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Method for preparing sulfenamide thiofide by catalyzing oxidization of molecular oxygen in water phase

A technology of sulfenamides and rubber accelerators, which is applied in the field of catalyzing molecular oxygen oxidation to prepare sulfenamides rubber vulcanization accelerators, can solve the problems of difficult to achieve clean production, a large amount of salt-containing wastewater, production safety problems, etc., and achieves strong performance. Prospects for industrial applications, high reaction efficiency, and the effect of less waste

Active Publication Date: 2017-06-20
WILLING NEW MATERIALS TECH CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the defect of this method is very obvious. During the production process, a large amount of salty wastewater will be accompanied, which is difficult to handle and difficult to achieve clean production. It is contrary to the national environmental protection policy and the production requirements of energy saving and emission reduction.
[0005] Chinese patents CN 101343257 A, CN 101717380 A, CN 104592157 A, and CN 104610193 A successively reported the method of using hydrogen peroxide as an oxidant to prepare a sulfenamide rubber accelerator, but the amount of hydrogen peroxide must be greater than the equivalent required for the reaction , and because hydrogen peroxide must be added dropwise, the reaction takes a long time, and the gradual accumulation of hydrogen peroxide in the body system will bring a series of production safety problems
However, these methods either use heterogeneous catalysts or use ammonia water as a solvent, which increases the difficulty and steps of post-processing and purification of products and limits their industrial application

Method used

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  • Method for preparing sulfenamide thiofide by catalyzing oxidization of molecular oxygen in water phase
  • Method for preparing sulfenamide thiofide by catalyzing oxidization of molecular oxygen in water phase
  • Method for preparing sulfenamide thiofide by catalyzing oxidization of molecular oxygen in water phase

Examples

Experimental program
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Effect test

Embodiment 1

[0034] Example 1: Catalytic oxidation of 2-mercaptobenzothiazole (M) in an oxygen atmosphere to synthesize a sulfenamide rubber accelerator.

[0035] In a 500 L reactor, put 60 Kg 2-mercaptobenzothiazole, 78.7 Kg tert-butylamine (3 eq), 0.48Kg tetracarboxymanganese tetrasodium phthalocyanine [MnPc(COONa) 4 ] and 180 L of water; heated to 40 °C under stirring, and oxygen was introduced to keep the pressure in the reactor at 0.15 MPa. After 15 hours of reaction, the reaction was stopped, cooled, filtered, washed with 20 L of water, and dried to obtain a white solid 83.8 Kg, the structure of the product was determined to be N-tert-butyl-2-benzothiazolesulfenamide (TBBS) by NMR, MS and other methods, the yield was 98%, and the purity of the product analyzed by liquid chromatography was 99.5%.

[0036] Filter and separate the mother liquor of N-tert-butyl-2-benzothiazole sulfenamide and return to the reactor, re-drop 60 Kg of 2-mercaptobenzothiazole, no need to add catalyst, contin...

Embodiment 2

[0037] Example 2: Synthesis of sulfenamide compounds by catalytic oxidation of 2-mercaptobenzothiazole (M) in air atmosphere.

[0038] In a 3000 L reactor, put 80 Kg 2-mercaptobenzothiazole, 175 Kg tert-butylamine (5 eq), 1.6 Kg cobalt tetrasodium tetracarboxyphthalocyanine [CoPc(COONa) 4 ], 0.8 Kg tetracarboxycopper tetrasodium phthalocyanine [CuPc(COONa) 4 ], and 1600 L of water; heated to 90 ° C under stirring, and air was pressed in to keep the pressure in the reactor at 1.0 MPa. After 18 hours of reaction, the reaction was stopped, cooled, filtered, washed with 100 L of water, and dried to obtain white Solid 110.6 Kg, yield is 97%, and liquid chromatography analysis product purity is 99%.

Embodiment 3

[0039] Example 3: Synthesis of organic matter containing sulfur-nitrogen bonds in an oxygen-enriched air atmosphere.

[0040] In a 300 L reactor, put 30 Kg 2-mercaptobenzothiazole, 36 Kg cyclohexylamine (2 eq), 40 g tungsten tetrapotassium tetrasulfonic acid phthalocyanine [WPc(SO 3 K) 4 ], 30 g nickel tetracarboxyphthalocyanine [NiPc(COOH) 4 ], 20 g cesium tetrasulfonate phthalocyanine [CePc(SO 3 h) 4 ] and 90 L of water; heated up to 65°C under stirring, and pressurized oxygen-enriched air [oxygen:air (wt:wt) = 1:2], kept the pressure in the reactor at 0.05 MPa, and stopped the reaction after 8 hours of reaction. Cool, filter, wash with water, and dry to obtain 46.1 Kg of the product N-cyclohexyl-2-benzothiazolesulfenamide (CBS), with a yield of 97%. The purity of the product analyzed by liquid chromatography was 99%.

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Abstract

The invention relates to a method for preparing sulfenamide thiofide by catalyzing oxidation of molecular oxygen in a water phase. According to the method, a water-soluble transition metal phthalocyanine compound is utilized as a catalyst, and 2-mercaptobenzothiazole generates oxidation cross coupling reaction with amine (tert-butylamine or cyclohexane) for 1 to 30 hours to generate sulfenamide thiofide in the water phase under the conditions that oxygen (or air) pressure is 0,01 to 1MPa, and temperature is 40 to 100 DEG C. Reaction of the preparation method disclosed by the invention is performed in the water phase, other organic solvents are prevented from being added, catalyst activity is high, reaction efficiency is high, the catalyst can be used repeatedly, a synthesizing technology is concise, product selectivity is high, by products are few, waste is little, environmental friendliness is achieved, and the preparation method has stronger industrial application prospect.

Description

technical field [0001] The invention belongs to the technical field of synthesis of sulfenamide rubber accelerators, and in particular relates to a method for preparing sulfenamide rubber vulcanization accelerators by catalyzing molecular oxygen oxidation. Background technique [0002] The sulfenamide rubber accelerator derived from 2-mercaptobenzothiazole (vulcanization accelerator M) is a widely used vulcanization accelerator. N - tert-butyl-2-benzothiazole sulfenamide (TBBS) and N -Cyclohexyl-2-benzothiazole sulfenamide is the two most widely used rubber vulcanization accelerators at home and abroad. [0003] At present, the industrial production of sulfenamide-based rubber accelerators (TBBS, CBS) mainly uses chemical oxidation, which is prepared by oxidative cross-coupling of 2-mercaptobenzothiazole (M) and amines (tert-butylamine or cyclohexylamine). The more commonly used production methods include sodium hypochlorite oxidation [Chinese patent CN 101676274 A] an...

Claims

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Application Information

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IPC IPC(8): C07D277/80
CPCY02P20/584C07D277/80
Inventor 杨贯羽丁俊杰杨利婷李宏喜豆颖超牛广文郭同新王志强宋风朝葛同伟王飞陈军凯尹跃宁
Owner WILLING NEW MATERIALS TECH CO LTD
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