CN101735171A

CN101735171A - Method for synthesizing thiofide NS by oxygen oxidation method

Info

Publication number: CN101735171A
Application number: CN200910228229A
Authority: CN
Inventors: 洪学斌; 尹红伟; 张超义
Original assignee: TIANJIN KEMAI CHEMICAL CO Ltd
Current assignee: TIANJIN KEMAI CHEMICAL CO Ltd
Priority date: 2009-11-16
Filing date: 2009-11-16
Publication date: 2010-06-16

Abstract

The invention discloses a method for synthesizing thiofide NS by an oxygen oxidation method. The method comprises the following steps of: adding promoter MBT and ammonia water in the molar ratio of 1:2-7 into a three-neck flask, dissolving and adding in a high-pressure oxidation kettle, dissolving the catalyst of copper sulfate with the ammonia water and adding into the high-pressure oxidation kettle, reacting at a temperature of 40-70 DEG C, introducing oxygen in the high-pressure oxidization kettle at a reaction pressure of 0.2-0.7MPa, adding tert-butylamine into the high-temperature oxidation kettle by using a constant-pressure sampling pump, reacting continuously for 0.2-0.7h after oxygen introduction, maintaining the pressure of the high-pressure oxidation kettle, stopping reaction; storing mother liquor into a sealed flask after filtering, preparing for reuse, washing and drying the product to obtain the thiofide NS with a product purity of above 98 percent. The invention has the advantages that the method has simple process and is easy to industrialized, the products have good quality and high yield as the mother liquor can be recycled and a small amount of tert-butylamine is consumed, and no three wastes are discharged in the synthesizing process.

Description

The method of synthesizing thiofide NS by oxygen oxidation method

Technical field

The present invention relates to the production method of a kind of rubber vulcanization accelerator N-tertiary butyl-2-[4-morpholinodithio sulphenamide (NS), belong to the rubber vulcanization accelerator NS production technical field.

Background technology

Along with the development of rubber industry, the research of vulcanization accelerator more and more is subject to people's attention with production.Vulcanization accelerator plays important effect in vulcanization of rubber process, it can accelerate the reaction of rubber and vulcanizing agent greatly, boost productivity, also can improve the physical and mechanical properties of vulcanized rubber simultaneously, NS is the requisite a kind of primary accelerator of present rubber industry.Functions such as that accelerator NS has is anti-scorch, safe, nontoxic, sulfuration is fast.Document (the Guangdong chemical industry, 2006,5:16) reported the method that oxidation style is synthesized NS.With stirring in the adding reactors such as captax, TERTIARY BUTYL AMINE, dilute sulphuric acid, water, make its salify; React cooling, suction filtration, washing, filtration, the dry product that gets as oxygenant with hydrogen peroxide.The TERTIARY BUTYL AMINE amount that this method is used is big, and the yield of accelerator NS is not high.Document (chemical science and technology market, 2001,4:24) reported the production method of new type NS.With stirring in the adding reactors such as captax, TERTIARY BUTYL AMINE, dilute sulphuric acid, water, make its salify; React cooling, suction filtration, washing, filtration, the dry product that gets as oxygenant with clorox.This method accelerator NS yield is low.

Summary of the invention

The object of the present invention is to provide a kind of method of synthesizing thiofide NS by oxygen oxidation method, this method Recycling Mother Solution is applied mechanically, and the TERTIARY BUTYL AMINE consumption is little, and good product quality, yield height do not have " three wastes " discharging in the building-up process.

For achieving the above object, the present invention is realized by following technical proposals: a kind of method of synthesizing thiofide NS by oxygen oxidation method is characterized in that comprising following process:

1. 1: 2 in molar ratio～7, be that 95～99% accelerant MBT and mass percent are that 10～25% ammoniacal liquor joins in the there-necked flask with mass percent, be that 35～45 ℃, stirring velocity are to dissolve under 10～100 rev/mins the condition in temperature.After MBT all dissolves, solution is joined in the high-pressure oxidizing kettle.With 10～20 grams, mass percent is that (mol ratio of catalyzer and MBT is 0.001～0.007: 1), join in the high-pressure oxidizing kettle for 10～28% ammonia solvent catalyst sulfuric acid copper.In temperature of reaction is that 40～70 ℃, stirring velocity are under 300～1000 rev/mins the condition, and aerating oxygen in high-pressure oxidizing kettle is to react 1～5 hour under the condition of 0.2～0.7MPa in reaction pressure.Mol ratio by MBT and TERTIARY BUTYL AMINE is 1: 1～3, being 97～99.5% TERTIARY BUTYL AMINE with mass percent with the constant voltage sampling pump joins in the high-pressure oxidizing kettle with 0.5～3ml/ minute flow velocity, continue reaction, after stopping logical oxygen 0.2～0.7 hour, high-pressure oxidizing kettle pressure is constant, and then reaction is reached home.After reaction finishes, the pressure of high-pressure oxidizing kettle is reduced to normal pressure, behind the suction filtration mother liquor is stored in the flask of sealing recycling preparation.With product washing, the dry rubber vulcanization accelerator NS product that gets, product purity reaches more than 98%.

The invention has the advantages that: this procedure is simple, is easy to industrialization, because Recycling Mother Solution is applied mechanically, the TERTIARY BUTYL AMINE consumption is little, and good product quality, yield height do not have " three wastes " discharging in the building-up process.

Embodiment

Example 1:

At 270～280 ℃, carry out condensation reaction under pressure 9～10MPa condition with aniline and curing charcoal, sulphur, generate mass content and be 92% MBT, obtain mass percent after the purification and be 95% MBT.With 50 gram MBT and 97 gram mass per-cents is that 10% ammoniacal liquor joins in the there-necked flask, is that 35 ℃, stirring velocity are to dissolve under 30 rev/mins the condition in temperature.After MBT all dissolves, solution is joined in the high-pressure oxidizing kettle.With 10 gram mass per-cents is 10% ammonia solvent catalyst sulfuric acid copper, 0.04 gram, joins in the high-pressure oxidizing kettle.In temperature of reaction is that 40 ℃, stirring velocity are under 300 rev/mins the condition, and aerating oxygen in high-pressure oxidizing kettle is reaction 1 hour under the condition of 0.2MPa in reaction pressure.Being 97% TERTIARY BUTYL AMINE with 21.3 gram mass per-cents with the constant voltage sampling pump joins in the high-pressure oxidizing kettle with 0.5ml/ minute flow velocity, continues reaction, and after stopping logical oxygen 0.2 hour, high-pressure oxidizing kettle pressure was constant, and then reaction is reached home.After reaction finishes, the pressure of high-pressure oxidizing kettle is reduced to normal pressure, behind the suction filtration mother liquor is stored in the flask of sealing recycling preparation.With product washing, the dry rubber vulcanization accelerator NS product that gets.The purity of this N tert butyl benzothiazole 2 sulfenamide is 98.3%.

Example 2:

At 270～280 ℃, carry out condensation reaction under pressure 9～10MPa condition with aniline and curing charcoal, sulphur, generate mass content and be 92% MBT, obtain mass percent after the purification and be 97% MBT.With 50 gram MBT and 123 gram mass per-cents is that 20% ammoniacal liquor joins in the there-necked flask, is that 40 ℃, stirring velocity are to dissolve under 30 rev/mins the condition in temperature.After MBT all dissolves, solution is joined in the high-pressure oxidizing kettle.With 15 gram mass per-cents is 20% ammonia solvent catalyst sulfuric acid copper, 0.16 gram, joins in the high-pressure oxidizing kettle.In temperature of reaction is that 55 ℃, stirring velocity are under 600 rev/mins the condition, and aerating oxygen in high-pressure oxidizing kettle is reaction 3 hours under the condition of 0.5MPa in reaction pressure.Being 99% TERTIARY BUTYL AMINE with 53.7 gram mass per-cents with the constant voltage sampling pump joins in the high-pressure oxidizing kettle with 2ml/ minute flow velocity, continues reaction, and after stopping logical oxygen 0.5 hour, high-pressure oxidizing kettle pressure was constant, and then reaction is reached home.After reaction finishes, the pressure of high-pressure oxidizing kettle is reduced to normal pressure, behind the suction filtration mother liquor is stored in the flask of sealing recycling preparation.With product washing, the dry rubber vulcanization accelerator NS product that gets.The purity of this N tert butyl benzothiazole 2 sulfenamide is 99.1%.

Example 3:

At 270～280 ℃, carry out condensation reaction under pressure 9～10MPa condition with aniline and curing charcoal, sulphur, generate mass content and be 92% MBT, obtain mass percent after the purification and be 99% MBT.With 50 gram MBT and 126 gram mass per-cents is that 25% ammoniacal liquor joins in the there-necked flask, is that 45 ℃, stirring velocity are to dissolve under 30 rev/mins the condition in temperature.After MBT all dissolves, solution is joined in the high-pressure oxidizing kettle.With 20 gram mass per-cents is 25% ammonia solvent catalyst sulfuric acid copper, 0.28 gram, joins in the high-pressure oxidizing kettle.In temperature of reaction is that 70 ℃, stirring velocity are under 1000 rev/mins the condition, and aerating oxygen in high-pressure oxidizing kettle is reaction 5 hours under the condition of 0.7MPa in reaction pressure.Being 99.5% TERTIARY BUTYL AMINE with 60.0 gram mass per-cents with the constant voltage sampling pump joins in the high-pressure oxidizing kettle with 3ml/ minute flow velocity, continues reaction, and after stopping logical oxygen 0.7 hour, high-pressure oxidizing kettle pressure was constant, and then reaction is reached home.After reaction finishes, the pressure of high-pressure oxidizing kettle is reduced to normal pressure, behind the suction filtration mother liquor is stored in the flask of sealing recycling preparation.With product washing, the dry rubber vulcanization accelerator NS product that gets.The purity of this N tert butyl benzothiazole 2 sulfenamide is 99.8%.

Claims

1. the method for a synthesizing thiofide NS by oxygen oxidation method, it is characterized in that comprising following process: 1: 2 in molar ratio～7, with mass percent is that 95～99% accelerant MBT and mass percent are that 10～25% ammoniacal liquor joins in the there-necked flask, is that 35～45 ℃, stirring velocity are to dissolve under 10～100 rev/mins the condition in temperature.After MBT all dissolves, solution is joined in the high-pressure oxidizing kettle.With 10～20 grams, mass percent is that (mol ratio of catalyzer and MBT is 0.001～0.007: 1), join in the high-pressure oxidizing kettle for 10～28% ammonia solvent catalyst sulfuric acid copper.In temperature of reaction is that 40～70 ℃, stirring velocity are under 300～1000 rev/mins the condition, and aerating oxygen in high-pressure oxidizing kettle is to react 1～5 hour under the condition of 0.2～0.7MPa in reaction pressure.Mol ratio by MBT and TERTIARY BUTYL AMINE is 1: 1～3, being 97～99.5% TERTIARY BUTYL AMINE with mass percent with the constant voltage sampling pump joins in the high-pressure oxidizing kettle with 0.5～3ml/ minute flow velocity, continue reaction, after stopping logical oxygen 0.2～0.7 hour, high-pressure oxidizing kettle pressure is constant, and then reaction is reached home.After reaction finishes, the pressure of high-pressure oxidizing kettle is reduced to normal pressure, behind the suction filtration mother liquor is stored in the flask of sealing recycling preparation.With product washing, the dry rubber vulcanization accelerator NS product that gets, product purity reaches more than 98%.