CN112661721A - New process for synthesizing 2-mercaptobenzothiazole zinc salt by solvent method - Google Patents
New process for synthesizing 2-mercaptobenzothiazole zinc salt by solvent method Download PDFInfo
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- CN112661721A CN112661721A CN202110070271.4A CN202110070271A CN112661721A CN 112661721 A CN112661721 A CN 112661721A CN 202110070271 A CN202110070271 A CN 202110070271A CN 112661721 A CN112661721 A CN 112661721A
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- Prior art keywords
- mercaptobenzothiazole
- synthesizing
- zinc salt
- catalyst
- solvent method
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- 238000000034 method Methods 0.000 title claims abstract description 34
- PGNWIWKMXVDXHP-UHFFFAOYSA-L zinc;1,3-benzothiazole-2-thiolate Chemical compound [Zn+2].C1=CC=C2SC([S-])=NC2=C1.C1=CC=C2SC([S-])=NC2=C1 PGNWIWKMXVDXHP-UHFFFAOYSA-L 0.000 title claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 11
- 239000002904 solvent Substances 0.000 title claims abstract description 9
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims abstract description 29
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000010992 reflux Methods 0.000 claims abstract description 9
- 239000011787 zinc oxide Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002351 wastewater Substances 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- GIUBHMDTOCBOPA-UHFFFAOYSA-N 3h-1,3-benzothiazole-2-thione;zinc Chemical compound [Zn].C1=CC=C2SC(S)=NC2=C1 GIUBHMDTOCBOPA-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N alpha-methyl toluene Natural products CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention belongs to the technical field of rubber accelerators, and discloses a novel process for synthesizing 2-mercaptobenzothiazole zinc salt by a solvent method, which comprises the following steps: adding raw materials 2-mercaptobenzothiazole and zinc oxide into an organic solvent, adding a catalyst, heating to reflux under normal pressure, reacting for 2-3 h, filtering and drying to obtain a light yellow solid. The process by-product only contains a small amount of pollution-free water, and compared with the traditional process, the process does not produce waste salt, reduces the generation of waste water, realizes clean production and reduces the production cost.
Description
Technical Field
The invention belongs to the technical field of rubber accelerators, and relates to a novel process for synthesizing 2-mercaptobenzothiazole zinc salt by a solvent method.
Background
The main production method of the 2-mercaptobenzothiazole zinc salt at the present stage is as follows: and dissolving the accelerator M (2-mercaptobenzothiazole) in a sodium hydroxide solution to generate sodium salt, then dropwise adding zinc sulfate to perform double decomposition reaction to finally obtain 2-mercaptobenzothiazole zinc salt (ZMBT), wherein the accompanying byproducts are a large amount of polluted salt and wastewater. The cost for treating the wastewater gradually rises, the environmental protection is more strict, and the comprehensive production cost rises. Therefore, a new clean and environment-friendly synthesis process of the 2-mercaptobenzothiazole zinc salt is needed.
Disclosure of Invention
The invention aims to provide a novel process for synthesizing 2-mercaptobenzothiazole zinc salt by a solvent method, wherein a byproduct of the process only contains a small amount of pollution-free water, and compared with the traditional process, the process does not produce waste salt, reduces the generation of waste water, realizes clean production and reduces the production cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a new process for synthesizing 2-mercaptobenzothiazole zinc salt by a solvent method, which comprises the following steps: adding raw materials 2-mercaptobenzothiazole and zinc oxide into an organic solvent, adding a catalyst, heating and refluxing for 2-3 h under normal pressure, and filtering and drying to obtain a light yellow solid.
The reaction equation for the above reaction is as follows:
preferably, the molar ratio of the 2-mercaptobenzothiazole to the zinc oxide is 1: 0.5-0.55.
Preferably, the mass ratio of the 2-mercaptobenzothiazole to the catalyst is 1: 0.005-0.01.
Preferably, the catalyst is glacial acetic acid or propionic acid.
Preferably, the organic solvent is benzene, toluene or ethyl acetate.
Compared with the prior art, the invention has the beneficial effects that:
the method adopts a solvent method to synthesize a target product MZ by a one-step method, the product yield is more than or equal to 97 percent, the melting point is more than or equal to 220 ℃, the product purity is high, and the production period is short; the process by-product only contains a small amount of pollution-free water, compared with the traditional process, no waste salt is generated, the generation of waste water is reduced, the clean production is realized, and the production cost is reduced; the process does not use strong acid and strong base, and does not corrode equipment.
Detailed Description
The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. The test methods in the following examples are conventional methods unless otherwise specified.
Reagents used in the following examples: 1) 2-mercaptobenzothiazole: the product is a light yellow powdery solid, has an initial melting point of not less than 174 ℃, is nontoxic and bitter, is insoluble in water, and is partially soluble in organic solvents such as ethanol, diethyl ether, acetone, ethyl acetate, benzene and the like. 2) Zinc oxide: white solid with content not less than 99.7%, is insoluble in water, and is soluble in acid and alkali. 3) Organic solvent: and industrial solvents are adopted for toluene, ethyl acetate and the like. 4) The catalyst glacial acetic acid or propionic acid, analytically pure.
Example one
88.13 g (0.5 mol) of 2-mercaptobenzothiazole, 20.7g (0.26 mol) of zinc oxide, 500ml of toluene solvent and 0.5g of catalyst glacial acetic acid are added into a four-mouth reaction bottle, a condensation reflux water diversion device is added, a rubber plug is used for sealing, the mixture is heated to a reflux state under normal pressure, the reaction is completed after 3 hours, and the product, namely the light yellow solid ZMBT, is obtained after the processes of filtering and drying. The reaction yield is 97.6 percent and the initial melting point is 220.8 ℃ through detection.
Example two
100 g (0.57 mol) of 2-mercaptobenzothiazole, 23.4g (0.29 mol) of zinc oxide, 500ml of ethyl acetate solvent and 0.5g of glacial acetic acid serving as a catalyst are added into a four-mouth reaction bottle, a condensation reflux water diversion device is added, a rubber plug is used for sealing, the mixture is heated to a reflux state under normal pressure, the reaction is completed after 3 hours, and a product, namely a light yellow solid ZMBT, is obtained through the processes of filtering and drying. The reaction yield was determined to be 98.1% with an initial melting point of 222.7 ℃.
EXAMPLE III
88.13 g (0.5 mol) of 2-mercaptobenzothiazole, 20.7g (0.26 mol) of zinc oxide, 500ml of toluene solvent and 0.5g of catalyst propionic acid are added into a four-mouth reaction bottle, a condensation reflux water diversion device is added, a rubber plug is used for sealing, the mixture is heated to a reflux state under normal pressure, the reaction is completed after 3 hours, and a product, namely a light yellow solid ZMBT, is obtained after the processes of filtering and drying. The reaction yield was determined to be 98.4% with an initial melting point of 222.5 ℃.
The above-mentioned embodiments are merely preferred embodiments of the present invention, which are merely illustrative and not restrictive, and it should be understood that other embodiments may be easily made by those skilled in the art by replacing or changing the technical contents disclosed in the specification, and therefore, all changes and modifications that are made on the principle of the present invention should be included in the scope of the claims of the present invention.
Claims (5)
1. A new process for synthesizing 2-mercaptobenzothiazole zinc salt by a solvent method is characterized by comprising the following steps: adding raw materials 2-mercaptobenzothiazole and zinc oxide into an organic solvent, adding a catalyst, heating and refluxing for 2-3 h under normal pressure, and filtering and drying to obtain a light yellow solid.
2. The novel process for synthesizing the zinc salt of 2-mercaptobenzothiazole according to claim 1, wherein the molar ratio of 2-mercaptobenzothiazole to zinc oxide is 1: 0.5-0.55.
3. The novel process for synthesizing the zinc salt of 2-mercaptobenzothiazole according to claim 1, wherein the mass ratio of the 2-mercaptobenzothiazole to the catalyst is 1: 0.005-0.01.
4. The novel process for synthesizing 2-mercaptobenzothiazole zinc salt according to claim 1, wherein said catalyst is glacial acetic acid or propionic acid.
5. The novel process for synthesizing 2-mercaptobenzothiazole zinc salt according to claim 1, wherein the organic solvent is benzene, toluene or ethyl acetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110070271.4A CN112661721A (en) | 2021-01-19 | 2021-01-19 | New process for synthesizing 2-mercaptobenzothiazole zinc salt by solvent method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110070271.4A CN112661721A (en) | 2021-01-19 | 2021-01-19 | New process for synthesizing 2-mercaptobenzothiazole zinc salt by solvent method |
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|---|---|
| CN112661721A true CN112661721A (en) | 2021-04-16 |
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|---|---|---|---|
| CN202110070271.4A Pending CN112661721A (en) | 2021-01-19 | 2021-01-19 | New process for synthesizing 2-mercaptobenzothiazole zinc salt by solvent method |
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| CN (1) | CN112661721A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124488A (en) * | 2022-03-16 | 2022-09-30 | 鹤壁中昊新材料科技有限公司 | Synthesis process of high-purity 2-mercaptobenzothiazole zinc with controllable particle size |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50129552A (en) * | 1974-03-19 | 1975-10-13 | ||
| SU1397442A1 (en) * | 1985-08-14 | 1988-06-15 | Березниковский Филиал Научно-Исследовательского Института Химикатов Для Полимерных Материалов | Method of producing zinc salt of 2-mercaptobenzothiazole |
| US6139610A (en) * | 1996-01-05 | 2000-10-31 | Wayne Pigment Corp. | Hybrid pigment grade corrosion inhibitor compositions and procedures |
| CN103510104A (en) * | 2013-09-29 | 2014-01-15 | 浙江工业大学 | Method for synthesizing 2-mercaptobenzothiazole metal compound |
| CN103772316A (en) * | 2013-12-31 | 2014-05-07 | 浙江工业大学 | Ball-milling synthesis method of mercaptothiazole metal compound |
| CN104592154A (en) * | 2013-10-30 | 2015-05-06 | 青岛旺裕橡胶制品有限公司 | Preparation method of rubber promoter 2-mercaptobenzothiazole |
| CN107810974A (en) * | 2017-11-14 | 2018-03-20 | 江苏师范大学 | A kind of efficient compound air purifying preparation |
| CN108239042A (en) * | 2017-12-16 | 2018-07-03 | 成都韦恩斯科技有限公司 | The process units of vulcanization accelerator 2-mercaptobenzothiazole zinc salt |
| CN111116512A (en) * | 2019-12-27 | 2020-05-08 | 鹤壁中昊新材料科技有限公司 | Preparation method of organic zinc salt containing nitrogen and sulfur benzo heterocycle |
-
2021
- 2021-01-19 CN CN202110070271.4A patent/CN112661721A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50129552A (en) * | 1974-03-19 | 1975-10-13 | ||
| SU1397442A1 (en) * | 1985-08-14 | 1988-06-15 | Березниковский Филиал Научно-Исследовательского Института Химикатов Для Полимерных Материалов | Method of producing zinc salt of 2-mercaptobenzothiazole |
| US6139610A (en) * | 1996-01-05 | 2000-10-31 | Wayne Pigment Corp. | Hybrid pigment grade corrosion inhibitor compositions and procedures |
| CN103510104A (en) * | 2013-09-29 | 2014-01-15 | 浙江工业大学 | Method for synthesizing 2-mercaptobenzothiazole metal compound |
| CN104592154A (en) * | 2013-10-30 | 2015-05-06 | 青岛旺裕橡胶制品有限公司 | Preparation method of rubber promoter 2-mercaptobenzothiazole |
| CN103772316A (en) * | 2013-12-31 | 2014-05-07 | 浙江工业大学 | Ball-milling synthesis method of mercaptothiazole metal compound |
| CN107810974A (en) * | 2017-11-14 | 2018-03-20 | 江苏师范大学 | A kind of efficient compound air purifying preparation |
| CN108239042A (en) * | 2017-12-16 | 2018-07-03 | 成都韦恩斯科技有限公司 | The process units of vulcanization accelerator 2-mercaptobenzothiazole zinc salt |
| CN111116512A (en) * | 2019-12-27 | 2020-05-08 | 鹤壁中昊新材料科技有限公司 | Preparation method of organic zinc salt containing nitrogen and sulfur benzo heterocycle |
Non-Patent Citations (1)
| Title |
|---|
| RICARDO BAGGIO ET AL.: "Interaction of Zinc and Cadmium Bis(benzothiazoIe-2- thiolates) with Nitrogen Bases" * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124488A (en) * | 2022-03-16 | 2022-09-30 | 鹤壁中昊新材料科技有限公司 | Synthesis process of high-purity 2-mercaptobenzothiazole zinc with controllable particle size |
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Application publication date: 20210416 |
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