CN113666855A - Method for preparing tetrabenzylthiuram disulfide - Google Patents
Method for preparing tetrabenzylthiuram disulfide Download PDFInfo
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- CN113666855A CN113666855A CN202111042078.6A CN202111042078A CN113666855A CN 113666855 A CN113666855 A CN 113666855A CN 202111042078 A CN202111042078 A CN 202111042078A CN 113666855 A CN113666855 A CN 113666855A
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- WITDFSFZHZYQHB-UHFFFAOYSA-N dibenzylcarbamothioylsulfanyl n,n-dibenzylcarbamodithioate Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)C(=S)SSC(=S)N(CC=1C=CC=CC=1)CC1=CC=CC=C1 WITDFSFZHZYQHB-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 28
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- 239000000243 solution Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006482 condensation reaction Methods 0.000 claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- NGCCQISMNZBKJJ-UHFFFAOYSA-N 2,6-dichloro-3-methylquinoline Chemical compound ClC1=CC=C2N=C(Cl)C(C)=CC2=C1 NGCCQISMNZBKJJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 239000007800 oxidant agent Substances 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical class [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 4
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 4
- 229920002907 Guar gum Polymers 0.000 claims description 2
- 239000001913 cellulose Chemical class 0.000 claims description 2
- 229920002678 cellulose Chemical class 0.000 claims description 2
- 239000000665 guar gum Substances 0.000 claims description 2
- 229960002154 guar gum Drugs 0.000 claims description 2
- 235000010417 guar gum Nutrition 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims 1
- 239000000194 fatty acid Substances 0.000 claims 1
- 229930195729 fatty acid Natural products 0.000 claims 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 45
- 239000002351 wastewater Substances 0.000 abstract description 11
- 239000000843 powder Substances 0.000 abstract description 9
- 229920001971 elastomer Polymers 0.000 abstract description 6
- 239000005060 rubber Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 28
- 238000003756 stirring Methods 0.000 description 15
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000013040 rubber vulcanization Methods 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- CYKFQSXTIVGYDT-QJWNTBNXSA-N (z,12r)-12-sulfooxyoctadec-9-enoic acid Chemical compound CCCCCC[C@@H](OS(O)(=O)=O)C\C=C/CCCCCCCC(O)=O CYKFQSXTIVGYDT-QJWNTBNXSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000315 carcinogenic Toxicity 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000005456 glyceride group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- IJRHDFLHUATAOS-DPMBMXLASA-M sodium ricinoleate Chemical compound [Na+].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O IJRHDFLHUATAOS-DPMBMXLASA-M 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000005843 Thiram Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/14—Dithiocarbamic acids; Derivatives thereof
- C07C333/30—Dithiocarbamic acids; Derivatives thereof having sulfur atoms of dithiocarbamic groups bound to other sulfur atoms
- C07C333/32—Thiuramsulfides; Thiurampolysulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/14—Dithiocarbamic acids; Derivatives thereof
- C07C333/16—Salts of dithiocarbamic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of rubber additive production, and relates to a method for preparing tetrabenzylthiuram disulfide. The method comprises the following steps: adding water, a sodium hydroxide aqueous solution and dibenzylamine into a reactor in sequence, then adding a dispersing agent, and then dropwise adding carbon disulfide for condensation reaction to obtain a sodium dibenzyl dithiocarbamate solution; and (3) filtering and drying after the oxidation reaction of the sodium dibenzyl dithiocarbamate solution to obtain the tetrabenzylthiuram disulfide. According to the invention, the dispersant is added in the condensation reaction process, the reaction system is in a uniform state, and the reaction process is carried out in the uniform system, so that the problem of poor reaction effect caused by two-phase reaction when carbon disulfide is dropwise added in the prior art is solved. The COD content in the wastewater is low, and the wastewater treatment is easy. The obtained tetrabenzylthiuram disulfide product is white powder in appearance, and the purity is over 98 percent.
Description
Technical Field
The invention belongs to the technical field of rubber additive production, and relates to a method for preparing tetrabenzylthiuram disulfide.
Background
Tetrabenzylthiuram disulfide, abbreviated as TBzTD, has the following structural formula:
the tetrabenzylthiuram disulfide is mainly used as a rubber vulcanization accelerator, is one of rubber accelerators thiuram products, is an overspeed vulcanization accelerator, is suitable for natural rubber, butadiene rubber, isoprene rubber, styrene butadiene rubber, nitrile rubber, butyl rubber, ethylene propylene diene monomer rubber and latex, has a vulcanization acceleration effect similar to that of TMTD, has a vulcanization speed slightly lower than that of TMTD, and has stability higher than that of TMTD. TBzTD is widely used in the manufacture of electric wires and cables, tires, tapes, colored transparent products, footwear, heat-resistant products, etc., and does not produce carcinogenic nitrosamine, and is a green, safe, environment-friendly, and efficient rubber vulcanization accelerator, which is specified in the catalogue of substitutes for toxic and harmful raw materials (products) encouraged by the state (2016 edition): the rubber vulcanization accelerator TBzTD (tetrabenzylthiuram disulfide) replaces rubber vulcanization accelerators TMTD and TETD, and the processing safety is better. TBzTD has large molecular weight, high melting point, difficult decomposition and no generation of carcinogenic nitrosamine, and is a new variety of thiram vulcanization accelerators with great development potential at present.
The conventional synthesis of tetrabenzylthiuram disulfide is to drop carbon disulfide into an aqueous solution or a solvent of dibenzylamine alkali under the condition of rapid stirring, then to obtain the product by oxidizing with oxidants such as hydrogen peroxide and the like, wherein the product is divided into two steps, each step is a strong reaction and releases heat, the dropping speed must be properly controlled to prevent the local temperature from rising too fast, and dibenzylamine is insoluble in water and shows a two-phase state when reacting with carbon disulfide and liquid alkali, so that the reaction is not uniform, and the product decomposition and side reaction are caused. Such as: CN 101462993A discloses a preparation method of a rubber accelerator tetrabenzylthiuram disulfide: under the stirring state, sequentially adding dibenzylamine and sodium hydroxide into a reaction kettle filled with water, cooling to 20-30 ℃, starting to dropwise add carbon disulfide, wherein the dropwise adding time is 2-3 hours, and stirring for 0.5 hour. And (3) heating to 58-63 ℃, dropwise adding hydrogen peroxide to carry out an oxidation reaction for 3-4 hours, adjusting the pH value to 6.5-7.5 by using sulfuric acid when the oxidation is finished, and then preserving heat for 1 hour to complete the reaction. In the technology, dibenzylamine is insoluble in water, so that the dibenzylamine is subjected to a two-phase reaction when carbon disulfide is dropwise added, the reaction effect is poor, and particularly, a side reaction is more easily generated during later-stage oxidation; the operation is complicated to finally adjust the PH value, and the PH value adjusting time by sulfuric acid is long and the amount is large due to the large amount of alkali participating in the reaction, so the reaction effect is poor; the reaction steps are more, the temperature is increased and reduced, energy is wasted, a large amount of gray particles exist in the obtained finished product, and the product purity is low. CN 103739534a discloses a synthesis method of a rubber accelerator tetrabenzylthiuram disulfide: after mixing a solvent and dibenzylamine in a reaction kettle, dropwise adding carbon disulfide at the temperature of 0-20 ℃ for 1.5-2 hours, stirring for reaction for 1-3 hours, then heating to 40-70 ℃, slowly introducing compressed air below the liquid level of a reactant for oxidation reaction, wherein the reaction time is 4-8 hours. The method has the defects that the sealing performance is poor in the kettle type reactor, organic solvents are discharged, and the production process has serious potential safety hazards and is inflammable and explosive; the energy consumption of the process is high, and the obtained product has low melting point and yellow appearance and is difficult to meet the market requirement; the reaction steps are long and difficult to form industrial continuous production.
Therefore, how to increase the dispersion degree of dibenzylamine in the reaction system is the key to increase the reaction yield and reduce the occurrence of side reactions. CN110577481A discloses a method for preparing a rubber accelerator TBzTD by using a novel solvent, wherein water and ethanol are used as solvents, sodium ricinoleate sulfate is added into the system, the ethanol and the water are mutually soluble, and the sodium ricinoleate sulfate is added; the contact surface of the oil phase and the water phase is increased by the ricinoleic acid sulfate sodium salt, so that the oil phase and the water phase are better contacted, the water-insoluble dibenzylamine and the carbon disulfide are uniformly dispersed in a solvent system of water and ethanol, reaction raw materials better participate in the reaction, the yield is improved to a great extent by adding the ricinoleic acid sulfate sodium salt, and the yield is more than 98%. However, this method requires first preparing the ricinoleic acid sulfate sodium salt, which makes the overall procedure cumbersome, increasing energy consumption and waste.
Disclosure of Invention
The invention provides a novel method for preparing tetrabenzylthiuram disulfide, aiming at the problems in the production of the traditional tetrabenzylthiuram disulfide.
Aiming at the defects of the prior art, in particular to the problems of strong reaction heat release, difficult energy timely removal, local hot spots of reaction mixture generation and easy generation of byproducts by the decomposition of tetrabenzylthiuram disulfide in the prior art, and the problems of poor product quality stability, large production consumption, high waste water COD (chemical oxygen demand) difficulty in treatment, complex operation and the like of products produced by the prior art. The invention provides a method for preparing tetrabenzylthiuram disulfide, which has high conversion rate, less byproducts and low COD in wastewater.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme:
a method for preparing tetrabenzylthiuram disulfide comprises the following steps:
(1) condensation reaction: adding water, a sodium hydroxide aqueous solution and dibenzylamine into a reactor in sequence, then adding a dispersing agent, and then dropwise adding carbon disulfide for condensation reaction to obtain a sodium dibenzyl dithiocarbamate solution;
(2) and (3) oxidation reaction: and (3) filtering and drying after the oxidation reaction of the sodium dibenzyl dithiocarbamate solution to obtain the tetrabenzylthiuram disulfide.
The reaction principle of the invention is as follows:
condensation reaction in step (1):
oxidation reaction in the step (2):
preferably, in the step (1), the dispersant is at least one of sodium dodecyl sulfate, cellulose derivatives, tween 20, guar gum, fatty glyceride and OP-10, and the use weight of the dispersant is 0.2-1.5% of the weight of dibenzylamine.
Preferably, in the step (1), the volume ratio of dibenzylamine to water is 1: 3-8, and the ratio of dibenzylamine: sodium hydroxide: the molar ratio of carbon disulfide is 1: (1.05-1.2): (1.1-1.3); the mass fraction of the sodium hydroxide water solution is 30-40%.
Preferably, the condensation reaction temperature in the step (1) is 30-50 ℃, and the reaction time is 0.5-5 h; the end point of the condensation reaction is controlled to be pH = 7.5-9.5.
Preferably, the condensation reaction temperature in the step (1) is 30-40 ℃, and the reaction time is 1-3 h.
Preferably, in the step (2), the oxidant is a mixture of a sulfuric acid aqueous solution and a hydrogen peroxide aqueous solution, the mass concentration of the sulfuric acid aqueous solution is 90-98%, and the mass concentration of the hydrogen peroxide aqueous solution is 25-30%; dibenzylamine: sulfuric acid: the molar ratio of hydrogen peroxide is 1: (0.50-0.60): (0.50-0.60).
Preferably, the oxidant is added in a dropping manner in the step (2), the dropping speed is slow and then fast, and the dropping time is 3-5 hours; and controlling the pH value to be 6-8 at the oxidation end point.
Preferably, the oxidation reaction temperature in the step (2) is 0-80 ℃, and the reaction time is 3-10 h.
Preferably, the oxidation reaction temperature in the step (2) is 60-80 ℃, and the retention time is 4-6 h.
Preferably, the reactor is any one of a tank reactor, a pipeline reactor or a micro-reaction device.
Compared with the prior art, the invention has the advantages and positive effects that:
1. according to the invention, the dispersant is added in the condensation reaction process, the reaction system is in a uniform state, and the reaction process is carried out in the uniform system, so that the problem of poor reaction effect caused by two-phase reaction when carbon disulfide is dropwise added in the prior art is solved. Meanwhile, the invention does not use organic solvent, adopts water as solvent, greatly reduces the COD content in the wastewater, determines the COD content in the wastewater to be below 1000mg/L, and is easy for wastewater treatment.
2. The method has the advantages of less raw materials required by the reaction, higher reactant conversion rate after the dispersant is added, less by-products, higher reaction selectivity and high product quality; the problems that strong heat release is formed in the preparation of tetrabenzylthiuram disulfide due to two-phase reaction, the temperature is difficult to control, the loss to equipment is low and the like are solved, and the working efficiency is improved; meanwhile, the method has the advantages of easy control of operation conditions and good industrial application prospect.
3. The tetrabenzylthiuram disulfide product obtained by the reaction of the invention has good quality, white powder appearance, melting point of more than 130 ℃ and purity of more than 98 percent. The yield of the tetrabenzylthiuram disulfide product is high and reaches more than 98 percent.
Detailed Description
In order that the above objects, features and advantages of the present invention may be more clearly understood, the present invention will be further described with reference to specific embodiments. It should be noted that the embodiments and features of the embodiments of the present application may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those specifically described herein, and thus the present invention is not limited to the specific embodiments of the present disclosure.
Example 1
This example provides a detailed process for the preparation of tetrabenzylthiuram disulfide, the procedure being as follows:
adding 350 g of water into a reaction kettle with a thermometer and a reflux condenser, starting stirring at the stirring speed of 200 r/min, adding 65g of sodium hydroxide solution with the mass fraction of 32% and 100g of dibenzylamine, then adding 1g of tween 20, heating to 35 ℃, slowly adding 42g of carbon disulfide dropwise for 2 hours, and measuring the pH value of the reaction solution to be 9 after the dropwise addition is finished.
Configuration of the oxidant: taking 170g of water, slowly adding 25g of concentrated sulfuric acid under the stirring state, cooling to room temperature, adding 40g of 27.5 mass percent hydrogen peroxide, and filling into a constant-pressure dropping funnel for later use.
After the condensation reaction is finished, heating to 75 ℃, slowly dripping an oxidant, slowly dripping at a certain speed in the early stage, controlling the dripping speed to be 0.1-0.5ml/min, gradually increasing the dripping speed after half an hour, keeping the total dripping time to be 5 hours, measuring the pH value to be 6 after the dripping is finished, finishing the reaction, and then carrying out suction filtration, washing and drying. The steps of suction filtration, water washing and drying are the same as the steps of the conventional preparation of tetrabenzylthiuram disulfide, in the embodiment, the water washing is carried out for 2 times, and the drying temperature is 40 ℃ for 2 hours.
And detecting the obtained finished product: the product is white powder in appearance, the melting point is 131.2 ℃, the purity is 99.6%, the yield is 99.2%, and the COD in the wastewater is 780 mg/L.
Example 2
This example and the following examples, where not otherwise specified, are in accordance with conventional procedures for the preparation of tetrabenzylthiuram disulfide.
A process for preparing tetrabenzylthiuram disulfide comprising the steps of:
200g of water is added into a reaction kettle with a thermometer and a reflux condenser, stirring is started, 65g of 32% sodium hydroxide solution and 100g of dibenzylamine are added, then 1.2g of OP-10 is added, the temperature is raised to 35 ℃, 42g of carbon disulfide is slowly dripped for 2.5 hours, and the pH value of the reaction solution is measured to be 8.5 after the dripping is finished.
Preparing an oxidizing agent: 170g of water is taken, 25g of concentrated sulfuric acid is slowly added under the stirring state, 40g of 27.5 percent hydrogen peroxide is added after the temperature is reduced to the natural temperature, and the mixture is put into a constant-pressure dropping funnel for standby.
After the condensation reaction is finished, heating to 70 ℃, slowly dripping an oxidant, slowly dripping at the earlier stage, controlling the dripping speed to be 0.1-0.5ml/min, gradually increasing the dripping speed, measuring the pH value to be 6.5 after the dripping is finished, and then carrying out suction filtration, washing and drying.
And detecting the obtained finished product: the product is white powder in appearance, the melting point is 131.5 ℃, the purity is 99.1%, the yield is 98.9%, and the COD in the wastewater is 850 mg/L.
Example 3
A process for preparing tetrabenzylthiuram disulfide comprising the steps of:
200g of water is added into a reaction kettle with a thermometer and a reflux condenser, stirring is started, 66g of 32% sodium hydroxide solution and 100g of dibenzylamine are added, then 1g of sodium dodecyl sulfate is added, the temperature is raised to 38 ℃, 42g of carbon disulfide is slowly dripped for 2.5 hours, and the pH of the reaction solution is measured to be 8.5 after the dripping is finished.
Preparing an oxidizing agent: 170g of water is taken, 25g of concentrated sulfuric acid is slowly added under the stirring state, 40g of 27.5 percent hydrogen peroxide is added after the temperature is reduced to the natural temperature, and the mixture is put into a constant-pressure dropping funnel for standby.
After the condensation reaction is finished, heating to 70 ℃, slowly dripping an oxidant, slowly dripping at the earlier stage, controlling the dripping speed to be 0.1-0.5ml/min, gradually increasing the dripping speed, measuring the pH value to be 6 after the dripping is finished, and then carrying out suction filtration, washing and drying.
And detecting the obtained finished product: the product is white powder in appearance, has a melting point of 131.0 ℃, a purity of 99.0 percent, a yield of 98.6 percent and a waste water COD of 860 mg/L.
Example 4
A process for preparing tetrabenzylthiuram disulfide comprising the steps of:
200g of water is added into a reaction kettle with a thermometer and a reflux condenser, stirring is started, 65g of 32% sodium hydroxide solution and 100g of dibenzylamine are added, then 0.5g of OP-10 and 0.5g of sodium dodecyl sulfate are added, the temperature is raised to 38 ℃, 42g of carbon disulfide is slowly dripped, the dripping time is 2.0 hours, and the pH value of the reaction solution is measured to be 8.5 after the dripping is finished.
Preparing an oxidizing agent: 170g of water is taken, 25g of concentrated sulfuric acid is slowly added under the stirring state, 40g of 27.5 percent hydrogen peroxide is added after the temperature is reduced to the natural temperature, and the mixture is put into a constant-pressure dropping funnel for standby.
After the condensation reaction is finished, heating to 75 ℃, slowly dripping an oxidant, slowly dripping at the earlier stage, controlling the dripping speed to be 0.1-0.5ml/min, gradually increasing the dripping speed, measuring the pH value to be 7 after the dripping is finished, and then carrying out suction filtration, washing and drying.
And detecting the obtained finished product: the product is white powder in appearance, the melting point is 132.5 ℃, the purity is 99.5%, the yield is 99.2%, and the COD of the wastewater is 800 mg/L.
Example 5
A process for preparing tetrabenzylthiuram disulfide comprising the steps of:
pipeline reaction: weighing 200g of water, adding 65g of 32% sodium hydroxide solution and 1.2g of fatty glyceride to prepare a solution, taking 100g of dibenzylamine, driving the two-phase solution to pass through a Y mixer by a flow pump to be mixed to serve as one strand, taking 42g of carbon disulfide as one strand, driving the two-phase solution to pass through the Y mixer by the flow pump to be mixed, and then entering a pipeline with the inner diameter of 10mm and the length of 10m to carry out condensation reaction, controlling the temperature in the pipeline to be 35 ℃ and controlling the reaction time to be 1 h.
Configuration of the oxidant: taking 170g of water, slowly adding 25g of concentrated sulfuric acid under stirring, cooling to natural temperature, adding 40g of 27.5% hydrogen peroxide as one strand, driving the two-phase solution to pass through a Y mixer by a flow pump, mixing, then entering a pipeline with the inner diameter of 10mm and the length of 35 meters for oxidation reaction, controlling the oxidation temperature to be 70 ℃, reacting for 1 hour, starting to collect reaction liquid after one period, then filtering and drying to obtain a finished product.
The yield is determined to be 98.9 percent by detection, the melting point is 131.2 ℃, the appearance is white powder, and the COD of the wastewater is 820 mg/L.
Example 6
A process for preparing tetrabenzylthiuram disulfide comprising the steps of:
pipeline reaction: weighing 200g of water, adding 65g of 32% sodium hydroxide solution, 0.5g of methyl cellulose and 0.5g of Guerban, blending to obtain a solution, taking 100g of dibenzylamine, driving the two-phase solution through a flow pump, mixing the two-phase solution through a Y mixer to serve as one strand, taking 42g of carbon disulfide as one strand, driving the two-phase solution through the flow pump, mixing the two-phase solution through the Y mixer, and then feeding the two-phase solution into a pipeline with the inner diameter of 10mm and the length of 10m for condensation reaction, wherein the temperature in the pipeline is controlled to be 35 ℃ and the reaction time is 1 h.
Preparing an oxidizing agent: taking 170g of water, slowly adding 25g of concentrated sulfuric acid under stirring, cooling to natural temperature, adding 40g of 27.5% hydrogen peroxide as one strand, driving the two-phase solution to pass through a Y mixer by a flow pump, mixing, then entering a pipeline with the inner diameter of 10mm and the length of 35 meters for oxidation reaction, controlling the oxidation temperature to be 70 ℃, reacting for 1 hour, starting to collect reaction liquid after one period, then filtering and drying to obtain a finished product.
The detection proves that the yield is 99.2 percent, the melting point is 131.2 ℃, the appearance is white powder, and the COD of the wastewater is 890 mg/L.
Comparative example 1
This comparative example differs from example 1 in that:
no Tween 20 dispersant is added during the condensation reaction, and the other conditions are kept consistent.
And detecting the obtained finished product: the appearance is light yellow crystal or powder, the initial melting point is more than or equal to 124 ℃, the ash content is less than or equal to 0.3 percent, the heating decrement is less than or equal to 0.3 percent, and the screen residue (80 meshes) is less than or equal to 0.1 percent.
It can be seen that the conversion is severely affected without the addition of a dispersant, and the impurity content of the product is increased, resulting in a yellowish appearance of the product.
The above description is only a preferred embodiment of the present invention, and not intended to limit the present invention in other forms, and any person skilled in the art may apply the above modifications or changes to the equivalent embodiments with equivalent changes, without departing from the technical spirit of the present invention, and any simple modification, equivalent change and change made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the technical spirit of the present invention.
Claims (10)
1. A method for preparing tetrabenzylthiuram disulfide is characterized by comprising the following steps:
(1) condensation reaction: adding water, a sodium hydroxide aqueous solution and dibenzylamine into a reactor in sequence, then adding a dispersing agent, and then dropwise adding carbon disulfide for condensation reaction to obtain a sodium dibenzyl dithiocarbamate solution;
(2) and (3) oxidation reaction: and (3) filtering and drying after the oxidation reaction of the sodium dibenzyl dithiocarbamate solution to obtain the tetrabenzylthiuram disulfide.
2. The method for preparing tetrabenzylthiuram disulfide according to claim 1, wherein the dispersant in step (1) is at least one selected from sodium laurylsulfate, cellulose derivatives, tween 20, guar gum, fatty acid glycerides, and OP-10, and the amount of the dispersant used is 0.2 to 1.5% by weight of dibenzylamine.
3. The method for producing tetrabenzylthiuram disulfide according to claim 1, wherein the volume ratio of dibenzylamine to water in step (1) is 1:3 to 8, and the ratio of dibenzylamine: sodium hydroxide: the molar ratio of carbon disulfide is 1: (1.05-1.2): (1.1-1.3); the mass fraction of the sodium hydroxide water solution is 30-40%.
4. The method for preparing tetrabenzylthiuram disulfide according to claim 1, wherein the condensation reaction temperature in step (1) is 30 to 50 ℃ and the reaction time is 0.5 to 5 hours; the end point of the condensation reaction is controlled to be pH = 7.5-9.5.
5. The method for preparing tetrabenzylthiuram disulfide according to claim 1, wherein the condensation reaction temperature in step (1) is 30 to 40 ℃ and the reaction time is 1 to 3 hours.
6. The method for producing tetrabenzylthiuram disulfide according to claim 1, wherein the oxidizing agent in step (2) is a mixture of an aqueous sulfuric acid solution having a mass concentration of 90% to 98% and an aqueous hydrogen peroxide solution having a mass concentration of 25% to 30%; dibenzylamine: sulfuric acid: the molar ratio of hydrogen peroxide is 1: (0.50-0.60): (0.50-0.60).
7. The method for preparing tetrabenzylthiuram disulfide according to claim 1, wherein the oxidizing agent is added dropwise in step (2), wherein the addition rate is slow and then fast, and the addition time is 3-5 hours; and controlling the pH value to be 6-8 at the oxidation end point.
8. The method for preparing tetrabenzylthiuram disulfide according to claim 1, wherein the oxidation reaction temperature in step (2) is 0 to 80 ℃ and the reaction time is 3 to 10 hours.
9. The method for preparing tetrabenzylthiuram disulfide according to claim 1, wherein the oxidation reaction temperature in step (2) is 60 to 80 ℃ and the residence time is 4 to 6 hours.
10. The process for producing tetrabenzylthiuram disulfide according to claim 1, wherein the reactor is any one of a tank reactor, a pipe reactor and a microreactor.
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