CN115109010A - Method for preparing accelerator NS by oxidizing hydrogen peroxide in organic solvent - Google Patents
Method for preparing accelerator NS by oxidizing hydrogen peroxide in organic solvent Download PDFInfo
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 232
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000003960 organic solvent Substances 0.000 title claims abstract description 34
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 38
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000004821 distillation Methods 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 32
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical group ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 abstract description 12
- 239000007800 oxidant agent Substances 0.000 abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 239000010815 organic waste Substances 0.000 abstract description 2
- 239000011949 solid catalyst Substances 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 description 26
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000005708 Sodium hypochlorite Substances 0.000 description 8
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- HNWAHFPYJHAAJE-UHFFFAOYSA-N n-tert-butyl-1,3-benzothiazole-2-sulfonamide Chemical compound C1=CC=C2SC(S(=O)(=O)NC(C)(C)C)=NC2=C1 HNWAHFPYJHAAJE-UHFFFAOYSA-N 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/70—Sulfur atoms
- C07D277/76—Sulfur atoms attached to a second hetero atom
- C07D277/80—Sulfur atoms attached to a second hetero atom to a nitrogen atom
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a method for preparing an accelerator NS by oxidizing hydrogen peroxide in an organic solvent, which comprises the following steps: adding an accelerator M and a catalyst into an organic solvent, uniformly stirring, heating to a certain temperature in a first stage, dropwise adding hydrogen peroxide in the first stage, and reacting for a period of time after dropwise adding hydrogen peroxide; adding tert-butylamine, dropwise adding hydrogen peroxide in the second stage, and carrying out oxidation reaction for a certain time after dropwise adding hydrogen peroxide; and (3) after the reaction is finished, standing and separating liquid, separating an upper organic solvent layer, and recovering the solvent through reduced pressure distillation to obtain the promoter NS. The invention utilizes a solid catalyst to react an accelerant M with tert-butylamine through a liquid-phase catalytic oxidation reaction to generate an accelerant NS; the catalytic reaction is carried out in an organic solvent medium, the solvent can be recycled and reused by distillation, and no organic waste liquid of a fixed source is discharged; the hydrogen peroxide is an oxidant, water is generated after oxidation reaction, and no salt-containing wastewater is discharged.
Description
Technical Field
The invention relates to the technical field of rubber accelerators, in particular to a method for preparing an accelerator NS by oxidizing hydrogen peroxide in an organic solvent.
Background
The accelerator NS (N-tertiary butyl-2-benzothiazole sulfonamide) has a primary amine structure, does not have the toxicity problem of nitrosamine, and can replace accelerators NOBS and the like which contain secondary amine groups and are possibly carcinogenic. Meanwhile, the sulfenamide vulcanization accelerator has the advantages of high vulcanization degree, good aging resistance, excellent mechanical property, high vulcanization activity, high vulcanization flatness, high vulcanization speed and the like, and is one of important varieties of sulfenamide rubber vulcanization accelerators.
The preparation method of the accelerator NS generally adopts the accelerator M (2-mercaptobenzothiazole) and tert-butylamine as raw materials and is synthesized by condensation reaction in the presence of an oxidant. The synthesis method is generally a sodium hypochlorite oxidation method, an oxygen catalytic oxidation method, a chlorine oxidation method, an electrolytic oxidation method, an aqueous medium hydrogen peroxide oxidation method, or the like, depending on the kind of the oxidizing agent.
Sodium hypochlorite oxidation process. The method is a main method for industrially synthesizing the accelerator NS at present and is also a mainstream production method. Has the advantages of mature process, mild reaction condition, stable product quality and the like. The method takes an accelerant M and tert-butylamine as raw materials, and carries out one-step condensation reaction in an aqueous phase in the presence of an oxidant sodium hypochlorite aqueous solution to prepare the accelerant NS. Although the sodium hypochlorite oxidation method has a mature process, the method has the disadvantages of large water consumption, high salt content of discharged large amount of wastewater, environmental harm, high treatment difficulty and obvious production cost increase due to large investment of wastewater treatment. Although the method is used in production, the production plant area and the production scale are limited, and the method tends to be gradually replaced by a more environment-friendly new process. In view of the progress of the production technology, it should be also considered to develop a new technology to replace the sodium hypochlorite oxidation process as early as possible.
In order to solve the serious defects of the sodium hypochlorite oxidation method, a plurality of improved preparation methods of the accelerator NS are disclosed and reported in succession, and the main reported new process technologies for preparing the accelerator NS comprise:
oxygen catalytic oxidation process. The method refers to an oxidation reaction which takes air, oxygen and the like as oxidants in the presence of catalysts, generally takes molecular oxygen as the oxidant, and the used catalysts comprise simple substances such as Cu, Co, Fe and the like or complexes thereof. The synthesis of NS by the catalytic oxygen oxidation method needs to be carried out in a water phase or an organic solvent (acetonitrile), and has more discharged wastewater, or the solvent acetonitrile is more expensive and has higher toxicity. In addition, the synthesis of NS by the catalytic oxygen oxidation method needs to be carried out under high pressure, so that the requirements on production equipment are high, the equipment investment is large, and the industrialization process is limited.
Chlorine oxidation method. The method takes chlorine as an oxidant and takes an accelerator M and tert-butylamine as raw materials to synthesize the accelerator NS. The tert-butylamine must be in large excess, more than 10 times that of accelerator M, otherwise the material will be very viscous and difficult to handle, producing large amounts of industrial waste water. In addition, the operation of chlorine is dangerous, and the method belongs to an intrinsic dangerous chemical reaction process. In view of safety, environmental protection and process operation difficulty, the chlorine oxidation method is difficult to be applied to large-scale industrial production at present.
Electrolytic oxidation method. The method is characterized in that a NaCl solution is used as an electrolyte solution in a diaphragm-free electrolytic cell, and an accelerator M and tert-butylamine are subjected to electrochemical oxidation condensation reaction to prepare an accelerator NS. The method has the problems of immature technology, low current efficiency, wastewater discharge and the like, is in a laboratory research stage, and has failed to carry out large-scale industrial production for a while.
Aqueous medium hydrogen peroxide oxidation process. Hydrogen peroxide is a green, mild and cheap oxidant, and is widely applied to green oxidation reaction. In recent years, the reaction using hydrogen peroxide as an oxidizing agent mainly includes oxidation of an ethylenic compound, oxidation of an alcohol, oxidation of a phenol, oxidation of a carbonyl compound, oxidation of a benzyl group, oxidation of a sulfur-containing organic compound, oxidation of an amine, and the like. The accelerator NS prepared by the hydrogen peroxide oxidation method reported at present takes water as a medium, and the accelerator M and tert-butylamine are subjected to oxidative condensation by hydrogen peroxide to form the accelerator NS. Hydrogen peroxide is required to be dripped into a water medium with strong alkalinity for oxidation reaction, and if the pH is more than 11, the yield and the purity of the obtained promoter NS are both more than 90 percent. There is also a process for carrying out hydrogen peroxide oxidation reaction in a sulfuric acid aqueous medium, for example, taking hydrogen peroxide as an oxidant, adding a 20% sulfuric acid solution into a reaction kettle filled with tert-butylamine, and then dropwise adding an accelerator M-Na salt and hydrogen peroxide. The prior hydrogen peroxide oxidation method uses strong acid water or alkaline water as a reaction medium, can discharge more acid or alkaline waste water, and is difficult to treat the waste water. Therefore, a cleaner and more environment-friendly production process is needed for the industrial production process of the accelerator NS.
Disclosure of Invention
The invention aims to provide a method for preparing an accelerator NS by oxidizing hydrogen peroxide in an organic solvent, aiming at the defects of the existing sodium hypochlorite production process and the researched and developed preparation method of the accelerator NS, such as the defects of large water consumption, large amount of discharged wastewater, high salt content of the wastewater, environmental disadvantage and high treatment difficulty of the sodium hypochlorite oxidation method, and the defect that the strong acid water or alkaline water is used as a reaction medium, more acidic or alkaline wastewater is discharged and the wastewater is difficult to treat.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for preparing an accelerator NS by oxidizing hydrogen peroxide in an organic solvent comprises the following steps:
(1) adding an accelerator M and a catalyst into an organic solvent, uniformly stirring, heating to a certain temperature in a first stage, dropwise adding hydrogen peroxide in the first stage, and reacting for a period of time after dropwise adding hydrogen peroxide;
(2) adding tert-butylamine, dropwise adding hydrogen peroxide in the second stage, and carrying out oxidation reaction for a certain time after dropwise adding hydrogen peroxide;
(3) and (3) after the reaction is finished, standing and separating liquid, separating an upper organic solvent layer, and recovering the solvent through reduced pressure distillation to obtain the promoter NS.
Further, the organic solvent in the step 1 is any one of toluene and xylene.
Further, the mass ratio of the organic solvent to the accelerator M in the step 1 is (3.5-6): 1.
further, in the step 1, the catalyst is iron phthalocyanine, and the mass ratio of the catalyst to the promoter M is (0.01-0.1): 1.
further, the temperature of the first-stage temperature rise in the step 1 is controlled to be 40-65 ℃.
Further, after the first-stage temperature rise in the step 1 is completed, hydrogen peroxide (with a molecular weight of 34 and a concentration of 30%) is used for the first-stage reaction, the dropping temperature of the hydrogen peroxide is 40-65 ℃, the dropping time of the hydrogen peroxide is 0.2-1h, and the mass ratio of the dropped hydrogen peroxide to the accelerator M (with a molecular weight of 167.3) is (0.5-0.8): 1, the reaction time is 1-5h after the hydrogen peroxide is added.
Further, the mass ratio of tert-butylamine (molecular weight 73) to accelerator M in step 2 is (1-1.8): 1.
further, the second stage of hydrogen peroxide is dropwise added in the step 2, the dropping temperature of the hydrogen peroxide is 40-65 ℃, the dropping time of the hydrogen peroxide is 0.2-1h, and the mass ratio of the dropwise added hydrogen peroxide to the accelerator M is (0.75-1.2): 1, the reaction time is 1-5h after the hydrogen peroxide is added, and the reaction temperature is 40-65 ℃.
The invention has the following beneficial effects: the invention utilizes a solid catalyst to react an accelerant M with tert-butylamine through a liquid-phase catalytic oxidation reaction to generate an accelerant NS; the catalytic reaction is carried out in an organic solvent medium, the solvent can be recycled and reused by distillation, and no organic waste liquid of a fixed source is discharged; the hydrogen peroxide is an oxidant, water is generated after oxidation reaction, and no salt-containing wastewater is discharged. The catalyst has longer service life and can be recycled and reused for many times; the technology of the invention is used for preparing the accelerator NS, has simple process and no high-salt-content wastewater discharge, belongs to a clean production process, and is beneficial to the industrial implementation of a new production technology of the accelerator NS.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
A method for preparing an accelerator NS by oxidizing hydrogen peroxide in an organic solvent comprises the following steps:
(4) adding an accelerator M and a catalyst into an organic solvent, uniformly stirring, heating to a certain temperature in a first stage, dropwise adding hydrogen peroxide in the first stage, and reacting for a period of time after dropwise adding hydrogen peroxide;
(5) adding tert-butylamine, dropwise adding hydrogen peroxide in the second stage, and carrying out oxidation reaction for a certain time after dropwise adding hydrogen peroxide;
(6) and (3) after the reaction is finished, standing and separating liquid, separating an upper organic solvent layer, and recovering the solvent through reduced pressure distillation to obtain the promoter NS.
The organic solvent in the step 1 is any one of toluene and xylene.
The mass ratio of the organic solvent to the promoter M in the step 1 is (3.5-6): 1.
in the step 1, the catalyst is iron phthalocyanine, and the mass ratio of the catalyst to the promoter M is (0.01-0.1): 1.
the temperature of the first-stage temperature rise in the step 1 is controlled to be 40-65 ℃.
After the first-stage heating in the step 1, the first-stage reaction is carried out by using hydrogen peroxide (with the molecular weight of 34 and the concentration of 30%), the dropping temperature of the hydrogen peroxide is 40-65 ℃, the dropping time of the hydrogen peroxide is 0.2-1h, and the mass ratio of the dropped hydrogen peroxide to an accelerator M (with the molecular weight of 167.3) is (0.5-0.8): 1, the reaction time is 1-5h after the hydrogen peroxide is added.
The mass ratio of the tert-butylamine (molecular weight 73) to the accelerator M in the step 2 is (1-1.8): 1.
and (2) beginning to dropwise add hydrogen peroxide of the second stage in the step (2), wherein the dropwise adding temperature of the hydrogen peroxide is 40-55-65 ℃, the dropwise adding time of the hydrogen peroxide is 0.2-1h, and the mass ratio of the dropwise added hydrogen peroxide to the accelerator M is (0.75-1.2): 1, the reaction time is 1-5h after the hydrogen peroxide is added, and the reaction temperature is 40-65 ℃.
Example 1
The mass ratio of the organic solvent toluene to the promoter M is 5: 1.
the mass ratio of the catalyst iron phthalocyanine to the accelerator M is 0.02: 1.
after the addition of the catalyst iron phthalocyanine, the temperature for the first-stage temperature rise was controlled at 55 ℃.
The dropping temperature of hydrogen peroxide for the first-stage reaction is 55 ℃, the dropping time of the hydrogen peroxide is 0.5 hour, and the mass ratio of the dropped hydrogen peroxide to the accelerator M is 0.7: 1, the reaction time after the hydrogen peroxide is added is 2 hours.
The mass ratio of the addition amount of the tert-butylamine to the accelerator M is 1.3: 1.
the temperature of beginning to dropwise add the second stage hydrogen peroxide is 55 ℃, the dropwise adding time of the hydrogen peroxide is 0.5 hour, and the mass ratio of the dropwise added hydrogen peroxide to the accelerator M is 1: 1, the reaction time after the hydrogen peroxide is added is 2 hours, and the reaction temperature is 55 ℃.
The specific operation of this embodiment is as follows:
weighing 8g of accelerator M (0.047 mol), 40g of solvent toluene and 0.16g of catalyst iron phthalocyanine, adding the materials into a reaction flask, stirring and mixing, heating to 55 ℃ at the beginning of the first stage, dropwise adding hydrogen peroxide at the beginning of the first stage, dropwise adding 5.6g of hydrogen peroxide at the dropwise adding temperature of 55 ℃ for 0.5 hour, and continuously reacting for 2 hours after the dropwise adding of the hydrogen peroxide is finished. Then 10.4g of tert-butylamine is added, 8g of hydrogen peroxide is dropwise added in the second stage, the temperature of the dropwise addition of the hydrogen peroxide in the second stage is 55 ℃, the dropwise addition time is 0.5 hour, the reaction is continued for 2 hours after the dropwise addition of the hydrogen peroxide is finished, and the reaction temperature is 55 ℃. And after the reaction is finished, pouring the reaction solution into a separating funnel, standing for 20min for layering, separating out an upper toluene solvent layer, distilling the upper layer solution under reduced pressure to remove the solvent to obtain the accelerator NS, and calculating to obtain the yield of the accelerator NS, wherein the yield of the accelerator NS is 96.4%.
Example 2
Some of the main conditions of this example are as follows:
the mass ratio of the organic solvent toluene to the promoter M is 6: 1.
the mass ratio of the catalyst iron phthalocyanine to the accelerator M is 0.1: 1.
after the catalyst iron phthalocyanine was added, the temperature for the first-stage temperature rise was controlled at 40 ℃.
The dropping temperature of the hydrogen peroxide for the first-stage reaction is 40 ℃, the dropping time of the hydrogen peroxide is 1 hour, and the mass ratio of the dropped hydrogen peroxide to the accelerator M is 0.8: 1, the reaction time after the hydrogen peroxide is added is 1 hour.
The mass ratio of the addition amount of the tert-butylamine to the accelerator M is 1.8: 1.
the temperature of the beginning of dropwise adding the second stage of hydrogen peroxide is 40 ℃, the dropwise adding time of the hydrogen peroxide is 1 hour, and the mass ratio of the dropwise adding hydrogen peroxide to the mass of the accelerator M is 0.75: 1, the reaction time after the hydrogen peroxide is added is 5 hours, and the reaction temperature is 40 ℃.
The specific operation of this embodiment is as follows:
weighing 8g of accelerator M (0.047 mol), 48g of solvent toluene and 0.8g of catalyst iron phthalocyanine, adding the materials into a reaction flask, stirring and mixing, heating to 40 ℃ at the beginning of the first stage, dropwise adding hydrogen peroxide at the beginning of the first stage, dropwise adding 6.4g of hydrogen peroxide at the dropping temperature of 40 ℃ for 1 hour, and continuing to react for 1 hour after the dropwise addition of the hydrogen peroxide is finished. Then 14.4g of tert-butylamine is added, 6g of hydrogen peroxide is dropwise added in the second stage, the temperature of the dropwise addition of the hydrogen peroxide in the second stage is 40 ℃, the dropwise addition time is 1 hour, the reaction is continued for 5 hours after the dropwise addition of the hydrogen peroxide is finished, and the reaction temperature is 40 ℃. And after the reaction is finished, pouring the reaction liquid into a separating funnel, standing for 20min for layering, separating out an upper toluene solvent layer, distilling the upper layer liquid under reduced pressure to remove the solvent to obtain the product accelerator NS, and calculating to obtain the yield of the accelerator NS, wherein the yield of the accelerator NS is 96.0%.
Example 3
Some of the main conditions of this example are as follows:
the mass ratio of the solvent toluene to the accelerator M is 3.5: 1.
the mass ratio of the catalyst iron phthalocyanine to the accelerator M is 0.01: 1.
after the catalyst iron phthalocyanine was added, the temperature for the first-stage temperature rise was controlled at 65 ℃.
The dropping temperature of hydrogen peroxide for the first-stage reaction is 65 ℃, the dropping time of the hydrogen peroxide is 0.2 hour, and the mass ratio of the dropped hydrogen peroxide to the accelerator M is 0.5: 1, the reaction time after the hydrogen peroxide is added is 5 hours.
The mass ratio of the addition amount of the tert-butylamine to the accelerator M is 1: 1.
the temperature for dropwise adding the hydrogen peroxide in the second stage is 65 ℃, the dropwise adding time of the hydrogen peroxide is 0.2 hour, and the mass ratio of the dropwise added hydrogen peroxide to the accelerator M is 1.2: 1, the reaction time after the hydrogen peroxide is added is 1 hour, and the reaction temperature is 65 ℃.
The specific operation of this embodiment is as follows:
weighing 8g of accelerator M (0.047 mol), 28g of solvent toluene and 0.08g of catalyst iron phthalocyanine, adding the materials into a reaction flask, stirring and mixing, heating to 65 ℃ at the beginning of the first stage, dropwise adding hydrogen peroxide at the beginning of the first stage, wherein the mass of the hydrogen peroxide is 4g, the dropwise adding temperature is 65 ℃, the dropwise adding time is 0.2 hour, and continuing to react for 5 hours after the dropwise adding of the hydrogen peroxide is finished. Then 8g of tert-butylamine is added, 9.6g of hydrogen peroxide is dropwise added in the second stage, the temperature of the dropwise addition of the hydrogen peroxide in the second stage is 65 ℃, the dropwise addition time is 0.2 hour, the reaction is continued for 1 hour after the dropwise addition of the hydrogen peroxide is finished, and the reaction temperature is 65 ℃. And after the reaction is finished, pouring the reaction liquid into a separating funnel, standing for 20min for layering, separating out an upper toluene solvent layer, distilling the upper layer liquid under reduced pressure to remove the solvent to obtain the product accelerator NS, and calculating to obtain the yield of the accelerator NS, wherein the yield of the accelerator NS is 96.5%.
Example 4
The same procedure as in example 1 was followed except that the solvent toluene was replaced with xylene, and the yield of the accelerator NS was calculated to be 96.1%.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (8)
1. A method for preparing an accelerator NS by oxidizing hydrogen peroxide in an organic solvent is characterized by comprising the following steps: the method comprises the following steps:
(1) adding an accelerator M and a catalyst into an organic solvent, uniformly stirring, heating to a certain temperature in a first stage, dropwise adding hydrogen peroxide in the first stage, and reacting for a period of time after dropwise adding hydrogen peroxide;
(2) adding tert-butylamine, dropwise adding hydrogen peroxide in the second stage, and carrying out oxidation reaction for a certain time after dropwise adding hydrogen peroxide;
(3) and (3) after the reaction is finished, standing and separating liquid, separating an upper organic solvent layer, and recovering the solvent through reduced pressure distillation to obtain the promoter NS.
2. The method for preparing the accelerator NS by oxidizing hydrogen peroxide in the organic solvent according to claim 1, which is characterized in that: the organic solvent in the step 1 is any one of toluene and xylene.
3. The method for preparing the accelerator NS by oxidizing hydrogen peroxide in the organic solvent according to claim 1, which is characterized in that: the mass ratio of the organic solvent to the promoter M in the step 1 is (3.5-6): 1.
4. the method for preparing the accelerator NS by oxidizing hydrogen peroxide in the organic solvent according to claim 1, which is characterized in that: in the step 1, the catalyst is iron phthalocyanine, and the mass ratio of the catalyst to the promoter M is (0.01-0.1): 1.
5. the method for preparing the accelerator NS by oxidizing the hydrogen peroxide in the organic solvent according to claim 1, which is characterized by comprising the following steps: the temperature of the first-stage temperature rise in the step 1 is controlled to be 40-65 ℃.
6. The method for preparing the accelerator NS by oxidizing hydrogen peroxide in the organic solvent according to claim 1, which is characterized in that: after the first-stage heating in the step 1, the first-stage reaction is carried out by using hydrogen peroxide (with the molecular weight of 34 and the concentration of 30%), the dropping temperature of the hydrogen peroxide is 40-65 ℃, the dropping time of the hydrogen peroxide is 0.2-1h, and the mass ratio of the dropped hydrogen peroxide to an accelerator M (with the molecular weight of 167.3) is (0.5-0.8): 1, the reaction time is 1-5h after the hydrogen peroxide is added.
7. The method for preparing the accelerator NS by oxidizing hydrogen peroxide in the organic solvent according to claim 1, which is characterized in that: the mass ratio of the tert-butylamine (molecular weight 73) to the accelerator M in the step 2 is (1-1.8): 1.
8. the method for preparing the accelerator NS by oxidizing hydrogen peroxide in the organic solvent according to claim 1, which is characterized in that: and (3) beginning to dropwise add second-stage hydrogen peroxide in the step (2), wherein the dropwise adding temperature of the hydrogen peroxide is 40-65 ℃, the dropwise adding time of the hydrogen peroxide is 0.2-1h, and the mass ratio of the dropwise added hydrogen peroxide to the accelerator M is (0.75-1.2): 1, the reaction time is 1-5h after the hydrogen peroxide is added, and the reaction temperature is 40-65 ℃.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6124467A (en) * | 1998-12-08 | 2000-09-26 | Bayer Aktiengesellschaft | Process for the preparation of dithiazolyl disulfides |
| CN104311565A (en) * | 2014-09-12 | 2015-01-28 | 沈阳化工大学 | Preparation method of iron phthalocyanine |
| CN108727302A (en) * | 2017-10-23 | 2018-11-02 | 科迈化工股份有限公司 | A kind of environment-friendly type N tert butyl benzothiazole 2 sulfenamide（NS）Synthesis technology |
| CN111303074A (en) * | 2020-03-19 | 2020-06-19 | 山东省化工研究院 | Process for preparing NS by oxidizing M tert-butylammonium salt with hydrogen peroxide |
-
2022
- 2022-07-20 CN CN202210850052.2A patent/CN115109010A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6124467A (en) * | 1998-12-08 | 2000-09-26 | Bayer Aktiengesellschaft | Process for the preparation of dithiazolyl disulfides |
| CN104311565A (en) * | 2014-09-12 | 2015-01-28 | 沈阳化工大学 | Preparation method of iron phthalocyanine |
| CN108727302A (en) * | 2017-10-23 | 2018-11-02 | 科迈化工股份有限公司 | A kind of environment-friendly type N tert butyl benzothiazole 2 sulfenamide（NS）Synthesis technology |
| CN111303074A (en) * | 2020-03-19 | 2020-06-19 | 山东省化工研究院 | Process for preparing NS by oxidizing M tert-butylammonium salt with hydrogen peroxide |
Non-Patent Citations (1)
| Title |
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| 倪立宠: "硫化促进剂的合成新工艺研究", 《中国优秀硕士学位论文全文数据库》, pages 13 * |
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