Heterogeneous modified sulfonic acid resin catalyst as well as preparation method and application thereof

Abstract

The invention discloses a heterogeneous modified sulfonic acid resin catalyst as well as a preparation method and application thereof, and the method comprises the following steps: by taking styrene and divinylbenzene as polymeric monomers, adding a comonomer containing double bonds and carboxyl and / or sulfydryl to synthesize a sulfonic acid resin particle matrix; hydrogel containing-NH2 is bonded with carboxyl and / or sulfydryl in a sulfonic acid resin matrix, finally, concentrated sulfuric acid containing chlorosulfonic acid is adopted for sulfonation treatment, and the modified sulfonic acid resin catalyst is obtained and can be used as a catalyst for synthesis of 3-methoxy-3-methyl-1-butanol. The shedding rate of a sulfonic acid group in the modified sulfonic acid resin catalyst is reduced to 0.5 wt% / half a year from 10 wt% before modification, the service life of the resin is prolonged to 7000 h from 3000 h, and the rectification yield of 3-methoxy-3-methyl-1-butanol is increased to 92 wt% from 85 wt%. The acidity of the outlet of the reactor is reduced due to the reduction of the falling rate of the sulfonic acid group, the blockage risk of rectification separation after neutralization treatment, alkalization and salification is avoided, and the purification process of the 3-methoxy-3-methyl-1-butanol is simplified.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of preparation of modified sulfonic acid resin, and particularly relates to a heterogeneous modified sulfonic acid resin catalyst and a preparation method, and application of the catalyst in preparation of 3-methoxy-3-methyl-1-butanol. BACKGROUND

[0002] 3-methoxy-3-methyl-1-butanol is a kind of fragrance product with slight mint flavor, and has better safety, environmental protection, solubility and compatibility, and has extremely wide application in many fields such as rattan fragrance, fragrant agent, cleaning agent, domestic detergent, emulsion and resin synthesis, printing chemicals and the like.

[0003] The main raw materials for synthesizing 3-methoxy-3-methyl-1-butanol at present include 4,4-dimethyl-1,3-dioxane, iso-isopentenol and isoprene, wherein the route for synthesizing 3-methoxy-3-methyl-1-butanol from iso-isopentenol and methanol has high raw material conversion rate, less by-products, high selectivity of main product, no generation and use of high-toxicity substances in the reaction process, and has high industrialization value. Iso-isopentenol and methanol generate main product 3-methoxy-3-methyl-1-butanol under the action of acid catalyst, and also generate by-products such as iso-isopentenol methyl ether and isopentenyl methyl ether.

[0004] In patent CN104203890A, a homogeneous acid catalyst is used to catalyze the reaction of iso-isopentenol, and the catalyst enters the downstream rectification tower with the reaction liquid. 3-methoxy-3-methyl-1-butanol generates side reactions in the high-temperature and strong-acid environment of the rectification tower tank in the acid environment, resulting in low rectification yield of 3-methoxy-3-methyl-1-butanol, only 80wt%.

[0005] In patent CN119191944A, a heterogeneous sulfonic acid resin catalyst is used to catalyze the reaction of isoisoamylene alcohol. Although the resin does not enter the subsequent rectification tower with the reaction liquid, the sulfonic acid group of the used sulfonic acid resin catalyst falls off, and the pH at the outlet of the reactor is about 4. During the rectification and purification of 3-methoxy-3-methyl-1-butanol, the 3-methoxy-3-methyl-1-butanol undergoes side reactions in the acidic environment at a relatively high operating temperature in the tower kettle. Although the rectification yield is increased to 85wt% compared with the homogeneous system, there is still a loss of 3-methoxy-3-methyl-1-butanol. In order to improve the rectification yield of 3-methoxy-3-methyl-1-butanol, lye is added to the process for neutralization. After neutralization, the rectification yield of 3-methoxy-3-methyl-1-butanol can be increased to 95wt%. However, sulfonate is generated during the neutralization process, and there is a risk of tower plugging during rectification operation. A scraped blade reboiler is added to the process to recover 3-methoxy-3-methyl-1-butanol. It can be seen that the use of sulfonic acid resin catalyst can improve the economy of 3-methoxy-3-methyl-1-butanol synthesis, but due to the falling off of the sulfonic acid group, a more complex process is required to achieve a higher rectification yield of 3-methoxy-3-methyl-1-butanol, and the production energy consumption is greatly increased.

[0006] Therefore, there is an urgent need in the art to find a heterogeneous sulfonic acid resin catalyst that can improve the selectivity and yield of 3-methoxy-3-methyl-1-butanol without falling off the sulfonic acid group, avoid the problem of generating sulfonate after neutralization in the subsequent purification process of 3-methoxy-3-methyl-1-butanol, reduce the risk of tower plugging during rectification separation, and thus simplify the process flow and reduce the energy consumption of the subsequent separation process. SUMMARY

[0007] In view of the problem that the sulfonic acid group of the existing acidic sulfonic acid resin catalyst easily falls off, the present application provides a heterogeneous modified sulfonic acid resin catalyst and a preparation method, aiming to reduce the falling off rate of the sulfonic acid group in the sulfonic acid resin catalyst, to solve the problems of high falling off rate of the sulfonic acid group, low rectification yield of 3-methoxy-3-methyl-1-butanol, and easy plugging of the rectification tower after neutralization and salification in the prior art.

[0008] The heterogeneous modified sulfonic acid resin catalyst provided by the present application uses styrene and divinylbenzene as the synthesis monomers of the sulfonic acid resin, adds a copolymerization monomer containing a double bond and a carboxyl group and / or a mercapto group to introduce a functional group containing a carboxyl group and / or a mercapto group into the sulfonic acid resin particle matrix. Then, a hydrogel containing an amino group (-NH2) is bonded with the -COOH or -SH in the sulfonic acid resin particle matrix, the hydrogel is introduced into the skeleton, and finally concentrated sulfuric acid containing chlorosulfonic acid is added for sulfonation reaction. The effective loading of the sulfonic acid group is realized by using the bonding effect of -NH2 in the hydrogel and the sulfonic acid group and the strong adhesion of the hydrogel, and the falling off rate of the sulfonic acid group is reduced.

[0009] The inventors have found that the hydrogel has very strong adhesion, which is related to the functional groups contained in the structure. The functional groups containing -NH2 are easy to bond with mercapto and carboxyl groups, thereby forming a stable structure. Based on the above special performance, the hydrogel is introduced into the sulfonic acid resin skeleton, and the dynamic covalent bond or coordination bond formed by -NH2 and sulfonic acid group is used to realize the loading of sulfonic acid group by the action of chemical bond and the physical adhesion of the hydrogel itself, thereby improving the problem of sulfonic acid group falling off.

[0010] To achieve the above object, the present application adopts the following technical solutions:

[0011] In the first aspect of the present application, a preparation method of a heterogeneous modified sulfonic acid resin catalyst is provided, comprising the following steps:

[0012] (1) A suspension copolymerization reaction is carried out in water by using styrene and divinylbenzene as polymerization monomers, a compound containing double bond and carboxyl and / or mercapto group, adding a pore-forming agent, an initiator and a dispersing agent, then filtering, drying to obtain a sulfonic acid resin particle matrix;

[0013] (2) The sulfonic acid resin particle matrix of step (1) is mixed with a eutectic solvent and a hydrogel containing amino group to react, then filtering, drying to obtain a sulfonic acid resin particle matrix loaded with hydrogel;

[0014] (3) The sulfonic acid resin particle matrix loaded with hydrogel of step (2) is mixed with chlorosulfonic acid and concentrated sulfuric acid to carry out a sulfonation reaction, then filtering, washing, drying to obtain the heterogeneous modified sulfonic acid resin catalyst.

[0015] Further, the compound containing double bond and carboxyl and / or mercapto group in step (1) meets the following characteristics: the number of C atoms is 3-7, such as 3, 4, 5, 6, 7, etc., containing one double bond, containing carboxyl and / or mercapto functional groups;

[0016] Alternatively, the compound containing double bond and carboxyl and / or mercapto group is at least one of acrylic acid, methacrylic acid, cinnamic acid, allyl mercaptan, 4-vinylbenzyl mercaptan, preferably acrylic acid.

[0017] Further, the amount of divinylbenzene added in step (1) is 1-4 times the mass of styrene, such as 1, 2, 3, 4 times, etc.

[0018] Further, the amount of the compound containing double bond and carboxyl and / or mercapto group added in step (1) is 10-50% of the mass of styrene, such as 10, 20, 30, 40, 50%, etc.

[0019] Further, the pore-making agent in step (1) is selected from at least one of dichloroethane, toluene, dimethylbenzene, n-hexane, polyethylene glycol, preferably n-hexane.

[0020] Optionally, the pore-making agent is added in an amount of 10-90% by mass of styrene, for example 10, 30, 50, 70, 90%, etc.

[0021] Further, the initiator in step (1) is selected from at least one of benzoyl peroxide, tert-butyl peroxy(2-ethylhexanoate), azobis isobutyronitrile, preferably tert-butyl peroxy(2-ethylhexanoate).

[0022] Optionally, the initiator is added in an amount of 1-10% by mass of styrene, for example 1, 3, 5, 7, 9, 10, etc.

[0023] Further, the dispersing agent in step (1) is selected from at least one of polyvinyl alcohol, gelatin, methyl cellulose, preferably polyvinyl alcohol (e.g. PVA-1799);

[0024] Optionally, the dispersing agent is added in an amount of 0.1-1% by mass of styrene, for example 0.1, 0.3, 0.5, 0.7, 0.9, 1%, etc.

[0025] Further, the water in step (1) is added in an amount of 10-20 times by mass of styrene, for example 10, 12, 14, 16, 18, 20 times, etc.

[0026] Further, the suspension copolymerization reaction in step (1) is carried out at a temperature of 50-100°C, for example 50, 55, 60, 70, 80, 90, 100°C, etc., for a time of 5-10h, for example 5, 6, 7.5, 8, 9, 10h, etc.

[0027] Optionally, the suspension copolymerization reaction is carried out in stages, first at 50-60°C for 2-3h, and then heated to 80-100°C for 3-7h;

[0028] Optionally, the suspension copolymerization reaction is carried out at a pressure of micro-positive pressure, preferably 10-20kPaG, for example 10, 13, 15, 18, 20kPaG, etc.

[0029] Further, the eutectic solvent in step (2) is selected from at least one of quaternary ammonium salt solvents: choline chloride / urea (1:2 mol), choline chloride / ethylene glycol (1:2 mol), choline chloride / glycerol (1:2 mol), choline chloride / lactic acid (1:2 mol), choline chloride / oxalic acid (1:1 mol); preferably, the eutectic solvent is choline chloride / urea eutectic solvent.

[0030] Optionally, the eutectic solvent is added in an amount of 20-30 times the mass of the sulfonic acid resin particle matrix, for example 20, 23, 25, 27, 30 times, etc. The eutectic solvent refers to a low-melting mixture of two or more components that interact through hydrogen bonding, with a melting point significantly lower than that of any single component. The conventional operation is to mix the two substances directly and then heat and stir to obtain, and the currently listed ratios in the present application are the lowest melting point of the obtained solvent, which is the classic ratio composition.

[0031] Further, the hydrogel containing amino (-NH2) in step (2) is at least one of chitosan, sulfomethylated polyacrylamide, and polylysine, preferably sulfomethylated polyacrylamide.

[0032] Optionally, the hydrogel containing amino is added in an amount of 1-10% of the mass of the sulfonic acid resin particle matrix, for example 1, 3, 5, 7, 10%, etc.

[0033] Further, the reaction in step (2) has a reaction temperature of 25-60°C, for example 25, 30, 40, 50, 60°C, etc., and a reaction time of 2-4h, for example 2, 3, 4h, etc.

[0034] Optionally, the reaction pressure is micro-positive pressure, preferably 10-20 kPaG, for example 10, 12, 15, 18, 20 kPaG, etc.

[0035] Further, the chlorosulfonic acid in step (3) is added in an amount of 20-50% of the mass of the sulfonic acid resin particle matrix loaded with the hydrogel, for example 20, 30, 40, 50%, etc.

[0036] Further, the concentrated sulfuric acid in step (3) is added in an amount of 5-10 times the mass of the sulfonic acid resin particle matrix loaded with the hydrogel, for example 5, 6, 7, 8, 9, 10 times, etc.

[0037] Optionally, the concentration of the concentrated sulfuric acid is 95-98 wt%, for example 95, 96, 97, 98 wt%, etc.

[0038] Further, the sulfonation reaction in step (3) has a reaction temperature of 50-100°C, for example 50, 60, 70, 80, 90, 100°C, etc., and a reaction time of 2-6h, for example 2, 3, 4, 5, 6h, etc.

[0039] In the preparation steps of the present application, filtration, washing, drying, etc. operations are also included, which are all conventional processing methods in the field and are not particularly required by the present application. Optionally, the filtration uses a 20-50μm filter; the washing uses water, acetone, etc. solvents for cleaning.

[0040] In the second aspect of the present application, a heterogeneous modified sulfonic acid resin catalyst is provided.

[0041] The heterogeneous modified sulfonic acid resin catalyst is prepared by the method described above.

[0042] In the third aspect of the present application, the application of the heterogeneous modified sulfonic acid resin catalyst is provided.

[0043] The heterogeneous modified sulfonic acid resin catalyst is suitable for catalyzing the reaction of isoisopentenol and methanol to prepare 3-methoxy-3-methyl-1-butanol.

[0044] Specifically, a method for preparing 3-methoxy-3-methyl-1-butanol, the method comprising the following contents:

[0045] Under the action of the heterogeneous modified sulfonic acid resin catalyst, isoisopentenol and methanol react to generate 3-methoxy-3-methyl-1-butanol.

[0046] Optionally, the reaction adopts the following operating conditions:

[0047] The molar ratio of the isoisopentenol and methanol feed is 1:5-10;

[0048] The reaction is carried out in a tank reactor, and the amount of the heterogeneous modified sulfonic acid resin catalyst is 8-15% of the total mass of methanol and ISPO;

[0049] The reaction temperature is 50-70°C, and the reaction time is 4-6h.

[0050] In the method, the conversion rate of ISPO can be as high as 95wt%, the selectivity of 3-methoxy-3-methyl-1-butanol can be as high as 92wt%, and the selectivity of the main by-product isopentenol methyl ether is as low as 6.5wt%.

[0051] The modified sulfonic acid resin has good stability, and the sulfonic acid group shedding rate can be as low as 0.5wt% per half year, and the service life can be as long as 7000h.

[0052] Compared with the prior art, the technical scheme of the present application has the beneficial effects that:

[0053] (1) The modified sulfonic acid resin catalyst, the introduced -COOH or -SH not only can be used as the functional group of the hydrogel, but also enhances the acidity of the resin catalyst, and the conversion rate of isoisopentenol is increased from 90wt% to 95wt%. After loading the hydrogel, due to the bonding effect of -NH2 in the hydrogel and the sulfonic acid group and the adhesion of the hydrogel itself, the sulfonic acid group of the obtained catalyst is less likely to fall off, and the sulfonic acid group shedding rate of the modified sulfonic acid resin catalyst is decreased from 10wt% per half year to 0.5wt% per half year, and the service life of the modified resin is extended to 7000h.

[0054] (2) due to the decrease of the sulfonic group shedding rate, the reactor outlet presents a slightly acidic environment, the subsequent rectification separation tower reactor tower 3-methoxy-3-methyl-1-butanol side reaction is greatly inhibited, the rectification yield of 3-methoxy-3-methyl-1-butanol is increased from 85wt% to 95wt% before the resin modification, the economic benefit of industrialization is greatly improved. At the same time, the process of using lye to neutralize the sulfonic group is avoided, the system does not generate salt, the risk of rectification tower plugging is reduced, the process of recovering 3-methoxy-3-methyl-1-butanol in the scraped evaporator recovery tower is avoided, the process is simplified, and the energy consumption is greatly reduced. DETAILED DESCRIPTION

[0055] In order to facilitate the understanding of the present application, the present application will be further described below in conjunction with examples. It should be understood that the following examples are only for better understanding of the present application, and do not mean that the present application is limited to the following examples.

[0056] The applicant declares that the present application is described by the above examples to illustrate the detailed process equipment and process flow of the present application, but the present application is not limited to the above detailed process equipment and process flow, that is, it does not mean that the present application must rely on the above detailed process equipment and process flow to be implemented. Any improvement on the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific mode, etc. of the present application, all fall within the scope of protection and disclosure of the present application.

[0057] It should be noted that the endpoints of the ranges and any values disclosed in this specification are not limited to the precise values stated. These ranges and values should be construed as being approximate. For ranges, the endpoints are provided as a separate point for use in the claims. For example, a range from 1 to 6 should be interpreted to include not only 1 to 6 and also 2 to 5, 3 to 4, etc.

[0058] 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 term "and / or" as used herein refers to and encompasses any and all possible combinations of one or more of the associated listed items.

[0059] Unless otherwise specified, the reagents, materials and instruments used in the following examples are conventional reagents, conventional materials and conventional instruments in the art, which can be obtained by commercial purchase, and the reagents involved can also be synthesized by conventional methods in the art.

[0060] In the examples and comparative examples of the present application, the main raw materials used are as follows,

[0061] Sulfomethylated polyacrylamide is prepared according to the existing method, and the specific steps are as follows:

[0062] The polyacrylamide (PAM), formaldehyde, sodium bisulfite and sodium hydroxide are all purchased from Araldin as finished products. (1) A certain amount of PAM is dissolved in deionized water to prepare an 8wt% solution for standby use; (2) the pH of the above solution is adjusted to 9-10 by using sodium hydroxide; (3) under stirring, formaldehyde (formaldehyde:PAM amide group = 1:1 mol) is added to the PAM aqueous solution, the solution temperature is kept at 60 DEG C, and sodium bisulfite (sodium bisulfite:amide group = 1:1 mol) is added dropwise; (4) the temperature is kept at 60 DEG C for 6h; (5) after the reaction is completed, it is cooled to room temperature, an excess of ethanol (2-2.5 times the mass of the aqueous solution) is added to precipitate the gel, and after multiple ethanol washes, it is naturally dried to obtain the final sulfomethylated polyacrylamide hydrogel.

[0063] The eutectic solvent is prepared as follows:

[0064] According to the molar ratio of choline chloride / urea (1:2 mol), choline chloride / glycol (1:2 mol) and choline chloride / glycerol (1:2 mol), the raw materials used are accurately weighed and purchased from Araldin as finished products. A magnetic stirrer is added to a 5ml sample bottle, and the mixture is stirred and mixed at 80 DEG C in a constant temperature heater for 2h. After the final clear and transparent liquid is obtained, it is cooled to room temperature and sealed for standby use.

[0065] The main analysis methods used in the examples and comparative examples of the present application are as follows:

[0066] The loading rate of the hydrogel, the ISPO conversion rate, the selectivity of the product and the by-product isoprenol methyl ether: after the sulfonic acid resin is loaded with the hydrogel, the residual amino content of the filtered filtrate is tested by gas chromatography, and the loading rate of the hydrogel in the sulfonic acid resin is calculated.

[0067] After the content of ISPO and the product and by-product in the reaction solution is analyzed by gas chromatography, the content is calculated, and the gas chromatography test conditions are as follows: chromatograph instrument: Agilent 7890A, chromatograph column type: DP-5, inner diameter: 320.00 mu m, length: 25.0 m, maximum temperature: 325.0 DEG C. Carrier gas: high-purity nitrogen, split ratio: 1:60, detector temperature 280 DEG C, temperature rising program: first 40 DEG C for 4 minutes, then 15 DEG C / min to 280 DEG C for 10 minutes, total running time 30 minutes.

[0068] Sulfonic group shedding rate: the resin before use and after use for half a year is taken, and the test reagent is tested according to the treatment method specified in GB / T 8144-2008.

[0069] Example 1:

[0070] Preparation of heterogeneous modified sulfonic acid resin catalyst A:

[0071] In a three-necked flask, 100 g of water, 10 g of styrene, 20 g of divinylbenzene, 1 g of acrylic acid, 1 g of n-hexane, 0.1 g of tert-butyl peroxide (2-ethylhexanoate), and 0.01 g of polyvinyl alcohol (PVA-1799) were added and stirred to perform a suspension copolymerization reaction. The reaction pressure was controlled to be 10 kPaG and the reaction temperature was controlled to be 50°C in the initial stage of the reaction. After 2 h of reaction, the reaction temperature was increased to 80°C and the reaction was continued for 3 h. After the reaction was completed, the temperature was decreased to room temperature, and the resin particle matrix was obtained by filtering with a 20-μm filter. The resin particle matrix was repeatedly washed with an aqueous solution to remove impurities on the surface, and then dried to obtain the resin particle matrix.

[0072] In a three-necked flask, 400 g of choline chloride / urea deep eutectic solvent was added, and 0.2 g of sulfomethylated polyacrylamide hydrogel and 20 g of the resin particle matrix were added and stirred to react. The reaction temperature was controlled to be constant at 25°C, and the reaction time was 2 h. After the reaction was completed, the reaction solution was filtered with a 20-μm filter, and then repeatedly washed with acetone and water, and then dried to obtain a resin particle matrix loaded with the hydrogel. The content of the remaining amide group in the solution was analyzed by gas chromatography, and the loading rate of the hydrogel in the resin particle matrix was calculated to be 10 wt%.

[0073] In a reaction kettle, 4 g of chlorosulfonic acid, 100 g of 98 wt% concentrated sulfuric acid, and 20 g of the resin particle matrix loaded with the hydrogel were added, and the reaction pressure was controlled to be 10 kPaG. After stirring at 50°C for 2 h, the temperature was decreased to room temperature. The reaction solution was filtered with a 20-μm filter, and then repeatedly washed with water and acetone, and then dried to obtain the heterogeneous modified sulfonic acid resin catalyst A.

[0074] Example 2:

[0075] Preparation of heterogeneous modified sulfonic acid resin catalyst B:

[0076] In a three-necked flask, 100 g of water, 10 g of styrene, 20 g of divinylbenzene, 3 g of cinnamic acid, 5 g of dichloroethane, 0.5 g of benzoyl peroxide, and 0.05 g of gelatin were added and stirred to perform a suspension copolymerization reaction. The reaction pressure was controlled to be 15 kPaG and the reaction temperature was controlled to be 55°C in the initial stage of the reaction. After 2.5 h of reaction, the reaction temperature was increased to 90°C and the reaction was continued for 5 h. After the reaction was completed, the temperature was decreased to room temperature, and the resin particle matrix was obtained by filtering with a 20-μm filter. The resin particle matrix was repeatedly washed with an aqueous solution to remove impurities on the surface, and then dried to obtain the resin particle matrix.

[0077] Into a three-necked flask, 500 g of choline chloride / ethylene glycol deep eutectic solvent was added, and 1 g of chitosan and 20 g of resin particle matrix were added, and the reaction was stirred, the reaction temperature was controlled at 40°C, and the reaction time was 3 h. After the reaction was completed, a 20-μm filter was used for filtration, and repeated washing with acetone and then water was performed, and drying was performed to obtain a resin particle matrix loaded with hydrogel. The content of the remaining amide group in the solution was analyzed by gas chromatography, and the loading rate of the hydrogel in the resin particle matrix was calculated to be 9.6 wt%.

[0078] Into a reaction kettle, 6 g of chlorosulfonic acid, 160 g of 98 wt% concentrated sulfuric acid, and 20 g of the resin particle matrix loaded with hydrogel were added, and the reaction pressure was controlled at 15 kPaG, and after stirring at 80°C for 4 h, the temperature was lowered to room temperature. After filtration with a 20-μm filter, repeated washing with water and acetone was performed, and drying was performed to obtain a heterogeneous modified sulfonic acid resin catalyst B.

[0079] Example 3:

[0080] Preparation of a heterogeneous modified sulfonic acid resin catalyst C:

[0081] Into a three-necked flask, 100 g of water, 10 g of styrene, 20 g of divinylbenzene, 5 g of allyl mercaptan, 9 g of toluene, 1 g of azobisisobutyronitrile, and 0.1 g of methyl cellulose were added, and the reaction was stirred to perform suspension copolymerization. The reaction pressure was controlled at 20 kPaG at the initial stage of the reaction, and the reaction temperature was 60°C. After 3 h of reaction, the temperature was increased to 100°C, and the reaction was continued for 7 h. After the reaction was completed, the temperature was lowered to room temperature, a 20-μm filter was used for filtration, repeated washing with an aqueous solution was performed to remove impurities on the surface, and drying was performed to obtain a resin particle matrix.

[0082] Into a three-necked flask, 600 g of choline chloride / glycerol deep eutectic solvent was added, and 2 g of polylysine hydrogel and 20 g of a resin particle matrix were added, and the reaction was stirred, the reaction temperature was controlled at 60°C, and the reaction time was 4 h. After the reaction was completed, a 20-μm filter was used for filtration, and repeated washing with acetone and then water was performed, and drying was performed to obtain a resin particle matrix loaded with hydrogel. The content of the remaining amide group in the solution was analyzed by gas chromatography, and the loading rate of the hydrogel in the resin particle matrix was calculated to be 9.2 wt%.

[0083] Into a reaction kettle, 10 g of chlorosulfonic acid, 200 g of 98 wt% concentrated sulfuric acid, and 20 g of the resin particle matrix loaded with hydrogel were added, and the reaction pressure was controlled at 20 kPaG, and after stirring at 100°C for 6 h, the temperature was lowered to room temperature. After filtration with a 20-μm filter, repeated washing with water and acetone was performed, and drying was performed to obtain a heterogeneous modified sulfonic acid resin catalyst C.

[0084] Comparative Example 1:

[0085] The heterogeneous modified sulfonic acid resin catalyst A' was prepared under the same conditions as in Example 1, except that no acrylic acid copolymerization agent was added in Example 1, and other synthesis conditions and material amounts were consistent with those described in Example 1. The hydrogel loading rate in the obtained sulfonic acid resin catalyst was only 1 wt%.

[0086] Comparative Example 2:

[0087] The heterogeneous modified sulfonic acid resin catalyst B' was prepared under the same conditions as in Example 1, except that dichloroethane (non- eutectic solvent) was used as the solvent to synthesize the sulfonic acid resin catalyst particle matrix loaded with hydrogel, and other synthesis conditions and material amounts were consistent with those described in Example 1. The hydrogel loading rate in the obtained sulfonic acid resin catalyst was only 5 wt%.

[0088] Application Example:

[0089] The heterogeneous modified sulfonic acid resin catalysts A-C prepared in Examples 1-3, and the heterogeneous modified sulfonic acid resin catalysts A' and B' prepared in Comparative Examples 1-2, were used to prepare 3-methoxy-3-methyl-1-butanol, and the results are shown in Table 1.

[0090] The preparation method is as follows:

[0091] A kettle reactor was used to prepare 3-methoxy-3-methyl-1-butanol. The reactor was loaded with 12.5 g of the modified sulfonic acid resin catalysts A-C and A' and B' described above, 26.48 g of ISPO, and 98.53 g of methanol. A water bath was used to maintain the reaction temperature at 60°C, and constant temperature stirring was performed for 5 h. After the reaction was completed, the reaction liquid was allowed to return to room temperature, a 20 μm filter was used to separate the modified sulfonic acid resin particles, and the separated catalyst was washed and then used in batch reactions to test the service life of the catalyst and the sulfonic acid group shedding rate. The batch use time was 8000 h. Gas chromatography was used to analyze the contents of 3-methoxy-3-methyl-1-butanol and ISPO in the filtered reaction liquid, and the conversion rate of ISPO and the selectivity of the product were calculated.

[0092] Table 1 Comparison of the effects of the self-prepared modified sulfonic acid resin catalysts in Examples and Comparative Examples on the synthesis of 3-methoxy-3-methyl-1-butanol

[0093] It is easily understood that the above examples are merely examples for clear illustration, and are not meant to limit the present application. Based on the above description, other different forms of changes or variations can be made by those of ordinary skill in the art. Here, it is not necessary or possible to exhaust all the embodiments. The obvious changes or variations derived therefrom are still within the protection scope of the present application.

Claims

1. A process for the preparation of a heterogeneous modified sulfonic acid resin catalyst, characterized in that, Comprising the following steps: (1) styrene and divinylbenzene as polymerization monomers, a compound containing double bond and carboxyl and / or thiol group, a pore-forming agent, an initiator, a dispersing agent, and water are used to perform a suspension copolymerization reaction, then filtered, dried to obtain a sulfonic acid resin particle matrix; (2) the sulfonic acid resin particle matrix of step (1) is mixed with a eutectic solvent and a hydrogel containing amino group to perform a reaction, then filtered, dried to obtain a sulfonic acid resin particle matrix loaded with hydrogel; (3) the sulfonic acid resin particle matrix loaded with hydrogel of step (2) is mixed with chlorosulfonic acid and concentrated sulfuric acid to perform a sulfonation reaction, then filtered, washed, dried to obtain the heterogeneous modified sulfonic acid resin catalyst.

2. The production method according to claim 1, characterized by, The compound containing double bond and carboxyl and / or thiol group in step (1) as a copolymerization agent meets the following characteristics: The number of C atoms is 3-7, containing one double bond, containing carboxyl and / or thiol functional groups; optionally, the compound containing double bond and carboxyl and / or thiol group is at least one of acrylic acid, methacrylic acid, cinnamic acid, allyl mercaptan, 4-vinylbenzyl mercaptan, preferably acrylic acid; and / or The amount of divinylbenzene added in step (1) is 1-4 times the mass of styrene; and / or The amount of the compound containing double bond and carboxyl and / or thiol group added in step (1) is 10-50% of the mass of styrene.

3. The production method according to claim 1 or 2, characterized by, The pore-forming agent in step (1) is selected from at least one of dichloroethane, toluene, xylene, n-hexane, and polyethylene glycol, preferably n-hexane; optionally, the amount of the pore-forming agent added is 10-90% of the mass of styrene; and / or The initiator in step (1) is selected from at least one of benzoyl peroxide, tert-butyl peroxy(2-ethylhexanoate), and azobisisobutyronitrile, preferably tert-butyl peroxy(2-ethylhexanoate); optionally, the amount of the initiator added is 1-10% of the mass of styrene; and / or The dispersing agent in step (1) is selected from at least one of polypropylene glycol, gelatin, and methyl cellulose, preferably polypropylene glycol; optionally, the amount of the dispersing agent added is 0.1-1% of the mass of styrene; and / or The amount of water added in step (1) is 10-20 times the mass of styrene.

4. The production method according to any one of claims 1 to 3, characterized by, The suspension copolymerization reaction in step (1) is carried out at a reaction temperature of 50-100℃ and a reaction time of 5-10h; Optionally, the suspension copolymerization reaction is carried out in stages, first at 50-60℃ for 2-3h, then heated to 80-100℃ for continued reaction for 3-7h; Optionally, the suspension copolymerization reaction is carried out at a micro-positive pressure, preferably 10-20kPaG.

5. The method of any one of claims 1-4, wherein the method further comprises, The eutectic solvent in step (2) is a quaternary ammonium salt eutectic solvent: at least one of choline chloride / urea, choline chloride / ethylene glycol, choline chloride / glycerol, choline chloride / lactic acid, and choline chloride / oxalic acid; preferably, the eutectic solvent is choline chloride / urea eutectic solvent; Optionally, the amount of the eutectic solvent added is 20-30 times the mass of the sulfonic acid resin particle matrix.

6. The method of any one of claims 1-5, wherein, The amino-containing hydrogel in step (2) is at least one of chitosan, sulfomethylated polyacrylamide and polylysine, preferably sulfomethylated polyacrylamide; optionally, the amino-containing hydrogel is added in an amount of 1-10% by mass of the sulfonic acid resin particle matrix; and / or The reaction in step (2) is carried out at a temperature of 25-60°C for 2-4 hours; optionally, the reaction is carried out under a micro-positive pressure, preferably 10-20 kPaG.

7. The method of any one of claims 1-6, wherein, The amount of chlorosulfonic acid added in step (3) is 20-50% by mass of the sulfonic acid resin particle matrix loaded with the hydrogel; and / or The amount of concentrated sulfuric acid added in step (3) is 5-10 times by mass of the sulfonic acid resin particle matrix loaded with the hydrogel; optionally, the concentration of the concentrated sulfuric acid is 95-98 wt%; and / or The sulfonation reaction in step (3) is carried out at a temperature of 50-100°C for 2-6 hours.

8. A heterogeneous modified sulfonic acid resin catalyst prepared by the preparation method of any one of claims 1-7.

9. Use of a heterogeneous modified sulfonic acid resin catalyst prepared by the preparation method of any one of claims 1-7. Preferably, the heterogeneous modified sulfonic acid resin catalyst is suitable for catalyzing the reaction of isoisopentenol and methanol to prepare 3-methoxy-3-methyl-1-butanol.

10. A process for the preparation of 3-methoxy-3-methyl-1-butanol, characterized in that, The method is a reaction of isoisopentenol and methanol to prepare 3-methoxy-3-methyl-1-butanol under the action of the heterogeneous modified sulfonic acid resin catalyst prepared by the preparation method of any one of claims 1-7.

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