CN102838557A - Method for synthesizing accelerator 2-mercaptobenzothiazole (MBT) by recycling intermediate product - Google Patents
Method for synthesizing accelerator 2-mercaptobenzothiazole (MBT) by recycling intermediate product Download PDFInfo
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- CN102838557A CN102838557A CN2012103624436A CN201210362443A CN102838557A CN 102838557 A CN102838557 A CN 102838557A CN 2012103624436 A CN2012103624436 A CN 2012103624436A CN 201210362443 A CN201210362443 A CN 201210362443A CN 102838557 A CN102838557 A CN 102838557A
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Abstract
The invention relates to a method for synthesizing an accelerator 2-mercaptobenzothiazole (MBT) by recycling an intermediate product, which comprises the following steps: preparing an accelerator MBT by a traditional method, extracting active components (including benzothiazole, aniline, sulfur and the like) in the obtained tarry resin, and recycling in the next reaction process in a certain proportion; weighing certain amounts of aniline, sulfur, carbon bisulfide and recycled active components, and adding into a high-pressure autoclave, wherein the mass percent of the recycled active components is 1-10 wt% of the total materials; sealing, and starting stirring and heating; reacting at 240-260 DEG C for 100-200 minutes, and discharging hydrogen sulfide after the reaction finishes, wherein the stirring speed is controlled at 80-300 rpm, and the final pressure is 8.5-9.5 MPa; refining the melt to obtain the qualified product; and recycling the active components from the resin, and proportionally sending to the next reaction. The invention has the advantages of milder reaction conditions, high reaction yield and the like, and is easy to control.
Description
Technical field
The present invention relates to a kind of thiofide 2-mercaptobenzothiazole (MBT) new synthetic method, belong to the rubber vulcanization accelerant MBT synthesis technical field.
Background technology
Accelerant MBT is the general purpose rubber vulcanization accelerator, is the parent stock of most of sulfenamide type acceleratorss simultaneously.Synthesis accelerant benzothiazole zinc salt, sulfenamide, sulphenamide etc. all be unable to do without the development of accelerant MBT, and the quality of accelerant MBT and output are directly connected to the development of rubber industry.At present the domestic high pressure aniline process that generally adopts is produced: aniline, and sulphur, dithiocarbonic anhydride drop into autoclave with certain proportioning, and under temperature 250-270 ℃, pressure was kept under the situation of 10Mpa reaction 2-4 hour, reaction synthesis accelerant MBT.This reacts HTHP, and condition is harsh, and reaction process is difficult to control, and reaction yield is merely 82%, can generate general 18% left and right sides tarry resin, can't handle contaminate environment.Wherein contain effective constituents such as unreacted aniline, sulphur, intermediate product and by product benzothiazole and account for 40%, this problem is the problem that all technologies exist.There is patent report (US3975394) benzothiazole etc. under proper ratio, to continue reaction and generates MBT with sulphur, and the benzothiazole reusable edible in the by product of accelerant MBT, the accelerant MBT reaction yield improved.If can the effective constituent recycle and reuse in the resin then both can be reduced environmental pollution, can improve Atom economy again, kill two birds with one stone.But it is not explained the concrete processing condition of middle product recycle.Therefore be the basis with this patent, my company has carried out further research to this technology.The object of the invention then is the processing condition of exploitation intermediate product reuse, finds out the MBT new synthetic process.
Summary of the invention
The object of the present invention is to provide a kind of rubber vulcanization accelerant MBT new synthetic method.
For achieving the above object, the present invention realizes through following technical proposals: a kind of method of intermediate product reuse synthesis accelerant 2-mercaptobenzothiazole, and its characteristic comprises following process, and is as shown in Figure 1:
A kind of method of intermediate product reuse synthesis accelerant 2-mercaptobenzothiazole, step is following:
1) take by weighing aniline, sulphur, dithiocarbonic anhydride and insert autoclave, the material molar ratio proportioning is an aniline: sulphur: dithiocarbonic anhydride is 1:1 ~ 1.5:1 ~ 2; Under temperature 260-270 ℃, rotating speed is at 80-300 rev/min, and pressure is kept under the situation of 9.5-10Mpa and reacted 120-240min, reaction synthesis accelerant MBT; The tarry resin that generates is carried heating up in a steamer to handle through water vapor and is obtained reclaiming effective constituent;
2) take by weighing aniline, sulphur, dithiocarbonic anhydride, recovery effective constituent and insert autoclave, the feed molar proportioning is an aniline: sulphur: dithiocarbonic anhydride is 1:1 ~ 1.5.:1-2, and reclaiming the effective constituent add-on is the 1%-10% of the total mass of the 3 kinds of raw materials in front; Stir and heat up, slowly heat up, reaction 120-200min under temperature 240-260 ℃, mixing speed is controlled at 80-300 commentaries on classics/min, and resulting pressure is 8.5-9.5MPa, and reaction finishes, discharging hydrogen sulfide, the refining accelerant MBT that obtains of melt warp.
Effective constituent comprises aniline, sulphur, benzothiazole, thiambutosine etc.;
The invention has the advantages that: reaction conditions is gentle more, control easily, and reaction yield reaches more than 84%, and yield is significantly improved.
Description of drawings
Fig. 1: be the process flow diagram of this technology.
Embodiment
Embodiment 1:
According to the material molar ratio proportioning is aniline: the ratio of sulphur: dithiocarbonic anhydride: 1:1:1 accurately takes by weighing aniline 280g, sulphur 96g, and dithiocarbonic anhydride 228.8g inserts in the 1L autoclave.Feeding intake finishes, and kettle is sealed.Open and stir, rotating speed is made as 80r/min, is warming up at 260 ℃, treats that pressure-stabilisation is in 10MPa afterreaction 180min.Reaction terminating, discharging hydrogen sulfide.After refining, get MBT product 412.3g, purity 98%, the single yield reaches 82%.The gained tar resin is carried through water vapor and is heated up in a steamer wherein recyclings such as effective constituent benzothiazole, thiambutosine.
According to the material molar ratio proportioning is aniline: the ratio of sulphur: dithiocarbonic anhydride: 1:1:1 accurately takes by weighing aniline 280g, sulphur 96g, and dithiocarbonic anhydride 228.8g reclaims product 60g and inserts in the 1L autoclave.Feeding intake finishes, and kettle is sealed.Open and stir, rotating speed is made as 80r/min, slowly is warming up at 250 ℃, treats that pressure-stabilisation is in 8.0MPa afterreaction 160min.Reaction terminating, discharging hydrogen sulfide.After refining, get MBT product 427.5g, purity 98%, the single yield reaches 85%.
Embodiment 2:
According to the material molar ratio proportioning is aniline: the ratio of sulphur: dithiocarbonic anhydride: 1:1.2:1.1 accurately takes by weighing aniline 280g, sulphur 115g, and dithiocarbonic anhydride 251.7g inserts in the 1L autoclave.Feeding intake finishes, and kettle is sealed.Open and stir, rotating speed is made as 120r/min, slowly is warming up at 265 ℃, treats that pressure-stabilisation is in 9.8MPa afterreaction 240min.Reaction terminating, discharging hydrogen sulfide.After refining, get MBT product 417.3g, purity 98%, the single yield reaches 83%.The gained tar resin is carried through water vapor and is heated up in a steamer wherein recyclings such as effective constituent benzothiazole, thiambutosine.
According to the material molar ratio proportioning is aniline: the ratio of sulphur: dithiocarbonic anhydride: 1:1.2:1.1 accurately takes by weighing aniline 280g, sulphur 115g, and dithiocarbonic anhydride 251.7g reclaims product 15g and inserts in the 1L autoclave.Feeding intake finishes, and kettle is sealed.Open and stir, rotating speed is made as 120r/min, slowly be warming up at 245 ℃, and, treat that pressure-stabilisation is in 8.5Mpa afterreaction 200min.
Reaction terminating, discharging hydrogen sulfide.After refining, get MBT product 432g, purity 98.6%, yield reaches 86%.
Claims (1)
1. the method for an intermediate product reuse synthesis accelerant 2-mercaptobenzothiazole is characterized in that step is following:
1) take by weighing aniline, sulphur, dithiocarbonic anhydride and insert autoclave, the material molar ratio proportioning is an aniline: sulphur: dithiocarbonic anhydride is 1:1 ~ 1.5:1 ~ 2; Under temperature 260-270 ℃, rotating speed is at 80-300 rev/min, and pressure is kept under the situation of 9.5-10Mpa and reacted 120-240min, reaction synthesis accelerant MBT; The tarry resin that generates is carried heating up in a steamer to handle through water vapor and is obtained reclaiming effective constituent;
2) aniline, sulphur, dithiocarbonic anhydride, recovery effective constituent are inserted autoclave, the feed molar proportioning is an aniline: sulphur: dithiocarbonic anhydride is 1:1 ~ 1.5.:1 ~ 2, and reclaiming the effective constituent add-on is the 1%-10% of the total mass of the 3 kinds of raw materials in front; Stir and heat up, react 120-200min down at temperature 240-260 ℃, mixing speed is controlled at 80-300 commentaries on classics/min, and resulting pressure is 8.5-9.5MPa, and reaction finishes, discharging hydrogen sulfide, and melt obtains accelerant MBT through making with extra care.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211658A (en) * | 2014-09-15 | 2014-12-17 | 河南省开仑化工有限责任公司 | Novel preparation method of rubber vulcanization accelerator MBT |
| CN106967007A (en) * | 2017-03-06 | 2017-07-21 | 山东尚舜化工有限公司 | A kind of processing method of rubber accelerator M resins |
| CN110643065A (en) * | 2019-10-30 | 2020-01-03 | 山东尚舜化工有限公司 | Preparation method and application of porous easily-dispersed multifunctional composite rubber additive |
| CN113461638A (en) * | 2020-03-30 | 2021-10-01 | 中石化南京化工研究院有限公司 | Recycling method of accelerator M tar |
| CN116120258A (en) * | 2022-12-21 | 2023-05-16 | 彤程化学（中国）有限公司 | Purification method of accelerator M |
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| CN101220004A (en) * | 2008-02-03 | 2008-07-16 | 天津市科迈化工有限公司 | Commercial scale high pressure synthesis method for rubber vulcanization accelerant MBT |
| CN101245052A (en) * | 2008-03-14 | 2008-08-20 | 何连峰 | Method for extracting benzothiazole with by-product for producing 2-mercaptobenzothiazole |
| CN101759660A (en) * | 2009-11-16 | 2010-06-30 | 天津市科迈化工有限公司 | Highly-efficient synthetic method of rubber vulcanization accelerator MBT |
| CN102304098A (en) * | 2011-08-24 | 2012-01-04 | 科迈化工股份有限公司 | Method for extracting intermediate product from byproduct of production of 2-mercaptobenzothiazole (MBT) accelerator |
| CN102304099A (en) * | 2011-07-11 | 2012-01-04 | 南开大学 | Improved method for synthesizing 2-mercaptobenzothiazole derivative |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101220004A (en) * | 2008-02-03 | 2008-07-16 | 天津市科迈化工有限公司 | Commercial scale high pressure synthesis method for rubber vulcanization accelerant MBT |
| CN101245052A (en) * | 2008-03-14 | 2008-08-20 | 何连峰 | Method for extracting benzothiazole with by-product for producing 2-mercaptobenzothiazole |
| CN101759660A (en) * | 2009-11-16 | 2010-06-30 | 天津市科迈化工有限公司 | Highly-efficient synthetic method of rubber vulcanization accelerator MBT |
| CN102304099A (en) * | 2011-07-11 | 2012-01-04 | 南开大学 | Improved method for synthesizing 2-mercaptobenzothiazole derivative |
| CN102304098A (en) * | 2011-08-24 | 2012-01-04 | 科迈化工股份有限公司 | Method for extracting intermediate product from byproduct of production of 2-mercaptobenzothiazole (MBT) accelerator |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211658A (en) * | 2014-09-15 | 2014-12-17 | 河南省开仑化工有限责任公司 | Novel preparation method of rubber vulcanization accelerator MBT |
| CN104211658B (en) * | 2014-09-15 | 2019-05-10 | 河南省开仑化工有限责任公司 | The production method of new type rubber sulphur accelerant MBT |
| CN106967007A (en) * | 2017-03-06 | 2017-07-21 | 山东尚舜化工有限公司 | A kind of processing method of rubber accelerator M resins |
| CN110643065A (en) * | 2019-10-30 | 2020-01-03 | 山东尚舜化工有限公司 | Preparation method and application of porous easily-dispersed multifunctional composite rubber additive |
| CN113461638A (en) * | 2020-03-30 | 2021-10-01 | 中石化南京化工研究院有限公司 | Recycling method of accelerator M tar |
| CN113461638B (en) * | 2020-03-30 | 2023-10-13 | 中石化南京化工研究院有限公司 | Recycling method of accelerator M tar |
| CN116120258A (en) * | 2022-12-21 | 2023-05-16 | 彤程化学（中国）有限公司 | Purification method of accelerator M |
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Application publication date: 20121226 |