CN102838565A - Production method of rubber vulcanization accelerator DZ - Google Patents

Abstract

The invention discloses a production method of a rubber vulcanization accelerator DZ, which comprises the following steps: preparing an oxidizer from 98% sulfuric acid, 27.5% oxydol and water in a weight ratio of 1:(3-3.6):9; adding solid sodium hydroxide according to the accelerator M:water weight ratio of 1:1 to control the pH value at 12, thereby preparing the M-Na salt; adding bicyclohexylamine and isopropanol into the reaction kettle according to the bicyclohexylamine:M mol ratio of 1:1 and isopropanol:M weight ratio of 6:1, dropwisely adding the M-Na salt at 30-80 DEG C at the rotation speed of 500-1200 rpm for 2-3 hours, and meanwhile dropwisely adding the oxidizer to control the pH value at 9-11; and after the reaction finishes, carrying out vacuum filtration, washing with water, filtering, and drying to obtain the rubber accelerator DZ product. The method has the advantage of simple process; since the oxidizer is oxydol, not too much brine waste can be generated in the reaction process; the method can easily implement industrialization; and the purity of the synthesized accelerator DZ is up to higher than 99%, and the yield is up to 93%.

Description

Production method of rubber vulcanization accelerator DZ

Technical field

The present invention relates to a kind of thiofide N, the working method of N-dicyclohexyl-2-[4-morpholinodithio sulphenamide (DZ) belongs to the rubber vulcanization accelerator DZ production technical field.

Background technology

DZ is a delayed action accelerator, is the requisite a kind of primary accelerator of present rubber industry.Be specially adapted to radial, have sulfuration and promote and adhesive effect.This procedure of patent (patent No. 200810053774.5) of delivering on July 8th, 2008 comprises: Virahol and dicyclohexyl amine are joined in the stills for air blowing, under stirring condition, make dicyclohexyl amine fully be dissolved in the Virahol; Add sulfuric acid again; Control the pH value simultaneously, drip M-Na salt then, simultaneously the dropping oxidizing agent Youxiaolin; Control pH value in the reaction process, suction filtration, washing, filtration, the dry rubber accelerator DZ product that gets after reaction finishes.Though the DZ quality that the method for this patent obtains has reached 99%, yield does not have concrete numerical value, and operation is gone up and need be dripped simultaneously by three kinds of raw materials, the operation more complicated.Document (scientific and technical information, 2005,7:23) reported the method for the synthetic DZ of big proportioning oxidation style.With stirring in captax, dicyclohexyl amine, the Virahol adding reactor drum, make its salify; React cooling, suction filtration, washing, filtration, the dry product that gets as oxygenant with Youxiaolin.The dicyclohexyl amine amount that this method is used is big, and the yield of accelerator DZ is not high.Document (China Synthetic Rubber Industry, 1996,19:317) reported the fast synthesis method of accelerator DZ.With stirring in captax, dicyclohexyl amine, the Virahol adding reactor drum, make its salify; React cooling, suction filtration, washing, filtration, the dry product that gets as oxygenant with ydrogen peroxide 50.This method accelerator DZ yield is low.Aforesaid method all can produce a large amount of brine wastes, and environment is polluted.

Summary of the invention

It is a kind of with ydrogen peroxide 50 that the purpose of production method of rubber vulcanization accelerator DZ of the present invention is to provide; Sulfuric acid is mixed into oxygenant by a certain percentage, is the method for raw material production rubber vulcanization accelerator DZ with M-Na salt; This method operation sheet; Do not produce a large amount of brine wastes, the dicyclohexyl amine consumption is an amount of, and the DZ yield that synthesizes, quality are all than higher.

Technical scheme of the present invention is following:

A kind of production method of rubber vulcanization accelerator DZ, step is following:

1) by weight 98% sulfuric acid: 27.5% ydrogen peroxide 50: water is 1:3～3.6:9, joins oxygenant;

2) by weight captax: water is 1:1, adds solid sodium hydroxide control pH=12, joins M-Na salt;

3) by dicyclohexyl amine: the M mol ratio is 1:1; Virahol: M weight ratio 6:1; In reaction kettle, adding dicyclohexyl amine and Virahol, is under 500～1200 rev/mins the condition at 30～80 ° of C, rotating speed, drips M-Na salt speed control at 2 ~ 3 hours; The pH=9-11 of dropping oxidizing agent control simultaneously, suction filtration, washing, filtration, the dry rubber accelerator DZ product that gets after reaction finishes.

The invention has the advantages that: this procedure is simple, and what oxygenant used is the ydrogen peroxide 50 that environment is not had pollution, and reaction does not produce a large amount of brine wastes; Be easy to industriallization; The dicyclohexyl amine that uses is an amount of, and the purity of the accelerator DZ that synthesizes reaches more than 99%, and yield has reached 93%.

Embodiment

Embodiment 1:

By 98% sulfuric acid: 27.5% ydrogen peroxide 50: water weight ratio is that 1:3:9 joins oxygenant.Get the M50 gram, add water 50 grams, add solid sodium hydroxide, control pH value is 12, joins M-Na salt.Get in dicyclohexyl amine 54.2 grams and the Virahol 300 gram hybrid reactors; Be under 500 rev/mins the condition at 30 ° of C, rotating speed, drip M-Na salt speed control 2.0 hours and under control pH9 condition control dropping oxidizing agent flow velocity, M-Na salt drips off; Stop oxygenant; Suction filtration, washing, filtration, the dry rubber accelerator DZ product that gets after reaction finishes, the purity of accelerator DZ reaches 99%, and yield has reached 93%.

Embodiment 2:

By 98% sulfuric acid: 27.5% ydrogen peroxide 50: water weight ratio is that 1:3.5:9 joins oxygenant.Get the M50 gram, add water 50 grams, add solid sodium hydroxide, control pH value is 12, joins M-Na salt.Get in dicyclohexyl amine 54.2 grams and the Virahol 300 gram hybrid reactors; Be under 800 rev/mins the condition at 50 ° of C, rotating speed, drip M-Na salt speed control 2.5 hours and under control pH10 condition control dropping oxidizing agent flow velocity, M-Na salt drips off; Stop oxygenant; Suction filtration, washing, filtration, the dry rubber accelerator DZ product that gets after reaction finishes, the purity of accelerator DZ reaches 99.1%, and yield has reached 93%.

Embodiment 3:

By 98% sulfuric acid: 27.5% ydrogen peroxide 50: water weight ratio is that 1:3.6:9 joins oxygenant.Get the M50 gram, add water 50 grams, add solid sodium hydroxide, control pH value is 12.Get in dicyclohexyl amine 54.2 grams and the Virahol 300 gram hybrid reactors; Be under 1200 rev/mins the condition at 80 ° of C, rotating speed, drip M-Na salt speed control 3.0 hours and under control pH11 condition control dropping oxidizing agent flow velocity, M-Na salt drips off; Stop oxygenant; Suction filtration, washing, filtration, the dry rubber accelerator DZ product that gets after reaction finishes, the purity of accelerator DZ reaches 99.2%, and yield has reached 93%.

Claims (1)

1. production method of rubber vulcanization accelerator DZ is characterized in that step is following:

1) by weight 98% sulfuric acid: 27.5% ydrogen peroxide 50: water is 1:3～3.6:9, joins oxygenant;

2) by weight captax: water is 1:1, adds solid sodium hydroxide control pH=12, joins M-Na salt;

3) by dicyclohexyl amine: the M mol ratio is 1:1; Virahol: M weight ratio 6:1; In reaction kettle, adding dicyclohexyl amine and Virahol, is under 500～1200 rev/mins the condition at 30～80 ° of C, rotating speed, drips M-Na salt speed control at 2 ~ 3 hours; The pH=9-11 of dropping oxidizing agent control simultaneously, suction filtration, washing, filtration, the dry rubber accelerator DZ product that gets after reaction finishes.