CN102391205A - Method for synthesizing rubber vulcanization accelerant 2-mercaptobenzothiazole - Google Patents
Method for synthesizing rubber vulcanization accelerant 2-mercaptobenzothiazole Download PDFInfo
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- CN102391205A CN102391205A CN2011102801763A CN201110280176A CN102391205A CN 102391205 A CN102391205 A CN 102391205A CN 2011102801763 A CN2011102801763 A CN 2011102801763A CN 201110280176 A CN201110280176 A CN 201110280176A CN 102391205 A CN102391205 A CN 102391205A
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Abstract
The invention provides a method for synthesizing a rubber vulcanization accelerant 2-mercaptobenzothiazole (MBT). Aniline, sulfur and carbon disulfide are used as synthesis raw materials, and the mass ratio of the aniline to the sulfur to the carbon disulfide is 1: (2-4): (1-2). The method comprises the following steps of: stirring and heating the raw materials, reacting for 100 to 300 minutes at the temperature of between 230 and 250 DEG C, controlling the stirring revolving speed at 40 to 1,000 revolutions per minute, controlling the pressure at 6 to 8MPa, and discharging hydrogen sulfide after the reaction is finished; pressing the melt into an extraction kettle filled with carbon disulfide in a volume which is 2 to 5 times that of the melt, and extracting, wherein the extracting temperature is 10 to 50 DEG C, the extracting time is 20 to 50 minutes, and the recovery rate of the sulfur is 10 to 80 percent; and distilling and recovering the carbon disulfide containing sulfur after filtration, and conveying the sulfur of a certain proportion to the reaction stage after the sulfur is separated out. The method is mild in reaction conditions; compared with a small proportion process, the method has the advantages of greatly reducing the reaction pressure and the reaction temperature and reducing equipment pressure and investment; and side reaction is reduced, the reaction yield is relatively high and reaches over 89 percent, and the purity of the prepared MBT product reaches over 98 percent.
Description
Technical field
The present invention relates to the new synthetic method of a kind of thiofide 2-mercaptobenzothiazole (MBT), belong to the rubber vulcanization accelerant MBT synthesis technical field.
Background technology
Along with the development of rubber industry, the research of vulcanization accelerator more and more receives people's attention with production.Vulcanization accelerator plays important effect in vulcanization of rubber process; It can accelerate the reaction of rubber and vulcanizing agent greatly; Boost productivity, also can improve the physical and mechanical properties of vulcanized rubber simultaneously, MBT is the requisite a kind of primary accelerator of present rubber industry.Generally, the MBT production technique is an aniline process, is about to certain proportioning aniline, sulphur, dithiocarbonic anhydride and inserts autoclave, and reaction certain hour under HTHP is through acid-base method purified product MBT.This technological reaction condition is harsh; Be difficult to control, the MBT yield is merely about 85%, also generates 15% tar by product; Be mainly the by product of unreacted aniline, sulphur intermediate product thiambutosine and benzothiazole etc. and other complicated components, the existence of impurity makes quality product not high.Auxiliary agent enterprise and research institutions have also made many improvement to the MBT production technique both at home and abroad in recent years.Being primarily aimed at reaction raw materials, reaction ratio, reaction conditions is optimized.But the result is not satisfactory; There is patent (US 3975394) to point out that benzothiazole can continue reaction with sulphur and generate 2-mercaptobenzothiazole; Therefore the sulphur proportioning strengthens in considering to react, and makes it to continue reaction with benzothiazole on the one hand and generates MBT, can suppress side reaction on the other hand and produce; Reduce by product, thereby improve reaction yield.But owing to after strengthening the sulphur proportioning, add the sulphur amount greater than the required sulphur amount of reaction, superfluous sulphur needs to handle, otherwise causes the wasting of resources, and contaminate environment.Effective measures are that sulphur recycles.Document is arranged, and (the journal V22 of Northwest Institute for Ethnic Minorities No3) has reported that big proportioning sulphur synthesizes MBT, and drawing optimum reaction condition in the report is 240～260 ℃ of temperature of reaction, reaction pressure 9.0～10.0Mpa, reaction times 3h, aniline: CS
2: S (mol ratio)=1: 1.1: 2.3, yield is increased to 86%.But its reaction conditions still carries out under HTHP, and the yield that improves M for a nearly step reduces reaction conditions, and my company is also studied the synthetic MBT technology of big proportioning sulphur.
Because the increase of the usage quantity of sulphur; Can cause and contain a large amount of unreacted sulphur in the resultant, thereby the M content of MBT reaction under high pressure resultant can all reduce, can not accurate response go out the quality of reaction result; So the yield that all uses M among the present invention is index as a reference, its method of calculation are following:
Wherein: m
M---the weight of gained MBT product in the experiment, g;
m
B---the charging capacity of aniline, g;
M
M---the molecular weight of MBT, M
M=167.24;
M
B---the molecular weight of aniline, M
B=93.13.
Summary of the invention
The object of the present invention is to provide a kind of new synthetic method of rubber vulcanization accelerant MBT, this method mild condition is easy to control, and the MBT purity that makes is high, fusing point is high, melting range is short, yield is high.
For achieving the above object, the present invention realizes through following technical proposals:
The compound method of a kind of rubber vulcanization accelerant MBT of the present invention, synthesis material are aniline, sulphur and dithiocarbonic anhydride, and raw material mass mixture ratio is an aniline: sulphur: dithiocarbonic anhydride is 1: 2～4: 1～2; With raw material stirring, intensification, react 100～300min down for 230～250 ℃ in temperature, mixing speed is controlled at 40～1000 commentaries on classics/min, and pressure is 6～8MPa, and reaction finishes, discharging hydrogen sulfide; Melt is pressed in the extraction with carbon disulfide still that is equipped with 2～5 times of volumes and extracts; Extraction temperature is 10～50 ℃, and the extraction time is 20～50min; The recovery sulier ratio is 10%-80% in the sulphur.
Extraction is filtered after finishing, and the dithiocarbonic anhydride distillation that contains sulphur after the filtration is reclaimed, and sulphur is separated out the entering step of reaction.
The quality proportioning of preferred sulphur is 2.5～3.2.The ratio of preferred recovery sulier is 60～75%.
Feed intake first and begin to add that the recovery sulier ratio is 10%-80% (weight percent) recovery sulier, the sulphur for fresh sulphur, from reaction for the second time.
The dithiocarbonic anhydride distillation that contains sulphur after the filtration is reclaimed, and sulphur is separated out back (being recovery sulier) and got into step of reaction with certain proportion.Filter cake gets product after washing, drying, purity reaches more than 98%.
The invention has the advantages that: reaction conditions is gentle, and reaction pressure and temperature have been compared with little proportioning process significantly and descended, and have reduced equipment pressure and investment; Side reaction reduces, and reaction yield is higher, reaches more than 89%, and prepared MBT product purity reaches more than 98%.
Embodiment
Embodiment 1:
According to the material molar ratio proportioning is aniline: sulphur: dithiocarbonic anhydride: 1: 3: 1 ratio accurately takes by weighing aniline 280g, fresh sulphur 289g, 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 1000r/min, slowly is warming up at 240 ℃, treats that pressure-stabilisation is in 6.0MPa afterreaction 120min.Reaction terminating, discharging hydrogen sulfide.Melt is pressed in the extraction kettle that fills 1400g dithiocarbonic anhydride and extracts.Filter the back mother liquid evaporation and get recovery sulier 190g.Filter cake gets product 447.5g after washing, drying, purity 98%, and yield reaches 86%.
Embodiment 2:
According to the material molar ratio proportioning is aniline: sulphur: dithiocarbonic anhydride: 1: 2.0: 1.1 ratio accurately takes by weighing aniline 280g, fresh sulphur 190g, and dithiocarbonic anhydride 252g, recovery sulier 10.5g accounts for total sulphur amount 10%, inserts in the 1L autoclave.Feeding intake finishes, and kettle is sealed.Open and stir, rotating speed is made as 40r/min, slowly is warming up at 230 ℃, treats that pressure-stabilisation is in 8.0MPa afterreaction 300min.Reaction terminating, discharging hydrogen sulfide.Melt is pressed in the extraction kettle that fills 1500g dithiocarbonic anhydride and extracts.Filter the back mother liquid evaporation and get recovery sulier 105g.Filter cake gets product 445g after washing, drying, purity 97.8%, and the single yield reaches 88.6%.
Embodiment 3:
According to the material molar ratio proportioning is aniline: sulphur: dithiocarbonic anhydride: 1: 4: 2 ratio accurately takes by weighing aniline 280g, fresh sulphur 77g, and dithiocarbonic anhydride 457.6g, recovery sulier 324.6g accounts for 80% of total sulphur amount, inserts in the 1L autoclave.Feeding intake finishes, and kettle is sealed.Open and stir, rotating speed is made as 200r/min, slowly is warming up at 250 ℃, treats that pressure-stabilisation is in 7.8MPa afterreaction 100min.Reaction terminating, discharging hydrogen sulfide.Melt is pressed in the extraction kettle that fills 2000g dithiocarbonic anhydride and extracts.Filter the back mother liquid evaporation and get recovery sulier 294g.Filter cake gets product 456g after washing, drying, purity 98.2%, and the single yield reaches 93%.
Embodiment 4:
According to the material molar ratio proportioning is aniline: sulphur: dithiocarbonic anhydride: 1: 2.8: 2 ratio accurately takes by weighing aniline 280g, fresh sulphur 69.4g, and dithiocarbonic anhydride 457.6g, recovery sulier 210g accounts for 75% of total sulphur amount, inserts in the 1L autoclave.Feeding intake finishes, and kettle is sealed.Open and stir, rotating speed is made as 300r/min, slowly is warming up at 245 ℃, treats that pressure-stabilisation is in 7.5MPa afterreaction 100min.Reaction terminating, discharging hydrogen sulfide.Melt is pressed in the extraction kettle that fills 2000g dithiocarbonic anhydride and extracts.Filter the back mother liquid evaporation and get recovery sulier 184g.Filter cake gets product 498g after washing, drying, purity 98.1%, and the single yield reaches 94%.
Embodiment 5:
According to the material molar ratio proportioning is aniline: sulphur: dithiocarbonic anhydride: 1: 3: 2 ratio accurately takes by weighing aniline 280g, fresh sulphur 115.6g, and dithiocarbonic anhydride 457.6g, recovery sulier 173g accounts for 60% of total sulphur amount, inserts in the 1L autoclave.Feeding intake finishes, and kettle is sealed.Open and stir, rotating speed is made as 300r/min, slowly is warming up at 245 ℃, treats that pressure-stabilisation is in 7.5MPa afterreaction 100min.Reaction terminating, discharging hydrogen sulfide.Melt is pressed in the extraction kettle that fills 2000g dithiocarbonic anhydride and extracts.Filter the back mother liquid evaporation and get recovery sulier 184g.Filter cake gets product 462.6g after washing, drying, purity 98.5%, and the single yield reaches 92%.
Although above the preferred embodiments of the present invention are described; But the present invention is not limited to above-mentioned embodiment, and above-mentioned embodiment only is schematically, is not restrictive; Those of ordinary skill in the art is under enlightenment of the present invention; Not breaking away under the scope situation that aim of the present invention and claim protect, can also make the concrete conversion of a lot of forms, these all belong within protection scope of the present invention.
Claims (4)
1. the compound method of a thiofide 2-mercaptobenzothiazole is characterized in that synthesis material is aniline, sulphur and dithiocarbonic anhydride, and raw material mass mixture ratio is an aniline: sulphur: dithiocarbonic anhydride is 1: 2～4: 1～2; With raw material stirring, intensification, react 100～300min down for 230～250 ℃ in temperature, mixing speed is controlled at 40～1000 commentaries on classics/min, and pressure is 6～8MPa, and reaction finishes, discharging hydrogen sulfide; Melt is pressed in the extraction with carbon disulfide still that is equipped with 2～5 times of volumes and extracts; Extraction temperature is 10～50 ℃, and the extraction time is 20～50min; The recovery sulier ratio is 10%-80% in the sulphur.
2. the method for claim 1 is characterized in that the quality proportioning of sulphur is 2.5～3.2.
3. the method for claim 1 is characterized in that filtering after extraction finishes, and the dithiocarbonic anhydride distillation that contains sulphur after the filtration is reclaimed, and sulphur is separated out the entering step of reaction.
4. like the described method of claim 1～3, the ratio that it is characterized in that said sulphur is 60～75%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718729A (en) * | 2012-07-01 | 2012-10-10 | 山东尚舜化工有限公司 | Method for producing refining M by calcium salt method |
| CN102827101A (en) * | 2012-09-25 | 2012-12-19 | 科迈化工股份有限公司 | Purification method of rubber vulcanization accelerator MBT (2-mercaptobenzthiazole) |
| 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 |
| CN106518803A (en) * | 2016-10-08 | 2017-03-22 | 扬中市橡胶塑料厂有限公司 | Rubber vulcanization accelerator for high-abrasion-resistance rubber sealing piece production |
| CN107629024A (en) * | 2017-10-13 | 2018-01-26 | 山东尚舜化工有限公司 | A kind of continuous synthesizer of rubber vulcanization accelerator M and its production technology |
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| US3975394A (en) * | 1974-11-14 | 1976-08-17 | American Cyanamid Company | Process for 2-mercaptobenzothiazole |
| CN101638396A (en) * | 2008-08-01 | 2010-02-03 | 河南省开仑化工有限责任公司 | Production process for rubber accelerator 2-thiol group benzothiazole |
| CN101693701A (en) * | 2009-10-21 | 2010-04-14 | 山东阳谷华泰化工股份有限公司 | Purification process for vulcanization accelerator 2-mercaptobenzothiazole |
-
2011
- 2011-09-20 CN CN2011102801763A patent/CN102391205A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US3975394A (en) * | 1974-11-14 | 1976-08-17 | American Cyanamid Company | Process for 2-mercaptobenzothiazole |
| CN101638396A (en) * | 2008-08-01 | 2010-02-03 | 河南省开仑化工有限责任公司 | Production process for rubber accelerator 2-thiol group benzothiazole |
| CN101693701A (en) * | 2009-10-21 | 2010-04-14 | 山东阳谷华泰化工股份有限公司 | Purification process for vulcanization accelerator 2-mercaptobenzothiazole |
Non-Patent Citations (1)
| Title |
|---|
| 范文革: "硫化促进剂M合成新工艺研究", 《西北民族学院学报（自然科学版）》, vol. 22, no. 3, 30 September 2001 (2001-09-30) * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718729A (en) * | 2012-07-01 | 2012-10-10 | 山东尚舜化工有限公司 | Method for producing refining M by calcium salt method |
| CN102718729B (en) * | 2012-07-01 | 2014-09-03 | 山东尚舜化工有限公司 | Method for producing refining M by calcium salt method |
| CN102827101A (en) * | 2012-09-25 | 2012-12-19 | 科迈化工股份有限公司 | Purification method of rubber vulcanization accelerator MBT (2-mercaptobenzthiazole) |
| 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 |
| CN106518803A (en) * | 2016-10-08 | 2017-03-22 | 扬中市橡胶塑料厂有限公司 | Rubber vulcanization accelerator for high-abrasion-resistance rubber sealing piece production |
| CN107629024A (en) * | 2017-10-13 | 2018-01-26 | 山东尚舜化工有限公司 | A kind of continuous synthesizer of rubber vulcanization accelerator M and its production technology |
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Application publication date: 20120328 |