CN105175353A - Method for performing ammonolysis on oxygen to obtain rubber accelerator MBT by oxidization-synthesis - Google Patents
Method for performing ammonolysis on oxygen to obtain rubber accelerator MBT by oxidization-synthesis Download PDFInfo
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- CN105175353A CN105175353A CN201510670075.5A CN201510670075A CN105175353A CN 105175353 A CN105175353 A CN 105175353A CN 201510670075 A CN201510670075 A CN 201510670075A CN 105175353 A CN105175353 A CN 105175353A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/70—Sulfur atoms
- C07D277/72—2-Mercaptobenzothiazole
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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Abstract
The invention relates to a method for performing ammonolysis on oxygen to obtain a rubber accelerator by oxidization-synthesis. The method comprises the following steps of synthesizing a crude product MBT in a molten state by aniline, carbon disulfide and sulfur according to a certain mole ratio under certain temperature and pressure, adding the crude product M in the molten state into an oxidization kettle with ammonia water, starting to feed oxygen into the oxidization kettle when the temperature meets the requirement, heating and concentrating ammonium salt which is oxidized to the end point when the temperature and the pressure are stabilized and not changed any more, namely the oxidization end point is achieved, directly putting the ammonium salt into a drying machine for solid-liquid separation when the ammonium salt is concentrated to a certain amount, and obtaining the qualified rubber accelerator MBT. According to the method, the crude product M in the molten state is directly added into the ammonia water in a normal temperature state, so that energy in a heating process is saved; oxygen is used as the oxidant, so that the environment pollution is low; ammonia can be directly absorbed and reused; the concentrated ammonium salt is not needed to be washed with water during drying; after mother liquor is removed, direct discharging is carried out. An MBT product separated by crystallization is high in quality, good in appearance color, high in purity and high in yield.
Description
Technical field
The present invention relates to a kind of method of ammonia solution dioxygen oxidation synthetic rubber accelerant MBT, utilize ammonia solvent crude 2-mercapto benzothiazole (MBT), and synthetic rubber accelerant MBT after utilizing dioxygen oxidation purification, concentrated recrystallization, belong to rubber accelerator MBT synthesis technical field.
Background technology
Rubber accelerator plays very important effect in Vulcanization Process of Rubber, accelerate the reaction of rubber and vulcanizing agent, improve production efficiency, MBT is very important a kind of promotor in current rubber accelerator industry, is also the parent stock of sulfenamide type accelerators simultaneously.About the production technique of MBT, also there are some to report both at home and abroad, mainly mostly adopt traditional alkali-soluble acid analysis method, this processing method good product quality at present, but comparatively large with alkali, acid molar ratio, and cost is high, and produces a large amount of brine waste, and wastewater treatment difficulty is large.Adopt toluene extracting process to synthesize MBT in patent CN1300123C, this processing method poor product quality, purity is low, and toluene solvant is inflammable and explosive, belongs to noxious solvent, there is potential safety hazard.Also report is had to adopt CS in document
2high-temperature extraction crystallization method prepares MBT, this processing method technological process more complicated, CS
2more dangerous, technique is wayward, and quality product is also poor.
Summary of the invention
The object of the present invention is to provide a kind of method of simple and effective production rubber accelerator MBT, the shortcoming of prior art can be overcome.Compared with above explained hereafter method, the invention solves above processing disadvantages, wherein with ammonia solvent crude product MBT, salt-free in ammonia mother liquid, can recycled, take oxygen as oxygenant, cost is low, and without the need to washing during drying, oxidation purification post-heating is concentrated, and to obtain MBT product purity high, quality is good, and technique is simply easy to control.
In order to achieve the above object, the present invention is achieved through the following technical solutions.
A kind of method of ammonia solution dioxygen oxidation synthetic rubber accelerant MBT; It is characterized in that comprising the following steps:
1) aniline, dithiocarbonic anhydride, melting sulphur are dropped into autoclave respectively, reaction pressure is 9-10.5MPa, and reaction 8-10 hour synthesis molten state temperature is 200-220 DEG C of rubber accelerator MBT crude product;
2) the crude product MBT of the molten state of 200-220 DEG C being delivered directly to band by pipeline stirs in the stills for air blowing of Sheng ammoniacal liquor, stirring and dissolving 0.5-1h;
3) by ready liquid oxygen by Cemented filling in stills for air blowing, oxidizing temperature 40-70 DEG C, oxidative pressure 0.35-0.45MPa, until it is be oxidation to reach home that oxidizing temperature and pressure-stabilisation no longer change, obtain the ammonium salt solution of clear;
4) stop heating when the heating of the ammonium salt solution of clear being concentrated to the 20-60% of cumulative volume, start to enter drier and be separated; Wet feed MBT after drying is carried out drying, obtains qualified rubber accelerator MBT.
Described raw material aniline: dithiocarbonic anhydride: sulphur mol ratio is 1:(1-1.2): (1-1.2).
The temperature of reaction of the autoclave of described step 1 is 240-265 DEG C.
The crude product MBT of described step 2 and the mol ratio of pure ammonia are 1:1-4, and ammonia concn is 2%-10%.
Described step 4 Recycling Mother Solution is applied mechanically and is directly added in stills for air blowing, heats the ammonia steamed and is directly absorbed by absorption kettle.Directly can return stills for air blowing after the ammoniacal liquor detection level reclaimed to use.
Qualified rubber accelerator MBT of the present invention, product yield can reach 90-95%, and product purity can reach 98-99%, and fusing point can reach 173-176 DEG C.
The invention has the advantages that:
1) aniline, dithiocarbonic anhydride, sulphur being synthesized 200-220 DEG C of crude product MBT at certain pressure, temperature directly joins in certain density ammoniacal liquor, dissolved state is relatively good, simultaneous temperature reaches oxidizing temperature just, temperature starts logical oxygen in stills for air blowing when reaching requirement, oxidation terminal is when temperature and pressure is stablized constant, concentrated for the ammonium salt heating being oxidized to terminal, directly enter drier when being concentrated to a certain amount of and carry out solid-liquid separation, isolated solid wet feed is carried out drying, qualified rubber accelerator MBT can be obtained.The crude product M of molten state directly joins in the ammoniacal liquor of normal temperature state, just reaches oxidizing temperature, has saved the energy in temperature-rise period, has reduced cost.Save the energy in temperature-rise period.
2) adopt oxygen to be oxygenant, product cost is low, and the mother liquor after concentrated can recycled, and do not produce brine waste, environmental pollution is smaller, solves environmental issue;
3), in the process that ammonium salt heating is concentrated, ammonia directly can absorb and again utilize; This technical process is simple, and be belong to recrystallization concentration process, product yield is high, and quality is good;
4) ammonium salt concentrated without the need to washing, deviates from directly discharging after mother liquor when drying, and drying mother liquor can recycled, do not produce waste water, the ammoniacal liquor that the present invention adopts concentration lower instead of organic solvent, is easy to control, easy handling, security is higher.The MBT quality product appearance color that concentrated recrystallization is separated out is good, purity is high, yield is high.
Accompanying drawing explanation
Fig. 1: process flow sheet of the present invention.
Embodiment
As shown in Figure 1, specific implementation process is implemented according to following steps in whole technical process, and following examples can make those skilled in the art better understand the present invention, but do not limit the present invention in any way.
Embodiment 1:
1. molten state rubber accelerator MBT crude product synthesis: aniline 1.785t, dithiocarbonic anhydride 1.461t, sulphur 0.614t are dropped in autoclave respectively, temperature of reaction is 240 DEG C, top pressure 9.5MPa, reacting 8 hours synthesis synthesis molten state temperature is 200-220 DEG C of rubber accelerator MBT crude product, and the content of crude product M reaches more than 90%.
2. ammonia is molten: join in reactor by the ammoniacal liquor preparing 2% concentration, and crude product M and ammoniacal liquor mol ratio are 1:1, open stirring, directly squeezes in the molten still of ammonia, stirring and dissolving 30 minutes by pipeline by 200 DEG C of crude product M.
3. oxidation purification M: forward in stills for air blowing by pipeline by M solvent for ammonia, starts logical oxygen, and oxidizing temperature controls at 40 DEG C, oxidative pressure 0.35MPa, when pressure and temperature stable no longer change, be oxidation terminal; Obtain the ammonium salt solution of clear.
4. ammonium salt concentrates recrystallization M: the ammonium salt of clear is carried out heating and concentrate, heating is stopped when being concentrated to 20% of cumulative volume, start to enter drier and carry out solid-liquid separation, stills for air blowing recycled can be directly entered after drying mother liquor detection level, gas time concentrated can directly absorb with absorption kettle, directly squeezes into stills for air blowing and use when next time joins ammonia after the ammoniacal liquor detection level of recovery.By the M wet feed convection drying after drying, qualified MBT finished product can be obtained.
Yield 90% after detecting, purity 98%, fusing point 173 DEG C.
Embodiment 2:
1. molten state rubber accelerator MBT crude product synthesis: aniline 1.785t, dithiocarbonic anhydride 1.608t, sulphur 0.675t are dropped in autoclave respectively, temperature of reaction is 250 DEG C, top pressure 10MPa, reacting 9 hours synthesis molten state temperature is 200-220 DEG C of rubber accelerator MBT crude product, and the content of crude product M reaches more than 90%.
2. ammonia is molten: join in reactor by the ammoniacal liquor preparing 6% concentration, and crude product M and ammoniacal liquor mol ratio are 1:2, open stirring, directly squeezes in the molten still of ammonia, stirring and dissolving 40 minutes by pipeline by 210 DEG C of crude product M.
3. oxidation purification M: forward in stills for air blowing by pipeline by M solvent for ammonia, starts logical oxygen, and oxidizing temperature controls at 50 DEG C, oxidative pressure 0.4MPa, is oxidation terminal, obtains the ammonium salt solution of clear when pressure and temperature stable no longer change.
4. ammonium salt concentrates recrystallization M: the ammonium salt of clear is carried out heating and concentrate, heating is stopped when being concentrated to 40% of cumulative volume, start to enter drier and carry out solid-liquid separation, stills for air blowing recycled can be directly entered after drying mother liquor detection level, gas time concentrated can directly absorb with absorption kettle, directly squeezes into stills for air blowing and use when next time joins ammonia after the ammoniacal liquor detection level of recovery.By the M wet feed convection drying after drying, qualified MBT finished product can be obtained.
Yield 93% after detecting, purity 98.5%, fusing point 175 DEG C.
Embodiment 3:
1. molten state rubber accelerator MBT crude product synthesis: aniline 1.785t, dithiocarbonic anhydride 1.754t, sulphur 0.737t are dropped in autoclave respectively, temperature of reaction is 265 DEG C, top pressure 10.5MPa, reacting 10 hours synthesis molten state temperature is 200-220 DEG C of rubber accelerator MBT crude product, and the content of crude product M reaches more than 90%.
2. ammonia is molten: join in reactor by the ammoniacal liquor preparing 10% concentration, and crude product M and ammoniacal liquor mol ratio are 1:4, open stirring, directly squeezes in the molten still of ammonia, stirring and dissolving 1 hour by pipeline by 220 DEG C of crude product M.
3. oxidation purification M: forward in stills for air blowing by pipeline by M solvent for ammonia, starts logical oxygen, and oxidizing temperature controls at 70 DEG C, oxidative pressure 0.45MPa, is oxidation terminal, obtains the ammonium salt solution of clear when pressure and temperature stable no longer change.
4. ammonium salt concentrates recrystallization M: the ammonium salt of clear is carried out heating and concentrate, heating is stopped when being concentrated to 60% of cumulative volume, start to enter drier and carry out solid-liquid separation, stills for air blowing recycled can be directly entered after drying mother liquor detection level, gas time concentrated can directly absorb with absorption kettle, directly squeezes into stills for air blowing and use when next time joins ammonia after the ammoniacal liquor detection level of recovery.By the M wet feed convection drying after drying, qualified MBT finished product can be obtained.
Yield 95% after detecting, purity 99%, fusing point 176 DEG C.
Open and a kind of method of ammonia solution dioxygen oxidation synthetic rubber accelerant MBT that proposes of the present invention, those skilled in the art are by using for reference present disclosure, the links such as appropriate change condition route realize, although method of the present invention and technology of preparing are described by preferred embodiment, person skilled obviously can change Method and Technology route as herein described or reconfigure not departing from content of the present invention, spirit and scope, realizes final technology of preparing.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the art, they are deemed to be included in spirit of the present invention, scope and content.
Claims (6)
1. the method for an ammonia solution dioxygen oxidation synthetic rubber accelerant MBT; It is characterized in that comprising the following steps:
1) aniline, dithiocarbonic anhydride, melting sulphur are dropped into autoclave respectively, reaction pressure is 9-10.5MPa, and reaction 8-10 hour synthesis molten state temperature is 200-220 DEG C of rubber accelerator MBT crude product;
2) the crude product MBT of the molten state of 200-220 DEG C being delivered directly to band by pipeline stirs in the stills for air blowing of Sheng ammoniacal liquor, stirring and dissolving 0.5-1h;
3) by ready liquid oxygen by Cemented filling in stills for air blowing, oxidizing temperature 40-70 DEG C, oxidative pressure 0.35-0.45MPa, until it is be oxidation to reach home that oxidizing temperature and pressure-stabilisation no longer change, obtain the ammonium salt solution of clear;
4) stop heating when the heating of the ammonium salt solution of clear being concentrated to the 20-60% of cumulative volume, start to enter drier and be separated; Wet feed MBT after drying is carried out drying, obtains qualified rubber accelerator MBT.
2. the method for claim 1, is characterized in that described raw material aniline: dithiocarbonic anhydride: sulphur mol ratio is 1:(1-1.2): (1-1.2).
3. the method for claim 1, is characterized in that the temperature of reaction of the autoclave of described step 1 is 240-265 DEG C.
4. the method for claim 1, is characterized in that the crude product MBT of described step 2 and the mol ratio of pure ammonia are 1:1-4.
5. method as claimed in claim 4, is characterized in that described ammonia concn is 2%-10%.
6. the method for claim 1, is characterized in that described step 4 Recycling Mother Solution is applied mechanically and directly adds in stills for air blowing, heats the ammonia steamed and is directly absorbed by absorption kettle.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727296A (en) * | 2017-10-23 | 2018-11-02 | 内蒙古科迈化工有限公司 | A kind of dioxygen oxidation one-step synthesis technique of rubber accelerator dibenzothiazyl disulfide |
| CN109535099A (en) * | 2018-10-24 | 2019-03-29 | 科迈化工股份有限公司 | Method by recycling MBT in resin |
| CN109608417A (en) * | 2018-10-24 | 2019-04-12 | 科迈化工股份有限公司 | Method by recycling the direct synthesis accelerant MBTS of crude product MBT in resin |
| CN116102520A (en) * | 2022-12-19 | 2023-05-12 | 山东尚舜化工有限公司 | Method for synthesizing accelerator MBTS (DM) by oxygen oxidation method |
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| CN101157662A (en) * | 2007-09-25 | 2008-04-09 | 天津市科迈化工有限公司 | Method for producing rubber vulcanization accelerator MBT |
| CN101717377A (en) * | 2009-11-16 | 2010-06-02 | 天津市科迈化工有限公司 | Method for large-scale high-pressure synthesis of MBT as rubber vulcanization accelerator |
| CN104031003A (en) * | 2014-06-30 | 2014-09-10 | 东北助剂化工有限公司 | Complex solvent refining method of MBT (2-mercaptobenzothiazole) |
| CN104211657A (en) * | 2014-09-01 | 2014-12-17 | 淄博高汇化工有限公司 | Refining method of rubber vulcanizing accelerant M |
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2015
- 2015-10-15 CN CN201510670075.5A patent/CN105175353B/en active Active
Patent Citations (4)
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| CN101157662A (en) * | 2007-09-25 | 2008-04-09 | 天津市科迈化工有限公司 | Method for producing rubber vulcanization accelerator MBT |
| CN101717377A (en) * | 2009-11-16 | 2010-06-02 | 天津市科迈化工有限公司 | Method for large-scale high-pressure synthesis of MBT as rubber vulcanization accelerator |
| CN104031003A (en) * | 2014-06-30 | 2014-09-10 | 东北助剂化工有限公司 | Complex solvent refining method of MBT (2-mercaptobenzothiazole) |
| CN104211657A (en) * | 2014-09-01 | 2014-12-17 | 淄博高汇化工有限公司 | Refining method of rubber vulcanizing accelerant M |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727296A (en) * | 2017-10-23 | 2018-11-02 | 内蒙古科迈化工有限公司 | A kind of dioxygen oxidation one-step synthesis technique of rubber accelerator dibenzothiazyl disulfide |
| CN109535099A (en) * | 2018-10-24 | 2019-03-29 | 科迈化工股份有限公司 | Method by recycling MBT in resin |
| CN109608417A (en) * | 2018-10-24 | 2019-04-12 | 科迈化工股份有限公司 | Method by recycling the direct synthesis accelerant MBTS of crude product MBT in resin |
| CN109608417B (en) * | 2018-10-24 | 2023-04-07 | 科迈化工股份有限公司 | Method for directly synthesizing accelerator MBTS by recovering crude MBT from resin |
| CN116102520A (en) * | 2022-12-19 | 2023-05-12 | 山东尚舜化工有限公司 | Method for synthesizing accelerator MBTS (DM) by oxygen oxidation method |
| CN116102520B (en) * | 2022-12-19 | 2024-06-07 | 山东尚舜化工有限公司 | Method for synthesizing accelerator MBTS (DM) by oxygen oxidation method |
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Effective date of registration: 20210203 Address after: 061000 east of Nantong 6th Road, chemical 2nd Road, East District, Lingang Economic and Technological Development Zone, Cangzhou City, Hebei Province Patentee after: Hebei Kemai New Material Technology Co.,Ltd. Address before: 029310 Baolongshan Industrial Park, Baolongshan Town, KeZuoZhong banner, Tongliao City, Inner Mongolia Autonomous Region Patentee before: INNER MONGOLIA KEMAI CHEMICAL Co.,Ltd. |