CN115521237A - Method for preparing tert-butyl peroxybenzoate with high yield - Google Patents
Method for preparing tert-butyl peroxybenzoate with high yield Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 64
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000001704 evaporation Methods 0.000 claims abstract description 58
- 238000001035 drying Methods 0.000 claims abstract description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 48
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000004821 distillation Methods 0.000 claims abstract description 42
- 239000007864 aqueous solution Substances 0.000 claims abstract description 41
- 239000000243 solution Substances 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000003960 organic solvent Substances 0.000 claims abstract description 32
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 28
- BBCAQPYJVYMQFB-UHFFFAOYSA-N sodium;2-methylpropane Chemical compound [Na+].C[C-](C)C BBCAQPYJVYMQFB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 23
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 abstract description 56
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 46
- 239000011259 mixed solution Substances 0.000 description 41
- 239000007788 liquid Substances 0.000 description 36
- 239000012044 organic layer Substances 0.000 description 31
- 238000001816 cooling Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 9
- 238000001514 detection method Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- CWPKTBMRVATCBL-UHFFFAOYSA-N 3-[1-[1-[(2-methylphenyl)methyl]piperidin-4-yl]piperidin-4-yl]-1h-benzimidazol-2-one Chemical compound CC1=CC=CC=C1CN1CCC(N2CCC(CC2)N2C(NC3=CC=CC=C32)=O)CC1 CWPKTBMRVATCBL-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 description 1
- YHOYYHYBFSYOSQ-UHFFFAOYSA-N 3-methylbenzoyl chloride Chemical compound CC1=CC=CC(C(Cl)=O)=C1 YHOYYHYBFSYOSQ-UHFFFAOYSA-N 0.000 description 1
- WNLMYNASWOULQY-UHFFFAOYSA-N 4-tert-butylbenzoyl chloride Chemical compound CC(C)(C)C1=CC=C(C(Cl)=O)C=C1 WNLMYNASWOULQY-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
- C07C407/003—Separation; Purification; Stabilisation; Use of additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing tert-butyl peroxybenzoate with high yield. The method of the invention comprises the following steps: under the condition of stirring, dropwise adding a tert-butyl hydrogen peroxide aqueous solution into a sodium hydroxide aqueous solution, and then reacting; adding an organic solvent which can generate azeotropy with water; then carrying out reduced pressure distillation until water in the system is completely evaporated out to obtain an organic solution of the tert-butyl sodium peroxide; dripping benzoyl chloride into an organic solution of tert-butyl sodium peroxide for reaction; then filtering, distilling under reduced pressure, washing with alkali, washing with water, and carrying out vacuum flash evaporation and drying to obtain the tert-butyl peroxybenzoate. The method avoids the hydrolysis of benzoyl chloride, improves the yield of the product and finally obtains the high-purity tert-butyl peroxybenzoate product.
Description
Technical Field
The invention relates to a method for preparing tert-butyl peroxybenzoate with high yield, belonging to the technical field of chemical synthesis.
Background
Tert-butyl peroxybenzoate (abbreviated as TBPB) is an organic peroxide which is widely applied and is widely used as an initiator in polymerization processes of ethylene, styrene, propylene, vinyl acetate, diallyl phthalate, isobutene and the like. In the unsaturated polyester curing process, the curing agent is widely applied to the forming process of pulling agents such as SMC, BMC, DMC and the like, and can also be applied to a two-component curing system formed by MEPK, BPO, TBPO and the like with higher activity.
At present, the synthesis of tert-butyl peroxybenzoate has been reported. Such as:
patent document US2567615 discloses a synthesis method of tert-butyl peroxybenzoate. The synthesis method comprises the steps of reacting tert-butyl hydroperoxide with benzoyl chloride and a potassium hydroxide aqueous solution, and carrying out liquid separation, alkali washing, water washing and drying to obtain tert-butyl peroxybenzoate.
Patent document JPS5792005A discloses a method for synthesizing a composition of tert-butyl peroxybenzoate and tert-butyl peroxy (3-methyl) benzoate. The synthesis method comprises the steps of dropwise adding tert-butyl hydroperoxide into a sodium hydroxide aqueous solution, then slowly dropwise adding a mixed solution of benzoyl chloride and 3-methylbenzoyl chloride, and carrying out liquid separation, alkali washing, water washing and drying to obtain the composition of tert-butyl peroxybenzoate and tert-butyl peroxy (3-methyl) benzoate.
Patent document GB1429510A discloses a synthesis process of tert-butyl peroxy (4-tert-butyl) benzoate. The synthesis process is to dissolve tert-butyl hydroperoxide in sodium hydroxide water solution. After decantation and washing with pentane, a small amount of an alkylaryl sulfonate solution is added, followed by slow dropwise addition of 4-tert-butylbenzoyl chloride to give tert-butyl peroxy (4-tert-butyl) benzoate.
In the above synthesis methods, water is used as a solvent for the synthesis reaction, however, benzoyl chloride is very easy to hydrolyze when meeting water, and in the dripping process of benzoyl chloride, benzoyl chloride is rapidly hydrolyzed when meeting water to generate a large amount of benzoic acid byproducts, so that the conversion rate of benzoyl chloride is reduced, and the purity and yield of the tert-butyl peroxybenzoate product are reduced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for preparing tert-butyl peroxybenzoate with high yield. The method avoids the hydrolysis of benzoyl chloride, improves the yield of the product and finally obtains the high-purity tert-butyl peroxybenzoate product.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a method for preparing tert-butyl peroxybenzoate with high yield comprises the following steps:
1) Under the condition of stirring, dropwise adding a tert-butyl hydrogen peroxide aqueous solution into a sodium hydroxide aqueous solution, and then reacting; adding an organic solvent which can generate azeotropy with water; then carrying out reduced pressure distillation until water in the system is completely evaporated out to obtain an organic solution of the tert-butyl sodium peroxide;
2) Dripping benzoyl chloride into an organic solution of tert-butyl sodium peroxide for reaction; then filtering, distilling under reduced pressure, washing with alkali, washing with water, and vacuum flash-evaporating and drying to obtain tert-butyl peroxybenzoate.
Preferably, according to the invention, in step (1), the aqueous sodium hydroxide solution has a concentration by mass of 30 to 40%, preferably 32%.
According to the invention, in step (1), the concentration by mass of the aqueous tert-butyl hydroperoxide solution is preferably 65 to 75%, preferably 70%.
Preferably, in step (1), the molar ratio of sodium hydroxide to tert-butyl hydroperoxide is (1-1.2): 1.
preferably, according to the invention, in step (1), the dropping rate is from 2 to 3g/min.
Preferably, in step (1), the temperature of the system is maintained at 5 ℃ to 20 ℃ during the dropwise addition.
Preferably, in step (1), the reaction temperature is room temperature, and the reaction time is 15min to 60min.
According to the present invention, in the step (1), the organic solvent which azeotropes with water is toluene.
According to the invention, in the step (1), the mass ratio of the organic solvent which generates the azeotrope with water and the tert-butyl hydrogen peroxide aqueous solution is (4.5-6) to 1.
Preferably, in step (1), the temperature of reduced pressure distillation is 45-60 ℃; condensing steam generated by reduced pressure distillation to obtain condensate, and recovering the condensate layer by layer to generate azeotropic organic solvent with water.
Preferably, according to the present invention, in step (2), the molar ratio of benzoyl chloride to tert-butyl hydroperoxide is 1: (1-1.2).
Preferably, according to the invention, in step (2), the dropping rate is 1-3g/min; in the dropping process, the temperature of the system is kept between 5 and 20 ℃.
Preferably, in step (2), the reaction temperature is 5-20 ℃ and the reaction time is 0.5-2 h.
Preferably, in step (2), the temperature of reduced pressure distillation is 45-60 ℃; condensing steam generated by reduced pressure distillation to obtain condensate, and recovering the condensate layer by layer to generate azeotropic organic solvent with water.
Preferably, in step (2), the alkaline solution used for alkaline washing is 3-8% of sodium carbonate aqueous solution by mass fraction.
Preferably, in step (2), the vacuum flash drying conditions are as follows: the drying temperature is 40-50 ℃, the drying pressure is-0.08 MPa-0.1 MPa, and the drying time is 0.5-3 h.
The invention has the following technical characteristics and beneficial effects:
(1) In the synthesis reaction, a specific type of organic solvent and water in a system form an azeotrope, and the water in the reaction system is removed through low-temperature reduced pressure distillation, so that the hydrolysis of benzoyl chloride is avoided, the occurrence of side reactions is reduced, and the purity and yield of the TBPB product are improved.
(2) In the synthesis reaction of the invention, toluene is preferably used as an organic solvent of the reaction system, so that the dispersibility of the reaction system is improved, the reaction rate is accelerated, the reaction time is shortened, and the reaction is more complete.
(3) The method adopts the organic solvent and the water to remove the water in the reaction system in the form of azeotrope, avoids the hydrolysis of the benzoyl chloride, reduces the generation of byproducts, and simultaneously reduces the content of the byproducts in the wastewater, thereby reducing the burden of wastewater treatment.
(4) The invention adopts the reduced pressure distillation mode, so that the azeotrope can be distilled out under the condition of the temperature lower than the theoretical azeotropic temperature (the temperature is also the safe temperature of the product), and simultaneously, the residual trace unreacted tert-butyl hydroperoxide can be distilled out.
(5) According to the invention, a vacuum flash evaporation drying mode is adopted, and the boiling point of the tert-butyl hydroperoxide at 2.66kPa is 36 ℃, so that the drying method can not only extract water, but also remove residual trace tert-butyl hydroperoxide, and improve the purity of the product; meanwhile, the product loss of tert-butyl peroxybenzoate and the generation of solid waste containing peroxide caused by incomplete filtration of the drying agent are avoided, so that the product yield is improved, the production cost and the pressure of solid waste treatment are reduced, and the implementation of a green environmental protection policy is facilitated.
(6) The preparation method provided by the invention has the advantages of low reaction temperature, mild operation conditions, high reaction rate, less side reactions, stable product yield and easiness in industrial production.
Detailed Description
The present invention will be further described with reference to specific examples, but is not limited thereto.
Meanwhile, the methods described in the following examples are all conventional methods unless otherwise specified; the materials are commercially available, unless otherwise specified.
Example 1
A method for preparing tert-butyl peroxybenzoate with high yield comprises the following steps in sequence:
1) Putting 137.5g of sodium hydroxide aqueous solution with the mass fraction of 32% into a reaction kettle, stirring and cooling;
2) Under the conditions of cooling and stirring, slowly dripping 141.62g of tert-butyl hydrogen peroxide aqueous solution with the mass fraction of 70% into the solution in the step 1), and then reacting to obtain an intermediate mixed solution A;
the dripping is finished within 1h in the dripping process;
the temperature of the system is kept between 10 and 15 ℃ in the process of dripping the tert-butyl hydrogen peroxide aqueous solution, the reaction time is 30min, and the reaction temperature is room temperature.
3) Adding 708.1g toluene into the intermediate mixed solution A obtained in the step 2) to obtain an intermediate mixed solution B;
4) And 3) carrying out reduced pressure distillation on the intermediate mixed solution B obtained in the step 3) until water in the system is completely evaporated. Condensing steam generated by evaporation to form condensate, recovering the organic solvent from the condensate, and taking the residual liquid after evaporation as the evaporation residual liquid, namely the organic solution of the tert-butyl sodium peroxide;
in step 4), the optimum temperature for distillation under reduced pressure was 55 ℃.
5) Slowly dripping 141.99g of benzoyl chloride with the mass fraction of 99% into the organic solution of the tert-butyl sodium peroxide obtained in the step 4), and reacting to obtain an intermediate mixed solution C;
the dripping process is completed within 2 h;
the temperature of the system is kept between 10 and 15 ℃ in the process of dripping benzoyl chloride, the reaction time is 0.5h, and the reaction temperature is 15 ℃.
6) Filtering the intermediate mixed solution C obtained in the step 5), carrying out reduced pressure distillation on the filtrate, condensing steam generated by evaporation to obtain condensate, recovering the organic solvent from the condensate, and obtaining the residual liquid after evaporation as the residual evaporation liquid;
the optimum temperature for the reduced pressure distillation was 55 ℃.
7) Carrying out alkaline washing on the evaporation residual solution obtained in the step 6) by using 200g of a sodium carbonate aqueous solution with the mass fraction of 5%, separating by using a separating funnel, wherein the upper layer is an organic layer, and the lower layer is an inorganic layer;
8) Washing the organic layer solution obtained in the step 7), separating liquid by using a separating funnel, wherein the upper layer is an inorganic layer, and the lower layer is an organic layer;
9) And (3) carrying out vacuum flash evaporation drying on the organic layer obtained in the step 8), and drying to obtain tert-butyl peroxybenzoate.
The vacuum flash drying conditions were: the drying temperature is 45 ℃, the drying pressure is-0.08 MPa to-0.1 MPa, and the drying time is 0.5h.
10 The condensate obtained by distillation and condensation in the steps 4) and 6) is kept stand, and then is separated by a separating funnel, and the organic solvent is recovered.
Through detection and measurement, the tert-butyl peroxybenzoate prepared in example 1 is colorless transparent oily liquid in appearance, the purity is 99.45%, and the yield is 97.79%.
Example 2
A method for preparing tert-butyl peroxybenzoate with high yield comprises the following steps in sequence:
1) Putting 137.5g of sodium hydroxide aqueous solution with the mass fraction of 32% into a reaction kettle, stirring and cooling;
2) Slowly dripping 141.62g of 70 mass percent tert-butyl hydrogen peroxide aqueous solution into the solution in the step 1) under the conditions of cooling and stirring, and then reacting to obtain an intermediate mixed solution A;
the dripping process is completed within 1 h;
and (3) keeping the system temperature at 10-15 ℃ in the process of dropwise adding the tert-butyl hydrogen peroxide aqueous solution, wherein the reaction time is 30min and the reaction temperature is room temperature.
3) Adding 708.1g of toluene into the intermediate mixed solution A obtained in the step 2) to obtain an intermediate mixed solution B;
4) And 3) carrying out reduced pressure distillation on the intermediate mixed solution B obtained in the step 3) until water in the system is completely evaporated. Condensing steam generated by evaporation to form condensate, recovering the organic solvent from the condensate, and taking the residual liquid after evaporation as the evaporation residual liquid, namely the organic solution of the tert-butyl sodium peroxide;
the optimum temperature for the reduced pressure distillation was 55 ℃.
5) Slowly dripping 141.99g of benzoyl chloride with the mass fraction of 99% into the organic solution of the tert-butyl sodium peroxide obtained in the step 4), and reacting to obtain an intermediate mixed solution C;
the dripping process is completed within 2 h;
keeping the system temperature at 10-15 ℃ in the process of dripping benzoyl chloride, and reacting for 1h at 15 ℃.
6) Filtering the intermediate mixed solution C obtained in the step 5), carrying out reduced pressure distillation on the filtrate, condensing steam generated by evaporation to obtain condensate, recovering the organic solvent from the condensate, and obtaining the residual liquid after evaporation as the residual evaporation liquid;
the optimum temperature for distillation under reduced pressure was 55 ℃.
7) Carrying out alkaline washing on the evaporation residual solution obtained in the step 6) by using 200g of a sodium carbonate aqueous solution with the mass fraction of 5%, separating by using a separating funnel, wherein the upper layer is an organic layer, and the lower layer is an inorganic layer;
8) Washing the organic layer solution obtained in the step 7), separating liquid by using a separating funnel, wherein the upper layer is an inorganic layer, and the lower layer is an organic layer;
9) And (3) carrying out vacuum flash evaporation drying on the organic layer obtained in the step 8), and obtaining the tert-butyl peroxybenzoate after drying.
In the step 9), the vacuum flash evaporation drying conditions are as follows: the drying temperature is 45 ℃, the drying pressure is-0.08 MPa to-0.1 MPa, and the drying time is 0.5h.
10 The condensate obtained by distillation and condensation in the steps 4) and 6) is kept stand, and then is separated by a separating funnel, and the organic solvent is recovered.
Through detection and measurement, the tert-butyl peroxybenzoate prepared in example 2 is colorless transparent oily liquid in appearance, the purity is 99.77%, and the yield is 98.92%.
Example 3
A method for preparing tert-butyl peroxybenzoate with high yield comprises the following steps in sequence:
1) Putting 137.5g of sodium hydroxide aqueous solution with the mass fraction of 32% into a reaction kettle, stirring and cooling;
2) Slowly dripping 141.62g of 70 mass percent tert-butyl hydrogen peroxide aqueous solution into the solution in the step 1) under the conditions of cooling and stirring, and then reacting to obtain an intermediate mixed solution A;
the dripping is finished within 1h in the dripping process;
and (3) keeping the system temperature at 10-15 ℃ in the process of dropwise adding the tert-butyl hydrogen peroxide aqueous solution, wherein the reaction time is 30min and the reaction temperature is room temperature.
3) Adding 708.1g of toluene into the intermediate mixed solution A obtained in the step 2) to obtain an intermediate mixed solution B;
4) And 3) carrying out reduced pressure distillation on the intermediate mixed solution B obtained in the step 3) until water in the system is completely evaporated. Condensing steam generated by evaporation to form condensate, recovering the organic solvent from the condensate, and taking the residual liquid after evaporation as the evaporation residual liquid, namely the organic solution of the tert-butyl sodium peroxide;
the optimum temperature for the reduced pressure distillation was 55 ℃.
5) Slowly dripping 141.99g of benzoyl chloride with the mass fraction of 99% into the organic solution of the tert-butyl sodium peroxide obtained in the step 4), and reacting to obtain an intermediate mixed solution C;
the dripping process is completed within 2 h;
the temperature of the system is kept between 10 and 15 ℃ in the process of dripping benzoyl chloride, the reaction time is 1.5h, and the reaction temperature is 15 ℃.
6) Filtering the intermediate mixed solution C obtained in the step 5), carrying out reduced pressure distillation on the filtrate, condensing steam generated by evaporation to obtain condensate, recovering the organic solvent from the condensate, and taking the residual liquid after evaporation as the residual evaporation liquid;
the optimum temperature for the reduced pressure distillation was 55 ℃.
7) Carrying out alkali washing on the evaporation residual liquid obtained in the step 6) by using 200g of sodium carbonate aqueous solution with the mass fraction of 5%, and separating by using a separating funnel, wherein the upper layer is an organic layer, and the lower layer is an inorganic layer;
8) Washing the organic layer solution obtained in the step 7), separating liquid by using a separating funnel, wherein the upper layer is an inorganic layer, and the lower layer is an organic layer;
9) And (3) carrying out vacuum flash evaporation drying on the organic layer obtained in the step 8), and obtaining the tert-butyl peroxybenzoate after drying.
In the step 9), the vacuum flash evaporation drying conditions are as follows: the drying temperature is 45 ℃, the drying pressure is-0.08 MPa to-0.1 MPa, and the drying time is 1h.
10 The condensate obtained by distillation and condensation in the steps 4) and 6) is kept stand, and then is separated by a separating funnel, and the organic solvent is recovered.
Through detection and measurement, the tert-butyl peroxybenzoate prepared in example 3 is colorless transparent oily liquid in appearance, the purity is 99.85%, and the yield is 99.03%.
Example 4
A method for preparing tert-butyl peroxybenzoate with high yield comprises the following steps in sequence:
1) Putting 137.5g of sodium hydroxide aqueous solution with the mass fraction of 32% into a reaction kettle, stirring and cooling;
2) Slowly dripping 141.62g of 70 mass percent tert-butyl hydrogen peroxide aqueous solution into the solution in the step 1) under the conditions of cooling and stirring, and then reacting to obtain an intermediate mixed solution A;
the dripping process is completed within 1 h;
and (3) keeping the system temperature at 10-15 ℃ in the process of dropwise adding the tert-butyl hydrogen peroxide aqueous solution, wherein the reaction time is 30min and the reaction temperature is room temperature.
3) Adding 708.1g of toluene into the intermediate mixed solution A obtained in the step 2) to obtain an intermediate mixed solution B;
4) And 3) carrying out reduced pressure distillation on the intermediate mixed solution B obtained in the step 3) until water in the system is completely evaporated. Condensing steam generated by evaporation to form condensate, recovering the organic solvent from the condensate, and taking the residual liquid after evaporation as the evaporation residual liquid, namely the organic solution of the tert-butyl sodium peroxide;
the optimum temperature for distillation under reduced pressure was 55 ℃.
5) Slowly dripping 141.99g of benzoyl chloride with the mass fraction of 99% into the organic solution of the tert-butyl sodium peroxide obtained in the step 4), and reacting to obtain an intermediate mixed solution C;
the dripping process is completed within 2 h;
the temperature of the system is kept between 10 and 15 ℃ in the process of dripping benzoyl chloride, the reaction time is 2 hours, and the reaction temperature is 15 ℃.
6) Filtering the intermediate mixed solution C obtained in the step 5), carrying out reduced pressure distillation on the filtrate, condensing steam generated by evaporation to obtain condensate, recovering the organic solvent from the condensate, and obtaining the residual liquid after evaporation as the residual evaporation liquid;
the optimum temperature for the reduced pressure distillation was 55 ℃.
7) Carrying out alkaline washing on the evaporation residual solution obtained in the step 6) by using 200g of a sodium carbonate aqueous solution with the mass fraction of 5%, separating by using a separating funnel, wherein the upper layer is an organic layer, and the lower layer is an inorganic layer;
8) Washing the organic layer obtained in the step 7) with water, separating the organic layer with a separating funnel, wherein the upper layer is an inorganic layer, and the lower layer is an organic layer;
9) And (3) carrying out vacuum flash evaporation drying on the organic layer obtained in the step 8), and drying to obtain tert-butyl peroxybenzoate.
In the step 9), the vacuum flash evaporation drying conditions are as follows: the drying temperature is 45 ℃, the drying pressure is-0.08 MPa to-0.1 MPa, and the drying time is 1h.
10 The condensate obtained by distillation and condensation in the steps 4) and 6) is kept stand, and then is separated by a separating funnel, and the organic solvent is recovered.
Through detection and measurement, the tert-butyl peroxybenzoate prepared in example 4 is colorless transparent oily liquid in appearance, the purity is 99.73%, and the yield is 98.80%.
Comparative example 1
A method for preparing tert-butyl peroxybenzoate with high yield comprises the following steps in sequence:
1) Putting 137.5g of sodium hydroxide aqueous solution with the mass fraction of 32% into a reaction kettle, stirring and cooling;
2) Slowly dripping 141.62g of 70 mass percent tert-butyl hydrogen peroxide aqueous solution into the solution in the step 1) under the conditions of cooling and stirring, and then reacting to obtain an intermediate mixed solution A;
the dripping process is completed within 1 h;
and (3) keeping the system temperature at 10-15 ℃ in the process of dropwise adding the tert-butyl hydrogen peroxide aqueous solution, wherein the reaction time is 30min and the reaction temperature is room temperature.
3) Slowly dripping 141.99g of benzoyl chloride with the mass fraction of 99% into the intermediate mixed solution A obtained in the step 2), and reacting to obtain an intermediate mixed solution C;
the dripping process is completed within 2 h;
the temperature of the system is kept between 10 and 15 ℃ in the process of dripping benzoyl chloride, the reaction time is 1.5h, and the reaction temperature is 15 ℃.
4) Filtering the intermediate mixed solution C obtained in the step 3), layering, and taking an organic layer;
5) Carrying out alkali washing on the organic layer obtained in the step 4) by using 200g of a sodium carbonate aqueous solution with the mass fraction of 5%, separating by using a separating funnel, wherein the upper layer is an organic layer, and the lower layer is an inorganic layer;
6) Washing the organic layer solution obtained in the step 5) with water, and separating the solution by using a separating funnel, wherein the upper layer is an inorganic layer, and the lower layer is an organic layer;
7) And (3) carrying out vacuum flash evaporation drying on the organic layer obtained in the step 6), and drying to obtain tert-butyl peroxybenzoate.
The vacuum flash drying conditions were: the drying temperature is 45 ℃, the drying pressure is-0.08 MPa to-0.1 MPa, and the drying time is 1h.
Through detection and measurement, the purity of the tert-butyl peroxybenzoate prepared by the comparative example is 98.85%, and the yield is 94.84%.
Comparative example 2
A method for preparing tert-butyl peroxybenzoate with high yield comprises the following steps in sequence:
1) Putting 137.5g of sodium hydroxide aqueous solution with the mass fraction of 32% into a reaction kettle, stirring and cooling;
2) Slowly dripping 141.62g of 70 mass percent tert-butyl hydrogen peroxide aqueous solution into the solution in the step 1) under the conditions of cooling and stirring, and then reacting to obtain an intermediate mixed solution A;
the dripping process is completed within 1 h;
and (3) keeping the system temperature at 10-15 ℃ in the process of dropwise adding the tert-butyl hydrogen peroxide aqueous solution, wherein the reaction time is 30min and the reaction temperature is room temperature.
3) Adding 708.1g of benzene into the intermediate mixed solution A obtained in the step 2) to obtain an intermediate mixed solution B;
4) Carrying out reduced pressure distillation on the intermediate mixed solution B obtained in the step 3) until water in the system is completely distilled out. Condensing steam generated by evaporation to form condensate, recovering the organic solvent from the condensate, and taking the residual liquid after evaporation as the evaporation residual liquid, namely the organic solution of the tert-butyl sodium peroxide;
the optimum temperature for the reduced pressure distillation was 45 ℃.
5) Slowly dripping 141.99g of benzoyl chloride with the mass fraction of 99% into the organic solution of the tert-butyl sodium peroxide obtained in the step 4), and reacting to obtain an intermediate mixed solution C;
the dripping process is completed within 2 h;
the temperature of the system is kept between 10 and 15 ℃ in the process of dripping benzoyl chloride, the reaction time is 1.5h, and the reaction temperature is 15 ℃.
6) Filtering the intermediate mixed solution C obtained in the step 5), carrying out reduced pressure distillation on the filtrate, condensing steam generated by evaporation to obtain condensate, recovering the organic solvent from the condensate, and taking the residual liquid after evaporation as the residual evaporation liquid;
the optimum temperature for the reduced pressure distillation was 45 ℃.
7) Carrying out alkaline washing on the evaporation residual solution obtained in the step 6) by using 200g of a sodium carbonate aqueous solution with the mass fraction of 5%, separating by using a separating funnel, wherein the upper layer is an organic layer, and the lower layer is an inorganic layer;
8) Washing the organic layer solution obtained in the step 7) with water, and separating with a separating funnel, wherein the upper layer is an inorganic layer, and the lower layer is an organic layer;
9) And (3) carrying out vacuum flash evaporation drying on the organic layer obtained in the step 8), and drying to obtain tert-butyl peroxybenzoate.
In the step 9), the vacuum flash evaporation drying conditions are as follows: the drying temperature is 45 ℃, the drying pressure is-0.08 MPa to-0.1 MPa, and the drying time is 1h.
10 The condensate obtained by distillation and condensation in the steps 4) and 6) is kept stand, and then is separated by a separating funnel, and the organic solvent is recovered.
Through detection and measurement, the purity of the tert-butyl peroxybenzoate prepared by the comparative example is 98.97%, and the yield is 95.55%.
Comparative example 3
A method for preparing tert-butyl peroxybenzoate with high yield comprises the following steps in sequence:
1) Putting 137.5g of sodium hydroxide aqueous solution with the mass fraction of 32% into a reaction kettle, adding 708.1g of toluene, stirring, and cooling to obtain an intermediate mixed solution A;
2) Slowly dripping 141.62g of 70 mass percent tert-butyl hydrogen peroxide aqueous solution into the mixed solution A obtained in the step 1) under the conditions of cooling and stirring, and then reacting to obtain an intermediate mixed solution B;
the dripping process is completed within 1 h;
and (3) keeping the system temperature at 10-15 ℃ in the process of dropwise adding the tert-butyl hydrogen peroxide aqueous solution, wherein the reaction time is 30min and the reaction temperature is room temperature.
3) Carrying out reduced pressure distillation on the intermediate mixed solution B obtained in the step 2) until water in the system is completely evaporated. Condensing steam generated by evaporation to form condensate, recovering the organic solvent from the condensate, and taking the residual liquid after evaporation as the evaporation residual liquid, namely the organic solution of the tert-butyl sodium peroxide;
the optimum temperature for the reduced pressure distillation was 55 ℃.
4) Slowly dripping 141.99g of benzoyl chloride with the mass fraction of 99% into the organic solution of the tert-butyl sodium peroxide obtained in the step 3), and reacting to obtain an intermediate mixed solution C;
the dripping process is completed within 2 h;
the temperature of the system is kept between 10 and 15 ℃ in the process of dripping benzoyl chloride, the reaction time is 1.5h, and the reaction temperature is 15 ℃.
5) Filtering the intermediate mixed solution C obtained in the step 4), distilling the filtrate under reduced pressure, condensing steam generated by evaporation to obtain condensate, recovering the organic solvent from the condensate, and taking the residual liquid after evaporation as the residual evaporation liquid;
the optimum temperature for the reduced pressure distillation was 55 ℃.
6) Carrying out alkali washing on the evaporation residual liquid obtained in the step 5) by using 200g of sodium carbonate aqueous solution with the mass fraction of 5%, and separating by using a separating funnel, wherein the upper layer is an organic layer, and the lower layer is an inorganic layer;
7) Washing the organic layer solution obtained in the step 6) with water, and separating with a separating funnel, wherein the upper layer is an inorganic layer, and the lower layer is an organic layer;
8) And (3) carrying out vacuum flash evaporation drying on the organic layer obtained in the step 7), and drying to obtain tert-butyl peroxybenzoate.
In the step 8), the vacuum flash evaporation drying conditions are as follows: the drying temperature is 45 ℃, the drying pressure is-0.08 MPa to-0.1 MPa, and the drying time is 1h.
9) Standing the condensate obtained by distillation and condensation in the steps 3) and 5), separating liquid by using a separating funnel, and recovering the organic solvent.
Through detection and measurement, the purity of the tert-butyl peroxybenzoate prepared by the comparative example is 97.85 percent, and the yield is 92.43 percent.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (9)
1. A method for preparing tert-butyl peroxybenzoate with high yield comprises the following steps:
1) Under the condition of stirring, dropwise adding a tert-butyl hydrogen peroxide aqueous solution into a sodium hydroxide aqueous solution, and then reacting; adding an organic solvent which can generate azeotropy with water; then carrying out reduced pressure distillation until water in the system is completely evaporated out to obtain an organic solution of the tert-butyl sodium peroxide;
2) Dripping benzoyl chloride into an organic solution of tert-butyl sodium peroxide for reaction; then filtering, distilling under reduced pressure, washing with alkali, washing with water, and vacuum flash-evaporating and drying to obtain tert-butyl peroxybenzoate.
2. The method for preparing tert-butyl peroxybenzoate with high yield according to claim 1, wherein step (1) comprises one or more of the following conditions:
i. the mass concentration of the sodium hydroxide aqueous solution is 30-40%, preferably 32%;
ii. The mass concentration of the tert-butyl hydrogen peroxide aqueous solution is 65-75%, preferably 70%;
iii, the molar ratio of the sodium hydroxide to the tert-butyl hydroperoxide is (1-1.2): 1;
iv, the dropping speed is 2-3g/min;
v, keeping the temperature of the system at 5-20 ℃ in the dropping process;
vi, the reaction temperature is room temperature, and the reaction time is 15-60 min.
3. The method for preparing tert-butyl peroxybenzoate in high yield according to claim 1, wherein the organic solvent that azeotropes with water in step (1) is toluene.
4. The method for producing tert-butyl peroxybenzoate in high yield according to claim 1, wherein the mass ratio of the organic solvent that azeotropes with water to the aqueous tert-butyl hydroperoxide in step (1) is (4.5-6): 1.
5. The method for preparing tert-butyl peroxybenzoate in high yield according to claim 1, wherein in the step (1), the temperature of reduced pressure distillation is 45 ℃ to 60 ℃; condensing steam generated by reduced pressure distillation to obtain condensate, and recovering the condensate layer by layer to generate azeotropic organic solvent with water.
6. The method for preparing tert-butyl peroxybenzoate with high yield according to claim 1, wherein the step (2) comprises one or more of the following conditions:
i. the molar ratio of benzoyl chloride to tert-butyl hydroperoxide is 1: (1-1.2);
ii. The dropping speed is 1-3g/min; in the dropping process, the temperature of the system is kept between 5 and 20 ℃;
and iii, the reaction temperature is 5-20 ℃, and the reaction time is 0.5-2 h.
7. The method for preparing tert-butyl peroxybenzoate with high yield according to claim 1, wherein in the step (2), the temperature of reduced pressure distillation is 45 ℃ to 60 ℃; condensing steam generated by reduced pressure distillation to obtain condensate, and recovering the condensate layer by layer to generate azeotropic organic solvent with water.
8. The method for preparing tert-butyl peroxybenzoate with high yield according to claim 1, characterized in that in the step (2), the alkaline washing solution used for alkaline washing is 3-8% of sodium carbonate aqueous solution by mass fraction.
9. The method for preparing tert-butyl peroxybenzoate in high yield according to claim 1, wherein in the step (2), the vacuum flash drying conditions are as follows: the drying temperature is 40 ℃ to 50 ℃, the drying pressure is-0.08 MPa to-0.1 MPa, and the drying time is 0.5h to 3h.
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| CN111825590A (en) * | 2020-08-13 | 2020-10-27 | 天津城建大学 | Preparation method of tert-butyl peroxybenzoate |
| CN112300044A (en) * | 2019-12-06 | 2021-02-02 | 广东中准新材料科技有限公司 | Synthesis and purification method of high-purity tert-butyl peroxy-2-ethylhexyl carbonate |
| CN113582900A (en) * | 2021-08-20 | 2021-11-02 | 山东阳谷华泰化工股份有限公司 | Preparation method of high-purity powdered dibenzoyl peroxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112300044A (en) * | 2019-12-06 | 2021-02-02 | 广东中准新材料科技有限公司 | Synthesis and purification method of high-purity tert-butyl peroxy-2-ethylhexyl carbonate |
| CN111825590A (en) * | 2020-08-13 | 2020-10-27 | 天津城建大学 | Preparation method of tert-butyl peroxybenzoate |
| CN113582900A (en) * | 2021-08-20 | 2021-11-02 | 山东阳谷华泰化工股份有限公司 | Preparation method of high-purity powdered dibenzoyl peroxide |
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