CN104230844A - Preparation method of vulcanization accelerator CZ - Google Patents
Preparation method of vulcanization accelerator CZ Download PDFInfo
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- CN104230844A CN104230844A CN201410437020.5A CN201410437020A CN104230844A CN 104230844 A CN104230844 A CN 104230844A CN 201410437020 A CN201410437020 A CN 201410437020A CN 104230844 A CN104230844 A CN 104230844A
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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 invention belongs to the field of chemical synthesis technology, and particularly relates to a preparation method of a vulcanization accelerator CZ. The preparation method comprises the following steps: pulping and salifying, oxidizing, carrying out suction filtering and washing, and drying, thus obtaining the vulcanization accelerator CZ. By adopting a step-by-step oxidization method, namely a technology of oxygen oxidization at the earlier stage of the reaction and sodium hypochlorite oxidization at the later stage, the salt content of the waste water generated by adopting a sodium hypochlorite oxidization method can be effectively reduced, and the preparation method has the advantages of being simple in technology, low in cost, less in environment pollution and the like, thus being a green and environment-friendly technological route having industrial application values.
Description
Technical field
The invention belongs to technical field of chemical synthesis, be specifically related to a kind of preparation method of accelerator CZ.
Background technology
At present, the production method of domestic and international accelerant CZ mainly contains hydrogen peroxide oxidation method, sodium hypochlorite oxidization, anaerobic agent synthesis method, dioxygen oxidation method etc. four kinds.
(1) hydrogen peroxide oxidation method
Hydrogen peroxide oxidation method is succeeded in developing by Dimit rova company of Czech for 1948, synthetic method drops into a certain amount of recovery hexahydroaniline first in the reactor, under agitation add 2 benzothiazolyl mercaptans (captax), after stirring, add fresh hexahydroaniline, continue to stir, make M and the abundant miscible pulp of hexahydroaniline.Then drip hydrogen peroxide within a certain period of time, add speed and guarantee that temperature of reaction is below 30 DEG C, stop adding hydrogen peroxide after reaction reaches terminal, suction strainer groove is put into after reaction solution is slightly lowered the temperature, through vacuum suction filter, filtrate removes Distillation recovery hexahydroaniline, and filter cake dehydrates and obtains product after washing repeatedly.Hydrogen peroxide oxidation method produces without salt, substantially harmless to environment, but the productive rate that can produce a large amount of waste water and products obtained therefrom in hydrogen peroxide oxidation process is lower.
(2) sodium hypochlorite oxidization
Sodium hypochlorite oxidization is succeeded in developing by About Monsanto Chemicals for 1948, and first synthetic method drops into aqueous sodium hydroxide solution in sodium hypochlorite reaction device, then passes into chlorine under lower than 20 DEG C of conditions and carry out reaction and prepare clorox.A certain amount of recovery hexahydroaniline is added in stills for air blowing, after under agitation input captax stirs, add fresh hexahydroaniline, continue stirring and make M and the abundant miscible pulp of amine, then drip clorox under lower than the condition of 30 DEG C to react, stop afterwards to terminal to add clorox, reaction solution is through suction strainer, filtrate send Distillation recovery hexahydroaniline, and filter cake is drying to obtain product through rinse dehydration.Sodium hypochlorite oxidization process stabilizing, simple to operate, low for equipment requirements and the yield of product is high, it is the domestic method generally adopted, but produce a large amount of brine wastes in this method reaction process, the difficult treatment of waste water and processing cost is high, have certain pollution to environment.
(3) anaerobic agent synthesis method
Anaerobic agent synthesis method is that German Bayer AG was in exploitation in 1984, first synthetic method is prepared in still at dibenzothiazyl disulfide (altax) and is added a certain amount of water, under agitation add captax and Sodium Nitrite, sulfuric acid is added with certain speed, under 60 DEG C of condition, pass into air reaction obtain altax, this DM through rinse dehydration for the next step.A certain amount of hexahydroaniline and water is added in accelerant CZ reactor, under agitation be heated to 50 DEG C, the DM of above-mentioned preparation is added in certain hour, add the NaOH aqueous solution of a certain amount of 50% simultaneously, pH value controls between 11 ~ 12, continue after reinforced to stir 2h, then sedimentation and filtration, washing and drying obtains product.But auxiliary material consumes more aborning, and technological process is comparatively complicated, and in producing, there is NO to release and contaminate environment, will a large amount of Na be had simultaneously
2sO
4the aqueous solution needs process.So, this technique at present not yet adopt by domestic and international each manufacturer.
(4) dioxygen oxidation method
Dioxygen oxidation method is succeeded in developing in 1987 by Dutch Aksu company, synthetic method adds water in the reactor with chuck, temperature and pressure proofing unit, agitator, add captax, catalyzer and ammoniacal liquor under vigorous stirring, then 50 DEG C are warming up to, passing into oxygen makes pressure reach 0.4MPa, a certain amount of hexahydroaniline is added in 3h, and then react 2h, when oxygen uptake is little, reaction reaches terminal, stops stirring, white precipitate after filtration, wash, dehydrate and obtain product, filtrate and water lotion send distillation, to reclaim ammonia and excessive hexahydroaniline.The key of dioxygen oxidation method is to select the suitable and catalyzer of excellent property, and the method is domestic at present is still in conceptual phase.
Summary of the invention
The object of this invention is to provide a kind of preparation method 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) making beating salify: take captax, water, hexahydroaniline and catalyzer for subsequent use; Add water in a kettle., under strong stirring, add captax, hexahydroaniline and catalyzer, make captax and hexahydroaniline carry out making beating salify fully;
(2) be oxidized: be warming up to 40-50 DEG C, pass into oxygen and make pressure reach 0.35-0.4MPa, reaction 2-4h; Then lower the temperature, under the condition of 30-40 DEG C, drip clorox react, stop afterwards to terminal to add clorox;
(3) suction filtration washing: suction filtration washing product, to neutral, obtains white precipitate; Containing excessive hexahydroaniline in filtrate, directly carry out reuse to the first step;
(4) dry: white precipitate filters, washes, dehydrates and obtains product.
Catalyzer described in step (1) is neutralized verdigris.
The mol ratio of the captax described in step (1) and hexahydroaniline 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 catalyzer described in step (1) and captax is 0.9-1.1:1000.
Drying temperature described in step (4) is 55-60 DEG C, and time of drying is 1.5-2h.
Composition principle:
The building-up reactions of promotor cz is divided into two steps, namely pull an oar salify and oxidation.
1. 2-mercaptobenzothiazole (captax) and hexahydroaniline react and generate 2-mercaptobenzothiazole hexahydroaniline thiazole salt;
2. cyclohexylamine salt of 2 mercaptobenzothioazole is generated CZ by oxygen or hypochlorite oxidation.
The experiment that processing condition affect CZ yield:
(1) main raw material and instrument
Essence M (industrial goods, massfraction>=95%), hexahydroaniline (industrial goods, C
6h
12massfraction>=98%), oxygen, neutralized verdigris, sodium hydroxide, chlorine.Reactor, under meter.
(2) synthesis step
The technological process of step-by-step oxidation method comprises making beating, oxidation, suction filtration washing and drying.
(1) making beating salify: take the M of certain proportioning, water, hexahydroaniline and catalyzer for subsequent use; In the reactor with chuck, temperature and pressure proofing unit, agitator, add water, under uniform stirring, add captax, hexahydroaniline and catalyzer, make M and hexahydroaniline carry out making beating salify fully.
(2) be oxidized: first heat up, after stirring for some time, pass into oxygen, after reaction for some time, then cooling drips clorox, and reaction terminates rear stopping stirring mixture indicator endpoint detection.
(3) suction filtration washing: suction filtration washing product is to neutral; Containing excessive hexahydroaniline in filtrate, by suction filtration and first time water lotion directly arrive the first step and carry out reuse.
(4) dry: wet product CZ puts into baking oven, dries 2h and obtain finished product under 60 DEG C of conditions.
(3) result and discussion
1, the impact of n (M): n (hexahydroaniline) (same under mol ratio) on CZ yield
For investigating n (M): n (hexahydroaniline) to the impact of reacting, still internal pressure is kept 0.4MPa, temperature of reaction 40 DEG C, under 400r/min agitation condition, reaction 4h, it the results are shown in Table 1.
Table 1 n (M): n (hexahydroaniline) is on the impact of CZ yield
| N (M): n (hexahydroaniline) | 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 | Yellowish-white | Defective |
As can be seen from Table 1, at n (M): n (hexahydroaniline) within the scope of 1:1.2-1:1.7, along with the increase of hexahydroaniline amount, yield also increases, and product colour and first fusing point also defectively to change to high-quality product from original.After n (M): n (hexahydroaniline) is for 1:1.8, the output of product declines on the contrary, and finds the sad filter of reacted mixture in experiment.This may cause dissolving CZ in the solution too much to make production declining due to hexahydroaniline too much.Therefore, n (M): n (hexahydroaniline) for 1:1.7 better.
2, oxygen reaction temperature is on the impact of CZ yield
Still internal pressure is remained on 0.4MPa, and n (M): n (hexahydroaniline), under 1:1.7,400r/min agitation condition, reacts 4h.Investigate the impact of temperature of reaction on reaction, it the results are shown in Table 2.
Table 2 temperature of reaction is on the impact of product yield and proterties
| Temperature of reaction 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 |
Known through testing, below 30 DEG C, reaction is carried out hardly, is grey 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 thereupon, product colour by yellowish-white to white transition.First fusing point by defective to qualified transformation.After 50 DEG C, the increase due to by product makes color become ash, and first fusing point also declines.It can thus be appreciated that 40 DEG C of reactions better.
3, oxygen reaction pressure is on the impact of CZ yield
Be 40 DEG C in temperature of reaction, n (M): n (hexahydroaniline) under 1:1.7,400r/min agitation condition, reaction 4h.Investigate the impact of reaction pressure on reaction, it the results are shown in Table 3.
Table 3 reaction pressure is on the impact of product yield and proterties
| Reaction pressure MPa | Product yield % | Product colour | Product is fusing point DEG C just |
| 0.5 | 90.5 | Lime look | 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, does not have 0.1-0.2MPa obvious like that.Reason may be the carrying out that the amount of dissolving oxygen in a liquid under low pressure limits 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 productive rate increase.Under 0.5MPa, reaction yield declines on the contrary, and this may be the result that oxygen pressure increase causes over oxidation.Also this point can be found out from the color of product.To sum up consider, reaction pressure is that 0.4MPa is better.
4, the oxygen reaction time is on the impact of CZ yield
Still internal pressure is remained on 0.4MPa, and temperature of reaction is 40 DEG C, and n (M): n (hexahydroaniline), under 1:1.7,400r/min agitation condition, is investigated the impact of reaction time on yield and proterties, be the results are shown in Table 4.
Table 4 reaction times is on the impact of product yield and proterties
| Reaction times 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 | Grey | More than 96 |
As can be seen from Table 4, product yield increases in time and increases, and product colour is constantly deepened, and may be because the increase of over oxidation and by product causes.Therefore, the reaction times with 4h as well.
5, the determination of stir speed (S.S.)
Through experiment find, increase stirring velocity can make each component evenly distribution, when also can avoid adding hexahydroaniline formed particle.By experiment, adopt low whipping speed to be add hexahydroaniline under 500r/min, after having added, change 400r/min into and continue reaction.
6, catalyst levels is on the impact of the yield of CZ
Experiment finds, catalyzer has larger impact to speed of response.Catalytic amount is few, and reaction is slow, and product yield is low; Catalytic amount is large, and by product increases, product colour and first fusing point all bad, and in product, have the metallic impurity of black.It the results are shown in Table 5.
Table 5 catalyst levels is on the impact of the yield of CZ
| 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 | Grey | 98 |
| 1.0 | 91.5 | White | 98 |
| 0.5 | 83.2 | Yellow-white | Defective |
As shown in Table 5, catalyst levels is advisable with 1.0mg/g captax.
7, clorox dropping temperature is on the impact of the yield of CZ
Under clorox time for adding is 30min condition, investigates the impact of dropping temperature on CZ productive rate and first fusing point, the results are shown in Table 6.Experimental result shows, when temperature of reaction is between 30-40 DEG C, the productive rate of products obtained therefrom is higher, and product is white crystal, first fusing point >=99.5 DEG C, quality better; Temperature of reaction is product color intensification later more than 45 DEG C, and by product increases.Therefore, selected clorox dropping temperature 30 DEG C.
Table 6 clorox dropping temperature is on the impact of the yield of CZ
| 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, clorox time for adding is on the impact of the yield of CZ
Under clorox dropping temperature 30 DEG C of conditions, investigate the impact of clorox time for adding on CZ productive rate, the results are shown in Table 7.The yield impact of speed to product of clorox rate of addition is not obvious, allows the dropping of fast speed, thus reduces the reaction times.But rate of addition is too fast, clorox does not have enough time to participate in reaction and decomposition will cause clorox to lose.Consider, the time for adding of clorox is 40min.
Table 7 clorox time for adding is on the impact of the yield of CZ
| Time for adding min | Product yield % |
| 20 | 94 |
| 30 | 94.8 |
| 40 | 95.1 |
| 50 | 94.9 |
| 60 | 94.5 |
Investigated the impact of the processing condition such as hexahydroaniline consumption, flow of oxygen, oxygen temperature and time, clorox dropping temperature and time on reaction, optimizing the processing condition obtaining being suitable for is that experiment show that top condition is: n (C
6h
12)/n (M) (mol ratio)=1:1.7, oxygen reaction temperature is 40 DEG C, and reaction pressure is under 0.4MPa, 400r/min agitation condition, and the time is 4.0h, and catalyst levels is with 1.0mg/g; Clorox dropping temperature is 30 DEG C, and time for adding is 40min, and make the average yield of product reach 95.0%, purity is 99.0%, reaches the standard of domestic industry premium grads.This technique need not additionally add other solvents, and hexahydroaniline is recycle in system, adopts the cheap and easy to get and oxygen of environmental protection as oxygenant, not only cost-saving, but also environmental sound; The productive rate of this method, close to the high yield level of traditional sodium hypochlorite oxidization, significantly reduces the saltiness of sodium-hypochlorite process waste water simultaneously, makes waste water saltiness 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 operational path having commercial exploitation and be worth.Products obtained therefrom reaches the industrial first grade standard of HG/T 2096-2006 with this understanding.
The present invention compared with prior art, has following beneficial effect:
The present invention improves oxidation style.This project research step-by-step oxidation method, namely reaction adopts dioxygen oxidation early stage, the technique of later stage employing hypochlorite oxidation, effective reduction sodium hypochlorite oxidization produces the saltiness of waste water, having the advantages such as technique is simple, cost is low, environmental pollution is few, is the operational path 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 prograding.Accelerant N-cyclohexyl-2-[4-morpholinodithio sulphenamide (being called for short cz) can not produce nitrosamine carcinogenic substance in sulfidation, one of environment-friendly type promotor generally adopted both at home and abroad at present, the research and development of this project are implemented, not only realize good economic benefit, and for developing a circular economy, there is active effect, there is good promotional value.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
(1) making beating salify: take captax 167g, water 27g, hexahydroaniline 128.7g and neutralized verdigris 0.15g for subsequent use; Add water in a kettle., under strong stirring, add captax, hexahydroaniline and neutralized verdigris, make captax and hexahydroaniline carry out making beating salify fully;
(2) be oxidized: be warming up to 40 DEG C, pass into oxygen and make pressure reach 0.35MPa, reaction 2h; Then lower the temperature, under the condition of 30 DEG C, drip clorox react, stop afterwards to terminal to add clorox;
(3) suction filtration washing: suction filtration washing product, to neutral, obtains white precipitate; Containing excessive hexahydroaniline in filtrate, directly carry out reuse to the first step;
(4) dry: white precipitate filters, washes, dehydrates, and drying temperature is 55 DEG C, and time of drying is 1.5h, obtains product.
Embodiment 2
(1) making beating salify: take captax 167g, water 30.6g, hexahydroaniline 168.3g and neutralized verdigris 0.18g for subsequent use; Add water in a kettle., under strong stirring, add captax, hexahydroaniline and neutralized verdigris, make captax and hexahydroaniline carry out making beating salify fully;
(2) be oxidized: be warming up to 50 DEG C, pass into oxygen and make pressure reach 0.4MPa, reaction 4h; Then lower the temperature, under the condition of 40 DEG C, drip clorox react, stop afterwards to terminal to add clorox;
(3) suction filtration washing: suction filtration washing product, to neutral, obtains white precipitate; Containing excessive hexahydroaniline in filtrate, directly carry out reuse to the first step;
(4) dry: white precipitate filters, washes, dehydrates, and drying temperature is 60 DEG C, and time of drying is 2h, obtains product.
Embodiment 3
(1) making beating salify: take captax 167g, water 30g, hexahydroaniline 150g and neutralized verdigris 0.16g for subsequent use; Add water in a kettle., under strong stirring, add captax, hexahydroaniline and neutralized verdigris, make captax and hexahydroaniline carry out making beating salify fully;
(2) be oxidized: be warming up to 45 DEG C, pass into oxygen and make pressure reach 0.38MPa, reaction 3h; Then lower the temperature, under the condition of 35 DEG C, drip clorox react, stop afterwards to terminal to add clorox;
(3) suction filtration washing: suction filtration washing product, to neutral, obtains white precipitate; Containing excessive hexahydroaniline in filtrate, directly carry out reuse to the first step;
(4) dry: white precipitate filters, washes, dehydrates, and drying temperature is 57 DEG C, and time of drying is 1.8h, obtains product.
Claims (6)
1. a preparation method for accelerator CZ, is characterized in that step is as follows:
(1) making beating salify: take captax, water, hexahydroaniline and catalyzer for subsequent use; Add water in a kettle., under strong stirring, add captax, hexahydroaniline and catalyzer, make captax and hexahydroaniline carry out making beating salify fully;
(2) be oxidized: be warming up to 40-50 DEG C, pass into oxygen and make pressure reach 0.35-0.4MPa, reaction 2-4h; Then lower the temperature, under the condition of 30-40 DEG C, drip clorox react, stop afterwards to terminal to add clorox;
(3) suction filtration washing: suction filtration washing product, to neutral, obtains white precipitate; Containing excessive hexahydroaniline in filtrate, directly carry out reuse to the first step;
(4) dry: white precipitate filters, washes, dehydrates and obtains product.
2. the preparation method of accelerator CZ according to claim 1, is characterized in that the catalyzer described in step (1) is neutralized verdigris.
3. the preparation method of accelerator CZ according to claim 1, is characterized in that the mol ratio of the captax described in step (1) and hexahydroaniline is 1:1.3-1.7.
4. the preparation method of accelerator CZ according to claim 1, is characterized 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, is characterized in that the mass ratio of the catalyzer described in step (1) and captax is 0.9-1.1:1000.
6. the preparation method of accelerator CZ according to claim 1, it is characterized in that the drying temperature described in step (4) is 55-60 DEG C, time of drying 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 |
| WO2023123753A1 (en) * | 2021-12-27 | 2023-07-06 | 科迈化工股份有限公司 | Method for catalytic synthesis of accelerator cbs by using ionic liquid protective agent |
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