WO2023060866A1 - Mbts空气氧化合成促进剂cbs的工艺 - Google Patents

Mbts空气氧化合成促进剂cbs的工艺 Download PDF

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WO2023060866A1
WO2023060866A1 PCT/CN2022/087698 CN2022087698W WO2023060866A1 WO 2023060866 A1 WO2023060866 A1 WO 2023060866A1 CN 2022087698 W CN2022087698 W CN 2022087698W WO 2023060866 A1 WO2023060866 A1 WO 2023060866A1
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mbts
cbs
reaction
catalyst
cyclohexylamine
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French (fr)
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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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    • 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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  • the invention belongs to the field of heterocyclic compounds, and in particular relates to a process for synthesizing accelerator CBS by air oxidation of MBTS.
  • the current industrialization method of the rubber vulcanization accelerator CBS is to use sodium hypochlorite or hydrogen peroxide as an oxidizing agent to oxidize the accelerator MBT or its sodium salt and cyclohexylamine to form the accelerator CBS.
  • the sodium hypochlorite method oxidation has the advantages of mature technology, mild reaction conditions, better product quality and higher yield (generally about 90%-92%).
  • the amount of waste water produced is large, about 8 tons of waste water is produced per ton of product, and the salt content is high, the COD is high (generally above 30000ppm), it is difficult to biochemically treat (there is biological toxicity), and it is not good for environmental protection.
  • the hydrogen peroxide method can avoid the problem of high salt content in wastewater, but hydrogen peroxide has strong activity, and there are more side reactions in the oxidation process than the sodium hypochlorite method, and the product yield is also lower than that of the sodium hypochlorite method.
  • the main problems can be divided into two categories: one is insufficient catalyst life.
  • the active sites or active components of this type of catalyst are combined with the carrier through simple loading (such as patent CN108084114B). During the reaction process, the active components gradually dissolve into the raw material liquid and are finally discharged out of the system with waste water and waste solvents. Although the catalyst has good activity, its service life is poor and it cannot be used for a long time.
  • the second is insufficient catalyst activity.
  • This type of catalyst generally has certain structural or compositional characteristics (such as patent CN109289922B), and compared with the first type of catalyst, the reaction activity or selectivity is slightly worse, resulting in a slightly lower product yield. Moreover, due to the special structure or composition of this type of catalyst, the preparation process is often complicated, the cost of the catalyst is high, and there is also a certain bottleneck for industrial scale-up.
  • the current industrial preparation process of MBTS is mainly sodium hypochlorite oxidation or hydrogen peroxide oxidation. From the perspective of the whole process, using MBTS instead of MBT as a synthetic raw material for CBS will not reduce pollutant emissions.
  • the object of the present invention is to provide a kind of technology of MBTS air oxidation synthetic accelerator CBS.
  • a kind of technology of MBTS air oxidation synthetic accelerator CBS comprises the following steps:
  • step (2) Put the raw material slurry and catalyst obtained in step (1) into the oxidation kettle, start stirring, and then pass air into it for oxidation. During the reaction, control the reaction pressure. When the quality of the air passing through meets the requirements, continue stirring until the reaction reaches End point; the mass ratio of MBTS and catalyst in the raw material liquid is 1:1-2;
  • the mass ratio of MBTS and cyclohexylamine in the step (1) is 1:0.7-1.2.
  • the mass ratio of MBTS to the mixed solvent is 1:1.2-3.
  • the strongly acidic cationic resin is cationic resin with sulfonic acid group [-SO 3 H]; the weakly basic anionic resin is anionic resin with tertiary amino group [-NR 2 ].
  • the catalyzer in the step (2) is the mixture of strongly acidic cationic resin (Xi'an Lanxiao LXC-107) and weakly basic anionic resin (Xi'an Lanxiao LXC-104); described strongly acidic cationic resin and weakly basic anionic resin
  • the mass ratio is 1:1.5-3.5.
  • the solvent in the step (1) is a mixture of water and toluene; water: the mass ratio of toluene is 1:3-5.
  • step (2) the reaction temperature is 25-40°C; the initial pressure of the reaction is controlled at 0.5Mpa; the mass ratio of MBTS in the raw material liquid to the air introduced is 1:0.5-0.75; the stirring time after the air is passed is controlled at 0.5 -1.5h.
  • Step (3) middle and lower layer aqueous solution vast majority is applied mechanically in the next batch of synthesis process according to the ratio of feeding intake, remaining a small amount then reclaims toluene and cyclohexylamine by atmospheric distillation.
  • the present invention has developed a process for the synthesis accelerator CBS of MBTS by air oxidation.
  • the technology uses air as oxidant, MBTS and cyclohexylamine as raw materials, strong acidic cationic resin and weakly basic anionic resin as catalyst, and water, toluene
  • the binary mixture is used as the solvent synthesis accelerator CBS.
  • the raw material is in slurry state, and the product is in liquid state.
  • the separation of the catalyst and the product can be effectively realized by means of simple filtration.
  • the product phase is separated from the solvent by cooling crystallization.
  • Strongly acidic cationic resin can further activate cyclohexylamine, and then accelerate the reaction between cyclohexylamine and MBTS to generate CBS and intermediate product MBT;
  • the weakly basic anion resin can weaken the "MBT-cyclohexylamine" structure formed by the complexation of the intermediate product MBT and excess cyclohexylamine, so that it can form a transition structure in the process of contacting the oxidant with air, thereby improving the selection of the oxidation reaction property, and ultimately improve the yield of the product CBS.
  • This technology uses water/toluene binary mixture as a solvent, which effectively realizes the separation of main products and by-products, and then effectively improves the purity of the product CBS to more than 99%.
  • a binary mixture solvent each component plays a different role.
  • toluene The role of toluene is mainly as a product solvent and a solvent for some oil-soluble impurities. During the reaction process, toluene can effectively dissolve the product CBS, and then effectively separate the unreacted raw material MBTS from the product. Secondly, because 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. Furthermore, 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 function of water is mainly to provide active ions for the catalyst. Since the catalyst is an ionic resin, it requires the presence of water to be effectively activated.
  • the main components of the upper organic phase are toluene, water, cyclohexylamine, CBS and other organic impurities (mainly from the organic impurities entrained in the raw material MBTS and this part of impurities further react with the raw materials in the system such as cyclohexylamine during the oxidation process generated impurities), which can be directly returned to the synthesis process.
  • the CBS content in the organic phase will gradually decrease, and the content of other organic impurities will gradually increase, which will affect the subsequent oxidation process and yield.
  • the organic phase is processed.
  • the toluene and cyclohexylamine in the organic phase are recovered by distillation and used mechanically.
  • the remaining residue is mainly a small amount of toluene, CBS and a large amount of resin (mainly from impurities in MBTS and a small amount of oxidized by-products), which can be directly incinerated.
  • MBT metal-oxide-semiconductor
  • cyclohexylamine air, and catalyst quaternary components
  • MBT concentration of MBT in the system.
  • MBT will directly complex with cyclohexylamine to form "
  • the structure of "MBT-cyclohexylamine” is precipitated out of the reaction system to form solid particles that are directly oxidized by the air. While generating CBS, it will also be converted into a large amount of peroxidation by-products, which will significantly reduce the selectivity and yield of the reaction. This is also the problem with most homogeneous catalysts.
  • the specific method can be to directly increase the proportioning ratio of MBT and cyclohexylamine or slowly add MBT beating into the reaction system dropwise.
  • the direct impact of the above approach is to make the reaction system homogeneous, and the CBS produced by the reaction is dissolved in a large amount of cyclohexylamine aqueous solution, and is continuously deeply oxidized to generate by-products as the reaction proceeds under the action of the catalyst.
  • a relatively large amount of cyclohexylamine in the reaction system can also be directly oxidized to generate by-products.
  • cyclohexylamine slightly higher than the reaction ratio mainly plays two roles.
  • a certain concentration of cyclohexylamine can effectively complex the MBT generated after the reaction between MBTS and cyclohexylamine, thereby protecting this part of MBT from It will be directly oxidized by air to form by-products other than MBTS, increasing the reaction yield.
  • the technical solution of the present application uses air as the oxidant, avoiding the generation of a large amount of waste salt and waste water.
  • this technology uses a mixture of resins as a solid catalyst, which avoids the pollution problem caused by the loss of liquid phase catalyst and improves the environmental protection of the technology.
  • the catalyst has extremely high selectivity, and the yield of the final product CBS is above 98.5% (calculated by pure conversion of raw material MBTS).
  • Embodiment 1 provides the present invention to solve above-mentioned technical problem, a kind of technique of MBTS air oxidation synthesis accelerator CBS, described method comprises the steps:
  • the oil phase was applied mechanically several times. When the oil phase was applied mechanically for 25 times, it was found that the yield of a single reaction began to decline, and the product purity also decreased. Therefore, the yield data was taken after applying the oil phase for 25 times.
  • the yield of CBS product is 99.2% (based on the content of pure MBTS in the raw material MBTS), the purity of CBS product is 99.2%, and the appearance is white crystalline powder.
  • Table 1 shows the effect of changing different parameters on the results of other embodiments.
  • the yield of the product CBS is only 60.5%, and the purity is 81.2%.
  • Example 6 because the excessive amount of air introduced is serious, the reaction speed between the raw material MBT, cyclohexylamine, catalyzer and air is strengthened in the reaction process, so that MBT and cyclohexylamine all have a certain overoxidation situation, And because the peroxidation of cyclohexylamine in the system is aggravated, the product purity is reduced more obviously. After detection and analysis, the yield of the product CBS was 84.7%, and the purity was 96.8%.

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

Abstract

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。

Description

MBTS空气氧化合成促进剂CBS的工艺 技术领域
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。
背景技术
目前橡胶硫化促进剂CBS的产业化方法为以次氯酸钠或双氧水为氧化剂，将促进剂MBT或者其钠盐与环己胺氧化生成促进剂CBS。其中，次氯酸钠法氧化具有工艺成熟，反应条件温和，产品质量较好，收率较高的优点(一般在90％-92％左右)。但其生产废水量大，1吨产品约产8吨废水，且含盐量高，COD高(一般在30000ppm以上)，难以生化处理(存在生物毒性)，对环境保护不利。而双氧水法则可以回避废水中含盐量高的问题，但双氧水活性强，氧化过程中副反应较次氯酸钠法多，产物收率亦较次氯酸钠法有所降低。
空气催化氧化法则由于废水产量大幅降低，有利于环境保护，近年来有高校和企业有在研究。专利CN108084114B、CN110305075A、CN109289922B、CN203018092U等多篇相关专利技术在空气催化氧化制备CBS的工艺流程、催化剂开发及应用设备开发等多方面进行了探索。但从多方报道结果看，以空气催化氧化法制备CBS的技术，仍存在一定的问题。
1)、采用均相催化剂进行CBS空气催化氧化法制备，多存在产品收率不足，产品纯度波动大的问题。以专利CN110305075A为例，采用水溶性钴系催化剂进行空气氧化，多数实施例中CBS收率不高，且产品熔点低波动较大，说明产品纯度波动大。此外，水溶性催化剂的使用过程中，多存在催化剂回收难，催化剂成本高，废水中含重金属等多种问题。这亦是该类催化工艺存在的另一个主要问题。
2)、采用非均相催化剂进行CBS空气催化氧化法制备，主要问题可分为两类：一是催化剂寿命不足。该类催化剂的活性点位或活性组分通过简单负载的方式与载体结合(诸如专利CN108084114B)，在反应过程中活性组分逐渐溶解到原料液中并最终随废水、废溶剂排出系统之外，使得催化剂尽管活性良好，但寿命较差，无法做到长期使用。二是催化剂活性不足。该类催化剂一般具有一定的结构或成分特征(诸如专利CN109289922B)，与第一类催化剂相比反应活性或者选择性略差，造成产品收率略低。且该类催化剂因为特殊结构或组成的问题，往往制备过程比较复杂，催化剂成本较高，对工业放大来说亦存在一定的瓶颈。
3)、除此以外，亦有部分研究通过改变原材料的方式来优化促进剂CBS的合成过程(诸如专利CN112625003A)。其多通过采用MBTS(亦称MBTS)或MBTS与MBT的混 合物作为原材料，利用MBTS与环己胺可以在水体系中自发缓慢反应生成CBS和MBT的原理来减少氧化剂的使用量，进而减少废水或废盐的产生。但该技术存在两个问题：一是MBTS由MBT氧化制备而来，且该技术的工业化收率不超过90％，进而造成MBTS成本较高。二是MBTS目前的工业化制备工艺主要是次氯酸钠氧化或双氧水氧化，从全流程来看采用MBTS代替MBT作为CBS的合成原料并不会减少污染物的排放。
综上所述，目前常见报道的CBS合成技术，无法有效回避三废的产生，且产生的“三废”亦存在处理难度大，处理成本高的问题，需要开发一种新的MBTS合成工艺去解决或缓解上述问题。
发明内容
本发明的目的在于提供一种MBTS空气氧化合成促进剂CBS的工艺。
为实现上述目的，本发明采用的技术方案为：
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中，开启搅拌后通入空气进行氧化，反应过程中控制反应压力，当通入空气的质量达到要求后，继续搅拌至反应达到终点；原料液中MBTS与催化剂的质量比为1:1-2；
(3)反应完成后，过滤系统中的催化剂，即可得到产物溶液，静置分相后，上层油相进行降温结晶，过滤后即可得到粗品CBS；该粗品经过水洗后即可得到目标产物CBS湿料。
步骤(1)中MBTS与环己胺的质量比为1:0.7-1.2。
步骤(1)中MBTS与混合溶剂的质量比为1:1.2-3。
所述的强酸性阳离子树脂为磺酸基[-SO 3H]的阳离子树脂；弱碱性阴离子树脂为具有叔氨基[-NR 2]的阴离子树脂。
步骤(2)中的催化剂为强酸性阳离子树脂(西安蓝晓LXC-107)与弱碱性阴离子树脂(西安蓝晓LXC-104)的混合物；所述的强酸性阳离子树脂与弱碱性阴离子树脂的质量比为1:1.5-3.5。
步骤(1)中的溶剂为水和甲苯的混合物；水：甲苯的质量比为1:3-5。
步骤(2)中反应温度为25-40℃；反应起始压力控制在0.5Mpa；原料液中MBTS与通入空气的质量比为1:0.5-0.75；通完空气后的搅拌时间控制在0.5-1.5h。
步骤(3)中下层水溶液绝大部分按照投料配比套用到下批次合成过程中，剩余少量 则通过常压蒸馏回收甲苯和环己胺。
与现有技术相比，本发明的有益效果是：
本发明开发了一种MBTS空气氧化合成促进剂CBS的工艺，该技术以空气为氧化剂，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。反应完成后通过简单过滤的手段可有效实现催化剂和产物的分离。产物相通过降温结晶的方式实现产物与溶剂的分离。
1、本申请中采用双离子型复合催化剂。
1.1、强酸性阳离子树脂可进一步活化环己胺，进而加速环己胺与MBTS反应，生成CBS和中间产物MBT；
1.2、弱碱性阴离子树脂可弱化中间产物MBT与过量环己胺络合生成的“MBT-环己胺”结构，使其在与氧化剂空气接触的过程中形成过渡结构，进而提高氧化反应的选择性，最终提高产品CBS的收率。
2、该技术采用水/甲苯二元混合液作为溶剂，有效实现了主产物与副产物的分离，进而有效提高了产品CBS的纯度至99％以上。在二元混合液溶剂中，各组分所起的作用各不相同。
2.1、甲苯的作用主要是产物溶剂和部分油溶性杂质的溶剂。在反应过程中甲苯可以有效溶解产物CBS，进而有效实现未反应的原材料MBTS与产物分离。其次由于催化剂为离子型树脂，氧化反应主要发生在水相，而甲苯作为油相主体成分可有效将催化剂和产物分离，降低产物CBS被深度氧化生成其他副产物，进而提高了产品的收率。再者甲苯可以作为原材料MBTS中的油溶性杂质的溶剂，减少其与在水相进行的氧化反应的干扰，进而进一步提高反应收率。
2.2、水的作用主要是为催化剂提供活性离子，由于催化剂为离子型树脂，需要水的存在方可有效激活。
2.3、同时采用有机相和水相作为溶剂，分离产物后的溶剂静置后分相，下层为水相，可直接套用回下批次合成，超过套用需求量的水(来源于氧化过程生成的水，质量约为原料MBTS质量的10％)则通过精馏回收水相中溶解的甲苯和环己胺。回收完剩余废水中溶解少量的水溶性副产物，COD在12000左右，经过高级氧化+生化处理后COD可降低至100以内。上层有机相主要成分为甲苯、水、环己胺、CBS和其他有机杂质(主要由原材料MBTS中夹带的有机杂质及这部分杂质在氧化过程中进一步与环己胺等系统中的原材料二次反应生 成的杂质)，可直接返回合成过程。随着有机相套用次数增加(套用次数控制在20-25次)，有机相中的CBS含量逐渐降低，其他有机杂质含量逐渐增加，进而会影响到后续的氧化过程和收率，故此时需要对有机相进行处理。通过蒸馏的方式回收有机相中的甲苯、环己胺进行套用，剩余釜残主要是少量甲苯、CBS和大量树脂(主要来自MBTS中的杂质和少量氧化副产物)，可直接焚烧处理。
3、该技术采用MBTS作为原材料而不是MBT，其原因为：
该技术的关键在于MBT、环己胺、空气、催化剂四元组分能够有效结合而形成过渡结构，进而提高反应的选择性和产物收率。而在该结构形成的过程中，需要控制系统中MBT的浓度，当MBT浓度过大时，由于催化剂活性位数量和体系中环己胺浓度的限制，会使得MBT直接与环己胺络合形成“MBT-环己胺”的结构并析出反应体系形成固体颗粒物直接被空气氧化，在生成CBS的同时，亦会较大量的转化为过氧化副产物，进而使得反应的选择性和收率明显降低，这也是大部分均相催化剂的问题所在。
而这个问题可以通过提高体系中的环己胺浓度来解决，具体的方法可以是直接增加MBT与环己胺的配比或者将MBT打浆缓慢滴加入反应体系中。但上述做法的直接影响是使得反应体系成为均相，反应生成的CBS溶解于大量的环己胺水溶液中，在催化剂作用下随着反应进行而不断被深度氧化生成副产物。此外，反应体系中较大量的环己胺亦可以直接被氧化生成副产物。这虽然不会影响MBT转化为CBS的选择性和收率，但会造成环己胺损失过大，CBS生成过程中环己胺消耗大大增加，依然不利于优化CBS的合成消耗。
而采用MBTS作为原材料则不会出现此种问题。通过阳离子树脂提高MBTS直接与环己胺生成CBS和MBT这个反应的速度，可以控制系统中的MBT浓度维持在一定程度，进而使得系统中环己胺、MBT的浓度均可控制在比较理想的范围之内，既可以保证整个反应的收率，同时可以有效抑制MBT和环己胺各自被深度氧化生成副产物的几率，进而有效降低CBS合成过程中原材料的消耗，使得该技术的产物收率进一步接近理论值。
此外，略高于反应配比的环己胺的投入主要起两方面的作用，一是一定浓度的环己胺可有效络合MBTS与环己胺反应后生成的MBT，进而保护这部分MBT不会直接被空气深度氧化成MBTS以外的副产物，提高反应收率。其次这部分MBT与环己胺络合后将生成难溶于水和甲苯的“MBT-环己胺”，而这部分中间产物可溶解于一定浓度的环己胺水溶液中，进而可以与催化剂有效结合生成过渡结构，进而提高反应收率。
总之，本申请的技术方案以空气为氧化剂，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。同时该催化剂具有极高的选择性，最终产品CBS的收率在98.5％(原料MBTS折纯计算)以上。
具体实施方式
为了使本技术领域的技术人员更好地理解本发明的技术方案，下面结合实施例对本发明作进一步的详细说明。
实施例1：本实施例提供了本发明为解决上述的技术问题，一种MBTS空气氧化合成促进剂CBS的工艺，所述方法包括如下步骤：
(1)在20℃条件下，将质量比为1:0.7:1.2的MBTS、环己胺和溶剂在搅拌条件下混合0.3h，溶剂为水和甲苯的混合物，溶剂中水：甲苯＝1:3；混合完成后即为原料液。
(2)将原料液投入高压釜后，再加入MBTS质量1倍质量的大孔树脂催化剂，开启搅拌后，通入空气至压力0.5Mpa，开始进行氧化反应。其中催化剂由阳离子树脂与阴离子树脂混合而成，两者质量比为1:1.5(强酸性阳离子树脂，西安蓝晓LXC-107；弱碱性阴离子树脂，西安蓝晓LXC-104)。过程中控制反应温度在25℃，待通入空气的总质量达到投入MBTS质量的0.5倍时，停止通入空气，继续搅拌1.5h后反应结束。
(3)反应完成后，将催化剂过滤回收，滤液静置1h后分相，下层水溶液套用到下个批次的合成过程中，剩余少量通过常压蒸馏回收环己胺和甲苯。
(4)上层油相进行结晶，过滤后得到的湿料经过湿料质量0.8倍的清水洗涤后，即可得到目标产品CBS湿料。滤液套用到下一批次即可。
为精确计量收率，油相进行多次套用，当油相套用到25次后发现单次反应收率开始下降，且产品纯度亦有所降低，故收率数据按照油相套用25次后取平均值，CBS产品的收率为99.2％(以原料MBTS中纯MBTS的含量计)，CBS产品的纯度为99.2％，外观为白色晶状粉末。
表1示出其他实施例改变不同的参数对结果的影响。
表1
Figure PCTCN2022087698-appb-000001
从表1中可以看出，不加入催化剂(实施例10)、单独加入阳离子树脂或者阴离子树脂(实施例8、9)以及阴阳离子的配比过高(实施例11、12)时，对产率以及纯度均有较大影响，其他的，如实施例4示出，温度过高时，使得空气可以将产物CBS深度氧化至其他产品，故反应收率降低，且产品纯度差。此外，本技术控制了氧化过程的整体进氧量，高温深度氧化将消耗过量的空气，使得反应过程中不仅产生了过氧化副产物，同时还存在原料MBTS未反应的情况。经检测分析，产物CBS收率仅为60.5％，且纯度为81.2％。如实施例6示出，由于通入空气总量过量严重，反应过程中使得原料MBT、环己胺、催化剂、空气间的反应速度增强，使得MBT与环己胺均存在一定的过氧化情况，且由于系统中环己胺的过氧化情况加剧，进而使得产品纯度降低比较明显。经检测分析，产物CBS收率为84.7％，且纯度为96.8％。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (1)

  1. 一种MBTS空气氧化合成促进剂CBS的工艺，其特征在于，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；MBTS与环己胺的质量比为1:0.7-1.2；混合溶剂为水和甲苯的混合物；水：甲苯的质量比为1：3-5；MBTS与混合溶剂的质量比为1:1.2-3；
    (2)将步骤(1)得到的原料浆液与催化剂投入氧化釜中，开启搅拌后通入空气进行氧化，反应温度为25-40℃；反应过程中控制反应起始压力在0.5Mpa；原料液中MBTS与通入空气的质量比为1:0.5-0.75；通完空气后的搅拌时间控制在0.5-1.5h至反应达到终点；
    原料液中MBTS与催化剂的质量比为1:1-2；催化剂为强酸性阳离子树脂与弱碱性阴离子树脂的混合物；所述的强酸性阳离子树脂与弱碱性阴离子树脂的质量比为1:1.5-3.5；强酸性阳离子树脂为磺酸基的阳离子树脂；弱碱性阴离子树脂为具有叔氨基的阴离子树脂；
    (3)反应完成后，过滤系统中的催化剂，即可得到产物溶液，静置分相后，上层油相进行降温结晶，过滤后即可得到粗品CBS；该粗品经过水洗后即可得到目标产物CBS湿料。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4182873A (en) * 1972-10-04 1980-01-08 Rhone-Poulenc S.A. Process for the preparation of thiazolesulphenamides
JP2002088056A (ja) * 2000-09-13 2002-03-27 Sanshin Chem Ind Co Ltd 酸化方法
CN113636986A (zh) * 2021-10-14 2021-11-12 科迈化工股份有限公司 Mbts空气氧化合成促进剂cbs的工艺

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DE3517084A1 (de) * 1985-05-11 1986-11-13 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von benzothiazolsulfenamiden
US5436346A (en) * 1991-12-21 1995-07-25 Akzo Nobel N.V. Process for the preparation of benzothiazolyl-2-sulphenamides
CN100404518C (zh) * 2005-05-31 2008-07-23 中国石油天然气集团公司 一种制备2-苯并噻唑次磺酰胺的方法及装置
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Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4182873A (en) * 1972-10-04 1980-01-08 Rhone-Poulenc S.A. Process for the preparation of thiazolesulphenamides
JP2002088056A (ja) * 2000-09-13 2002-03-27 Sanshin Chem Ind Co Ltd 酸化方法
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