CN105541755A

CN105541755A - Synthetic method for rubber vulcanizing accelerator CZ with sodium hypochlorite as oxidizing agent

Info

Publication number: CN105541755A
Application number: CN201510964283.6A
Authority: CN
Inventors: 李树东
Original assignee: Kemai Chemical Co Ltd
Current assignee: Kemai Chemical Co Ltd
Priority date: 2015-12-17
Filing date: 2015-12-17
Publication date: 2016-05-04

Abstract

The invention provides a synthetic method for a rubber vulcanizing accelerator CZ with sodium hypochlorite as an oxidizing agent. The method comprises the following steps: in terms of a weight ratio of 1: 1.5 of an accelerator M with a mass content of 85% to 90% to cyclohexylamine, adding cyclohexylamine into an oxidation reactor, adding slurry composed of the accelerator M with a mass content of 85% to 90% and isopropanol in a weight ratio of 1: 1.5 into the cyclohexylamine-contained oxidation reactor, dropwise adding a sodium hypochlorite solution into the obtained solution under the conditions of the temperature of 40 to 60 DEG C and a rotating speed of 400 to 600 r/min, after 70 to 120 minutes, carrying out sampling and observing, judging a reaction endpoint with a potassium iodide-starch test paper, stopping dropwise adding of the sodium hypochlorite solution when the test paper turns black, and subjecting the obtained product to vacuum-filtering, water washing, filtering and drying so as to obtain the rubber vulcanizing accelerator CZ. The synthetic method provided by the invention has simple process, directly uses the accelerator M as a raw material, and uses isopropanol to replace water for pulping of the accelerator M, so the method provided by the invention has the advantage that produced wastewater is reduced by 60% or above compared with the prior art; and the rubber vulcanizing accelerator CZ has a purity of 98% or above and a yield of 95% or above.

Description

Take clorox as the method for oxygenant synthesizing rubber vulcanization accelerator CZ

Technical field

The present invention relates to a kind of production method of thiofide N cyclohexyl 2 benzothiazole sulfenamide (CZ), belong to rubber vulcanization accelerant CZ production technical field.

Background technology

Along with the development of rubber industry, the R & D and manufacture of vulcanization accelerator is more and more subject to people's attention.Vulcanization accelerator plays very important effect in Vulcanization Process of Rubber, it can accelerate the reaction of rubber and vulcanizing agent greatly, boost productivity, also can improve the physical and mechanical properties of vulcanized rubber, CZ is the requisite a kind of primary accelerator of current rubber industry simultaneously.Accelerant CZ is rear validity half ultra fast accelerator that a kind of height is active, and scorching quality is excellent, process safety, and curing time is short.Document (fine chemistry industry, 2006,23:923) reports the method for catalytic oxidation synthesis CZ.Captax, hexahydroaniline, catalyzer, water are added in reactor and stirs, make its salify; React as oxygenant with hydrogen peroxide, cooling, suction filtration, washing, filtration, dry product.The hexahydroaniline amount that this method uses is large, and mother liquor is through Distillation recovery hexahydroaniline, and the yield of accelerant CZ is not high.Document (Guangxi Chemical Industry, 1994,23:58) reports the fast synthesis method of accelerant CZ.Captax, hexahydroaniline, catalyzer, water are added in reactor and stirs, make its salify; React as oxygenant with hydrogen peroxide, suction filtration, washing, filtration, dry product.Mother liquor is through Distillation recovery hexahydroaniline.Current technical process is as shown in Figure 1. captax (2-thiol benzothiazole) condensation, and purify, dry, making beating, synthesis.This method accelerant CZ yield is low, and water consumption is large.

Summary of the invention

The object of the present invention is to provide a kind of be oxygenant with clorox, Virahol is solvent, the method that mass content 85% ~ 90%M (2-thiol benzothiazole) is raw material production rubber vulcanization accelerant CZ, the method is simple to operate, good product quality, the brine waste amount produced is few, and yield is high.

For achieving the above object, the present invention is realized by following technical proposals:

Of the present invention take clorox as the method for oxygenant synthesizing rubber vulcanization accelerator CZ, by mass content 85% ~ 90% captax and hexahydroaniline by weight being 1:1.5, hexahydroaniline is joined in stills for air blowing, the slip being 1:1.5 the weight ratio of mass content 85% ~ 90% captax and Virahol is again added to containing in hexahydroaniline stills for air blowing, at 40-60 DEG C, rotating speed is under the condition of 400-600 rev/min, chlorine bleach liquor is dripped in solution, after 70-120 minute, sampling is observed, reaction end is judged with starch potassium iodide paper, when test paper blackening, stop dripping clorox, product is through suction filtration, washing, filter, dry rubber accelerator CZ product.

Described sodium chlorate available chlorine content is 16-18mg/100ml; The rate of addition of chlorine bleach liquor is 1ml/ minute.

Of the present inventionly a kind ofly take clorox as oxygen agent, the method that is raw material production rubber vulcanization accelerant CZ with mass content 85% ~ 90% captax, technical process as shown in Figure 2: captax (2-thiol benzothiazole) condensation, making beating, synthesis.

The invention has the advantages that: the method process is simple, direct is raw material with mass content 85% ~ 90%M, and eliminate M and purify and water used, acid, alkali, dries operation.The M making beating of water is replaced with Virahol.Make the older technique of the waste water of production reduce more than 60%, isopropanol recovering is recycling, and the purity of the accelerant CZ synthesized reaches more than 98%.Yield reaches more than 95% (in captax).

Accompanying drawing explanation

Fig. 1: the schema of original technique;

Fig. 2: process flow sheet of the present invention.

Embodiment

Example 1:

With aniline and dithiocarbonic anhydride, sulphur is at 270 ~ 280 DEG C, and condensation reaction under pressure 9 ~ 10Mpa condition, gets mass content 85%M50g, Virahol 75g is mixed into oar, join in the reactor of existing 75 grams of hexahydroaniline, 40 DEG C, under rotating speed is the condition of 400 revs/min, add with the flow velocity of 1ml/ minute the oxidizing agent sodium hypochlorite that available chlorine is 16mg/100ml, time for adding is 70 minutes, judge reaction end with starch potassium iodide paper, when test paper blackening, stop dripping clorox.Suction filtration, washing, filtration, dry rubber accelerator CZ product after completion of the reaction, the purity of accelerant CZ reaches more than 98.4%, and yield reaches 95.2%.

Example 2:

With aniline and dithiocarbonic anhydride, sulphur is at 270 ~ 280 DEG C, and condensation reaction under pressure 9 ~ 10Mpa condition, gets mass content 87%M50g, Virahol 75g is mixed into oar, join in the reactor of existing 75 grams of hexahydroaniline, 50 DEG C, under rotating speed is the condition of 500 revs/min, add with the flow velocity of 1ml/ minute the oxidizing agent sodium hypochlorite that available chlorine is 17mg/100ml, time for adding is 90 minutes, judge reaction end with starch potassium iodide paper, when test paper blackening, stop dripping clorox.Suction filtration, washing, filtration, dry rubber accelerator CZ product after completion of the reaction, the purity of promotor reaches more than 98.5%, and yield reaches 95.3%.

Example 3:

With aniline and dithiocarbonic anhydride, sulphur is at 270 ~ 280 DEG C, and condensation reaction under pressure 9 ~ 10Mpa condition, gets mass content 90%M50g, Virahol 75g is mixed into oar, join in the reactor of existing 75 grams of hexahydroaniline, 60 DEG C, under rotating speed is the condition of 600 revs/min, add with the flow velocity of 1ml/ minute the oxidizing agent sodium hypochlorite that available chlorine is 18mg/100ml, time for adding is 120 minutes, judge reaction end with starch potassium iodide paper, when test paper blackening, stop dripping clorox.Suction filtration, washing, filtration, dry rubber accelerator CZ product after completion of the reaction, the purity of accelerant CZ reaches more than 98.6%, and yield reaches 95.4%.

Claims

1. be the method for oxygenant synthesizing rubber vulcanization accelerator CZ with clorox, it is characterized in that by mass content 85% ~ 90% captax and hexahydroaniline be 1:1.5 by weight, hexahydroaniline is joined in stills for air blowing, the slip being 1:1.5 the weight ratio of mass content 85% ~ 90% captax and Virahol is again added to containing in hexahydroaniline stills for air blowing, at 40-60 DEG C, rotating speed is under the condition of 400-600 rev/min, chlorine bleach liquor is dripped in solution, after 70-120 minute, sampling is observed, reaction end is judged with starch potassium iodide paper, when test paper blackening, stop dripping clorox, product is through suction filtration, washing, filter, dry rubber accelerator CZ product.

2. the method for claim 1, is characterized in that sodium chlorate available chlorine content is 16-18mg/100ml.

3. the method for claim 1, is characterized in that the rate of addition of chlorine bleach liquor is 1ml/ minute.