CN104844536B - Method used for extracting benzothiazole from rubber accelerator production byproduct resin - Google Patents
Method used for extracting benzothiazole from rubber accelerator production byproduct resin Download PDFInfo
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- CN104844536B CN104844536B CN201510173607.4A CN201510173607A CN104844536B CN 104844536 B CN104844536 B CN 104844536B CN 201510173607 A CN201510173607 A CN 201510173607A CN 104844536 B CN104844536 B CN 104844536B
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- resin
- benzothiazole
- caustic soda
- liquid caustic
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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
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- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a method used for extracting benzothiazole from a rubber accelerator production byproduct resin, and belongs to the technical field of fine chemical engineering. The method comprises following steps: a byproduct resin obtained via non-aqueous polarity method accelerant M production is delivered into a modification reaction kettle, temperature is increased to 100 DEG C, stirring is carried out, and a small amount of an oxidizing agent is added; heat preservation oxidation is carried out, and liquid caustic soda is added so as to adjusted pH value for neutralization reaction; resin obtained via modification reaction in the above step is delivered into a distillation kettle, stirring is carried out, and heating and pressure reducing are carried out at the same time, wherein adding amount accounts for 1/2 to 2/3 of the volume of the distillation kettle; in rectification processes, cut fraction collected at a temperature lower than 70 DEG C is water, and is recycled as the dilution water of the oxidizing agent and liquid caustic soda, first fraction collected at a temperature lower than 120 DEG C is mixed with resin at the bottom of distillation kettle, and an obtained mixture is taken as a waterproof material, and a fraction collected at a temperature ranging from 120 to 140 DEG C is a benzothiazole finished product. According to the method, separation of benzothiazole becomes easily via modification and neutralization of unmodified resin, and solidification of a part of low boiling point resin.
Description
Technical field
The present invention relates to technical field of fine, refer in particular to produce rubber accelerator m byproduct in process from non-aqueous polar method
The method extracting benzothiazole in product resin
Background technology
Rubber accelerator is one of most important rubber chemicals kind, plays very important work in Vulcanization Process of Rubber
With it can greatly speed up the speed of the vulcanization of rubber, improve production efficiency, also can improve the Physical Mechanical of vulcanite simultaneously
Energy.
Accelerator m (chemical name is 2-mercaptobenzothiazole) is the important kind of one of accelerator, is also that downstream is many
The raw materials for production of many accelerator product, it uses as rubber accelerator has excellent sulfuration promotion performance, and purposes is wider, consumes
Amount is maximum, is the parent synthesizing other delayed action accelerators (as thiazole accelerator, sulfenamide type accelerators) simultaneously.
State-of-the-art production technology is non-aqueous polar method production technology both at home and abroad at present, produces big in this art production process
The resin of amount uses as waterproof material, but contains about 20% benzothiazole in this resin, and benzothiazole exists and resin
In, have impact on resin as the serviceability of waterproof material, after needing this resin is modified, qualified waterproof could be produced
Material.Benzothiazole is the extremely important heterocyclic compound of a class, has extensive use in fields such as medicine, pesticide, material engineering
On the way.Pharmaceutically, it can serve as antibacterial, fungicidal agent etc., can be also used for parasiticide, antituberculosis, wind resistance damp disease and resists
Cancer etc.；Agriculturally, it has anti-agricultural funguses, parasite killing, weeding, plant growth regulating isoreactivity；In material engineering field, it can
For use as the ultraviolet absorber in thiofide, dyeing of plastics agent, cosmetics and sunglassess, liquid crystal display material, electricity
Electroluminescent material and fluorescence probe material etc..Additionally, benzothiazole heterocycle is also excellent molecule construction stripping and slicing, extensively used
In structure various functions organic molecule.
Benzothiazole market demand is very big.As using its modified together with other resins use as waterproof material, be
Significant wastage to resource, and this waterproof material is subject to market clout larger, when there is stockpiling of unsold product, can overstock in a large number in factory,
Produce stacking problem, even entrust as solid waste when part producer seriously overstocks and dispose, environment be also result in certain impact.
Content of the invention
The present invention in order to overcome the above-mentioned deficiencies of the prior art, develops the technology extracting benzothiazole from this resin,
Solve the wasting of resources and environmental issue, and considerable economic benefit can be produced.
Produce, from rubber accelerator, the method extracting benzothiazole side-product resin, carry out as steps described below:
(1) non-aqueous polar method accelerator m is produced the side-product resin producing to be added in modified-reaction kettle, be warming up to
100 DEG C, stir and add a small amount of oxidant, be incubated oxidation reaction 30min, be subsequently adding liquid caustic soda regulation ph value and enter to 8.5-9
Row neutralization reaction 30min；
(2) the good resin of above modified-reaction is put in distillating still, dosage accounts for the 1/2-2/3 of reactor volume, side
Stirring side heating decompression (Stress control is in 4-5kpa)；In distillation process, collecting less than 70 DEG C fractions is water, and oxidant is done in reuse
With liquid caustic soda dilution water, collect after less than 120 DEG C first fractions and bottom mixed with resin as waterproof material；Collect 120-140 DEG C to evaporate
Part is benzothiazole finished product.
The hydrogen peroxide that wherein said oxidant is 27.5% for volumetric concentration.
Wherein said liquid caustic soda is sodium hydroxide, the aqueous solution of potassium hydroxide.
Sell after detection, packaging, residual resin can be sold as waterproof material, its performance is much better than modified using primary resin
Waterproof material, range is wide.
Advantages of the present invention:
A is modified to primary resin, neutralisation treatment, cured portion low boiling resin, so that benzothiazole is can be easily separated.
B adopts advanced rectification under vacuum technique to extract benzothiazole, it is to avoid is extracted using chemical method and causes to produce into
This height and problem of environmental pollution.
After c benzothiazole extracts, residual resin does not need to be modified, and can be directly used as waterproof material, and its performance is good,
Range is wide.
D waterproof resin market price is 200 yuan/ton, and about 30000 yuan/ton of the benzothiazole field price therefrom extracted, so
Avoid the waste of resource, create considerable economic benefit simultaneously.
Brief description
Fig. 1 is the process chart of the present invention.
Specific embodiment
Embodiment 1:
Modified-reaction kettle 30m3, rectifying still 30m3.
Add 20 tons of non-aqueous polar method accelerator m and produce the side-product resin producing, stirring is warming up to 100 DEG C, adds
27.5% hydrogen peroxide (27.5% refers to the mass concentration of hydrogen peroxide) 40kg, react 30min, then plus alkali (mass concentration be 10%
Sodium hydrate aqueous solution) adjust ph to 8.5, stirring reaction 30min.
Then modified resin is put into distillating still to open, starts rectification under vacuum, control pressure 4.5kpa.
Collect less than 70 DEG C fractions, be cycling use of water.
Collect less than 130 DEG C fractions.
Collecting 130-135 DEG C of fraction is benzothiazole.
Produce 3 batches by process above is continuous, product average yield 21%, benzothiazole purity average out to 98%.
Embodiment 2:
Modified-reaction kettle 30m3, rectifying still 30m3
Add 15 tons of resins, stirring is warming up to 95 DEG C, and (27.5% refers to that the quality of hydrogen peroxide is dense to add 27.5% hydrogen peroxide
Degree) 30kg, react 30min, then plus alkali (mass concentration is the aqueous solution of 10% potassium hydroxide) adjust ph to 8.5, stirring is anti-
Answer 30min.
Then modified resin is put into distillating still to open, starts rectification under vacuum, control pressure 4.5kpa.
Collect less than 70 DEG C fractions, be cycling use of water.
Collect less than 125 DEG C fractions.
Collecting 125-130 DEG C of fraction is benzothiazole.
Produce 3 batches by process above is continuous, product average yield 24%, benzothiazole purity average out to 95%.
The economic analysis of the present invention
This resin is sold as waterproof material at present, and price per ton is 200 yuan/ton, and benzothiazole market price is 30000
Yuan/ton.
1 ton of resin is processed using present invention process and can extract benzothiazole 200kg, income from sales is 6000 yuan, remaining
800kg resin is 160 yuan as waterproof material income from sales, and production cost is 610 yuan.Often process 1 ton of resin, warp can be produced
5550 yuan of benefit of Ji.
Claims (3)
1. produce from rubber accelerator and extract the method for benzothiazole side-product resin it is characterised in that entering as steps described below
OK: non-aqueous polar method accelerator m is produced the side-product resin producing and is added in modified-reaction kettle by (1), is warming up to 100 DEG C,
Stir and add a small amount of oxidant, be incubated oxidation reaction 30min, be subsequently adding liquid caustic soda regulation ph value and be neutralized to 8.5-9
Reaction 30min；
(2) the good resin of above modified-reaction is put in distillating still, dosage accounts for the 1/2-2/3 of reactor volume, side is stirred
Side heating decompression, after decompression, Stress control is in 4-5kpa；In distillation process, collecting less than 70 DEG C fractions is water, and reuse aoxidizes
Agent and liquid caustic soda dilution water, as waterproof material after less than 120 DEG C first fractions of collection and bottom mixed with resin；Collect 120-140 DEG C
Fraction is benzothiazole finished product.
2. the method producing extraction benzothiazole side-product resin from rubber accelerator according to claim 1, it is special
Levy the hydrogen peroxide being that wherein said oxidant is 27.5% for volumetric concentration.
3. the method producing extraction benzothiazole side-product resin from rubber accelerator according to claim 1, it is special
Levy the one kind of the aqueous solution being that wherein said liquid caustic soda is the aqueous solution of sodium hydroxide or potassium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510173607.4A CN104844536B (en) | 2015-04-13 | 2015-04-13 | Method used for extracting benzothiazole from rubber accelerator production byproduct resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510173607.4A CN104844536B (en) | 2015-04-13 | 2015-04-13 | Method used for extracting benzothiazole from rubber accelerator production byproduct resin |
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| Publication Number | Publication Date |
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| CN104844536A CN104844536A (en) | 2015-08-19 |
| CN104844536B true CN104844536B (en) | 2017-02-01 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201510173607.4A Active CN104844536B (en) | 2015-04-13 | 2015-04-13 | Method used for extracting benzothiazole from rubber accelerator production byproduct resin |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106243059A (en) * | 2016-07-26 | 2016-12-21 | 濮阳蔚林化工股份有限公司 | A kind of method extracting benzothiazole from 2 benzothiazolyl mercaptans production by-products |
| CN109111409A (en) * | 2018-10-18 | 2019-01-01 | 河南省化工研究所有限责任公司 | A method of benzothiazole is produced from the waste material of production 2-mercaptobenzothiazole |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245052A (en) * | 2008-03-14 | 2008-08-20 | 何连峰 | Method for extracting benzothiazole with by-product for producing 2-mercaptobenzothiazole |
| CN102838237A (en) * | 2012-09-25 | 2012-12-26 | 科迈化工股份有限公司 | Treatment method of rubber vulcanization accelerator MBTS (2,2'-dithiobis(benzothiazole)) wastewater |
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