CN106810480A

CN106810480A - A kind of green industrialized preparation method of rubber peptizer DBD

Info

Publication number: CN106810480A
Application number: CN201510869096.XA
Authority: CN
Inventors: 李春梅
Original assignee: Qingdao Senmeike Chemical Technology Co Ltd
Current assignee: Qingdao Senmeike Chemical Technology Co Ltd
Priority date: 2015-12-01
Filing date: 2015-12-01
Publication date: 2017-06-09

Abstract

The invention discloses a kind of green industrialized preparation method of rubber peptizer DBD, belong to rubber chemicals field.Step of the present invention is as follows：1) benzothiazole open loop under water and NaOH existence condition；2) with sodium acid carbonate and hydrogen peroxide as oxidant, ring-opening product is oxidized to diphenylamines disulphide；3) step 2) add toluene and chlorobenzoyl chloride to prepare DBD in gained reaction solution.Present invention process, step 1) reaction finishes and is not required to purified product and directly carries out step 2), and step 2) product not purified directly carry out step 3), technique is simplified a lot, and reduces the loss of yield that purification process brings；In addition, toluene, sodium acid carbonate and part water are also repeated utilizing, 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 using sodium acid carbonate and hydrogen peroxide as oxidant, whole process is easy to control, and yield is high.

Description

A kind of green industrialized preparation method of rubber peptizer DBD

Technical field

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

Background technology

China is rubber processing big country, consumes glue amount year up to more than 700 ten thousand tons, is ranked first in the world, and wherein natural rubber accounts for 46%, synthetic rubber Account 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 peptizer is present seriously , during especially with being the rubber of food correlation, there is serious harm to health in pollution, it is extremely difficult to degrade.Later, as sulphur The rubber peptizer DBD (2,2- dibenzamidodiphenyl disulfide) of phenols peptizer substitute is developed, its low toxicity, degradable And with superior processing performance, by as environment-friendly type peptizer extensive use.

The traditional preparation methods of rubber peptizer DBD 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 shortcoming of this technique：

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

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

3rd, material cost and power cost is high, yield is low, there is obvious inferior position in the market price, be thiophenols product price compared with thiophenols product Twice more than；Thus while it is environmentally friendly peptizer, but the market share is low.

In order to make up, the above is not enough, and application publication number discloses a rubber peptizer DBD's for the Chinese invention patent of " CN 102153495A " Preparation method, when open-loop products being carried out into oxidation in its step 2 preparing diphenylamines disulphide, oxidant used is mixed for sulfuric acid and hydrogen peroxide Close liquid.It is very high to dropping temperature and rate of addition requirement when this mixed liquor is added dropwise in actual operating process, if rate of addition is too fast, or Person's temperature is too high will to occur the diphenylamines disulphide that side reaction is more difficult to get ideal recovery；And the HCL that subsequent step is produced also needs to absorb It is higher to equipment requirement；The larger intermediate steps of wastewater treatment burden are relatively complicated, and people's labour intensity is big.

The content of the invention

It is in order to make up the above not enough, the invention provides a kind of process is simple, it is easy to control, low cost, the rubber peptizer DBD of high income Green industrialized preparation method.

The technical scheme is that：

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

1) water and NaOH are put into successively in a kettle., stirring dissolves it, adds benzothiazole, is warming up to 70-80 DEG C, reaction 2.5-3.5 hours, it is down to normal temperature standby；

2) sodium acid carbonate is put into step 1) in gained reaction solution and add water, controlling reaction temperature is 10-45 DEG C, and hydrogen peroxide oxidation is added dropwise, and is obtained Reaction solution containing diphenylamines disulphide；

3) by toluene put into step 2) gained containing diphenylamines disulphide reaction solution in, controlling reaction temperature be 40-50 DEG C, be added dropwise benzene first Acyl chlorides, stirring reaction is filtered after completion of the reaction, filter cake washing, drying rubber peptizer DBD；Filtrate stratification, upper toluene circulation Use, sodium acid carbonate and sodium chloride are isolated in lower floor's water phase.

The immediate prior art pointed out in the present invention and background technology, i.e. application publication number are special for the Chinese invention of " CN 102153495A " Profit, compares, step 1) essentially identical, step 2) concentrated sulfuric acid is substituted using sodium acid carbonate, sulfuric acid is substituted using sodium acid carbonate, to speed is added dropwise The requirement of degree is substantially reduced, and side reaction is few, and due to substituting the concentrated sulfuric acid using sodium acid carbonate,

Step 3) in will not produce a large amount of hydrogen chloride, reduce hydrogen chloride collect link, it is low for equipment requirements and cause production process it is safer； Furthermore due to step 2) using sodium acid carbonate substitute the concentrated sulfuric acid, step 2) reaction solution need not process, can directly carry out step 3) Acylation reaction, solves the problems, such as that this is cumbersome closest to prior art processes, and improves yield due to reducing purification link.

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

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

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

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

Preferably, step 3) in, lower floor's water mutually goes out sodium acid carbonate and sodium chloride, wherein sodium acid carbonate by distillation, cooling, Crystallization Separation In step 2) recycle, the water recycling that distillation is obtained.

Beneficial effects of the present invention are：

Present invention process, step 1) reaction finishes and is not required to purified product and directly carries out step 2), and step 2) product not purified directly enter Row step 3), technique is simplified a lot, and reduces loss of yield that purification process brings in addition, toluene, sodium acid carbonate and part water can also be again Multiple to utilize, whole process greatly reduces cost and energy resource consumption almost without discharge, is environment-protective process；In addition, step 2) in sodium acid carbonate With hydrogen peroxide as oxidant, whole process is easy to control, and yield is high.

Specific embodiment

Embodiment 1

The preparation method of rubber peptizer DBD, using following steps：

1) water 100kg and NaOH 65kg is put into successively in equipped with thermometer, the reactor of agitator, stirring dissolves it, then Benzothiazole 100kg is added, 80 DEG C are warmed up to, it is standby that back flow reaction is down to normal temperature in 3 hours；

2) by 65kg sodium acid carbonates put into step 1) reaction solution in, add 100L water, below 45 DEG C of temperature control be added dropwise 45kg concentration be 27.5% hydrogen peroxide, drop finishes stirring 30 minutes；

3) to adding 400kg toluene, 40 DEG C -50 DEG C of temperature control that 105kg chlorobenzoyl chlorides are added dropwise in step 2, drop finishes stirring 30 minutes. 20 DEG C -25 DEG C are cooled to, are centrifuged, filter cake washing, drying obtain rubber peptizer DBD 162kg, melt 142 DEG C -144 DEG C. Yield about 96% (in terms of benzothiazole) filtrate stratification, lower floor's water phase carries out the operations such as distillation decrease temperature crystalline, isolates sodium acid carbonate about 30kg, can be used for step 2).Upper toluene about 405kg can be recycled, and be directly used in next group.

Embodiment 2：

The preparation method of rubber peptizer DBD, using following steps：

1) water 100kg and NaOH 65kg is put into successively in equipped with thermometer, the reactor of agitator, stirring dissolves it, so Benzothiazole 100kg is added afterwards, 80 DEG C are warmed up to, and it is standby that back flow reaction is down to normal temperature in 3 hours；

2) the 30kg sodium acid carbonates input step 1 isolated filtrate in embodiment 1) reaction solution in, then add 35kg bicarbonates Sodium, plus 100L water, are added dropwise the hydrogen peroxide that 45kg concentration is 27.5% below 45 DEG C of temperature control, drop finishes stirring 30 minutes；

3) to step 2) in add the 405kg toluenic mother liquors that separate in embodiment 1,40 DEG C -50 DEG C of temperature control that 105kg benzene first is added dropwise Acyl chlorides, drop finishes stirring 30 minutes.20 DEG C -25 DEG C are cooled to, are centrifuged, filter cake is washed, dries, obtains rubber peptizer 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 is steamed The operations such as decrease temperature crystalline are evaporated, sodium acid carbonate about 31kg is isolated, can be used for step 2).Upper toluene about 403kg can be recycled, directly Connect for next group.

Embodiment 3：

The preparation method of rubber peptizer DBD, using following steps：

1) water 300kg and NaOH 200kg is put into successively in equipped with thermometer, the reactor of agitator, stirring dissolves it, so Benzothiazole 300kg is added afterwards, 80 DEG C are warmed up to, and it is standby that back flow reaction is down to normal temperature in 3 hours；

2) by 200kg sodium acid carbonates put into step 1) reaction solution in, add 500L water, below 45 DEG C of temperature control be added dropwise 85kg concentration It is 45% hydrogen peroxide, drop finishes stirring 30 minutes；

3) to step 2) middle addition 1500kg toluene, 40 DEG C -50 DEG C of temperature control, dropwise addition 315kg chlorobenzoyl chlorides, drop is complete to stir 30 points Clock.20 DEG C -25 DEG C are cooled to, are centrifuged, filter cake washing, drying obtain rubber peptizer DBD 489kg, 141 DEG C of fusing point -144℃.Yield about 96.5% (in terms of benzothiazole) filtrate stratification, lower floor's water phase carries out the operations such as distillation decrease temperature crystalline, isolates Sodium acid carbonate about 97kg, can be used for step 2).Upper toluene about 1506kg can be recycled, and be directly used in next group.

Claims

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

1) water and NaOH are put into successively in a kettle., stirring dissolves it, adds benzothiazole, is warming up to 70-80 DEG C, reacts 2.5-3.5 Hour, it is down to normal temperature standby；

2) sodium acid carbonate is put into step 1) in gained reaction solution and add water, controlling reaction temperature is 10-45 DEG C, and hydrogen peroxide oxidation is added dropwise, The reaction solution of diphenylamines disulphide must be contained；

3) by toluene put into step 2) gained containing diphenylamines disulphide reaction solution in, controlling reaction temperature be 40-50 DEG C, be added dropwise benzoyl Chlorine, stirring reaction is filtered after completion of the reaction, filter cake washing, drying rubber peptizer DBD；Filtrate stratification, upper strata first Benzene is recycled, and sodium acid carbonate and sodium chloride are isolated in lower floor's water phase.

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

3. the green industrialized preparation method of rubber peptizer DBD as claimed in claim 1 or 2, it is characterised in that：Step 2) in Sodium acid carbonate, water, the parts by weight of hydrogen peroxide are respectively 65-100 parts, 100-200 parts, 45-80 parts, and the quality of wherein hydrogen peroxide is dense It is 25%-50% to spend.

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

5. the green industrialized preparation method of rubber peptizer DBD as claimed in claim 1, it is characterised in that：Step 3) middle filtering Worry is got rid of using centrifuge.

6. the green industrialized preparation method of rubber peptizer DBD as claimed in claim 1, it is characterised in that：Step 3) in, under Layer water mutually goes out sodium acid carbonate and sodium chloride by distillation, cooling, Crystallization Separation, and wherein sodium acid carbonate is in step 2) recycle, distill The water recycling for obtaining.