CN103724202B - A kind of process for purification of antioxidant 1076 - Google Patents
A kind of process for purification of antioxidant 1076 Download PDFInfo
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- CN103724202B CN103724202B CN201410011068.XA CN201410011068A CN103724202B CN 103724202 B CN103724202 B CN 103724202B CN 201410011068 A CN201410011068 A CN 201410011068A CN 103724202 B CN103724202 B CN 103724202B
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- 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
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Abstract
Antioxidant 1076 crude product is dissolved in a certain amount of organic solvent, the reducing 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 reducing agent, organic phase is through washing, separatory, distillating recovering solvent, obtain pretreated antioxidant 1076 crude product, purify and can obtain light transmittance and reach the qualified products of professional standard through solvent recrystallization again, in finished product antioxidant 1076, light transmittance: 425nm > 97%, 500nm > 98%, and yield is higher than 85%. the foreign pigment that the method can effectively be gone out in antioxidant 1076 crude product, thus 15～50% recrystallization solvent use amount and operation easier reduced, with low cost.
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 octadecanolEster, is a kind of Hinered phenols antioxidant of function admirable, can suppress many organic compounds and polymerizationThe oxidative degradation of thing and thermal degradation.
The scope of application of antioxidant 1076 comprises polyolefin, as polyethylene, polypropylene, polybutene, alsoRecommend the high polymer for other types, as engineering plastics, as aldehyde resin, polyurethane, styreneHomopolymerization or copolymer, elastomer, adhesive and other organic materials.
Simultaneously antioxidant 1076 can use with other additives such as BA simultaneously, as auxiliary stabilizer (thioether,Phosphite ester), light stabilizer and other functional additives, the binary that itself and IRGAF0S168 combineCompound system (IRGANOXB batch mixing) and ternary built system IRGANOXGX(IRGANOX1010, IRGAF0S168, HP-136) has significant synergistic function. ToolHave compatibility good, antioxygen usefulness is high, not painted, do not pollute, and wash resistant, extraction, heat-resisting, volatilizationThe feature such as property is little. Within 2009, the average annual growth rate to Chinese antioxidant 1076 in 2012 is 22.3%,The supply requirement of Chinese market antioxidant 1076 in 2013 will reach 14400 tons.
Antioxidant 1076 crude product is to be that raw material is through adding with 2,6-DI-tert-butylphenol compounds, methyl acrylate and 18 alcoholThe product of purifying without recrystallization that becomes reaction and ester exchange reaction to obtain, wherein antioxidant 1076 contentBe 90～95%, 2,6-DI-tert-butylphenol compounds content is that 0～2.0%, 18 alcohol content are 0～2.0, quinones substanceContent is 1.0～5.0%. The raw material of antioxidant 1076 and synthetic antioxidant 1076--β-(tertiary fourth of 3,5-bis-Base-4-hydroxy phenyl) propionic ester all belongs to aldehydes matter, in the process of ester exchange reaction, is subject to heightIn gentle system, the impact of oxygen, is very easily oxidized to dark quinones substance, and this class material has and boilsPoint is high, is insoluble in the shortcoming of antioxidant 1076 recrystallization solvent, purifies to follow-up antioxidant 1076 and is withCarry out 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 recrystallizationSolvent use amount, effectively reduces 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) pretreatment of antioxidant 1076 crude product
Antioxidant 1076 crude product is dissolved in organic solvent and forms mixed liquor, reducing agent is configured toThe aqueous solution of 5～60wt% joins in described mixed liquor, stirs, and at 20～70 DEG C, reacts 0.5～3h(extremelyOrganic phase color is white in color or rice white), in reactant liquor, add the diluted acid of 5～35wt% to neutralizeTo faintly acid or neutrality, separatory, washing, then separatory, dry, filter, Distillation recovery organic solvent,Obtain pretreated antioxidant 1076;
2) refining antioxidant 1076
Pretreated antioxidant 1076 is added in recrystallization solvent and is recrystallized, and what obtain refining is anti-Oxygen agent 1076.
Further, step 2) in described recrystallization process, crystallization temperature is-5～15 DEG C, crystallization timeBe 3～5h, crystalline product obtains refining antioxidant 1076 after 35～45 DEG C of vacuum drying.
Separately, described organic solvent is ethyl acetate or toluene.
And, the quality volume of the consumption of the crude product consumption of antioxidant 1076 described in step 1) and organic solventThan being 1:2～4, g/ml. Step 2) described in antioxidant 1076 in the consumption of recrystallization solvent and step 1)The mass ratio of crude product consumption is 4～6:1, g/g.
Again, described reducing agent is selected from the one in following material: sodium thiosulfate, sodium sulfite, sulfuric acidFerrous iron, sodium borohydride or potassium borohydride. Described reducing agent consumption is 5mol%～15mol%.
Again, described diluted acid is selected from the one in following material: watery hydrochloric acid, dilute sulfuric acid or spirit of vinegar.
Separately, described recrystallization solvent is selected from the one in following material: ethyl acetate/methanol mixed liquor,Ethyl acetate/alcohol mixeding liquid, ethyl acetate/isopropyl alcohol mixed liquor, absolute ethyl alcohol or isopropyl alcohol.
Wherein, in ethyl acetate/methanol mixed liquor, the volume ratio of ethyl acetate and methyl alcohol is 1:2; Acetic acidIn ethyl ester/alcohol mixeding liquid, the volume ratio of ethyl acetate and ethanol is 1:2; Ethyl acetate/isopropyl alcohol is mixedClose in liquid, 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, and the reducing agent of antioxidant 1076 is made intoThe finite concentration aqueous solution, carries out reduction reaction with antioxidant 1076, after having reacted, utilizes in diluted acidAnd reducing agent, organic phase through washing, separatory, distillating recovering solvent, obtains pretreated antioxidant1076 crude products, then purify and can obtain light transmittance and reach the qualified products of professional standard through solvent recrystallization,In finished product antioxidant 1076, light transmittance: 425nm > 97%, 500nm > 98%, and yield is higher than 85%.It (is mainly phenols by the foreign pigment producing in antioxidant 1076 building-up process that the method is utilized reducing agentThe quinones substance that substance oxidation produces) be reduced to colourless aldehydes matter, effectively reduce antioxidant 1076The color of crude product, and then reduce in follow-up antioxidant 1076 purification process 15～50% recrystallization solventsUse amount, improves light transmittance, and can reduce operation easier, with low cost.
Detailed description of the invention
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,53.1g (0.1mol) antioxidant 1076 crude product (HPLC detects: quinones substance content 3.4%), will0.007mol sodium thiosulfate is mixed with the 10wt% aqueous solution and joins in reactor, controls reaction temperature45 DEG C, stirring reaction 2.0h. With 20wt% spirit of vinegar neutralization reaction liquid to pH value ≈ 7, separatory, thenWater washing once, separatory, anhydrous sodium sulfate drying, filters, Distillation recovery ethyl acetate obtains pre-Antioxidant 1076 after treatment (HPLC detects: quinones substance content 0.8%), then uses 319 nothingsWater-ethanol recrystallization, 5 DEG C of crystallization temperatures, crystallization time is 4.0h, 40 DEG C of vacuum drying, obtain 46.5gSolid, i.e. refining antioxidant 1076, yield: 87.6%, antioxidant 1076 content 99.8%, quinoneClass content of material < 0.1%, 18 alcohol content 0.1%, light transmittance: 425nm98.5%, 500nm100.2%。
Embodiment 2
In with heating, stirring, thermometer reactor, add respectively 4000ml ethyl acetate,1062g (2.0mol) antioxidant 1076 crude product (HPLC detects: quinones substance content 2.9%), will0.12mol sodium thiosulfate is mixed with the 25wt% aqueous solution and joins in reactor, controls reaction temperature50 DEG C, stirring reaction 1.5h. With 20wt% spirit of vinegar neutralization reaction liquid to pH value ≈ 7, separatory, thenWater washing once, separatory, anhydrous sodium sulfate drying, filters, Distillation recovery ethyl acetate obtains pre-Antioxidant 1076 after treatment (HPLC detects: quinones substance content 0.7%), then uses 5310gAbsolute ethyl alcohol recrystallization, 10 DEG C of crystallization temperatures, crystallization time is 3.5h, 40 DEG C of vacuum drying obtain922.9g solid, i.e. refining antioxidant 1076, antioxidant 1076 content 99.7%, quinones substance containsAmount < 0.1%, 18 alcohol content 0.2%, yield: 86.9%, light transmittance: 425nm99.1%, 500nm101.0%。
Embodiment 3
In with heating, stirring, thermometer reactor, add respectively 400ml toluene, 106.2g(0.2mol) antioxidant 1076 crude product (HPLC detects: quinones substance content 3.3%), by 0.01molSodium borohydride is mixed with the 10wt% aqueous solution and joins in reactor, controls 45 DEG C of reaction temperatures, stirsReaction 0.5h. With 15wt% watery hydrochloric acid neutralization reaction liquid to pH value ≈ 7, separatory, then water washing is once,Separatory, anhydrous sodium sulfate drying, filters, and Distillation recovery toluene, obtains pretreated antioxidant 1076(HPLC detects: quinones substance content 0.5%), then mixes molten with 425g ethyl acetate/ethanolLiquid (volume ratio of ethyl acetate and methyl alcohol is 1:2) recrystallization, crystallization temperature-5 DEG C, crystallization time is4.5h, 35 DEG C of vacuum drying obtain 95.9g solid, i.e. refining antioxidant 1076, antioxidant 1076Content 99.9%, quinones substance content < 0.1%, yield: 90.3%, light transmittance: 425nm99.5%,500nm103.2%。
Embodiment 4
In with heating, stirring, thermometer reactor, add respectively 400ml toluene,106.2g (0.2mol) antioxidant 1076 crude product (HPLC detects: quinones substance content 3.3%), will0.01mol potassium borohydride is mixed with the 10wt% aqueous solution and joins in reactor, controls reaction temperature45 DEG C, stirring reaction 1.0h. With 15wt% watery hydrochloric acid neutralization reaction liquid to pH value ≈ 7, separatory, thenWater washing once, separatory, anhydrous sodium sulfate drying, filter, Distillation recovery toluene, obtains pretreatmentAfter antioxidant 1076 (HPLC detect: quinones substance content 0.6%), then use 531g acetic acidEthyl ester/alcohol mixed solution (volume ratio of ethyl acetate and methyl alcohol is 1:2) recrystallization, crystallization temperature 5DEG C, crystallization time is 4.0h, 40 DEG C of vacuum drying obtain 94.1g solid, i.e. and refining antioxidant 1076,Antioxidant 1076 content 99.8%, quinones substance content < 0.1%, 18 alcohol content 0.1%, yield:88.6%, light 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 be to this after having read the content of the present invention's instructionInvention makes various changes or modifications, and these equivalent form of values fall within the application's appended claims institute equallyThe scope limiting.
Claims (6)
1. a process for purification for antioxidant 1076, is characterized in that, comprises the steps:
1) pretreatment of antioxidant 1076 crude product
Antioxidant 1076 crude product is dissolved in organic solvent and forms mixed liquor, reducing agent is configured toThe aqueous solution of 5～60wt% joins in described mixed liquor, stirs reaction at 20～70 DEG C0.5～3h, being neutralized to pH value to the diluted acid that adds 5～35wt% in reactant liquor is 6～7, separatory,Washing, then separatory, dry, filter, Distillation recovery organic solvent, obtains pretreated anti-Oxygen agent 1076;
Wherein, described organic solvent is ethyl acetate or toluene; Described reducing agent is selected from following materialIn one: sodium thiosulfate, sodium sulfite, ferrous sulfate, sodium borohydride or potassium borohydride;
2) refining antioxidant 1076
Pretreated antioxidant 1076 is added in recrystallization solvent and is recrystallized, refinedAntioxidant 1076;
Wherein, described recrystallization solvent is selected from the one in following material: ethyl acetate/methanol is mixedClose liquid, ethyl acetate/alcohol mixeding liquid, ethyl acetate/isopropyl alcohol mixed liquor, absolute ethyl alcohol or differentPropyl alcohol.
2. the process for purification of a kind of antioxidant 1076 according to claim 1, is characterized in that, step2) in described recrystallization process, crystallization temperature is-5～15 DEG C, and crystallization time is 3～5h, and crystallization is producedProduct obtain refining antioxidant 1076 after 35～45 DEG C of vacuum drying.
3. the process for purification of a kind of antioxidant 1076 according to claim 1, is characterized in that, step1) mass volume ratio of the consumption of the crude product consumption of antioxidant 1076 described in and organic solvent is1:2～4, its unit is g/ml.
4. the process for purification of a kind of antioxidant 1076 according to claim 1, is characterized in that, step2) consumption and the step 1 of recrystallization solvent described in) in the quality of antioxidant 1076 crude product consumptionThan being 4～6:1.
5. according to the process for purification of a kind of antioxidant 1076 described in claim 1 or 3, it is characterized in that,Described reducing agent consumption is 5mol%～15mol%.
6. the process for purification of a kind of antioxidant 1076 according to claim 1, is characterized in that, described inDiluted acid is selected from the one in following material: watery hydrochloric acid, dilute sulfuric acid or spirit of vinegar.
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| CN201410011068.XA CN103724202B (en) | 2014-01-10 | 2014-01-10 | A kind of process for purification of antioxidant 1076 |
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| CN103724202B true CN103724202B (en) | 2016-05-18 |
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| CN102020562B (en) * | 2010-11-24 | 2013-09-25 | 上海华谊（集团）公司 | Synthesis method of antioxidant 1076 using solid base catalyst |
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