CN117304087B - Preparation method of 1, 3-tetramethylbutyl hydroperoxide - Google Patents
Preparation method of 1, 3-tetramethylbutyl hydroperoxide Download PDFInfo
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- CN117304087B CN117304087B CN202311215278.6A CN202311215278A CN117304087B CN 117304087 B CN117304087 B CN 117304087B CN 202311215278 A CN202311215278 A CN 202311215278A CN 117304087 B CN117304087 B CN 117304087B
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 138
- 239000007787 solid Substances 0.000 claims abstract description 40
- 239000003930 superacid Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000007791 liquid phase Substances 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- JYVLIDXNZAXMDK-UHFFFAOYSA-N 2-pentanol Substances CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 32
- 238000001816 cooling Methods 0.000 abstract description 8
- 150000002978 peroxides Chemical class 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 24
- 239000011973 solid acid Substances 0.000 description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 10
- 238000010992 reflux Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention belongs to the technical field of peroxide preparation, and particularly relates to a preparation method of 1, 3-tetramethylbutyl hydroperoxide. In the presence of solid super acid and citric acid, hydrogen peroxide reacts with 2, 4-trimethyl-2-amyl alcohol, the solid super acid and a liquid phase are obtained through cooling and solid-liquid separation, and after the liquid phase is layered, the upper layer is 1, 3-tetramethylbutyl hydrogen peroxide. The product prepared by the method has high yield, high purity, less waste water and reusable catalyst.
Description
Technical Field
The invention belongs to the technical field of peroxide preparation, and particularly relates to a preparation method of 1, 3-tetramethylbutyl hydroperoxide.
Background
The organic peroxide is a derivative of hydrogen peroxide molecule with one or two hydrogen atoms replaced by organic groups, and has the general formula R 1 -O-O-R 2 . The 1, 3-tetramethylbutyl hydroperoxide is a common organic peroxide, has stable property, does not need expensive low-temperature storage conditions, can be stored below 50 ℃, has no obvious change of activity within three months, can be used for polymerization reaction of polyethylene, and is also suitable for acrylic resin, low-density polyethylene resin and MBS treePolymerization and modification reactions of resins such as fats. In addition, 1, 3-tetramethylbutyl hydroperoxide is also an important organic synthetic intermediate, and can be used for preparing related ester peroxides, such as 1, 3-tetramethylbutyl peroxyneodecanoate and the like.
The traditional alkyl hydrogen peroxide production generally adopts concentrated sulfuric acid as a catalyst, the concentrated sulfuric acid has high catalytic activity but relatively poor selectivity, byproducts such as dialkyl peroxide and the like can be generated in the production process, meanwhile, the concentrated sulfuric acid has strong corrosiveness and high requirements on a kettle, and waste acid water generated by the final reaction also needs to be correspondingly treated.
European patent EP0395803A1 discloses a process for the preparation of 1, 3-tetramethylbutyl hydroperoxide, which uses 98wt.% concentrated sulfuric acid as catalyst, which is laboratory prepared in general yields, although the purity of the product produced is relatively high; most critical is the safety problem of concentrated sulfuric acid as a catalyst, and thus, industrial production using this method is extremely limited.
In summary, the traditional preparation method of the 1, 3-tetramethylbutyl hydroperoxide has harsh conditions, byproducts are easy to generate, the potential safety hazard is large in the use process of the catalyst concentrated sulfuric acid in the production process, the generated waste acid is more, the environmental protection pressure in the production process is larger, and the method does not accord with the trend of green production.
Disclosure of Invention
The invention aims to provide a preparation method of 1, 3-tetramethylbutyl hydroperoxide, which ensures the selectivity of solid superacid and the catalytic activity by adopting citric acid as a cocatalyst, improves the yield and purity of the 1, 3-tetramethylbutyl hydroperoxide and realizes the large-scale production of the 1, 3-tetramethylbutyl hydroperoxide.
In the preparation method of the 1, 3-tetramethylbutyl hydroperoxide, hydrogen peroxide reacts with 2, 4-trimethyl-2-amyl alcohol in the presence of solid super acid and citric acid, solid super acid and liquid phase are obtained through cooling and solid-liquid separation, and the upper layer is the 1, 3-tetramethylbutyl hydroperoxide after the liquid phase is layered.
Wherein:
the mass ratio of the solid super acid to the citric acid is (7-12): 1.
The mass ratio of the solid super acid to the 2, 4-trimethyl-2-amyl alcohol is (0.8-1.3): 1.
The solid super acid is H 2 SO 4 /SiO 2 、SO 4 2- /ZrO 2 Or a silicosulfonic acid.
The solid super acid content is more than or equal to 0.6mmol H + Preferably the amount of solid super acid per gram is 1-1.5mmol H + /g。
The molar ratio of the hydrogen peroxide to the 2, 4-trimethyl-2-amyl alcohol is (1-1.3): 1.
The concentration of hydrogen peroxide is 25-55wt.%.
The concentration of the 2, 4-trimethyl-2-pentanol is 60-85wt.%.
Adding solid super acid, citric acid and 2, 4-trimethyl-2-amyl alcohol at the temperature lower than 25 ℃.
The reaction temperature is 60-75 ℃, the reaction time is 4-9h, and the temperature is reduced to below 40 ℃.
Preferably, the preparation method of the 1, 3-tetramethylbutyl hydroperoxide comprises the following steps:
adding citric acid and 2, 4-trimethyl-2-amyl alcohol into hydrogen peroxide, adding a solid acid catalyst for reaction, cooling, and carrying out solid-liquid separation to obtain solid superacid and a liquid phase; after liquid phase layering, the upper layer is 1, 3-tetramethylbutyl hydroperoxide, and the lower layer is citric acid, a solid acid catalyst and citric acid for recycling.
More preferably, the preparation method of the 1, 3-tetramethylbutyl hydroperoxide comprises the following steps:
adding citric acid and 2, 4-trimethyl-2-amyl alcohol into hydrogen peroxide at the temperature lower than 25 ℃, adding a solid acid catalyst, controlling the temperature not to exceed 30 ℃, refluxing by a condensing tube, heating to react, cooling to the temperature lower than 40 ℃, and carrying out solid-liquid separation to obtain solid super acid and a liquid phase; after liquid phase layering, the upper layer is 1, 3-tetramethylbutyl hydroperoxide, and the lower layer is citric acid, a solid acid catalyst and citric acid for recycling.
The beneficial effects of the invention are as follows:
(1) The invention selects the composite catalytic system of solid super acid and citric acid, and the obtained product has high purity, less byproducts, high yield, the purity of the final product is more than 90 percent, and the yield is more than 91 percent.
(2) The solid superacid catalyst has the characteristic of high selectivity, but the reaction speed is relatively slow due to the limiting of the acid quantity and the acid center of the solid superacid catalyst; the invention not only maintains the high selectivity of the solid super acid, but also plays a role of strong citric acid activity by selecting the composite catalytic system of the solid super acid and the citric acid; the existence of the citric acid enables the hydrogen peroxide and the 2, 4-trimethyl-2-amyl alcohol to be combined in advance, when the combined hydrogen peroxide and the 2, 4-trimethyl-2-amyl alcohol meet a solid super acidic catalyst, the hydrogen peroxide and the 2, 4-trimethyl-2-amyl alcohol can be catalyzed to react to generate a1, 3-tetramethylbutyl hydrogen peroxide product, and the generated product is separated from the solid super acidic catalyst together with the citric acid, so that separation is realized; in addition, the existence of the citric acid can enable the acid catalytic center of the solid super acid to be in an optimal state all the time, so that the loss of the active center is reduced.
The mechanism is that the citric acid contains three carboxyl groups and one hydroxyl group, and when in reaction, the three carboxyl groups and one hydroxyl group form hydrogen bonds with hydrogen peroxide and 2, 4-trimethyl-2-amyl alcohol to promote the mutual attraction of the hydrogen peroxide and the 2, 4-trimethyl-2-amyl alcohol, so that the hydrogen peroxide and the 2, 4-trimethyl-2-amyl alcohol are combined in advance, because three carboxyl groups and one hydroxyl group on the citric acid are mutually attracted with an acid group on the solid super acid, the citric acid drives hydrogen peroxide and 2, 4-trimethyl-2-amyl alcohol to contact with the solid super acid, and the corresponding 1, 3-tetramethylbutyl hydrogen peroxide is generated by catalytic reaction; after that, 1, 3-tetramethylbutyl hydroperoxide and citric acid are separated from the solid super acidic catalyst, and then settled and layered, wherein the upper layer is 1, 3-tetramethylbutyl hydroperoxide and the lower layer is citric acid.
(3) The solid super acid catalyst can be reused after being separated from the product.
(4) The process for preparing the 1, 3-tetramethylbutyl hydroperoxide generates less waste water, has lower acidity, is simple in waste water treatment and is more environment-friendly.
In conclusion, the preparation method of the 1, 3-tetramethylbutyl hydroperoxide has the advantages of high product yield, high purity, less waste water and reusable catalyst.
Drawings
FIG. 1 is a gas chromatogram of the product of example 1.
Detailed Description
The invention is further described below with reference to examples.
Example 1
Firstly, weighing 5400g 30wt.% hydrogen peroxide, slowly adding the hydrogen peroxide into a 25L reaction kettle, starting stirring, controlling the temperature not to exceed 20 ℃ in the stirring process, adding 600g of citric acid, adding 7500g of 75wt.% 2, 4-trimethyl-2-pentanol, and finally slowly adding 6000g of acid with the amount of 1.04mmol H + Solid acid catalyst H/g 2 SO 4 /SiO 2 Controlling the temperature not to exceed 30 ℃, refluxing by a condensing tube, heating to 60 ℃, reacting for 5 hours, stopping stirring, cooling to below 40 ℃, and carrying out solid-liquid separation to obtain solid superacid and liquid phase; after liquid phase layering, the upper layer is 1, 3-tetramethylbutyl hydroperoxide, the lower layer is citric acid, and the solid acid catalyst and the citric acid are recycled; the purity of 1, 3-tetramethylbutyl hydroperoxide was 91.04%, and the yield was 93.51%.
The product of example 1 was subjected to gas chromatography, and the gas chromatography and data are shown in FIG. 1. Meanwhile, a simple qualitative method commonly used in a laboratory is adopted to carry out gas chromatography detection on the 1, 3-tetramethylbutyl hydroperoxide standard sample, and the main peak position is the same as that of the gas chromatography of the embodiment 1.
Example 2
Firstly weighing 4600g of 35wt.% hydrogen peroxide, slowly adding the hydrogen peroxide into a 25L reaction kettle, starting stirring, controlling the temperature not to exceed 25 ℃ in the stirring process, adding 600g of citric acid, adding 7500g of 70wt.% 2, 4-trimethyl-2-pentanol, and finally slowly adding 5500g of acid with the acid content of 1.36mmol H + Solid acid catalyst H/g 2 SO 4 /SiO 2 Controlling the temperature not to exceed 30 ℃ and returning the condensing tubeAfter the temperature is raised to 70 ℃, the reaction is carried out for 6 hours, stirring is stopped, the temperature is reduced to below 40 ℃, and solid-liquid separation is carried out to obtain solid superacid and liquid phase; after liquid phase layering, the upper layer is 1, 3-tetramethylbutyl hydroperoxide, the lower layer is citric acid, and the solid acid catalyst and the citric acid are recycled; the purity of the 1, 3-tetramethylbutyl hydroperoxide was 90.16%, and the yield was 95.33%.
Example 3
Firstly weighing 4600g of 35wt.% hydrogen peroxide, slowly adding the hydrogen peroxide into a 25L reaction kettle, starting stirring, controlling the temperature not to exceed 25 ℃ in the stirring process, adding 750g of citric acid, adding 7500g of 80wt.% 2, 4-trimethyl-2-pentanol, and finally slowly adding 7500g of acid with the acid content of 1.36mmol H + Solid acid catalyst SO/g 4 2- /ZrO 2 Controlling the temperature not to exceed 30 ℃, refluxing by a condensing tube, heating to 75 ℃, reacting for 6 hours, stopping stirring, cooling to below 40 ℃, and carrying out solid-liquid separation to obtain solid superacid and liquid phase; after liquid phase layering, the upper layer is 1, 3-tetramethylbutyl hydroperoxide, the lower layer is citric acid, and the solid acid catalyst and the citric acid are recycled; the purity of the 1, 3-tetramethylbutyl hydroperoxide is 91.28 percent, and the yield is 95.81 percent.
Example 4
Firstly, 3800g of 50wt.% hydrogen peroxide is weighed and slowly added into a 25L reaction kettle, stirring is started, the temperature is controlled to be not higher than 20 ℃ in the stirring process, 700g of citric acid is added, 7500g of 80wt.% 2, 4-trimethyl-2-amyl alcohol is added, and finally 5200g of acid with the acid content of 1.17mmol H is slowly added + The solid acid catalyst of/g is silicic sulfonic acid, the temperature is controlled to be not more than 30 ℃, a condensing tube is used for reflux, the reaction is carried out for 4 hours after the temperature is raised to 75 ℃, stirring is stopped, the temperature is reduced to be below 40 ℃, and solid super acid and liquid phase are obtained through solid-liquid separation; after liquid phase layering, the upper layer is 1, 3-tetramethylbutyl hydroperoxide, the lower layer is citric acid, and the solid acid catalyst and the citric acid are recycled; the purity of 1, 3-tetramethylbutyl hydroperoxide was 90.42%, and the yield was 93.67%.
Example 5
Firstly, weighing 4800g of 35wt.% hydrogen peroxide, slowly adding the hydrogen peroxide into a 25L reaction kettle, starting stirring, controlling the temperature not to exceed 20 ℃ in the stirring process, adding 900g of citric acid, and adding 70wt.%7500g of 2, 4-trimethyl-2-pentanol and finally 6700g of acid 1.28mmol of H are slowly added + The solid acid catalyst of/g is silicic sulfonic acid, the temperature is controlled to be not more than 30 ℃, a condensing tube is used for reflux, the reaction is carried out for 5 hours after the temperature is raised to 65 ℃, stirring is stopped, the temperature is reduced to be below 40 ℃, and solid super acid and liquid phase are obtained through solid-liquid separation; after liquid phase layering, the upper layer is 1, 3-tetramethylbutyl hydroperoxide, the lower layer is citric acid, and the solid acid catalyst and the citric acid are recycled; the purity of 1, 3-tetramethylbutyl hydroperoxide was 90.95%, and the yield was 91.6%.
Comparative example 1
Citric acid was not added, and the rest was as in example 1.
Firstly, weighing 5400g 30wt.% hydrogen peroxide, slowly adding the hydrogen peroxide into a 25L reaction kettle, starting stirring, controlling the temperature not to exceed 20 ℃ in the stirring process, adding 7500g of 75wt.% 2, 4-trimethyl-2-pentanol, and finally slowly adding 6000g of acid with 1.04mmol of H + Solid acid catalyst H/g 2 SO 4 /SiO 2 Controlling the temperature not to exceed 30 ℃, refluxing by a condensing tube, heating to 60 ℃, reacting for 5 hours, stopping stirring, cooling to below 40 ℃, and carrying out solid-liquid separation to obtain solid super acid and 1, 3-tetramethylbutyl hydroperoxide; the purity of the 1, 3-tetramethylbutyl hydroperoxide is 80.85%, and the yield is 87.32%.
Comparative example 2
Without addition of solid acid catalyst H 2 SO 4 /SiO 2 The remainder were as in example 1.
Firstly, weighing 5400g of 30wt.% hydrogen peroxide, slowly adding the hydrogen peroxide into a 25L reaction kettle, starting stirring, controlling the temperature in the stirring process to be not more than 20 ℃, adding 600g of citric acid, adding 75wt.% 2, 4-trimethyl-2-pentanol to 7500g of the citric acid, controlling the temperature to be not more than 30 ℃, refluxing by a condensing tube, heating to 60 ℃, reacting for 5 hours, stopping stirring, cooling to below 40 ℃, layering, wherein the upper layer is 1, 3-tetramethylbutyl hydrogen peroxide, the lower layer is citric acid, the purity of the 1, 3-tetramethylbutyl hydrogen peroxide is 72.58%, and the yield is 69.29%.
Comparative example 3
Without addition of citric acid and solid acid catalyst H 2 SO 4 /SiO 2 With only 70wt.%Instead of sulfuric acid, the rest is as in example 1.
Firstly, weighing 5400g 30wt.% hydrogen peroxide, slowly adding into a 25L reaction kettle, starting stirring, controlling the temperature not to exceed 20 ℃ in the stirring process, adding 7500g of 75wt.% 2, 4-trimethyl-2-pentanol, and finally slowly adding 1820g H of 70wt.% 2 SO 4 Reflux of a condensing tube is controlled at a temperature not exceeding 30 ℃, reaction is carried out for 5 hours after the temperature is raised to 60 ℃, stirring is stopped, the temperature is reduced to below 40 ℃, layering is carried out, the upper layer is 1, 3-tetramethylbutyl hydroperoxide, and the lower layer is H 2 SO 4 Can be reused; the purity of 1, 3-tetramethylbutyl hydroperoxide was 84.37%, and the yield was 89.26%.
From the above, the present invention selects the composite catalytic system of the solid super acid and the citric acid, and the obtained product has high purity and high yield, the purity of the products of the examples 1-5 is more than 90%, and the yield is more than 91%. While comparative examples 1-3 were lower in purity and yield than the present invention.
Comparative example 3 uses 70wt.% sulfuric acid as a catalyst, and does not use 98wt.% sulfuric acid as a catalyst, because the production of 98wt.% concentrated sulfuric acid has the disadvantages of high operating process requirements, obvious thermal effect, high corrosiveness, high risk, and the like. Thus, to ensure operator safety, a comparative experiment was performed using 70wt.% sulfuric acid as catalyst.
Claims (9)
1. A preparation method of 1, 3-tetramethylbutyl hydroperoxide is characterized by comprising the following steps: in the presence of solid superacid and citric acid, hydrogen peroxide reacts with 2, 4-trimethyl-2-amyl alcohol, the temperature is reduced, solid-liquid separation is carried out to obtain solid superacid and liquid phase, and after layering of the liquid phase, the upper layer is 1, 3-tetramethylbutyl hydroperoxide; the solid super acid is H 2 SO 4 /SiO 2 、SO 4 2- /ZrO 2 Or a silicosulfonic acid.
2. The process for the preparation of 1, 3-tetramethylbutyl hydroperoxide as claimed in claim 1, wherein: the mass ratio of the solid super acid to the citric acid is (7-12): 1.
3. The process for the preparation of 1, 3-tetramethylbutyl hydroperoxide as claimed in claim 1, wherein: the mass ratio of the solid super acid to the 2, 4-trimethyl-2-amyl alcohol is (0.8-1.3): 1.
4. The process for the preparation of 1, 3-tetramethylbutyl hydroperoxide as claimed in claim 1, wherein: the solid super acid content is more than or equal to 0.6mmol H + /g。
5. The process for producing 1, 3-tetramethylbutyl hydroperoxide as claimed in claim 4, wherein: the solid super acid content is 1-1.5mmol H + /g。
6. The process for the preparation of 1, 3-tetramethylbutyl hydroperoxide as claimed in claim 1, wherein: the molar ratio of the hydrogen peroxide to the 2, 4-trimethyl-2-amyl alcohol is (1-1.3): 1.
7. The process for the preparation of 1, 3-tetramethylbutyl hydroperoxide as claimed in claim 1, wherein: the concentration of hydrogen peroxide is 25-55wt.%.
8. The process for the preparation of 1, 3-tetramethylbutyl hydroperoxide as claimed in claim 1, wherein: the concentration of the 2, 4-trimethyl-2-pentanol is 60-85wt.%.
9. The process for the preparation of 1, 3-tetramethylbutyl hydroperoxide as claimed in claim 1, wherein: adding solid super acid, citric acid and 2, 4-trimethyl-2-amyl alcohol at the temperature lower than 25 ℃; the reaction temperature is 60-75 ℃, the reaction time is 4-6h, and the temperature is reduced to below 40 ℃.
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| EP3666755A1 (en) * | 2017-08-12 | 2020-06-17 | Shanghai Hybrid-Chem Technologies | Online full continuous flow production process for directly preparing organic peroxide with hydrogen peroxide as raw material |
| CN113454064A (en) * | 2019-02-22 | 2021-09-28 | 诺力昂化学品国际有限公司 | Process for producing organic peroxide |
| CN114292219A (en) * | 2021-12-24 | 2022-04-08 | 兰州助剂厂有限责任公司 | Preparation method of 1, 1-dimethyl-3-hydroxybutyl hydroperoxide |
| CN114409582A (en) * | 2022-02-23 | 2022-04-29 | 兰州助剂厂有限责任公司 | Method for preparing peroxyacetic acid and improving stability of peroxyacetic acid by adopting heterogeneous catalyst |
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