CN107868027A - A kind of rubber peptizer DBD green industrialized preparation method - Google Patents

Abstract

The invention discloses a kind of rubber peptizer DBD green industrialized preparation method, belong to rubber chemicals field.Step of the present invention is as follows：1) benzothiazole open loop under water and sodium hydroxide existence condition；2) using sodium acid carbonate and hydrogen peroxide as oxidant, ring-opening product is oxidized to diphenylamines disulphide；3) toluene is added in reaction solution obtained by step 2) and chlorobenzoyl chloride prepares DBD.Present invention process, step 1) reaction, which finishes, to be not required to purified product and directly carries out step 2), and the not purified directly progress step 3) of the product of step 2), and technique simplifies a lot, and reduces the loss of yield that purification process is brought；Utilized in addition, toluene, sodium acid carbonate and part water are also repeatable, whole process is almost without discharge, and greatly reduce cost and energy resource consumption, be environment-protective process in addition, it is rapid 2) in oxidant is used as using sodium acid carbonate and hydrogen peroxide, whole process is easy to control, and yield is high.

Description

A kind of rubber peptizer DBD green industrialized preparation method

Technical field

The present invention relates to rubber chemicals preparation field, more particularly to a kind of rubber peptizer DBD green industrialized preparation Method.

Background technology

China is rubber processing big country, consumes glue amount year up to more than 700 ten thousand tons, ranks first in the world, wherein natural rubber accounts for 46%, synthetic rubber accounts for 54%.With the development of rubber industry, application and the development of rubber chemicals achieve considerable progress.

Originally, rubber peptizer only has the pentachlorothiophenol of thiophenols, zinc salt of pentachlorothiophenol, later it is found that thiophenols are moulded Solve agent and serious pollution be present, it is extremely difficult to degrading, during especially with being the related rubber of food, existing to health tight Endanger again.Later, the rubber peptizer DBD (sulphur of 2,2- dibenzamidodiphenyl two as thiophenols peptizer substitute Compound) it is developed, its is less toxic, degradable and has superior processing performance, extensively should as environment-friendly type peptizer With.

Rubber peptizer DBD traditional preparation methods are as follows：

1st, 2,2- nitrobenzene disulphide is prepared by nitrobenzene and sulfur monochloride reaction；

2nd, 2,2- nitrobenzene disulphide is 2,2- diphenylamino disulphide through high temperature, high-tension apparatus hydrogenating reduction；

3rd, 2,2- diphenylaminos disulphide and chlorobenzoyl chloride acylation reaction obtain product.

The shortcomings that this technique：

1st, due to hydrogenation reduction process be present, using high-temperature high-pressure apparatus, investment of production is big, power consumption is high；

2nd, production process is difficult to control, and low yield, cost are high；

3rd, material cost and power cost height, yield are low, and the market price has obvious inferior position compared with thiophenols product, is More than twice of thiophenols product price；Thus while it is environmentally friendly peptizer, but the market share is low.

In order to make up above deficiency, application publication number discloses a rubber for the Chinese invention patent of " A of CN 102153495 " Glue peptizer DBD preparation method, it is used when open-loop products being carried out into oxidation in its step 2 preparing diphenylamines disulphide Oxidant is the mixed liquor of sulfuric acid and hydrogen peroxide.In the operating process of reality, when this mixed liquor is added dropwise, to dropping temperature and drop Acceleration requires very high, if rate of addition is too fast, or temperature is too high side reaction will occur is more difficult to get ideal recovery Diphenylamines disulphide；And HCL caused by subsequent step also need to absorb it is higher to equipment requirement；Wastewater treatment burden is larger Intermediate steps are relatively complicated, and people's labor intensity is big.

The content of the invention

In order to make up above deficiency, the invention provides a kind of technique it is simple, be easy to that control, cost is low, rubber of high income Glue peptizer DBD green industrialized preparation method.

The technical scheme is that：

A kind of rubber peptizer DBD green industrialized preparation method, step are as follows：

1) water and sodium hydroxide are put into successively in a kettle, stirring makes its dissolving, adds benzothiazole, is warming up to 70- 80 DEG C, 2.5-3.5 hours are reacted, it is standby to be down to normal temperature；

2) sodium acid carbonate is put into reaction solution obtained by step 1) and adds water, controlling reaction temperature is 10-45 DEG C, is added dropwise Hydrogen peroxide oxidation, obtain the reaction solution of the disulphide containing diphenylamines；

3) toluene is put into the reaction solution of the disulphide containing diphenylamines obtained by step 2), controlling reaction temperature 40-50 DEG C, chlorobenzoyl chloride is added dropwise, stirring reaction, filters after completion of the reaction, filter cake washing, drying rubber peptizer DBD；Filtrate is quiet Layering is put, upper toluene is recycled, and sodium acid carbonate and sodium chloride are isolated in lower floor's aqueous phase.

The present invention and the immediate prior art pointed out in background technology, i.e. application publication number is " CN 102153495A " Chinese invention patent, is compared, and step 1) is essentially identical, and step 2) substitutes the concentrated sulfuric acid using sodium acid carbonate, adopts Sulfuric acid is substituted with sodium acid carbonate, the requirement to rate of addition substantially reduces, and side reaction is few, and due to being substituted using sodium acid carbonate The concentrated sulfuric acid,

A large amount of hydrogen chloride will not be produced in step 3), reduces hydrogen chloride and collects link, low for equipment requirements and so that life Production process is safer；Furthermore because step 2) uses sodium acid carbonate to substitute the concentrated sulfuric acid, the reaction solution of step 2) need not be handled, can The acylation reaction of step 3) is directly carried out, solves the problems, such as that this is cumbersome closest to prior art processes, and carry due to reducing Pure link and improve yield.

Preferably, step 1) reclaimed water, sodium hydroxide, the parts by weight of benzothiazole are respectively 100-200 parts, 60-100 Part, 100-150 parts.

Preferably, sodium acid carbonate, water, the parts by weight of hydrogen peroxide are respectively 65-100 parts, 100-200 in step 2) Part, 45-80 parts, the wherein mass concentration of hydrogen peroxide is 25%-50%.

Further, toluene, the parts by weight of chlorobenzoyl chloride are respectively 400-1000 parts, 100-170 parts in step 3).

Preferably, filtering gets rid of worry using centrifuge in step 3).

Preferably, in step 3), lower floor's aqueous phase goes out sodium acid carbonate and sodium chloride by distillation, cooling, Crystallization Separation, wherein Sodium acid carbonate recycles in step 2), distills obtained water recycling.

Beneficial effects of the present invention are：

Present invention process, step 1) reaction, which finishes, to be not required to purified product and directly carries out step 2), and the product of step 2) is not Purified directly to carry out step 3), technique simplifies a lot, and reduce the loss of yield that purification process brings in addition, toluene, Sodium acid carbonate and the also repeatable utilization of part water, whole process greatly reduce cost and energy resource consumption, are ring almost without discharge Protect technique；In addition, using sodium acid carbonate and hydrogen peroxide as oxidant in step 2), whole process is easy to control, and yield is high.

Embodiment

Embodiment 1

Rubber peptizer DBD preparation method, using following steps：

1) equipped with thermometer, agitator reactor in put into water 100kg and sodium hydroxide 65kg successively, stirring makes it Dissolving, benzothiazole 100kg is then added, is warming up to 80 DEG C, it is standby that back flow reaction is down to normal temperature in 3 hours；

2) 65kg sodium acid carbonates are put into the reaction solution of step 1), adds 100L water, 45kg is added dropwise below 45 DEG C of temperature control Concentration is 27.5% hydrogen peroxide, drips and finishes stirring 30 minutes；

3) 400kg toluene is added into step 2,40 DEG C -50 DEG C of temperature control, 105kg chlorobenzoyl chlorides are added dropwise, drips and finishes 30 points of stirring Clock.20 DEG C -25 DEG C are cooled to, is centrifuged, filter cake washing, drying, rubber peptizer DBD 162kg is obtained, melts 142 ℃-144℃.Yield about 96% (in terms of benzothiazole) filtrate stratification, lower floor's aqueous phase, carry out distilling the works such as decrease temperature crystalline Sequence, sodium acid carbonate about 30kg is isolated, available for step 2).Upper toluene about 405kg can be recycled, and be directly used in next Batch.

Embodiment 2：

Rubber peptizer DBD preparation method, using following steps：

1) equipped with thermometer, agitator reactor in put into water 100kg and sodium hydroxide 65kg successively, stirring makes it Dissolving, benzothiazole 100kg is then added, is warming up to 80 DEG C, it is standby that back flow reaction is down to normal temperature in 3 hours；

2) the 30kg sodium acid carbonates for isolating filtrate in embodiment 1 are put into the reaction solution of step 1), then add 35kg Sodium acid carbonate, add 100L water, the hydrogen peroxide that 45kg concentration is 27.5% is added dropwise below 45 DEG C of temperature control, drips and finishes stirring 30 minutes；

3) the 405kg toluenic mother liquors separated are added in embodiment 1 into step 2), 40 DEG C -50 DEG C of temperature control, 105kg are added dropwise Chlorobenzoyl chloride, drip and finish stirring 30 minutes.20 DEG C -25 DEG C are cooled to, is centrifuged, filter cake is washed, dries, obtains rubber plastic Solve agent DBD 165kg, 140 DEG C -142 DEG C of fusing point.Yield about 97.5% (in terms of benzothiazole) filtrate stratification, lower floor's water Phase, carry out distilling the processes such as decrease temperature crystalline, sodium acid carbonate about 31kg is isolated, available for step 2).Upper toluene about 403kg can Recycle, be directly used in next group.

Embodiment 3：

Rubber peptizer DBD preparation method, using following steps：

1) equipped with thermometer, agitator reactor in put into water 300kg and sodium hydroxide 200kg successively, stirring makes It dissolves, and then adds benzothiazole 300kg, is warming up to 80 DEG C, it is standby that back flow reaction is down to normal temperature in 3 hours；

2) 200kg sodium acid carbonates are put into the reaction solution of step 1), adds 500L water, 85kg is added dropwise below 45 DEG C of temperature control Concentration is 45% hydrogen peroxide, drips and finishes stirring 30 minutes；

3) 1500kg toluene is added into step 2), 40 DEG C -50 DEG C of temperature control, 315kg chlorobenzoyl chlorides are added dropwise, drips and finishes stirring 30 Minute.20 DEG C -25 DEG C are cooled to, is centrifuged, filter cake washing, drying, obtains rubber peptizer DBD 489kg, fusing point 141℃-144℃.Yield about 96.5% (in terms of benzothiazole) filtrate stratification, lower floor's aqueous phase, carries out distillation decrease temperature crystalline Etc. process, sodium acid carbonate about 97kg is isolated, available for step 2).Upper toluene about 1506kg can be recycled, and be directly used in Next group.

Claims (6)

1. a kind of rubber peptizer DBD green industrialized preparation method, it is characterised in that step is as follows：

1) water and sodium hydroxide are put into successively in a kettle, stirring makes its dissolving, adds benzothiazole, is warming up to 70-80 DEG C, 2.5-3.5 hours are reacted, it is standby to be down to normal temperature；

2) sodium acid carbonate is put into reaction solution obtained by step 1) and adds water, controlling reaction temperature is 10-45 DEG C, and dioxygen is added dropwise Water oxygen, obtain the reaction solution of the disulphide containing diphenylamines；

3) toluene is put into the reaction solution of the disulphide containing diphenylamines obtained by step 2), controlling reaction temperature is 40-50 DEG C, drop Add chlorobenzoyl chloride, stirring reaction, filter after completion of the reaction, filter cake washing, drying rubber peptizer DBD；Filtrate, which stands, divides Layer, upper toluene are recycled, and sodium acid carbonate and sodium chloride are isolated in lower floor's aqueous phase.

2. rubber peptizer DBD as claimed in claim 1 green industrialized preparation method, it is characterised in that：In step 1), Water, sodium hydroxide, the parts by weight of benzothiazole are respectively 100-200 parts, 60-100 parts, 100-150 parts.

3. rubber peptizer DBD as claimed in claim 1 or 2 green industrialized preparation method, it is characterised in that：Step 2) Middle sodium acid carbonate, water, the parts by weight of hydrogen peroxide are respectively 65-100 parts, 100-200 parts, the matter of 45-80 parts, wherein hydrogen peroxide Amount concentration is 25%-50%.

4. rubber peptizer DBD as claimed in claim 3 green industrialized preparation method, it is characterised in that：In step 3) Toluene, the parts by weight of chlorobenzoyl chloride are respectively 400-1000 parts, 100-170 parts.

5. rubber peptizer DBD as claimed in claim 1 green industrialized preparation method, it is characterised in that：In step 3) Filtering gets rid of worry using centrifuge.

6. rubber peptizer DBD as claimed in claim 1 green industrialized preparation method, it is characterised in that：In step 3), Lower floor's aqueous phase goes out sodium acid carbonate and sodium chloride by distillation, cooling, Crystallization Separation, and wherein sodium acid carbonate circulates profit in step 2) With the water for distilling to obtain reuses.