CN109336844A - The synthetic method and composition of a kind of 2- anilino- benzothiazole and application - Google Patents
The synthetic method and composition of a kind of 2- anilino- benzothiazole and application Download PDFInfo
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- CN109336844A CN109336844A CN201811516376.2A CN201811516376A CN109336844A CN 109336844 A CN109336844 A CN 109336844A CN 201811516376 A CN201811516376 A CN 201811516376A CN 109336844 A CN109336844 A CN 109336844A
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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
- C07D277/82—Nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
- C08K5/47—Thiazoles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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Abstract
The present invention relates to a kind of synthetic method of 2- anilino- benzothiazole in thiofide field and composition and applications.The synthetic method of the 2- anilino- benzothiazole, comprising the following steps: firstly, aniline, carbon disulfide and sulphur are put into high-temperature-resistant high-pressure-resistant reactor tank, be passed through nitrogen, air therein is discharged；Then, temperature, time, the pressure of reaction are controlled, is reacted under magnetic agitation state；It cools after reaction, the gas of generation is discharged, burn or absorbed with lye；Finally, organic solvent 1 is added in reactor tank, unreacted raw material and captax are washed away；Its insoluble matter further washs after filtering, with organic solvent 2, takes its insoluble matter ingredient, obtains the 2- anilino- benzothiazole of high-purity；The present invention can get the by-product anilino- benzothiazole of captax, be the friendly process research deposit requisite information of captax, while anilino- benzothiazole also has unique advantage separately as vulcanization accelerator.
Description
Technical field
The present invention relates to thiofide fields, furtherly, are related to a kind of conjunction of 2- anilino- benzothiazole
At method and composition and application.
Background technique
Vulcanization accelerator refers in the vulcanization of rubber, can accelerate curingprocess rate, reduce curing temperature, reduces vulcanizing agent use
Amount, and a kind of auxiliary agent of the physical mechanical property of vulcanizate, abbreviation promotor can be changed.It is essential in rubber industry
One of basic material.
With the continuous development of synthetic rubber kind and purposes, existing promotor item are many and diverse, according to the big of promotion efficiency
Small, promotor can be divided into ultras, half ultras, medium promotor, weak promotor and delayed action accelerator again；According to
The chemical structure of promotor is usually classified as thiazoles, thiurams, sulfenamide, guanidine, dithiocar-bamate
Class, aldehyde amines, xanthic acid salt and Thiourea.Wherein sulfenamide and the comprehensive performance of thiazoles are best.
The development of promotor is gradually intended to environmental protection, functionalization and centralization.From the point of view of technical standpoint.It is international in recent years
On to certain promotors during rubber processing, be also easy to produce the toxicity problem pay attention to day by day of the promotor of harmful nitrosamine,
Given this many restricted regulations in the whole world are put into effect in succession at present, thus form environmental protection vulcanization promotion system, and development and production
Some environmental protection new varieties replace the product of carcinogenic danger.Rubber accelerator by using for many years, wash the sand by billow, and kind is raw
It produces and increasingly tends to concentrate with application, sulfenamide type accelerators predominantly pollution-free, of good performance.Sulfenamide promotes
The raising of agent ratio depends on the reform of its production technology.In raw material field, the emphasis of this reform is captax
Technological transformation.Captax itself is the important species of thiazole accelerator, while being production sulfenamide type accelerators again
Important source material, cleanly production are directly related to the greenization problem of rubber accelerator production.
Captax, chemical name are 2-mercaptobenzothiazole, are one of maximum promotor types of rubber materials dosage.
In promotor preparation field, usual this field staff aniline, carbon disulfide, sulphur are mixed after in high temperature and high pressure containers
Reaction preparation.
In general, in the preparation process of captax, when aniline, carbon disulfide, sulphur fail sufficiently to react completely
It waits, has the generation of part by-product, the by-product mainly reported in many documents is benzothiazole, about its separating-purifying
Deng also there is correlative study.However, there has been no further deep at present about this by-product of by-product anilino- benzothiazole
Research.In order to solve the problems, such as cleanly production and the greenization of captax, obtaining by-product anilino- benzothiazole sterling has
Significance.
Summary of the invention
In order to solve the above-mentioned problems in the prior art, the present invention proposes a kind of synthesis of 2- anilino- benzothiazole
Method.Relate in particular to the synthetic method and composition and application of a kind of 2- anilino- benzothiazole.
The present inventor has found in practical study, the dosage of reaction raw materials sulphur is controlled in right amount, in certain reaction condition
Lower reaction, under the premise of generating principal product captax, and meanwhile available a certain amount of 2- anilino- benzothiazole, knot
Shown in the following structure I of structure.
In order to further verify the performance for the 2- anilino- benzothiazole being prepared, the present inventor is to it in tire
Performance has done further verifying, and by having comparable physical parameter with the comparative test of captax, equally having can
The performance for promoting the vulcanization of rubber can be used as a kind of thiofide use.
It is an object of the present invention to provide a kind of synthetic methods of 2- anilino- benzothiazole, and synthetic method is as schemed
It is shown:
Specifically, the synthetic method of the 2- anilino- benzothiazole, this method include the synthesis using aniline as starting material
Reaction condition and product post-treatment condition.Specifically it can comprise the following steps that
Firstly, aniline, carbon disulfide and sulphur are put into high-temperature-resistant high-pressure-resistant reactor tank, it is passed through nitrogen, it will be therein
Air discharge；
Then, temperature, time, the pressure of reaction are controlled, is reacted under magnetic agitation state；It cools after reaction,
The gas generated is discharged, burned (specifically can be such as incinerator) or is inhaled with lye (specifically can be as used sodium hydroxide lye)
It receives；
Finally, organic solvent 1 is added in reactor tank, unreacted raw material and captax are washed away；Its insoluble matter passes through
After filter, is further washed with organic solvent 2, take its insoluble matter ingredient, obtain the 2- anilino- benzothiazole of high-purity.
Wherein,
The aniline, carbon disulfide, sulphur molar ratio be 1: (0.3~0.7): (0.2~0.8)；Preferably 1: (0.4
~0.6): (0.4~0.6)；
The sulphur can be selected from least one of elemental sulfur or crystallization sulphur.
The temperature of the reaction can be 250~300 DEG C, preferably 260~280 DEG C.
Nitrogen pressure in the reactor tank can for 5~10MPa, preferably 6~9MPa, further preferably 7~
8MPa。
The time of the reaction can be 200~360min, preferably 300~360min.
The organic solvent 1 and organic solvent 2, is respectively and independently selected from toluene, dimethylbenzene, methanol, ethyl alcohol, acetone, two
Nitric sulfid, at least one of ether, preferably toluene and/or ethyl alcohol；Meanwhile the organic solvent 1 and organic solvent 2 is
Different solvents.
Specifically, synthetic method of the present invention can comprise the following steps that
(1) raw material aniline, carbon disulfide and sulphur are put into the resistance to height with magnetic stirring apparatus according to the molar ratio
In the high pressure resistant reactor tank of temperature；
(2) it is passed through a certain amount of nitrogen, air therein is discharged, and keeps 5~10MPa of pressure；
(3) 250~300 DEG C of reaction temperature are controlled；
(4) 200~360min of reaction time is controlled；
(5) it is reacted under magnetic agitation state；
(6) after cooling after reaction, the hydrogen sulfide gas of generation is discharged, is absorbed with sodium hydroxide lye；
(7) organic solvent 1 is added in reactor tank, washes away unreacted raw material and captax；Its insoluble matter is through filtering
Afterwards, it is further washed with organic solvent 2, takes its insoluble matter ingredient, obtain the 2- anilino- benzothiazole of high-purity.
The second object of the present invention is to providing the high-purity 2- anilino- benzothiazole of the synthetic method preparation.
The three of the object of the invention are to provide a kind of rubber composition, specifically may include the following components of parts by weight meter:
The rubber of 100 mass parts；
The 2- anilino- benzothiazole of 1~10 mass parts；It is preferred that 1~5 mass parts；
The sulphur of 1~5 mass parts；It is preferred that 1~3 mass parts；
The zinc oxide of 0.5~6 mass parts；It is preferred that 1.5~3 mass parts；
The stearic acid of 1~4 mass parts.
The four of the object of the invention are to provide the application of the 2- anilino- benzothiazole of the method preparation, and the application can wrap
It includes in the composite material preparation for participating in the vulcanization of rubber, preferably includes to need to participate in rubber sulphur for adhesive tape, tire, sebific duct etc.
The composite material of change.
It is captax the invention has the advantages that obtaining the anilino- benzothiazole of the by-product high-purity of captax
Friendly process research deposit requisite information, while anilino- benzothiazole also have separately as vulcanization accelerator it is unique excellent
Gesture.
Detailed description of the invention
Fig. 1 is the GC-MS spectrogram of the 2- anilino- benzothiazole product of embodiment 3；As we can see from the figure when its appearance
Between be 23.49min, the structural analysis of substance clearly demonstrates that it for 2- anilino- benzothiazole.
Fig. 2 is the HPLC spectrogram of the 2- anilino- benzothiazole product of embodiment 3；The substance is pure as we can see from the figure
Spend very high, purity 98.8%.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated.But the present invention is not restricted by the embodiments.
Raw material and reagent
1 raw material of table and reagent
| Material name | Source |
| Aniline | Chinese medicines group |
| Carbon disulfide | Chinese medicines group |
| S sulphur | Flexsys Inc. |
| Toluene | Chinese medicines group |
| Ethyl alcohol | Chinese medicines group |
| Ethyl acetate | Chinese medicines group |
| Sodium hydroxide | Chinese medicines group |
| The Yunnan NR 5# marks glue | Shanghai Zheng Shang Chemical Industry Science Co., Ltd |
| BR butadiene rubber | Yanshan Petrochemical company |
| N330 carbon black | Tianjin day century Chemical Co., Ltd. |
| ZnO zinc oxide | Tianjin Yu Sheng Chemical Co., Ltd. |
| SA (stearic acid) | Tai Ke brownification Co., Ltd |
| P50 oil | Dao Daer |
| SL1801 tackifying resin | Magnificent surprise chemical industry |
| RD anti-aging agent | Nanjing chemical plant |
| 4020 anti-aging agents | Shanghai addition Chemical Co., Ltd. |
| M promotor | Shanghai Jun Pu Chemical Co., Ltd. |
| S sulphur (OT20) | Flexsys Inc. |
Embodiment 1
93g aniline, 36g carbon disulfide and 12g sulphur are added, and there is the high-temperature-resistant high-pressure-resistant of magnetic stirring apparatus to react
In tank, it is passed through nitrogen, air therein is discharged, pressure inside the tank 5MPa before control is reacted；
Then, 260 DEG C of reaction temperature, time 300min are controlled, is reacted under magnetic agitation state；Cooling drop after reaction
Wen Hou is discharged the hydrogen sulfide gas of generation, is absorbed with sodium hydroxide lye；
Finally, toluene 200g is added in reactor tank, unreacted raw material and captax are washed away；
Its insoluble matter after filtering, is further washed with organic solvent ethyl alcohol 100g, is taken its insoluble matter ingredient, is obtained high-purity
The 2- anilino- benzothiazole of degree；Through liquid chromatographic detection, the 2- anilino- benzothiazole purity after purification is 97%.
Embodiment 2~5
Under the premise of not changing reaction step, change each reaction raw materials with when reaction time, temperature, pressure, solvent
The conditions such as ingredient and dosage, reaction result such as the following table 2:
Table 2
| Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Aniline (g) | 93 | 93 | 93 | 93 |
| Carbon disulfide (g) | 38 | 53 | 30 | 45 |
| Sulphur (g) | 16 | 24 | 10 | 20 |
| Temperature (DEG C) | 300 | 280 | 260 | 250 |
| Time (min) | 360 | 300 | 200 | 250 |
| Pressure (MPa) | 7 | 8 | 6 | 10 |
| Solvent 1 | Toluene | Dimethylbenzene | Carbon disulfide | Toluene |
| Solvent usage (g) | 200 | 200 | 250 | 250 |
| Solvent 2 | Ethyl alcohol | Methanol | Acetone | Methanol |
| Solvent usage (g) | 150 | 150 | 100 | 100 |
| Purity (%) | 97.5 | 98.8 | 98.2 | 97.6 |
The preparation and performance test of rubber composition
The preparation of sample
Test verifying is carried out in rubber compounding according to 2- anilino- benzothiazole prepared by embodiment 1 and captax.
It is formulated according to shown in table 3,1.6 liters of Banbury mixer (FARREL companies is added in rubber, carbon black, zinc oxide, stearic acid
Production) in mixing be warming up to 155 DEG C；It then is 140 DEG C or so the rubber components for being mixed into mixer in temperature by anti-aging agent, cobalt salt
In；The masterbatch is cooled to 90 DEG C or so；Then mixed accelerators, sulphur in masterbatch, 50 DEG C at a temperature of it is right
Said mixture carries out mixing 5min, to obtain rubber composition (masterbatch)；The composition obtained by the above method is existed
(production of Jiangdu area town Zhen Wu Bo Hai test machines factory) forms on BH-25T vulcanizing press, and vulcanized rubber plate or thin is made
Piece to carry out the test of physical property, mechanical performance, or it is squeezed out in the form of molded part.
Table 3
Masterbatch made from table 3 tests its curability, and carry out after curing physical in 150 DEG C of vulcanization 30min
The test of energy, mechanical performance and steel wire bond properties, test result are shown in Table 4.
Table 4
It is learnt by the data of table 4, according to the 2- anilino- benzothiazole of the preparation of embodiment 1 compared with commercially available captax,
As being formulated shown in 2,3, under conditions of additive amount is 1.5 parts, whole vulcanization time relatively commercially available captax；When adding
Dosage increases to after 2.5 parts, and as shown in formula 2,4, curingprocess rate is faster than commercially available captax；Equally, time of scorch also has
Same feature, the product that the application is added can extend time of scorch.
Though incipient scorch and cure data show that the promotor product of the application preparation is the by-product for preparing captax, property
It can be close to commercial product.
Claims (10)
1. a kind of synthetic method of 2- anilino- benzothiazole, comprising the following steps:
Firstly, aniline, carbon disulfide and sulphur are put into reactor tank, it is passed through nitrogen, air therein is discharged；
Then, temperature, time, the pressure of reaction are controlled, is reacted under stirring；It cools after reaction, discharge generates
Gas, carry out burn or absorbed with lye；
Finally, organic solvent 1 is added in reactor tank, unreacted raw material and captax are washed away；Its insoluble matter is through filtering
Afterwards, it is further washed with organic solvent 2, takes its insoluble matter ingredient, obtain 2- anilino- benzothiazole.
2. the synthetic method of 2- anilino- benzothiazole according to claim 1, it is characterised in that:
The aniline, carbon disulfide, sulphur molar ratio be 1:(0.3~0.7): (0.2~0.8).
3. the synthetic method of 2- anilino- benzothiazole according to claim 1, it is characterised in that:
The sulphur is selected from least one of elemental sulfur or crystallization sulphur.
4. the synthetic method of 2- anilino- benzothiazole according to claim 1, it is characterised in that:
The temperature of the reaction is 250~300 DEG C, preferably 260~280 DEG C.
5. the synthetic method of 2- anilino- benzothiazole according to claim 1, it is characterised in that:
The pressure of the reaction is 5~10MPa, preferably 6~9MPa.
6. the synthetic method of 2- anilino- benzothiazole according to claim 1, it is characterised in that:
The time of the reaction is 200~360min, preferably 300~360min.
7. the synthetic method of 2- anilino- benzothiazole according to claim 1, it is characterised in that:
The organic solvent 1 and organic solvent 2, is respectively and independently selected from toluene, dimethylbenzene, methanol, ethyl alcohol, acetone, curing
Carbon, at least one of ether, preferably toluene and/or ethyl alcohol；Meanwhile the organic solvent 1 and organic solvent 2 is difference
Solvent.
8. the 2- anilino- benzothiazole that described in any item synthetic methods according to claim 1~7 are prepared.
9. including a kind of rubber composition of 2- anilino- benzothiazole according to any one of claims 8, it is characterised in that the rubber
Composition includes the following components of parts by weight meter:
The rubber of 100 mass parts；
The 2- anilino- benzothiazole of 1~10 mass parts, preferably 1~5 mass parts；
The sulphur of 1~5 mass parts, preferably 1~3 mass parts；
The zinc oxide of 0.5~6 mass parts, preferably 1.5~3 mass parts；
The stearic acid of 1~4 mass parts.
10. the application of the 2- anilino- benzothiazole of any one the method preparation according to claim 1~7, the application
Including preferably including the preparation for adhesive tape, tire, sebific duct in the composite material preparation for participating in the vulcanization of rubber.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111548591A (en) * | 2020-06-22 | 2020-08-18 | 安徽立信橡胶科技有限公司 | Oil-resistant high-temperature-resistant acrylate rubber and preparation method thereof |
| CN111943909A (en) * | 2020-08-31 | 2020-11-17 | 华南理工大学 | Rubber accelerator selenobenzothiazole and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102070562A (en) * | 2010-12-21 | 2011-05-25 | 天津大学 | Method for preparing 2-mercaptobenzothiazole |
| CN104004234A (en) * | 2014-05-26 | 2014-08-27 | 芜湖风雪橡胶有限公司 | Rubber material composition for soles and method for preparing rubber material for soles |
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2018
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102070562A (en) * | 2010-12-21 | 2011-05-25 | 天津大学 | Method for preparing 2-mercaptobenzothiazole |
| CN104004234A (en) * | 2014-05-26 | 2014-08-27 | 芜湖风雪橡胶有限公司 | Rubber material composition for soles and method for preparing rubber material for soles |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111548591A (en) * | 2020-06-22 | 2020-08-18 | 安徽立信橡胶科技有限公司 | Oil-resistant high-temperature-resistant acrylate rubber and preparation method thereof |
| CN111943909A (en) * | 2020-08-31 | 2020-11-17 | 华南理工大学 | Rubber accelerator selenobenzothiazole and preparation method and application thereof |
| CN111943909B (en) * | 2020-08-31 | 2022-10-25 | 华南理工大学 | Rubber accelerator selenobenzothiazole and preparation method and application thereof |
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