-drying.
3. the process for purification of a kind of antioxidant 1076 according to claim 1, is characterized in that, described organic solvent is ethyl acetate or toluene.
4. the process for purification of a kind of antioxidant 1076 according to claim 1, is characterized in that, the mass volume ratio of the consumption of the crude product consumption of antioxidant 1076 described in step 1) and organic solvent is 1:2～4, g/ml.
5. the process for purification of a kind of antioxidant 1076 according to claim 1, is characterized in that step 2) described in the consumption of recrystallization solvent and step 1) the mass ratio of antioxidant 1076 crude product consumption be 4～6:1, g/g.
6. the process for purification of a kind of antioxidant 1076 according to claim 1, is characterized in that, described reductive agent is selected from a kind of in following material: Sulfothiorine, S-WAT, ferrous sulfate, sodium borohydride or POTASSIUM BOROHYDRIDE.
7. a kind of process for purification of antioxidant 1076 according to claim 1 or 5, is characterized in that, described reductive agent consumption is 5mol%～15mol%.
8. the process for purification of a kind of antioxidant 1076 according to claim 1, is characterized in that, described diluted acid is selected from a kind of in following material: dilute hydrochloric acid, dilute sulphuric acid or dilute acetic acid.
9. the process for purification of a kind of antioxidant 1076 according to claim 1, it is characterized in that, described recrystallization solvent is selected from a kind of in following material: ethyl acetate/methanol mixed solution, ethyl acetate/alcohol mixeding liquid, ethyl acetate/Virahol mixed solution, dehydrated alcohol or Virahol.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115160138A (en) * | 2022-08-16 | 2022-10-11 | 宁波市鼎瑞翔新材料科技有限公司 | Method for preparing antioxidant 1076 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020562A (en) * | 2010-11-24 | 2011-04-20 | 上海华谊（集团）公司 | Synthesis method of antioxidant 1076 using solid base catalyst |
| CN102452937A (en) * | 2010-10-19 | 2012-05-16 | 天津三农金科技有限公司 | Production method of synthetic antioxidant 1076 |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102452937A (en) * | 2010-10-19 | 2012-05-16 | 天津三农金科技有限公司 | Production method of synthetic antioxidant 1076 |
| CN102020562A (en) * | 2010-11-24 | 2011-04-20 | 上海华谊（集团）公司 | Synthesis method of antioxidant 1076 using solid base catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 刘鸿雁 等: "合成抗氧剂1076工艺条件的优化", 《吉林化工学院学报》, vol. 17, no. 1, 30 March 2000 (2000-03-30), pages 14 - 16 * |
| 张卫华 等: "抗氧剂1076的合成研究", 《化工科技》, vol. 9, no. 6, 31 December 2001 (2001-12-31), pages 29 - 31 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115160138A (en) * | 2022-08-16 | 2022-10-11 | 宁波市鼎瑞翔新材料科技有限公司 | Method for preparing antioxidant 1076 |
| CN115160138B (en) * | 2022-08-16 | 2024-01-02 | 宁波市鼎瑞翔新材料科技有限公司 | Method for preparing antioxidant 1076 |
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