CN108047161A - A kind of catalysis hydrogen peroxide oxidation synthetic method of vulcanization accelerator TBBS - Google Patents
A kind of catalysis hydrogen peroxide oxidation synthetic method of vulcanization accelerator TBBS Download PDFInfo
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- CN108047161A CN108047161A CN201711394739.5A CN201711394739A CN108047161A CN 108047161 A CN108047161 A CN 108047161A CN 201711394739 A CN201711394739 A CN 201711394739A CN 108047161 A CN108047161 A CN 108047161A
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- mbt
- hydrogen peroxide
- tert
- butylamine
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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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Abstract
The present invention relates to the catalysis hydrogen peroxide oxidation synthetic methods of vulcanization accelerator TBBS a kind of.Tert-butylamine is dissolved under stirring in a certain amount of water, stirring is maintained, MBT is added in into tert-butylamine solution, and is stirred, prepares MBT slurries；Dilute sulfuric acid is added in into MBT slurries and adjusts pH value 34, then adds in catalysts；Stirring；Afterwards at 20 DEG C 80 DEG C, the hydrogen peroxide that is added dropwise into reaction system, and time for adding is controlled in 30min 120min；After the completion of reaction, mixed liquor is filtered, filter cake is washed to obtain target product TBBS with clear water.The technology, as oxidant, solves the problems, such as that technique waste water salt content is high using hydrogen peroxide；Catalysis oxidation is carried out using catalyst simultaneously, reaction yield is improved to more than 96%, product purity can also be improved to more than 98%, solved and used the problem of hydrogen peroxide is low as oxidizer product yield, and purity is low, and by-product amount is big merely.
Description
Technical field
The invention belongs to rubber chemicals field, the catalysis hydrogen peroxide oxidation for being specifically related to a kind of vulcanization accelerator TBBS closes
Into method.
Background technology
During with the various rubbers such as rubber production tire, sebific duct, rubber overshoes, it is necessary to five big analog assistants are used,
They are that thiofide (abbreviation accelerating agent), rubber antioxidant, the vulcanization of rubber and vulcanizing activator, processing type rubber help
Agent and special functional auxiliary agent.Accelerating agent can promote the substance of sulfurization, can shorten vulcanization time, reduce curing temperature, subtract
Few vulcanizing agent dosage and the physical mechanical property of raising rubber etc..
Rubber vulcanizing accelerator TBBS (chemical name N tert butyl benzothiazole 2 sulfenamide, also known as NS) is time sulphur
One of important kind of amides accelerating agent, its safety and low toxicity do not generate carcinogenic nitrosamine.Rubber vulcanizing accelerator TBBS has
Anti-scorch, the nontoxic, functions such as vulcanization is fast, are referred to as " standard accelerating agent " and are mainly used in natural rubber, butadiene rubber, butylbenzene rubber
Glue, in isoprene rubber.
There are three types of the synthesis technology of the current vulcanization accelerator TBBS for being clear to report is total to：
(1) sodium hypochlorite oxidization.The method is using sodium hypochlorite as oxidant, by raw material MBT or its sodium salt and tert-butylamine
Oxidation generation accelerator TBBS.Sodium hypochlorite oxidization has technical maturity, and reaction condition is mild, and product quality is preferable, yield
The advantages of higher.But its production wastewater flow rate is big, and 1 ton of product about produces 8 tons of waste water, and waste water salt content is high, COD high, and is difficult to give birth to
Change is handled, unfavorable to environmental protection.In addition its waste water after processing, will obtain a large amount of intractable organic matters and contain organic matter
Sodium chloride, further increase environmental risk, do not meet the requirement of current friendly process.
(2) hydrogen peroxide direct method.The method aoxidizes raw material MBT or its sodium salt with tert-butylamine using hydrogen peroxide as oxidant
Generate accelerator TBBS.But hydrogen peroxide oxidation current potential is higher than sodium hypochlorite, and oxidation reaction is more complicated, and amount of by-products is big and difficult
With processing, principal product TBBS yields are low and product purity is poor, it is seen that document report highest yield also only has 90%, and raw material utilize
Rate is low compared with other techniques.Although not containing salinity in its waste water, by-product amount of resin is wanted high several times compared with other techniques and is difficult to back
Receipts processing so that the industrialization economy of the technique is not high, does not also meet requirement of the current friendly process for raw material availability.
(3) oxygen catalytic oxidation method.The method is using oxygen as oxidant, under the effect of the catalyst by raw material MBT and tertiary fourth
Amine oxidation generation accelerator TBBS.The oxidant that the technique uses is not aqueous, and without salinity, waste water yield is relatively low, therefore by
It is considered the TBBS production technologies of green.But raw material tert-butylamine highly volatile in the technique, while pure oxygen is used as oxidant,
It easily explodes after unreacted oxygen is mixed with tert-butylamine steam in system, process dangerous is very big；The reaction oxygen simultaneously
The change cycle is longer, and production efficiency is low compared with other techniques, and oxidation technology, using reaction under high pressure, device fabrication difficulty is high, operation
It easily goes wrong in the process so that the technique high-volume industrialization promotion runs into bottleneck.
In conclusion in current TBBS synthesis technologies, still there is no a kind of safety coefficient is higher, while product yield
Height, the small ideal green technique of three wastes yield.
The content of the invention
In view of the above-mentioned problems, the present invention is using catalytic oxidation technique, using Cu/Mn metal complexes as catalyst, hydrogen peroxide
For oxidant, catalysis oxidation 2-mercaptobenzothiazole (MBT) and tert-butylamine synthesis accelerant TBBS.
Technical scheme is as follows：
The catalysis hydrogen peroxide oxidation synthetic method of vulcanization accelerator TBBS a kind of, it comprises the following steps：
1st, tert-butylamine is dissolved under stirring in a certain amount of water, maintains stirring, added into tert-butylamine solution
Enter MBT, and stir, prepare MBT slurries；
2nd, add in dilute sulfuric acid into MBT slurries and adjust pH value 3-4, then add in catalysts；Stirring；Afterwards at 20 DEG C -80
At DEG C, the hydrogen peroxide that is added dropwise into reaction system, and time for adding is controlled in 30min-120min；After the completion of reaction, it will mix
Liquid is filtered, and filter cake is washed with clear water, obtains target product TBBS.
The molar ratio of MBT and tert-butylamine is controlled 1:1-4, preferably 1:3；
The amount control for being used to prepare the water of MBT slurries adds 100-300ml, preferably 150ml in the M of every 0.1mol；
Mixing time is controlled in 10-30min, preferably 15min
Catalyst is copper acetate, copper chloride, copper sulphate, copper nitrate, cupric ethylene diamine tetraacetate sodium, ethylenediamine tetra-acetic acid manganese
One or more in sodium, manganese sulfate, manganese nitrate, preferably copper acetate+ethylenediamine tetra-acetic acid manganese sodium.
The mass ratio of catalyst MBT is in order to control in 1%-5%, preferably 1%；
The amount of the substance of MBT and hydrogen peroxide is than control 1:1-2, preferably 1:1.5；
Preferably 50 DEG C of reaction temperature；
The preferred 60min of time for adding；
The beneficial effects of the invention are as follows：
The present invention provides one kind using Cu/Mn metal complexes as catalyst, hydrogen peroxide is oxidant, catalysis oxidation 2- mercaptos
The synthesis technology of base benzothiazole (MBT) and tert-butylamine synthesis accelerant TBBS.The technique is using hydrogen peroxide as oxidant, solution
Determined technique waste water saliferous the problem of；Catalysis oxidation is carried out using catalyst simultaneously, reaction yield is made to be increased to more than 96%, production
Object TBBS can be increased to more than 98% through HPLC tests purity, solve and use hydrogen peroxide as oxidizer product yield merely
The problem of low, purity is low, and by-product amount is big；Simultaneous reactions do not use enclosed high pressure reaction condition, there is no inflammable without using oxygen
The problem of explosive, and reaction carries out under normal pressure, industrial device investment is small, and device fabrication is simple, is less prone to and asks in operation
Topic, it may be said that disposably solve many problems for being difficult to overcome in current TBBS synthesis technologies.
Specific embodiment
It is described in detail below with reference to the embodiment of the present invention.
Embodiment 1
The catalysis hydrogen peroxide oxidation synthetic process of vulcanization accelerator TBBS a kind of, includes the following steps：
1st, tert-butylamine is dissolved under stirring in a certain amount of water, maintains stirring, added into tert-butylamine solution
Enter MBT, and stir 15min, prepare MBT slurries.The molar ratio of MBT and tert-butylamine is controlled 1:3, for the amount control of the water of mashing
In MBTs of the 150ml per 0.1mol.
2nd, add in dilute sulfuric acid into MBT slurries and adjust pH value 3-4, then add in the catalysts vinegar of MBT mass fractions 1%
Sour copper and ethylenediamine tetra-acetic acid manganese sodium.After stirring evenly at 50 DEG C, the hydrogen peroxide that is slowly added dropwise into reaction system, during dropwise addition
Between 60min, dripping quantity is 1.5 times of MBT moles.After the completion of reaction, mixed liquor is filtered, filter cake is washed 3 times with clear water,
It can obtain target product TBBS.
After COMPREHENSIVE CALCULATING, which is 96.2%, and product TBBS is 98.6% through HPLC test purity.
Embodiment 2
1st, it is tert-butylamine is soluble in water under stirring, stirring is maintained, MBT is added in into tert-butylamine solution, and
20min is stirred, prepares MBT slurries.The molar ratio of MBT and tert-butylamine is controlled 1:1, water rate control is the every 0.1mol's of 100ml
MBT。
2nd, add in dilute sulfuric acid into MBT slurries and adjust pH value 3-4, then add in the catalysts vinegar of MBT mass fractions 2%
Sour copper.After stirring evenly at 20 DEG C, the hydrogen peroxide with MBT equimolar amounts that is slowly added dropwise into reaction system, time for adding
30min.After the completion of reaction, mixed liquor is filtered, filter cake is washed 3 times with clear water, you can obtains target product TBBS.
After COMPREHENSIVE CALCULATING, which is 66.3%, and product TBBS is 85.6% through HPLC test purity.
Embodiment 3
1st, tert-butylamine is dissolved under stirring in a certain amount of water, maintains stirring, added into tert-butylamine solution
Enter MBT, and stir 30min, prepare MBT slurries.The molar ratio of MBT and tert-butylamine is controlled 1:2, for the amount control of the water of mashing
In MBTs of the 300ml per 0.1mol.
2nd, add in dilute sulfuric acid into MBT slurries and adjust pH value 3-4, then add in the catalysts second of MBT mass fractions 3%
Ethylenediamine tetraacetic acid (EDTA) manganese sodium.After stirring evenly at 80 DEG C, the hydrogen peroxide that is slowly added dropwise into reaction system, time for adding
120min, dripping quantity are 2 times of MBT moles.After the completion of reaction, mixed liquor is filtered, filter cake washes 3 times with clear water, i.e.,
It can obtain target product TBBS.
After COMPREHENSIVE CALCULATING, which is 50.1%, and product TBBS is 85.2% through HPLC test purity.
Embodiment 4
1st, tert-butylamine is dissolved under stirring in a certain amount of water, maintains stirring, added into tert-butylamine solution
Enter MBT, and stir 20min, prepare MBT slurries.The molar ratio of MBT and tert-butylamine is controlled 1:3, for the amount control of the water of mashing
In MBTs of the 200ml per 0.1mol.
2nd, add in dilute sulfuric acid into MBT slurries and adjust pH value 3-4, then add in the catalysts sulphur of MBT mass fractions 1%
Sour copper+manganese sulfate.After stirring evenly at 50 DEG C, the hydrogen peroxide that is slowly added dropwise into reaction system, time for adding 60min, drop
Dosage is 2 times of MBT moles.After the completion of reaction, mixed liquor is filtered, filter cake is washed 3 times with clear water, you can obtains target
Product TBBS.
After COMPREHENSIVE CALCULATING, which is 90.6%, and product TBBS is 96.1% through HPLC test purity.
Embodiment 5
1st, tert-butylamine is dissolved under stirring in a certain amount of water, maintains stirring, added into tert-butylamine solution
Enter MBT, and stir 15min, prepare MBT slurries.The molar ratio of MBT and tert-butylamine is controlled 1:2.5, for the amount control of the water of mashing
Make the MBT per 0.1mol in 200ml.
2nd, add in dilute sulfuric acid into MBT slurries and adjust pH value 3-4, then add in the catalysts second of MBT mass fractions 2%
Ethylenediamine tetraacetic acid (EDTA) copper sodium+ethylenediamine tetra-acetic acid manganese sodium.After stirring evenly at 50 DEG C, the dioxygen that is slowly added dropwise into reaction system
Water, time for adding 80min, dripping quantity are 2 times of MBT moles.After the completion of reaction, mixed liquor is filtered, filter cake is with clearly
Washing 3 times, you can obtain target product TBBS.
After COMPREHENSIVE CALCULATING, which is 94.1%, and product TBBS is 97.2% through HPLC test purity.
Claims (10)
1. a kind of catalysis hydrogen peroxide oxidation synthetic method of vulcanization accelerator TBBS, it is characterized in that comprising the following steps：
1), tert-butylamine is dissolved under stirring in a certain amount of water, stirring is maintained, is added in into tert-butylamine solution
MBT, and stir, prepare MBT slurries；
2), dilute sulfuric acid is added in into MBT slurries and adjust pH value 3-4, then add in catalysts；After stirring at 20 DEG C -80 DEG C
Reaction, the hydrogen peroxide being added dropwise into reaction system, and time for adding is controlled in 30min-120min；After the completion of reaction, it will mix
Liquid is filtered, and filter cake is washed with clear water, obtains target product TBBS.
2. the method as described in claim 1, it is characterized in that the control of the molar ratio of MBT and tert-butylamine is 1:1-4.
3. the method as described in claim 1, the amount control that feature is used to prepare the water of MBT slurries is added in the M of every 0.1mol
100-300ml。
4. the method as described in claim 1, feature mixing time is controlled in 10-30min.
5. the method as described in claim 1, feature catalyst is copper acetate, copper chloride, copper sulphate, copper nitrate, ethylenediamine
One or more in tetraacethyl copper sodium, ethylenediamine tetra-acetic acid manganese sodium, manganese sulfate, manganese nitrate.
6. the method as described in claim 1, feature catalyst is copper acetate+ethylenediamine tetra-acetic acid manganese sodium.
7. the method as described in claim 1, the mass ratio of feature catalyst MBT is in order to control in 1%-5%.
8. the amount of the substance of the method as described in claim 1, feature MBT and hydrogen peroxide is than control 1:1-2.
9. the method as described in claim 1, characteristic reaction temperature 50 C.
10. the method as described in claim 1, feature time for adding 60min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111269196A (en) * | 2020-03-23 | 2020-06-12 | 山东省化工研究院 | Method for preparing NS by UHP oxidation |
| CN111303074A (en) * | 2020-03-19 | 2020-06-19 | 山东省化工研究院 | Process for preparing NS by oxidizing M tert-butylammonium salt with hydrogen peroxide |
Citations (2)
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| CN101717380A (en) * | 2009-12-09 | 2010-06-02 | 河南省开仑化工有限责任公司 | Clean production method of rubber vulcanizing accelerator TBBS |
| CN102838562A (en) * | 2012-09-25 | 2012-12-26 | 科迈化工股份有限公司 | Method for synthesizing rubber vulcanization accelerator NS (N-tertiary butyl-2-benzothiazole sulfenamide) through two-step method by taking hydrogen peroxide as oxidant |
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2017
- 2017-12-21 CN CN201711394739.5A patent/CN108047161A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717380A (en) * | 2009-12-09 | 2010-06-02 | 河南省开仑化工有限责任公司 | Clean production method of rubber vulcanizing accelerator TBBS |
| CN102838562A (en) * | 2012-09-25 | 2012-12-26 | 科迈化工股份有限公司 | Method for synthesizing rubber vulcanization accelerator NS (N-tertiary butyl-2-benzothiazole sulfenamide) through two-step method by taking hydrogen peroxide as oxidant |
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| 孟庆森 等: ""过氧化氢催化合成促进剂NS的工艺研究"", 《橡胶科技》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111303074A (en) * | 2020-03-19 | 2020-06-19 | 山东省化工研究院 | Process for preparing NS by oxidizing M tert-butylammonium salt with hydrogen peroxide |
| CN111303074B (en) * | 2020-03-19 | 2022-06-17 | 山东省化工研究院 | Process for preparing NS by oxidizing M tert-butylammonium salt with hydrogen peroxide |
| CN111269196A (en) * | 2020-03-23 | 2020-06-12 | 山东省化工研究院 | Method for preparing NS by UHP oxidation |
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Application publication date: 20180518 |