CN113582900A - Preparation method of high-purity powdered dibenzoyl peroxide - Google Patents
Preparation method of high-purity powdered dibenzoyl peroxide Download PDFInfo
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- CN113582900A CN113582900A CN202110957269.9A CN202110957269A CN113582900A CN 113582900 A CN113582900 A CN 113582900A CN 202110957269 A CN202110957269 A CN 202110957269A CN 113582900 A CN113582900 A CN 113582900A
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- 235000019400 benzoyl peroxide Nutrition 0.000 title claims abstract description 62
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 88
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000243 solution Substances 0.000 claims abstract description 39
- 239000003960 organic solvent Substances 0.000 claims abstract description 32
- 238000001816 cooling Methods 0.000 claims abstract description 29
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002425 crystallisation Methods 0.000 claims abstract description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000008025 crystallization Effects 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 126
- 238000003756 stirring Methods 0.000 claims description 42
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 238000010791 quenching Methods 0.000 claims description 13
- 230000000171 quenching effect Effects 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 239000003444 phase transfer catalyst Substances 0.000 claims description 12
- 239000012442 inert solvent Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229960001701 chloroform Drugs 0.000 abstract description 13
- 238000010828 elution Methods 0.000 abstract description 9
- 230000035484 reaction time Effects 0.000 abstract description 8
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 238000001953 recrystallisation Methods 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- 239000002245 particle Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
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 application provides a preparation method of high-purity powdered dibenzoyl peroxide, which comprises the steps of dissolving benzoyl chloride in an organic solvent to obtain a mixed solution of the benzoyl chloride and the organic solvent, then reacting the mixed solution with a sodium peroxide solution, and then obtaining the dibenzoyl peroxide in a recrystallization mode combining liquid separation, cooling crystallization and elution crystallization, wherein the organic solvent is trichloromethane, dichloromethane or benzene; the hydrolysis of benzoyl chloride is reduced, the occurrence of side reactions is reduced, the reaction concentration of the benzoyl chloride is reduced, the dispersibility of a reaction system is improved, the reaction rate is accelerated, the reaction time is shortened, and the reaction is more complete; the purity of the dibenzoyl peroxide is improved, and the purity of the obtained dibenzoyl peroxide is more than or equal to 99.70 wt%; the grain diameter of the obtained dibenzoyl peroxide is less than or equal to 100 mu m; the reaction temperature is not high, the operation condition is mild, the reaction rate is high, the yield is 80.0-90.0%, and the industrial production is easy to realize.
Description
Technical Field
The invention relates to the technical field of synthesis and preparation of dibenzoyl peroxide, in particular to a preparation method of high-purity powdered dibenzoyl peroxide.
Background
Dibenzoyl peroxide, also known as benzoyl peroxide (BPO for short), is a diacyl organic peroxide with wide application, is mainly used for alkene monomer polymerization initiators, unsaturated resin curing agents, vulcanizing machines of silicone rubber and fluororubber, crosslinking agents and antioxidant and anticorrosive additives in feed industry, and can also be used as a bleaching agent and an oxidant.
However, the dibenzoyl peroxide product in powder form is mainly used as a polymerization initiation catalyst for acrylic resins, MMA resins, and the like. In recent years, the adhesive is popularized and applied to the aspects of highway engineering and the like as a quick adhesive, and paste products are used as curing catalysts for polyester resin molding processing. The liquid form is used as a polymerization catalyst for preparing polystyrene resin.
At present, the methods for synthesizing dibenzoyl peroxide at home and abroad mainly comprise:
the first method comprises the following steps: adding hydrogen peroxide into a sodium hydroxide solution under a cooling condition to generate a sodium peroxide solution; then, benzoyl chloride is added dropwise under the condition of stirring to generate dibenzoyl peroxide. Then cooling, filtering and washing to obtain the dibenzoyl peroxide. Since benzoyl chloride is very easy to hydrolyze, a large amount of benzoic acid by-products are generated in the dripping process of benzoyl chloride, thereby reducing the purity and yield of the final product. In addition, the method generates a large amount of synthetic mother liquor and washing water, and the waste water contains water-soluble sodium hydroxide, sodium chloride and sodium benzoate, thereby causing serious environmental pollution. Meanwhile, the dibenzoyl peroxide product synthesized by the method is granular and has larger grain size.
The second method comprises the following steps: the dibenzoyl peroxide is produced by adopting ammonium bicarbonate or sodium bicarbonate to replace sodium hydroxide and matching with a surfactant. The method does not solve the problems of hydrolysis of benzoyl chloride and large wastewater quantity, and simultaneously, when ammonium bicarbonate or sodium bicarbonate is used as an alkaline medium, the reaction completion time is long and reaches more than 6 hours, materials are easy to agglomerate in the reaction, so that stirring is difficult, the particle size of a final product is large, and the purity and the yield are low.
The third method comprises the following steps: sodium carbonate is used as the alkaline medium for the synthesis reaction. This process still does not improve the benzoyl chloride hydrolysis and waste water volume problems. Meanwhile, the sodium carbonate is very easy to react with benzoic acid generated by hydrolysis of benzoyl chloride to generate carbon dioxide gas, namely, a large amount of bubbles are found in the synthesis reaction process, so that the yield and the purity of the product are reduced.
Disclosure of Invention
The invention aims to provide a preparation method of high-purity powdered dibenzoyl peroxide, which comprises the steps of dissolving benzoyl chloride in an organic solvent to obtain a uniform and stable benzoyl chloride organic solution, reacting a mixed solution of benzoyl chloride and the organic solvent with a sodium peroxide solution, and then obtaining the high-purity powdered dibenzoyl peroxide through a recrystallization mode combining liquid separation, cooling crystallization and elution crystallization.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of high-purity powdered dibenzoyl peroxide comprises the following steps of:
1) adding a sodium hydroxide solution into a first reaction kettle, and stirring and cooling;
2) under the conditions of cooling and stirring, dropwise adding a hydrogen peroxide solution into the sodium hydroxide solution obtained in the step 1), mixing the sodium hydroxide and the hydrogen peroxide, carrying out a chemical reaction to generate sodium peroxide, and obtaining an intermediate liquid A after the reaction is finished;
3) adding a phase transfer catalyst into the intermediate liquid A prepared in the step 2), and uniformly mixing to obtain an intermediate liquid B;
4) dissolving benzoyl chloride in an organic solvent to obtain a mixed solution of the benzoyl chloride and the organic solvent;
5) under the conditions of cooling and increasing the stirring speed, dropwise adding the uniformly mixed benzoyl chloride and organic solvent mixed solution prepared in the step 4) into the intermediate liquid B prepared in the step 3), and carrying out chemical reaction on sodium peroxide and benzoyl chloride in the presence of a phase transfer catalyst to generate dibenzoyl peroxide, thus obtaining an intermediate liquid C;
6) adding water into the intermediate liquid C prepared in the step 5), then sequentially stirring and separating by using a separating funnel, wherein the upper layer is an aqueous solution and the lower layer is an organic liquid after the separation is finished;
7) adding the organic liquid obtained in the step 6) into an inert solvent in a second reaction kettle, using the inert solvent as a dissolving-out agent to perform dissolving-out crystallization, using an ice maker to perform quenching operation on the liquid in the second reaction kettle, and continuously stirring at a low temperature to perform cooling crystallization to obtain an intermediate liquid D;
8) filtering the intermediate liquid D prepared in the step 7), and obtaining filter residue and filtrate after filtering;
9) drying the filter residue obtained in the step 8) at a low temperature to obtain powdered dibenzoyl peroxide after drying.
Preferably, in step 1), the sodium hydroxide solution is 32% sodium hydroxide aqueous solution by mass fraction.
Preferably, in the step 2), the amount of the hydrogen peroxide is 1 (2 to 2.5);
and (3) dropwise adding a hydrogen peroxide solution when the temperature of the sodium hydroxide solution in the first reaction kettle is controlled to be 5-10 ℃.
Preferably, in step 3), the phase transfer catalyst is sodium dodecyl sulfate, sodium dodecyl sulfate or sodium dodecyl benzene sulfonate;
the mass of the phase transfer catalyst, that of benzoyl chloride (0.2-0.5%), is 1.
Preferably, in step 4), the organic solvent is chloroform, dichloromethane or benzene; the amount of benzoyl chloride substance is equal to (2-2.3) 1; the mass of the organic solvent, that of benzoyl chloride (3-6), is 1.
Preferably, in the step 5), when the temperature of the intermediate liquid B in the first reaction kettle is controlled to be 5-10 ℃, the mixed solution of benzoyl chloride and the organic solvent is dropwise added.
Preferably, in step 6), the stirring time is 5 to 15min, where the mass of water is 32% and the mass of the aqueous solution of sodium hydroxide is 1 (0.5 to 2).
Preferably, in the step 7), the liquid in the second reaction kettle is subjected to quenching operation until the temperature of the liquid in the second reaction kettle is reduced to-15 ℃ to-5 ℃;
the inert solvent is methanol or acetone;
continuously stirring for 20min to 30min at the temperature of between 15 ℃ below zero and 5 ℃ below zero.
Preferably, in the step 9), the temperature for low-temperature drying is 45-50 ℃.
The application obtains the following beneficial technical effects:
(1) synthetic reaction in this application adopts trichloromethane, dichloromethane or benzene as the organic solvent of benzoyl chloride, compare in prior art directly with benzoyl chloride dropwise add to sodium peroxide solution, organic solvent's addition makes the concentration of benzoyl chloride in organic solvent reduce, make benzoyl chloride molecule wrapped up in hydrophobic organic solvent simultaneously, at the organic solvent solution in-process of dropwise add benzoyl chloride, benzoyl chloride molecule that is wrapped up by organic solvent preferentially reacts with the sodium peroxide crystal of precipitation, thereby the contact of benzoyl chloride with water has been reduced, the hydrolysis of benzoyl chloride has been reduced, the emergence of side reaction has been reduced.
(2) According to the method, trichloromethane, dichloromethane or benzene is used as a solvent of benzoyl chloride, and simultaneously methanol or acetone is used as a elution agent for elution crystallization, because dibenzoyl peroxide has higher solubility in trichloromethane, dichloromethane or benzene, dibenzoyl peroxide has lower solubility in methanol or acetone, and a by-product benzoic acid has higher solubility in methanol or acetone, the purity of dibenzoyl peroxide is improved by the elution crystallization method, and the purity of the obtained dibenzoyl peroxide is more than or equal to 99.70 wt%.
(3) In the application, trichloromethane, dichloromethane or benzene is used as a solvent of benzoyl chloride, methanol or acetone is used as a dissolving agent of dissolving crystal, and the process of preparing dibenzoyl peroxide by recrystallization reduces the processes of soaking, alkali washing and water washing in the synthesis process, thereby improving the reaction efficiency, quickening the reaction rate, shortening the reaction time, controlling the whole period of preparing dibenzoyl peroxide to be about 6-7 h, and ensuring that the reaction is more complete.
(4) On the basis of adopting the elution crystallization, the method is matched with a cooling crystallization mode of low-temperature quenching, so that the particle size of the dibenzoyl peroxide is reduced, the solubility of a product in the solution is rapidly reduced due to the low-temperature quenching, the product is further separated out, and the growth of crystal grains is also favorably inhibited by the low temperature, so that powdery dibenzoyl peroxide is obtained, and the particle size of the obtained dibenzoyl peroxide is less than or equal to 100 mu m.
(5) The preparation method provided by the application has the advantages of few side reactions, high and stable product yield of 80.0-90.0%, and easy industrial production.
Drawings
FIG. 1 is a graph showing a distribution of a particle size measurement of high purity powdered dibenzoyl peroxide prepared in example 1 of the present invention;
FIG. 2 is a graph showing a distribution of a particle size measurement of high purity powdered dibenzoyl peroxide prepared in example 2 of the present invention;
FIG. 3 is a graph showing a distribution of a particle size measurement of high purity powdered dibenzoyl peroxide prepared in example 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The application provides a preparation method of high-purity powdered dibenzoyl peroxide, which comprises the following steps of:
1) adding a sodium hydroxide solution into a first reaction kettle, and stirring and cooling;
2) under the conditions of cooling and stirring, dropwise adding a hydrogen peroxide solution into the sodium hydroxide solution obtained in the step 1), mixing the sodium hydroxide and the hydrogen peroxide, carrying out a chemical reaction to generate sodium peroxide, and obtaining an intermediate liquid A after the reaction is finished;
3) adding a phase transfer catalyst into the intermediate liquid A prepared in the step 2), and uniformly mixing to obtain an intermediate liquid B;
4) dissolving benzoyl chloride in an organic solvent to obtain a mixed solution of the benzoyl chloride and the organic solvent;
5) under the conditions of cooling and increasing the stirring speed, dropwise adding the uniformly mixed benzoyl chloride and organic solvent mixed solution prepared in the step 4) into the intermediate liquid B prepared in the step 3), and carrying out chemical reaction on sodium peroxide and benzoyl chloride in the presence of a phase transfer catalyst to generate dibenzoyl peroxide, thus obtaining an intermediate liquid C;
6) adding water into the intermediate liquid C prepared in the step 5), then sequentially stirring and separating by using a separating funnel, wherein the upper layer is an aqueous solution (inorganic salt aqueous solution) and the lower layer is an organic liquid after the separation is finished;
7) adding the organic liquid obtained in the step 6) into an inert solvent in a second reaction kettle, using the inert solvent as a dissolving-out agent to perform dissolving-out crystallization, using an ice maker to perform quenching operation on the liquid in the second reaction kettle, and continuously stirring at a low temperature to perform cooling crystallization to obtain an intermediate liquid D;
8) filtering the intermediate liquid D prepared in the step 7), and obtaining filter residue and filtrate after filtering;
9) drying the filter residue obtained in the step 8) at a low temperature to obtain powdered dibenzoyl peroxide after drying.
In one embodiment of the present application, in step 1), the sodium hydroxide solution is a 32% mass fraction sodium hydroxide aqueous solution.
In one embodiment of the application, in the step 2), the amount of the hydrogen peroxide is 1 (2-2.5);
and (3) dropwise adding a hydrogen peroxide solution when the temperature of the sodium hydroxide solution in the first reaction kettle is controlled to be 5-10 ℃.
In one embodiment of the present application, in step 3), the phase transfer catalyst is sodium dodecyl sulfate, or sodium dodecyl benzene sulfonate;
the mass of the phase transfer catalyst, that of benzoyl chloride (0.2-0.5%), is 1.
In one embodiment of the present application, in step 4), the organic solvent is chloroform, dichloromethane or benzene; the amount of benzoyl chloride substance is equal to (2-2.3) 1; the mass of the organic solvent, that of benzoyl chloride (3-6), is 1.
In one embodiment of the present application, in the step 5), when the temperature of the intermediate liquid B in the first reaction tank is controlled to be 5 to 10 ℃, a mixed solution of benzoyl chloride and an organic solvent is added dropwise.
In one embodiment of the present application, in the step 6), the mass of water, i.e., the mass of the aqueous solution of sodium hydroxide with a mass fraction of 32% (0.5 to 2), is 1, and the stirring time is 5 to 15 min.
In one embodiment of the application, in the step 7), the liquid in the second reaction kettle is subjected to a quenching operation until the temperature of the liquid in the second reaction kettle is reduced to-15 ℃ to-5 ℃;
the inert solvent is methanol or acetone;
continuously stirring for 20min to 30min at the temperature of between 15 ℃ below zero and 5 ℃ below zero.
In one embodiment of the present application, in step 9), the temperature of the low-temperature drying is 45 ℃ to 50 ℃.
In the application, the organic liquid obtained in the step 6) is added into an inert solvent in a second reaction kettle, and the inert solvent is used as a elution agent to perform elution crystallization; carrying out rapid cooling operation on the liquid in the second reaction kettle by using an ice maker and continuously stirring at a low temperature, namely cooling crystallization; the elution crystallization and the cooling crystallization are carried out simultaneously.
In this application, in step 6), water is added to the intermediate liquid C prepared in step 5), and in this case, the water is added in order to completely dissolve the sodium chloride solid generated by the reaction, and since the solubility of the sodium chloride solid in water at 10 ℃ is 35.8g/100g, the amount of sodium chloride generated by the reaction cannot be completely dissolved in the upper aqueous solution, and the amount of sodium chloride is large but the amount of water is small, it is necessary to add water so that the sodium chloride is completely dissolved in water, and to remove the sodium chloride in the upper aqueous solution by liquid separation.
Methods and devices not described in detail in the present invention are all the prior art and are not described in detail.
For further understanding of the present invention, the following examples are provided to illustrate the preparation of dibenzoyl peroxide in the form of high purity powder, and the scope of the present invention is not limited by the following examples.
Example 1
A preparation method of high-purity powdered dibenzoyl peroxide comprises the following steps of:
1) adding 150g of sodium hydroxide solution into a first reaction kettle, and stirring and cooling;
in the step 1), the sodium hydroxide solution is 32% sodium hydroxide aqueous solution in mass fraction;
2) under the conditions of cooling and stirring, 74.18g of aqueous solution of 27.5 percent hydrogen peroxide is dropwise added into the sodium hydroxide solution in the step 1), the sodium hydroxide and the hydrogen peroxide are mixed and then undergo a chemical reaction to generate sodium peroxide, and an intermediate liquid A is obtained after the reaction is finished;
when the temperature of the sodium hydroxide solution in the first reaction kettle is controlled to be 5 ℃, dropwise adding a hydrogen peroxide solution;
the dropwise adding is completed within 1h, the reaction temperature is 5-10 ℃, and the reaction time is 0.5 h;
3) adding 0.57g of sodium dodecyl sulfate into the intermediate liquid A prepared in the step 2), and uniformly mixing to obtain an intermediate liquid B;
4) fully dissolving 141.99g of benzoyl chloride with the mass fraction of 99% into 567.96g of trichloromethane, and uniformly mixing to obtain a uniform and stable trichloromethane solution of benzoyl chloride with the mass fraction of 20%;
5) under the conditions of cooling and increasing the stirring speed, dropwise adding the uniformly mixed benzoyl chloride and organic solvent mixed solution prepared in the step 4) into the intermediate liquid B prepared in the step 3), and obtaining an intermediate liquid C after completion;
the dropwise adding is completed within 2 hours, the reaction temperature is 5-10 ℃, and the reaction time is 2 hours;
6) adding 150g of water into the intermediate liquid C prepared in the step 5), then sequentially stirring for 10min, and separating by using a separating funnel to obtain an upper layer which is an aqueous solution and a lower layer which is an organic liquid after the separation is finished;
7) adding the organic liquid obtained in the step 6) into a second reaction kettle which is low in temperature and contains 500g of methanol, carrying out quenching operation on the liquid in the second reaction kettle by using an ice maker, and continuously stirring at low temperature to obtain an intermediate liquid D;
in the step 7), carrying out quenching operation on the liquid in the second reaction kettle until the temperature of the liquid in the second reaction kettle is reduced to-15 ℃;
continuously stirring at-15 deg.C for 25 min;
8) filtering the intermediate liquid D prepared in the step 7), and obtaining filter residue and filtrate after filtering;
9) drying the filter residue obtained in the step 8) at a low temperature to obtain powdered dibenzoyl peroxide after drying;
in the step 9), the temperature for low-temperature drying is 50 ℃.
Through detection and measurement, the dibenzoyl peroxide prepared in example 1 is 104.66g, the yield is 86.41%, the dibenzoyl peroxide is white powder in appearance, the purity is 99.83 wt%, and the particle size is less than or equal to 100 mu m.
Example 2
A preparation method of high-purity powdered dibenzoyl peroxide comprises the following steps of:
1) adding 150g of sodium hydroxide solution into a first reaction kettle, and stirring and cooling;
in the step 1), the sodium hydroxide solution is 32% sodium hydroxide aqueous solution in mass fraction;
2) under the conditions of cooling and stirring, 74.18g of aqueous solution of 27.5 percent hydrogen peroxide is dropwise added into the sodium hydroxide solution in the step 1), the sodium hydroxide and the hydrogen peroxide are mixed and then undergo a chemical reaction to generate sodium peroxide, and an intermediate liquid A is obtained after the reaction is finished;
when the temperature of the sodium hydroxide solution in the first reaction kettle is controlled to be 5 ℃, dropwise adding a hydrogen peroxide solution;
the dropwise adding is completed within 1h, the reaction temperature is 5-10 ℃, and the reaction time is 0.5 h;
3) adding 0.57g of sodium dodecyl sulfate into the intermediate liquid A prepared in the step 2), and uniformly mixing to obtain an intermediate liquid B;
4) fully dissolving 141.99g of benzoyl chloride with the mass fraction of 99% into 567.96g of trichloromethane solution, and uniformly mixing to obtain a uniform and stable trichloromethane solution of benzoyl chloride with the mass fraction of 20%;
5) under the conditions of cooling and increasing the stirring speed, dropwise adding the uniformly mixed benzoyl chloride and organic solvent mixed solution prepared in the step 4) into the intermediate liquid B prepared in the step 3), and obtaining an intermediate liquid C after completion;
the dropwise adding is completed within 2 hours, the reaction temperature is 5-10 ℃, and the reaction time is 2 hours;
6) adding 150g of water into the intermediate liquid C prepared in the step 5), then sequentially stirring for 10min, and separating by using a separating funnel to obtain an upper layer which is an aqueous solution and a lower layer which is an organic liquid after the separation is finished;
7) adding the organic liquid obtained in the step 6) into a second reaction kettle which is low in temperature and contains 500g of methanol, carrying out quenching operation on the liquid in the second reaction kettle by using an ice maker, and continuously stirring at low temperature to obtain an intermediate liquid D;
in the step 7), carrying out quenching operation on the liquid in the second reaction kettle until the temperature of the liquid in the second reaction kettle is reduced to-10 ℃;
continuously stirring at-10 deg.C for 25 min;
8) filtering the intermediate liquid D prepared in the step 7), and obtaining filter residue and filtrate after filtering;
9) drying the filter residue obtained in the step 8) at a low temperature to obtain powdered dibenzoyl peroxide after drying;
in the step 9), the temperature for low-temperature drying is 50 ℃.
Through detection and measurement, the dibenzoyl peroxide prepared in example 2 is 102.88g, the yield is 84.95%, the dibenzoyl peroxide is white powder in appearance, the purity is 99.76 wt%, and the particle size is less than or equal to 100 microns.
Example 3
A preparation method of high-purity powdered dibenzoyl peroxide comprises the following steps of:
1) adding 150g of sodium hydroxide solution into a first reaction kettle, and stirring and cooling;
in the step 1), the sodium hydroxide solution is 32% sodium hydroxide aqueous solution in mass fraction;
2) under the conditions of cooling and stirring, 74.18g of aqueous solution of 27.5 percent hydrogen peroxide is dropwise added into the sodium hydroxide solution in the step 1), the sodium hydroxide and the hydrogen peroxide are mixed and then undergo a chemical reaction to generate sodium peroxide, and an intermediate liquid A is obtained after the reaction is finished;
when the temperature of the sodium hydroxide solution in the first reaction kettle is controlled to be 5 ℃, dropwise adding a hydrogen peroxide solution;
the dropwise adding is completed within 1h, the reaction temperature is 5-10 ℃, and the reaction time is 0.5 h;
3) adding 0.57g of sodium dodecyl sulfate into the intermediate liquid A prepared in the step 2), and uniformly mixing to obtain an intermediate liquid B;
4) fully dissolving 141.99g of benzoyl chloride with the mass fraction of 99% into 567.96g of trichloromethane, and uniformly mixing to obtain a uniform and stable trichloromethane solution of benzoyl chloride with the mass fraction of 20%;
5) under the conditions of cooling and increasing the stirring speed, dropwise adding the uniformly mixed benzoyl chloride and organic solvent mixed solution prepared in the step 4) into the intermediate liquid B prepared in the step 3), and obtaining an intermediate liquid C after completion;
the dropwise adding is completed within 2 hours, the reaction temperature is 5-10 ℃, and the reaction time is 2 hours;
6) adding 150g of water into the intermediate liquid C prepared in the step 5), then sequentially stirring for 10min, and separating by using a separating funnel to obtain an upper layer which is an aqueous solution and a lower layer which is an organic liquid after the separation is finished;
7) adding the organic liquid obtained in the step 6) into a second reaction kettle which is low in temperature and contains 500g of methanol, carrying out quenching operation on the liquid in the second reaction kettle by using an ice maker, and continuously stirring at low temperature to obtain an intermediate liquid D;
in the step 7), carrying out quenching operation on the liquid in the second reaction kettle until the temperature of the liquid in the second reaction kettle is reduced to-5 ℃;
continuously stirring at-5 deg.C for 25 min;
8) filtering the intermediate liquid D prepared in the step 7), and obtaining filter residue and filtrate after filtering;
9) drying the filter residue obtained in the step 8) at a low temperature to obtain powdered dibenzoyl peroxide after drying;
in the step 9), the temperature for low-temperature drying is 50 ℃.
By detection and measurement, the dibenzoyl peroxide prepared in example 3 was 102.02g, the yield was 84.23%, the dibenzoyl peroxide was white powder in appearance, the purity was 99.79 wt%, and the particle size was not more than 100. mu.m.
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 preparation method of high-purity powdered dibenzoyl peroxide is characterized by comprising the following steps of:
1) adding a sodium hydroxide solution into a first reaction kettle, and stirring and cooling;
2) under the conditions of cooling and stirring, dropwise adding a hydrogen peroxide solution into the sodium hydroxide solution obtained in the step 1), mixing the sodium hydroxide and the hydrogen peroxide, carrying out a chemical reaction to generate sodium peroxide, and obtaining an intermediate liquid A after the reaction is finished;
3) adding a phase transfer catalyst into the intermediate liquid A prepared in the step 2), and uniformly mixing to obtain an intermediate liquid B;
4) dissolving benzoyl chloride in an organic solvent to obtain a mixed solution of the benzoyl chloride and the organic solvent;
5) under the conditions of cooling and increasing the stirring speed, dropwise adding the uniformly mixed benzoyl chloride and organic solvent mixed solution prepared in the step 4) into the intermediate liquid B prepared in the step 3), and carrying out chemical reaction on sodium peroxide and benzoyl chloride in the presence of a phase transfer catalyst to generate dibenzoyl peroxide, thus obtaining an intermediate liquid C;
6) adding water into the intermediate liquid C prepared in the step 5), then sequentially stirring and separating by using a separating funnel, wherein the upper layer is an aqueous solution and the lower layer is an organic liquid after the separation is finished;
7) adding the organic liquid obtained in the step 6) into an inert solvent in a second reaction kettle, using the inert solvent as a dissolving-out agent to perform dissolving-out crystallization, using an ice maker to perform quenching operation on the liquid in the second reaction kettle, and continuously stirring at a low temperature to perform cooling crystallization to obtain an intermediate liquid D;
8) filtering the intermediate liquid D prepared in the step 7), and obtaining filter residue and filtrate after filtering;
9) drying the filter residue obtained in the step 8) at a low temperature to obtain powdered dibenzoyl peroxide after drying.
2. The method for preparing dibenzoyl peroxide in the form of high purity powder according to claim 1, wherein in step 1), the sodium hydroxide solution is 32% by mass sodium hydroxide solution.
3. The method for preparing high-purity powdered dibenzoyl peroxide according to claim 1, wherein in step 2), the amount of hydrogen peroxide is 1 (2-2.5);
and (3) dropwise adding a hydrogen peroxide solution when the temperature of the sodium hydroxide solution in the first reaction kettle is controlled to be 5-10 ℃.
4. The method for preparing dibenzoyl peroxide in the form of powder with high purity according to claim 1, wherein in step 3), the phase transfer catalyst is sodium dodecyl sulfate, sodium dodecyl sulfate or sodium dodecyl benzene sulfonate;
the mass of the phase transfer catalyst, that of benzoyl chloride (0.2-0.5%), is 1.
5. The method for preparing dibenzoyl peroxide in the form of high purity powder according to claim 1, wherein in step 4), the organic solvent is chloroform, dichloromethane or benzene; the amount of benzoyl chloride substance is equal to (2-2.3) 1; the mass of the organic solvent, that of benzoyl chloride (3-6), is 1.
6. The method for preparing dibenzoyl peroxide in the form of a high purity powder according to claim 1, wherein, in step 5), a mixed solution of benzoyl chloride and an organic solvent is added dropwise while controlling the temperature of the intermediate liquid B in the first reaction tank to be 5 ℃ to 10 ℃.
7. The method for preparing high-purity powdered dibenzoyl peroxide according to claim 1, wherein in step 6), the mass of water is 32% by mass of the aqueous solution of sodium hydroxide (0.5-2): 1, and the stirring time is 5-15 min.
8. The method for preparing dibenzoyl peroxide in powder form with high purity as claimed in claim 1, wherein, in step 7), the liquid in the second reaction vessel is quenched until the temperature of the liquid in the second reaction vessel is reduced to-15 ℃ to-5 ℃;
the inert solvent is methanol or acetone;
continuously stirring for 20min to 30min at the temperature of between 15 ℃ below zero and 5 ℃ below zero.
9. The method for preparing dibenzoyl peroxide in the form of high purity powder according to claim 1, wherein the low-temperature drying temperature in step 9) is 45 to 50 ℃.
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| CN115043767A (en) * | 2022-07-15 | 2022-09-13 | 睦化(上海)流体工程有限公司 | Microchannel reaction process and device for preparing benzoyl peroxide |
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| CN115521237A (en) * | 2022-11-03 | 2022-12-27 | 山东阳谷华泰化工股份有限公司 | Method for preparing tert-butyl peroxybenzoate with high yield |
| CN115521237B (en) * | 2022-11-03 | 2024-06-04 | 山东阳谷华泰化工股份有限公司 | Method for preparing tert-butyl peroxybenzoate in high yield |
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