WO2023056739A1 - Procédé de production de dcbs accélérateur - Google Patents

Procédé de production de dcbs accélérateur Download PDF

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Publication number
WO2023056739A1
WO2023056739A1 PCT/CN2022/087695 CN2022087695W WO2023056739A1 WO 2023056739 A1 WO2023056739 A1 WO 2023056739A1 CN 2022087695 W CN2022087695 W CN 2022087695W WO 2023056739 A1 WO2023056739 A1 WO 2023056739A1
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Prior art keywords
reaction
dcbs
mbts
raw material
catalyst
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PCT/CN2022/087695
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English (en)
Chinese (zh)
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孟庆森
赵玉军
陆平
回俊博
孔令鑫
黄汇江
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科迈化工股份有限公司
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Publication of WO2023056739A1 publication Critical patent/WO2023056739A1/fr

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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

Definitions

  • the invention belongs to the field of heterocyclic compounds, and in particular relates to a production process of accelerator DCBS.
  • Accelerator DCBS (Chinese name N, N-dicyclohexyl-2-benzothiazole sulfenamide) is an aftereffect accelerator, which has good dispersion performance in rubber, long burning time in rubber, and high operating safety , with vulcanization acceleration and adhesion, suitable for high-activity reinforcing materials, especially for radial tires. Therefore, with the increase of tire output and tire radialization rate, the consumption of accelerators CBS, TBBS and DCBS has increased significantly in recent years. According to the statistics of China Rubber Industry Association, the total output of accelerators in my country was 375,000 tons in 2014, among which the slow-acting sulfenamide accelerators represented by CBS, TBBS and DCBS accounted for 42.51% of accelerator output.
  • the current industrialization method of the rubber vulcanization accelerator DCBS is to use sodium hypochlorite as an oxidant to oxidize the sodium salt of the raw material MBT and dicyclohexylamine to generate the accelerator DCBS.
  • the process yield is low (the selectivity of the raw material MBT is not more than 80%), and the amount of waste water produced is large. 1 ton of product produces about 8-10 tons of waste water, and the salt content is high, and the COD is high (generally above 30000ppm) , difficult to biochemical treatment (there is biological toxicity), unfavorable to environmental protection.
  • this process Compared with the direct oxidation preparation of sodium hypochlorite, this process has the advantage that the conversion rate of raw material MBTS is extremely high, generally exceeding 98%, and there is basically no side reaction. However, the process still cannot avoid the use of sodium hypochlorite, which will inevitably produce sodium chloride-containing brine.
  • the process uses ammonia as the acid-binding agent, ammonium chloride will be produced as a by-product, and if sodium methoxide is used as the acid-binding agent, sodium chloride will be produced as a by-product; and these by-product salts are mixed with the product DCBS Together, they need to be separated by washing with hot water, and saline wastewater will also be produced here.
  • the process uses anhydrous methanol as a solvent, and its recyclability is low, which is also a major problem hindering the industrialization of this process.
  • the purpose of the present invention is to overcome the shortcoming in the prior art, provide a kind of production technology of accelerator DCBS.
  • a kind of production technique of promotor DCBS comprises the steps:
  • the mixed solvent is a mixture of isopropanol, water and toluene.
  • the catalyst is a cationic resin with a sulfonic acid group (-SO 3 H) Mixture with anionic resins with tertiary amino groups (-NR 2 ).
  • the mass ratio of isopropanol, water and toluene in step 1) is 1:2-4:3-6.
  • the mass ratio of MBTS to the catalyst in the raw material slurry in step 2) is 1:0.5-0.8; the mass ratio of the cationic resin with sulfonic acid groups (-SO 3 H) to the anionic resin with tertiary amino groups (-NR 2 ) in the catalyst It is 1:0.3-0.5.
  • the ratio of MBTS to the mixed solvent in step 1) is 1:5-7.
  • the reaction temperature in step 2) is 40-70°C; the pressure in the reactor is controlled at 0.3-1.0Mpa.
  • step 2) the mass ratio of MBTS in the raw material slurry to oxygen is 1:0.1-0.15, and the oxygen feeding time is controlled at 4.5-6h.
  • step 3 The product solution in step 3) is allowed to stand still for 1-1.5 hours for phase separation; the crystallization temperature of the upper oil phase is cooled to 0-5°C.
  • this technology uses oxygen as the oxidant to avoid the generation of waste salt, solve the problem of difficult treatment of NaCl-containing high COD wastewater in the traditional process, and the difficulty of further application of waste salt, solve environmental problems, and avoid waste of resources.
  • the technology uses an anion-cation composite macroporous resin solid catalyst, which has high selectivity, and the yield of the final product DCBS is above 95% (calculated in terms of pure raw material MBTS). The reasons are as follows:
  • MBT-dicyclohexylamine salt Due to the complexation of MBT and dicyclohexylamine formed in the first step reaction [MBT-dicyclohexylamine salt] has poor solubility and is difficult to dissolve through a solvent, which makes it exist in the form of solid particles In the reaction system, it is also difficult to be further oxidized into DCBS after contacting with catalyst and oxygen. Therefore, the reaction process cannot directly mix MBTS, dicyclohexylamine, solvent and catalyst and then feed oxygen into the reaction system. It is necessary to drop dicyclohexylamine into the mixed reaction system. With the addition of dicyclohexylamine, the Under the catalysis of acidic resin, the reaction gradually produces DCBS and MBT.
  • this technology uses isopropanol/water/toluene ternary mixed solution as solvent, which effectively realizes the separation of main product and by-product, and then effectively improves the purity of the product DCBS to more than 99%.
  • ternary mixture solvent each component plays a different role.
  • the effect of toluene is mainly the solvent of product solvent and part oil-soluble impurity.
  • toluene can effectively dissolve the product DCBS, and then effectively separate the unreacted raw material MBTS from the product.
  • the catalyst is an ionic resin, the oxidation reaction mainly occurs in the water phase, and toluene, as the main component of the oil phase, can effectively separate the catalyst from the product, reduce the deep oxidation of the product CBS to form other by-products, and increase the yield of the product.
  • toluene can be used as a solvent for oil-soluble impurities in the raw material MBTS, reducing its interference with the oxidation reaction carried out in the water phase, and further improving the reaction yield.
  • the solubility of the final product DCBS in toluene varies greatly with temperature fluctuations, and it is easy to separate by crystallization.
  • isopropanol is mainly relied on to complete the effect of the above toluene, but the biggest difference between this technology and the traditional technology is that oxygen is used as the oxidant, and no brine is produced during the reaction process, and the function of a small amount of water in the system is mainly for The catalyst provides an activation environment. If there is a large amount of isopropanol in the system, the entire reaction system will appear homogeneous due to solubility problems, and thus cannot effectively protect the product.
  • the function of water is mainly to provide active ions for the catalyst. Since the catalyst is an ionic resin, it needs the presence of water to be effectively activated.
  • the role of a small amount of isopropanol in the system is as a solvent for the MBT-dicyclohexylamine complex, so that it can slowly participate in the oxidation process, and then generate DCBS and other oxidation products.
  • the MBT-dicyclohexylamine complex needs certain conditions before it can be converted into DCBS, in the traditional process, the pH of the system needs to be stable above 10 and the system is in a peroxidized state before it can be converted into DCBS. Therefore, the selectivity of this part of the reaction is not high, which is also the main reason why the yield of DCBS in this technology can only be controlled at 95%.
  • the technology uses MBTS as the raw material instead of MBT for the reason.
  • the core innovation of this technology is to rely on the microcirculation in the reaction process shown in Figure 1 to achieve high DCBS selectivity and yield. Namely: at first, by acidic catalyst activation dicyclohexylamine and MBTS reaction generate DCBS and free MBT; Secondly, catalyze free MBT and oxygen reaction by basic resin and generate MBTS and then react with dicyclohexylamine.
  • the final product DCBS all can be suspended in the reaction system with solid form, so introduce this water-soluble solvent of isopropanol to increase the dissolubility of reaction intermediate product in water, and then make part intermediate product and oxidant sodium hypochlorite in water
  • the reaction in the phase changes from a heterogeneous reaction to a homogeneous reaction, thereby increasing the reaction speed and reaction yield, and reducing the side reactions caused by deep oxidation during the long-term contact between sodium hypochlorite and solid-phase intermediate products.
  • the introduction of isopropanol solvent can only partially increase the reaction rate, and cannot essentially solve the process of preparing DCBS as a heterogeneous reaction. Therefore, most industrialization implementations have found that after the industrialization of this technology, the conversion rate of the raw material MBT is basically below 80%, or even lower.
  • the present invention adopts MBTS as the main raw material, avoids the reaction process of directly oxidizing the MBT-dicyclohexylamine complex to a large extent, and then greatly improves the yield of the reaction, and the process is relatively simple, and industrial transformation is also relatively easy .
  • Figure 1 is a schematic diagram of the cycle in which MBT reacts with oxygen to generate MBTS and then reacts with dicyclohexylamine.
  • Embodiment 1 a kind of technique of MBTS oxygen oxidation synthesis promotor DCBS, comprises the steps:
  • a macroporous resin catalyst with a mass of 0.5 times the mass of MBTS. After starting the stirring, turn on the dicyclohexylamine feed pump and start to feed oxygen to start the oxidation reaction.
  • the catalyst is mixed with cationic resin and anionic resin (the cationic resin is cationic resin with sulfonic acid group (-SO 3 H), Xi’an Lanxiao LXC501; the anionic resin is anionic resin with tertiary amino group (-NR 2 ), Xi’an Lanxiao D301), the mass ratio of the two is 1:0.3.
  • the reaction temperature was controlled at 40° C.
  • the reaction pressure was 0.3 Mpa
  • the oxygen gas was introduced for 6 hours.
  • the catalyst is recovered by filtration, the filtrate is allowed to stand for 1 h, and the phases are separated.
  • the aqueous solution of the lower layer is applied to the synthesis process of the next batch, and the remaining small amount is recovered through normal pressure distillation to recover isopropanol and toluene.
  • the temperature of the upper oil phase was lowered to 5°C for crystallization, and the wet material obtained after filtration was washed with water to obtain the target product DCBS.
  • Table 1 shows the influence of different parameters on the results.
  • Example 3 since the reaction temperature is too high, oxygen can deeply oxidize the product DCBS to other products, so the reaction yield decreases and the product purity is poor.
  • this technology controls the overall oxygen intake in the oxidation process, and high-temperature deep oxidation will consume excess oxygen, so that not only peroxidation by-products are produced during the reaction process, but also the raw material MBTS is unreacted. After detection and analysis, the yield of the product DCBS is only 49.9%, and the purity is 76.7%.
  • Example 4 shows that due to the removal of the isopropanol component in the solvent, MBT-dicyclohexylamine exists in the system in solid form in the reaction, and it is difficult to oxidize to generate DCBS, so that the reaction yield is reduced, and the product purity is reduced . After detection and analysis, the yield of the product DCBS is only 88.0%, and the purity is 89.8%.
  • Example 5 shows that due to the lack of core component anion resin in the catalyst, the microcirculation of the reaction can only be completed halfway, that is, the reaction of MBTS and dicyclohexylamine to generate DCBS and MBT, and the MBT produced will be complexed in the system. dicyclohexylamine, which hinders the reaction. After detection and analysis, the yield of the product DCBS is only 35.6%, and the purity is 55.8%.
  • Example 6 shows that due to the excessive amount of dicyclohexylamine dropped into the system, the amount of complexation between MBT and dicyclohexylamine in the reaction microcirculation is too large, resulting in a low yield. And dicyclohexylamine is also a solvent for the product DCBS, excessive input will cause incomplete crystallization, further affecting the yield.
  • Example 7 shows that due to the lack of water in the solvent, the catalyst cannot be effectively activated, and the catalytic efficiency is extremely low. Only a part of MBTS reacts with dicyclohexylamine within the reaction time to form the target product DCBS. And due to the existence of oxygen in the reaction system, there are certain oxidation side reactions in the system, which affects the purity of the product, and because the product is difficult to completely separate from the raw material MBTS, the purity of the product is extremely low. After detection and analysis, the yield of the product DCBS is only 26.7%, and the purity is 39.6%.
  • Example 8 shows that due to the lack of toluene in the solvent, the solvent is homogeneous, and part of the product DCBS is deeply oxidized into other by-products during the oxidation process, resulting in insufficient yield of the final product. After detection and analysis, the yield of the product DCBS was 89.3%, and the purity was 98.3%.
  • Example 9 shows that due to the lack of the core component cationic resin in the catalyst, the reaction microcirculation cannot be effectively started, that is, MBTS cannot effectively react with dicyclohexylamine to generate DCBS and MBT, resulting in extremely low reaction yield. And because the product is difficult to completely separate from the raw material MBTS, the purity of the product is extremely low. After detection and analysis, the yield of the product DCBS is only 16.6%, and the purity is 21.2%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

La présente invention relève du domaine des composés hétérocycliques, et concerne en particulier un procédé de production d'un DCBS accélérateur. Le procédé de production comprend les étapes suivantes consistant à : 1) Mélanger du MBTS et un solvant mixte dans des conditions d'agitation jusqu'à uniformité pour obtenir une matière première en suspension épaisse ; 2) ajouter la matière première en suspension épaisse mélangée et un catalyseur à un réacteur d'oxydation pour oxydation ; et 3) acquérir un produit cible DCBS après achèvement de la réaction. Dans la présente invention, du MBTS est utilisé en tant que matière première principale, de telle sorte que le procédé de réaction d'oxydation directe d'un complexe MBT-dicyclohexylamine est évité dans une large mesure, et en outre, le rendement de réaction est amélioré de manière considérable. De plus, le procédé est relativement simple, et sa transformation vers l'industrie est relativement facile.
PCT/CN2022/087695 2021-10-08 2022-04-19 Procédé de production de dcbs accélérateur WO2023056739A1 (fr)

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CN113582944B (zh) * 2021-10-08 2022-03-15 科迈化工股份有限公司 促进剂dcbs的生产工艺

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0721946A1 (fr) * 1995-01-13 1996-07-17 Bayer Ag Procédé pour la préparation de N,N-dialkyl-, -dicycloalkyl-, -diaryl- oder -diaralkyl-benzthiazolyl-sulfenamides
JP2002088256A (ja) * 2000-09-18 2002-03-27 Polymatech Co Ltd 熱伝導性高分子組成物及び熱伝導性成形体
CN101143856A (zh) * 2007-09-10 2008-03-19 天津市科迈化工有限公司 橡胶硫化促进剂dz的生产方法
CN101723916A (zh) * 2008-11-03 2010-06-09 刘要进 橡胶硫化促进剂dz的生产方法
CN108586383A (zh) * 2018-05-23 2018-09-28 科迈化工股份有限公司 一种硫化促进剂dcbs的连续化生产方法
CN109232472A (zh) * 2018-10-24 2019-01-18 科迈化工股份有限公司 硫化促进剂mbt及其制备方法
CN110156718A (zh) * 2019-06-21 2019-08-23 科迈化工股份有限公司 一种以液氯为氧化剂连续生产硫化促进剂dcbs的方法
CN112645900A (zh) * 2020-12-25 2021-04-13 科迈化工股份有限公司 促进剂dcbs的合成方法
CN113582944A (zh) * 2021-10-08 2021-11-02 科迈化工股份有限公司 促进剂dcbs的生产工艺

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002088056A (ja) * 2000-09-13 2002-03-27 Sanshin Chem Ind Co Ltd 酸化方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0721946A1 (fr) * 1995-01-13 1996-07-17 Bayer Ag Procédé pour la préparation de N,N-dialkyl-, -dicycloalkyl-, -diaryl- oder -diaralkyl-benzthiazolyl-sulfenamides
JP2002088256A (ja) * 2000-09-18 2002-03-27 Polymatech Co Ltd 熱伝導性高分子組成物及び熱伝導性成形体
CN101143856A (zh) * 2007-09-10 2008-03-19 天津市科迈化工有限公司 橡胶硫化促进剂dz的生产方法
CN101723916A (zh) * 2008-11-03 2010-06-09 刘要进 橡胶硫化促进剂dz的生产方法
CN108586383A (zh) * 2018-05-23 2018-09-28 科迈化工股份有限公司 一种硫化促进剂dcbs的连续化生产方法
CN109232472A (zh) * 2018-10-24 2019-01-18 科迈化工股份有限公司 硫化促进剂mbt及其制备方法
CN110156718A (zh) * 2019-06-21 2019-08-23 科迈化工股份有限公司 一种以液氯为氧化剂连续生产硫化促进剂dcbs的方法
CN112645900A (zh) * 2020-12-25 2021-04-13 科迈化工股份有限公司 促进剂dcbs的合成方法
CN113582944A (zh) * 2021-10-08 2021-11-02 科迈化工股份有限公司 促进剂dcbs的生产工艺

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