WO2017059614A1 - 2-巯基苯并噻唑的制备方法 - Google Patents

2-巯基苯并噻唑的制备方法 Download PDF

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Publication number
WO2017059614A1
WO2017059614A1 PCT/CN2015/093613 CN2015093613W WO2017059614A1 WO 2017059614 A1 WO2017059614 A1 WO 2017059614A1 CN 2015093613 W CN2015093613 W CN 2015093613W WO 2017059614 A1 WO2017059614 A1 WO 2017059614A1
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Prior art keywords
aniline
ionic liquid
mercaptobenzothiazole
preparation
sulfonic acid
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PCT/CN2015/093613
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English (en)
French (fr)
Inventor
陈新民
武历保
石松
高尚
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江苏圣奥化学科技有限公司
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Priority to MX2018004321A priority Critical patent/MX2018004321A/es
Priority to CA3001053A priority patent/CA3001053C/en
Priority to AU2015411254A priority patent/AU2015411254B2/en
Priority to SG11201802900VA priority patent/SG11201802900VA/en
Priority to MYPI2018000489A priority patent/MY184092A/en
Priority to JP2018537702A priority patent/JP6524354B2/ja
Priority to ES15905712T priority patent/ES2890659T3/es
Application filed by 江苏圣奥化学科技有限公司 filed Critical 江苏圣奥化学科技有限公司
Priority to EA201890877A priority patent/EA033216B1/ru
Priority to PL15905712T priority patent/PL3360867T3/pl
Priority to RS20211173A priority patent/RS62393B1/sr
Priority to KR1020187013002A priority patent/KR102118465B1/ko
Priority to EP15905712.4A priority patent/EP3360867B1/en
Priority to BR112018007111-0A priority patent/BR112018007111B1/pt
Publication of WO2017059614A1 publication Critical patent/WO2017059614A1/zh
Priority to IL258520A priority patent/IL258520B/en
Priority to US15/948,321 priority patent/US10106513B2/en
Priority to CONC2018/0004330A priority patent/CO2018004330A2/es
Priority to ZA2018/02897A priority patent/ZA201802897B/en
Priority to HK19100200.5A priority patent/HK1258438A1/zh

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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
    • C07D277/72—2-Mercaptobenzothiazole
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/14—Silica and magnesia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
    • B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium

Definitions

  • the present invention relates to the field of organic synthesis, and in particular to a method for preparing 2-mercaptobenzothiazole.
  • 2-Mercaptobenzothiazole also known as accelerator M or accelerator MBT, also known as fast-heating powder
  • accelerator M or accelerator MBT also known as fast-heating powder
  • 2-Mercaptobenzothiazole is a general-purpose vulcanization accelerator for rubber. It has the characteristics of fast vulcanization promotion, low vulcanization flatness, and no early vulcanization during kneading, and is widely used in the rubber processing industry.
  • aniline production to promote M are that the source of raw materials is stable, the operation is difficult, and the material requirements of the reactor are low. However, it still has defects such as low product purity, large tar amount, and low yield.
  • the invention aims to provide a preparation method of 2-mercaptobenzothiazole to solve the problems of low purity, large tar amount and low yield of the product in the prior art production of aniline.
  • a process for the preparation of 2-mercaptobenzothiazole which comprises reacting a catalyst with a aniline method to prepare 2-mercaptobenzothiazole, and a catalyst A sulfonic acid type imidazolyl ionic liquid is included.
  • the sulfonic acid type imidazolyl ionic liquid is [TSVM]HSO 4 and/or [MPS] 2 HSO 4 .
  • the catalyst further comprises a support for supporting a sulfonic acid type imidazolyl ionic liquid.
  • the carrier is selected from one or more of the group consisting of activated alumina, cordierite honeycomb ceramics, sulfhydryl silica gel, ion exchange resins, and HSZM molecular sieves.
  • the weight ratio between the sulfonic acid type imidazolyl ionic liquid and the carrier is from 0.1 to 20:100.
  • reaction temperature of the reaction is 200 to 280 ° C
  • reaction pressure is 3.0 to 8.0 MPa
  • reaction time is 2 to 12 hours.
  • reaction temperature of the reaction is 240 to 250 ° C
  • reaction pressure is 4.5 to 5.5 MPa
  • reaction time is 4 to 6 hours.
  • aniline, carbon disulfide and sulfur are used as reaction raw materials, and the molar ratio between aniline, carbon disulfide and sulfur is 1:1.0 to 1.3:1.1 to 2, and between the aniline and the sulfonic acid type imidazolium ionic liquid The weight ratio is 100:1 to 5.
  • the molar ratio between aniline, carbon disulfide and sulfur is 1:1.0 to 1.1:1.2 to 1.5, and the weight ratio between the aniline and the sulfonic acid type imidazolyl ionic liquid is 100:1 to 2.
  • 2-mercaptobenzothiazole is prepared by a batch or continuous production process.
  • 2-mercaptobenzothiazole is prepared by the aniline method under the catalysis of a sulfonic acid type imidazolyl ionic liquid.
  • the sulfonic acid type imidazolium ionic liquid is a kind of acidic functionalized ionic liquid, which has the advantages of both solid acid and liquid acid.
  • a sulfonic acid type imidazolyl ionic liquid is used as an active component of the catalyst, which can significantly improve the conversion rate of the reaction raw material and increase the yield of 2-mercaptobenzothiazole.
  • the preparation method provided by the invention has the advantages of simple process, low cost, low tar amount and high environmental protection. Comprehensive advantages.
  • the existing aniline process produces 2-mercaptobenzothiazole, which has the problems of low product purity, large tar amount, and low yield.
  • the inventors of the present invention provide a process for preparing 2-mercaptobenzothiazole by using an aniline method under the action of a catalyst to prepare 2-mercaptobenzothiazole, and the catalyst includes a sulfonic acid type. Imidazolyl ionic liquid.
  • 2-mercaptobenzothiazole is prepared by the aniline method under the catalysis of a sulfonic acid type imidazolyl ionic liquid.
  • the sulfonic acid type imidazolium ionic liquid is a kind of acidic functionalized ionic liquid, which has the advantages of both solid acid and liquid acid.
  • a sulfonic acid type imidazolyl ionic liquid is used as an active component of the catalyst, which can significantly improve the conversion rate of the reaction raw material and improve the yield and purity of 2-mercaptobenzothiazole.
  • the preparation method provided by the invention has the advantages of simple process, low cost, low tar amount and high environmental protection. Comprehensive advantages.
  • the reaction process can have the advantages of high yield, low cost, environmental protection and the like.
  • the sulfonic acid type imidazolyl ionic liquid is [TSVM]HSO 4 and/or [MPS] 2 HSO 4 .
  • the above two sulfonic acid type imidazolium ionic liquids have high catalytic activity, low cost and wide source, and the use of the catalyst as an active ingredient of the catalyst can further increase the yield of 2-mercaptobenzothiazole, reduce the discharge of three wastes, and reduce Cost of production.
  • the sulfonic acid type imidazolyl ionic liquid can be directly used as a catalyst to prepare the preparation of 2-mercaptobenzothiazole, that is, the non-supporting sulfonic acid type imidazolyl ionic liquid can be directly added to the reaction system for catalytic reaction.
  • a supported sulfonic acid type imidazolyl ionic liquid is employed as the catalyst, i.e., the catalyst further comprises a support for supporting a sulfonic acid type imidazolyl ionic liquid.
  • the immobilized sulfonic acid type imidazolyl ionic liquid catalyst can be installed in a fixed column in addition to being suitable for use in a usual batch reactor or a tank continuous reactor for catalytic reaction, and continuously feeds in and out through the reaction raw material to realize continuous production. Large capacity, low energy consumption, and low production costs.
  • the carrier includes, but is not limited to, one or more of activated alumina, cordierite honeycomb ceramics, sulfhydryl silica gel, ion exchange resins, and HSZM molecular sieves. All of these carriers have the advantages of stable physical properties, large specific surface area, and high binding with the sulfonic acid type imidazolium ionic liquid. In addition to these, these carriers also have lower costs.
  • the weight ratio of the sulfonic acid type imidazolyl ionic liquid to the carrier is from 0.1 to 20:100.
  • the reaction temperature in the above preparation is 200-280 ° C
  • the reaction pressure is 3.0-8.0 MPa
  • the reaction time is 2-12 h.
  • the use of a sulfonic acid type imidazolyl ionic liquid as a catalytically active component itself can reduce the difficulty of operation of 2-mercaptobenzothiazole and make the reaction conditions milder.
  • the reaction temperature of the above reaction is 240 to 250 ° C
  • the reaction pressure is 4.5 to 5.5 MPa
  • the reaction time is 4 to 6 hours.
  • the aniline method uses aniline, carbon disulfide and sulfur as reaction raw materials, and the molar ratio between aniline, carbon disulfide and sulfur is 1:1.0-1.3:1.1-2, and the aniline and sulfonic acid type
  • the weight ratio between the imidazolyl ionic liquids is from 100:1 to 5. Setting the amount ratio between the raw materials within the above range is advantageous for further increasing the conversion rate of the reaction, and at the same time, having a higher reaction rate and a target product yield.
  • controlling the amount of the catalyst within the above range is also advantageous for cost saving, making the entire reaction more suitable for industrial large-scale applications.
  • the molar ratio between aniline, carbon disulfide and sulfur is from 1:1.0 to 1.1:1.2 to 1.5, and the weight ratio between the aniline and the sulfonic acid type imidazolyl ionic liquid is from 100:1 to 2.
  • the 2-mercaptobenzothiazole is prepared using a batch or continuous production process.
  • the batch type is a batch tank type catalytic reaction mode
  • the continuous type is a continuous column type reaction mode (such as a fixed bed reaction mode or a trickle bed reaction mode).
  • the crude product melt is pressed into a crystallizer containing solvent toluene, and the discharged hydrogen sulfide is treated with an alkali solution, melt-crystallized, washed, filtered, and dried to obtain a 2-mercaptobenzothiophene product.
  • the purity of the product is above 98% and the yield is 90%.
  • the preparation method is the same as that of Example 1, except that the reaction temperature, the reaction pressure and the reaction time are different.
  • the process conditions and product results of the respective examples are shown in the following table:
  • the preparation method was the same as that of Example 1, except that the molar ratio of each raw material was different, and the raw material relationship and product results of the respective examples are shown in the following table:
  • the preparation method was the same as that of Example 1, except that the types of catalysts were different, and the catalyst types and product results of the respective examples are shown in the following table:
  • the above-mentioned embodiments of the present invention achieve the following technical effects: using a sulfonic acid type imidazolium ionic liquid as an active component of the catalyst, the conversion rate of the aniline reaction raw material can be remarkably improved, and 2- The yield of mercaptobenzothiazole.
  • the preparation method provided by the invention has the comprehensive advantages of simple process, low cost, low tar amount and high environmental protection.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

本发明公开了一种2-巯基苯并噻唑的制备方法。其采用苯胺法，在催化剂的作用下进行反应制备2-巯基苯并噻唑，且催化剂包括磺酸型咪唑基离子液体。磺酸型咪唑基离子液体是一类酸性功能化离子液体，兼有固体酸和液体酸的优点。采用磺酸型咪唑基离子液体作为催化剂的活性成分，能够显著改善反应原料的转化率、提高2-巯基苯并噻唑的收率。与此同时，由于2-巯基苯并噻唑高催化活性、无挥发、低腐蚀、热稳定性好等特点，使得上述制备方法还具有工艺简单、成本低、焦油量低、环保性高等综合性优势。

Description

2-巯基苯并噻唑的制备方法 技术领域
本发明涉及有机合成领域，具体而言，涉及一种2-巯基苯并噻唑的制备方法。
背景技术
2-巯基苯并噻唑(又称为促进剂M或促进剂MBT，还可称作快热粉)，是一种橡胶通用型硫化促进剂。其具有硫化促进作用快、硫化平坦性低、以及混炼时无早期硫化等特点，被广泛用于橡胶加工工业中。
促进剂M的合成方法有多种，按照所采用的原料可以分为邻硝基氯苯法、苯胺法、硝基苯和苯胺混合法、硝基苯法、亚硝基苯法等，通常采用较多的是邻硝基氯苯法、苯胺法、硝基苯和苯胺混合法这三种方法。然而，邻硝基氯苯法生产促进剂M时由于原料价格高，生产工艺复杂，不适合工业化大规模应用；硝基苯和苯胺混合法生产成本低，且可以使反应产生的H2S比苯胺法降低1/3，但由于其存在着反应难以控制和对反应器材质要求高的问题，目前国内较少采用该法。因此，苯胺法合成促进M是各助剂厂家普遍采用的方法。
苯胺法生产促进M的特点是原料来源稳定，操作难度小，对反应器材质要求低。然而，其仍然存在产物纯度较低、焦油量大、收率较低等缺陷。
发明内容
本发明旨在提供一种2-巯基苯并噻唑的制备方法，以解决现有技术中苯胺法生产促进M时产物纯度较低、焦油量大、收率较低的问题。
为了实现上述目的，根据本发明的一个方面，提供了一种2-巯基苯并噻唑的制备方法，其包括，采用苯胺法，在催化剂的作用下进行反应制备2-巯基苯并噻唑，且催化剂包括磺酸型咪唑基离子液体。
进一步地，磺酸型咪唑基离子液体为[TSVM]HSO4和/或[MPS]2HSO4。
进一步地，催化剂还包括用于负载磺酸型咪唑基离子液体的载体。
进一步地，载体选自由活性氧化铝、堇青石蜂窝陶瓷、巯基硅胶、离子交换树脂及HSZM分子筛组成的组中的一种或多种。
进一步地，磺酸型咪唑基离子液体与载体之间的重量比为0.1～20:100。
进一步地，反应的反应温度为200～280℃，反应压力为3.0～8.0MPa，反应时间为2～12h。
进一步地，反应的反应温度为240～250℃，反应压力为4.5～5.5MPa，反应时间为4～6h。
进一步地，苯胺法中，以苯胺、二硫化碳和硫磺为反应原料，苯胺、二硫化碳及硫磺之间的摩尔比为1:1.0～1.3:1.1～2，且苯胺与磺酸型咪唑基离子液体之间的重量比为100:1～5。
进一步地，苯胺、二硫化碳及硫磺之间的摩尔比为1:1.0～1.1:1.2～1.5，且苯胺与磺酸型咪唑基离子液体之间的重量比为100:1～2。
进一步地，采用间歇式或连续式的生产工艺制备2-巯基苯并噻唑。
本发明提供的制备方法中，采用苯胺法，在磺酸型咪唑基离子液体的催化作用下制备2-巯基苯并噻唑。磺酸型咪唑基离子液体是一类酸性功能化离子液体，兼有固体酸和液体酸的优点。本发明中采用磺酸型咪唑基离子液体作为催化剂的活性成分，能够显著改善反应原料的转化率、提高2-巯基苯并噻唑的收率。与此同时，由于2-巯基苯并噻唑高催化活性、无挥发、低腐蚀、热稳定性好等特点，使得本发明提供的制备方法还具有工艺简单、成本低、焦油量低、环保性高等综合性优势。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。
正如背景技术部分所描述的，现有的苯胺法生产2-巯基苯并噻唑时存在产物纯度较低、焦油量大、收率较低的问题。为了解决这一问题，本发明发明人提供了一种2-巯基苯并噻唑的制备方法，采用苯胺法，在催化剂的作用下进行反应以制备2-巯基苯并噻唑，且催化剂包括磺酸型咪唑基离子液体。
本发明提供的制备方法中，采用苯胺法，在磺酸型咪唑基离子液体的催化作用下制备2-巯基苯并噻唑。磺酸型咪唑基离子液体是一类酸性功能化离子液体，兼有固体酸和液体酸的优点。本发明中采用磺酸型咪唑基离子液体作为催化剂的活性成分，能够显著改善反应原料的转化率、提高2-巯基苯并噻唑的收率和纯度。与此同时，由于2-巯基苯并噻唑高催化活性、无挥发、低腐蚀、热稳定性好等特点，使得本发明提供的制备方法还具有工艺简单、成本低、焦油量低、环保性高等综合性优势。
本发明提供的制备方法中，只要采用磺酸型咪唑基离子液体作为活性成分催化苯胺、二硫化碳和硫磺之间的反应，就能够使反应过程兼具高收率、低成本、环保等优点。在一种优选的实施方式中，磺酸型咪唑基离子液体为[TSVM]HSO4和/或[MPS]2HSO4。
其中，[TSVM]HSO4离子液体的结构如下：
Figure PCTCN2015093613-appb-000001
[MPS]2HSO4离子液体的结构如下：
Figure PCTCN2015093613-appb-000002
上述两种磺酸型咪唑基离子液体均具有较高的催化活性，且成本较低、来源广泛，使用其作为催化剂活性成分能够进一步提高2-巯基苯并噻唑的收率，减少三废排放，降低生产成本。
本发明上述制备方法中，磺酸型咪唑基离子液体可以直接作为催化剂催化制备2-巯基苯并噻唑的制备，即可以直接将非固载型磺酸型咪唑基离子液体加入反应体系进行催化反应。在一种优选的实施方式中，采用固载型磺酸型咪唑基离子液体作为催化剂，即：催化剂还包括用于负载磺酸型咪唑基离子液体的载体。固载型磺酸型咪唑基离子液体催化剂除了适用于通常的间歇反应釜或釜式连续反应器中进行催化反应，还可以安装于固定塔中，通过反应原料连续进出，实现连续化生产，具有产能较大，能耗较低，生产成本较低等优势。
根据本发明上述的教导，本领域技术人员可以选择具体的固载型磺酸型咪唑基离子液体催化剂的载体。在一种优选的实施方式中，上述载体包括但不限于活性氧化铝、堇青石蜂窝陶瓷、巯基硅胶、离子交换树脂及HSZM分子筛中的一种或多种。这几种载体均具有物理性质稳定、比表面积大、与磺酸型咪唑基离子液体结合作用较高的优势。除此以外，这几种载体还具有较低的成本。
上述固载型催化剂中，本领域技术人员可以选择催化活性成分与载体之间的比例关系。在一种优选的实施方式中，磺酸型咪唑基离子液体与载体之间的重量比为0.1～20:100。将二者之间的用量关系设置在上述范围内，能够使催化剂活性成分更为均匀地分散在载体上，使其具有较高的催化活性。同时，还能够节约成本、降低反应操作难度。
在一种优选的实施方式中，上述制备过程中反应的反应温度为200～280℃，反应压力为3.0～8.0MPa，反应时间为2～12h。本发明提供的上述制备方法中，采用磺酸型咪唑基离子液体作为催化活性成分本身能够降低2-巯基苯并噻唑的操作难度，使反应的条件更为温和。而在上述反应温度、压力和时间条件下，有利于在提高反应速率的同时，减少副反应的发生，使反应兼具较高的速率和收率。更优选地，上述反应的反应温度为240～250℃，反应压力为4.5～5.5MPa，反应时间为4～6h。
本发明提供的上述制备方法中，本领域技术人员可以选择各原料之间的用量关系。在一种优选的实施方式中，上述苯胺法中以苯胺、二硫化碳和硫磺为反应原料，苯胺、二硫化碳及硫磺之间的摩尔比为1:1.0～1.3:1.1～2，且苯胺与磺酸型咪唑基离子液体之间的重量比为100:1～5。将各原料之间的用量比设置在上述范围内，有利于进一步提高反应的转化率，同时，具有更高的反应速度和目标产物收率。此外，将催化剂的用量控制在上述范围内还有利于节约成本，使整个反应更加适用于工业化大规模应用。更优选地，苯胺、二硫化碳及硫磺之间的摩尔比为1:1.0～1.1:1.2～1.5，且苯胺与磺酸型咪唑基离子液体之间的重量比为100:1～2。
本发明提供的上述制备方法适用于任何生产模式。在一种优选的实施方式中，采用间歇式或连续式的生产工艺制备2-巯基苯并噻唑。间歇式即间歇釜式催化反应方式，连续式为连续塔式反应方式(如固定床反应方式或滴流床反应方式)。
以下结合具体实施例对本发明作进一步详细描述，这些实施例不能理解为限制本发明所要求保护的范围。
实施例1
将93g苯胺、76g二硫化碳和38.4g硫磺(三者摩尔比为1:1:1.2)加至压力反应器中，并向体系中加入1.86g非固载型磺酸型咪唑基离子液体[TSVM]HSO4(苯胺与其重量比为100:2)。控制反应温度为250℃，反应压力为4.5MPa，反应6h后，得到粗产品熔体。
将上述粗产品熔体压入装有溶剂甲苯的结晶器中，排出的硫化氢用碱液吸收处理，熔体结晶后，洗涤、过滤、干燥，得到2-巯基苯并噻吩产品。其中产品纯度为98％以上，收率为90％。
实施例2至7
制备方法同实施例1，不同之处在于反应温度、反应压力及反应时间不同，各实施例的工艺条件和产品结果如下表所示：
  反应温度(℃) 反应压力(MPa) 反应时间(h) 产品纯度(％) 产品收率(％)
实施例2 240 5.5 6 98 92
实施例3 240 4.0 4 97.5 92
实施例4 200 8.0 12 97 84
实施例5 200 8.0 14 97.2 83
实施例6 280 3.0 2 95.4 84
实施例7 300 10.0 2 96.3 83
实施例8至13
制备方法同实施例1，不同之处在于各原料的摩尔比不同，各实施例的原料关系和产品结果如下表所示：
Figure PCTCN2015093613-appb-000003
Figure PCTCN2015093613-appb-000004
实施例14至19
制备方法同实施例1，不同之处在于催化剂的种类不同，各实施例的催化剂类型和产品结果如下表所示：
Figure PCTCN2015093613-appb-000005
从以上的描述中，可以看出，本发明上述的实施例实现了如下技术效果：采用磺酸型咪唑基离子液体作为催化剂的活性成分，能够显著改善苯胺法反应原料的转化率、提高2-巯基苯并噻唑的收率。同时，本发明提供的制备方法还具有工艺简单、成本低、焦油量低、环保性高等综合性优势。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种2-巯基苯并噻唑的制备方法，其特征在于，采用苯胺法，在催化剂的作用下进行反应制备所述2-巯基苯并噻唑，且所述催化剂包括磺酸型咪唑基离子液体。
  2. 根据权利要求1所述的制备方法，其特征在于，所述磺酸型咪唑基离子液体为[TSVM]HSO4和/或[MPS]2HSO4。
  3. 根据权利要求1或2所述的制备方法，其特征在于，所述催化剂还包括用于负载所述磺酸型咪唑基离子液体的载体。
  4. 根据权利要求3所述的制备方法，其特征在于，所述载体选自由活性氧化铝、堇青石蜂窝陶瓷、巯基硅胶、离子交换树脂及HSZM分子筛组成的组中的一种或多种。
  5. 根据权利要求4所述的制备方法，其特征在于，所述磺酸型咪唑基离子液体与所述载体之间的重量比为0.1～20:100。
  6. 根据权利要求4或5所述的制备方法，其特征在于，所述反应的反应温度为200～280℃，反应压力为3.0～8.0MPa，反应时间为2～12h。
  7. 根据权利要求6所述的制备方法，其特征在于，所述反应的反应温度为240～250℃，反应压力为4.5～5.5MPa，反应时间为4～6h。
  8. 根据权利要求1所述的制备方法，其特征在于，所述苯胺法中，以苯胺、二硫化碳和硫磺为反应原料，所述苯胺、所述二硫化碳及所述硫磺之间的摩尔比为1:1.0～1.3:1.1～2，且所述苯胺与所述磺酸型咪唑基离子液体之间的重量比为100:1～5。
  9. 根据权利要求8所述的制备方法，其特征在于，所述苯胺、所述二硫化碳及所述硫磺之间的摩尔比为1:1.0～1.1:1.2～1.5，且所述苯胺与所述磺酸型咪唑基离子液体之间的重量比为100:1～2。
  10. 根据权利要求1所述的制备方法，其特征在于，采用间歇式或连续式的生产工艺制备所述2-巯基苯并噻唑。
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