A post-treatment method for epoxycyclododecadiene synthesis reaction liquid

Abstract

The invention discloses a post-treatment method for epoxy cyclododecadiene synthesis reaction liquid. The method comprises the steps of using ferrocene-modified bisphenol A epoxy resin porous microspheres as an adsorbent to adsorb and catalytically decompose residual tert-butyl hydroperoxide in the epoxy cyclododecadiene synthesis reaction liquid. The reaction liquid passes through a fixed bed reactor loaded with a metal-modified epoxy resin porous microsphere adsorbent, and the residual peroxide is adsorbed and decomposed, and then enters a distillation system for separation and purification to obtain a product, which effectively solves the problems of cumbersome post-treatment, poor thermal stability, and low product yield in the existing process.

Description

Technical Field

[0001] The invention relates to a post-treatment method for a synthetic reaction liquid produced by epoxidation of cyclododecadiene with tert-butyl hydroperoxide, and belongs to the technical field of organic chemistry. Background Art

[0002] Epoxycyclododecadiene (ECDD) is an important chemical intermediate for the synthesis of musk ketone and nylon 12. The synthesis of epoxy compounds is generally obtained by epoxidation of olefins under the catalysis of a catalyst and the oxidation of an oxidant. Due to the differences in catalysts and oxidants, the epoxidation reaction activity and the selectivity of epoxidation products are different. The recovery method, the chlorohydrin method, the hydrogen peroxide oxidation method and the peroxide oxidation method are currently the commonly used methods for producing epoxides. Patents CN104650007A, CN106964337A, CN111704633A, etc. have developed a method for preparing ECDD, that is, cyclododecatriene (CDT) is selectively epoxidized with tert-butyl hydroperoxide (TBHP) under the action of a molybdenum catalyst to produce tert-butyl alcohol (TBA). The reaction equation is shown below:

[0003]

[0004] Although the conversion rate of the oxidant TBHP in the reaction of epoxycyclododecadiene can reach more than 99.5%, 500-5000ppm of TBHP still remains in the reaction liquid at the reaction outlet. The residual TBHP has a great influence on the post-treatment of the reaction liquid. It can decompose and produce oxygen in the subsequent distillation high-temperature system, causing TBA to enter the explosion limit, and there is a risk of flash fire and explosion, and a large amount of nitrogen dilution is usually required; in addition, the residual TBHP can further catalyze the CDT raw material and ECDD product to undergo ring-opening polymerization at high temperature to generate high molecular polymers, affecting the yield of the product. Patent CN110721745A provides a water-soluble peroxide decomposition catalyst that is resistant to poisoning, which has a complex structure, high cost, is difficult to mass produce and cannot be applied to organic systems; Patent CN106317398A discloses a method for decomposing peroxides in perfluoroethers, which requires high temperature and is only for fluorine-containing systems and cannot be widely used; in addition, according to the reported thermal decomposition conditions, high temperature and long residence time are usually required, and the decomposition of trace peroxides is incomplete.

[0005] Therefore, it is urgent to develop a post-treatment method for the epoxycyclododecadiene synthesis reaction liquid so as to completely decompose the residual oxidant TBHP so that the reaction liquid can be safely and stably separated in the subsequent distillation system. Summary of the invention

[0006] In view of the above problems existing in the prior art, the object of the present invention is to provide a post-treatment method for epoxy cyclododecadiene synthesis reaction liquid. When epoxy cyclododecadiene is prepared by epoxidation of cyclododecatriene (CDT) and tert-butyl hydroperoxide (TBHP), the epoxy cyclododecadiene synthesis reaction liquid at the outlet of the reactor is preliminarily passed through a fixed bed adsorption device loaded with ferrocene-modified bisphenol A type epoxy resin porous microspheres to completely decompose the residual tert-butyl peroxide TBHP in the reaction liquid. The reaction liquid subsequently enters a distillation system to further separate and obtain an ECDD product.

[0007] To achieve the above object, the present invention adopts the following technical solution:

[0008] The invention provides a post-treatment method for epoxy cyclododecadiene synthesis reaction liquid. The method comprises the steps of using ferrocene-modified bisphenol A epoxy resin porous microspheres as an adsorbent to adsorb and catalytically decompose residual tert-butyl hydroperoxide in the epoxy cyclododecadiene synthesis reaction liquid.

[0009] In a specific embodiment, the epoxy cyclododecadiene synthesis reaction liquid is prepared by an epoxidation reaction of cyclododecatriene (CDT) and tert-butyl hydroperoxide (TBHP) under the action of a catalyst. This method is a known method in the art. The specific catalyst and operating parameters and other conditions can refer to any prior art, and the present invention has no special requirements.

[0010] Preferably, the epoxycyclododecadiene synthesis reaction solution contains 100 to 10,000 ppm, preferably 1,000 to 6,000 ppm, of tert-butyl hydroperoxide.

[0011] In a specific embodiment, the ferrocene-modified bisphenol A epoxy resin porous microspheres have an iron content of 0.2 to 5 wt%, preferably 0.5 to 3 wt%;

[0012] Preferably, the ferrocene-modified bisphenol A epoxy resin porous microspheres have a particle size of 0.5 to 5 mm, preferably 2 to 3 mm, and a specific surface area of ​​200 to 1000 m 2 / g, preferably 400-600m 2 / g.

[0013] In a specific embodiment, the preparation method of the ferrocene-modified bisphenol A epoxy resin porous microspheres is:

[0014] Firstly, ferrocene modified with carboxyl group undergoes dehydration condensation reaction with bisphenol A epoxy resin to obtain ferrocene modified bisphenol A epoxy resin, and then undergoes curing reaction with curing agent and porogen to obtain ferrocene modified bisphenol A epoxy resin porous microspheres.

[0015] Preferably, the method for preparing the ferrocene-modified bisphenol A epoxy resin porous microspheres comprises the following specific steps:

[0016] 1) In a nitrogen environment, a bisphenol A epoxy resin is mixed with carboxyl-modified ferrocene and a solvent, and then triethylamine and a condensing agent are added to carry out a dehydration condensation reaction, and then filtered and distilled to obtain a ferrocene-modified bisphenol A epoxy resin;

[0017] 2) The ferrocene-modified bisphenol A epoxy resin prepared in step 1) is mixed with a curing agent and a porogen to carry out a curing reaction, and then washed with water, filtered, and dried to obtain ferrocene-modified bisphenol A epoxy resin porous microspheres.

[0018] Wherein, the carboxyl-modified ferrocene in step 1) is selected from at least one of 1,1'-dicarboxyferrocene, monocarboxyferrocene, etc., preferably 1,1'-dicarboxyferrocene;

[0019] Wherein, the mass ratio of the bisphenol A epoxy resin to the carboxyl-modified ferrocene in step 1) is 1:0.2-3, preferably 1:0.5-2.

[0020] Wherein, the amount of the solvent in step 1) is 0.5 to 5 times, preferably 1 to 3 times, the total mass of the bisphenol A epoxy resin and the carboxyl-modified ferrocene;

[0021] Preferably, the solvent is selected from at least one of benzene, toluene, ethylbenzene and xylene, preferably benzene and / or xylene.

[0022] Wherein, the amount of triethylamine used in step 1) is 0.1-3% of the mass of the solvent, preferably 0.5-1.5%.

[0023] Wherein, the amount of the condensing agent in step 1) is 0.1-3% of the mass of the solvent, preferably 1-2%;

[0024] Preferably, the condensing agent is selected from one or both of 1,3-dicyclohexylcarbodiimide (DCC) and 4-N,N-dimethylpyridine (DMAP).

[0025] Wherein, in step 1), the dehydration condensation reaction is carried out at normal pressure, at a temperature of 30 to 200° C., preferably 60 to 120° C., and for a time of 1 to 10 hours, preferably 3 to 6 hours.

[0026] Wherein, the mass ratio of the curing agent in step 2) to the bisphenol A epoxy resin modified with ferrocene is 1:10-20, preferably 1:14-16;

[0027] Preferably, the curing agent is selected from at least one of diethylenetriamine and triethylenetetramine.

[0028] Wherein, the mass ratio of the porogen in step 2) to the bisphenol A epoxy resin modified with ferrocene is 1-8:1, preferably 2-6:1;

[0029] Preferably, the porogen is selected from polyethylene glycol (PEG), preferably polyethylene glycol with a molecular weight of 1000 to 10000, more preferably at least one of PEG2000, PEG4000, PEG6000 and the like.

[0030] Wherein, in step 2), the curing reaction is carried out at a temperature of 30-100°C, preferably 50-80°C, and for a time of 0.5-6h, preferably 1-3h.

[0031] In the method for preparing the ferrocene-modified bisphenol A epoxy resin porous microspheres of the present invention, the processing methods such as filtration, distillation, water washing, and drying involved are all conventional operations in the art and have no special requirements in the present invention.

[0032] In a specific embodiment, the post-treatment method is carried out in an adsorption device;

[0033] Preferably, the adsorption device is a fixed bed reactor, and the feeding method is bottom-in and top-out.

[0034] In a specific embodiment, in the post-treatment method, during the adsorption and catalytic decomposition process, the temperature is 40-160°C, preferably 60-100°C; the residence time is 20-50 min, preferably 30-40 min.

[0035] In a specific embodiment, the post-treatment method of the epoxycyclododecadiene synthesis reaction liquid is described, wherein the treated reaction liquid enters a distillation system, the number of distillation plates is 20-80 theoretical plates, preferably 40-60 theoretical plates; the pressure is 1-10 KPaA, preferably 2-4 KPaA; and the distillation temperature is 100-180°C, preferably 130-160°C.

[0036] Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

[0037] In the post-treatment method of epoxycyclododecadiene synthesis reaction liquid provided by the present invention, ferrocene-modified bisphenol A epoxy resin porous microspheres are used as adsorbents, which can efficiently adsorb and catalytically decompose trace amounts of TBHP in the reaction liquid; the reaction liquid is pretreated in a fixed bed reactor, the conditions are mild, the operation is simple, and the production efficiency is effectively improved; the method of the present invention can efficiently decompose residual TBHP, so that subsequent distillation can operate safely and stably, effectively avoid the reduction of product quality, and improve the product yield. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1This is an electron microscope characterization picture of the ferrocene-modified bisphenol A epoxy resin porous microspheres prepared in Example. DETAILED DESCRIPTION

[0039] The present invention is explained in more detail with reference to the following examples, which do not limit the scope of the present invention.

[0040] The main analytical instruments and conditions used in the examples of the present invention are:

[0041] Gas phase analysis conditions: instrument model: Shimadzu 2010 Plus, inlet temperature: 280 °C; split ratio: 30:1; chromatographic column: DB-5 (30m×0.25mm×0.25μm); heating program: 50 °C for 2 minutes, increase the temperature to 80 °C at 5 °C / min, maintain for 10 minutes, increase the temperature to 300 °C at 15 °C / min, maintain for 10 minutes; FID detector temperature: 300 °C.

[0042] The model of the NMR analysis instrument is BRUKER Ultrashield 400Plus. The deuterated reagent is deuterated chloroform with a purity of 97 wt%.

[0043] Metal analysis conditions: Instrument model: SPECTRO plasma emission spectrometer ICP.

[0044] Electron microscopy (using transmission electron microscope, JEM-2100, JEOL).

[0045] Peroxide analysis conditions: fully automatic potentiometric titrator, model ZD50, titrant sodium thiosulfate, measuring range ±1999mV, resolution 0.1mV, 15mL burette capacity tolerance ±0.025mL.

[0046] The sources of the main reagents and samples used in the examples of the present invention are as follows. Other materials are common commercially available unless otherwise specified:

[0047] Epoxy cyclododecadiene synthesis reaction liquid: produced by the device, specifically prepared by epoxidation of cyclododecatriene (CDT) and tert-butyl hydroperoxide (TBHP) under the action of a catalyst;

[0048] Tert-butyl alcohol, CAS: 75-65-0, AR, Tianjin Kemeiou Chemical Reagent Company;

[0049] Tert-butyl hydroperoxide (TBHP) solution, 55%, Lanzhou Additive Factory;

[0050] 1,1'-Dicarboxyferrocene, CAS: 1293-87-4, 98%, Tianjin Komiou Chemical Reagent Company;

[0051] Bisphenol A epoxy resin, CAS: 1675-54-3, Merck Life Science Chemical Products;

[0052] Diethylenetriamine, CAS: 111-40-0, AR, Tianjin Komiou Chemical Reagent Company;

[0053] Triethylamine, CAS: 121-44-8, AR, Tianjin Komiou Chemical Reagent Company;

[0054] Benzene, CAS: 71-43-2, AR, Tianjin Kemeiou Chemical Reagent Company;

[0055] Ferric chloride, CAS: 7705-08-0, AR, Tianjin Kemeiou Chemical Reagent Company;

[0056] Cupric acetate, CAS: 6046-93-1, AR, Tianjin Komiou Chemical Reagent Company;

[0057] Polyethylene glycol 4000 (PEG-4000), CAS: 25322-68-3, >99%, Tianjin Komiou Chemical Reagent Co., Ltd.;

[0058] Polyethylene glycol 6000 (PEG-6000), CAS: 25322-68-3, >99%, Tianjin Komiou Chemical Reagent Co., Ltd.;

[0059] 1,3-Dicyclohexylcarbodiimide (DCC), CAS: 538-75-0, AR, Tianjin Komiou Chemical Reagent Company.

[0060] Example 1

[0061] Preparation of ferrocene-modified bisphenol A epoxy resin porous microspheres:

[0062] 1) Weigh 1084 g of bisphenol A epoxy resin, 1636 g of benzene, and 552 g of 1,1'-dicarboxyferrocene respectively into a 5L reactor, stir and mix thoroughly, add 16.36 g of triethylamine and 24.54 g of 1,3-dicyclohexylcarbodiimide into the reactor, replace with nitrogen, heat to 80°C, maintain stirring for dehydration condensation reaction for 5 hours, cool to room temperature, filter and obtain a solution for distillation (90°C, 40 KPaA), remove the distillate, cool and filter to obtain 1524 g of ferrocene-modified bisphenol A epoxy resin.

[0063] 2) Weigh 1500 g of the resin obtained in step 1), add 100 g of diethylenetriamine, add 3000 g of PEG-4000, control the reaction temperature to 60° C., carry out curing reaction, maintain for 2 h, repeatedly soak and wash with a large amount of deionized water, filter and dry at 60° C. for 48 h to obtain 5400 g of ferrocene-modified bisphenol A epoxy resin porous microspheres, and the ICP test shows that the Fe content is 2.5 wt%.

[0064] Electron microscopy characterization pictures such as Figure 1 As shown, the particle size is 2.2 mm, and the specific surface area measured by BET is 567 m 2 / g.

[0065] The bisphenol A epoxy resin porous microspheres modified with ferrocene prepared above are used to post-treat the epoxycyclododecadiene synthesis reaction solution:

[0066] The epoxycyclododecadiene synthesis reaction liquid has a TBHP content of 4500 ppm;

[0067] The ferrocene-modified bisphenol A epoxy resin porous microspheres were loaded into a fixed bed reactor, and the epoxycyclododecadiene synthesis reaction solution was introduced, with the reaction temperature controlled to be 60°C and the residence time to be 30 min. The TBHP content of the outlet sample was tested to be less than 1 ppm.

[0068] The reaction liquid treated by the fixed bed reactor was introduced into a distillation device, and the distillation temperature was controlled at 150° C. and the pressure was 2.5 kPaA. ECDD product was obtained by distillation with a purity of 99.8% and a yield of 96.5%.

[0069] Example 2

[0070] Preparation of ferrocene-modified bisphenol A epoxy resin porous microspheres:

[0071] 1) Weigh 1084 g of bisphenol A epoxy resin, 3270 g of benzene, and 1084 g of 1,1'-dicarboxyferrocene respectively into a 5L reactor, stir and mix thoroughly, add 16.36 g of triethylamine and 24.54 g of 1,3-dicyclohexylcarbodiimide into the reactor, replace with nitrogen, heat to 120°C, maintain stirring for dehydration condensation reaction for 4 hours, cool to room temperature, filter and obtain a solution for distillation (90°C, 40 KPaA), remove the distillate, cool and filter to obtain 2025 g of ferrocene-modified bisphenol A epoxy resin.

[0072] 2) Weigh 2000 g of the resin obtained in step 1), add 125 g of diethylenetriamine, add 8000 g of PEG-6000, control the reaction temperature to 80°C, carry out curing reaction, maintain for 3 hours, soak and wash repeatedly with a large amount of deionized water, filter and dry at 60°C for 48 hours to obtain 9600 g of ferrocene-modified bisphenol A epoxy resin porous microspheres, the Fe content of which is 2.1 wt% by ICP test, the particle size is 2.8 mm, and the specific surface area is 425 m by BET test. 2 / g.

[0073] The bisphenol A epoxy resin porous microspheres modified with ferrocene prepared above are used to post-treat the epoxycyclododecadiene synthesis reaction solution:

[0074] The epoxycyclododecadiene synthesis reaction liquid has a TBHP content of 5800 ppm;

[0075] The bisphenol A epoxy resin porous microspheres modified by ferrocene are loaded into a fixed bed reactor, and the epoxycyclododecadiene reaction liquid is introduced, with the reaction temperature controlled to be 100° C. and the residence time to be 40 min. The TBHP content of the outlet sample is tested to be less than 1 ppm. The reaction liquid treated by the fixed bed reactor is introduced into a distillation device, and the distillation temperature is controlled to be 160° C. and the pressure is controlled to be 4 kPaA. The ECDD product is obtained by distillation, and the purity is 99.6% and the yield is 94.8%.

[0076] Example 3

[0077] The bisphenol A epoxy resin porous microspheres modified with ferrocene prepared in Example 1 were used to post-treat the epoxycyclododecadiene synthesis reaction solution:

[0078] The epoxycyclododecadiene synthesis reaction liquid has a TBHP content of 1100 ppm;

[0079] The ferrocene-modified bisphenol A epoxy resin porous microspheres were loaded into a fixed bed reactor, and the epoxycyclododecadiene reaction solution was introduced, with the reaction temperature controlled to be 80°C and the residence time to be 30 min. The TBHP content of the outlet sample was tested to be less than 1 ppm.

[0080] The reaction liquid treated by the fixed bed reactor was introduced into a distillation device, and the distillation temperature was controlled at 130° C. and the pressure was 1 kPaA. ECDD product was obtained by distillation with a purity of 99.7% and a yield of 95.5%.

[0081] Comparative Example 1

[0082] Referring to the method of Example 1, the only difference is that the adsorbent is not modified with ferrocene, that is, when preparing ferrocene-modified bisphenol A epoxy resin porous microspheres, step 1) is omitted, and the bisphenol A epoxy resin is directly added to step 2) for reaction, and other operations and conditions remain unchanged to obtain bisphenol A epoxy resin porous microspheres.

[0083] The bisphenol A epoxy resin porous microspheres prepared above were used to post-treat the epoxycyclododecadiene synthesis reaction solution according to the same raw materials and methods as in Example 1: the TBHP content of the outlet sample was 4210 ppm; the ECDD product obtained by distillation had a purity of 95.2% and a yield of 88.6%.

[0084] Comparative Example 2

[0085] Referring to the method of Example 1, the only difference is that the adsorbent is modified with ferric chloride. When preparing bisphenol A epoxy resin porous microspheres modified with ferric chloride, ferrocene in step 1) is replaced by ferric chloride, and the added mass is 213g. Other operating conditions remain unchanged to obtain ferric chloride bisphenol A epoxy resin porous microspheres. ICP measured its iron content to be 0.2%, the particle size to be 2.2mm, and the specific surface area to be 551m 2 / g;

[0086] The porous microspheres prepared as above were used to post-treat the epoxycyclododecadiene synthesis reaction solution according to the same raw materials and methods as in Example 1: the TBHP content of the outlet sample was 3736 ppm;

[0087] The reaction liquid treated by the fixed bed reactor was introduced into a distillation device, and the distillation temperature was controlled at 160° C. and the pressure was 4 kPaA. ECDD product was obtained by distillation with a purity of 96.3% and a yield of 85.1%.

[0088] Comparative Example 3

[0089] Referring to the method of Example 1, the only difference is that the adsorbent is modified with copper acetate. When preparing copper acetate modified bisphenol A type epoxy resin porous microspheres, ferrocene in step 1) is replaced by copper acetate, and the added mass is 398g. Other operating conditions remain unchanged to obtain copper acetate bisphenol A type epoxy resin porous microspheres. ICP measured its copper content to be 0.4%, the particle size to be 2.3mm, and the specific surface area to be 528m 2 / g;

[0090] The porous microspheres prepared as above were used to post-treat the epoxycyclododecadiene synthesis reaction solution according to the same raw materials and methods as in Example 1: the TBHP content of the outlet sample was tested to be 4326 ppm;

[0091] The reaction liquid treated by the fixed bed reactor was introduced into a distillation device, and the distillation temperature was controlled at 160° C. and the pressure was 4 kPaA. The ECDD product was obtained by distillation with a purity of 96.8% and a yield of 82.7%.

[0092] Comparative Example 4

[0093] The epoxycyclododecadiene reaction solution of Example 1 was directly fed into a distillation device without being treated with ferrocene-modified bisphenol A epoxy resin porous microspheres. The distillation temperature was controlled at 150° C. and the pressure was 2.5 kPaA. ECDD product was obtained by distillation with a purity of 90.5% and a yield of 82.3%.

[0094] It can be seen from the above embodiments and comparative examples that the ferrocene-modified bisphenol A epoxy resin porous microspheres provided by the present invention can effectively adsorb and catalytically decompose the residual organic peroxide TBHP in the epoxy cyclododecadiene synthesis reaction liquid, and the TBHP content in the reaction liquid after decomposition is less than 1ppm, which effectively ensures the safety of the distillation system and the stability of the product quality and improves the yield. The present invention effectively provides a post-treatment method for the epoxy cyclododecadiene synthesis reaction liquid.

[0095] Although the content of the present invention has been described in detail through the above preferred embodiments, it should be appreciated that the above description should not be considered as limiting the present invention. Those skilled in the art will appreciate that, under the guidance of this specification, some modifications or adjustments may be made to the present invention. These modifications or adjustments should also be within the scope defined by the claims of the present invention.

Claims

1. A post-treatment method for epoxycyclododecadiene synthesis reaction solution, characterized in that: The method comprises the steps of using ferrocene-modified bisphenol A epoxy resin porous microspheres as adsorbents to adsorb and catalytically decompose residual tert-butyl hydroperoxide in epoxycyclododecadiene synthesis reaction liquid.

2. The post-processing method according to claim 1, characterized in that: The epoxycyclododecadiene synthesis reaction liquid is prepared by epoxidation reaction of cyclododecatriene and tert-butyl hydroperoxide.

3. The post-processing method according to claim 2, characterized in that: The epoxycyclododecadiene synthesis reaction liquid contains 100 to 10000 ppm of tert-butyl hydroperoxide.

4. The post-processing method according to claim 3, characterized in that: The epoxycyclododecadiene synthesis reaction liquid contains 1000 to 6000 ppm of tert-butyl hydroperoxide.

5. The post-processing method according to claim 1, characterized in that: The ferrocene-modified bisphenol A epoxy resin porous microspheres have an iron content of 0.2-5 wt %.

6. The post-processing method according to claim 5, characterized in that: The ferrocene-modified bisphenol A epoxy resin porous microspheres have an iron content of 0.5-3 wt %.

7. The post-processing method according to claim 1, characterized in that: The ferrocene-modified bisphenol A epoxy resin porous microspheres have a particle size of 0.5 to 5 mm and a specific surface area of ​​200 to 1000 m 2 / g.

8. The post-processing method according to claim 7, characterized in that: The ferrocene-modified bisphenol A epoxy resin porous microspheres have a particle size of 2 to 3 mm and a specific surface area of ​​400 to 600 m 2 / g.

9. The post-processing method according to claim 1, characterized in that: The preparation method of the ferrocene-modified bisphenol A epoxy resin porous microspheres comprises the following steps: a dehydration condensation reaction of carboxyl-modified ferrocene and bisphenol A epoxy resin is performed to obtain the ferrocene-modified bisphenol A epoxy resin, and then a curing reaction is performed with a curing agent and a porogen to obtain the ferrocene-modified bisphenol A epoxy resin porous microspheres.

10. The post-processing method according to claim 9, characterized in that: The method for preparing the ferrocene-modified bisphenol A epoxy resin porous microspheres comprises the following steps: 1) In a nitrogen environment, a bisphenol A epoxy resin is mixed with carboxyl-modified ferrocene and a solvent, and then triethylamine and a condensing agent are added to carry out a dehydration condensation reaction, and then filtered and distilled to obtain a ferrocene-modified bisphenol A epoxy resin; 2) The ferrocene-modified bisphenol A epoxy resin prepared in step 1) is mixed with a curing agent and a porogen to carry out a curing reaction, and then washed with water, filtered, and dried to obtain ferrocene-modified bisphenol A epoxy resin porous microspheres.

11. The post-processing method according to claim 10, characterized in that: In step 1), the carboxyl-modified ferrocene is selected from at least one of 1,1'-dicarboxyl ferrocene and monocarboxyl ferrocene; The mass ratio of the bisphenol A epoxy resin to the carboxyl-modified ferrocene is 1:0.2-3; The amount of the solvent is 0.5 to 5 times the total mass of the bisphenol A epoxy resin and the carboxyl-modified ferrocene; The triethylamine is used in an amount of 0.1 to 3% of the solvent mass; The amount of the condensing agent is 0.1 to 3% of the solvent mass; The dehydration condensation reaction is carried out at normal pressure, at a temperature of 30 to 200° C., and for 1 to 10 hours.

12. The post-processing method according to claim 11, characterized in that: The mass ratio of the bisphenol A epoxy resin to the carboxyl-modified ferrocene is 1:0.5-2.

13. The post-processing method according to claim 11, characterized in that: The amount of the solvent used is 1 to 3 times the total mass of the bisphenol A epoxy resin and the carboxyl-modified ferrocene.

14. The post-processing method according to claim 11, characterized in that: The amount of triethylamine used is 0.5-1.5% of the mass of the solvent.

15. The post-processing method according to claim 11, characterized in that: The amount of the condensing agent is 1-2% of the mass of the solvent.

16. The post-processing method according to claim 11, characterized in that: The dehydration condensation reaction has a temperature of 60 to 120° C. and a time of 3 to 6 hours.

17. The post-processing method according to claim 10, characterized in that: In step 1), the solvent is selected from at least one of benzene, toluene, ethylbenzene and xylene.

18. The post-processing method according to claim 10, characterized in that: In step 1), the condensing agent is selected from one or both of 1,3-dicyclohexylcarbodiimide and 4-N,N-dimethylpyridine.

19. The post-processing method according to claim 10, characterized in that: In step 2), the mass ratio of the curing agent to the ferrocene-modified bisphenol A epoxy resin is 1:10-20; The mass ratio of the porogen to the ferrocene-modified bisphenol A epoxy resin is 1-8:1; The curing reaction has a temperature of 30-100° C. and a time of 0.5-6 hours.

20. The post-processing method according to claim 19, characterized in that: The mass ratio of the curing agent to the ferrocene-modified bisphenol A epoxy resin is 1:14-16.

21. The post-processing method according to claim 19, characterized in that: The mass ratio of the porogen to the ferrocene-modified bisphenol A epoxy resin is 2-6:

1.

22. The post-processing method according to claim 19, characterized in that: The curing reaction has a temperature of 50-80° C. and a time of 1 to 3 hours.

23. The post-processing method according to claim 10, characterized in that: In step 2), the curing agent is selected from at least one of diethylenetriamine and triethylenetetramine.

24. The post-processing method according to claim 10, characterized in that: In step 2), the porogen is selected from polyethylene glycol.

25. The post-processing method according to claim 24, characterized in that: The porogen is selected from polyethylene glycol with a molecular weight of 1000 to 10000.

26. The post-processing method according to claim 25, characterized in that: The porogen is selected from at least one of PEG2000, PEG4000 and PEG6000.

27. The post-processing method according to claim 1, characterized in that: Carried out in an adsorption device.

28. The post-processing method according to claim 27, characterized in that: The adsorption device is a fixed bed reactor, and the feeding method is bottom-in and top-out.

29. The post-processing method according to claim 1, characterized in that: During the adsorption and catalytic decomposition process, the temperature is 40-160°C and the residence time is 20-50 minutes.

30. The post-processing method according to claim 29, characterized in that: During the adsorption and catalytic decomposition process, the temperature is 60-100°C and the residence time is 30-40 minutes.

31. The post-processing method according to claim 1, characterized in that: The treated reaction liquid enters the distillation system, the number of distillation plates is 20-80 theoretical plates; the pressure is 1-10KPaA, and the distillation temperature is 100-180℃.

32. The post-processing method according to claim 31, characterized in that: The number of distillation tower plates is 40-60 theoretical plates.

33. The post-processing method according to claim 31, characterized in that: The pressure is 1-10KPaA and the distillation temperature is 130-160℃.

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