CN101899020A

CN101899020A - DZ synthesized by mixing mother solution

Info

Publication number: CN101899020A
Application number: CN2010101285062A
Authority: CN
Inventors: 田少华
Original assignee: TIANJIN KEMAI CHEMICAL CO Ltd
Current assignee: TIANJIN KEMAI CHEMICAL CO Ltd
Priority date: 2010-03-22
Filing date: 2010-03-22
Publication date: 2010-12-01

Abstract

The invention discloses a method for producing a thiofide DZ by taking sodium hypochlorite as an oxidizing agent mother solution. The method comprises the following steps of: adding 50 to 800ml of isopropanol, 50 to 1,200ml of mother solution and 50 to 1,200g of dicyclohexylamine into a reaction kettle, wherein the mixing ration of mother solution is 0.2 to 1; under the condition of the temperature of 15 to 100 DEG C and the rotation speed of 50 to 1,400 revolutions per minute, fully dissolving the dicyclohexylamine in the isopropanol; dripping 10 to 40 mass percent of sulfuric acid, 10 to 40 mass percent of M-Na salt and 8.0 to 18.0 mass percent of oxidizing agent, namely sodium hypochlorite, at the flow rates of 10 to 50ml/minute, 30 to 100ml/minute and 10 to 100ml/minute respectively in a way of 'three drops', wherein the dripping time is .5 to 3.0 hours, the pH value is controlled to be between 9.0 to 12.5 in the process; and after the reaction is finished, pumping and filtering, washing with water, filtering and drying to obtain the rubber accelerator DZ product, wherein the purity of the accelerator DZ is over 99 percent. The method has the advantages of simple process and easy industrialization. Because the mother solution is directly reclaimed, the discharge of salt-containing sewage is reduced; the pressure for distilling and reclaiming a solvent is reduced; the energy consumption is decreased; the yield of the product is increased; the consumption of the cyclohexylamine and the solvent is reduced; the production cost is reduced; and the purity of the accelerator DZ is over 99 percent.

Description

DZ synthesized by mixing mother solution

Technical field

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

Background technology

Rubber vulcanization accelerator DZ is a kind of good slow effect type promotor, dispersing property is good in rubber, the time of burning in sizing material is long, and the processing safety height is applicable to that the big sizing material of thick product and high reactivity reinforcement dosage is applicable to that also polybutadiene rubber or regenerated rubber are main sizing material.The mechanical property of the vulcanized rubber of producing with this product, especially dynamic property is relatively good, the elasticity and the intensity height that composes oneself.Being mainly used in and making tire, adhesive tape and anti-vibration article, is one of main raw material of producing thick of radial, wire belt and rubber assembling etc., has good development prospect.According to the literature the method for the synthetic DZ of existing big proportioning oxidation style (scientific and technical information, 2005,7:23), captax, dicyclohexyl amine, Virahol added in the reactor stir, make its salify; React cooling, suction filtration, washing, filtration, the dry product that gets as oxygenant with clorox.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, captax, dicyclohexyl amine, Virahol are added in the reactor stir, make its salify; React cooling, suction filtration, washing, filtration, the dry product that gets as oxygenant with hydrogen peroxide.This method accelerator DZ yield is low.Document (Speciality Petrochemicals, 2006,23:7) reported that single stage method synthesizes DZ, this method adopts M-Na and the method that sulphuric acid soln and oxygenant drip simultaneously to synthesize DZ, but the quality of DZ and yield are on the low side, and mother liquor needs further processing.The synthetic method of these accelerator DZs exists the DZ yield on the low side mostly, and solvent consumption is big, problems such as the processing of brine waste.Therefore, with the mother liquor direct reuse, reducing the discharging of saline sewage, alleviate the pressure of distillating recovering solvent, cut down the consumption of energy, is the key that accelerator DZ can widespread use.

Summary of the invention

The object of the present invention is to provide a kind of mother liquid recycle to produce the method for accelerator DZ, this procedure is simple, is easy to industrialization.The mother liquor direct reuse has not only reduced the discharging of saline sewage, has alleviated the pressure of distillating recovering solvent, has reduced energy consumption, and product yield increases, and the consumption of hexahydroaniline and solvent decreases, and has reduced production cost.

For achieving the above object, the present invention is realized by following technical proposals: a kind of hypochlorous sodium is the method for oxidant production rubber vulcanization accelerator DZ, it is characterized in that comprising following process:

1. add 50～800ml Virahol, 50～1200ml mother liquor and 50～1200 gram dicyclohexyl amines in reactor, the mother liquid recycle ratio is 20%～100%.At 15～100 ℃, rotating speed is under 50～1400 rev/mins the condition, make dicyclohexyl amine fully be dissolved in the Virahol, respectively with 10～50ml/ minute, 30～100ml/ minute, 10～100ml/ minute flow velocity, beginning " three drip " adding mass content is 10～40% sulfuric acid, M-Na salt and mass content are 8.0～18.0% oxygenant clorox, the dropping time is 0.5～3.0 hour, the control pH value is 9.0～12.5 in the process, suction filtration after reaction finishes, washing, filter, the dry rubber accelerator DZ product that gets, the purity of accelerator DZ reaches more than 99%.

The invention has the advantages that: process is simple, is easy to industrialization.The mother liquor direct reuse has not only reduced the discharging of saline sewage, has alleviated the pressure of distillating recovering solvent, reduced energy consumption, and product yield increases, the consumption of hexahydroaniline and solvent decreases, reduced production cost, the purity of accelerator DZ reaches more than 99%.

Embodiment

Example 1:

Add 120ml Virahol, 120ml mother liquor and 70 gram dicyclohexyl amines in reactor, the mother liquid recycle ratio is 100%.At 30 ℃, rotating speed is under 600 rev/mins the condition, make dicyclohexyl amine fully be dissolved in the Virahol, respectively with 20ml/ minute, 30ml/ minute, 30ml/ minute flow velocity, it is that 40% sulfuric acid, M-Na salt and mass content are 8.0% oxygenant clorox that beginning " three drip " adds mass content, the dropping time is 1.0 hours, the control pH value is 9.0 in the process, suction filtration, washing, filtration, the dry rubber accelerator DZ product that gets after reaction finishes, the purity of accelerator DZ reaches more than 99.0%.

Example 2:

Add 200ml Virahol, 200ml mother liquor and 182 gram dicyclohexyl amines in reactor, the mother liquid recycle ratio is 100%.At 35 ℃, rotating speed is under 900 rev/mins the condition, make dicyclohexyl amine fully be dissolved in the Virahol, respectively with 25ml/ minute, 40ml/ minute, 40ml/ minute flow velocity, it is that 20% sulfuric acid, M-Na salt and mass content are 12.0% oxygenant clorox that beginning " three drip " adds mass content, the dropping time is 2.0 hours, the control pH value is 11.0 in the process, suction filtration, washing, filtration, the dry rubber accelerator DZ product that gets after reaction finishes, the purity of accelerator DZ reaches more than 99.2%.

Example 3:

Add 240ml Virahol, 240ml mother liquor and 218 gram dicyclohexyl amines in reactor, the mother liquid recycle ratio is 100%.At 75 ℃, rotating speed is under 400 rev/mins the condition, make dicyclohexyl amine fully be dissolved in the Virahol, respectively with 50ml/ minute, 800ml/ minute, 800ml/ minute flow velocity, it is that 40% sulfuric acid, M-Na salt and mass content are 18.0% oxygenant clorox that beginning " three drip " adds mass content, the dropping time is 3.0 hours, the control pH value is 12.5 in the process, suction filtration, washing, filtration, the dry rubber accelerator DZ product that gets after reaction finishes, the purity of accelerator DZ reaches more than 99.4%.

Claims

1. the method for a DZ synthesized by mixing mother solution is characterized in that comprising following process: add 50～800ml Virahol, 50～1200ml mother liquor and 50～1200 gram dicyclohexyl amines in reactor, the mother liquid recycle ratio is 20%～100%.At 15～100 ℃, rotating speed is under 50～1400 rev/mins the condition, make dicyclohexyl amine fully be dissolved in the Virahol, respectively with 10～50ml/ minute, 30～100ml/ minute, 10～100ml/ minute flow velocity, beginning " three drip " adding mass content is 10～40% sulfuric acid, M-Na salt and mass content are 8.0～18.0% oxygenant clorox, the dropping time is 0.5～3.0 hour, the control pH value is 9.0～12.5 in the process, suction filtration after reaction finishes, washing, filter, the dry rubber accelerator DZ product that gets, the purity of accelerator DZ reaches more than 99%.