CN109651213A - The production method of antioxidant 300 - Google Patents
The production method of antioxidant 300 Download PDFInfo
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- CN109651213A CN109651213A CN201910097944.8A CN201910097944A CN109651213A CN 109651213 A CN109651213 A CN 109651213A CN 201910097944 A CN201910097944 A CN 201910097944A CN 109651213 A CN109651213 A CN 109651213A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of production methods of antioxidant 300, belong to alkylphenol sulfide antioxidant manufacturing technology field.The production method, comprising the following steps: 1. using the aliphatic saturated hydrocarbon solvent naphtha of high boiling range as solvent, and 6- tertiary butyl metacresol and sulfur dichloride carry out thio reaction, generates 4,4 '-thiobis (6- tertiary butyl metacresol)；2. after the completion of thio reaction, low-molecular-weight alcohol is added；3. heating, steams hydrogen chloride and alcohol, it is cooled to room temperature, weak base aqueous solution is added and adjusts material pH value to neutrality, filtering obtains crude product.Production method provided by the present invention, it is scientific and reasonable, it is simple and easy, the minimal amount of residual chloride hydrogen for needing to neutralize only is generated in production process, antioxidant 300 crude product impurity obtained is few, purity is high.
Description
Technical field
The present invention relates to a kind of production methods of antioxidant 300, belong to alkylphenol sulfide antioxidant manufacturing technology field.
Background technique
The reaction of alkyl phenol and sulfur chloride has hydrogen chloride generation, and the hydrogen chloride gas of generation is handled with water absorption, but is reacted
Many hydrogen chloride release can also be remained in material not come out, equipment can be corroded in subsequent process, needed remaining chlorination
Hydrogen is driven away clean or is fallen with alkali neutralization.
As described in patent of invention CN1318401C: from the point of view of the technique used by current domestic production producer, generally adopting
It is under conditions of 5 DEG C to 15 DEG C, sulfur dichloride and 5- methyl -2-TBP are in the medium that petroleum ether makees solvent
It is reacted, antioxidant 300 crude product is obtained, then by being recrystallized to give fine work." the hydrogen chloride gas generated due to reaction process
There is larger dissolution in the solution in body ", " more traditional way is to lead to N to reaction system in the latter stage of thio reaction2, drive away
A certain amount of hydrogen chloride gas, while extending the reaction time, but effect is less desirable ", therefore, " in original thio reaction
Latter stage, change over logical N2Method, using logical NH3Gas protects reaction system, NH3The chlorination generated with reaction
Hydrogen can be neutralized thoroughly, so that the hydrogen chloride remaining dissolved in reaction system is less, while take WATER-WASHING METHOD removal reaction life
At ammonium chloride and reaction process in the by-product and impurity that generate ".
The ammonium chloride quantity washed out in today that environmental consciousness is constantly reinforced, antioxidant 300 production process is larger, from
The ammonium chloride that being purified into sewage can sell is difficult, and can only rethink the method for how exorcising a large amount of residual chloride hydrogen.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of production method of antioxidant 300, science is closed
Reason, it is simple and easy, in production process, only generate the residual chloride hydrogen that minute quantity needs to neutralize, antioxidant 300 crude product obtained
Impurity is few, purity is high.
Hydrogen chloride gas is soluble in ethyl alcohol and ether, can also be dissolved in other gas chromatographies, and it is molten to be but practically insoluble in aliphatic hydrocarbon
Agent.Synthesizing the hydrogen chloride gas that antioxidant 300 generates is typically all to absorb hydrochloric acid sale processing with water；Remaining chlorine in material
Change hydrogen, if the method using heating is driven away, since petroleum ether boiling range is mostly at 70-90 DEG C, hydrogen chloride is by consolidating in material
Body granular absorption, it is unobvious that effect is driven away in heating；So we select the higher aliphatic solvent oil of boiling range to replace petroleum
Ether is used for thio reaction, and material is then heated to solid matter and is completely dissolved, to release the hydrogen chloride that it is adsorbed, this
Temperature is at 126 DEG C or so.
It was found that, solubility increase of the solid product in aliphatic hydrocarbon is not obvious in temperature-rise period, but at 126 DEG C
When left and right, it largely can start to dissolve suddenly, the dissolution of this when can be understood as the high temperature melting of product, and product has oxidation to become
Black trend, temperature is higher, and the time under high temperature is longer, and blackening is more serious, and the product appearance obtained after purification blacks.
The production method of antioxidant 300 of the present invention, comprising the following steps:
1) using the aliphatic saturated hydrocarbon solvent naphtha of high boiling range as solvent, 6- tertiary butyl metacresol and sulfur dichloride progress are thio anti-
It answers, generates 4,4 '-thiobis (6- tertiary butyl metacresol)；
2) after the completion of thio reaction, low-molecular-weight alcohol is added；
3) it heats up, steams hydrogen chloride and alcohol, be cooled to room temperature, weak base aqueous solution is added and adjusts material pH value to neutrality,
Filtering, obtains crude product.
At 130 DEG C or more, boiling range is 130-140 DEG C for the aliphatic saturated hydrocarbon solvent naphtha initial boiling point of the high boiling range.
The low-molecular-weight alcohol is one or more of methanol, ethyl alcohol or isopropanol.
The envelope-bulk to weight ratio of the low-molecular-weight alcohol dosage and 6- tertiary butyl metacresol dosage is 0.1-2.
Preferably, the envelope-bulk to weight ratio of the low-molecular-weight alcohol dosage and 6- tertiary butyl metacresol dosage is 0.5-1；Its
In, by volume, by weight, envelope-bulk to weight ratio unit is ml/g to 6- tertiary butyl metacresol dosage to low-molecular-weight alcohol dosage.
In the step 3, temperature when heating steams hydrogen chloride and alcohol is 110-130 DEG C.
Preferably, in the step 3, temperature when heating steams hydrogen chloride and alcohol is 110-120 DEG C.
Preferably, the weak base aqueous solution is one of ammonium hydroxide or carbonic acid sodium water solution.
The low-molecular-weight alcohol very big to antioxidant 300 solubility is selected to be added in reaction mass as cosolvent, so that
Solid product in material fully dissolved during low temperature or heating, and the hydrogen chloride released is also dissolved in alcohol material solution
In, if the boiling point of methanol and ethyl alcohol is respectively 64.4 DEG C, 78.3 DEG C, the small-molecular-weight alcohol of low boiling point is added in reaction mass
Afterwards, alcohol is steamed after heating to go, to also release the hydrogen chloride in material, although the reactant meeting after alcohol cosolvent is added
It is divided into aliphatic solvent phase and alcohol material phase two-phase, but during stirring steams hydrogen chloride and alcohol, it is very flat steams process
Surely, pure and mild aliphatic solvent oil solvent forms azeotropic mixture and is distilled out of, when temperature is raised between 110 DEG C -120 DEG C, hydrogen chloride and
Alcohol, which has been bordering on, to be steamed completely, and the solvent selection initial boiling point for being accordingly used in thio reaction is replaced often by 130 DEG C of aliphatic solvent oil
Petroleum ether can complete the purpose for steaming pure and mild hydrogen chloride, and solvent major part remains in material, does not select national standard
200# solvent naphtha is because solvent boiling range is excessively high, and crude product is not easy drying, so the aliphatic saturated hydrocarbon that boiling range is 130-140 DEG C
Solvent naphtha is optimal selection.The hydrogen chloride alkyd solution steamed can be added directly into material in use next time to be used, with
Afterwards that the material for steaming pure and mild hydrogen chloride is cooling, product can recrystallize out, be cooled to room temperature, adjust object with weak base aqueous solution
Expect that neutrality, crude product is obtained by filtration in pH value.
If fruit mother liquor will be reused, due to that cannot have the presence of alcohol in reaction mass, this can add in material and afterwards
Enter little water to refilter, the product yield of lower secondary response would not be influenced by releasing water phase from mother liquor bottom after filtering.
Compared with prior art, the invention has the following beneficial effects:
Production method described in 1., it is scientific and reasonable, it is simple and easy, compared with conventional production methods, needed in production process
The quantity of the residual chloride hydrogen of neutralization reduces 98.6-99.72%, significantly reduces the improvement hardly possible of sewage dirt during pollution treatment
Degree；
2. production method provided by the invention have passed through primary recrystallization during obtaining crude product, purity is significantly
It improves, creates better condition for subsequent product purification.
Specific embodiment
The present invention will be further explained with reference to the examples below.
Comparative example 1
It is added between 112 grams of 6- tertiary butyls in 1000 milliliters of four-hole boiling flasks equipped with blender, thermometer and constant pressure funnel
Cresols and 290 milliliters of petroleum ethers, under stirring, material is cooled to 10 DEG C, by the petroleum ether of solvent sulfur dichloride (31.15 grams)
(100 milliliters) solution moves into constant pressure funnel, and is slowly dropped in reaction flask in 80 ± 10 minutes, during which controls material
Temperature is kept the temperature after sixty minutes again at 8 ± 2 DEG C, under stirring, and ammonium hydroxide reagent is gradually added then, and pH test paper tester stops when expecting alkalescence
Only, amount to and be added 18 milliliters of ammonium hydroxide；Filtering, obtains crude product.
Embodiment 1
With 1 device of comparative example and step, the difference is that: petroleum ether is changed to the aliphatic saturated hydrocarbon that boiling range is 130-140 DEG C
Solvent naphtha；The operation that ammonium hydroxide reagent is added is changed to: using the oily-water seperating equipment that aliphatic solvent oil takes alcohol out of is steamed, then being existed
100 ml methanols are added in reaction mass, heat up, when temperature is slowly raised to 115 ± 5 DEG C, when no distillate, stops heating, obtains
To 137 milliliters of azeotropic mixture, wherein 112 milliliters of methanol phase；It is cooled to room temperature under material stirring, instills 1 drop ammonium hydroxide reagent, material color
When turning ash, pH test paper tests alkalescence；Crude product is obtained by filtration.
Compared with the ammonium hydroxide quantity added by the comparative example 1, by 1 drop, 0.05 milliliter of calculating, the quantity than ammonium hydroxide added by embodiment 1 subtracts
Lack 99.72%.
During the experiment, ammonia vol is added dropwise usually between 1-5 drop, therefore reduces the amount for needing the hydrogen chloride neutralized
For 98.6-99.72%.
Embodiment 2
With 1 device of embodiment and step, the difference is that: petroleum ether is changed to 130-140 DEG C of boiling range of saturated fat hydrocarbon solvent
Oil, methanol are changed to dehydrated alcohol, and additional amount is 50 milliliters, are warming up to 115 DEG C, directly steam alcohol-aliphatic solvent oil azeotropic liquid
85 milliliters, wherein ethyl alcohol is mutually 48 milliliters.After being cooled to room temperature, 1 drop ammonium hydroxide reagent, the discoloration of material solution color, pH test paper are instilled
Test is in alkalescence；Compared with example 1, the quantity of added ammonium hydroxide reduces 99.72%.
Embodiment 3
With 1 device of embodiment and step, the difference is that: petroleum ether is changed to 130-140 DEG C of boiling range of saturated fat hydrocarbon solvent
Oil, methanol are changed to isopropanol, and additional amount is 50 milliliters, directly steam alcohol-aliphatic solvent oil azeotropic liquid, temperature is raised to 125 DEG C
When stop heating, steam 107.5 milliliters of azeotropic mixture total amount, after azeotropic mixture does not have split-phase, material to be cooled to room temperature, instill 2 milliliters of ammonia
Water reagent, pH test paper test alkalescence, this shows that remaining alkyd is more in material, but compares with comparative example 1, added ammonium hydroxide
Quantity reduces 88.89%, this shows after making cosolvent use with isopropanol, to the number that residual chloride hydrogen in material is greatly reduced
Amount is same effective.
Claims (8)
1. a kind of production method of antioxidant 300, it is characterised in that: the following steps are included:
1) using the aliphatic saturated hydrocarbon solvent naphtha of high boiling range as solvent, 6- tertiary butyl metacresol and sulfur dichloride carry out thio reaction,
It generates 4,4 '-thiobis (6- tertiary butyl metacresol)；
2) after the completion of thio reaction, low-molecular-weight alcohol is added；
3) it heats up, steams hydrogen chloride and alcohol, be cooled to room temperature, weak base aqueous solution is added and adjusts material pH to neutrality, filtering obtains
To crude product.
2. the production method of antioxidant 300 according to claim 1, it is characterised in that: the aliphatic saturated hydrocarbon of high boiling range is molten
For the initial boiling point of agent oil at 130 DEG C or more, boiling range is 130-140 DEG C.
3. the production method of antioxidant 300 according to claim 1, it is characterised in that: low-molecular-weight alcohol is methanol, ethyl alcohol
Or one or more of isopropanol.
4. the production method of antioxidant 300 according to claim 3, it is characterised in that: low-molecular-weight alcohol dosage and 6- are special
The envelope-bulk to weight ratio of butyl metacresol dosage is 0.1-2.
5. the production method of antioxidant 300 according to claim 4, it is characterised in that: low-molecular-weight alcohol dosage and 6- are special
The envelope-bulk to weight ratio of butyl metacresol dosage is 0.5-1.
6. the production method of antioxidant 300 according to claim 1, it is characterised in that: in step 3, heating steams chlorination
Temperature when hydrogen and alcohol is 110-130 DEG C.
7. the production method of antioxidant 300 according to claim 6, it is characterised in that: in step 3, heating steams chlorination
Temperature when hydrogen and alcohol is 110-120 DEG C.
8. the production method of antioxidant 300 according to claim 1, it is characterised in that: in step 3, weak base aqueous solution is
One of ammonium hydroxide or carbonic acid sodium water solution.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910097944.8A CN109651213B (en) | 2019-01-31 | 2019-01-31 | Method for producing antioxidant 300 |
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| CN201910097944.8A CN109651213B (en) | 2019-01-31 | 2019-01-31 | Method for producing antioxidant 300 |
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| CN109651213B CN109651213B (en) | 2020-09-04 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113200893A (en) * | 2021-04-20 | 2021-08-03 | 江苏极易新材料有限公司 | Synthesis method of 4, 4' -thiobis (6-tert-butyl-3-methylphenol) |
| CN117534599A (en) * | 2024-01-10 | 2024-02-09 | 淄博万科化工有限公司 | Solvent-free production method of antioxidant 323 with low chlorine content |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1206003A (en) * | 1997-07-22 | 1999-01-27 | 北京燕化石油化工股份有限公司化工三厂 | Preparation of high-purity thiobisphenol oligomer antioxidant |
| CN1760180A (en) * | 2005-11-10 | 2006-04-19 | 淄博市新材料研究所 | Method for synthesizing modified-antioxidant 300 |
| CN108586206A (en) * | 2018-04-13 | 2018-09-28 | 淄博万科化工有限公司 | One kettle way prepares 4,4 '-butylidenebis（6- tertiary butyl metacresols）Method |
-
2019
- 2019-01-31 CN CN201910097944.8A patent/CN109651213B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1206003A (en) * | 1997-07-22 | 1999-01-27 | 北京燕化石油化工股份有限公司化工三厂 | Preparation of high-purity thiobisphenol oligomer antioxidant |
| CN1760180A (en) * | 2005-11-10 | 2006-04-19 | 淄博市新材料研究所 | Method for synthesizing modified-antioxidant 300 |
| CN108586206A (en) * | 2018-04-13 | 2018-09-28 | 淄博万科化工有限公司 | One kettle way prepares 4,4 '-butylidenebis（6- tertiary butyl metacresols）Method |
Non-Patent Citations (1)
| Title |
|---|
| 朱永国: "抗氧剂300的合成及应用", 《适用技术市场》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113200893A (en) * | 2021-04-20 | 2021-08-03 | 江苏极易新材料有限公司 | Synthesis method of 4, 4' -thiobis (6-tert-butyl-3-methylphenol) |
| CN117534599A (en) * | 2024-01-10 | 2024-02-09 | 淄博万科化工有限公司 | Solvent-free production method of antioxidant 323 with low chlorine content |
| CN117534599B (en) * | 2024-01-10 | 2024-03-19 | 淄博万科化工有限公司 | Solvent-free production method of antioxidant 323 with low chlorine content |
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Denomination of invention: Production method of antioxidant 300 Effective date of registration: 20211130 Granted publication date: 20200904 Pledgee: Industrial Commercial Bank of China Ltd. Zibo Zhangdian branch Pledgor: Zibo Wanke Chemical Co.,Ltd. Registration number: Y2021980013667 |
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