CN104230844B - The preparation method of accelerator CZ - Google Patents
The preparation method of accelerator CZ Download PDFInfo
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- CN104230844B CN104230844B CN201410437020.5A CN201410437020A CN104230844B CN 104230844 B CN104230844 B CN 104230844B CN 201410437020 A CN201410437020 A CN 201410437020A CN 104230844 B CN104230844 B CN 104230844B
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- cyclohexylamine
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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
Abstract
The invention belongs to technical field of chemical synthesis, the preparation method being specifically related to a kind of accelerator CZ, be beaten into salt, oxidation, sucking filtration washing, dry, and get final product.The present invention adopts step-by-step oxidation method, namely reaction early stage adopts dioxygen oxidation, the technique that later stage adopts hypochlorite oxidation, effectively reduce sodium hypochlorite oxidization and produce the salinity of waste water, there is the advantages such as technique is simple, cost is low, environmental pollution is few, be the process route with industrial application value of an environmental protection.
Description
Technical field
The invention belongs to technical field of chemical synthesis, the preparation method being specifically related to a kind of accelerator CZ.
Background technology
At present, the production method of domestic and international accelerant CZ mainly has hydrogen peroxide oxidation method, sodium hypochlorite oxidization, anaerobic agent synthetic method, dioxygen oxidation method etc. four kinds.
(1) hydrogen peroxide oxidation method
Hydrogen peroxide oxidation method is to be succeeded in developing by Dimitrova company of Czech for 1948, synthetic method puts into a certain amount of recovery cyclohexylamine first in the reactor, under agitation add 2 benzothiazolyl mercaptans (captax), after stirring, add fresh cyclohexylamine, continue stirring, make M and the abundant miscible pulp of cyclohexylamine.Then dripping hydrogen peroxide within a certain period of time, add speed and guarantee that reaction temperature is below 30 DEG C, reaction stops adding hydrogen peroxide after reaching terminal, reactant liquor is made to put in suction strainer groove after slightly lowering the temperature, through vacuum suction filter, filtrate removes Distillation recovery cyclohexylamine, and namely filter cake dehydrate after washing repeatedly obtains product.Hydrogen peroxide oxidation method produces without salt, and environment is substantially harmless, but the productivity that can produce a large amount of waste water and products obtained therefrom in hydrogen peroxide oxidation process is relatively low.
(2) sodium hypochlorite oxidization
Sodium hypochlorite oxidization is to be succeeded in developing by About Monsanto Chemicals for 1948, and first synthetic method puts into sodium hydrate aqueous solution in sodium hypochlorite reaction device, then passes into chlorine under lower than 20 DEG C of conditions and reacts and prepare sodium hypochlorite.Stills for air blowing add a certain amount of recovery cyclohexylamine, after under agitation input captax stirs, add fresh cyclohexylamine, continue stirring and make M and the abundant miscible pulp of amine, then dripping sodium hypochlorite lower than 30 DEG C when to react, stop to add sodium hypochlorite to terminal afterwards, reactant liquor is through suction strainer, filtrate send Distillation recovery cyclohexylamine, and filter cake is drying to obtain product through rinse dehydration.Sodium hypochlorite oxidization process stabilizing, yield simple to operate, low for equipment requirements and product are high, it it is domestic commonly used method, but producing substantial amounts of brine waste in this method course of reaction, the difficult treatment of waste water and processing cost are high, and environment has certain pollution.
(3) anaerobic agent synthetic method
Anaerobic agent synthetic method is that Bayer AG of Germany developed in 1984, first synthetic method is prepared at dibenzothiazyl disulfide (altax) and is added a certain amount of water in still, under agitation add captax and sodium nitrite, sulphuric acid is added with certain speed, pass under 60 DEG C of conditions air reaction prepare altax, this DM through rinse dehydration for the next step.Accelerant CZ reactor adds a certain amount of cyclohexylamine and water, under agitation heat to 50 DEG C, the DM of above-mentioned preparation is added within certain time, it is simultaneously introduced the NaOH aqueous solution of a certain amount of 50%, pH value controls between 11～12, continuing stirring 2h after reinforced, then precipitate filtration, washing and drying obtains product.But auxiliary material consumes more aborning, and technical process is complex, and production there is NO release and contaminated environment, will have substantial amounts of Na simultaneously2SO4Aqueous solution needs to process.So, this technique is not yet adopted by domestic and international each manufacturer at present.
(4) dioxygen oxidation method
Dioxygen oxidation method is succeeded in developing in 1987 by Aksu company of Holland, synthetic method adds water in the reactor with chuck, temperature and pressure detecting device, agitator, add captax, catalyst and ammonia under vigorous stirring, then heat to 50 DEG C, passing into oxygen makes pressure reach 0.4MPa, a certain amount of cyclohexylamine is added in 3h, then 2h is reacted again, when oxygen uptake is little, reaction reaches terminal, stops stirring, and namely white precipitate obtains product through filtration, washing, dehydrate, filtrate and water lotion send distillation, to reclaim ammonia and excessive cyclohexylamine.It is critical only that of dioxygen oxidation method selects properly and the catalyst of function admirable, and the method is domestic at present is still in conceptual phase.
Summary of the invention
The preparation method that it is an object of the invention to provide a kind of accelerator CZ, technique is simple, cost is low, environmental pollution is few.
The preparation method of accelerator CZ of the present invention, step is as follows:
(1) it is beaten into salt: weigh captax, water, cyclohexylamine and catalyst standby；Add water in a kettle., under strong stirring, add captax, cyclohexylamine and catalyst, make captax and cyclohexylamine carry out fully being beaten into salt；
(2) oxidation: be warming up to 40-50 DEG C, passes into oxygen and makes pressure reach 0.35-0.4MPa, react 2-4h；Then lower the temperature, drip sodium hypochlorite when 30-40 DEG C and react, stop afterwards to terminal to add sodium hypochlorite；
(3) sucking filtration washing: sucking filtration washing product, to neutral, obtains white precipitate；Containing excessive cyclohexylamine in filtrate, directly carry out reuse to the first step；
(4) dry: namely white precipitate obtains product through filtration, washing, dehydrate.
Catalyst described in step (1) is Schweinfurt green.
The mol ratio of the captax described in step (1) and cyclohexylamine is 1:1.3-1.7.
The mol ratio of the captax described in step (1) and water is 1:1.5-1.7.
The mass ratio of the catalyst described in step (1) and captax is 0.9-1.1:1000.
Baking temperature described in step (4) is 55-60 DEG C, and drying time is 1.5-2h.
Composition principle:
The synthetic reaction of accelerator cz is divided into two steps, is namely beaten into salt and oxidation.
1. 2-mercaptobenzothiazole (captax) and cyclohexylamine react generation 2-mercaptobenzothiazole cyclohexylamine thiazole salt；
2. cyclohexylamine salt of 2 mercaptobenzothioazole is generated CZ by oxygen or hypochlorite oxidation.
The experiment that CZ yield is affected by process conditions:
(1) primary raw material and instrument
Essence M (industrial goods, mass fraction >=95%), cyclohexylamine (industrial goods, C6H12Mass fraction >=98%), oxygen, Schweinfurt green, sodium hydroxide, chlorine.Reactor, effusion meter.
(2) synthesis step
The technical process of step-by-step oxidation method includes making beating, oxidation, sucking filtration washing and dries.
(1) it is beaten into salt: weigh the M of certain proportioning, water, cyclohexylamine and catalyst standby；The reactor with chuck, temperature and pressure detecting device, agitator adds water, under uniform stirring, adds captax, cyclohexylamine and catalyst, make M and cyclohexylamine carry out fully being beaten into salt.
(2) oxidation: first heat up, after stirring a period of time, passes into oxygen, after reaction a period of time, then cooling dropping sodium hypochlorite, reaction stops stirring mixed indicator after terminating and detects terminal.
(3) sucking filtration washing: sucking filtration washing product is to neutral；Containing excessive cyclohexylamine in filtrate, sucking filtration and first time water lotion are directly arrived the first step and carry out reuse.
(4) dry: wet product CZ puts in baking oven, dry 2h under 60 DEG C of conditions and obtain finished product.
(3) result and discussion
1, n (M): n (cyclohexylamine) (same under the mol ratio) impact on CZ yield
For investigating n (M): n (cyclohexylamine) impact on reaction, intrinsic pressure for still trying hard to keep is held 0.4MPa, reaction temperature 40 DEG C, under 400r/min stirring condition, react 4h, its result is in Table 1.
Table 1n (M): n (cyclohexylamine) impact on CZ yield
| N (M): n (cyclohexylamine) | Yield % | Product colour | Product is fusing point DEG C just |
| 1:1.8 | 89.0 | In vain | More than 98 |
| 1:1.7 | 91.5 | In vain | More than 98 |
| 1:1.4 | 87.7 | In vain | More than 98 |
| 1:1.3 | 81.6 | In vain | More than 98 |
| 1:1.2 | 80.2 | HUANGBAI(sic) | Defective |
As can be seen from Table 1, at n (M): n (cyclohexylamine) is within the scope of 1:1.2-1:1.7, and along with the increase of cyclohexylamine amount, yield also increases, and product colour and first fusing point also defective change to high-quality product from original.As n (M): n (cyclohexylamine) for 1:1.8 after, the yield of product declines on the contrary, and test in find the sad filter of reacted mixture.This is likely to be due to cyclohexylamine and causes the CZ dissolved in the solution too much to make yield decline too much.Therefore, n (M): n (cyclohexylamine) is better for 1:1.7.
2, the oxygen reaction temperature impact on CZ yield
Intrinsic pressure for still power is maintained at 0.4MPa, n (M): n (cyclohexylamine) for, under 1:1.7,400r/min stirring condition, reacting 4h.Investigating the reaction temperature impact on reaction, its result is in Table 2.
The impact on product yield and character of table 2 reaction temperature
| Reaction temperature DEG C | Yield % | Product colour | Product is fusing point DEG C just |
| 50 | 90.0 | Light grey | More than 96 |
| 45 | 90.8 | Canescence | More than 96 |
| 40 | 91.5 | White | More than 98 |
| 35 | 90.6 | Canescence | More than 97 |
| 30 | 77.9 | Yellow-white | Defective |
Through experiment it can be seen that react below 30 DEG C and carry out hardly, it is Lycoperdon polymorphum Vitt or black more than 55 DEG C of products.As can be seen from Table 2, below 40 DEG C, along with the rising product yield of temperature increases therewith, product colour is changed to white by HUANGBAI(sic).First fusing point by defective to qualified transformation.After 50 DEG C, owing to the increase of by-product makes color graying, first fusing point also declines.It can thus be appreciated that 40 DEG C of reactions are better.
3, the oxygen reaction pressure impact on CZ yield
Being 40 DEG C in reaction temperature, n (M): n (cyclohexylamine) is for, under 1:1.7,400r/min stirring condition, reacting 4h.Investigating the reaction pressure impact on reaction, its result is in Table 3.
The impact on product yield and character of table 3 reaction pressure
| Reaction pressure MPa | Product yield % | Product colour | Product is fusing point DEG C just |
| 0.5 | 90.5 | White lime color | More than 98 |
| 0.4 | 91.5 | White | More than 98 |
| 0.3 | 90.0 | White | More than 98 |
| 0.2 | 89.3 | White | More than 98 |
| 0.1 | 60.5 | Light yellow | Defective |
As can be seen from Table 3, before 0.4MPa, product yield increases with the increase of reaction pressure.But reaction pressure is raised to 0.4MPa from 0.2MPa, the amplitude that product yield increases is little, it does not have 0.1-0.2MPa is obvious like that.Reason is probably under low pressure to dissolve the amount of oxygen in a liquid and limits the carrying out of reaction, and namely oxygen presses to ratedeterming step；With the raising of reaction pressure, dissolved oxygen content increases, and oxygen pressure is no longer ratedeterming step, then improves oxygen pressure and can not continue to make productivity increase.Under 0.5MPa, reaction yield declines on the contrary, and this is probably oxygen pressure increase and causes the result of over oxidation.From the color of product it can also be seen that this point.To sum up considering, reaction pressure is that 0.4MPa is better.
4, the oxygen reaction time impact on CZ yield
Intrinsic pressure for still power is maintained at 0.4MPa, and reaction temperature is 40 DEG C, and n (M): n (cyclohexylamine), for, under 1:1.7,400r/min stirring condition, investigating the impact of reaction time on yield and character, result is in Table 4.
The impact on product yield and character of table 4 response time
| Response time h | Product yield % | Product colour | Product is fusing point DEG C just |
| 2 | 89.5 | White | More than 98 |
| 3 | 91.3 | White | More than 98 |
| 4 | 91.5 | White | More than 98 |
| 5 | 90.8 | Canescence | More than 98 |
| 6 | 89.3 | Lycoperdon polymorphum Vitt | More than 96 |
As can be seen from Table 4, product yield increases in time and increases, and product colour is constantly deepened, it may be possible to owing to the increase of over oxidation and by-product causes.Therefore, response time 4h is as well.
5, the determination of stir speed (S.S.)
Find through experiment, increase mixing speed and can make the distribution evenly of each component, when being also avoided that addition cyclohexylamine, form granule.By experiment, adopting low whipping speed is addition cyclohexylamine under 500r/min, after having added, changes 400r/min into and continues reaction.
6, the catalyst amount impact on the yield of CZ
Experiment finds, response speed is had large effect by catalyst.Catalytic amount is few, and reaction is slow, and product yield is low；Catalytic amount is big, and by-product increases, and product colour and first fusing point are all bad, and have the metal impurities of black in product.Its result is in Table 5.
The impact on the yield of CZ of table 5 catalyst amount
| Catalytic amount mg/gM | Product yield % | Product colour and state | Product is fusing point DEG C just |
| 2.0 | 90.8 | Greyish white and have black slag | 96 |
| 1.5 | 90.7 | Lycoperdon polymorphum Vitt | 98 |
| 1.0 | 91.5 | White | 98 |
| 0.5 | 83.2 | Yellow-white | Defective |
As shown in Table 5, catalyst amount is advisable with 1.0mg/g captax.
7, the sodium hypochlorite dropping temperature impact on the yield of CZ
When sodium hypochlorite time for adding is 30min, having investigated the dropping temperature impact on CZ productivity and first fusing point, result is in Table 6.Test result indicate that, when reaction temperature is between 30-40 DEG C, the productivity of products obtained therefrom is higher, and product is white crystal, first fusing point >=99.5 DEG C, quality better；Reaction temperature is product color intensification later more than 45 DEG C, and by-product increases.Therefore, selected sodium hypochlorite dropping temperature 30 DEG C.
The impact on the yield of CZ of the table 6 sodium hypochlorite dropping temperature
| Dropping temperature DEG C | Product yield % | Product is fusing point DEG C just |
| 20 | 95 | 94.6 |
| 25 | 95.1 | 96.2 |
| 30 | 96.3 | 98.0 |
| 35 | 95.3 | 98.3 |
| 40 | 94.5 | 98.9 |
| 45 | 94.0 | 99.9 |
8, the sodium hypochlorite time for adding impact on the yield of CZ
Investigating the impact on CZ productivity of the sodium hypochlorite time for adding under 30 DEG C of conditions of sodium hypochlorite dropping temperature, result is in Table 7.The speed of sodium hypochlorite rate of addition is inconspicuous to the yield impact of product, it is allowed to the dropping of fast speed, thus reducing the response time.But rate of addition is too fast, sodium hypochlorite has not enough time to participate in reaction and decompose and will result in sodium hypochlorite loss.Considering, the time for adding of sodium hypochlorite is 40min.
The impact on the yield of CZ of the table 7 sodium hypochlorite time for adding
| Time for adding min | Product yield % |
| 20 | 94 |
| 30 | 94.8 |
| 40 | 95.1 |
| 50 | 94.9 |
| 60 | 94.5 |
Having investigated the impact on reaction of the process conditions such as cyclohexylamine consumption, flow of oxygen, oxygen temperature and time, sodium hypochlorite dropping temperature and time, optimizing the process conditions obtaining being suitable for is that experiment show that optimum condition is: n (C6H12)/n (M) (mol ratio)=1:1.7, oxygen reaction temperature is 40 DEG C, and reaction pressure is under 0.4MPa, 400r/min stirring condition, and the time is 4.0h, and catalyst amount is with 1.0mg/g；Sodium hypochlorite dropping temperature is 30 DEG C, and time for adding is 40min so that the average yield of product reaches 95.0%, and purity is 99.0%, reaches the standard of domestic industry high-class product.This technique need not additionally add other solvents, and cyclohexylamine recycles in system, adopts the oxygen of cheap and easy to get and environmental protection as oxidant, has not only saved cost, but also environmental sound；The productivity of this method, close to the high yield level of tradition sodium hypochlorite oxidization, simultaneously effective reduces the salinity of sodium-hypochlorite process waste water, makes waste water salinity reduce 70%.This technique uses for reference the dioxygen oxidation method technique in the past proposed, and makes improvements, and eliminates Ammonia as Solvent one step, environmental protection more economically, is a green process route with commercial development value.Products obtained therefrom reaches HG/T2096 2006 industry primes standard with this understanding.
The present invention compared with prior art, has the advantages that
Oxidizing process is improved by the present invention.This project research step-by-step oxidation method, namely reaction early stage adopts dioxygen oxidation, the technique that later stage adopts hypochlorite oxidation, effectively reduce sodium hypochlorite oxidization and produce the salinity of waste water, there is the advantages such as technique is simple, cost is low, environmental pollution is few, be the process route with industrial application value of an environmental protection.The popularization of this technology, the healthy and sustainable development for China's rubber accelerator has great progradation.Accelerant N-cyclohexyl-2-[4-morpholinodithio sulfenamide (is called for short cz) will not produce nitrosamine carcinogen in sulfidation, it is one of current environment-friendly type accelerator commonly used both at home and abroad, the research and development of this project are implemented, not only realize good economic benefit, and for developing a circular economy, there is positive role, there is good promotional value.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
(1) it is beaten into salt: weigh captax 167g, water 27g, cyclohexylamine 128.7g and Schweinfurt green 0.15g standby；Add water in a kettle., under strong stirring, add captax, cyclohexylamine and Schweinfurt green, make captax and cyclohexylamine carry out fully being beaten into salt；
(2) oxidation: be warming up to 40 DEG C, passes into oxygen and makes pressure reach 0.35MPa, react 2h；Then lower the temperature, drip sodium hypochlorite when 30 DEG C and react, stop afterwards to terminal to add sodium hypochlorite；
(3) sucking filtration washing: sucking filtration washing product, to neutral, obtains white precipitate；Containing excessive cyclohexylamine in filtrate, directly carry out reuse to the first step；
(4) dry: white precipitate is through filtration, washing, dehydrate, and baking temperature is 55 DEG C, and drying time is 1.5h, obtains product.
Embodiment 2
(1) it is beaten into salt: weigh captax 167g, water 30.6g, cyclohexylamine 168.3g and Schweinfurt green 0.18g standby；Add water in a kettle., under strong stirring, add captax, cyclohexylamine and Schweinfurt green, make captax and cyclohexylamine carry out fully being beaten into salt；
(2) oxidation: be warming up to 50 DEG C, passes into oxygen and makes pressure reach 0.4MPa, react 4h；Then lower the temperature, drip sodium hypochlorite when 40 DEG C and react, stop afterwards to terminal to add sodium hypochlorite；
(3) sucking filtration washing: sucking filtration washing product, to neutral, obtains white precipitate；Containing excessive cyclohexylamine in filtrate, directly carry out reuse to the first step；
(4) dry: white precipitate is through filtration, washing, dehydrate, and baking temperature is 60 DEG C, and drying time is 2h, obtains product.
Embodiment 3
(1) it is beaten into salt: weigh captax 167g, water 30g, cyclohexylamine 150g and Schweinfurt green 0.16g standby；Add water in a kettle., under strong stirring, add captax, cyclohexylamine and Schweinfurt green, make captax and cyclohexylamine carry out fully being beaten into salt；
(2) oxidation: be warming up to 45 DEG C, passes into oxygen and makes pressure reach 0.38MPa, react 3h；Then lower the temperature, drip sodium hypochlorite when 35 DEG C and react, stop afterwards to terminal to add sodium hypochlorite；
(3) sucking filtration washing: sucking filtration washing product, to neutral, obtains white precipitate；Containing excessive cyclohexylamine in filtrate, directly carry out reuse to the first step；
(4) dry: white precipitate is through filtration, washing, dehydrate, and baking temperature is 57 DEG C, and drying time is 1.8h, obtains product.
Claims (5)
1. the preparation method of an accelerator CZ, it is characterised in that step is as follows:
(1) it is beaten into salt: weigh captax, water, cyclohexylamine and catalyst standby；Add water in a kettle., under strong stirring, add captax, cyclohexylamine and catalyst, make captax and cyclohexylamine carry out fully being beaten into salt；
(2) oxidation: be warming up to 40-50 DEG C, passes into oxygen and makes pressure reach 0.35-0.4MPa, react 2-4h；Then lower the temperature, drip sodium hypochlorite when 30-40 DEG C and react, stop afterwards to terminal to add sodium hypochlorite；
(3) sucking filtration washing: sucking filtration washing product, to neutral, obtains white precipitate；Containing excessive cyclohexylamine in filtrate, directly carry out reuse to the first step；
(4) dry: namely white precipitate obtains product through filtration, washing, dehydrate；
The mass ratio of the catalyst described in step (1) and captax is 0.9-1.1:1000.
2. the preparation method of accelerator CZ according to claim 1, it is characterised in that the catalyst described in step (1) is Schweinfurt green.
3. the preparation method of accelerator CZ according to claim 1, it is characterised in that the mol ratio of the captax described in step (1) and cyclohexylamine is 1:1.3-1.7.
4. the preparation method of accelerator CZ according to claim 1, it is characterised in that the mol ratio of the captax described in step (1) and water is 1:1.5-1.7.
5. the preparation method of accelerator CZ according to claim 1, it is characterised in that the baking temperature described in step (4) is 55-60 DEG C, drying time is 1.5-2h.
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| CN106800540A (en) * | 2017-03-30 | 2017-06-06 | 山东斯递尔化工科技有限公司 | A kind of method that utilization micro passage reaction prepares rubber vulcanizing accelerator CBS |
| CN107445918A (en) * | 2017-08-14 | 2017-12-08 | 青岛奥克凯姆化学助剂有限公司 | Solvent purifications method rubber accelerator M synthesis sulfenamide type accelerators CBS method |
| CN112409291A (en) * | 2020-12-03 | 2021-02-26 | 鹤壁市恒力橡塑股份有限公司 | Preparation method of rubber accelerator CBS |
| CN113979967B (en) * | 2021-12-27 | 2022-04-08 | 科迈化工股份有限公司 | Method for catalytic synthesis of accelerator CBS by ionic liquid protective agent |
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