CN108586384A - Dioxygen oxidation method prepares rubber vulcanizing accelerator TBBS - Google Patents
Dioxygen oxidation method prepares rubber vulcanizing accelerator TBBS Download PDFInfo
- Publication number
- CN108586384A CN108586384A CN201810668925.1A CN201810668925A CN108586384A CN 108586384 A CN108586384 A CN 108586384A CN 201810668925 A CN201810668925 A CN 201810668925A CN 108586384 A CN108586384 A CN 108586384A
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- CN
- China
- Prior art keywords
- tbbs
- oxidation method
- accelerator tbbs
- dioxygen oxidation
- rubber vulcanizing
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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
- C07D277/76—Sulfur atoms attached to a second hetero atom
- C07D277/80—Sulfur atoms attached to a second hetero atom to a nitrogen atom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Processing Of Solid Wastes (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to thiofide preparing technical fields, and in particular to a kind of dioxygen oxidation method prepares rubber vulcanizing accelerator TBBS, and tert-butylamine and accelerant MBT are uniformly mixed, and using acetate as catalyst, oxygen reacts 2 ~ 3h as oxidant；It is filtered after being cooled to room temperature, filters out catalyst；A certain amount of water is added into filtrate, stands 8 ~ 12h, filtering drying is to get TBBS；Filtrate in previous step is distilled, tert-butylamine is recycled.The present invention, as oxidant, not will produce a large amount of waste water with high salt and rich in organic matter, alleviate the wastewater treatment pressure in workshop, while also reducing the production cost of enterprise, and yield can reach 95% or so using oxygen cheap and easy to get.
Description
Technical field
The present invention relates to thiofide preparing technical fields, and in particular to a kind of dioxygen oxidation method prepares rubber sulphur
Change accelerator TBBS.
Background technology
Thiofide N- tertiary butyl benzos thiazolesulfenamide (TBBS or NS), is with primary amine structure
Organic matter, nitrosamine toxicant is generated in the middle part of sulfidation, after being a kind of sulfenamide of high comprehensive performance
Effect property thiofide.The existing production technology of TBBS according to the difference of oxidant can be divided into time sodium method, peroxide passivation,
Three kinds of oxygen method.Secondary sodium method will produce a large amount of waste water with high salt and rich in organic matter, it is difficult to handle, pollute environment；Peroxide passivation
Yield it is relatively low always, industrialized production can not be carried out.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of dioxygen oxidation methods to prepare thiofide
TBBS, product are water, avoid the pollution of a large amount of inorganic salts, and yield can reach 95% or so.
In order to solve the above-mentioned technical problem, the present invention is achieved by the following technical solutions：A kind of dioxygen oxidation legal system
Standby rubber vulcanizing accelerator TBBS, includes the following steps：
（1）（1）A certain amount of tert-butylamine is put into autoclave, and a certain amount of accelerant MBT and vinegar are added under stiring
Phosphate catalyst stirs evenly；
（2）60 ~ 80 DEG C are heated to, is passed through oxygen under stiring, when pressure reaches 0.6 ~ 0.7 MPa in autoclave, is stopped
Only lead to oxygen, when the pressure in autoclave is less than 0.2MPa, oxygen is passed through again, repeatedly repeatedly, until reaction under high pressure
Pressure in kettle no longer changes, and the reaction time is 2 ~ 3h；
（3）It is cooled to room temperature, is filtered, filter out thick accelerator TBBS, filtrate enters collecting tank；
（4）It is added a certain amount of water into accelerator TBBS, filtering is to get TBBS filter cakes, then drying TBBS；
（5）By step（3）、（4）In filtrate distilled, vapo(u)rizing temperature be 30 ~ 50 DEG C, recycle tert-butylamine.
Preferably, the molar ratio of the accelerant MBT and tert-butylamine is 1：20~25.
Preferably, the quality of the acetate catalyst is the 8% ~ 10% of accelerant MBT quality.
Preferably, the acetate catalyst is one kind in copper acetate or lead acetate or zinc acetate.
Preferably, the step（4）The mass ratio of the middle quality that water is added and crude product is 2 ~ 3:1.
Compared with prior art, the beneficial effects of the invention are as follows：The present invention using oxygen cheap and easy to get as oxidant,
It not will produce a large amount of waste water with high salt and rich in organic matter, alleviate the wastewater treatment pressure in workshop, while also reducing enterprise
Production cost, and yield can reach 95% or so.
Specific implementation mode
Embodiment described here is some preferred implementation methods, for further describing and demonstrating the present invention, it is not intended to
Limit the invention to the details of following determinations.
Embodiment 1：
（1）The tert-butylamine that 167.9kg is put into autoclave, is added 16.7kg accelerant MBTs and 1.5kg vinegar under stiring
Sour copper catalyst, stirs evenly；
（2）70 DEG C are heated to, is passed through oxygen under stiring, when pressure reaches 0.65 MPa in autoclave, stops leading to oxygen,
When the pressure in autoclave is less than 0.2MPa, it is passed through oxygen again, repeatedly repeatedly, until the pressure in autoclave
Power no longer changes, reaction time 2.5h；
（3）It is cooled to room temperature, is filtered, filter out thick accelerator TBBS, filtrate enters collecting tank；
（4）The water of 465L is added into accelerator TBBS, filtering is to get TBBS filter cakes, then drying TBBS；
（5）By step（3）、（4）In filtrate distilled, vapo(u)rizing temperature be 40 DEG C, recycle tert-butylamine.
Embodiment 2：
（1）The tert-butylamine that 146kg is put into autoclave, is added 16.7kg accelerant MBTs and 1.34kg vinegar under stiring
Lead plumbate catalyst, stirs evenly；
（2）60 DEG C are heated to, is passed through oxygen under stiring, when pressure reaches 0.65 MPa in autoclave, stops leading to oxygen,
When the pressure in autoclave is less than 0.2MPa, it is passed through oxygen again, repeatedly repeatedly, until the pressure in autoclave
Power no longer changes, reaction time 3h；
（3）It is cooled to room temperature, is filtered, filter out thick accelerator TBBS, filtrate enters collecting tank；
（4）The water of 300L is added into accelerator TBBS, filtering is to get TBBS filter cakes, then drying TBBS；
（5）By step（3）、（4）In filtrate distilled, vapo(u)rizing temperature be 45 DEG C, recycle tert-butylamine.
Embodiment 3：
（1）The tert-butylamine that 182.5kg is put into autoclave, is added 16.7kg accelerant MBTs and 1.67kg under stiring
Zinc acetate catalyst stirs evenly；
（2）80 DEG C are heated to, is passed through oxygen under stiring, when pressure reaches 0.65 MPa in autoclave, stops leading to oxygen,
When the pressure in autoclave is less than 0.2MPa, it is passed through oxygen again, repeatedly repeatedly, until the pressure in autoclave
Power no longer changes, reaction time 2h；
（3）It is cooled to room temperature, is filtered, filter out thick accelerator TBBS, filtrate enters collecting tank；
（4）600 water is added into accelerator TBBS, filtering is to get TBBS filter cakes, then drying TBBS；
（5）By step（3）、（4）In filtrate distilled, vapo(u)rizing temperature be 50 DEG C, recycle tert-butylamine.
Claims (5)
1. a kind of dioxygen oxidation method prepares rubber vulcanizing accelerator TBBS, which is characterized in that include the following steps：
（1）A certain amount of tert-butylamine is put into autoclave, and a certain amount of accelerant MBT and acetate are added under stiring
Catalyst stirs evenly；
（2）60 ~ 80 DEG C are heated to, is passed through oxygen under stiring, when pressure reaches 0.6 ~ 0.7 MPa in autoclave, is stopped
Only lead to oxygen, when the pressure in autoclave is less than 0.2MPa, oxygen is passed through again, repeatedly repeatedly, until reaction under high pressure
Pressure in kettle no longer changes, and the reaction time is 2 ~ 3h；
（3）It is cooled to room temperature, is filtered, filter out thick accelerator TBBS, filtrate enters collecting tank；
（4）It is added a certain amount of water into accelerator TBBS, filtering is to get TBBS filter cakes, then drying TBBS；
（5）By step（3）、（4）In filtrate distilled, vapo(u)rizing temperature be 30 ~ 50 DEG C, recycle tert-butylamine.
2. dioxygen oxidation method according to claim 1 prepares rubber vulcanizing accelerator TBBS, it is characterised in that：The promotion
The molar ratio of agent MBT and tert-butylamine is 1：20~25.
3. dioxygen oxidation method according to claim 1 prepares rubber vulcanizing accelerator TBBS, it is characterised in that：The acetic acid
The quality of salt catalyst is the 8% ~ 10% of accelerant MBT quality.
4. dioxygen oxidation method according to claim 1 prepares rubber vulcanizing accelerator TBBS, it is characterised in that：The acetic acid
Salt catalyst is one kind in copper acetate or lead acetate or zinc acetate.
5. dioxygen oxidation method according to claim 1 prepares rubber vulcanizing accelerator TBBS, it is characterised in that：The step
（4）The mass ratio of the middle quality that water is added and crude product is 2 ~ 3：1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810668925.1A CN108586384A (en) | 2018-06-22 | 2018-06-22 | Dioxygen oxidation method prepares rubber vulcanizing accelerator TBBS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810668925.1A CN108586384A (en) | 2018-06-22 | 2018-06-22 | Dioxygen oxidation method prepares rubber vulcanizing accelerator TBBS |
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| Publication Number | Publication Date |
|---|---|
| CN108586384A true CN108586384A (en) | 2018-09-28 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201810668925.1A Pending CN108586384A (en) | 2018-06-22 | 2018-06-22 | Dioxygen oxidation method prepares rubber vulcanizing accelerator TBBS |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112427049A (en) * | 2020-12-18 | 2021-03-02 | 科迈化工股份有限公司 | Catalyst for producing vulcanization accelerator TBBS by heterogeneous oxygen method and application method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102146063A (en) * | 2010-02-10 | 2011-08-10 | 鹤壁联昊化工有限公司 | Synthesis method of rubber auxiliary NS |
| CN102295620A (en) * | 2011-06-28 | 2011-12-28 | 山东阳谷华泰化工股份有限公司 | Co-production synthesizing technology of rubber vulcanization promoter NS |
| CN103102328A (en) * | 2012-11-16 | 2013-05-15 | 江苏国立化工科技有限公司 | Preparation method of rubber accelerator NS (N-tert-butyl benzothiazole-2-sulphenamide) |
| CN104610193A (en) * | 2014-12-29 | 2015-05-13 | 内蒙古科迈化工有限公司 | Preparation method of rubber vulcanizing accelerator TBBS |
-
2018
- 2018-06-22 CN CN201810668925.1A patent/CN108586384A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102146063A (en) * | 2010-02-10 | 2011-08-10 | 鹤壁联昊化工有限公司 | Synthesis method of rubber auxiliary NS |
| CN102295620A (en) * | 2011-06-28 | 2011-12-28 | 山东阳谷华泰化工股份有限公司 | Co-production synthesizing technology of rubber vulcanization promoter NS |
| CN103102328A (en) * | 2012-11-16 | 2013-05-15 | 江苏国立化工科技有限公司 | Preparation method of rubber accelerator NS (N-tert-butyl benzothiazole-2-sulphenamide) |
| CN104610193A (en) * | 2014-12-29 | 2015-05-13 | 内蒙古科迈化工有限公司 | Preparation method of rubber vulcanizing accelerator TBBS |
Non-Patent Citations (1)
| Title |
|---|
| 曹耀强等: "硫化促进剂TBBS合成研究", 《石化技术与应用》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112427049A (en) * | 2020-12-18 | 2021-03-02 | 科迈化工股份有限公司 | Catalyst for producing vulcanization accelerator TBBS by heterogeneous oxygen method and application method thereof |
| CN112427049B (en) * | 2020-12-18 | 2023-02-28 | 科迈化工股份有限公司 | Catalyst for producing vulcanization accelerator TBBS by heterogeneous oxygen method and application method thereof |
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Application publication date: 20180928 |