CN115010842B - Fluorine-containing strong-alkaline anion resin catalyst, preparation method thereof and preparation method of hydroxyethyl (meth) acrylate - Google Patents

Fluorine-containing strong-alkaline anion resin catalyst, preparation method thereof and preparation method of hydroxyethyl (meth) acrylate Download PDF

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CN115010842B
CN115010842B CN202210558631.XA CN202210558631A CN115010842B CN 115010842 B CN115010842 B CN 115010842B CN 202210558631 A CN202210558631 A CN 202210558631A CN 115010842 B CN115010842 B CN 115010842B
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catalyst
fluorine
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郑京涛
李俊平
黎源
张永振
李晶
孙亚明
王漭
初晓东
温道宏
曹文健
张礼昌
胡展
康学青
李盼
刘岩
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Wanhua Chemical Group Co Ltd
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    • C08F214/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
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Abstract

The invention aims to provide a fluorine-containing strong-alkali anion resin catalyst and a preparation method thereof, and a method for preparing (methyl) hydroxyethyl acrylate by adopting the catalyst.

Description

Fluorine-containing strong-alkaline anion resin catalyst, preparation method thereof and preparation method of hydroxyethyl (meth) acrylate
Technical Field
The invention belongs to the field of organic compound preparation, and in particular relates to a fluorine-containing strong-alkaline anion resin catalyst, a preparation method and application thereof, and a preparation method of hydroxyethyl (meth) acrylate.
Background
Hydroxyethyl (meth) acrylate, abbreviated as HE (M) A. The use of hydroxyethyl (meth) acrylate in thermosetting coatings is particularly important. On the one hand, hydroxy (methyl) acrylic acid hydroxyethyl ester can be prepared into acrylic resin containing hydroxyl through homopolymerization or copolymerization with other vinyl monomers, and the resin can form a double-component thermosetting coating with polyfunctional crosslinking components such as HDI trimer, melamine formaldehyde and the like which can react with the hydroxyl; on the other hand, hydroxyethyl (meth) acrylate can be prepared from hydroxyl groups, isocyanate, epoxy resin and the like to obtain prepolymer terminated with unsaturated double bonds, and can be cured under the external conditions of ultraviolet and the like, which is the principle of UV curing resin and coating. Both are very important applications of hydroxyethyl (meth) acrylate and are currently in the most important position in the coating industry.
The hydroxy (meth) acrylate may be obtained by direct esterification of (meth) acrylic acid and ethylene oxide, or may be obtained by transesterification of methyl (meth) acrylate with ethylene glycol. The current method for industrially producing (methyl) hydroxyethyl acrylate mainly adopts (methyl) acrylic acid and ethylene oxide to react and synthesize under the condition of homogeneous catalyst, but the process method has the defect that the catalyst is difficult to recycle and reuse, and simultaneously, the process waste water is large, and the environment is polluted.
CN201810058378.5 provides a preparation method of hydroxyethyl (meth) acrylate, at a certain temperature, (meth) acrylic acid and ethylene oxide react in a tubular reactor in the presence of a catalyst and a polymerization inhibitor to obtain a crude hydroxyethyl (meth) acrylate, wherein the catalyst comprises hexamethylenetetramine and imidazole, the polymerization inhibitor comprises phenothiazine and para-hydroxyanisole, and the homogeneous catalyst hexamethylenetetramine and imidazole are used in the reaction process, so that recycling is difficult, and environmental pollution is easy to cause;
CN201410334216.1 provides a preparation method of hydroxyethyl (meth) acrylate, which adopts a combined process of a three-stage tubular reactor and a tower reactor: firstly mixing a catalyst, a polymerization inhibitor and (methyl) acrylic acid until solids are dissolved, then mixing the mixture with part of propylene oxide, then entering a first tubular reactor for reaction, mixing a reaction liquid flowing out of the first tubular reactor with a certain amount of ethylene oxide, entering a second tubular reactor for reaction, mixing the reaction liquid flowing out of the second tubular reactor with a certain amount of ethylene oxide, entering a third tubular reactor, ageing the reaction liquid flowing out of the third tubular reactor through a section of adiabatic tower reactor, and collecting the product liquid. The catalyst used is one or more of an amine compound, an iron compound and a chromium compound, which are homogeneous catalysts, are difficult to recycle and can easily cause environmental pollution;
CN201310194477.3 provides a method for synthesizing hydroxyethyl methacrylate, which comprises adding methacrylic acid into a reaction kettle, adding magnetic zeolite molecular sieve, stirring, adding ethylene oxide, heating the reaction kettle for a certain temperature, reacting for 2-3 h, distilling to obtain hydroxyethyl methacrylate, wherein the method is an intermittent synthesis process, continuous production and high labor intensity.
CN201110224818.8 provides a method for synthesizing hydroxyethyl methacrylate, in a four-mouth flask, adding ferric oxide as catalyst, heating to 80-85 deg.c, then carrying out nitrogen substitution, after ferric oxide is completely dissolved in methacrylic acid, introducing ethylene oxide gas, introducing ethylene oxide for 3.5-4.5 h, then continuously reacting for 0.5-1.5 h, obtaining crude hydroxyethyl methacrylate reaction solution, the catalyst used in the method is ferric oxide, it is difficult to recycle, and at the same time, polymerization effect of polymerization inhibitor para-hydroxyanisole is poor at this high temperature and in nitrogen atmosphere, methacrylic acid and hydroxyethyl methacrylate are easy to polymerize, and normal production is affected.
CN201810058913.7 provides a continuous production method of hydroxyethyl methacrylate, the mixed solution of methacrylic acid, ferric chloride serving as a catalyst and a polymerization inhibitor ZJ-705 is fed into a tubular reactor, ethylene oxide is introduced and ring-opening reaction is carried out at 60-80 ℃ and 0.25-1.0 MPaG, so that crude hydroxyethyl methacrylate reaction solution is obtained.
CN201811365889.8 provides a preparation method of hydroxyethyl methacrylate, which comprises dissolving a catalyst and a polymerization inhibitor a in methacrylic acid to form a feed liquid a, and dissolving ethylene oxide in a dispersing agent to form a feed liquid B; according to the different temperatures, the micro-channel reaction device is divided into a high-temperature control section and a low-temperature control section, and the feed liquid A and the feed liquid B are continuously fed into the micro-channel reaction device to sequentially flow through the high-temperature control section and the low-temperature control section, so that the feed liquid A and the feed liquid B flow in the micro-channel reaction device and perform ring-opening reaction, and the adopted catalysts are iron catalysts and chromium catalysts, and are one or a mixture of more than two of iron methacrylate, iron acrylate, iron hydroxide, iron sulfate, iron nitrate, iron acetate, chromium methacrylate, chromium trioxide, chromium picolinate and chromium formate, so that a pipeline filter is easy to block, and the recycling is difficult.
CN201210012409.6 provides a process for preparing hydroxyethyl methacrylate, which adopts a ring-opening addition process to prepare, and the catalyst is selected from chromium compounds such as chromium methacrylate, chromium chloride, chromium oxaloacetate, chromium acetate, sodium methyl dichromate, chromium methacrylate and the like, iron catalysts such as ferric chloride, iron powder, ferric formate, ferric methacrylate and the like, and chromium catalysts, which are easy to block a pipeline filter and difficult to recycle.
CN201811244356.4 provides a method for producing hydroxyethyl methacrylate by transesterification, which uses methyl methacrylate and ethylene glycol as raw materials, p-toluenesulfonic acid as catalyst, phenothiazine as polymerization inhibitor, and reacts at 100-120 deg.c to obtain target product.
CN201310756127.1 provides a process for preparing perfluorinated quaternary ammonium type strongly basic anion exchange resins, which employs chloromethylated polystyrene to react with perfluorinated tertiary amines and trimethylamine simultaneously to prepare strong base anion exchange resins. According to the invention, perfluorinated tertiary amine and trimethylamine are simultaneously used as an amination agent, and fluorine is introduced, so that the bonding force of the bond between alkyl benzylamine and alkyl N-C is enhanced, amino is not easy to fall off, the resin can be used at a higher temperature, but the electronegativity of the fluorine is higher, the catalytic activity of a quaternary ammonium salt group is reduced, and the wide application of the resin in the field of catalysts is limited.
Based on the defects of the catalyst of the traditional direct ring-opening reaction of (methyl) acrylic acid and ethylene oxide, development of a novel reaction form and catalyst type continuous production process is needed to replace the prior art, continuous and stable production of hydroxyethyl (meth) acrylate is realized, the environment is protected and the safety is improved, meanwhile, the operation is reduced, and the labor is saved.
Disclosure of Invention
The invention aims to provide a catalyst for direct ring-opening reaction of (methyl) acrylic acid and ethylene oxide and a preparation method thereof, wherein active groups of the catalyst are not easy to fall off, and compared with the existing catalyst, the catalyst has long service life and stable catalyst activity.
The invention also aims to provide a preparation method of the hydroxyethyl (meth) acrylate, which can realize the advantages of continuous production operation of the hydroxyethyl (meth) acrylate, high product selectivity, small environmental pollution, lower production cost, low labor intensity and the like by combining the sectional fixed bed reactor and the catalyst dilution scheme.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a fluorine-containing strong-alkaline anion resin catalyst, which has at least one of the following structural formulas:
Wherein m and n are each independently 5 to 20, preferably 7 to 16; styrene and perfluoroolefin units in the catalyst are randomly copolymerized.
In the present invention, the fluorine-containing strongly basic anionic resin catalyst preferably has the following structure
In the invention, the number average molecular weight of the fluorine-containing strong-alkaline anion resin catalyst is 2600-4000, preferably 2800-3500;
in the invention, the fluorine content of the fluorine-containing strong-alkali anion resin catalyst is 10 to 60wt%, preferably 15 to 30%
In the invention, the content of nitrogen element in the fluorine-containing strong-alkaline anion resin catalyst is 1-6wt%, preferably 3-5wt%.
The invention also provides a preparation method of the fluorine-containing strong-alkaline anion resin catalyst, which comprises the following steps:
(1) Polymerizing styrene, divinylbenzene and perfluoroolefin to prepare copolymer white balls;
(2) Adding a chloromethylation reagent, preferably chloromethyl methyl ether, into the copolymer white balls obtained in the step (1) to carry out chloromethylation reaction so as to prepare chloromethylation white balls;
(3) And (3) adding an amination reagent, preferably a methanol solution of trimethylamine, into the chloromethylated white balls obtained in the step (2) to perform amination reaction to obtain the fluorine-containing strong-alkali anion resin catalyst.
In the step (1) of the invention, the polymerization reaction is carried out at a temperature of 70-120 ℃, preferably 80-110 ℃ for 2-15 hours, preferably 7-10 hours, and at a pressure of 1-6 MPaG, preferably 2-5 MPaG, and the pressure is released to normal pressure after the reaction is completed.
The molar ratio of the styrene to the divinylbenzene is 4-7:1, preferably 5-6:1.
The molar ratio of the perfluoroolefin to the divinylbenzene is 5-8:1, preferably 6-7:1.
The perfluoroolefin is at least one of tetrafluoroethylene and/or hexafluoropropylene, preferably tetrafluoroethylene.
Preferably, the polymerization reaction further comprises a post-treatment process such as preparation of oil beads after completion.
In the step (2) of the present invention, the chloromethylation reaction is carried out at a temperature of 20 to 50 ℃, preferably 30 to 60 ℃ for 3 to 15 hours, preferably 5 to 10 hours.
The mass ratio of chloromethyl methyl ether to the copolymerized white balls is 0.5-3:1, preferably 1-2:1.
Preferably, the chloromethylation reaction further comprises a post-treatment process such as methanol washing and the like after the chloromethylation reaction is completed.
In the step (3) of the present invention, the amination is carried out at a temperature of 20 to 70 ℃, preferably 30 to 60 ℃ for a time of 5 to 20 hours, preferably 8 to 15 hours.
The mass ratio of the trimethylamine methanol solution to the chloromethylated white balls is 1-4:1, preferably 2-3:1.
Preferably, the amination reaction further comprises post-treatment processes such as adding acid to adjust the pH value after the amine balls are obtained.
Preferably, the polymerization reaction of step (1) and/or the amination reaction of step (3) are carried out in a nitrogen atmosphere.
The invention also aims to provide a method for preparing the hydroxyethyl (meth) acrylate by using the fluorine-containing strong-base anion resin catalyst.
In the invention, the sectional type fixed bed tubular reactor is adopted, more than three sections of fixed bed tubular reactors are preferred, and the upper, middle and lower three sections of fixed bed tubular reactors are more preferred, so that the content of the byproduct DEGMA can be effectively controlled; if the residence time is prolonged, the selectivity of the by-product DEGMA is improved, and the selectivity of the product is affected.
According to the invention, by controlling the concentration of different sections of catalysts in the sectional type fixed bed tubular reactor, the reaction (heat) in each part of the inside of the fixed bed tubular reactor is uniformly distributed, and the selective rise of a byproduct DEGMA caused by overhigh local temperature is avoided.
In the invention, the segmented tubular fixed bed reactor adopts blank resin pellets to dilute catalysts in different segments, and the mixing proportion of diluted catalysts filled in the uppermost segment is the blank resin pellets: fluorine-containing strong-base anionic resin catalyst=1 to 4:1 (volume ratio), preferably 2.5 to 3:1 (volume ratio); the mixing proportion of the diluted catalyst filled in the middle section is that the blank resin pellets are: fluorine-containing strong-base anionic resin catalyst=1 to 4:1 (volume ratio), preferably 2 to 2.5:1; the mixing proportion of the diluted catalyst filled in the lowest stage is blank resin pellets: the fluorine-containing strongly basic anionic resin catalyst=1 to 4:1 (volume ratio), preferably 1.5 to 2:1 (volume ratio).
The catalyst concentration of the lower section of the sectional type tubular fixed bed reactor is preferably higher than that of the upper section, materials are fed from top to bottom, the concentration of raw materials is gradually reduced from top to bottom, and in order to increase the reaction rate, the catalyst concentration of the lower section of the reactor is increased to increase the reaction rate, so that the conversion rate of the raw materials and the product yield are increased.
In the sectional type tubular fixed bed reactor, the ratio (volume ratio) of the catalyst filled in the uppermost section to the catalyst filled in the lowermost section in the sectional type tubular fixed bed reactor is 0.2-2:1, the ratio of the catalyst filled in the middle section to the catalyst filled in the lowermost section is (0.1n+0.2) to 1:1, wherein n=2, 3, 4, 5, 6, 7, 8 and the like, and n represents the number of reaction sections from the uppermost section to the lower.
Preferably, the volume ratio of the catalyst filled in the uppermost stage to the catalyst filled in the middle stage and the catalyst filled in the lowermost stage in the segmented tubular fixed bed reactor is (0.3-1): 1 (0.5-1), preferably (0.4-0.7): 0.5-0.9): 1 (volume ratio).
In the invention, in order to better realize the uniform distribution of the reaction heat of the sectional type fixed bed tubular reactor, heat exchange is carried out by using a heat exchange medium, and the heat exchange medium used in different sections is selected from one or more of conduction oil head NOT 66, conduction oil head NOT 55, conduction oil WD-55 and dimethyl silicone oil with different temperatures.
Preferably, the temperature of the heat exchange medium adopted by the uppermost stage jacket of the fixed bed tubular reactor is 30-80 ℃, the temperature of the heat exchange medium adopted by the lowermost stage jacket is 40-90 ℃, the temperature of the heat exchange medium adopted by the middle stage jacket is (29+n) - (79+n) DEG C, wherein n=2, 3, 4, 5, 6, 7, 8 and the like, and n represents the number of the reaction stages from the uppermost stage to the lower.
In the invention, the polymerization inhibitor is at least one of ZJ-701, ZJ-705, beijing Mo Li 5105, beijing Mo Li 5115 and Beijing Wanli 5125, preferably ZJ-701;
in the invention, the mass ratio of the polymerization inhibitor to the (methyl) acrylic acid is 0.0001-0.005: 1, preferably 0.0005 to 0.001:1, more preferably 0.0006 to 0.0008:1.
In the present invention, the molar ratio of (meth) acrylic acid to ethylene oxide is 0.1 to 3:1, preferably 1.0 to 2:1, more preferably 1.01 to 1.2:1;
in the present invention, mixing in a fixed bed tubular reactorThe volume space velocity of the material feeding is 0.2-3 h -1 Preferably 0.6 to 2.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the And/or the reaction hot spot temperature in the fixed bed tubular reactor is 50 to 90 ℃, preferably 60 to 80 ℃; the reaction pressure is 0.2 to 1.0MPaG, preferably 0.4 to 0.7MPaG.
In the invention, compressed nitrogen is required to be continuously introduced in the reaction process, and the pressure of a reaction system can be maintained by the compressed nitrogen; preferably, the maximum pressure of compressed nitrogen required to replenish the system pressure is 0.1 to 1.0MPaG, more preferably 0.4 to 0.7MPaG.
The technical scheme of the invention has the beneficial effects that:
1. the fluorine-containing strong-alkalinity anion resin catalyst is adopted, the catalyst activity is high, the service life of the catalyst is long, the reaction condition is mild, the selectivity of the (methyl) hydroxyethyl ester prepared by continuous production is up to more than 98 percent, and the conversion rate of the (methyl) acrylic acid is up to more than 99.9 percent.
2. The sectional fixed bed reactor, preferably an upper, middle and lower three-section fixed bed tubular reactor, is adopted to realize continuous production, and has low production cost and low labor intensity;
3. the concentration of the catalyst at different sections is controlled, so that the generated reaction heat in the reaction process can be removed in time more uniformly in the whole reactor bed, and the conditions of higher selectivity and lower product selectivity of the byproduct DEGMA caused by overhigh local temperature of the bed are avoided.
4. The production process is free of waste water, environment-friendly, and can be used for large-scale continuous production of the hydroxyethyl (meth) acrylate.
Drawings
FIG. 1 is a GPC chart of a fluorine-containing strongly basic anion resin catalyst prepared in example 1;
FIG. 2 is a GPC chart of a fluorine-containing strongly basic anion resin catalyst prepared in example 2;
FIG. 3 is a GPC chart of a fluorine-containing strongly basic anion resin catalyst prepared in example 3;
FIG. 4 is a GPC chart of a fluorine-containing strongly basic anionic resin catalyst prepared in example 4;
FIG. 5 is a schematic illustration of the reaction process flow of hydroxyethyl (meth) acrylate according to the present invention; wherein, 1-raw material mixing tank, 2-feed pump, 3-sectional fixed bed reactor, 4-reaction liquid tank, 5-first pipeline, 6-second pipeline, 7-third pipeline, 8-fourth pipeline, 9-fifth pipeline, 10-sixth pipeline, 11-seventh pipeline, 12-eighth pipeline, 13-ninth pipeline, 14-tenth pipeline, 15-eleventh pipeline, 16-twelfth pipeline, 17-thirteenth pipeline.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The invention extends to any novel one, or any novel combination, of the features disclosed in this specification, and to any novel one, or any novel combination, of the steps of the method or process disclosed.
1. The main raw material sources in the examples are:
1. methacrylic acid, wanhua chemical groups Co., ltd., technical grade;
2. acrylic acid, wanhua chemical groups Co., ltd., technical grade;
3. ethylene oxide, wanhua chemical groups Co., ltd., technical grade;
4. Tetrafluoroethylene, dalianda gas limited, industrial grade;
5. hexafluoropropylene, large company, industrial grade;
6. t-butyl hydroperoxide, wanhua chemical group Co., ltd., technical grade;
7. styrene, tianjin Dagu chemical Co., ltd., industrial grade;
8. divinylbenzene, jiangsu Zhengdan chemical industry Co., ltd, technical grade;
9. gelatin, heng shui Hongyuan adhesive Co., ltd, technical grade;
10. methylene blue, shanghai Ala Biotechnology Co., ltd., analytical grade;
11. n-hexane, a chemical industry company, giant bang, yangzhou, technical grade;
12. chloromethyl methyl ether, wuhan Chu Jianghao Yu chemical technology development Co., ltd, industrial grade;
13. trimethylamine methanol solution (33 wt%) was obtained from the company, polyfeng chemical Co., ltd., technical grade, in Changzhou.
2. Product analysis method in the examples:
potentiometric titrators measure the chlorine content of the catalyst, and instrument manufacturers and models: METROHM 905TITRANDO;
physical adsorption instrument for measuring BET value of catalyst, instrument manufacturer and model: MICromerites (U.S.) ASAP 2020;
the elemental analyzer is used for measuring the nitrogen content of the catalyst, and the manufacturer and model of the instrument are as follows: euro Vector (Italy) EA3000;
The molecular weight of the catalyst was measured by gel chromatography (GPC), instrument manufacturer and model: shimadzu (Japan) LC-20AD; a detector: ultraviolet absorption detector/differential refraction detector, light source: SPD-20A D2 lamp, wavelength: 550nm, flow: 0.015mL/min;
the fluorine content of the catalyst is measured by an X-ray fluorescence spectrometer (XRF), and the manufacturer and model of the instrument are as follows: PANalytical (netherlands) Axios mAX; test conditions: rh target-SST light pipe voltage 44kV, current 25mA power 4.0kw, vacuum/He atmosphere, vacuum degree 4pa, goniometer accuracy 0.0025 °;
the gas chromatographic analysis uses a correction factor method, instrument manufacturer and model: island fluid 1020-plus. The analysis method is as follows: type of column: DB-5 (30 x 0.25), carrier gas velocity: 1mL/min, sample injection amount: 0.2 microliter.
As shown in fig. 5, in the case of the upper, middle and lower three-stage fixed bed tubular reactors, the blank resin pellets and the fluorine-containing strong base anion resin catalyst are mixed uniformly in a certain (volume ratio) dilution ratio, and then are charged into the upper, middle and lower stages of the divided fixed bed tubular reactor 3, the (meth) acrylic acid and the ethylene oxide are added into the raw material mixing tank 1 in a certain ratio, then the polymerization inhibitor ZJ-701 is added thereto, finally the raw material mixing tank 1 is supplemented with compressed nitrogen to a certain pressure through the first pipeline 5 and mixed uniformly, the reaction liquid storage tank and the divided fixed bed reactor are supplemented with compressed nitrogen to a reaction pressure through the twelfth pipeline 16, oil baths with different temperatures are respectively charged into the upper, middle and lower stages of the jacket of the tubular reactor through the fourth pipeline 8 and the sixth pipeline 10 and the eighth pipeline 12, and are respectively charged into the raw material mixing liquid in the raw material mixing tank 1 through the fifth pipeline 9 and the seventh pipeline 11 and the ninth pipeline 13, the raw material mixing liquid is charged into the divided fixed bed reactor 3 through the second pipeline 2 for reaction, the reaction liquid is discharged through the tenth pipeline 14 and the obtained through the intermediate pipeline 14, the reaction liquid is discharged through the thirteenth pipeline 17, and the reaction system is kept stable, and the obtained product is discharged through the intermediate pipeline 17.
Example 1:
the preparation method of the fluorine-containing strong-alkaline anion resin catalyst comprises the following steps:
1) Tetrafluoroethylene (60 kg), styrene (52 kg) and divinylbenzene (13 kg) were added to 1m 3 Mixing uniformly in a batching kettle, and adding 2.6kg of tert-butyl hydroperoxide to prepare an oil phase; adding 210kg of pure water, 1kg of gelatin and 0.3kg of a proper amount of methylene blue solution into a reaction kettle, heating to 95 ℃, then dripping oil for reaction for 8.5 hours, cooling to 25 ℃, filtering to obtain beads, and washing, filtering and drying with 320kg of n-hexane to obtain copolymer white balls;
2) Mixing 150kg of chloromethyl methyl ether with the copolymer white ball obtained in the step 1) according to the mass ratio of 1.5:1, heating to 40 ℃, dropwise adding 30kg of anhydrous aluminum chloride for reaction for 7.5 hours, cooling to 25 ℃, filtering to obtain a bead body, washing with 400kg of ethanol, washing, filtering and drying to obtain chloromethylated white balls;
3) Mixing 150kg of anhydrous methanol with the chloromethylated white balls obtained in the step 2) according to the mass ratio of 2:1, heating to 45 ℃, dropwise adding 40kg of 33wt% trimethylamine methanol solution for reaction for 8.5h, cooling to 25 ℃, filtering to obtain beads, soaking the obtained beads in saturated saline solution, adding hydrochloric acid to adjust the pH value to 4, and washing, cleaning and filtering with 300kg of pure water to obtain amine balls, namely the fluorine-containing strong-alkali anion resin catalyst;
The fluorine-containing strongly basic anionic resin catalyst prepared in example 1 (GPC chart is shown in FIG. 1) has a fluorine content of 24.6 wt.% and a nitrogen content of 4.5 wt.% as measured, and has a molecular weight of about 2959 (Mn); styrene and perfluoroolefin units in the catalyst are randomly copolymerized.
Example 2:
the preparation method of the fluorine-containing strong-alkaline anion resin catalyst comprises the following steps:
1) Tetrafluoroethylene (70 kg), styrene (62.4 kg) and divinylbenzene (13 kg) were added to 1m 3 Mixing uniformly in a batching kettle, and adding 3.12kg of tert-butyl hydroperoxide to prepare an oil phase; adding 250kg of pure water, 1.2kg of gelatin and 0.4kg of proper amount of methylene blue solution into a reaction kettle, heating to 100 oiling phase reaction for 9.5h, cooling to 25 ℃, filtering to obtain beads, and washing, filtering and drying with 400kg to obtain copolymer white balls;
2) Mixing 200kg of chloromethyl methyl ether with the copolymer white ball obtained in the step 1) according to the mass ratio of 2:1, heating to 45, dropwise adding 39kg of anhydrous aluminum chloride for reaction for 7.5h, cooling to 25 ℃, filtering to obtain a bead body, washing with 500kg of ethanol, washing, filtering and drying to obtain chloromethylation white ball;
3) Mixing 200kg of anhydrous methanol with the chloromethylated white balls obtained in the step 2) according to the mass ratio of 2:1, heating to 50 ℃, dropwise adding 50kg of 33wt% trimethylamine methanol solution for reacting for 9.5h, cooling to 25 ℃, filtering to obtain beads, soaking the obtained beads in saturated saline solution, adding hydrochloric acid to adjust the pH value to 4, washing with 400kg of pure water, and filtering to obtain amine balls, namely the fluorine-containing strong-alkali anion resin catalyst;
The fluorine-containing strongly basic anion resin catalyst prepared in example 2 (GPC chart is shown in FIG. 2), wherein m is about 9, n is about 10, fluorine content is 26.0wt%, nitrogen content is 4.3wt%, and molecular weight is about 3074 (Mn);
example 3:
the preparation method of the fluorine-containing strong-alkaline anion resin catalyst comprises the following steps:
1) Tetrafluoroethylene (60 kg), styrene (52 kg) and divinylbenzene (13 kg) were added to 1m 3 Mixing uniformly in a batching kettle, and adding 2.6kg of tert-butyl hydroperoxide to prepare an oil phase; adding 210kg of pure water, 1kg of gelatin and 0.3kg of a proper amount of methylene blue solution into a reaction kettle, heating to 105 ℃, then dripping oil for reaction for 9.5 hours, cooling to 25 ℃, filtering to obtain beads, and washing, filtering and drying with 320kg of n-hexane to obtain copolymer white balls;
2) Mixing 250kg of chloromethyl methyl ether with the copolymer white ball obtained in the step 1) according to the mass ratio of 2.5:1, heating to 45 ℃, dropwise adding 34kg of anhydrous aluminum chloride for reaction for 8.5 hours, cooling to 25 ℃, filtering to obtain a bead body, washing with 450kg of ethanol, washing, filtering and drying to obtain chloromethylated white balls;
3) Mixing 250kg of anhydrous methanol with the chloromethylated white balls obtained in the step 2) according to the mass ratio of 2:1, heating to 55 ℃, dropwise adding 40kg of 33wt% trimethylamine methanol solution for reacting for 9.5h, cooling to 25 ℃, filtering to obtain beads, soaking the obtained beads in saturated saline solution, adding hydrochloric acid to adjust the pH value to 4, washing with 500kg of pure water, and filtering to obtain amine balls, namely the fluorine-containing strong-alkali anion resin catalyst;
The fluorine-containing strongly basic anion resin catalyst prepared in example 3 (GPC chart is shown in FIG. 3), wherein m is about 10, n is about 10, fluorine content is 25.5wt%, nitrogen content is 4.1wt%, and molecular weight is about 3271 (Mn);
example 4:
the preparation method of the fluorine-containing strong-alkaline anion resin catalyst comprises the following steps:
1) Hexafluoroethylene (90 kg), styrene (52 kg) and divinylbenzene (13 kg) were added to 1m 3 Mixing uniformly in a batching kettle, and adding 2.6kg of tert-butyl hydroperoxide to prepare an oil phase; adding 240kg of pure water, 1.1kg of gelatin and 0.35kg of proper amount of methylene blue solution into a reaction kettle, heating to 105 ℃, then dripping oil for reaction for 9.5h, cooling to 25 ℃, then filtering to obtain beads, and washing, filtering and drying with 380kg of n-hexane to obtain copolymer white balls;
2) Mixing 250kg of chloromethyl methyl ether with the copolymer white ball obtained in the step 1) according to the mass ratio of 2.5:1, heating to 45 ℃, dropwise adding 34kg of anhydrous aluminum chloride for reaction for 8.5 hours, cooling to 25 ℃, filtering to obtain a bead body, washing with 450kg of ethanol, washing, filtering and drying to obtain chloromethylated white balls;
3) Mixing 250kg of anhydrous methanol with the chloromethylated white balls obtained in the step 2) according to the mass ratio of 2:1, heating to 55 ℃, dropwise adding 40kg of 33wt% trimethylamine methanol solution for reacting for 9.5h, cooling to 25 ℃, filtering to obtain beads, soaking the obtained beads in saturated saline solution, adding hydrochloric acid to adjust the pH value to 4, washing with 400kg of pure water, and filtering to obtain amine balls, namely the fluorine-containing strong-alkali anion resin catalyst;
The fluorine-containing strongly basic anion resin catalyst prepared in example 4 (GPC chart is shown in FIG. 4), wherein m is about 11, n is about 7, fluorine content is 24.1wt%, nitrogen content is 4.6wt%, and molecular weight is about 3556 (Mn);
examples 5 to 10
The blank resin pellets and the fluorine-containing strong basic anionic resin catalyst prepared in example 1 were mixed according to a ratio of 2.5:1 (volume ratio) and then loading into the upper section of a sectional fixed bed tubular reactor 3, uniformly mixing blank resin pellets and the fluorine-containing strong-alkali anion resin catalyst prepared in example 1 according to the dilution ratio of 2:1 (volume ratio), loading into the middle section of the sectional fixed bed tubular reactor 3, uniformly mixing blank resin pellets and the fluorine-containing strong-alkali anion resin catalyst prepared in example 1 according to the dilution ratio of 1.5:1 (volume ratio), loading into the lower section of the sectional fixed bed tubular reactor 3, adding ethylene oxide and methacrylic acid into the raw material mixing tank 1 according to a certain ratio, adding a polymerization inhibitor ZJ-701, wherein the mass ratio of ZJ-701 to methacrylic acid is 0.0006:1, finally supplementing compressed nitrogen to 0.45MPaG to the raw material mixing tank 1 through a first pipeline 5, supplementing compressed nitrogen to 0.45MPaG to the reaction liquid storage tank and the sectional fixed bed tubular reactor through a twelfth pipeline 16, and then pumping the raw material into the fixed bed tubular reactor 3 in the sectional fixed bed tubular reactor 1 according to a certain ratio, and maintaining the space velocity of the raw material mixing tank 1 to be 0.0006 h, and feeding the raw material into the reactor 1 to maintain the space velocity of the reactor to be 0.6h -1 The temperature of hot spots at the middle and lower sections in the reactor is controlled to be 65 ℃ by adjusting the temperature of the oil bath in the fourth pipeline 8, the sixth pipeline 10 and the eighth pipeline 12, the ratio of methacrylic acid to ethylene oxide in the raw material mixed solution is changed, and specific reaction process conditions and reaction results of examples 5-9 are shown in table 1.
TABLE 1
Example number 5 6 7 8 9 10
Ethylene oxide to methacrylic acid (molar ratio) 1.01 1.04 1.08 1.12 1.16 1.2
Upper stage catalyst dilution ratio 2.5:1 2.5:1 2.5:1 2.5:1 2.5:1 2.5:1
Upper stage reaction hot spot temperature/°c 65 65 65 65 65 65
Upper stage oil bath control temperature/°c 45 45 45 45 45 45
Upper stage temperature difference/°c 20 20 20 20 20 20
Dilution ratio of the catalyst in the middle section 2:1 2:1 2:1 2:1 2:1 2:1
Intermediate reaction hot spot temperature/°c 65 65 65 65 65 65
Intermediate section oil bath control temperature/°c 50 50 50 50 50 50
Temperature difference/DEGC of intermediate section 15 15 15 15 15 15
Lower catalyst dilution ratio 1.5:1 1.5:1 1.5:1 1.5:1 1.5:1 1.5:1
Lower reaction hot spot temperature/°c 65 65 65 65 65 65
Lower stage oil bath control temperature/°c 60 60 60 60 60 60
Lower temperature difference/DEGC 5 5 5 5 5 5
By-product DEGMA selectivity/% 1.11 1.2 1.22 1.26 1.31 1.39
Conversion of methacrylic acid/% 99.91 99.92 99.92 99.93 99.91 99.91
Selectivity/% 98.58 98.47 98.55 98.41 98.29 98.23
Example 6 was run stably for 2000 hours, the conversion of methacrylic acid was stabilized at 99.9% or more, the selectivity of hydroxyethyl methacrylate was maintained at 98.0% or more, and the selectivity of by-product DEGMA was maintained at 1.5% or less;
examples 11 to 13
Uniformly mixing the blank resin pellets and the fluorine-containing strong-alkali anion resin catalyst prepared in the example 1 according to the dilution ratio of 2:1 (volume ratio), filling the mixture into the middle section of a segmented fixed bed tubular reactor 3, uniformly mixing the blank resin pellets and the fluorine-containing strong-alkali anion resin catalyst prepared in the example 1 according to the dilution ratio of 1.5:1 (volume ratio), filling the mixture into the lower section of the segmented fixed bed tubular reactor 3, adding ethylene oxide and methacrylic acid into the raw material mixing tank 1 according to the mol ratio of 1.04:1, and adding a polymerization inhibitor ZJ-701 into the mixture, wherein the mass ratio of ZJ-701 to methacrylic acid is 0.0007:1, finally, supplementing compressed nitrogen to 0.50MPaG to the raw material mixing tank 1 through a first pipeline 5 and uniformly mixing, supplementing compressed nitrogen to 0.50MPaG to a reaction liquid storage tank and a sectional fixed bed reactor through a twelfth pipeline 16, then, pumping the raw material liquid in the raw material mixing tank 1 into the sectional fixed bed reactor 3 through a feed pump 2 for reaction, wherein the feeding airspeed is kept to be 0.6h in the feeding process -1 The temperatures of hot spots at the middle and lower sections in the reactor are controlled to be 65 ℃ by adjusting the temperatures of the oil baths in the fourth pipeline 8, the sixth pipeline 10 and the eighth pipeline 12, and the hot spots are filled into the upper section of the sectional fixed bed tubular reactor 3 after the dilution ratio of the blank resin pellets and the fluorine-containing strong-alkali anionic resin catalyst is adjusted and uniformly mixed, wherein specific reaction process conditions and reaction results in examples 11 to 13 are shown in table 2.
TABLE 2
Example number 11 12 13
Ethylene oxide to methacrylic acid (molar ratio) 1.04 1.04 1.04
Upper stage catalyst dilution ratio 2.55:1 2.75:1 3.0:1
Upper stage reaction hot spot temperature/°c 65 65 65
Upper stage oil bath control temperature/°c 45 46 47
Upper stage temperature difference/°c 20 19 18
Dilution ratio of the catalyst in the middle section 2:1 2:1 2:1
Intermediate reaction hot spot temperature/°c 65 65 65
Intermediate section oil bath control temperature/°c 50 50 50
Temperature difference/DEGC of intermediate section 15 15 15
Lower catalyst dilution ratio 1.5:1 1.5:1 1.5:1
Lower reaction hot spot temperature/°c 65 65 65
Lower stage oil bath control temperature/°c 60 60 60
Lower temperature difference/DEGC 5 5 5
By-product DEGMA selectivity/% 1.18 1.24 1.23
Conversion of methacrylic acid/% 99.93 99.92 99.92
Selectivity/% 98.48 98.57 98.61
Examples 14 to 16
The blank resin pellets and the fluorine-containing strong basic anionic resin catalyst prepared in example 1 were mixed according to a ratio of 2.5:1 (volume ratio), mixing uniformly, loading into the upper section of a sectional fixed bed tubular reactor 3, mixing uniformly blank resin pellets and the fluorine-containing strong-alkali anion resin catalyst prepared in the example 1 according to the dilution ratio of 1.5:1 (volume ratio), loading into the lower section of the sectional fixed bed tubular reactor 3, adding ethylene oxide and methacrylic acid into a raw material mixing tank 1 according to the mol ratio of 1.08:1, and then adding a polymerization inhibitor ZJ-701, wherein the mass ratio of ZJ-701 to methacrylic acid is 0.0007:1, finally, supplementing compressed nitrogen to the raw material mixing tank 1 to 0.55MPaG through a first pipeline 5 and uniformly mixing, supplementing compressed nitrogen to the reaction liquid storage tank and the sectional type fixed bed reactor to 0.55MPaG through a twelfth pipeline 16, then, pumping the raw material liquid in the raw material mixing tank 1 into the sectional type fixed bed reactor 3 through a feed pump 2 for reaction, wherein the feeding airspeed is kept to be 0.6h in the feeding process -1 The hot spot temperatures of the middle and lower sections in the reactor are controlled to be 65 ℃ by adjusting the oil bath temperatures in the fourth pipeline 8, the sixth pipeline 10 and the eighth pipeline 12, and the hot spot temperatures are filled into the middle section of the sectional fixed bed tubular reactor 3 after the dilution ratio of the blank resin pellets and the fluorine-containing strong-alkali anionic resin catalyst is adjusted and evenly mixed, thus specific reactions in examples 14 to 16 are carried outThe reaction conditions and the reaction results are shown in Table 3.
TABLE 3 Table 3
Example number 14 15 16
Ethylene oxide to methacrylic acid (molar ratio) 1.08 1.08 1.08
Upper stage catalyst dilution ratio 2.5:1 2.5:1 2.5:1
Upper stage reaction hot spot temperature/°c 65 65 65
Upper stage oil bath control temperature/°c 45 45 45
Upper stage temperature difference/°c 20 20 20
Dilution ratio of the catalyst in the middle section 2:1 2.25:1 2.5:1
Intermediate reaction hot spot temperature/°c 65 65 65
Intermediate section oil bath control temperature/°c 50 51 52
Temperature difference/DEGC of intermediate section 15 14 13
Lower catalyst dilution ratio 1.5:1 1.5:1 1.5:1
Lower reaction hot spot temperature/°c 65 65 65
Lower stage oil bath control temperature/°c 60 60 60
Lower temperature difference/DEGC 5 5 5
By-product DEGMA selectivity/% 1.16 1.26 1.32
Conversion of methacrylic acid/% 99.92 99.93 99.91
Selectivity/% 98.47 98.56 98.64
Examples 17 to 19
The blank resin pellets and the fluorine-containing strong basic anionic resin catalyst prepared in example 1 were mixed according to a ratio of 2.5:1 (volume ratio), mixing uniformly, loading into the upper section of a sectional fixed bed tubular reactor 3, mixing uniformly blank resin pellets and the fluorine-containing strong-alkali anion resin catalyst prepared in the example 1 according to the dilution ratio of 2:1 (volume ratio), loading into the middle section of the sectional fixed bed tubular reactor 3, adding ethylene oxide and methacrylic acid into a raw material mixing tank 1 according to the mol ratio of 1.08:1, and then adding a polymerization inhibitor ZJ-705, wherein the mass ratio of ZJ-705 to methacrylic acid is 0.0008:1, and finally, supplementing compressed nitrogen to 0 to the raw material mixing tank 1 through a first pipeline 5 And 65MPaG, supplementing compressed nitrogen to the reaction liquid storage tank and the sectional fixed bed reactor through a twelfth pipeline 16 to 0.65MPaG, and then pumping the raw material liquid in the raw material mixing tank 1 into the sectional fixed bed reactor 3 through a feed pump 2 for reaction, wherein the feeding space velocity is kept to be 0.6h in the feeding process -1 The temperatures of hot spots at the middle and lower sections in the reactor are controlled to be 65 ℃ by adjusting the temperatures of the oil baths in the fourth pipeline 8, the sixth pipeline 10 and the eighth pipeline 12, and the hot spots are filled into the lower section of the sectional type fixed bed tubular reactor 3 after the hot spots are uniformly mixed by adjusting the dilution ratio of the blank resin pellets and the fluorine-containing strong-alkali anionic resin catalyst, wherein specific reaction process conditions and reaction results in examples 17 to 19 are shown in Table 4.
TABLE 4 Table 4
Examples 20 to 25
The blank resin pellets and the fluorine-containing strong basic anionic resin catalyst prepared in example 1 were mixed according to a ratio of 2.5:1 (volume ratio), mixing uniformly, loading into the upper section of a sectional fixed bed tubular reactor 3, mixing uniformly the blank resin pellets and the fluorine-containing strong-alkali anion resin catalyst prepared in the example 1 according to the dilution ratio of 2:1 (volume ratio), loading into the middle section of the sectional fixed bed tubular reactor 3, mixing uniformly the blank resin pellets and the fluorine-containing strong-alkali anion resin catalyst prepared in the example 1 according to the dilution ratio of 1.5:1 (volume ratio), loading into the lower section of the sectional fixed bed tubular reactor 3, adding ethylene oxide and methacrylic acid into the raw material mixing tank 1 according to the mol ratio of 1.05:1, and then adding a polymerization inhibitor 5125 and methacrylic acid into the mixture, wherein the mass ratio of 5125 to methacrylic acid is 0.0008:1, and finally, supplementing compressed nitrogen to the raw material mixing tank 1 to 0.70MPaG through a first pipeline 5, uniformly mixing, and storing the reaction liquid through a twelfth pipeline 16 The tank and the sectional fixed bed reactor are supplemented with compressed nitrogen to 0.70MPaG, then the raw material liquid in the raw material mixing tank 1 is pumped into the sectional fixed bed reactor 3 by a feed pump 2 for reaction, and the feeding space velocity is kept to be 2h in the feeding process -1 The temperature of hot spots at the middle and lower stages in the reactor was controlled by adjusting the temperature of the oil bath in the fourth and sixth pipes 8 and 10 and the eighth pipe 12, and the specific reaction process conditions and reaction results of examples 20 to 24 are shown in Table 5.
TABLE 5
As can be seen from the data in the above tables 1, 2, 3, 4 and 5, the conversion rate of methacrylic acid can reach 99.9% under the better reaction process conditions by adjusting the raw material ratio and changing the dilution ratio of the catalysts at the upper and lower sections of the fixed bed tubular reactor, the selectivity of hydroxyethyl methacrylate can reach 98.64%, and the selectivity of the byproduct DEGMA is only 1.49%.
Comparative example 1
The preparation method of the hydroxyethyl methacrylate is different from that of the example 5 in that the reaction verification is carried out by adopting an unsegmented fixed bed reactor, the jacket oil bath temperature is 36 ℃, the hot spot temperature is controlled to be 65 ℃, the catalyst dilution ratio of the whole reactor is 2:1 (volume ratio), the conversion of the methacrylic acid is 97.9%, the selectivity of the byproduct DEGMA is 5.5%, and the selectivity of the hydroxyethyl methacrylate is 93.3%, and the selectivity of the byproduct DEGMA is higher by adopting the unsegmented fixed bed reactor although the ring-opening addition reaction can be carried out as well.
Comparative example 2
Into a 1.8L stainless steel reaction kettle, 0.7L reactant solution (comprising 860g (10 mol) reactant methacrylic acid, 43g of the fluorine-containing strong-base anion resin catalyst prepared in example 1 and 0.69g of polymerization inhibitor ZJ-701) is added; after nitrogen is adopted to charge to 0.45MPaG, the stirring rotation speed is kept at 500rpm, the temperature programming is started, the temperature rising rate is 2 ℃/min, when the temperature of the mixed solution of the reaction raw materials is raised to 65 ℃, 457.6g (10.4 mol) of ethylene oxide is started to be added, the heat preservation is continued for about 8 hours after the addition is finished, the reaction solution is cooled to room temperature, gas is discharged, sampling analysis is carried out, the selectivity of a byproduct DEGMA is 4.9%, and the selectivity of hydroxyethyl methacrylate is 94.2%. The intermittent kettle type reactor can be used for ring-opening addition reaction, but the selectivity of the product is low, the selectivity of the byproduct DEGMA is high, and meanwhile, the manual operation is more.
Comparative example 3
The difference from example 6 is that: the method is characterized in that an outsourcing fluorine-free D201 strong-alkaline anion resin catalyst is adopted, the upper-stage reaction hot spot temperature, the middle-stage reaction hot spot temperature and the lower-stage reaction hot spot temperature are maintained to be 65 ℃, after 155 hours of operation, the methacrylic acid conversion rate is obviously reduced, the initial conversion rate is reduced to 59 percent by 99.9 percent, the main catalyst is caused by the falling of a quaternary ammonium salt active component, in contrast, a self-made fluorine-containing strong-alkaline anion resin catalyst is adopted, the quaternary ammonium salt active component is not easy to fall off due to the attraction effect of fluorine atoms on the quaternary ammonium salt group, the service life of the catalyst is up to 2000 hours or more, and the catalyst activity is stable in the operation process.
Comparative example 4
In the preparation of the fluorine-containing strong-alkaline anion resin catalyst, in the step 1), the molar ratio of the perfluoroolefin to the divinylbenzene is not in the range of 5-8:1 of the invention, and the steps are as follows:
1) Tetrafluoroethylene (10 kg), styrene (52 kg) and divinylbenzene (13 kg) were added to 1m 3 Mixing uniformly in a batching kettle, and adding 2.6kg of 0.5wt% tertiary butyl hydroperoxide (based on styrene) to prepare an oil phase; adding 210kg of pure water, 1kg of gelatin and 0.3kg of methylene blue solution into a reaction kettle, heating to 95 ℃, then dripping oil for reaction for 8.5 hours, cooling to 25 ℃, filtering to obtain beads, and washing, filtering and drying with 320kg of n-hexane to obtain copolymer white balls;
2) Mixing 150kg of chloromethyl methyl ether with the copolymer white ball obtained in the step 1) according to the mass ratio of 1.5:1, heating to 40 ℃, dropwise adding anhydrous aluminum chloride to react for 7.5h, cooling to 25 ℃, filtering to obtain a bead body, washing with 400kg of ethanol, washing, filtering and drying to obtain chloromethyl white ball;
3) Mixing 150kg of anhydrous methanol with chloromethylated white balls obtained in the step 2) according to the mass ratio of 2:1, heating to 45 ℃, dropwise adding 40kg of trimethylamine methanol solution for reaction for 8.5h, cooling to 25 ℃, filtering to obtain beads, soaking the obtained beads in saturated saline solution, adding hydrochloric acid to adjust the pH value to 4, washing with 400kg of pure water, cleaning, and filtering to obtain amine balls, namely the fluorine-containing strong-alkali anion resin catalyst;
The obtained structural formula has the approximate value of m of 12, the approximate value of n of 2, the fluorine content of 6.9 weight percent, the nitrogen content of 6.2 weight percent and the molecular weight of 2738 (Mn); the catalyst is used for life experiments, other process conditions are the same as those of the example 6, the conversion rate of methacrylic acid is obviously reduced from the initial 99.9% to 62% after 270 hours of operation, and the preparation process of the comparative example changes the ratio of perfluoroolefin to divinylbenzene, so that the n value, the molecular weight, the fluorine content and the nitrogen content in the structural formula of the obtained fluorine-containing strong-alkaline anion resin are all beyond the range of the invention, and the service life of the catalyst is obviously reduced.
Comparative example 5:
the preparation method of hydroxyethyl methacrylate is different from example 5 in that the catalyst in the preparation method of example 1 in the perfluorinated quaternary ammonium type strong-base anion exchange resin of patent CN201310756127.1 is adopted for reaction verification, the conversion rate of methacrylic acid is 88.3%, the selectivity of byproduct DEGMA is 7.2%, and the selectivity of hydroxyethyl methacrylate is 89.7%, and the catalyst in the preparation method of the perfluorinated quaternary ammonium type strong-base anion exchange resin of patent CN201310756127.1 is adopted, so that the catalyst can catalyze the ring-opening addition reaction, but has poor catalyst activity, the conversion rate of methacrylic acid is obviously reduced, the selectivity of byproduct DEGMA is increased, and the catalytic activity of the byproduct DEGMA is reduced due to the introduction of fluorine element under the same conditions.

Claims (11)

1. A method for preparing hydroxyethyl (meth) acrylate, which is characterized in that: the method comprises the following steps: adding (methyl) acrylic acid, ethylene oxide and polymerization inhibitor into a sectional type fixed bed tubular reactor filled with fluorine-containing strong-alkali anionic resin catalyst according to a certain proportion, wherein the sectional type fixed bed tubular reactor is more than three sections of fixed bed tubular reactors, and the reaction is carried out to generate (methyl) hydroxyethyl acrylate, wherein the preparation method of the fluorine-containing strong-alkali anionic resin catalyst comprises the following steps:
(1) Polymerizing styrene, divinylbenzene and perfluoroolefin to prepare copolymer white balls;
(2) Adding a chloromethylation reagent into the copolymer white balls obtained in the step (1) to carry out chloromethylation reaction so as to prepare chloromethylation white balls;
(3) Adding an amination reagent into the chloromethylation white balls obtained in the step (2) to perform amination reaction to obtain a fluorine-containing strong-alkali anion resin catalyst, wherein the molar ratio of perfluoroolefin to divinylbenzene is 5-8:1, the catalyst in different sections is diluted by adopting blank resin balls in a sectional fixed bed tubular reactor, and the volume ratio of the catalyst filled in the uppermost section to the catalyst filled in the middle section to the catalyst filled in the lowermost section in the sectional fixed bed tubular reactor is (0.3-1): 1.
2. The method of manufacturing according to claim 1, characterized in that: the chloromethylation reaction reagent in the step (2) is chloromethyl methyl ether, and the amination reaction reagent in the step (3) is a methanol solution of trimethylamine.
3. The preparation method according to claim 1, wherein in the step (1), the polymerization reaction is carried out at a temperature of 70 to 120 ℃ for 2 to 15 hours under a pressure of 1 to 6MPaG; and/or the molar ratio of the styrene to the divinylbenzene is 4-7:1; and/or the perfluoroolefin is at least one of tetrafluoroethylene and hexafluoropropylene, and the molar ratio of the perfluoroolefin to divinylbenzene is 6-7:1.
4. A method of preparation as claimed in any one of claims 1 to 3 wherein: in the step (2), the reaction temperature of the chloromethylation reaction is 20-50 ℃ and the reaction time is 3-15 h; and/or the mass ratio of the chloromethylation reaction reagent to the copolymer white ball is 0.5-3:1.
5. A method of preparation as claimed in any one of claims 1 to 3 wherein: in the step (3), the amination reaction is carried out at the reaction temperature of 20-70 ℃ for 5-20 hours; and/or the mass ratio of the amination reagent to the chloromethylated white balls is 1-4:1.
6. A process according to any one of claims 1 to 3, wherein the reactor is selected from the group consisting of fixed bed tubular reactors of upper, middle and lower stages, the mixing ratio of the diluted catalyst packed in the upper stage being a blank resin pellet: the volume ratio of the fluorine-containing strong-alkaline anion resin catalyst is=1-4:1; the mixing proportion of the diluted catalyst filled in the middle section is blank resin pellets: the volume ratio of the fluorine-containing strong-alkaline anion resin catalyst is=1.5-2.5:1; the mixing proportion of the diluted catalyst filled in the lower section is blank resin pellets: the volume ratio of the fluorine-containing strong-alkaline anion resin catalyst is=1-4:1.
7. A production method according to any one of claims 1 to 3, wherein the volume ratio of the uppermost stage packed catalyst to the intermediate stage packed catalyst and the lowermost stage packed catalyst in the segmented tubular fixed bed reactor is (0.4 to 0.7): (0.5 to 0.9): 1.
8. a production method according to any one of claims 1 to 3, wherein the polymerization inhibitor is at least one of ZJ-701, ZJ-705, 5105, 5115 and 5125, and/or the mass ratio of the polymerization inhibitor to (meth) acrylic acid is 0.0001 to 0.005:1, and/or the molar ratio of (meth) acrylic acid to ethylene oxide is from 0.1 to 4:1.
9. A process according to any one of claims 1 to 3, wherein the volumetric space velocity of the feed of the mixture in the fixed bed tubular reactor is from 0.2 to 3h "1; and/or the reaction hot spot temperature in the fixed bed tubular reactor is 50-90 ℃; the reaction pressure is 0.2-1.0 MPaG.
10. A process according to any one of claims 1 to 3, wherein the staged fixed bed tubular reactor uses a heat exchange medium for heat exchange, the heat exchange medium used in the different stages being selected from one or more of dimethicone and heat transfer oil at different temperatures; the temperature of the heat exchange medium adopted in the uppermost section is 30-80 ℃; the temperature of the heat exchange medium adopted in the uppermost section of the middle section is 40-90 ℃; the temperature of the heat exchange medium adopted in the lowest section is 50-100 ℃.
11. A process according to any one of claims 1 to 3, wherein compressed nitrogen is continuously introduced during the reaction; the highest pressure of compressed nitrogen required for supplementing the system pressure is 0.1-1.0 MPaG.
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