CN104326881A - Preparation method of 3,5-dimethyl-4-chlorophenol - Google Patents
Preparation method of 3,5-dimethyl-4-chlorophenol Download PDFInfo
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- CN104326881A CN104326881A CN201410547193.2A CN201410547193A CN104326881A CN 104326881 A CN104326881 A CN 104326881A CN 201410547193 A CN201410547193 A CN 201410547193A CN 104326881 A CN104326881 A CN 104326881A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a preparation method of 3,5-dimethyl-4-chlorophenol, which takes tetrachloroethylene as a solvent, benzyl thiophenol and aluminium chloride as cocatalysts, sulfuric chloride as a chloridizing agent, orientation chlorination is carried out through two phases of low-temperature chlorination and high-temperature chlorination, the mass ratio of tetrachloroethylene to MX is 0.5-4: 1; the mass ratio of the cocatalyst to MX is 2.5-6.5:1000; at low temperature chlorination phase, the mass ratio of sulfuric chloride dropping amount to MX is 0.9-1.2: 1; at high temperature chlorination phase, the mass ratio of sulfuric chloride dropping amount to MX is 0.1-0.2: 1; the temperature at the low temperature chlorination phase is controlled at 30-45 DEG C, chlorination is carried out for 4-6 hours; the temperature at high temperature chlorination phase is controlled at 50-65 DEG C, and chlorination is carried out for 1-2 hours, insulation reaction is carried out after the dropping process of sulfuric chloride is completed, tail gas is removed for 1-2 hours, and steps of water-washing layering, cooling and crystallizing, centrifuging and washing, and drying to obtain the product. According to the method, the conversion rate can reach more than 95%, finished product PCMX yield is increased, and the by-product can be effectively reduced.
Description
Technical field
The invention belongs to fine chemistry industry chloridization process, be specifically related to a kind of preparation method of 3,5-dimethyl-4-chlorophenol.
Background technology
3,5-dimethyl-4-chlorophenol english abbreviation PCMX is a kind of sterilant of safe, efficient, wide spectrum, be united states drug food control office (FDA) certification is first-selected germ killing drugs, various bacteria, mould, fungi and germ can be killed, be widely used in industry and cosmetic industry.PCMX is due to the sterilization of its excellence and anti-corrosion function, and development prospect is had an optimistic view of, recognized by consumers.
The constitutional formula of PCMX is as follows:
Periodical < application chemical industry > the 35th volume the 2nd phase describes Institutes Of Technology Of Taiyuan Wei Wen jade for asking rain etc. in " New technics for synthesis of chloroxylenol ", have studied with an xylenol and chlorine as raw material, tetracol phenixin is solvent, aluminum chloride is catalyzer, the optimum process condition of synthesis PCMX is: m-xylene phenol 30 g, catalyzer aluminum chloride 0.25 g, solvent tetracol phenixin 70 ml temperature of reaction 60 DEG C, logical chlorine time 120 min, yield can reach 61.1 %.
Periodical < application chemical industry > the 36th volume o. 11th describes Institutes Of Technology Of Taiyuan Wei Wen jade for asking rain etc. in " chlorxylone synthesis recent studies on ", result is thought: with an xylenol for raw material, sulfuryl chloride is chlorizating agent, tetracol phenixin is solvent, the mol ratio of sulfuryl chloride and an xylenol is 1.00:1.00, reaction times is 5 h, drip sulfuryl chloride at reflux, synthesis PCMX effect is ideal, product yield can reach 82.57 % efficient liquid phase chromatographic analysis, product content reaches 97.67 %, bactericidal property is investigated, product bactericidal property is suitable with standard specimen.
The synthesis PCMX technique that above two sections of documents are introduced, has reaction conditions gentleness, and technique is comparatively simple, the advantages such as raw material is easy to get, and selectivity is better.Useful test has been carried out to the synthesis of PCMX, but lower on the boiling point of the recovery of solvent, the applying mechanically of washing water, solvent, on environment impact etc., also should investigate further in course of industrialization and inquire into.
It is solvent with water that Chinese patent CN101823941A provides a kind of, sulfuryl chloride or chlorine are chlorizating agent, an xylenol is carried out chlorination reaction by the mode of multistage temperature control, avoid use expensive, reclaim the catalyzer of difficulty and avoid the use of organic solvent, achieve 3PCMX suitability for industrialized production, there is environment friendly and green.And set forth 60 ~ 70 DEG C theoretically and carry out partial oxidation reaction, then discharge by being warmed up to 75 ~ 100 DEG C of reaction substrates making to be wrapped up by product (m-xylene phenol), proceed chlorination reaction cooling between 0 ~ 70 DEG C, this explains theoretically, be conducive to because temperature is low forming hydrogen bond between substrate and water, the ortho position space steric effect increasing hydroxyl makes ortho position chlorination be obstructed, thus without the need to adding contraposition catalyst for oriented chlorination, higher p-Chlorination selectivity can be reached, but the not mentioned problem how avoiding sulfuryl chloride and water reaction to generate sulfurous gas and hydrogenchloride of patent.
Chinese patent CN102659528A provides a kind of kettle type chlorination technology continuously, and its technique is simple, and becomes continuous seepage by batch production, and transformation efficiency brings up to 90 ~ 100 %.But do not introduce in document and carry out in the reactor of much volumes, how stability, the repeatability of continuous prodution control and realize, and how solvent reclaims and apply mechanically, and produce the separating and purifying method etc. of PCMX.
The shortcomings such as it is lower that existing technique exists transformation efficiency, and chlorination reaction is incomplete, and by product is added, and PCMX content is on the low side, the non-recovery of a large amount of washing water, and environmental pollution is large, and production cost is high.
Summary of the invention
Technical problem to be solved by this invention overcomes above-mentioned the deficiencies in the prior art, and provide a kind of technical process simple, feed stock conversion is high, product yield is high, and PCMX content is high, and washing water are recyclable to be applied mechanically, emissions reduction, has 3 of environment friendly, the preparation method of 5 dimethyl-4-chlorophenols.
The technical scheme that the present invention solves the problems of the technologies described above employing is: a kind of 3, the preparation method of 5-dimethyl-4-chlorophenol, it is with 3,5-xylenol (MX) is raw material, and zellon is solvent, and benzyl thiophenol and aluminum chloride are co-catalyst, sulfuryl chloride is chlorizating agent, carry out oriented chlorination reaction by low temperature chlorination, high-temp chlorination two benches, it is characterized in that: the mass ratio of described zellon and substrate MX (MX) is between 0.5-4:1; The mass ratio of described co-catalyst and substrate MX (MX) is between 2.5-6.5:1000; Zellon and co-catalyst dispersed with stirring are in substrate MX (MX); In the low temperature chlorination stage, the mass ratio of described sulfuryl chloride dripping quantity and substrate MX (MX) is between 0.9-1.2:1; In the high-temp chlorination stage, the mass ratio of described sulfuryl chloride dripping quantity and substrate MX (MX) is between 0.1-0.2:1; Described low temperature chlorination phase temperature controls at 30 ~ 45 DEG C, drips sulfuryl chloride chlorination 4 ~ 6 h, carries out partial oxidation reaction; Described high-temp chlorination phase temperature controls at 50 ~ 65 DEG C, and drip sulfuryl chloride and continue chlorination 1 ~ 2 h, after sulfuryl chloride dropwises, insulation reaction removes tail gas 1 ~ 2 h again; And after through washing layering, crystallisation by cooling, centrifuge washing, drying, obtain 3,5-dimethyl-4-chlorophenols.
The mass ratio of described solvent zellon and substrate MX is between 1:1 to 3:1.
The amount of one of described co-catalyst composition benzyl thiophenol and the mass ratio of substrate MX are between 0.5-1.5:1000, and the amount of another composition aluminum chloride of co-catalyst and the mass ratio of substrate MX are between 2-5:1000.
The present invention utilizes co-catalyst to carry out oriented chlorination, and by adding catalyst for oriented chlorination and low temperature, the chlorination of high temperature ladder, the transformation efficiency of substrate MX reaches 95 more than %.Against existing technologies, its technical process is simple, and feed stock conversion is high, and product yield is high, and PCMX content is high, decreases the generation of by product, improves yield and the quality of product.Washing water are recyclable to be applied mechanically, and greatly reduces three waste discharge, has environment friendly.A kind of preparation method of 3,5 desirable dimethyl-4-chlorophenols.
Accompanying drawing explanation
Fig. 1 is PCMX production process route figure.
embodiment:
The following examples are further described technical scheme of the present invention, and these embodiments are in order to the present invention instead of limitation of the present invention are described.
A kind of 3, the preparation method of 5-dimethyl-4-chlorophenol, it is with 3,5-xylenol (MX) is raw material, and zellon is solvent, and benzyl thiophenol and aluminum chloride are co-catalyst, sulfuryl chloride is chlorizating agent, carry out oriented chlorination reaction by low temperature chlorination, high-temp chlorination two benches, the mass ratio of described zellon and substrate MX (MX) is between 0.5-4:1; The mass ratio of described co-catalyst and substrate MX (MX) is between 2.5-6.5:1000; Zellon and co-catalyst dispersed with stirring are in substrate MX (MX); In the low temperature chlorination stage, the mass ratio of described sulfuryl chloride dripping quantity and substrate MX (MX) is between 0.9-1.2:1; In the high-temp chlorination stage, the mass ratio of described sulfuryl chloride dripping quantity and substrate MX (MX) is between 0.1-0.2:1; Described low temperature chlorination phase temperature controls at 30 ~ 45 DEG C, drips sulfuryl chloride chlorination 4 ~ 6 h, carries out partial oxidation reaction; Then be warmed up to and carry out high-temperature chlorination.Described high-temp chlorination phase temperature controls at 50 ~ 65 DEG C, and drip sulfuryl chloride and continue chlorination 1 ~ 2 h, after sulfuryl chloride dropwises, insulation reaction removes tail gas 1 ~ 2 h again; When the transformation efficiency of substrate MX reaches 95 more than %, can stopped reaction.And after through washing layering, crystallisation by cooling, centrifuge washing, drying, obtain 3,5-dimethyl-4-chlorophenols.
In described preparation method, preferred method: the mass ratio of described solvent zellon and substrate MX is between 1:1 to 3:1.
In described preparation method, preferred method: the amount of one of described co-catalyst composition benzyl thiophenol and the mass ratio of substrate MX are between 0.5-1.5:1000, and the amount of another composition aluminum chloride of co-catalyst and the mass ratio of substrate MX are between 2-5:1000.
The invention will be further described below: its oriented chlorination preparation process of producing PCMX comprises the following steps.
Step (1) is prepared burden: in chlorination tank, add a certain amount of solvent zellon, starts whipping appts and adds substrate MX (MX), be warmed up to about 30 DEG C, stirring and dissolving.
Step (2) low temperature chlorination: open tail gas absorbing system, adds co-catalyst benzyl thiophenol and aluminum chloride, temperature control 30 ~ 45 DEG C, drips sulfuryl chloride 4 ~ 6 h and carries out low temperature chlorination.
Step (3) high-temp chlorination: between temperature control 50 ~ 65 DEG C, drips sulfuryl chloride 1 ~ 2 h, carries out high-temp chlorination.
Step (4) insulation reaction, removes tail gas: after sulfuryl chloride dropwises, and between 50 ~ 60 DEG C, tiny structure insulation reaction 1 ~ 2 h also removes tail gas, when the transformation efficiency of substrate MX reaches more than 95%, and stopped reaction.
Step (5) once washes layering, in washing layering tank, process water (new water) is added when first time drives to produce, its amount is about 1/3 of substrate MX, wash separatory water out to utilize secondary during after washing to wash, in 60 ~ 70 DEG C after suction water, stir 0.5 h, leave standstill 2 h, separate upper strata organism, in the storage tank of the sour water suction tail gas absorption of lower floor, use as the recirculated water absorbing tail gas HCl.
The washing of step (6) secondary, layering: organism carries out secondary washing in suction washing kettle again, and with the new water of vacuum suction, its amount is about 1/3 of substrate, stir 0.5 h, then leave standstill 2 h, then separate upper organic layer, the sour water of lower floor, for once washing in suction chlorination tank.
Step (7) crystallisation by cooling: in organism suction stainless steel crystallization kettle, open stirring, logical chilled brine is to 0 ~ 5 DEG C of crystallization.
Step (8) centrifuge washing: work as crystallisate, when material temperature reaches 0 ~ 5 DEG C, carry out centrifugal drying from, PCMX crystallization is washed with zellon, is washed again.Filtrate zellon cover is used for lower batch of chlorination.
Step (9) is dry: drying temperature 80 ~ 85 DEG C.
The whole oriented chlorination reaction process of the present invention is electrophilic substitution, and its main reaction equation is:
The present invention utilizes co-catalyst to carry out oriented chlorination, and the transformation efficiency of substrate MX reaches 95 more than %.Against existing technologies, its technical process is simple, and feed stock conversion is high, and product yield is high, and PCMX content is high, decreases the generation of by product, improves yield and the quality of product.Washing water are recyclable to be applied mechanically, and greatly reduces three waste discharge, has environment friendly.A kind of preparation method of 3,5 desirable dimethyl-4-chlorophenols.
Embodiment 1:
Shown in route map, zellon 1000 kg is added in chlorination tank, substrate MX500 kg (4 kmol), start and stir, temperature control is between 30 ~ 45 DEG C, substrate MX is dissolved, add benzyl thiophenol 0.5 kg, aluminum chloride 2 kg, and slowly drip 540 kg (4 kmol) sulfuryl chloride at this temperature, time for adding is 4.5 ~ 5 h, after dropwising, be warming up to 50 ~ 65 DEG C, drip 54 kg (0.4 kmol) sulfuryl chloride again, time for adding is 1 ~ 1.5 h, after dropwising, in-0.02 ~-0.04 MPa, after 50 ~ 65 DEG C of insulations remove tail gas 1 ~ 2 h, reactant carries out aftertreatment by [0029] route map, obtain product 550 kg, yield 85.80 % (molar yield based on MX), content 99.01 %.
Embodiment 2:
Shown in route map, zellon 1000 kg is added to chlorination tank, substrate MX500 kg (4 kmol) starts stirring, between temperature control 30 ~ 45 DEG C, substrate is dissolved, add benzyl thiophenol 0.5 kg, aluminum chloride 2 kg, slowly drip 560 kg (4.15 kmol) sulfuryl chloride at this temperature, time for adding is 4.5 ~ 5 h, dropwise rear intensification 50 ~ 65 DEG C, drip 70 kg (0.52 kmol) sulfuryl chloride again, time for adding is 1 ~ 1.5 h, after dropwising, in-0.02 ~-0.04 MPa, 50 ~ 65 DEG C, after insulation removes tail gas 1 ~ 2 h, reactant carries out product 560 kg of aftertreatment by [0029] route map, yield 87.3 % (molar yield based on MX), content 98.81 %.
Embodiment 3:
Shown in route map, zellon 1000 kg is added to chlorination tank, substrate MX500 kg (4 kmol) starts stirring, between temperature control 30 ~ 45 DEG C, substrate is dissolved, add benzyl thiophenol 0.5 kg, aluminum chloride 2.5 kg, slowly drip 560 kg (4.15 kmol) sulfuryl chloride at this temperature, time for adding is 4.5 ~ 5 h, dropwise rear intensification 50 ~ 65 DEG C, drip 70 kg (0.52 kmol) sulfuryl chloride again, time for adding is 1 ~ 1.5 h, after dropwising, in-0.02 ~-0.04 MPa, 50 ~ 65 DEG C, after keeping removing tail gas 1 ~ 2 h, reactant carries out aftertreatment by [0029] route map, obtain product 530 kg, yield 82.6 % (molar yield based on MX), content 98.58 %.
The oriented chlorination process products of each embodiment PCMX, GC analytical results is:
| Embodiment | MX% | OCMX% | DCMX% | Other % | PCMX% | Σ |
| 1 | 0.13 | 0.44 | 0.22 | 0.20 | 99.01 | 100 |
| 2 | 0.22 | 0.56 | 0.18 | 0.23 | 98.81 | 100 |
| 3 | 0.23 | 0.59 | 0.25 | 0.35 | 98.58 | 100 |
MX:3,5-xylenol
The chloro-MX of OCMX:2-
The chloro-MX of DCMX:2,4-bis-
The chloro-MX of PCMX:4-.
Claims (3)
1. one kind 3, the preparation method of 5-dimethyl-4-chlorophenol, it is with 3,5-xylenol (MX) is raw material, and zellon is solvent, and benzyl thiophenol and aluminum chloride are co-catalyst, sulfuryl chloride is chlorizating agent, carry out oriented chlorination reaction by low temperature chlorination, high-temp chlorination two benches, it is characterized in that: the mass ratio of described zellon and substrate MX (MX) is between 0.5-4:1; The mass ratio of described co-catalyst and substrate MX (MX) is between 2.5-6.5:1000; Zellon and co-catalyst dispersed with stirring are in substrate MX (MX); In the low temperature chlorination stage, the mass ratio of described sulfuryl chloride dripping quantity and substrate MX (MX) is between 0.9-1.2:1; In the high-temp chlorination stage, the mass ratio of described sulfuryl chloride dripping quantity and substrate MX (MX) is between 0.1-0.2:1; Described low temperature chlorination phase temperature controls at 30 ~ 45 DEG C, drips sulfuryl chloride chlorination 4 ~ 6 h, carries out partial oxidation reaction; Described high-temp chlorination phase temperature controls at 50 ~ 65 DEG C, and drip sulfuryl chloride and continue chlorination 1 ~ 2 h, after sulfuryl chloride dropwises, insulation reaction removes tail gas 1 ~ 2 h again; And after through washing layering, crystallisation by cooling, centrifuge washing, drying, obtain 3,5-dimethyl-4-chlorophenols.
2. the preparation method of 3,5-dimethyl-4-chlorophenols according to claim 1, is characterized in that: the mass ratio of described solvent zellon and substrate MX is between 1:1 to 3:1.
3. according to claim 13, the preparation method of 5-dimethyl-4-chlorophenol, it is characterized in that: the amount of one of described co-catalyst composition benzyl thiophenol and the mass ratio of substrate MX are between 0.5-1.5:1000, and the amount of another composition aluminum chloride of co-catalyst and the mass ratio of substrate MX are between 2-5:1000.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037104A (en) * | 2015-06-02 | 2015-11-11 | 铜陵市恒兴化工有限责任公司 | Preparation method of 4-chloro-3,5-dimethylphenol |
| CN109081772A (en) * | 2018-08-06 | 2018-12-25 | 江苏焕鑫新材料股份有限公司 | A kind of technique and device effectively improving the chloro- 3,5- xylenol chlorination reaction production efficiency of 4- |
| CN109081309A (en) * | 2018-08-01 | 2018-12-25 | 江苏焕鑫新材料股份有限公司 | A method of improving the quality of the technical hydrochloric acid containing polyphenol mixture and sulfurous acid |
| CN111574329A (en) * | 2020-05-18 | 2020-08-25 | 万华化学集团股份有限公司 | Reactive distillation device and method for producing 4-chloro-3, 5-dimethylphenol |
| CN112250549A (en) * | 2020-10-30 | 2021-01-22 | 浙江金科日化原料有限公司 | Preparation method of 3, 5-dimethyl-4-chlorophenol |
| CN113603569A (en) * | 2021-07-13 | 2021-11-05 | 山东新和成维生素有限公司 | Method for preparing 4-chloro-3, 5-dimethylphenol by low-temperature chlorination |
| CN113666805A (en) * | 2021-08-23 | 2021-11-19 | 山东新和成维生素有限公司 | Method and production system for continuously producing 4-chloro-3, 5-dimethylphenol |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037104A (en) * | 2015-06-02 | 2015-11-11 | 铜陵市恒兴化工有限责任公司 | Preparation method of 4-chloro-3,5-dimethylphenol |
| CN109081309A (en) * | 2018-08-01 | 2018-12-25 | 江苏焕鑫新材料股份有限公司 | A method of improving the quality of the technical hydrochloric acid containing polyphenol mixture and sulfurous acid |
| CN109081772A (en) * | 2018-08-06 | 2018-12-25 | 江苏焕鑫新材料股份有限公司 | A kind of technique and device effectively improving the chloro- 3,5- xylenol chlorination reaction production efficiency of 4- |
| CN111574329A (en) * | 2020-05-18 | 2020-08-25 | 万华化学集团股份有限公司 | Reactive distillation device and method for producing 4-chloro-3, 5-dimethylphenol |
| CN111574329B (en) * | 2020-05-18 | 2022-09-20 | 万华化学集团股份有限公司 | Reactive distillation device and method for producing 4-chloro-3, 5-dimethylphenol |
| CN112250549A (en) * | 2020-10-30 | 2021-01-22 | 浙江金科日化原料有限公司 | Preparation method of 3, 5-dimethyl-4-chlorophenol |
| CN112250549B (en) * | 2020-10-30 | 2023-05-05 | 浙江金科日化原料有限公司 | Preparation method of 3, 5-dimethyl-4-chlorophenol |
| CN113603569A (en) * | 2021-07-13 | 2021-11-05 | 山东新和成维生素有限公司 | Method for preparing 4-chloro-3, 5-dimethylphenol by low-temperature chlorination |
| WO2023284525A1 (en) * | 2021-07-13 | 2023-01-19 | 山东新和成维生素有限公司 | Method for preparing 4-chloro-3,5-dimethylphenol by means of low-temperature chlorination |
| CN113666805A (en) * | 2021-08-23 | 2021-11-19 | 山东新和成维生素有限公司 | Method and production system for continuously producing 4-chloro-3, 5-dimethylphenol |
| CN113666805B (en) * | 2021-08-23 | 2023-08-25 | 山东新和成维生素有限公司 | Method and system for continuously producing 4-chloro-3, 5-dimethylphenol |
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