CN103739569A - Method for purifying rubber vulcanization accelerator MBT (2-mercaptobenzothiazole) - Google Patents
Method for purifying rubber vulcanization accelerator MBT (2-mercaptobenzothiazole) Download PDFInfo
- Publication number
- CN103739569A CN103739569A CN201410009840.4A CN201410009840A CN103739569A CN 103739569 A CN103739569 A CN 103739569A CN 201410009840 A CN201410009840 A CN 201410009840A CN 103739569 A CN103739569 A CN 103739569A
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- China
- Prior art keywords
- weight concentration
- mbt
- solution
- sodium salt
- clear
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- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000013040 rubber vulcanization Methods 0.000 title claims abstract description 8
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 title abstract description 55
- 239000000243 solution Substances 0.000 claims abstract description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 9
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000007664 blowing Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000001117 sulphuric acid Substances 0.000 claims description 10
- 235000011149 sulphuric acid Nutrition 0.000 claims description 10
- 238000002386 leaching Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- -1 MBT sodium salt Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for purifying a rubber vulcanization accelerator MBT (2-mercaptobenzothiazole). The method comprises the following steps: completely dissolving crude M by using a sodium hydroxide solution with the weight concentration of 30%, controlling the final pH of the sodium salt solution to be 9.5, adding deionized water to dilute, controlling the weight concentration of the sodium salt solution to be 3-8%, blowing and oxidizing for 1.5-2.5 hours, dropwise adding a sulfuric acid solution with the weight concentration of 1-3% at the speed of 1-3L/min at the same time till the pH is 9 and the solution is clear and transparent, filtering, heating the sodium salt solution to 25-95 DEG C till a clear and transparent state is achieved, dropwise adding a sulfuric acid solution with the weight concentration of 5-10% to neutralize till the pH is 5-7, filtering, dewatering, washing and drying the solid to obtain the finished product MBT. The method disclosed by the invention has the advantages that the method is simple in process and easy in industrialization; the purity of the prepared high content MBT is up to more than 99%.
Description
Technical field
The present invention relates to the method for purification of a kind of rubber vulcanization accelerant 2-mercaptobenzothiazole (MBT), belong to rubber vulcanization accelerant MBT purification techniques field.
Background technology
Along with the development of rubber industry, the research of vulcanization accelerator is more and more subject to people's attention with production.Vulcanization accelerator plays very important effect in Vulcanization Process of Rubber, it can accelerate reacting of rubber and vulcanizing agent greatly, boost productivity, also can improve the physical and mechanical properties of vulcanized rubber, MBT is the requisite a kind of primary accelerator of current rubber industry simultaneously.
Generally, the impurity in this promotor is mainly resin and intermediate product (as benzothiazole), and the existence of impurity makes quality product not high.Document (fine chemical material and intermediate, 2003,1:40) reported the method for refining MBT.Thick MBT melt is dissolved in the mixture of toluene and aqueous sodium hydroxide solution, then divides and be separated, use toluene aqueous phase extracted; With sulfuric acid, MBT is precipitated out from MBT sodium salt solution, can obtains refining MBT.This method can only be removed a small amount of resin and impurity, and the MBT purity after refining is not high.Refining out the MBT that foreign matter content is low, fusing point is high, melting range is short is the key that realizes refining MBT widespread use.
Summary of the invention
The method of purification that the object of the present invention is to provide a kind of rubber vulcanization accelerant MBT, the method is simple to operate, and the MBT purity that makes is high, fusing point is high, melting range is short.
The present invention is realized by following technical proposals:
The method of purification of rubber vulcanization accelerant MBT of the present invention, is characterized in that comprising following process:
1) with the sodium hydroxide solution of weight concentration 30%, thick M is dissolved completely, controlling M-Na salts solution terminal is PH=9.5;
2) add deionized water dilution, controlling sodium salt solution weight concentration is 3 ~ 8%;
3) blowing oxidation is 1.5 ~ 2.5 hours, drips weight concentration simultaneously and be 1 ~ 3% sulphuric acid soln, and rate of addition is 1 ~ 3L/min, drops to PH=9, solution clear;
4) cross leaching sodium salt liquid and be heated to 25 ~ 95 ℃, while reaching clear state, the sulphuric acid soln that to drip weight concentration be 5 ~ 10% is neutralized to PH=5 ~ 7, then crosses leaching solid through dehydration, washing, the dry finished product MBT of obtaining.
Blowing is in solution, to be blown into air with gas blower, provides oxygen to be oxidized, and the resin small-particle oxidation in suspension liquid is become to the cotton-shaped resin contamination precipitation of bulk thing, is deposited to container bottom, and solution reaches running balance, presents clear state.Filter out sodium salt liquid, be in order to remove resin precipitated thing, thereby remove most of impurity.Solution becomes muddiness again after a period of time, therefore will heat and make it again reach clear.
The invention has the advantages that: the method process is simple, is easy to industrialization, prepared high-content MBT purity reaches more than 99%, and the MBT purity that makes is high, fusing point is high, melting range is short.
Embodiment
Example 1:
The thick M that is 50～80% by mass content is molten through alkali is that the sodium hydroxide solution of weight concentration 30% dissolves thick M completely and PH=9.5, after add deionized water and be diluted to weight concentration 3%, then blow oxidation 1.5 hours, drip weight concentration simultaneously and be 3% sulphuric acid soln, rate of addition is 3L/min, drop to PH=9, solution clear.After filtration, M-Na salts solution is warming up to 25 ℃, while reaching clear state, then to drip weight concentration be that 10% sulphuric acid soln is neutralized to PH=5, then crosses leaching solid through dehydration, washing, the dry finished product MBT of obtaining.The mass content of this 2-mercaptobenzothiazole promotor is 99.1%, fusing point is 181.1 ℃.
Example 2:
The thick M that is 50～80% by mass content is molten through alkali is that the sodium hydroxide solution of weight concentration 30% dissolves thick M completely and PH=9.5, after add deionized water and be diluted to weight concentration 5%, then blow oxidation 2 hours, drip weight concentration simultaneously and be 2% sulphuric acid soln, rate of addition is 2L/min, drop to PH=9, solution clear.After filtration, M-Na salts solution is warming up to 55 ℃, while reaching clear state, then to drip weight concentration be that 8% sulphuric acid soln is neutralized to PH=6, after leaching solid through dewatering, wash, be drying to obtain finished product MBT.The mass content of this 2-mercaptobenzothiazole promotor is 99.3%, fusing point is 181.8 ℃.
Example 3:
The thick M that is 50～80% by mass content is molten through alkali is that the sodium hydroxide solution of weight concentration 30% dissolves thick M completely and PH=9.5, after add deionized water and be diluted to weight concentration 8%, then blow oxidation 2.5 hours, drip weight concentration simultaneously and be 1% sulphuric acid soln, rate of addition is 1L/min, drop to PH=9, solution clear.After filtration, M-Na salts solution is warming up to 95 ℃, while reaching clear state, then to drip weight concentration be that 5% sulphuric acid soln is neutralized to PH=7, after leaching solid through dewatering, wash, be drying to obtain finished product MBT.The mass content of this 2-mercaptobenzothiazole promotor is 99.7%, fusing point is 182.8 ℃.
Claims (1)
1. a method of purification for rubber vulcanization accelerant MBT, is characterized in that: comprise the following steps:
1) with the sodium hydroxide solution of weight concentration 30%, thick M is dissolved completely, controlling sodium salt solution terminal is PH=9.5;
2) add deionized water dilution, controlling sodium salt solution weight concentration is 3 ~ 8%;
3) blowing oxidation is 1.5 ~ 2.5 hours, drips weight concentration simultaneously and be 1 ~ 3% sulphuric acid soln, and rate of addition is 1 ~ 3L/min, drops to PH=9, solution clear;
4) cross leaching sodium salt liquid and be heated to 25 ~ 95 ℃, while reaching clear state, the sulphuric acid soln that to drip weight concentration be 5 ~ 10% is neutralized to PH=5 ~ 7, then crosses leaching solid through dehydration, washing, the dry finished product MBT of obtaining.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410009840.4A CN103739569B (en) | 2014-01-09 | 2014-01-09 | A kind of method of purification of rubber vulcanization accelerant MBT |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410009840.4A CN103739569B (en) | 2014-01-09 | 2014-01-09 | A kind of method of purification of rubber vulcanization accelerant MBT |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103739569A true CN103739569A (en) | 2014-04-23 |
| CN103739569B CN103739569B (en) | 2016-03-23 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410009840.4A Expired - Fee Related CN103739569B (en) | 2014-01-09 | 2014-01-09 | A kind of method of purification of rubber vulcanization accelerant MBT |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103739569B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110615773A (en) * | 2019-09-09 | 2019-12-27 | 山东尚舜化工有限公司 | Method for refining rubber accelerator MBT |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1631871A (en) * | 1923-08-07 | 1927-06-07 | Goodyear Tire & Rubber | Process of manufacturing mercapto-benzo-thiazole |
| CN1123277A (en) * | 1995-10-17 | 1996-05-29 | 杨秉德 | New method for refinement of crude 2-mercapto benzothiazole |
| CN101260087A (en) * | 2008-04-21 | 2008-09-10 | 天津市科迈化工有限公司 | Method for purifying rubber vulcanization accelerator MBT |
| CN101402615A (en) * | 2008-11-12 | 2009-04-08 | 山东阳谷华泰化工有限公司 | Fine purification method for rubber vulcanization accelerant 2-mercaptobenzothiazole (M) |
| CN101591305A (en) * | 2009-04-10 | 2009-12-02 | 天津市科迈化工有限公司 | The production method of high-content pharmaceutical grade MBT |
| CN102304099A (en) * | 2011-07-11 | 2012-01-04 | 南开大学 | Improved method for synthesizing 2-mercaptobenzothiazole derivative |
| CN102675242A (en) * | 2012-05-08 | 2012-09-19 | 中国石油化工股份有限公司 | Refining method of vulkacit M |
| 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 |
| CN102827102A (en) * | 2012-09-25 | 2012-12-19 | 科迈化工股份有限公司 | Refinement method of rubber vulcanization accelerator MBT (2-mercaptobenzthiazole) |
-
2014
- 2014-01-09 CN CN201410009840.4A patent/CN103739569B/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1631871A (en) * | 1923-08-07 | 1927-06-07 | Goodyear Tire & Rubber | Process of manufacturing mercapto-benzo-thiazole |
| CN1123277A (en) * | 1995-10-17 | 1996-05-29 | 杨秉德 | New method for refinement of crude 2-mercapto benzothiazole |
| CN101260087A (en) * | 2008-04-21 | 2008-09-10 | 天津市科迈化工有限公司 | Method for purifying rubber vulcanization accelerator MBT |
| CN101402615A (en) * | 2008-11-12 | 2009-04-08 | 山东阳谷华泰化工有限公司 | Fine purification method for rubber vulcanization accelerant 2-mercaptobenzothiazole (M) |
| CN101591305A (en) * | 2009-04-10 | 2009-12-02 | 天津市科迈化工有限公司 | The production method of high-content pharmaceutical grade MBT |
| CN102304099A (en) * | 2011-07-11 | 2012-01-04 | 南开大学 | Improved method for synthesizing 2-mercaptobenzothiazole derivative |
| CN102675242A (en) * | 2012-05-08 | 2012-09-19 | 中国石油化工股份有限公司 | Refining method of vulkacit M |
| 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 |
| CN102827102A (en) * | 2012-09-25 | 2012-12-19 | 科迈化工股份有限公司 | Refinement method of rubber vulcanization accelerator MBT (2-mercaptobenzthiazole) |
Non-Patent Citations (1)
| Title |
|---|
| 刘秀兰 等: "促进剂M精制新工艺研究", 《甘肃科技》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110615773A (en) * | 2019-09-09 | 2019-12-27 | 山东尚舜化工有限公司 | Method for refining rubber accelerator MBT |
| CN110615773B (en) * | 2019-09-09 | 2022-12-09 | 山东尚舜化工有限公司 | Method for refining rubber accelerator MBT |
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| Publication number | Publication date |
|---|---|
| CN103739569B (en) | 2016-03-23 |
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Granted publication date: 20160323 |