CN110563556A - method for recovering 2, 4-di-tert-butylphenol from double-helix phosphite antioxidant 626 mother liquor - Google Patents
method for recovering 2, 4-di-tert-butylphenol from double-helix phosphite antioxidant 626 mother liquor Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/005—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by obtaining phenols from products, waste products or side-products of processes, not directed to the production of phenols, by conversion or working-up
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
- C07C37/0555—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group being esterified hydroxy groups
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Abstract
The invention belongs to the field of chemical industry, and particularly relates to a method for recovering 2, 4-di-tert-butylphenol from a double-helix phosphite antioxidant 626 mother liquor, which comprises the steps of carrying out reduced pressure distillation treatment, acid hydrolysis, reduced pressure distillation and liquid separation on the specific double-helix phosphite antioxidant 626 mother liquor to obtain a crude product of the 2, 4-di-tert-butylphenol, and finally obtaining a pure product of the 2, 4-di-tert-butylphenol by a rectification mode.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a method for recovering 2, 4-di-tert-butylphenol from double-helix phosphite antioxidant 626 mother liquor.
background
Antioxidants are a class of chemicals which, when present in only small amounts in polymer systems, retard or inhibit the progress of the polymer oxidation process, thereby preventing the aging of the polymer and extending its useful life, also known as "age resistors".
The antioxidant 626 is a high-performance solid organic phosphite antioxidant, has good protection effect on the color of a polymer, is superior to other phosphites, is generally not used independently, is often used in a compound way with phenol main antioxidants such as antioxidant 1010 and the like, and can improve the thermal stability of the polymer in the processing process. After being compounded with the phenol antioxidant, the antioxidant 626 is widely used for high polymer materials such as PE, PP, PS, polyamide, polycarbonate, ABS and the like. The 2, 4-di-tert-butylphenol is an important raw material for producing plastic antioxidants, is an important intermediate of fine chemical products, is widely used for plastics, rubber, fuel oil and the like, and can also be used as a raw material of hindered phenol antioxidants, light stabilizers, insecticides, phenolic resins, coatings, adhesives and the like.
At present, the production process of the domestic antioxidant 626 mainly adopts pentaerythritol, 2, 4-di-tert-butylphenol and phosphorus trichloride to synthesize under alkaline conditions. Zhangyinghong et al (Zhangyihong, Zhang Xinjun, Zhang Yi, Shijian.A. synthetic process research on antioxidant 626. J proceedings of northern academy of Hebei province) studied that phosphorus trichloride reacted with pentaerythritol to produce dichloropentaerythritol phosphite (I), which then reacted with 2, 4-di-tert-butylphenol to produce antioxidant 626 (II). The influence of the raw material ratio, the reaction temperature, the reaction time, the solvent, the catalyst and other factors on the raw material conversion rate and the product yield is researched, the process conditions of the two-step reaction are optimized by utilizing the orthogonal design, and the optimized process conditions for synthesizing the antioxidant 626 are obtained: the mass ratio of the raw materials is pentaerythritol, phosphorus trichloride, 2, 4-di-tert-butylphenol, 10:2.25: 2.52; in the step 1, the reaction temperature is 60 ℃, and the reaction time is 8 hours; in the step 2, the reaction temperature is 62 ℃, and the reaction time is 10 hours; the dosage of the catalyst is 3 percent of the total feeding mass of the raw materials; the solvent is dimethylbenzene, the system pressure is 0.08-0.06MPa, the crystallization solvent is isopropanol, and the washing solvent is methanol; the yield of the target product was about 75% based on 2, 4-di-tert-butylphenol. Phosphorus trichloride is reacted with 2, 4-di-tert-butylphenol to synthesize an intermediate (2, 4-di-tert-butylphenyl) dichlorophosphite, and then the intermediate is reacted with pentaerythritol to synthesize a product. The influence of reaction conditions, the types of solvents and catalysts and other factors on the yield and the quality of the product is explored, and the optimal synthesis process conditions are screened out as follows: and (2) taking methylbenzene or dimethylbenzene as a fusing agent, keeping the system at a negative pressure to normal pressure, and keeping the reaction temperature of the first step at 40-50 ℃. The reaction is carried out for 2 hours, the reaction temperature in the second step is 50-130 ℃, the reaction is carried out for 6 hours, and the reaction yield is 86%.
the yield of the antioxidant 626 varies from 75 to 86%, the low yield results in partial unreacted 2, 4-di-tert-butylphenol and partial side reaction, the reaction is complicated, the research on the recovery of the 2, 4-di-tert-butylphenol consumed from the side reaction is few, and if the 2, 4-di-tert-butylphenol lost in the synthesis of the antioxidant 626 can be completely recovered, the cost of the antioxidant 626 can be greatly reduced.
Disclosure of Invention
Aiming at the technical problems, the invention provides a method for recovering 2, 4-di-tert-butylphenol from double-helix phosphite ester antioxidant 626 mother liquor, and the method has the advantages of mild and easily-controlled process conditions and high recovery rate.
The technical scheme of the invention is as follows:
A method for recovering 2, 4-di-tert-butylphenol from a double helix phosphite antioxidant 626 mother liquor comprises the following steps:
(1) Pretreating double helix phosphite antioxidant 626 mother liquor: distilling the double helix phosphite antioxidant 626 mother liquor under reduced pressure to remove the solvent I to obtain residual mother liquor, and adding methanol into the residual mother liquor to obtain a solution;
(2) Acidolysis of the solution: adding dilute hydrochloric acid with the mass fraction of 8-15% into the solution, and refluxing for 2-3h at 55-60 ℃ to obtain hydrolysate;
(3) Liquid separation: removing methanol from the hydrolysate through reduced pressure distillation, and separating liquid to obtain a crude product of 2, 4-di-tert-butylphenol;
(4) And (3) rectification: the pure product of the 2, 4-di-tert-butylphenol is obtained by rectification.
preferably, the amount of methanol added in step (1) is 2-2.5 times of the mass of the remaining mother liquor.
Preferably, the amount of 10% diluted hydrochloric acid added in step (2) is 0.5 to 1.5 times the mass of methanol.
Preferably, in step (3): in order to ensure smooth liquid separation, the liquid separation temperature is 60-70 ℃. The 2, 4-di-tert-butylphenol is solidified at the excessively low temperature, and the operation is difficult due to the excessively high temperature.
Preferably, the step (3) is carried out under the control of reduced pressure distillation at 10Kpa and 40-55 ℃.
Preferably, the solvent I is one or two of isopropanol and ethanol, but is not limited to these solvents, and the distilled solvent is determined according to the method for preparing the antioxidant 626 mother liquor.
Preferably, preparation of the bis-spiro phosphite antioxidant 626 mother liquor: mixing pentaerythritol and a solvent II, adding triethylamine, dropwise adding phosphorus trichloride at 45 ℃, reacting for 3 hours, adding 2, 4-di-tert-butylphenol, reacting for 3 hours, adding triethylamine to neutralize to neutrality, filtering triethylamine hydrochloride, decompressing and desolventizing the solvent II, adding the solvent I, refluxing for 3 hours, cooling and carrying out solid-liquid separation, wherein the solid is a pure product of the double-helix phosphite antioxidant 626, and the residual solution is a mother solution of the double-helix phosphite antioxidant 626. However, the preparation of the present bis-helical phosphite antioxidant 626 mother liquor is not limited to this method.
Preferably, the main components of the residue in the double helix phosphite antioxidant 626 mother liquor are:
Preferably, the molar ratio of pentaerythritol, 2, 4-di-tert-butylphenol and phosphorus trichloride is 1:2.1:2.1 and the amount of triethylamine is 0.5 to 1 percent of the mass of 2, 4-di-tert-butylphenol.
Preferably, the solvent II is one or two selected from toluene and xylene.
The methanol and the water recovered in the invention can be recycled, thereby saving energy, reducing waste and cost.
In the invention, the acidolysis method is adopted to completely dissociate 2, 4-di-tert-butylphenol consumed by the side reaction, and obtain a crude product with unreacted 2, 4-di-tert-butylphenol in a liquid separation mode, and then the crude product is obtained by rectification to obtain a pure product, so that the method has the advantages of no high-temperature and high-pressure reaction, mild conditions and high recovery rate, solves the problem of water and methanol treatment, and recovers 2, 4-di-tert-butylphenol in the mother liquor, thereby achieving the purpose of recycling, saving resources, realizing the unification of environmental benefits and economic benefits, and greatly reducing the cost for producing the antioxidant 626.
Detailed Description
The invention is further illustrated by the following examples. These examples are for illustrative purposes only and do not limit the scope and spirit of the present invention. For those skilled in the art to which the invention pertains, several simple deductions or substitutions may be made without departing from the inventive concept, and all shall be considered as belonging to the protection scope of the present invention.
Example 1
200.00g of pentaerythritol, 3000g of toluene and 6.2g of triethylamine are added into a 5L four-neck round-bottom flask provided with a mechanical stirring device, a thermometer and a reflux condenser, the temperature is raised to 45 ℃, 423g of phosphorus trichloride is dropwise added, the dropwise addition is completed, the reaction is carried out for 3h, 621g of 2, 4-di-tert-butylphenol is added, the reflux is carried out for 3h, triethylamine is added for neutralization to neutrality, triethylamine hydrochloride is filtered out, the toluene is removed under reduced pressure, 3000g of isopropanol is added, the reflux is carried out for 3h, the temperature is reduced, the solid is separated from the liquid, the solid is a pure double-helix phosphite antioxidant 626, and the residual.
Distilling isopropanol in the mother liquor of the double helix phosphite antioxidant 626 at 5Kpa and 60 ℃, adding 300g of methanol to 150g of residue for dissolution, then adding 150g of 10% diluted hydrochloric acid, refluxing at 60 ℃ for 2h to obtain hydrolysate, distilling methanol at 10Kpa and 55 ℃ under reduced pressure to obtain a mixture of 2, 4-di-tert-butylphenol and water, separating the mixture at 70 ℃ to obtain a crude product of 2, 4-di-tert-butylphenol, and rectifying to obtain a pure product, wherein the recovery rate of the 2, 4-di-tert-butylphenol is 97.54%.
Example 2
200.00g of pentaerythritol, 3000g of toluene and 6.2g of triethylamine are added into a 5L four-neck round-bottom flask provided with a mechanical stirring device, a thermometer and a reflux condenser, the temperature is raised to 45 ℃, 423g of phosphorus trichloride is dropwise added, the dropwise addition is completed, the reaction is carried out for 3h, 621g of 2, 4-di-tert-butylphenol is added, the reflux is carried out for 3h, triethylamine is added for neutralization to neutrality, triethylamine hydrochloride is filtered out, the toluene is removed under reduced pressure, 3000g of isopropanol is added, the reflux is carried out for 3h, the temperature is reduced, the solid is separated from the liquid, the solid is a pure double-helix phosphite antioxidant 626, and the residual.
Distilling isopropanol in the mother liquor of the double helix phosphite antioxidant 626 at 5Kpa and 60 ℃, adding 300g of methanol to 100g of residue for dissolution, then adding 300g of 8% diluted hydrochloric acid, refluxing for 1h at 60 ℃ to obtain hydrolysate, distilling methanol at 10Kpa and 40 ℃ under reduced pressure to obtain a mixture of 2, 4-di-tert-butylphenol and water, separating at 60 ℃ to obtain a crude product of 2, 4-di-tert-butylphenol, and rectifying to obtain a pure product, wherein the recovery rate of the 2, 4-di-tert-butylphenol is 92.15%.
Example 3
200.00g of pentaerythritol, 3000g of toluene and 6.2g of triethylamine are added into a 5L four-neck round-bottom flask provided with a mechanical stirring device, a thermometer and a reflux condenser, the temperature is raised to 45 ℃, 423g of phosphorus trichloride is dropwise added, the reaction is carried out for 3 hours after the dropwise addition, and then 621g of 2, 4-di-tert-butylphenol is added and the reflux is carried out for 3 hours. Adding triethylamine to neutralize to neutrality, filtering out triethylamine hydrochloride, reducing pressure to remove toluene, adding 3000g of isopropanol, refluxing for 3h, cooling, performing solid-liquid separation, wherein the solid is pure double helix phosphite antioxidant 626, and the residual solution is double helix phosphite antioxidant 626 mother liquor.
distilling off isopropanol in the mother liquor of the double helix phosphite antioxidant 626 at 5Kpa and 60 ℃, adding 300g of methanol to 200g of residue for dissolution, then adding 450g of 15% diluted hydrochloric acid, refluxing at 55 ℃ for 3h to obtain hydrolysate, distilling off methanol at 10Kpa and 50 ℃ under reduced pressure to obtain a mixture of 2, 4-di-tert-butylphenol and water, separating the mixture at 65 ℃ to obtain a crude product of 2, 4-di-tert-butylphenol, and rectifying to obtain a pure product, wherein the recovery rate of the 2, 4-di-tert-butylphenol is 95.32%.
Comparative example 1
200.00g of pentaerythritol, 3000g of toluene and 6.2g of triethylamine are added into a 5L four-neck round-bottom flask provided with a mechanical stirring device, a thermometer and a reflux condenser, the temperature is raised to 45 ℃, 423g of phosphorus trichloride is dropwise added, the reaction is carried out for 3 hours after the dropwise addition, and then 621g of 2, 4-di-tert-butylphenol is added and the reflux is carried out for 3 hours. Adding triethylamine to neutralize to neutrality, filtering out triethylamine hydrochloride, reducing pressure to remove toluene, adding 3000g of isopropanol, refluxing for 3h, cooling, performing solid-liquid separation, wherein the solid is pure double helix phosphite antioxidant 626, and the residual solution is double helix phosphite antioxidant 626 mother liquor.
Distilling isopropanol in the mother liquor of the double helix phosphite antioxidant 626 at 5Kpa and 60 ℃, adding 300g of methanol to 150g of residue for dissolution, then adding 150g of 10% diluted hydrochloric acid, refluxing at 30 ℃ for 2h to obtain hydrolysate, and distilling the methanol at 10Kpa and 55 ℃ under reduced pressure to obtain a mixture of 2, 4-di-tert-butylphenol and water, separating the mixture at 70 ℃ to obtain a crude product of 2, 4-di-tert-butylphenol, and rectifying to obtain a pure product, wherein the recovery rate of the 2, 4-di-tert-butylphenol is 55.12%.
Comparative example 2
200.00g of pentaerythritol, 3000g of toluene and 6.2g of triethylamine are added into a 5L four-neck round-bottom flask provided with a mechanical stirring device, a thermometer and a reflux condenser, the temperature is raised to 45 ℃, 423g of phosphorus trichloride is dropwise added, the reaction lasts for 3 hours after the dropwise addition, and 621g of 2, 4-di-tert-butylphenol is added and the reflux lasts for 3 hours. Adding triethylamine to neutralize to neutrality, filtering out triethylamine hydrochloride, reducing pressure to remove toluene, adding 3000g of isopropanol, refluxing for 3h, cooling, performing solid-liquid separation, wherein the solid is pure double helix phosphite antioxidant 626, and the residual solution is double helix phosphite antioxidant 626 mother liquor.
distilling off isopropanol in the mother liquor of the double helix phosphite antioxidant 626, adding 300g of methanol into 100g of residues for dissolution, then adding 300g of 8% dilute hydrochloric acid, refluxing for 0.5h at 60 ℃ to obtain hydrolysate, distilling off the methanol at 10Kpa under reduced pressure at 40 ℃ to obtain a mixture of 2, 4-di-tert-butylphenol and water, separating the liquid at 60 ℃ to obtain a crude product of the 2, 4-di-tert-butylphenol, and rectifying to obtain a pure product, wherein the recovery rate of the 2, 4-di-tert-butylphenol is 75.49%.
Comparative example 3
200.00g of pentaerythritol, 3000g of toluene and 6.2g of triethylamine are added into a 5L four-neck round-bottom flask provided with a mechanical stirring device, a thermometer and a reflux condenser, the temperature is raised to 45 ℃, 423g of phosphorus trichloride is dropwise added, the reaction is carried out for 3 hours after the dropwise addition, and then 621g of 2, 4-di-tert-butylphenol is added and the reflux is carried out for 3 hours. Adding triethylamine to neutralize to neutrality, filtering out triethylamine hydrochloride, reducing pressure to remove toluene, adding 3000g of isopropanol, refluxing for 3h, cooling, performing solid-liquid separation, wherein the solid is pure double helix phosphite antioxidant 626, and the residual solution is double helix phosphite antioxidant 626 mother liquor.
Distilling off isopropanol in the mother liquor of the double helix phosphite antioxidant 626 at 5Kpa and 60 ℃, adding 300g of methanol to 200g of residue for dissolution, then adding 450g of 15% diluted hydrochloric acid, refluxing at 75 ℃ for 3h to obtain hydrolysate, distilling off methanol at 10Kpa and 50 ℃ under reduced pressure to obtain a mixture of 2, 4-di-tert-butylphenol and water, separating the mixture at 75 ℃ to obtain a crude product of 2, 4-di-tert-butylphenol, and rectifying to obtain a pure product, wherein the recovery rate of the 2, 4-di-tert-butylphenol is 85.62%.
Comparative example 4
200.00g of pentaerythritol, 3000g of toluene and 6.2g of triethylamine are added into a 5L four-neck round-bottom flask provided with a mechanical stirring device, a thermometer and a reflux condenser, the temperature is raised to 45 ℃, 423g of phosphorus trichloride is dropwise added, the reaction lasts for 3 hours after the dropwise addition, and 621g of 2, 4-di-tert-butylphenol is added and the reflux lasts for 3 hours. Adding triethylamine to neutralize to neutrality, filtering out triethylamine hydrochloride, reducing pressure to remove toluene, adding 3000g of isopropanol, refluxing for 3h, cooling, performing solid-liquid separation, wherein the solid is pure double helix phosphite antioxidant 626, and the residual solution is double helix phosphite antioxidant 626 mother liquor.
Distilling off isopropanol in the mother liquor of the double helix phosphite antioxidant 626 at 5Kpa and 50 ℃, adding 300g of methanol to dissolve 300g of residues, then adding 100g of 5% diluted hydrochloric acid, refluxing for 1h at 50 ℃ to obtain hydrolysate, distilling off methanol at 10Kpa and 30 ℃ under reduced pressure to obtain a mixture of 2, 4-di-tert-butylphenol and water, separating the mixture at 50 ℃ to obtain a crude product of 2, 4-di-tert-butylphenol, and rectifying to obtain a pure product, wherein the recovery rate of the 2, 4-di-tert-butylphenol is 50.38%.
The recovery rate of the 2, 4-di-tert-butylphenol recovered by the method can reach more than 92 percent, the recovery rate of the embodiment is far higher than that of a comparative example, the method has the advantages of no high-temperature and high-pressure reaction, mild conditions and high recovery rate, the problem of water and methanol treatment is solved, and the 2, 4-di-tert-butylphenol in the mother liquor is recovered, so that the aim of recycling is fulfilled, resources are saved, the unification of environmental benefits and economic benefits is realized, and the cost for producing the antioxidant 626 can be greatly reduced.
Claims (8)
1. a method for recovering 2, 4-di-tert-butylphenol from a double helix phosphite antioxidant 626 mother liquor is characterized by comprising the following steps:
(1) Pretreating double helix phosphite antioxidant 626 mother liquor: distilling the double helix phosphite antioxidant 626 mother liquor under reduced pressure to remove the solvent I to obtain residual mother liquor, and adding methanol into the residual mother liquor to obtain a solution;
(2) Acidolysis of the solution: adding dilute hydrochloric acid with the mass fraction of 8-15% into the solution, and refluxing for 2-3h at 55-60 ℃ to obtain hydrolysate;
(3) Liquid separation: removing methanol from the hydrolysate through reduced pressure distillation, and separating liquid to obtain a crude product of 2, 4-di-tert-butylphenol;
(4) And (3) rectification: the pure product of the 2, 4-di-tert-butylphenol is obtained by rectification.
2. The method for recovering 2, 4-di-tert-butylphenol from the mother liquor of the double helix phosphite antioxidant 626 as claimed in claim 1, wherein the mother liquor of the double helix phosphite antioxidant 626 is a mother liquor generated in the synthesis of pentaerythritol, 2, 4-di-tert-butylphenol and phosphorus trichloride under alkaline conditions.
3. The method for recovering 2, 4-di-tert-butylphenol from the mother liquor of the double helix phosphite antioxidant 626 as claimed in claim 1, wherein the solvent I is distilled off under reduced pressure in the step (1) under the control of 5Kpa and 60 ℃.
4. The method for recovering 2, 4-di-tert-butylphenol from the mother liquor of double helix phosphite antioxidant 626 as claimed in claim 1, wherein in step (3): the temperature of liquid separation is 60-70 ℃.
5. The method for recovering 2, 4-di-tert-butylphenol from the mother liquor of the double helix phosphite antioxidant 626 as claimed in claim 1, wherein the control conditions of the reduced pressure distillation in the step (3) are 10Kpa and 40-55 ℃.
6. the method for recovering 2, 4-di-tert-butylphenol from the mother liquor of the double helix phosphite antioxidant 626 as claimed in claim 1, wherein the amount of methanol added in step (1) is 2-3 times of the mass of the rest mother liquor.
7. the method for recovering 2, 4-di-tert-butylphenol from the mother liquor of double helix phosphite antioxidant 626 as claimed in claim 1, characterized in that the addition amount of the dilute hydrochloric acid with the mass fraction of 8-15% in step (2) is 0.5-1.5 times of the mass of methanol.
8. The method for recovering 2, 4-di-tert-butylphenol from the mother liquor of the double helix phosphite antioxidant 626 as claimed in claim 1, wherein the solvent I is one or two of isopropanol and ethanol.
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|---|---|---|---|---|
| CN114057548A (en) * | 2021-12-03 | 2022-02-18 | 陕西艾科莱特新材料有限公司 | Method for recovering 2, 4-di-tert-butylphenol from antioxidant 168 concentrated mother liquor |
| CN114057548B (en) * | 2021-12-03 | 2024-03-01 | 陕西艾科莱特新材料有限公司 | Method for recovering 2, 4-di-tert-butylphenol from concentrated mother liquor of antioxidant 168 |
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Application publication date: 20191213 |