Catalyst for chloromethylation reaction and preparation method thereof, and preparation method of chlorobenzyl compound

Abstract

The present application relates to a kind of catalyst for chloromethylation reaction and its preparation method, the catalyst includes zeolite molecular sieve and the metal salt and long-chain alkyl silane supported on the zeolite molecular sieve.The present application also relates to a kind of preparation method of chlorobenzene compound, in the presence of the catalyst, aromatic hydrocarbon and its derivative and chloromethyl reagent are carried out chloromethylation reaction, after reaction, chlorobenzene compound is obtained by separation.The catalyst of the present application is used in chloromethylation reaction, can improve reaction efficiency, reaction selectivity and yield, and catalyst can be recycled, greatly reduce production cost, be conducive to industrial production.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic synthesis, and particularly relates to a catalyst for a chloromethylation reaction and a preparation method thereof, and a preparation method of a chlorobenzyl compound. BACKGROUND

[0002] In 1898, Grassi and Maselliz first reported the chloromethylation reaction, and benzyl chloride was prepared by introducing hydrogen chloride gas into a mixed solution of benzene and trioxymethylene with zinc chloride as a catalyst. However, it was not until 1923 that Blanc elaborated on the extensive use of the reaction. Therefore, the method of introducing a chloromethyl group into an aromatic hydrocarbon, a halogenated aromatic hydrocarbon, an aromatic ether and the like by using HCHO or (HCHO)n and hydrochloric acid in the presence of a condensing agent such as ZnCl2 (or H2SO4, CH3COOH, AlCl3, SnCl4 and the like) is referred to as the Blanc chloromethylation reaction.

[0003] The chlorobenzyl compound obtained by introducing a chloromethyl group into an aromatic ring through the chloromethylation reaction can be further functionalized into other groups such as -CH2OH, -CH2OR, -CH2OAc, -CHO, -CH2CN, -CH2CO2H, -CH2NH2, -CH2NRR' and the like, so that a series of new derivatives can be obtained to realize the transformation of substances and the improvement of product performance. Specifically, the chlorobenzyl compound is widely used in the fields of active drugs, agricultural chemicals, dyes, fragrances, additives, polymer modifiers, organic functional materials, polymer materials and other fine organic chemical specialties, and the use of the chlorobenzyl compound to synthesize fragrances began to be easily reported in the 1970s. The chlorobenzyl compound is mainly used to synthesize benzyl alcohol, aldehyde, ketone and ester fragrances, and many of them have been commercialized.

[0004] The classical chloromethylation reaction has the following general formula:

[0005]

[0006] The reaction mechanism is as follows: first, formaldehyde reacts with an acid to generate a formaldehyde cation, then the formaldehyde cation electrophilically attacks the aromatic ring of an aromatic hydrocarbon ArH to generate a benzyl alcohol and release a hydrogen cation, and then the benzyl alcohol reacts with hydrogen chloride to obtain a chloromethyl aromatic hydrocarbon compound, which is specifically shown as follows:

[0007]

[0008] It can be seen that there are mainly two methods for chloromethylation: one is to use sulfuric acid as catalyst and dehydrating agent, which has the advantage of simplicity, but the disadvantage is obvious, i.e. the amount of waste acid is particularly large, which is difficult to handle; the other is to use aluminum chloride or zinc chloride as Lewis acid catalyst, which generally reacts under anhydrous conditions, and the product has many by-products, and the treatment process will also produce a lot of wastewater containing high concentration of salt or heavy metals.

[0009] Patent GB1026365 discloses a chloromethylation method using paraformaldehyde, acetic acid, hydrochloric acid, and then purging hydrogen chloride to produce a pressure of about 3 atm. However, the reaction takes a long time and has the additional disadvantage that it needs to be carried out at high temperature.

[0010] Patent US2945894 discloses a method of chloromethylation using paraformaldehyde, concentrated hydrochloric acid, anhydrous zinc chloride and sodium chloride, but this method has the disadvantage of producing a large amount of effluent in the post-treatment process.

[0011] Patents US2485680 and US2485681 describe a method of chloromethylation of dihydrocinnamaldehyde by mixing with 40% formaldehyde and concentrated hydrochloric acid at about 20°C and stirring for 36 hours, however, under these conditions, the chloromethylated product is usually accompanied by impurities formed by side reactions.

[0012] Patent US2878266 improves the above process by contacting 90% dihydrocinnamaldehyde, paraformaldehyde, 35% hydrochloric acid and calcium chloride at high temperature to obtain the chloromethylated product. However, the harsh conditions used in this method plus the effluent problem make this process unattractive for the chloromethylation of substituted benzene compounds, which are not stable in acidic environment and at higher temperatures, such as alkoxy, methylenedioxy and ethylenedioxy substituted benzene.

[0013] Patent GB1067988 discloses a chloromethylation method comprising reacting a substituted benzene with anhydrous hydrogen chloride and paraformaldehyde in the presence of three-fold excess of anhydrous ZnCl2 and an emulsifying agent. However, this method requires the use of lithium chloride as a co-catalyst and the use of glacial acetic acid as a reaction medium, and there are problems of difficult handling and product separation.

[0014] In summary, the chloromethylation reaction of aromatic hydrocarbons and their derivatives mainly uses protonic acid, Lewis acid or quaternary ammonium salt as catalyst, but this type of catalyst is difficult to recover and cannot be recycled, causing environmental pollution and waste. Moreover, the chloromethylation method has problems such as large amount of wastewater, many side reactions, low reaction yield, and difficult product separation. Therefore, it is of great significance to develop an environmentally friendly, efficient and economical chloromethylation method. SUMMARY

[0015] Based on this, it is necessary to provide a catalyst for chloromethylation reaction and a preparation method thereof, which can improve the reaction efficiency, reaction selectivity and yield, and the catalyst can be recycled, which is conducive to industrial production.

[0016] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application is: a catalyst for chloromethylation reaction, which comprises a zeolite molecular sieve and a metal salt and a long-chain alkyl silane supported on the zeolite molecular sieve.

[0017] In one of the embodiments, the catalyst further satisfies at least one of the following conditions:

[0018] (1) the metal salt is selected from at least one of iron salt, nickel salt, copper salt, zinc salt, tin salt or zirconium salt;

[0019] (2) the long-chain alkyl silane is selected from C12-C18 alkyl silane;

[0020] (3) the zeolite molecular sieve is selected from at least one of Y-type molecular sieve, HY molecular sieve, ZSM-5 molecular sieve, HZSM-5 molecular sieve, MCM-41 molecular sieve, SBA-15 molecular sieve, TS-1 molecular sieve, TS-2 molecular sieve and Hβ molecular sieve;

[0021] (4) the mass ratio of metal ions in the metal salt to the zeolite molecular sieve is 0.03:1-0.12:1;

[0022] (5) the mass ratio of the long-chain alkyl silane to the zeolite molecular sieve is 6:1-18:1.

[0023] In one of the embodiments, the catalyst further satisfies at least one of the following conditions:

[0024] (1) the metal salt is selected from at least two of iron salt, nickel salt, copper salt, zinc salt, tin salt or zirconium salt;

[0025] (2) the long-chain alkyl silane is selected from at least one of long-chain alkyl trimethoxysilane or long-chain alkyl triethoxysilane;

[0026] (3) the mass ratio of metal ions in the metal salt to the zeolite molecular sieve is 0.05:1-0.09:1;

[0027] (4) the mass ratio of the long-chain alkyl silane to the zeolite molecular sieve is 8:1-12:1.

[0028] In one of the embodiments, the long-chain alkyl silane is selected from at least one of hexadecyltrimethoxysilane, hexadecyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, octadecyltrimethoxysilane, and tridecafluoro octyltrimethoxysilane.

[0029] In another aspect of the present application, a preparation method of the catalyst for the chloromethylation reaction is also provided, comprising the following steps:

[0030] S1, adding a zeolite molecular sieve into a metal salt solution for adsorption, and separating to obtain a first precursor;

[0031] S2, calcining the first precursor in an inert atmosphere to obtain a second precursor;

[0032] S3, mixing the second precursor, a long-chain alkyl silane, and an organic solvent for modification treatment, and then separating to obtain the catalyst.

[0033] In one of the embodiments, step S1 satisfies at least one of the following conditions:

[0034] (1) the mass ratio of the metal ions in the metal salt solution to the zeolite molecular sieve is 0.03:1-0.12:1;

[0035] (2) the adsorption temperature is 40-80°C, and the time is 4-8 hours.

[0036] In one of the embodiments, in step S2, the calcination temperature is 400-600°C, and the time is 2-4 hours.

[0037] In one of the embodiments, step S3 satisfies at least one of the following conditions:

[0038] (1) the mass ratio of the long-chain alkyl silane to the zeolite molecular sieve is 6:1-18:1;

[0039] (2) the modification treatment temperature is 60-100°C, and the time is 4-6 hours.

[0040] In another aspect of the present application, a preparation method of a chlorobenzyl compound is also provided, in which an aromatic hydrocarbon and its derivative and a chloromethyl reagent are subjected to a chloromethylation reaction in the presence of the catalyst, and the chlorobenzyl compound is separated after the reaction.

[0041] In one of the embodiments, the preparation method also satisfies at least one of the following conditions:

[0042] (1) the aromatic hydrocarbon and its derivative is selected from at least one of p-xylene, 1,2-methylenedioxybenzene, o-dimethyl ether, or anisole;

[0043] (2) the chloromethyl reagent comprises a formaldehyde compound and hydrochloric acid, the molar ratio of the formaldehyde compound to the aromatic hydrocarbon and its derivative, the formaldehyde compound and the hydrochloric acid is 1:1-2:1-2, wherein the formaldehyde compound is selected from at least one of formaldehyde, trioxane or polyoxymethylene;

[0044] (3) the mass ratio of the catalyst to the aromatic hydrocarbon and its derivative is 0.03:1-0.09:1;

[0045] (4) the temperature of the chloromethylation reaction is 60-100 DEG C, and the time is 6-10 hours;

[0046] (5) after the reaction is completed, the catalyst is separated and obtained and recycled for preparing a chlorobenzyl compound.

[0047] The application uses a long-chain alkyl silane modified and metal salt loaded zeolite molecular sieve as a catalyst to catalyze a chloromethylation reaction. On one hand, the modified catalyst has obviously enhanced hydrophobicity, while the density of acid sites is not reduced, the contact opportunity of the catalyst and the reaction substrate is greatly increased, and the catalytic efficiency of the catalyst is improved. On the other hand, the catalyst has strong acid sites and micropore volume, not only provides a large number of active sites for the reaction, but also reduces the occurrence of side reactions. Meanwhile, the catalyst has strong mass transfer capacity, the reaction substrate is more easily desorbed from the catalyst surface, the occurrence of alkylation and other side reactions is eliminated or weakened, and the main reaction obtains high reaction selectivity and yield.

[0048] In addition, in the catalyst of the application, the metal ions in the zeolite molecular sieve and the metal ions in the metal salt can be combined by M-O-Si (M is a metal ion) bonding, which can not only enhance the activity of the catalyst, but also reduce the loss rate during use, and improve the service life of the catalyst. Therefore, the catalyst of the application is used to catalyze the chloromethylation reaction, the catalyst can be stably used, the production cost is greatly reduced, and it is beneficial to industrial production. DETAILED DESCRIPTION

[0049] In order to facilitate the understanding of the application, the application will be described in more detail below. However, it should be understood that the application can be realized in many different forms, and is not limited to the embodiments or examples described herein. On the contrary, the purpose of providing these embodiments or examples is to make the disclosure of the application more thorough and comprehensive.

[0050] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description herein is for describing specific embodiments or examples only and is not intended to be limiting. The use herein of the terms "and / or" and "at least one of" means any one of the referenced items constituting an element, combinaton of elements, propositon, or predicate that might exist or possess some characteristic relative to each reference element, and means also that zeroes, one or more, or a combination of reference elements might exist or possess some characteristic relative to each reference element. The use herein of "at least one of" followed by a listing of two or more items means that at least one of each item is present.

[0051] The present application provides a catalyst for chloromethylation reaction, which comprises a zeolite molecular sieve and a metal salt and a long-chain alkylsilane supported on the zeolite molecular sieve.

[0052] The zeolite molecular sieve not only has strong acid sites, but also has a large specific surface area and a porous structure. The present application uses the long-chain alkylsilane modified and metal salt supported zeolite molecular sieve as a catalyst to catalyze the chloromethylation reaction. On the one hand, the modified catalyst has significantly enhanced hydrophobicity, while the density of the acid sites is not reduced, greatly increasing the contact opportunity of the catalyst and the reaction substrate, and improving the catalytic efficiency of the catalyst. On the other hand, the catalyst has strong acid sites and micropore volume, not only providing a large number of active sites for the reaction, but also reducing the occurrence of side reactions. At the same time, the catalyst has strong mass transfer capacity, and the reaction substrate is more easily desorbed from the surface of the catalyst, eliminating or weakening the occurrence of alkylation and other side reactions, thereby making the main reaction obtain higher reaction selectivity and yield.

[0053] In addition, in the catalyst of the present application, the metal ions in the zeolite molecular sieve and the metal ions in the metal salt can both be combined with the long-chain alkylsilane through M-O-Si (M is a metal ion) bonding, which not only enhances the activity of the catalyst, but also reduces the loss rate during use, thereby improving the service life of the catalyst. Therefore, the catalyst of the present application is used to catalyze the chloromethylation reaction, and the catalyst can be stably reused, greatly reducing the production cost and being beneficial to industrial production.

[0054] Optionally, the zeolite molecular sieve is selected from at least one of Y-type molecular sieve, HY molecular sieve, ZSM-5 molecular sieve, HZSM-5 molecular sieve, MCM-41 molecular sieve, SBA-15 molecular sieve, TS-1 molecular sieve, TS-2 molecular sieve, and Hβ molecular sieve.

[0055] Optionally, the long-chain alkylsilane is selected from C12-C18 alkylsilane, so that the catalyst has better hydrophobicity and acid site density.

[0056] In addition, if the long-chain alkyl silane contains methoxy or ethoxy, it can form a hydrogen bond with formaldehyde compounds, thereby activating the reaction substrate, reducing the potential energy barrier, and making the reaction efficient. Therefore, as a preferred embodiment, the long-chain alkyl silane is selected from at least one of long-chain alkyl trimethoxysilane or long-chain alkyl triethoxysilane, such as at least one of hexadecyl trimethoxysilane, hexadecyl triethoxysilane, dodecyl trimethoxysilane, dodecyl triethoxysilane, octadecyl trimethoxysilane, and tridecafluorooctyl trimethoxysilane.

[0057] Optionally, the metal salt is selected from at least one of iron salt, nickel salt, copper salt, zinc salt, tin salt, or zirconium salt, so that the combination of the metal salt and the long-chain alkyl silane is more firm, and the activity of the catalyst is stronger.

[0058] As a preferred embodiment, the metal salt is selected from at least two of iron salt, nickel salt, copper salt, zinc salt, tin salt, or zirconium salt, so that the catalyst has more excellent catalytic activity.

[0059] As a preferred embodiment, the metal salt is selected from at least one of nitrate, hydrochloride, sulfate, acetylacetone salt, acetate, and hydrates thereof.

[0060] Optionally, the mass ratio of the metal ion in the metal salt to the zeolite molecular sieve is preferably 0.03:1 to 0.12:1, and further preferably 0.05:1 to 0.09:1, and the mass ratio of the long-chain alkyl silane to the zeolite molecular sieve is preferably 6:1 to 18:1, and further preferably 8:1 to 12:1, so that the catalyst has more excellent hydrophobicity and strong acid sites, and the density of the acid sites is high.

[0061] The present application also provides a preparation method of the catalyst, comprising the following steps:

[0062] S1. Adding the zeolite molecular sieve to the metal salt solution for adsorption, and separating to obtain a first precursor;

[0063] S2. Roasting the first precursor in an inert atmosphere to obtain a second precursor;

[0064] S3. Mixing the second precursor, long-chain alkyl silane, and organic solvent for modification treatment, and then separating to obtain the catalyst.

[0065] In step S1, when the zeolite molecular sieve is added to the metal salt solution for adsorption, the metal salt is first dissolved in a solvent, which is an organic solvent or water capable of dissolving the metal salt, and preferably water, and then the zeolite molecular sieve is added, wherein the mass ratio of metal ions in the metal salt solution to the zeolite molecular sieve is preferably 0.03:1 to 0.12:1, and further preferably 0.05:1 to 0.09:1.

[0066] In order to improve the adsorption efficiency and effect of the metal salt, in step S1, the adsorption is carried out at a temperature of 40℃ to 80℃, and the time is preferably 4 hours to 8 hours.

[0067] In step S2, the calcination temperature is preferably 400℃ to 600℃, and the time is preferably 2 hours to 4 hours. By calcining in an inert atmosphere, the binding ability of the metal salt and the zeolite molecular sieve can be enhanced, so that the metal salt can be more stably loaded on the zeolite molecular sieve, reducing the loss rate during use and improving the service life of the catalyst.

[0068] In step S3, when the second precursor, long-chain alkylsilane and organic solvent are mixed, the long-chain alkylsilane is first dispersed in the organic solvent, and the organic solvent is preferably at least one of methanol, ethanol, acetone and the like, and more preferably ethanol, and then the second precursor is added, wherein the long-chain alkylsilane and the zeolite molecular sieve are preferably 6:1 to 18:1, and further preferably 8:1 to 12:1.

[0069] In order to improve the modification effect of the long-chain alkylsilane, in step S3, when the modification treatment is carried out, the temperature is preferably 60℃ to 100℃, and the time is preferably 4 hours to 6 hours.

[0070] In this step, the long-chain alkylsilane can be combined with the metal salt and the zeolite molecular sieve through M-O-Si bonding, which can not only enhance the activity of the catalyst, but also reduce the loss rate during use and improve the service life of the catalyst.

[0071] The preparation method of the catalyst is simple, the conditions are mild, and the preparation process is environmentally friendly.

[0072] The application also provides a preparation method of chlorobenzyl compounds, in which an aromatic hydrocarbon and its derivative and a chloromethyl reagent are subjected to chloromethylation reaction in the presence of the catalyst, and the chlorobenzyl compound is separated after the reaction is completed.

[0073] Optionally, the aromatic hydrocarbon and its derivative is selected from at least one of p-xylene, 1,2-methylenedioxybenzene, o-dimethyl ether or anisole; and the chloromethyl reagent comprises a formaldehyde compound and hydrochloric acid, wherein the formaldehyde compound is selected from at least one of formaldehyde, trioxane or polyoxymethylene.

[0074] Optionally, the molar ratio of the formaldehyde compound, the aromatic hydrocarbon and its derivatives, and hydrochloric acid is 1:1 to 2:1 to 2.

[0075] Therefore, the formaldehyde compound, such as formaldehyde, trioxane, or polyoxymethylene, and hydrochloric acid are used as the chloromethylation reagent, the raw material is low in price, convenient to store and transport, and low in toxicity, which is conducive to reducing the production cost and easy to industrialized mass production.

[0076] Optionally, the mass ratio of the catalyst to the aromatic hydrocarbon and its derivatives is 0.03:1 to 0.09:1.

[0077] Optionally, the temperature of the chloromethylation reaction is 60°C to 100°C, and the time is 6 hours to 10 hours.

[0078] Optionally, after the reaction is completed, the catalyst is separated and recycled for preparing the chlorobenzyl compound, which can reduce the production cost and is conducive to industrialized production.

[0079] Optionally, the chloromethylation reaction of the present application can be continuous feeding or intermittent feeding, and the intermittent feeding is preferred.

[0080] Hereinafter, the catalyst for chloromethylation reaction and its preparation method, and the preparation method of the chlorobenzyl compound will be further described through the following specific examples.

[0081]

Catalyst for chloromethylation reaction and its preparation method

[0082] Example 1

[0083] 0.521g of ZnCl2 was dissolved in 10mL of deionized water, 5.0g of Y-type molecular sieve was added, the temperature was raised to 40°C, and constant temperature stirring was carried out for 6 hours, then the temperature was lowered, and filtration was carried out, to obtain a first precursor.

[0084] The obtained first precursor was placed in a muffle furnace, calcined at 500°C for 4 hours in a nitrogen atmosphere, and then taken out after natural cooling to room temperature, to obtain a second precursor.

[0085] Then, 40g of hexadecyltrimethoxysilane was dispersed in 50g of ethanol, and the second precursor was added, the temperature was raised to 80°C, and constant temperature stirring was carried out for 6 hours, and then the solvent was removed by rotary evaporation under reduced pressure, and the obtained solid was placed in a vacuum drying oven at 80°C, and dried to constant weight, to obtain a catalyst for chloromethylation reaction, which was marked as catalyst 1 and ready for use.

[0086] Example 2

[0087] Dissolve 1.539 g of ZnS04-7H20 in 10 mL of deionized water, add 5.0 g of HY type molecular sieve, warm to 60°C, and stir at constant temperature for 6 hours. Then, cool, filter, and obtain a first precursor.

[0088] Place the first precursor in a muffle furnace, and calcine at 500°C for 4 hours in a nitrogen atmosphere. After natural cooling to room temperature, remove the second precursor.

[0089] Then, disperse 50 g of hexadecyl triethoxysilane in 50 g of ethanol, add the second precursor, warm to 100°C, and stir at constant temperature for 6 hours. Remove the solvent by rotary evaporation under reduced pressure, and dry the obtained solid in a vacuum drying oven at 80°C until constant weight to obtain a catalyst for chloromethylation reaction, marked as catalyst 2, for standby.

[0090] Example 3

[0091] Dissolve 1.539 g of Cu(OAc)2-H20 in 10 mL of deionized water, add 5.0 g of ZSM-5 molecular sieve, warm to 40°C, and stir at constant temperature for 6 hours. Then, cool, filter, and obtain a first precursor.

[0092] Place the first precursor in a muffle furnace, and calcine at 600°C for 4 hours in a nitrogen atmosphere. After natural cooling to room temperature, remove the second precursor.

[0093] Then, disperse 60 g of dodecyl trimethoxysilane in 70 g of ethanol, add the second precursor, warm to 100°C, and stir at constant temperature for 4 hours. Remove the solvent by rotary evaporation under reduced pressure, and dry the obtained solid in a vacuum drying oven at 80°C until constant weight to obtain a catalyst for chloromethylation reaction, marked as catalyst 3, for standby.

[0094] Example 4

[0095] Dissolve 0.657 g of Ni(acac)2 in 10 mL of deionized water, add 5.0 g of HZSM-5 molecular sieve, warm to 80°C, and stir at constant temperature for 6 hours. Then, cool, filter, and obtain a first precursor.

[0096] Place the first precursor in a muffle furnace, and calcine at 600°C for 4 hours in a nitrogen atmosphere. After natural cooling to room temperature, remove the second precursor.

[0097] Then, 40 g of octadecyltrimethoxysilane was dispersed in 60 g of ethanol, and the second precursor was added. The temperature was raised to 60 °C, and constant temperature stirring was continued for 6 hours. The solvent was removed by rotary evaporation under reduced pressure, and the obtained solid was placed in a vacuum drying oven at 80 °C, and dried to constant weight to obtain a catalyst for chloromethylation reaction, labeled as catalyst 5, for standby.

[0098] Example 5

[0099] 1.239 g of Ni (NO3)2·6H2O was dissolved in 10 mL of deionized water, and 5.0 g of Hβ molecular sieve was added. The temperature was raised to 45 °C, and constant temperature stirring was continued for 7 hours. After that, the temperature was lowered, and filtration was performed to obtain a first precursor.

[0100] The obtained first precursor was placed in a muffle furnace, and calcination was performed at 600 °C for 4 hours in a nitrogen atmosphere. After natural cooling to room temperature, it was taken out to obtain a second precursor.

[0101] Then, 30 g of octadecyltrimethoxysilane was dispersed in 40 g of ethanol, and the second precursor was added. The temperature was raised to 60 °C, and constant temperature stirring was continued for 6 hours. The solvent was removed by rotary evaporation under reduced pressure, and the obtained solid was placed in a vacuum drying oven at 80 °C, and dried to constant weight to obtain a catalyst for chloromethylation reaction, labeled as catalyst 5, for standby.

[0102] Example 6

[0103] 0.436 g of anhydrous FeCl3 was dissolved in 10 mL of deionized water, and 5.0 g of MCM-41 molecular sieve was added. The temperature was raised to 45 °C, and constant temperature stirring was continued for 4 hours. After that, the temperature was lowered, and filtration was performed to obtain a first precursor.

[0104] The obtained first precursor was placed in a muffle furnace, and calcination was performed at 400 °C for 2 hours in a nitrogen atmosphere. After natural cooling to room temperature, it was taken out to obtain a second precursor.

[0105] Then, 40 g of octadecyltrimethoxysilane was dispersed in 40 g of ethanol, and the second precursor was added. The temperature was raised to 60 °C, and constant temperature stirring was continued for 6 hours. The solvent was removed by rotary evaporation under reduced pressure, and the obtained solid was placed in a vacuum drying oven at 80 °C, and dried to constant weight to obtain a catalyst for chloromethylation reaction, labeled as catalyst 5, for standby.

[0106] Example 7

[0107] 1.808 g of Fe (NO3)3·9H2O was dissolved in 10 mL of deionized water, and 5.0 g of SBA-15 molecular sieve was added. The temperature was raised to 40 °C, and constant temperature stirring was continued for 6 hours. After that, the temperature was lowered, and filtration was performed to obtain a first precursor.

[0108] The obtained first precursor was placed in a muffle furnace, calcined at 400°C for 4 hours in a nitrogen atmosphere, and then taken out after natural cooling to room temperature to obtain a second precursor.

[0109] Then, 60 g of hexadecyltrimethoxysilane was dispersed in 70 g of ethanol, and the second precursor was added. The temperature was raised to 100°C, and constant temperature stirring was continued for 4 hours. The solvent was removed by rotary evaporation under reduced pressure, and the obtained solid was placed in a vacuum drying oven at 80°C to dry to constant weight to obtain a catalyst for chloromethylation reaction, which was labeled as catalyst 7 and reserved for use.

[0110] Example 8

[0111] 1.742 g of FeSO4·7H2O was dissolved in 10 mL of deionized water, and 5.0 g of TS-1 molecular sieve was added. The temperature was raised to 40°C, and constant temperature stirring was continued for 6 hours. Then, the temperature was lowered, and the mixture was filtered to obtain a first precursor.

[0112] The obtained first precursor was placed in a muffle furnace, calcined at 500°C for 4 hours in a nitrogen atmosphere, and then taken out after natural cooling to room temperature to obtain a second precursor.

[0113] Then, 90 g of dodecyltrimethoxysilane was dispersed in 100 g of ethanol, and the second precursor was added. The temperature was raised to 100°C, and constant temperature stirring was continued for 4 hours. The solvent was removed by rotary evaporation under reduced pressure, and the obtained solid was placed in a vacuum drying oven at 80°C to dry to constant weight to obtain a catalyst for chloromethylation reaction, which was labeled as catalyst 8 and reserved for use.

[0114] Example 9

[0115] 0.988 g of SnCl4 was dissolved in 10 mL of deionized water, and 5.0 g of TS-2 molecular sieve was added. The temperature was raised to 40°C, and constant temperature stirring was continued for 8 hours. Then, the temperature was lowered, and the mixture was filtered to obtain a first precursor.

[0116] The obtained first precursor was placed in a muffle furnace, calcined at 600°C for 4 hours in a nitrogen atmosphere, and then taken out after natural cooling to room temperature to obtain a second precursor.

[0117] Then, 60 g of octadecyltrimethoxysilane was dispersed in 70 g of ethanol, and the second precursor was added. The temperature was raised to 100°C, and constant temperature stirring was continued for 4 hours. The solvent was removed by rotary evaporation under reduced pressure, and the obtained solid was placed in a vacuum drying oven at 80°C to dry to constant weight to obtain a catalyst for chloromethylation reaction, which was labeled as catalyst 9 and reserved for use.

[0118] Example 10

[0119] Dissolve 1.172 g of SnCl4 in 10 mL of deionized water, add 5.0 g of HZSM-5 molecular sieve, heat to 40°C, and stir at constant temperature for 8 hours, after which, cool, filter, to obtain a first precursor.

[0120] Place the obtained first precursor in a muffle furnace, and calcine at 600°C for 4 hours in a nitrogen atmosphere, and take out after natural cooling to room temperature, to obtain a second precursor.

[0121] Then, disperse 60 g of tridecafluorooctyltrimethoxysilane in 70 g of ethanol, and add the second precursor, heat to 100°C, and stir at constant temperature for 4 hours, and remove the solvent by rotary evaporation under reduced pressure, and place the obtained solid in a vacuum drying oven at 80°C, and dry to constant weight, to obtain a catalyst for chloromethylation reaction, marked as catalyst 10, for standby.

[0122] Example 11

[0123] Dissolve 1.239 g of Ni(NO3)2·6H2O and 0.313 g of ZnCl2 in 10 mL of deionized water, add 5.0 g of MCM-41 molecular sieve, heat to 50°C, and stir at constant temperature for 6 hours, after which, cool, filter, to obtain a first precursor.

[0124] Place the obtained first precursor in a muffle furnace, and calcine at 400°C for 4 hours in a nitrogen atmosphere, and take out after natural cooling to room temperature, to obtain a second precursor.

[0125] Then, disperse 50 g of hexadecyltrimethoxysilane in 60 g of ethanol, and add the second precursor, heat to 100°C, and stir at constant temperature for 4 hours, and remove the solvent by rotary evaporation under reduced pressure, and place the obtained solid in a vacuum drying oven at 80°C, and dry to constant weight, to obtain a catalyst for chloromethylation reaction, marked as catalyst 11, for standby.

[0126] Comparative Example 1

[0127] Add 5.0 g of Hβ molecular sieve in 10 mL of deionized water, heat to 45°C, and stir at constant temperature for 7 hours, after which, cool, filter, to obtain a first precursor.

[0128] Place the obtained first precursor in a muffle furnace, and calcine at 600°C for 4 hours in a nitrogen atmosphere, and take out after natural cooling to room temperature, to obtain a second precursor.

[0129] Then, disperse 30 g of octadecyltrimethoxysilane in 40 g of ethanol, and add the second precursor, heat to 60°C, and stir at constant temperature for 6 hours, and remove the solvent by rotary evaporation under reduced pressure, and place the obtained solid in a vacuum drying oven at 80°C, and dry to constant weight, to obtain a catalyst, marked as comparative catalyst 1, for standby.

[0130] Comparative Example 2

[0131] Dissolve 1.239 g of Ni(NO3)2·6H2O in 10 mL of deionized water, add 5.0 g of Hβ molecular sieve, heat to 45°C, and stir at constant temperature for 7 hours. Then, cool, filter, and obtain a first precursor.

[0132] Place the obtained first precursor in a muffle furnace, and calcine at 600°C for 4 hours in a nitrogen atmosphere. Take out after natural cooling to room temperature, and obtain a second precursor.

[0133] Add the second precursor to 40 g of ethanol, heat to 60°C, and stir at constant temperature for 6 hours. Remove the solvent by rotary evaporation under reduced pressure, and place the obtained solid in a vacuum drying oven at 80°C to dry to constant weight, and obtain a catalyst, which is labeled as Comparative Catalyst 2, and is ready for use.

[0134] Comparative Example 3

[0135] Dissolve 1.239 g of Ni(NO3)2·6H2O in 10 mL of deionized water, add 5.0 g of SiO2 carrier, heat to 40°C, and stir at constant temperature for 9 hours. Then, cool, filter, and obtain a first precursor.

[0136] Place the obtained first precursor in a muffle furnace, and calcine at 600°C for 4 hours in a nitrogen atmosphere. Take out after natural cooling to room temperature, and obtain a second precursor.

[0137] Then, disperse 30 g of octadecyltrimethoxysilane in 40 g of ethanol, and add the second precursor. Heat to 60°C, and stir at constant temperature for 8 hours. Remove the solvent by rotary evaporation under reduced pressure, and place the obtained solid in a vacuum drying oven at 80°C to dry to constant weight, and obtain a catalyst for chloromethylation reaction, which is labeled as Comparative Catalyst 3, and is ready for use.

[0138] Preparation of chlorobenzyl compounds

[0139] Example 12

[0140] Into a 500 mL autoclave, sequentially add 61.06 g of 1,2-methylenedioxybenzene (0.5 mol, 99%), 59.11 g of concentrated hydrochloric acid (0.60 mol, 37%), 19.58 g of polyformaldehyde [0.6 mol (calculated as formaldehyde), 92%], and 3.05 g of Catalyst 1. Close the reactor, and start stirring. Heat to 70°C, and maintain the temperature for 8 hours. After the reaction is completed, cool the system to room temperature, and filter to recover the catalyst. Separate the organic layer, and distill under reduced pressure to obtain 81.20 g of product, with a content of 99.0% and a yield of 95.20%.

[0141] Example 13

[0142] Into a 500 mL autoclave, 69.08 g of o-dichlorobenzene (0.5 mol, 99%), 73.89 g of concentrated hydrochloric acid (0.75 mol, 37%), 24.48 g of paraformaldehyde [0.75 mol (as formaldehyde), 92%] and 3.45 g of catalyst 2 were sequentially added, the reaction kettle was closed, stirring was started, the temperature was raised to 70°C, and the reaction was kept at this temperature for 10 hours. After the reaction was completed, the system was cooled to room temperature, the reaction solution was pressed out, the catalyst was recovered by filtration, the organic layer was separated from the filtrate by standing, and 90.13 g of product was obtained by vacuum rectification, with a content of 99.0% and a yield of 96.60%.

[0143] Example 14

[0144] Into a 500 mL autoclave, 54.07 g of anisole (0.5 mol, 99%), 73.89 g of concentrated hydrochloric acid (0.75 mol, 37%), 9.79 g of paraformaldehyde [0.75 mol (as formaldehyde), 92%] and 3.78 g of catalyst 3 were sequentially added, the reaction kettle was closed, stirring was started, the temperature was raised to 60°C, and the reaction was kept at this temperature for 10 hours. After the reaction was completed, the system was cooled to room temperature, the reaction solution was pressed out, the catalyst was recovered by filtration, the organic layer was separated from the filtrate by standing, and 76.19 g of product was obtained by vacuum rectification, with a content of 99.0% and a yield of 97.32%.

[0145] Example 15

[0146] Into a 500 mL autoclave, 53.09 g of p-xylene (0.5 mol, 99%), 59.11 g of concentrated hydrochloric acid (0.6 mol, 37%), 16.32 g of paraformaldehyde [0.5 mol (as formaldehyde), 92%] and 1.59 g of catalyst 4 were sequentially added, the reaction kettle was closed, stirring was started, the temperature was raised to 70°C, and the reaction was kept at this temperature for 8 hours. After the reaction was completed, the system was cooled to room temperature, the reaction solution was pressed out, the catalyst was recovered by filtration, the organic layer was separated from the filtrate by standing, and 76.20 g of product was obtained by vacuum rectification, with a content of 99.0% and a yield of 98.57%.

[0147] Example 16

[0148] Into a 500 mL autoclave, 61.06 g of 1,2-methylenedioxybenzene (0.5 mol, 99%), 88.66 g of concentrated hydrochloric acid (0.9 mol, 37%), 29.38 g of paraformaldehyde [0.9 mol (as formaldehyde), 92%] and 3.05 g of catalyst 4 were sequentially added, the reaction kettle was closed, stirring was started, the temperature was raised to 70°C, and the reaction was kept at this temperature for 10 hours. After the reaction was completed, the system was cooled to room temperature, the reaction solution was pressed out, the catalyst was recovered by filtration, the organic layer was separated from the filtrate by standing, and 84.29 g of product was obtained by vacuum rectification, with a content of 99.0% and a yield of 98.82%.

[0149] Example 17

[0150] Into a 500 mL autoclave, 69.08 g of o-dichlorobenzene (0.5 mol, 99%), 98.51 g of concentrated hydrochloric acid (1.0 mol, 37%), 32.64 g of paraformaldehyde [1.0 mol (as formaldehyde), 92%] and 4.84 g of catalyst 5 were added in sequence, the reaction kettle was closed, stirring was started, the temperature was raised to 60°C, and reaction was carried out for 6 hours while maintaining the temperature. After the reaction ended, the system was cooled to room temperature, the reaction solution was pressed out, the catalyst was recovered by filtration, the filtrate was allowed to stand to separate the organic layer, and vacuum rectification was carried out to obtain 92.42 g of product with a content of 99.0% and a yield of 99.05%.

[0151] Example 18

[0152] Into a 500 mL autoclave, 61.06 g of 1,2-methylenedioxybenzene (0.5 mol, 99%), 73.89 g of concentrated hydrochloric acid (0.75 mol, 37%), 24.48 g of paraformaldehyde [0.75 mol (as formaldehyde), 92%] and 4.27 g of catalyst 6 were added in sequence, the reaction kettle was closed, stirring was started, the temperature was raised to 100°C, and reaction was carried out for 10 hours while maintaining the temperature. After the reaction ended, the system was cooled to room temperature, the reaction solution was pressed out, the catalyst was recovered by filtration, the filtrate was allowed to stand to separate the organic layer, and vacuum rectification was carried out to obtain 84.16 g of product with a content of 99.0% and a yield of 98.66%.

[0153] Example 19

[0154] Into a 500 mL autoclave, 54.07 g of anisole (0.5 mol, 99%), 73.89 g of concentrated hydrochloric acid (0.75 mol, 37%), 24.48 g of paraformaldehyde [0.75 mol (as formaldehyde), 92%] and 3.78 g of catalyst 7 were added in sequence, the reaction kettle was closed, stirring was started, the temperature was raised to 90°C, and reaction was carried out for 10 hours while maintaining the temperature. After the reaction ended, the system was cooled to room temperature, the reaction solution was pressed out, the catalyst was recovered by filtration, the filtrate was allowed to stand to separate the organic layer, and vacuum rectification was carried out to obtain 76.22 g of product with a content of 99.0% and a yield of 97.36%.

[0155] Example 20

[0156] Into a 500 mL autoclave, 68.08 g of anisole (0.5 mol, 99%) was added, followed by 73.89 g of concentrated hydrochloric acid (0.75 mol, 37%), 24.48 g of paraformaldehyde [0.75 mol (calculated as formaldehyde), 92%], and 4.87 g of catalyst 8. The reactor was closed, stirring was started, and the temperature was raised to 80°C. The reaction was maintained at this temperature for 8 hours. After the reaction was completed, the system was cooled to room temperature, the reaction solution was filtered to recover the catalyst, the filtrate was allowed to stand to separate the organic layer, and the product was obtained by vacuum distillation at a reduced pressure. The yield of the product was 76.47 g, the content was 99.0%, and the yield was 97.68%.

[0157] Example 21

[0158] Into a 500 mL autoclave, 69.08 g of o-dianisole (0.5 mol, 99%) was added, followed by 73.89 g of concentrated hydrochloric acid (0.75 mol, 37%), 24.48 g of paraformaldehyde [0.75 mol (calculated as formaldehyde), 92%], and 4.84 g of catalyst 9. The reactor was closed, stirring was started, and the temperature was raised to 120°C. The reaction was maintained at this temperature for 8 hours. After the reaction was completed, the system was cooled to room temperature, the reaction solution was filtered to recover the catalyst, the filtrate was allowed to stand to separate the organic layer, and the product was obtained by vacuum distillation at a reduced pressure. The yield of the product was 91.45 g, the content was 99.0%, and the yield was 98.01%.

[0159] Example 22

[0160] Into a 500 mL autoclave, 61.06 g of 1,2-methylenedioxybenzene (0.5 mol, 99%) was added, followed by 73.89 g of concentrated hydrochloric acid (0.75 mol, 37%), 24.48 g of paraformaldehyde [0.75 mol (calculated as formaldehyde), 92%], and 5.50 g of catalyst 10. The reactor was closed, stirring was started, and the temperature was raised to 100°C. The reaction was maintained at this temperature for 10 hours. After the reaction was completed, the system was cooled to room temperature, the reaction solution was filtered to recover the catalyst, the filtrate was allowed to stand to separate the organic layer, and the product was obtained by vacuum distillation at a reduced pressure. The yield of the product was 81.30 g, the content was 99.0%, and the yield was 95.31%.

[0161] Example 23

[0162] Into a 500 mL autoclave, 61.06 g of 1,2-methylenedioxybenzene (0.5 mol, 99%) was added, followed by 59.11 g of concentrated hydrochloric acid (0.6 mol, 37%), 19.58 g of paraformaldehyde [0.6 mol (calculated as formaldehyde), 92%], and 1.83 g of catalyst 11. The reactor was closed, stirring was started, and the temperature was raised to 60°C. The reaction was maintained at this temperature for 7 hours. After the reaction was completed, the system was cooled to room temperature, the reaction solution was filtered to recover the catalyst, the filtrate was allowed to stand to separate the organic layer, and the product was obtained by vacuum distillation at a reduced pressure. The yield of the product was 85.06 g, the content was 99.0%, and the yield was 99.72%.

[0163] Example 24

[0164] Into a 500 mL autoclave were added 61.06 g of 1,2-methylenedioxybenzene (0.5 mol, 99%), 59.11 g of concentrated hydrochloric acid (0.6 mol, 37%), 18.20 g of trioxane [0.6 mol (as formaldehyde), 99%], and 1.83 g of catalyst 11 successively, the reaction kettle was closed, stirring was started, the temperature was raised to 70°C, and reaction was performed with heat preservation for 6 hours. After the reaction ended, the system was cooled to room temperature, the reaction solution was pressed out, the catalyst was recovered by filtration, the organic layer was separated by standing of the filtrate, and 84.67 g of product was obtained by distillation under reduced pressure, with a content of 99.0% and a yield of 99.26%.

[0165] Example 25

[0166] Into a 500 mL autoclave were added 61.06 g of 1,2-methylenedioxybenzene (0.5 mol, 99%), 59.11 g of concentrated hydrochloric acid (0.6 mol, 37%), 48.70 g of formaldehyde solution [0.6 mol, 37%], and 1.83 g of catalyst 11 successively, the reaction kettle was closed, stirring was started, the temperature was raised to 50°C, and reaction was performed with heat preservation for 8 hours. After the reaction ended, the system was cooled to room temperature, the reaction solution was pressed out, the catalyst was recovered by filtration, the organic layer was separated by standing of the filtrate, and 83.43 g of product was obtained by distillation under reduced pressure, with a content of 99.0% and a yield of 97.81%.

[0167] Comparative Example 4

[0168] Into a 500 mL autoclave were added 61.06 g of 1,2-methylenedioxybenzene (0.5 mol, 99%), 59.11 g of concentrated hydrochloric acid (0.6 mol, 37%), 24.48 g of paraformaldehyde [0.6 mol (as formaldehyde), 92%], and 6.11 g of comparative catalyst 1 successively, the reaction kettle was closed, stirring was started, the temperature was raised to 100°C, and reaction was performed with heat preservation for 10 hours. After the reaction ended, the system was cooled to room temperature, the reaction solution was pressed out, the catalyst was recovered by filtration, the organic layer was separated by standing of the filtrate, and 34.54 g of product was obtained by distillation under reduced pressure, with a content of 95.1% and a yield of 38.51%.

[0169] Comparative Example 5

[0170] Into a 500 mL autoclave, 61.06 g of 1,2-methylenedioxybenzene (0.5 mol, 99%), 59.11 g of concentrated hydrochloric acid (0.6 mol, 37%), 24.48 g of polyformaldehyde [0.6 mol (calculated as formaldehyde), 92%] and 6.11 g of comparative catalyst 2 were sequentially added, the reaction kettle was closed, stirring was started, the temperature was raised to 100°C, and the reaction was kept at this temperature for 10 hours. After the reaction was completed, the system was cooled to room temperature, the reaction solution was discharged, filtered to recover the catalyst, the filtrate was allowed to stand to separate the organic layer, and vacuum rectification was performed to obtain 37.30 g of product with a content of 96.2% and a yield of 42.07%.

[0171] Comparative Example 6

[0172] Into a 500 mL autoclave, 61.06 g of 1,2-methylenedioxybenzene (0.5 mol, 99%), 59.11 g of concentrated hydrochloric acid (0.6 mol, 37%), 24.48 g of polyformaldehyde [0.6 mol (calculated as formaldehyde), 92%] and 6.11 g of comparative catalyst 2 were sequentially added, the reaction kettle was closed, stirring was started, the temperature was raised to 100°C, and the reaction was kept at this temperature for 10 hours. After the reaction was completed, the system was cooled to room temperature, the reaction solution was discharged, filtered to recover the catalyst, the filtrate was allowed to stand to separate the organic layer, and vacuum rectification was performed to obtain 37.30 g of product with a content of 96.2% and a yield of 42.07%.

[0173]

Catalyst reuse example

[0174] The catalyst recovered from Example 23 was used for a reuse experiment, and the reaction conditions and operations were the same as in Example 23. The experimental results are shown in Table 1.

[0175] Table 1

[0176]

[0177]

[0178] The technical features of the above-described examples can be combined in any manner. To make the description concise, not all possible combinations of the technical features in the above-described examples are described, but as long as the combinations of the technical features do not contradict each other, they should be considered within the scope of the present disclosure.

[0179] The above-described examples only express several embodiments of the present application, and the description is relatively specific and detailed, but it should not be construed as limiting the scope of the patent. It should be noted that for ordinary skilled persons in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are within the scope of the present application. Therefore, the scope of protection of the present patent should be subject to the appended claims.

Claims

1. A catalyst for chloromethylation reaction, characterized by, The catalyst comprises a zeolite molecular sieve and a metal salt and a long-chain alkyl silane supported on the zeolite molecular sieve, the metal salt being selected from at least one of iron salt, nickel salt, copper salt, zinc salt, tin salt or zirconium salt.

2. The catalyst for chloromethylation reaction according to claim 1, wherein, The catalyst further satisfies at least one of the following conditions: (1) the long-chain alkyl silane is selected from C12-C18 alkyl silane; (2) the zeolite molecular sieve is selected from at least one of Y-type molecular sieve, HY molecular sieve, ZSM-5 molecular sieve, HZSM-5 molecular sieve, MCM-41 molecular sieve, SBA-15 molecular sieve, TS-1 molecular sieve, TS-2 molecular sieve, Hβ molecular sieve; (3) the mass ratio of metal ions in the metal salt to the zeolite molecular sieve is 0.03:1-0.12:1; (4) the mass ratio of the long-chain alkyl silane to the zeolite molecular sieve is 6:1-18:

1.

3. The catalyst for chloromethylation reaction according to claim 2, characterized by, The catalyst further satisfies at least one of the following conditions: (1) the metal salt is selected from at least two of iron salt, nickel salt, copper salt, zinc salt, tin salt or zirconium salt; (2) the long-chain alkyl silane is selected from at least one of long-chain alkyl trimethoxysilane or long-chain alkyl triethoxysilane; (3) the mass ratio of metal ions in the metal salt to the zeolite molecular sieve is 0.05:1-0.09:1; (4) the mass ratio of the long-chain alkyl silane to the zeolite molecular sieve is 8:1-12:

1.

4. The catalyst for chloromethylation reaction according to claim 3, wherein The long-chain alkyl silane is selected from at least one of hexadecyl trimethoxysilane, hexadecyl triethoxysilane, dodecyl trimethoxysilane, dodecyl triethoxysilane, octadecyl trimethoxysilane, tridecafluoro octyl trimethoxysilane.

5. A process for producing a catalyst for chloromethylation according to any one of claims 1 to 4, characterized by, The method comprises the following steps: S1, adding a zeolite molecular sieve in a metal salt solution for adsorption, and separating to obtain a first precursor; S2, calcining the first precursor in an inert atmosphere to obtain a second precursor; S3, mixing the second precursor, long-chain alkyl silane and organic solvent for modification treatment, and then separating to obtain a catalyst.

6. The method for producing a catalyst for chloromethylation according to claim 5, wherein Step S1 satisfies at least one of the following conditions: (1) the mass ratio of metal ions in the metal salt solution to the zeolite molecular sieve is 0.03:1-0.12:1; (2) the adsorption temperature is 40-80℃, and the time is 4-8 hours.

7. The method for producing a catalyst for chloromethylation according to claim 5, wherein In step S2, the calcination temperature is 400-600℃, and the time is 2-4 hours.

8. The method for producing a catalyst for chloromethylation according to claim 5, wherein Step S3 satisfies at least one of the following conditions: (1) the mass ratio of the long-chain alkyl silane to the zeolite molecular sieve is 6:1-18:1; (2) the modification treatment temperature is 60-100℃, and the time is 4-6 hours.

9. A process for the preparation of a chlorobenzyl compound, characterized in that, In the presence of the catalyst as claimed in any one of claims 1-4, an aromatic hydrocarbon and derivatives thereof and a chloromethyl reagent are subjected to chloromethylation reaction, and after the reaction is completed, a chlorobenzene compound is separated.

10. The method for preparing benzyl chloride compounds according to claim 9, characterized in that, The preparation method further satisfies at least one of the following conditions: (1) the aromatic hydrocarbon and derivatives thereof are selected from at least one of p-xylene, 1,2-methylenedioxybenzene, o-dianisole or anisole; (2) the chloromethyl reagent comprises a formaldehyde compound and hydrochloric acid, the formaldehyde compound is calculated as formaldehyde, and a molar ratio of the formaldehyde compound, the aromatic hydrocarbon and a derivative thereof, and the hydrochloric acid is 1:1-2:1-2, wherein the formaldehyde compound is at least one selected from formaldehyde, trioxane or polyoxymethylene; (3) a mass ratio of the catalyst to the aromatic hydrocarbon and a derivative thereof is 0.03:1-0.09:1; (4) a temperature of the chloromethylation reaction is 60-100 DEG C, and a time is 6-10 hours; (5) after the reaction is completed, the catalyst is separated and recycled for preparation of a chlorobenzyl compound.

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