阅读说明：本技术 Mbts空气氧化合成促进剂cbs的工艺 (Process for synthesizing accelerator CBS by MBTS air oxidation ) 是由 孟庆森 赵玉军 陆平 回俊博 孔令鑫 黄汇江 于 2021-10-14 设计创作，主要内容包括：本发明属于杂环化合物领域,具体涉及一种MBTS空气氧化合成促进剂CBS的工艺；包括下述步骤：(1)将MBTS、环己胺与混合溶剂在搅拌条件下混合均匀,得到原料浆液；(2)将步骤(1)得到的原料浆液与催化剂投入氧化釜进行氧化；(3)反应完成后,即可得到粗品CBS；本发明开发了一种以空气为氧化剂,以MBTS、环己胺为原料,以强酸性阳离子树脂与弱碱性阴离子树脂为催化剂,以水、甲苯的二元混合液作为溶剂合成促进剂CBS。合成过程中原材料为浆料态,产物为液态。避免了大量废盐、废水的产生。同时,该技术采用树脂的混合物作为固体催化剂,避免了液相催化剂损失造成的污染问题,提高了技术的环保性。(The invention belongs to the field of heterocyclic compounds, and particularly relates to a process for synthesizing an accelerator CBS by MBTS air oxidation; the method comprises the following steps: (1) uniformly mixing MBTS, cyclohexylamine and a mixed solvent under the stirring condition to obtain a raw material slurry; (2) putting the raw material slurry obtained in the step (1) and a catalyst into an oxidation kettle for oxidation; (3) after the reaction is finished, a crude product CBS can be obtained; the invention develops an accelerator CBS synthesized by taking air as an oxidant, MBTS and cyclohexylamine as raw materials, strong acid cation resin and weak base anion resin as catalysts and binary mixed solution of water and toluene as a solvent. In the synthesis process, the raw material is in a slurry state, and the product is in a liquid state. The production of a large amount of waste salt and waste water is avoided. Meanwhile, the technology adopts the mixture of resin as the solid catalyst, avoids the pollution problem caused by the loss of the liquid phase catalyst, and improves the environmental protection property of the technology.)

1. The process for synthesizing the accelerator CBS by MBTS air oxidation is characterized by comprising the following steps:

(1) uniformly mixing MBTS, cyclohexylamine and a mixed solvent under the stirring condition to obtain a raw material slurry;

(2) putting the raw material slurry obtained in the step (1) and a catalyst into an oxidation kettle, starting stirring, introducing air for oxidation, controlling the initial pressure of the reaction in the reaction process, and continuing stirring until the end point of the reaction is reached after the quality of the introduced air meets the requirement; the mass ratio of the MBTS to the catalyst in the raw material liquid is 1: 1-2;

(3) after the reaction is finished, filtering the catalyst in the system to obtain a product solution, standing for phase splitting, cooling and crystallizing the upper oil phase, and filtering to obtain a crude product CBS; the crude product is washed by water to obtain a target product CBS wet material.

2. The process for synthesizing accelerator CBS by MBTS air oxidation according to claim 1, wherein the mass ratio of MBTS to cyclohexylamine in step (1) is 1: 0.7-1.2.

3. The process for the air oxidation synthesis of MBTS to obtain promoter CBS according to claim 1, wherein the catalyst in step (2) is a mixture of a strongly acidic cation resin and a weakly basic anion resin; the mass ratio of the strong acid cation resin to the weak base anion resin is 1: 1.5-3.5.

4. The process for synthesizing accelerator CBS for MBTS air oxidation according to claim 3, wherein the strongly acidic cation resin is sulfonic acid [ -SO ]₃H]The cationic resin of (4); the weakly basic anionic resin is a resin having a tertiary amino group [ -NR ]₂]The anionic resin of (4).

5. The process for the air oxidation synthesis of MBTS to obtain the accelerator CBS according to claim 1, wherein the mixed solvent in step (1) is a mixture of water and toluene; water: the mass ratio of the toluene is 1: 3-5.

6. The process for synthesizing accelerator CBS by MBTS air oxidation according to claim 1, wherein the mass ratio of MBTS to the mixed solvent in step (1) is 1: 1.2-3.

7. The process for the air oxidation synthesis of MBTS to accelerator CBS according to claim 1, wherein the reaction temperature in step (2) is 25-40 ℃; the initial pressure of the reaction is controlled to be 0.5 Mpa; the mass ratio of the MBTS in the raw material liquid to the introduced air is 1:0.5-0.75; the stirring time after the air is introduced is controlled to be 0.5-1.5 h.

Technical Field

The invention belongs to the field of heterocyclic compounds, and particularly relates to a process for synthesizing an accelerator CBS by MBTS (methyl butyl benzene) air oxidation.

Background

At present, the rubber vulcanization accelerator CBS is produced by an industrialization method of oxidizing an accelerator MBT or sodium salt thereof and cyclohexylamine by using sodium hypochlorite or hydrogen peroxide as an oxidant. Wherein, the sodium hypochlorite method oxidation has the advantages of mature process, mild reaction condition, better product quality and higher yield (generally about 90-92 percent). But the production wastewater amount is large, about 8 tons of wastewater are produced by 1 ton of products, the salt content is high, the COD is high (generally more than 30000 ppm), the biochemical treatment is difficult (the biotoxicity exists), and the environmental protection is not favorable. The hydrogen peroxide method can avoid the problem of high salt content in the wastewater, but the hydrogen peroxide has strong activity, more side reactions are generated in the oxidation process compared with the sodium hypochlorite method, and the product yield is also reduced compared with the sodium hypochlorite method.

The air catalytic oxidation method is favorable for environmental protection due to the great reduction of the wastewater yield, and colleges and enterprises have been researched in recent years. Many related patent technologies such as patents CN108084114B, CN110305075A, CN109289922B, and CN203018092U have been explored in many aspects such as the process flow of preparing CBS by air catalytic oxidation, the development of catalyst, and the development of application equipment. However, from the results reported in many ways, the technology for preparing CBS by the air catalytic oxidation method still has certain problems:

1) the preparation method adopts a homogeneous catalyst to carry out the CBS air catalytic oxidation method, and has the problems of insufficient product yield and large product purity fluctuation. In the patent CN110305075A, a water-soluble cobalt catalyst is used for air oxidation, in most of the examples, the CBS yield is not high, and the fluctuation of the melting point of the product is large, which indicates that the fluctuation of the product purity is large. In addition, in the using process of the water-soluble catalyst, various problems such as difficult catalyst recovery, high catalyst cost, heavy metal contained in wastewater and the like exist. This is also another major problem with such catalytic processes.

2) The preparation method adopts a heterogeneous catalyst to carry out the CBS air catalytic oxidation method, and the main problems can be divided into two types: one is insufficient catalyst life. The active sites or active components of the catalyst are combined with a carrier in a simple loading mode (such as patent CN 108084114B), and the active components are gradually dissolved into a raw material liquid in the reaction process and are finally discharged out of a system along with waste water and a waste solvent, so that the catalyst has poor service life despite good activity and cannot be used for a long time. Secondly, the catalyst activity is insufficient. Such catalysts generally have certain structural or compositional characteristics (such as patent CN 109289922B), and are slightly less reactive or selective than the first type of catalysts, resulting in slightly lower product yields. And because of the problems of special structure or composition, the preparation process is complex, the catalyst cost is high, and a certain bottleneck also exists for industrial amplification.

3) Besides, there have been some studies on optimizing the synthesis process of promoter CBS by changing the raw materials (such as patent CN 112625003A). MBTS (also called MBTS) or a mixture of MBTS and MBT is used as a raw material, and the consumption of an oxidant is reduced by utilizing the principle that the MBTS and cyclohexylamine can spontaneously and slowly react in a water system to generate CBS and MBT, so that the generation of waste water or waste salt is reduced. However, this technique has two problems: firstly, the MBTS is prepared by oxidizing MBT, and the industrialized yield of the technology is not more than 90%, so that the cost of the MBTS is higher. And secondly, the current industrial preparation process of the MBTS mainly comprises sodium hypochlorite oxidation or hydrogen peroxide oxidation, and the emission of pollutants can not be reduced by adopting the MBTS to replace MBT as a synthetic raw material of CBS from the view of the whole flow.

In summary, the CBS synthesis technology commonly reported at present cannot effectively avoid the generation of three wastes, and the generated "three wastes" also have the problems of high treatment difficulty and high treatment cost, and a new MBTS synthesis process needs to be developed to solve or alleviate the problems.

Disclosure of Invention

The invention aims to provide a process for synthesizing an accelerator CBS by MBTS air oxidation.

In order to achieve the purpose, the invention adopts the technical scheme that:

a process for synthesizing accelerator CBS by MBTS air oxidation comprises the following steps:

(1) uniformly mixing MBTS, cyclohexylamine and a mixed solvent under the stirring condition to obtain a raw material slurry;

(2) putting the raw material slurry obtained in the step (1) and a catalyst into an oxidation kettle, starting stirring, introducing air for oxidation, controlling the reaction pressure in the reaction process, and continuing stirring until the reaction reaches the end point after the quality of the introduced air meets the requirement; the mass ratio of the MBTS to the catalyst in the raw material liquid is 1: 1-2;

(3) after the reaction is finished, filtering the catalyst in the system to obtain a product solution, standing for phase splitting, cooling and crystallizing the upper oil phase, and filtering to obtain a crude product CBS; the crude product is washed by water to obtain a target product CBS wet material.

The mass ratio of the MBTS to the cyclohexylamine in the step (1) is 1: 0.7-1.2.

The mass ratio of the MBTS to the mixed solvent in the step (1) is 1: 1.2-3.

The strong acid cation resin is sulfonic acid group [ -SO ]₃H]The cationic resin of (4); the weakly basic anionic resin is a resin having a tertiary amino group [ -NR ]₂]The anionic resin of (4).

The catalyst in the step (2) is a mixture of a strong acid cation resin (Sian blue Xiao LXC-107) and a weak base anion resin (Sian blue Xiao LXC-104); the mass ratio of the strong acid cation resin to the weak base anion resin is 1: 1.5-3.5.

The solvent in the step (1) is a mixture of water and toluene; water: the mass ratio of the toluene is 1: 3-5.

The reaction temperature in the step (2) is 25-40 ℃; the initial pressure of the reaction is controlled to be 0.5 Mpa; the mass ratio of MBTS in the raw material liquid to the introduced air is 1:0.5-0.75, and the stirring time after the air introduction is controlled to be 0.5-1.5 h.

And (4) in the step (3), most of the lower-layer aqueous solution is applied to the next batch of synthesis process according to the feeding proportion, and the residual small amount of the lower-layer aqueous solution is subjected to atmospheric distillation to recover toluene and cyclohexylamine.

Compared with the prior art, the invention has the beneficial effects that:

the invention discloses a process for synthesizing accelerator CBS by MBTS air oxidation, which takes air as an oxidant, MBTS and cyclohexylamine as raw materials, strong acid cation resin and weak base anion resin as catalysts, and binary mixed solution of water and toluene as a solvent to synthesize the accelerator CBS. In the synthesis process, the raw material is in a slurry state, and the product is in a liquid state. After the reaction is finished, the catalyst and the product can be effectively separated by a simple filtration method. The product phase is separated from the solvent by cooling crystallization.

1. The application adopts a double-ion type composite catalyst:

1.1, the strong acid cation resin can further activate cyclohexylamine, so that the reaction of the cyclohexylamine and MBTS is accelerated, and CBS and an intermediate product MBT are generated;

1.2, the weak alkaline anion resin can weaken the MBT-cyclohexylamine structure generated by complexing the intermediate product MBT and excessive cyclohexylamine, so that a transition structure is formed in the process of contacting the intermediate product MBT with oxidant air, the selectivity of the oxidation reaction is further improved, and the yield of the CBS product is finally improved.

2. The technology adopts water/toluene binary mixed solution as a solvent, effectively realizes the separation of a main product and a byproduct, and further effectively improves the purity of the product CBS to more than 99%. In the binary mixed solution solvent, the functions of the components are different.

2.1 the role of toluene is mainly as product solvent and solvent for some oil-soluble impurities. During the reaction process, the toluene can effectively dissolve the product CBS, and further, the separation of the unreacted raw material MBTS and the product is effectively realized. And secondly, because the catalyst is ionic resin, the oxidation reaction mainly occurs in a water phase, and the toluene serving as an oil phase main component can effectively separate the catalyst from a product, so that the deep oxidation of the product CBS to generate other byproducts is reduced, and the yield of the product is improved. Toluene can be used as a solvent for oil-soluble impurities in the raw material MBTS, interference between the oil-soluble impurities and an oxidation reaction carried out in a water phase is reduced, and the reaction yield is further improved.

2.2, the function of water is mainly to provide active ions for the catalyst, and the catalyst is ionic resin, so that the catalyst can be effectively activated by the existence of water.

And 2.3, simultaneously adopting an organic phase and a water phase as solvents, standing the solvent after product separation, then carrying out phase separation, directly recycling the lower layer of the solvent into the water phase for batch synthesis, and recovering the toluene and the cyclohexylamine dissolved in the water phase through rectification when the water (which is derived from water generated in the oxidation process and has the mass of about 10 percent of the mass of the raw material MBTS) in an amount exceeding the recycling requirement is recycled. A small amount of water-soluble byproducts are dissolved in the residual wastewater after recovery, the COD is about 12000, and the COD can be reduced to less than 100 after advanced oxidation and biochemical treatment. The upper organic phase mainly comprises toluene, water, cyclohexylamine, CBS and other organic impurities (mainly generated by organic impurities carried in raw material MBTS and impurities generated by secondary reaction of the impurities with raw materials in systems such as cyclohexylamine and the like in the oxidation process), and can be directly returned to the synthesis process. Along with the increase of the organic phase sleeving times (the sleeving times are controlled to be 20-25 times), the content of CBS in the organic phase is gradually reduced, the content of other organic impurities is gradually increased, and further the subsequent oxidation process and yield are influenced, so that the organic phase needs to be treated. Toluene and cyclohexylamine in an organic phase are recovered by a distillation mode for reuse, and residual kettle residues mainly comprise a small amount of toluene and CBS and a large amount of resin (mainly from impurities and a small amount of oxidation byproducts in MBTS) and can be directly incinerated.

3. This technique uses MBTS as a raw material rather than MBT for the following reasons:

the key point of the technology is that quaternary components of MBT, cyclohexylamine, air and a catalyst can be effectively combined to form a transition structure, so that the selectivity of the reaction and the yield of the product are improved. In the process of forming the structure, the concentration of MBT in the system needs to be controlled, when the concentration of MBT is too high, due to the limitation of the number of active sites of the catalyst and the concentration of cyclohexylamine in the system, MBT is directly complexed with cyclohexylamine to form an 'MBT-cyclohexylamine' structure, solid particles formed in the reaction system are separated out and are directly oxidized by air, a large amount of MBT is converted into a peroxide byproduct while CBS is generated, and further the selectivity and yield of the reaction are obviously reduced, which is also the problem of most homogeneous catalysts.

The problem can be solved by increasing the concentration of cyclohexylamine in the system, and the specific method can be directly increasing the ratio of MBT to cyclohexylamine or slowly adding MBT into the reaction system by beating. However, the direct effect of the above method is that the reaction system becomes homogeneous, the CBS generated by the reaction is dissolved in a large amount of cyclohexylamine aqueous solution, and is continuously deeply oxidized to generate byproducts as the reaction proceeds under the action of the catalyst. In addition, a larger amount of cyclohexylamine in the reaction system can also be directly oxidized to generate a byproduct. Although the selectivity and yield of converting MBT into CBS are not influenced, the cyclohexylamine loss is too large, the cyclohexylamine consumption is greatly increased in the CBS generation process, and the CBS synthesis consumption is still not optimized.

This problem does not occur when MBTS is used as a raw material. The reaction speed of the direct CBS and MBT generation of MBTS and cyclohexylamine is improved through the cationic resin, the concentration of MBT in the system can be controlled to be maintained at a certain degree, and further the concentrations of cyclohexylamine and MBT in the system can be controlled within a more ideal range, so that the yield of the whole reaction can be ensured, the probability of generating byproducts by deep oxidation of MBT and cyclohexylamine respectively can be effectively inhibited, the consumption of raw materials in the CBS synthesis process is effectively reduced, and the product yield of the technology is further close to a theoretical value.

In addition, the cyclohexane slightly higher than the reaction ratio is added to play two roles, firstly, the cyclohexylamine with a certain concentration can effectively complex MBTS and MBT generated after the cyclohexylamine reacts, so that the MBT is protected from being directly and deeply oxidized into byproducts except the MBTS by air, and the reaction yield is improved. And secondly, after the MBT and the cyclohexylamine are complexed, MBT-cyclohexylamine which is insoluble in water and toluene is generated, the intermediate product can be dissolved in cyclohexylamine aqueous solution with certain concentration, and then the intermediate product can be effectively combined with a catalyst to generate a transition structure, so that the reaction yield is improved.

In a word, the technical scheme of this application uses the air as the oxidant, has avoided the production of a large amount of waste salt, waste water. Meanwhile, the technology adopts the mixture of resin as the solid catalyst, avoids the pollution problem caused by the loss of the liquid phase catalyst, and improves the environmental protection property of the technology. Meanwhile, the catalyst has extremely high selectivity, and the yield of the final product CBS is more than 98.5 percent (calculated by the raw material MBTS depuration).

Detailed Description

In order to make those skilled in the art better understand the technical solution of the present invention, the following provides a detailed description of the present invention with reference to the embodiments.

Example 1: in order to solve the above technical problems, the present invention provides a process for synthesizing an accelerator CBS by air oxidation of MBTS, where the process includes the following steps:

(1) mixing MBTS, cyclohexylamine and a solvent in a mass ratio of 1:0.7:1.2 at 20 ℃ for 0.3h under stirring, wherein the solvent is a mixture of water and toluene, and the solvent is water: toluene =1: 3; and obtaining the raw material liquid after mixing.

(2) And (3) putting the raw material liquid into an autoclave, adding a macroporous resin catalyst with the mass 1 time that of the MBTS, starting stirring, introducing air to the pressure of 0.5Mpa, and starting an oxidation reaction. The catalyst is prepared by mixing cation resin and anion resin, and the mass ratio of the cation resin to the anion resin is 1:1.5 (strong acid cation resin, Xian lan Xiao LXC-107; weak base anion resin, Xian lan Xiao LXC-104). And in the process, the reaction temperature is controlled at 25 ℃, when the total mass of the introduced air reaches 0.5 time of the mass of the added MBTS, the introduction of the air is stopped, and the reaction is finished after the stirring is continued for 1.5 hours.

(3) And after the reaction is finished, filtering and recovering the catalyst, standing the filtrate for 1h, then carrying out phase separation, sleeving the lower-layer aqueous solution in the synthesis process of the next batch, and recovering the cyclohexylamine and the toluene from a small amount of the residual aqueous solution through atmospheric distillation.

(4) Crystallizing the upper oil phase, and washing the wet material obtained after filtering by using clear water with the mass of 0.8 time of that of the wet material to obtain the target product CBS wet material. The filtrate is used for the next batch.

In order to accurately measure the yield, the oil phase is repeatedly used, when the oil phase is used for 25 times, the yield of a single reaction begins to decrease, and the purity of the product is also reduced, so that the yield data is averaged after the oil phase is used for 25 times, the yield of the CBS product is 99.2% (based on the content of pure MBTS in raw material MBTS), the purity of the CBS product is 99.2%, and the CBS product is white crystalline powder in appearance.

Table 1 shows the effect of varying different parameters on the results for other examples.

TABLE 1

As can be seen from Table 1, when the catalyst is not added (example 10), the cationic resin or the anionic resin is added alone (examples 8 and 9), and the ratio of the cations to the anions is too high (examples 11 and 12), the yield and purity are greatly affected, and when the temperature is too high, the CBS product can be deeply oxidized to other products by air, as shown in example 4, so that the reaction yield is reduced, and the purity of the product is poor. In addition, the technology controls the whole oxygen inlet amount in the oxidation process, and the high-temperature deep oxidation consumes excessive air, so that not only peroxide byproducts are generated in the reaction process, but also the raw material MBTS is unreacted. The detection and analysis show that the yield of the CBS product is only 60.5 percent, and the purity is 81.2 percent. As shown in example 6, because the total amount of air introduced is excessive, the reaction speed between the raw materials MBT, cyclohexylamine, catalyst and air is increased during the reaction process, so that both MBT and cyclohexylamine have a certain peroxidation condition, and the product purity is obviously reduced because the peroxidation condition of cyclohexylamine in the system is increased. The detection and analysis show that the yield of the product CBS is 84.7 percent, and the purity is 96.8 percent.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.