阅读说明：本技术 一种担载型催化剂的制备方法及其在橡胶促进剂cbs合成中的应用 (A kind of preparation method of supported catalyst and its application in rubber accelerator CBS synthesis ) 是由 黄家辉 谢妍 金新新 于 2018-05-25 设计创作，主要内容包括：本发明涉及一种担载型催化剂的制备方法及其在橡胶促进剂CBS合成中的应用。制备方法包括：将不同的金属盐采用浸渍法负载在载体上经马弗炉焙烧制备担载型催化剂；将一定质量的M与去离子水以及表面活性剂于反应釜中加热混合搅拌；加入一定摩尔比的环己胺后继续加热搅拌后通入一定配比的氧气进行催化氧化反应；反应后经水洗、干燥得到产品橡胶促进剂CBS。该制备方法采用环保型氧化剂且具有催化剂制备工艺简单有效、稳定安全,同时得到的产品CBS选择性高、底物的转化率高,反应后催化剂易于回收且回收率高等优点。(The present invention relates to a kind of preparation method of supported catalyst and its applications in rubber accelerator CBS synthesis.Preparation method includes: to be supported on different metal salts on carrier using infusion process to prepare supported catalyst through Muffle furnace roasting；The M of certain mass and deionized water and surfactant are heated into mixing in reaction kettle；The oxygen progress catalytic oxidation centainly matched is passed through after continuing heating stirring after the cyclohexylamine of addition certain mol proportion；It washed after reaction, be dried to obtain product rubber accelerator CBS.The advantages that preparation method is using environment-friendly type oxidant and simple and effective, stable safe with catalyst preparation process, while selective high, substrate the high conversion rate of obtained products C BS, and post catalyst reaction is easily recycled and the rate of recovery is high.)

1. a kind of preparation method of supported catalyst, comprising the following steps:

Metal salt is supported on carrier using infusion process, through drying, obtains sample；Sample is placed in Muffle kiln roasting, obtains institute State supported catalyst；

The metal salt is chlorauride, gold chloride, chloroplatinic acid, potassium platinic chloride, Platinous Potassium Chloride, palladium nitrate, palladium acetate, chlorine Change at least one of palladium, radium chloride；

The carrier is MnO₂、TiO₂、MgO、Al₂O₃At least one of.

2. preparation method according to claim 1, which is characterized in that

The mass ratio of contained metal and the carrier is 0.01~2.0 in the metal salt；

The temperature of the drying is 50~80 DEG C, and the time is 8~12h；

The temperature of the roasting is 200~500 DEG C；The time of roasting is 0.5~6h.

3. supported catalyst made from preparation method as claimed in claim 1 or 2.

4. application of the supported catalyst described in claim 3 in synthetic rubber accelerator CBS.

5. application according to claim 4, which is characterized in that synthetic rubber accelerator CBS the following steps are included:

(1) M, deionized water, surfactant are placed in reaction kettle, agitating and heating obtains mixed liquor；

(2) cyclohexylamine is added in Xiang Suoshu mixed liquor, continues agitating and heating, the supported catalyst is added, in oxygen-containing atmosphere Middle carry out oxidation reaction, obtains product；

(3) by product washing, drying, the rubber accelerator CBS is obtained.

6. application according to claim 5, which is characterized in that in step (1), the molar ratio of the M and deionized water It is 0.5~20,；The surfactant is at least one in OP-4, OP-7, OP-9, OP-10, OP-15, OP-20, OP-30 Kind；The volume of surfactant is 1~3ml.

7. application according to claim 5, which is characterized in that in step (1), the temperature of the heating is 20~60 DEG C； Time is 30~120min.

8. application according to claim 5, which is characterized in that in step (2), the molar ratio of the cyclohexylamine and M are 0.1~2.0；The temperature of heating is 30~50 DEG C；Time is 30~60min；It is 1/10000 according to the molar ratio of noble metal and M ~1/500 is added supported catalyst.

9. application according to claim 5, which is characterized in that in step (2), the pressure of the oxidation reaction is 0.2~ 4.0MPa；Reaction temperature is 40~60 DEG C；Reaction atmosphere is 20~100% oxygen nitrogen balance gas；Reaction time be 4~for 24 hours；Stirring Rate is 200~1000rpm.

10. the rubber accelerator CBS synthesized in any one of the claim 5-9 application.

Technical field

The invention belongs to the production technical fields of thiofide, are related to a kind of preparation method of supported catalyst And its application in rubber accelerator CBS synthesis.

Background technique

With the fast development of China's automobile and tyre industry, to the important source material rubber chemicals during rubber processing Demand also increases with it.Thiofide N- cyclohexyl -2- benzo sulfenamide (CBS) is a kind of milky or rice Color powder, there is glue to burn, and the time is long, and curingprocess rate is fast, and sizing material can be processed at high temperature, belongs to sulfenamide aftereffect and partly exceeds the speed limit sulphur Change promotor.At 138 DEG C of curing temperature or more, facilitation is very strong.Often it is used as the second promotor with alkaline accelerator cooperation. Alkaline accelerator such as thiurams and dithiocarbamates can enhance its activity.Mainly for the manufacture of tire, sebific duct, glue The industrial rubber articles such as shoes, cable.Accelerator CBS is usually by 2-mercaptobenzothiazole (hereinafter referred to as captax) or 2- mercapto After base benzothiazole-sodium salt is mixed with cyclohexylamine, process water, reaction is condensed and obtains under oxidant effect.Main synthesis technology There are chlorine oxidation process, sodium hypochlorite oxidization, Oxygen Catalytic Oxidation method, hydrogen peroxide oxidation method etc..Publication number [CN104672171A] discloses a kind of production technology of rubber accelerator CBS, and this method is with the sodium hypochlorite of preparation first Oxidant, then by a certain proportion of M, water and cyclohexylamine in carrying out oxidation reaction in stills for air blowing, most afterwards through washing, dehydration, Drying prepares finished product CBS.This method can be improved the yield and purity of accelerator CBS, improve the yield and quality of product, drop Low production cost, the yield of accelerator CBS is up to 98%, and purity is up to 99%, and still, it is useless that this method can generate a large amount of saliferous Water, post-processing is difficult, and discharge causes environmental pollution.Publication number [107445918 A of CN] disclose it is a kind of with rubber accelerator M, Cyclohexylamine is raw material, using hydrogen peroxide and sodium hypochlorite as oxidant, prepares accelerator CBS as catalyst using sulfuric acid.This method Although the industrial applications of hydrogen peroxide, sodium hypochlorite combination oxidant are realized, due to being related to hydrogen peroxide, secondary in reaction Sodium chlorate and catalyst sulfuric acid, this, which allows for reacting subsequent devil liquor recovery process, becomes complicated and time-consuming, therefore, develops one The process route of environmentally protective production CBS is particularly important.

Summary of the invention

It is synthesized the purpose of the present invention is to provide a kind of preparation method of supported catalyst and its in rubber accelerator CBS In application.Catalyst in this method have the characteristics that preparation process it is simple, it is easily controllable, be easy to amplify synthesis, adopt simultaneously With environment-friendly type oxidant, obtained CBS good product quality, production cost is low.

One aspect of the present invention provides a kind of preparation method of supported catalyst, comprising the following steps: uses infusion process will Metal salt is supported on carrier, through drying, obtains sample；Sample is placed in Muffle kiln roasting, obtains the supported catalyst；Institute The metal salt stated be chlorauride, gold chloride, chloroplatinic acid, potassium platinic chloride, Platinous Potassium Chloride, palladium nitrate, palladium acetate, palladium chloride, Radium chloride etc.；The carrier is MnO₂、TiO₂、MgO、Al₂O₃Deng.

Further, the mass ratio of contained metal and the carrier is 0.01~2.0 in the metal salt；The drying Temperature is 50~80 DEG C, and the time is 8~12h；The temperature of the roasting is 200~500 DEG C；The time of roasting is 0.5~6h.

Another aspect of the present invention provides supported catalyst made from above-mentioned preparation method.

Further aspect of the present invention provides application of the above-mentioned supported catalyst in synthetic rubber accelerator CBS.

Further, the application, which is characterized in that synthetic rubber accelerator CBS the following steps are included:

(1) M (2-mercaptobenzothiazole), deionized water, surfactant are placed in reaction kettle, agitating and heating obtains mixed Close liquid；

(2) cyclohexylamine is added in Xiang Suoshu mixed liquor, continues agitating and heating, the supported catalyst is added, oxygen-containing Oxidation reaction is carried out in atmosphere, obtains product；

(3) by product washing, drying, the rubber accelerator CBS is obtained.

Further, in step (1), the molar ratio of the M and deionized water is 0.5~20；The surface-active Agent is at least one of OP-4, OP-7, OP-9, OP-10, OP-15, OP-20, OP-30；The volume of surfactant be 1~ 3ml。

Further, in step (1), the temperature of the heating is 20~60 DEG C；Time is 30~120min.

Further, in step (2), the molar ratio of the cyclohexylamine and M are 0.1~2.0；The temperature of the heating is 30~50 DEG C；Time is 30~60min；It is 1/10000~1/500 loaded catalysis of addition according to the molar ratio of noble metal and M Agent.

Further, in step (2), the pressure of the oxidation reaction is 0.2~4.0MPa；Reaction temperature is 40~60 ℃；Reaction atmosphere is 20~100% oxygen nitrogen balance gas；Reaction time be 4~for 24 hours；Stirring rate is 200~1000rpm.

Another aspect of the present invention also provides the rubber accelerator CBS synthesized in above-mentioned application.

Under conditions of being oxidant as catalyst, oxygen the present invention is directed to the loaded material synthesized using oneself, one is provided Safe and environment-friendly free of contamination technique is planted to prepare CBS.Compared with the preparation method of reported rubber vulcanizing accelerator CBS, this The catalyst preparation process of the method for invention is simple, it is mature to stablize, will not generate a large amount of brine wastes, energy saving nothing after catalysis reaction Pollution, good product quality, by the experiment parameter in control oxidation process, the rubber product being prepared is easy to industrialize and anti- Rear catalyst is answered to be easily recycled.

Specific embodiment

Do specific description to the present invention below in conjunction with example: the reaction equation for preparing product CBS is as follows: