Modified epoxy resin and preparation method thereof

Abstract

The invention discloses a modified epoxy resin and a preparation method thereof, and belongs to the field of epoxy resins, the modified epoxy resin comprises a hyperbranched polymer modified epoxy resin matrix, a Cu < 2 + > molecular imprinting-chelating composition and a Cu < 2 + > autocatalytic degradation agent; the Cu < 2 + > autocatalytic degradation agent takes an acid-responsive ascorbic acid microcapsule as a main component; under the enrichment effect of the Cu < 2 + > molecular imprinting-chelating composition on Cu < 2 + >, the Cu < 2 + > autocatalytic degradation agent degrades phenol organic matters in sewage containing H2O2, Cu < 2 + > and phenol organic matters, wherein the pH value of the sewage is 3-4. The Cu < 2 + > molecular imprinting-chelating composition actively captures Cu < 2 + > in sewage, increases the content of Cu < 2 + > adsorbed on a coating, and makes full contact with ascorbic acid released by microcapsules in the coating to generate a reduction reaction, generation sites of the reduction reaction are mainly concentrated on the coating and around the coating, a large amount of generated Cu < + > surrounds the coating, and the Cu < + > is combined with H2O2 in the sewage, so that the content of Cu < 2 + > adsorbed on the coating is increased. A large number of. OH free radicals are distributed around the coating, and the coating has a remarkable degradation effect on phenol adsorbed on the coating.

Description

Technical Field

[0001] The present invention belongs to the field of epoxy resins and relates to a modified epoxy resin and a preparation method thereof. Background Art

[0002] As a polymer material, epoxy resin has excellent adhesion, chemical corrosion resistance, water resistance, heat and humidity resistance and other properties, making it an ideal choice for the anti-corrosion of sewage pools; however, in acidic sewage containing copper ion-H 2 O 2 -phenol organic matter triple pollutants, the following situations will occur: when the concentration of phenol is low, due to the low concentration of phenol organic matter, it is difficult to be recognized and adsorbed by conventional adsorbents (activated carbon), etc., and epoxy resin has a certain adsorption effect on phenol substances. Low-concentration phenol substances will be adsorbed on the surface of the epoxy resin coating. Due to the easy adsorption and difficult removal of phenol substances on the epoxy resin coating, the accumulation of phenol substances will reduce the coating quality of epoxy resin and shorten its service life. At present, there is a lack of an epoxy resin that can be used for a long time as a protective layer for sewage pools containing copper ion-H 2 O 2 -low-concentration phenol organic matter triple pollutant sewage pools. Summary of the Invention

[0003] The purpose of the present invention is to provide a modified epoxy resin and a preparation method thereof, which solve the problem that the current ordinary epoxy resin is slowly corroded by low-concentration phenol when used in sewage pools containing copper ion-H 2 O 2 -low-concentration phenol organic matter triple pollutants, affecting its service life.

[0004] The technical solution adopted by the present invention is as follows:

[0005] A modified epoxy resin, comprising a hyperbranched polymer modified epoxy resin matrix, a Cu 2+ molecular imprinting-chelation composition and a Cu 2+ self-catalytic degradation agent; the Cu 2+ self-catalytic degradation agent is mainly composed of acid-responsive ascorbic acid microcapsules;

[0006] Under the enrichment effect of the Cu 2+ molecular imprinting-chelation composition on Cu 2+ , the Cu 2+ self-catalytic degradation agent degrades phenol organic matter in sewage with pH of 3-4 containing H 2 O 2 , Cu 2+ and phenol organic matter.

[0007] The present invention provides a method that can utilize copper ions and H in acidic sewage2 O 2 Modified epoxy resin of phenol on a degradable coating. The modified epoxy resin in the present invention does not belong to the general type of epoxy resin. The modified epoxy resin in the present invention is applicable to acidic sewage containing copper ion-H 2 O 2 -phenol organic matter triple pollutants, where copper ions and phenol substances in the sewage can coexist. On the one hand, due to the low concentration of phenol substances, it is difficult to promote the complexation reaction. On the other hand, the complexation reaction between phenol and copper ions generally occurs under heating and aerobic conditions; containing copper ion-H 2 O 2 -acidic sewage containing phenol organic matter triple pollutants is common in current multi-process comprehensive chemical engineering and other processes.

[0008] The principle of the present invention is as follows: In the present invention, hyperbranched polymer-modified epoxy resin is used as the substrate. The hyperbranched polymer-modified epoxy resin provides a three-dimensional loading network, ensuring the basic function of high anti-permeability of the sewage pool to the coating; in addition, its hyperbranched structure provides more terminal functional groups, facilitating the connection of other components. In the present invention, Cu 2+ Molecular imprinting-chelation composition is used to specifically recognize and enrich Cu in the sewage 2+ ,Cu 2+ The molecular imprinting-chelation composition captures Cu 2+ ,Cu 2+ The local concentration can be increased by 100 times; in the present invention, the main component of the Cu 2+ self-catalytic degradation agent is an acid-responsive ascorbic acid microcapsule. The core substance of the capsule is ascorbic acid, and the capsule shell gradually breaks under acidic conditions, releasing the internal ascorbic acid. Ascorbic acid is a reducing agent. Under the action of ascorbic acid, Cu 2+ is reduced to Cu + ,Cu + reacts with H 2 O 2 to obtain ·OH free radicals and Cu 2+ ,degrading phenol organic matter, where Cu 2+ will be captured again by the Cu 2+ molecular imprinting-chelation composition and be reduced and oxidized again.

[0009] After the modified epoxy resin of the present invention forms a coating, the Cu 2+ molecular imprinting-chelation composition actively captures Cu in the sewage 2+ ,increasing the content of Cu adsorbed on the coating 2+ ,fully contacting with the ascorbic acid released from the microcapsules in the coating to undergo a reduction reaction. The occurrence site of the reduction reaction mainly concentrates on and around the coating, and the generated Cu +A large amount surrounds the coating, combined with H in the sewage 2 O 2 , resulting in a large amount of ·OH free radicals distributed around the coating, which has a significant degradation effect on the phenol adsorbed on the coating and can extend the service life of the coating.

[0010] During the sewage treatment process, the sewage is in a flowing state. It is very difficult for Cu in the sewage 2+ to be firmly and largely adsorbed on the coating by physical adsorption, etc. The adsorption amount of Cu 2+ on the coating seriously affects the degradation rate of phenol substances on the coating; in addition, during actual use, the concentration of Cu in the sewage 2+ is uncertain. When the concentration of Cu in the sewage 2+ is too low and in a dispersed state, it is very difficult to accumulate a large amount of ·OH free radicals around the coating and the degradation degree of phenol substances on the coating layer will also be reduced. Therefore, the present invention specifically enriches Cu 2+ , on the one hand, it can avoid other ions in the sewage from being largely adsorbed on the coating and competing for sites with Cu 2+ , and on the other hand, it reduces the influence of the Cu 2+ concentration in the sewage on the degradation degree of phenol substances on the coating, and improves the application range of the modified epoxy resin of the present invention.

[0011] In the present invention, the acid-responsive ascorbic acid microcapsules release ascorbic acid under acidic conditions, avoiding ineffective consumption in neutral / alkaline environments; the slow-release characteristics of the microcapsules extend the action time of ascorbic acid, prevent rapid failure, and effectively extend the cleaning period of the coating prepared by the present invention for phenol substances. During actual use, the release rate of ascorbic acid can be controlled by adjusting the pH value in the sewage tank. The sewage tank is not used continuously. When it is in an unused state, the microcapsules will not release ascorbic acid in a large amount and quickly and ineffectively.

[0012] Further, the Cu 2+ molecularly imprinted-chelation composition includes the following components: Cu(NO 3 ) 2 , monomer, ethylene glycol dimethacrylate, initiator, porogen, EDTA-modified graphene, EDTA eluent;

[0013] Among them, the monomer includes acrylamide and EDTA-methyl methacrylate with a mass ratio of 3-4:1; the porogen includes a mixture of acetonitrile and water with a volume ratio of 1:1.

[0014] The Cu 2+ molecularly imprinted-chelation composition of the present invention synthesizes a polymer with specific cavities, grafts multi-dentate chelating groups around the cavities, and through synergy, can bind Cu 2+The local concentration is increased by about 100 times.

[0015] Further, the addition amount of Cu(NO 3 ) 2 is 20 - 25% of the total mass of the monomers, the addition amount of EDTA-modified graphene is 1 - 2% of the total mass of the monomers, the addition amount of ethylene glycol dimethacrylate is 80 - 85% of the total mass of the monomers, and the addition amount of the initiator is 1 - 2% of the total mass of the monomers.

[0016] Further, the acid-responsive ascorbic acid microcapsule includes a core and a shell, the core is ascorbic acid, and the shell is a PMMA-co-PAA polymer.

[0017] Further, the Cu 2+ self-catalytic degrading agent further includes conductive carbon nanotubes, and the addition amount of the conductive carbon nanotubes is 2 - 3% of the total mass of the acid-responsive ascorbic acid microcapsules.

[0018] The conductive carbon nanotubes have a promoting effect on the reduction reaction and help improve the utilization rate of ascorbic acid.

[0019] Further, the addition amount of the Cu 2+ molecularly imprinted-chelation composition is 8 - 10% of the mass of the hyperbranched polymer-modified epoxy resin matrix, and the mass ratio of ascorbic acid to the Cu2+ molecularly imprinted-chelation composition in the Cu2+ self-catalytic degrading agent is 1:2 - 3.

[0020] Further, the hyperbranched polymer-modified epoxy resin matrix includes an epoxy resin modified by an end-epoxy-group hyperbranched polyester and a silane coupling agent.

[0021] Further, the acid-responsive ascorbic acid microcapsule is a microcapsule surface-modified by amination, and the Cu 2+ molecularly imprinted-chelation composition is a composition surface-activated by carboxylation.

[0022] A preparation method of a modified epoxy resin includes the following steps:

[0023] S1. Prepare the Cu 2+ molecularly imprinted-chelation composition: Dissolve Cu(NO 3 ) 2 , acrylamide, and EDTA-methyl methacrylate in an acetonitrile / water mixed solution, and magnetically stir at room temperature for 1 - 1.5 h to form a Cu 2+ -AM-EDTA-MA complex; in the Cu 2+Add a crosslinking agent, an initiator, and EDTA-graphene to the -AM-EDTA-MA complex. Ultrasonically disperse for 10 - 15 minutes, deoxygenate by passing nitrogen for 15 min, and then react in a water bath at 60 °C for 12 h with magnetic stirring at 200 rpm. After the reaction, perform elution, drying, pulverization, and sieving to obtain Cu 2+ Molecularly imprinted-chelation composition;

[0024] S2. Activate the carboxyl group of the Cu 2+ Molecularly imprinted-chelation composition by the EDC / NHS activation method to obtain a first substance for standby;

[0025] S3. Prepare Cu 2+ Self-catalytic degrading agent: Prepare acid-responsive ascorbic acid microcapsules with ascorbic acid as the core and PMMA-co-PAA polymer as the shell by microcapsule emulsion polymerization for standby; Obtain a copper ion reduction promoter, and the copper ion reduction promoter is conductive carbon nanotubes for standby;

[0026] S4. Disperse the ascorbic acid microcapsules in Tris buffer, add polyethyleneimine for reaction, perform surface amination modification on the ascorbic acid microcapsules, and mix the conductive carbon nanotubes with the surface aminated ascorbic acid microcapsules under the action of an adhesive, and then freeze-dry to obtain a second substance for standby;

[0027] S5. Mix and disperse the first substance and the second substance in PBS buffer and react at 25 °C for 12 hours to obtain a third substance;

[0028] S6. Disperse the third substance in acetone and then ultrasonically mix it with an epoxy resin modified by a terminal epoxy group hyperbranched polyester containing a silane coupling agent to obtain a modified epoxy resin.

[0029] Furthermore, after adding a curing agent to the modified epoxy resin, it is used for the protective layer of a sewage pool, and the sewage in the sewage pool is acidic and contains H 2 O 2 、Cu 2+ and phenolic organic compounds.

[0030] In summary, due to the adoption of the above technical solutions, the beneficial effects of the present invention are:

[0031] 1. After a coating is formed by a modified epoxy resin of the present invention, the Cu 2+ Molecularly imprinted-chelation composition actively captures Cu 2+ in the sewage, increases the content of Cu 2+ adsorbed on the coating, and fully contacts with the ascorbic acid released from the microcapsules in the coating to undergo a reduction reaction. The occurrence sites of the reduction reaction are mainly concentrated on and around the coating, and the generated Cu +A large amount of it surrounds the coating, and combined with H in the sewage 2 O 2 , a large amount of ·OH free radicals are distributed around the coating, which has a significant degradation effect on the phenol adsorbed on the coating and can extend the service life of the coating;

[0032] 2. In the preparation method of the modified epoxy resin of the present invention, the carboxyl group of the Cu 2+ molecular imprinting-chelation composition is activated, and the surface of the ascorbic acid microcapsule is modified with amino groups, so that the two can be connected together to form a complex, which is beneficial to the full reaction of Cu 2+ with ascorbic acid, reduces the diffusion range and diffusion distance of ascorbic acid, improves its utilization rate, and can also effectively avoid the risk of the ascorbic acid microcapsule falling off under the scouring of sewage. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the drawings required for the embodiments. It should be understood that the following drawings only show some embodiments of the present invention, and therefore should not be regarded as limiting the scope. For those of ordinary skill in the art, without creative efforts, other related drawings can also be obtained based on these drawings, where:

[0034] Figure 1 is the SEM surface morphology diagram of the coating within the scope of Example 2;

[0035] Figure 2 is the SEM surface morphology diagram of the coating within the scope of Comparative Example 17;

[0036] Figure 3 is the SEM surface morphology diagram of the coating within the scope of Comparative Example 13;

[0037] Figure 4 is the TEM diagram of the ascorbic acid microcapsule of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0038] In order to make the purpose, technical solutions and advantages of the present invention clearer, the following will further describe the present invention in detail with reference to the drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, and are not used to limit the present invention, that is, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Usually, the components of the embodiments of the present invention described and shown in the drawings here can be arranged and designed in various different configurations.

[0039] Accordingly, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely represents selected embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative efforts fall within the scope of protection of the present invention.

[0040] It should be noted that relational terms such as "first" and "second" are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variant thereof are intended to cover non-exclusive inclusion, such that a process, method, article or device comprising a series of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article or device. Without further limitation, an element defined by the phrase "comprising one..." does not exclude the presence of additional identical elements in the process, method, article or device comprising the element.

[0041] The features and properties of the present invention will be further described in detail below in conjunction with embodiments.

[0042] Embodiment 1

[0043] A modified epoxy resin provided by a preferred embodiment of the present invention includes a hyperbranched polymer-modified epoxy resin matrix, Cu 2+ a molecularly imprinted-chelation composition, and Cu 2+ a self-catalytic degradation agent; the Cu 2+ self-catalytic degradation agent is mainly composed of acid-responsive ascorbic acid microcapsules;

[0044] Under the enrichment effect of the Cu 2+ molecularly imprinted-chelation composition on Cu 2+ , the Cu 2+ self-catalytic degradation agent degrades phenolic organic compounds in sewage containing H 2 O 2 , Cu 2+ and phenolic organic compounds at a pH of 3-4.

[0045] The Cu 2+ molecularly imprinted-chelation composition includes the following components: Cu(NO 3 ) 2 , monomer, ethylene glycol dimethacrylate, initiator, pore-forming agent, EDTA-modified graphene, EDTA eluent;

[0046] Among them, the monomer includes acrylamide and EDTA-methyl methacrylate with a mass ratio of 3-4:1; the pore-forming agent includes a mixture of acetonitrile and water with a volume ratio of 1:1.

[0047] Among them, the addition amount of Cu(NO 3 ) 2 is 20% of the total mass of the monomer, the addition amount of EDTA-modified graphene is 1-2% of the total mass of the monomer, the addition amount of ethylene glycol dimethacrylate is 80% of the total mass of the monomer, and the addition amount of the initiator is 1-2% of the total mass of the monomer.

[0048] The acid-responsive ascorbic acid microcapsule includes a core and a shell. The core is ascorbic acid, and the shell is a PMMA-co-PAA polymer.

[0049] The Cu 2+ self-catalytic degrading agent further includes conductive carbon nanotubes, and the addition amount of the conductive carbon nanotubes is 2-3% of the total mass of the acid-responsive ascorbic acid microcapsule.

[0050] Cu 2+ The addition amount of the molecularly imprinted-chelation composition is 8-10% of the mass of the hyperbranched polymer-modified epoxy resin matrix. The mass ratio of ascorbic acid to the Cu2+-molecularly imprinted-chelation composition in the Cu2+ self-catalytic degrading agent is 1:2-3.

[0051] The hyperbranched polymer-modified epoxy resin matrix includes epoxy resin modified by terminal epoxy group hyperbranched polyester and a silane coupling agent.

[0052] The acid-responsive ascorbic acid microcapsule is a microcapsule surface-modified by amination, and the Cu 2+ molecularly imprinted-chelation composition is a composition surface-activated by carboxyl groups.

[0053] The preparation method of a modified epoxy resin includes the following steps:

[0054] S1. Prepare the Cu 2+ molecularly imprinted-chelation composition: Dissolve Cu(NO 3 ) 2 , acrylamide, and EDTA-methyl methacrylate in the acetonitrile / water mixture, and magnetically stir at room temperature for 1-1.5 h to form a Cu 2+ -AM-EDTA-MA complex; add a cross-linking agent, an initiator, and EDTA-graphene to the Cu 2+ -AM-EDTA-MA complex, ultrasonically disperse for 10-15 minutes, deoxygenate by passing nitrogen for 15 min, and then carry out a water bath reaction at 60 °C for 12 h with magnetic stirring at 200 rpm; after the reaction is completed, carry out elution, drying, pulverization, and sieving to obtain Cu 2+Molecularly imprinted-chelation composition;

[0055] S2. Activate the carboxyl group of the molecularly imprinted-chelation composition by the EDC / NHS activation method to obtain a first substance for standby; 2+ Molecularly imprinted-chelation composition is carboxyl-activated to obtain a first substance for standby;

[0056] S3. Prepare Cu 2+ Self-catalytic degrading agent: Use the microcapsule emulsion polymerization method to prepare ascorbic acid microcapsules with ascorbic acid as the core and PMMA-co-PAA polymer as the shell for standby; Obtain a copper ion reduction promoter, and the copper ion reduction promoter is conductive carbon nanotubes for standby; The TEM image of the ascorbic acid microcapsules with ascorbic acid as the core and PMMA-co-PAA polymer as the shell is as Figure 4 shown, showing a light-colored core and a dark-colored shell, indicating that the PMMA-co-PAA polymer and ascorbic acid can be used to prepare a microcapsule structure by the microcapsule emulsion polymerization method. The present invention has no specific requirements for the ratio of the PMMA-co-PAA polymer and ascorbic acid, and only needs to successfully prepare microcapsules that rupture under acidic conditions by using the existing technology;

[0057] S4. Disperse the ascorbic acid microcapsules in Tris buffer and add polyethyleneimine for reaction to perform surface amino modification on the ascorbic acid microcapsules. Under the action of an adhesive, mix the conductive carbon nanotubes with the surface amino-modified ascorbic acid microcapsules, and perform freeze-drying to obtain a second substance for standby;

[0058] S5. Mix and disperse the first substance and the second substance in PBS buffer and react at 25 °C for 12 hours to obtain a third substance;

[0059] S6. Disperse the third substance in acetone and then ultrasonically mix it with an epoxy resin modified with a terminal epoxy group hyperbranched polyester containing a silane coupling agent to obtain a modified epoxy resin.

[0060] After adding a curing agent to the modified epoxy resin, it is used for the protective layer of a sewage tank, and the sewage in the sewage tank is acidic and contains H 2 O 2 , Cu 2+ and phenolic organic compounds.

[0061] Example 2

[0062] This example is based on Example 1. The difference from Example 1 is that in this example, the Cu 2+ molecularly imprinted-chelation composition includes the following components: Cu(NO 3 ) 2 , monomer, ethylene glycol dimethacrylate, initiator, porogen, EDTA-modified graphene, EDTA eluent;

[0063] Among them, the monomer includes acrylamide and EDTA-methyl methacrylate with a mass ratio of 3-4:1; the pore-forming agent includes a mixture of acetonitrile and water with a volume ratio of 1:1.

[0064] Among them, the addition amount of Cu(NO 3 ) 2 is 23% of the total mass of the monomers, the addition amount of EDTA-modified graphene is 1-2% of the total mass of the monomers, the addition amount of ethylene glycol dimethacrylate is 83% of the total mass of the monomers, and the addition amount of the initiator is 1-2% of the total mass of the monomers.

[0065] Example 3

[0066] This example is based on Example 1. The difference from Example 1 is that: in this example, the Cu 2+ The molecularly imprinted-chelating composition includes the following components: Cu(NO 3 ) 2 , monomer, ethylene glycol dimethacrylate, initiator, pore-forming agent, EDTA-modified graphene, EDTA eluent;

[0067] Among them, the monomer includes acrylamide and EDTA-methyl methacrylate with a mass ratio of 3-4:1; the pore-forming agent includes a mixture of acetonitrile and water with a volume ratio of 1:1.

[0068] Among them, the addition amount of Cu(NO 3 ) 2 is 25% of the total mass of the monomers, the addition amount of EDTA-modified graphene is 1-2% of the total mass of the monomers, the addition amount of ethylene glycol dimethacrylate is 85% of the total mass of the monomers, and the addition amount of the initiator is 1-2% of the total mass of the monomers.

[0069] Comparative Example 1

[0070] This comparative example is based on Example 2. The difference from Example 2 is that: the Cu 2+ The molecularly imprinted-chelating composition includes the following components: Cu(NO 3 ) 2 , monomer, ethylene glycol dimethacrylate, initiator, pore-forming agent, EDTA-modified graphene, EDTA eluent;

[0071] Among them, the monomer includes acrylamide and EDTA-methyl methacrylate with a mass ratio of 2:1; the pore-forming agent includes a mixture of acetonitrile and water with a volume ratio of 1:1.

[0072] Comparative Example 2

[0073] This comparative example is based on Example 2. The difference from Example 2 is that: the Cu 2+The molecularly imprinted - chelating composition comprises the following components: Cu(NO 3 ) 2 , monomer, ethylene glycol dimethacrylate, initiator, porogen, EDTA - modified graphene, EDTA eluent;

[0074] Among them, the monomer comprises acrylamide and EDTA - methyl methacrylate with a mass ratio of 5:1; the porogen comprises a mixed solution of acetonitrile and water with a volume ratio of 1:1.

[0075] Comparative Example 3

[0076] This comparative example is based on Example 2, and the difference from Example 2 is that: the Cu 2+ self - catalytic degrading agent does not include conductive carbon nanotubes.

[0077] Comparative Example 4

[0078] This comparative example is based on Example 2, and the difference from Example 2 is that: the addition amount of the Cu 2+ molecularly imprinted - chelating composition is 7% of the mass of the hyperbranched polymer - modified epoxy resin matrix, and the mass ratio of ascorbic acid to the Cu

[0079] molecularly imprinted - chelating composition in the Cu2+ self - catalytic degrading agent is 1:2 - 3.

[0080] This comparative example is based on Example 2, and the difference from Example 2 is that: the addition amount of the Cu 2+ molecularly imprinted - chelating composition is 11% of the mass of the hyperbranched polymer - modified epoxy resin matrix, and the mass ratio of ascorbic acid to the Cu

[0081] molecularly imprinted - chelating composition in the Cu2+ self - catalytic degrading agent is 1:2 - 3.

[0082] This comparative example is based on Example 2, and the difference from Example 2 is that: the addition amount of the Cu 2+ molecularly imprinted - chelating composition is 8 - 10% of the mass of the hyperbranched polymer - modified epoxy resin matrix, and the mass ratio of the ascorbic acid microcapsule to the Cu 2+ molecularly imprinted - chelating composition in the Cu 2+ self - catalytic degrading agent is 1:1.

[0083] Comparative Example 7

[0084] This comparative example is based on Example 2, and the difference from Example 2 is that: the addition amount of the Cu 2+ molecularly imprinted - chelating composition is 8 - 10% of the mass of the hyperbranched polymer - modified epoxy resin matrix, and the mass ratio of the ascorbic acid microcapsule to the Cu 2+ molecularly imprinted - chelating composition in the Cu 2+The mass ratio of the molecularly imprinted-chelation composition is 1:4.

[0085] Comparative Example 8

[0086] Based on Example 2, the difference in this comparative example from Example 2 is that: Cu 2+ molecularly imprinted polymer is used instead of Cu 2+ molecularly imprinted-chelation composition, without a chelation system, not including EDTA-methyl methacrylate and EDTA-modified graphene; that is, in this comparative example, Cu 2+ molecularly imprinted polymer includes the following components: Cu(NO 3 ) 2 , acrylamide, ethylene glycol dimethacrylate, initiator, porogen, EDTA eluent; Cu 2+ The preparation method of the molecularly imprinted polymer refers to the preparation method of the Cu 2+ molecularly imprinted-chelation composition in Example 1.

[0087] Comparative Example 9

[0088] Based on Example 2, the difference in this comparative example from Example 2 is that: a chelate is used instead of Cu 2+ molecularly imprinted-chelation composition, without Cu 2+ molecularly imprinted polymer, and EDTA-methyl methacrylate and EDTA-modified graphene are directly introduced into the hyperbranched polymer-modified epoxy resin.

[0089] Comparative Example 10

[0090] Based on Example 2, the difference in this comparative example from Example 2 is that: the Cu 2+ molecularly imprinted-chelation composition does not include EDTA-modified graphene.

[0091] Comparative Example 11

[0092] Based on Example 2, the difference in this comparative example from Example 2 is that: it does not contain Cu 2+ molecularly imprinted-chelation composition.

[0093] Comparative Example 12

[0094] Based on Example 2, the difference in this comparative example from Example 2 is that: graphene is used instead of EDTA-modified graphene in the Cu 2+ molecularly imprinted-chelation composition.

[0095] Comparative Example 13

[0096] Based on Example 2, the difference in this comparative example from Example 2 is that: it does not contain Cu 2+ self-catalytic degradation agent.

[0097] Comparative Example 14

[0098] Based on Example 2, the difference from Example 2 in this comparative example is that the surface of the acid-responsive ascorbic acid microcapsules is not modified by amination, and the surface of the Cu 2+ molecularly imprinted-chelation composition is not modified by carboxyl activation;

[0099] The preparation method of a modified epoxy resin described above includes the following steps:

[0100] S1. Preparation of Cu 2+ molecularly imprinted-chelation composition: Dissolve Cu(NO 3 ) 2 , acrylamide, and EDTA-methyl methacrylate in an acetonitrile / water mixture, and stir magnetically at room temperature for 1 - 1.5 h to form a Cu 2+ -AM-EDTA-MA complex; Add a crosslinking agent, an initiator, and EDTA-graphene to the Cu 2+ -AM-EDTA-MA complex, ultrasonically disperse for 10 - 15 minutes, deoxygenate by passing nitrogen for 15 min, and then react in a water bath at 60 °C for 12 h with magnetic stirring at 200 rpm; After the reaction, perform elution, drying, pulverization, and sieving to obtain the Cu 2+ molecularly imprinted-chelation composition;

[0101] S2. Preparation of Cu 2+ self-catalytic degrading agent: Using the microcapsule emulsion polymerization method, prepare acid-responsive ascorbic acid microcapsules with ascorbic acid as the core and PMMA-co-PAA polymer as the shell, and set aside; Obtain a copper ion reduction promoter, and the copper ion reduction promoter is a conductive carbon nanotube, and set aside;

[0102] S3. Disperse the Cu 2+ molecularly imprinted-chelation composition, acid-responsive ascorbic acid microcapsules, and conductive carbon nanotubes in acetone, and then ultrasonically mix with an epoxy resin modified by a terminal epoxy group hyperbranched polyester containing a silane coupling agent to obtain a modified epoxy resin.

[0103] Comparative Example 15

[0104] Based on Example 2, the difference from Example 2 in this comparative example is that the Cu 2+ self-catalytic degrading agent includes ascorbic acid and conductive carbon nanotubes, does not have a microcapsule structure, and ascorbic acid is directly added and used in the modified epoxy resin.

[0105] Comparative Example 16

[0106] On the basis of Example 2, the difference between this comparative example and Example 2 is that ordinary epoxy resin is used instead of hyperbranched polymer modified epoxy resin as the matrix, and the ordinary epoxy resin is bisphenol A epoxy resin E39D.

[0107] Comparative Example 17

[0108] Different from the above examples, the epoxy resin used to prepare the coating in this comparative example is ordinary bisphenol A epoxy resin E39D without any modification.

[0109] Test Example 1

[0110] In Examples 1-3 and Comparative Examples 1-17, an acid anhydride curing agent accounting for 10% of the mass of the modified epoxy resin was added to the prepared modified epoxy resin to prepare a coating. Comparative Example 17 was ordinary bisphenol A epoxy resin E39D, which was used as a coating after adding an equal amount of the same curing agent; in simulated sewage with different pollutant concentrations, the degradation rate of phenolic substances in the sewage was detected for 4 h. The higher the degradation rate, the more significant the role of the coating of the present invention in degrading phenol, and further indicating that the coating can effectively prevent the accumulation of phenol on its surface. The test results are shown in Table 1.

[0111] The detection method is as follows: The modified epoxy resin is scrape-coated into a film on a glass plate (thickness 200 ± 10 μm), and after complete curing, a coating sample is obtained. The coating sample is immersed in simulated sewage, and the difference in phenol concentration in the simulated sewage before and after 4 hours is detected, and then the phenol degradation rate is calculated based on the difference in phenol concentration;

[0112] Simulated sewage 1: 25 °C, pH = 3.5 ± 0.2, 5 mg / L phenol (simulant), 50 mg / L CuSO 4 、170 mg / L H 2 O 2 ;

[0113] Simulated sewage 2: 25 °C, pH = 3.5 ± 0.2, 5 mg / L phenol (simulant), 20 mg / L CuSO 4 、170 mg / L H 2 O 2 ;

[0114] Simulated sewage 3: 25 °C, pH = 3.5 ± 0.2, 5 mg / L phenol (simulant), 10 mg / L CuSO 4 、170 mg / L H 2 O 2 ;

[0115] Simulated sewage 4: 25 °C, pH = 3.5 ± 0.2, 5 mg / L phenol (simulant), 5 mg / L CuSO 4 、170 mg / L H 2 O2 。

[0116] Table 1 Phenol degradation rate

[0117] Simulated Sewage 1 Simulated Sewage 2 Simulated Sewage 3 Simulated Sewage 4 Example 1 ＞98.5％ ＞98％ 95-95.5％ 90-91％ Example 2 ＞98.6％ ＞98％ 96-96.3％ 91.3-91.5％ Example 3 ＞98％ 96.8-97％ 95-95.5％ 90-91％ Comparative Example 1 ≤85.2％ ≤80.1％ ≤72.3％ ≤65.5％ Comparative Example 2 ≤88.7％ ≤83.5％ ≤75.6％ ≤68.2％ Comparative Example 3 ≤92.1％ ≤89.4％ ≤82.7％ ≤76.8％ Comparative Example 4 ≤90.5％ ≤86.3％ ≤78.9％ ≤70.2％ Comparative Example 5 ≤94.2％ ≤90.1％ ≤85.6％ ≤79.8％ Comparative Example 6 ≤89.8％ ≤84.6％ ≤77.5％ ≤69.3％ Comparative Example 7 ≤93.5％ ≤88.7％ ≤81.2％ ≤73.6％ Comparative Example 8 ≤75.3％ ≤68.9％ ≤60.2％ ≤52.4％ Comparative Example 9 ≤65.8％ ≤58.7％ ≤50.1％ ≤42.3％ Comparative Example 10 ≤82.6％ ≤76.5％ ≤68.9％ ≤61.2％ Comparative Example 11 ≤30.2％ ≤25.6％ ≤18.9％ ≤12.3％ Comparative Example 12 ≤78.5％ ≤72.3％ ≤64.8％ ≤56.7％ Comparative Example 13 ≤15.8％ ≤10.2％ ＜5％ ＜5％ Comparative Example 14 ≤87.3％ ≤81.6％ ≤74.2％ ≤66.8％ Comparative Example 15 ≤45.6％ ≤38.9％ ≤30.2％ ≤22.5％ Comparative Example 16 ≤62.3％ ≤55.7％ ≤48.2％ ≤40.1％ Comparative Example 17 ＜5％ ＜5％ ＜5％ ＜5％

[0118] Without adding Cu in the epoxy resin coating 2+ Molecularly imprinted-chelation composition and Cu 2+ In the case of the autocatalytic degradation agent system, the concentration of phenol in the sewage will decrease, mainly because the epoxy resin coating will adsorb phenol.

[0119] After the coating samples of Examples 1-3 of the present invention were taken out, no phenolic substances were detected on the coating surface; the coating surface of Comparative Example 17 carried detectable phenolic substances. The coating prepared in Example 2 of the present invention effectively avoided the accumulation of phenolic substances on its surface and had a longer service life compared with the prior art.

[0120] The SEM surface morphology after continuously monitoring for 12 months of the coating prepared from the modified epoxy resin within the scope of Example 2 of the present invention in a flow cell (flow rate 0.5 L / min) with continuous introduction of simulated sewage 1 is as Figure 1 shown. The coating surface is dense and has no visible defects to the naked eye; the SEM surface morphology after continuously monitoring for 12 months of the coating within the scope of Comparative Example 11 in the same flow cell (flow rate 0.5 L / min) with continuous introduction of simulated sewage 1 is as Figure 2 shown, with obvious holes and other defects; the SEM surface morphology after continuously monitoring for 12 months of the coating within the scope of Comparative Example 13 in the same flow cell (flow rate 0.5 L / min) with continuous introduction of simulated sewage 1 is as Figure 3 shown, with obvious cracks and other defects; the present invention has a longer service life and stronger sewage corrosion resistance in acidic sewage containing copper ion-H 2 O 2 -phenolic organic matter triple pollutants.

[0121] Test Example 2

[0122] Detect the performance of the coatings prepared from the epoxy resins prepared in Examples 1-3 and Comparative Example 17, and the inspection method refers to the existing coating inspection methods.

[0123] Adhesion (GB / T 9286-1998): Cross-cut method (1 mm spacing) to evaluate the bonding strength between the coating and the substrate;

[0124] Abrasion resistance (GB / T 1768-2006): 500 g load, 500 revolutions of rubber wheel friction, measure the mass loss;

[0125] Impact resistance (GB / T 1732-2020): A 1 kg steel ball is freely dropped from a height of 50 cm. Observe whether the coating cracks. If it does not crack, it indicates that the impact resistance is greater than 50 cm.

[0126] Table 2 Coating Performance Detection

[0127] Adhesion Abrasion Resistance (mg / 500 revolutions) Impact Resistance (cm) Example 1 Grade 0 12.5±1.2 ＞50 Example 2 Grade 0 10.8±0.9 ＞50 Example 3 Grade 0 13.1±1.1 ＞50 Comparative Example 17 Grade 2 25.6±2.3 ≤50

[0128] Based on the data in Table 1 and Table 2, it can be seen that Example 2 of the present invention is the best ratio. The coating performances of Examples 1-3 of the present invention are all superior to those of a conventional epoxy resin in Comparative Example 17. The modified epoxy resin of the present invention can be used as a protective layer for sewage pools.

[0129] The above are only the preferred embodiments of the present invention and are not intended to limit the protection scope of the present invention. Any modifications, equivalent substitutions, and improvements made by those skilled in the art within the spirit and principles of the present invention shall be included in the protection scope of the present invention.

Claims

1. A modified epoxy resin, characterized in that: Including hyperbranched polymer modified epoxy resin matrix, Cu 2+ Molecular imprinting-chelating composition and Cu 2+ Self-catalytic degradation agent; the Cu 2+ The autocatalytic degradation agent has acid-responsive ascorbic acid microcapsules as the main component; In Cu 2+ Molecularly imprinted-chelating composites for Cu 2+ Under the enrichment effect of 2+ The autocatalytic degradation agent is in the presence of H2O2, Cu at pH 3-4 2+ And degrade phenolic organic matter in wastewater containing phenolic organic matter.

2. A modified epoxy resin according to claim 1, characterized in that: The Cu 2+ The molecular imprinting-chelating composition comprises the following components: Cu(NO3)2, monomer, ethylene glycol dimethacrylate, initiator, porogen, EDTA-modified graphene, and EDTA eluent; The monomers include acrylamide and EDTA-methyl methacrylate in a mass ratio of 3-4:1; the porogen includes a mixed solution of acetonitrile and water in a volume ratio of 1:

1.

3. A modified epoxy resin according to claim 2, characterized in that: The amount of Cu(NO3)2 added is 20-25% of the total mass of the monomer, the amount of EDTA-modified graphene added is 1-2% of the total mass of the monomer, the amount of ethylene glycol dimethacrylate added is 80-85% of the total mass of the monomer, and the amount of initiator added is 1-2% of the total mass of the monomer.

4. A modified epoxy resin according to claim 1, characterized in that: The acid-responsive ascorbic acid microcapsules comprise an inner core and an outer shell, wherein the inner core is ascorbic acid and the outer shell is a PMMA-co-PAA polymer.

5. A modified epoxy resin according to claim 1, characterized in that: The Cu 2+ The self-catalytic degradation agent also includes conductive carbon nanotubes, and the added amount of the conductive carbon nanotubes is 2-3% of the total mass of the acid-responsive ascorbic acid microcapsules.

6. A modified epoxy resin according to claim 1, characterized in that: Cu 2+ The added amount of the molecular imprinting-chelating composition is 8-10% of the mass of the hyperbranched polymer modified epoxy resin matrix, and the mass ratio of ascorbic acid to the Cu2+ molecular imprinting-chelating composition in the Cu2+ self-catalytic degradation agent is 1:2-3.

7. A modified epoxy resin according to claim 1, characterized in that: The hyperbranched polymer modified epoxy resin matrix comprises an epoxy resin modified by a terminal epoxy group hyperbranched polyester and a silane coupling agent.

8. A modified epoxy resin according to claim 1, characterized in that: The acid-responsive ascorbic acid microcapsules are microcapsules whose surfaces are modified by amino. 2+ The molecular imprinting-chelating composition is a composition whose surface is modified by carboxyl activation.

9. A method for preparing a modified epoxy resin according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1. Preparation of Cu 2+ Molecular imprinting-chelating composition: Cu(NO3)2, acrylamide, and EDTA-methyl methacrylate were dissolved in an acetonitrile / water mixture and stirred magnetically at room temperature for 1-1.5 h to form Cu 2+ -AM-EDTA-MA complex; in Cu 2+ -AM-EDTA-MA complex was added with crosslinker, initiator and EDTA-graphene, ultrasonically dispersed for 10-15 minutes, deoxygenated with nitrogen for 15 minutes, and then reacted in a water bath at 60°C for 12 hours with magnetic stirring at 200 rpm; after the reaction, it was eluted, dried, crushed and sieved to obtain Cu 2+ Molecularly imprinted-chelating compositions; S2, using EDC / NHS activation method to activate Cu 2+ Activating the carboxyl group of the molecular imprinting-chelating composition to obtain a first substance for standby use; S3. Preparation of Cu 2+ Self-catalytic degradation agent: using microcapsule emulsion polymerization method, prepare acid-responsive ascorbic acid microcapsules with ascorbic acid as the core and PMMA-co-PAA polymer as the shell, and set aside; obtain a copper ion reduction promoter, the copper ion reduction promoter is conductive carbon nanotubes, and set aside; S4, dispersing ascorbic acid microcapsules in Tris buffer and adding polyethyleneimine to react, performing surface amino modification on the ascorbic acid microcapsules, mixing the conductive carbon nanotubes and the ascorbic acid microcapsules with surface amino modification under the action of an adhesive, and freeze-drying to obtain a second substance for later use; S5, mixing and dispersing the first substance and the second substance in a PBS buffer, and reacting at 25° C. for 12 hours to obtain a third substance; S6. Dispersing the third substance in acetone and then ultrasonically mixing it with the epoxy resin modified with the terminal epoxy hyperbranched polyester containing a silane coupling agent to obtain a modified epoxy resin.

10. The method for preparing a modified epoxy resin according to claim 9, characterized in that: After adding a curing agent to the modified epoxy resin, it is used as a protective layer for a sewage pool. The sewage in the sewage pool is acidic and contains H2O2, Cu 2+ and phenolic organic compounds.

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