Degradable epoxy resin composition and application thereof, body, composite material and recovery method thereof, and product application

Abstract

The invention provides a degradable epoxy resin composition, application of the degradable epoxy resin composition, a body, a composite material, a recovery method of the composite material and application of a product, and belongs to the technical field of recoverable epoxy resin. The component B comprises amino-terminated polyether, aromatic amine, alicyclic amine and an accelerant, the epoxy value of the epoxy resin ranges from 0.571 mol / 100 g to 0.694 mol / 100 g, the viscosity of the epoxy resin at 25 DEG C ranges from 1500 cps to 5000 cps, and the selection standard of the amino-terminated polyether is that the molecular weight ranges from 230 to 5000, the amino-terminated polyether is provided with at least two amino-terminated groups, the main chain is of a polyether structure, and the active functional group at the tail end is an amino polymer. The degradable epoxy resin composition has the advantages of low viscosity, high fluidity, low degradation cost, and excellent mechanical properties and heat resistance of a cured material.

Description

Technical Field

[0001] The present invention relates to the technical field of recyclable epoxy resins, and in particular to a degradable epoxy resin composition and its application, a main body, a composite material and its recycling method, and product application. Background Art

[0002] Epoxy resins have a wide range of applications, for example, they can be used in large wind turbine blades, GIS (gas insulated switch) insulators, battery housings, lightweight body parts and aircraft structural parts. However, epoxy resin products will age with the change of service life. For example, in direct sunlight and harsh environments, the service life is generally 3-5 years. This also means that every year, a large number of large wind turbine blades, GIS (gas insulated switch) insulators, battery housings, lightweight body parts and aircraft structural parts will be replaced. Among them, how to reasonably and scientifically recycle and reuse various retired epoxy resin products has become a difficult problem in the epoxy resin field.

[0003] Driven by environmental protection policies, degradable epoxy resins have become a key direction. This type of resin can still maintain high strength after vacuum infusion, but after retirement, it still needs to be chemically decomposed to recycle fibers and monomers to reduce waste pollution. Moreover, degradable resins need to rely on specific conditions (such as strong acid and other degradation liquids), the degradation energy consumption is high, and the catalyst (such as ruthenium-based) is expensive. Summary of the invention

[0004] Therefore, in order to overcome the shortcomings of the above-mentioned prior art, the present invention provides a degradable epoxy resin composition and its use, a body, a composite material and its recovery method, and a product use. The degradable epoxy resin composition has low viscosity and high fluidity, and the viscosity is low enough to meet the infusion requirements of large structural parts, and the cured product has excellent mechanical properties and heat resistance. The recovery method of the degradable epoxy resin body is simple, and no additional separation of the degradation product and its degradation liquid is required. It can be 100% directly recovered and added to the epoxy resin system, and has excellent heat resistance and mechanical properties, further reducing the degradation cost.

[0005] In order to achieve the above object, the present invention provides a degradable epoxy resin composition for vacuum infusion process, comprising component A and component B, wherein component A comprises epoxy resin, epoxy resin modifier, epoxy reactive diluent and degradation aid, component B comprises amino-terminated polyether, aromatic amine, alicyclic amine and accelerator, the epoxy value of the epoxy resin ranges from 0.571 to 0.694 mol / 100 g, the viscosity at 25° C. is 1500 to 5000 cps, the epoxy resin modifier is poly[(2-oxirane)-1,2-cyclohexanediol] At least one of 2-ethyl-2-(hydroxymethyl)-1,3-propylene glycol ether, cyclohexane-1,2-dicarboxylic acid di(oxiranyl methyl) ester, 4-cyclohexene-1,2-dicarboxylic acid diglycidyl ester, and 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester; the selection criteria of the amino-terminated polyether are polymers with a molecular weight of 230 to 5000, at least two terminal amino groups, a main chain of a polyether structure, and an amino group as the terminal active functional group.

[0006] In one embodiment, the epoxy resin comprises at least one of the following components: , and , The epoxy value is 0.571-0.588 mol / 100g, and the viscosity at 25℃ is 3000-5000cps. The epoxy value is 0.575-0.595 mol / 100g, and the viscosity at 25℃ is 2000-4800cps. The epoxy value is 0.640-0.694 mol / 100g and the viscosity at 25°C is 1500-4000cps.

[0007] In one embodiment, the epoxy resin modifier is at least one of poly[(2-oxiranyl)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propylene glycol ether, cyclohexane-1,2-dicarboxylic acid di(oxiranyl methyl) ester, 4-cyclohexene-1,2-dicarboxylic acid diglycidyl ester, and 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester.

[0008] In one embodiment, the amino-terminated polyether is at least one of D230, MA223, D400, MA240, D2000, MA2200, T403, MA340, T5000, and MA3500.

[0009] In one embodiment, the weight ratio of component A to component B is 100:29-35, wherein every 100 parts of component A contains the following parts by weight: 15-45.5 parts of epoxy resin, 35-75.5 parts of epoxy resin modifier, 1-12 parts of epoxy reactive diluent and 0.01 parts-1.0 parts of degradation aid, and every 100 parts of component B contains the following parts by weight: 40 parts-80 parts of amino-terminated polyether, 0-15 parts of aromatic amine, 5 parts-30 parts of alicyclic amine, and 0.2 parts-12 parts of accelerator.

[0010] In one embodiment, the epoxy reactive diluent is at least one of 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, benzyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and C12-C14 alkyl glycidyl ether.

[0011] In one embodiment, the degradation agent is at least one of N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureapropyltriethoxysilane, 3-ureapropyltrimethoxysilane, 3-ureapropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, hexamethyldisilazane, hexamethylcyclotrisilazane, and triethylenetrimethylcyclotrisilazane.

[0012] In one embodiment, the aromatic amine is at least one of m-phenylenediamine, diaminodiphenylmethane, o-(β-aminoethoxy)aniline, methylaniline, 2,3-dimethylaniline, and diethyltoluenediamine.

[0013] In one embodiment, the alicyclic amine is at least one of isophorone diamine, menthane diamine, 1,3-bis(aminomethyl)cyclohexane, diaminodicyclohexylmethane, methylcyclohexanediamine, cyclohexanediamine, and 4,4-diamino-dicyclohexylmethane.

[0014] In one embodiment, the accelerator is at least one of 3-diethylaminopropylamine, aminoethylpiperazine, diethylenetriamine, 2,4,6-tris(dimethylaminomethyl)phenol, o-hydroxybenzoic acid, phthalic acid dihydrazide, and furandicarboxylic acid dihydrazide.

[0015] In one embodiment, the epoxy resin is obtained by molecular distillation and has a purity of ≥90.0%.

[0016] A use of a degradable epoxy resin composition, wherein the epoxy resin composition is used for preparing a degradable epoxy resin body or a degradable epoxy resin composite material by adopting a vacuum infusion process, and the epoxy resin composition is the above-mentioned epoxy resin composition.

[0017] A degradable epoxy resin body is prepared by mixing and curing the epoxy resin composition as described above. The preparation method of the degradable epoxy resin body comprises: weighing component A and component B according to set weight proportions respectively; mixing the component A and the component B respectively and evenly, and then mixing to obtain a mixture; and curing the mixture after vacuum infusion to obtain the degradable epoxy resin body.

[0018] A method for recovering the above-mentioned degradable epoxy resin body comprises the following steps: immersing the degradable epoxy resin body in a degradation liquid, heating it to 80-180°C for a degradation reaction for 4-68 hours, and obtaining a first comprehensive product after degradation; the degradation liquid is composed of a cyclic compound or a branched compound containing at least one lone pair of electrons.

[0019] A use of the above-mentioned first comprehensive product, after the first comprehensive product is mixed with epoxy resin, is used to prepare a degradable epoxy resin body or a degradable epoxy resin composite material using a vacuum infusion process.

[0020] A degradable epoxy resin composite material is prepared by mixing the above epoxy resin composition, compounding with a reinforcing material, and then curing.

[0021] In one embodiment, the reinforcing material is at least one of glass fiber, carbon fiber, polyester fiber and polyamide fiber.

[0022] A method for recycling the above-mentioned degradable epoxy resin composite material comprises the following steps: immersing the degradable epoxy resin composite material in a degradation liquid, heating it to 80-180°C for a degradation reaction for 4-68 hours, and obtaining a second comprehensive product after degradation; the degradation liquid is composed of a cyclic compound or a branched compound containing at least one lone pair of electrons.

[0023] A use of the second comprehensive product as mentioned above, wherein the second comprehensive product is mixed with epoxy resin and then used to prepare a degradable epoxy resin composite material by a vacuum infusion process.

[0024] Compared with the prior art, the advantages of the present invention are: by selecting epoxy resin, epoxy resin modifier and amino-terminated polyether, the degradable epoxy resin composition has low viscosity and high fluidity, and the viscosity is low enough to meet the infusion requirements of large structural parts, and the cured product has excellent mechanical properties and heat resistance. The recovery method of the degradable epoxy resin body is simple, and no additional separation of degradation products and degradation liquid is required. It can be directly recovered and added to the epoxy resin system 100%, and has excellent heat resistance and mechanical properties, further reducing the degradation cost. DETAILED DESCRIPTION

[0025] The embodiments of the present application are described in detail below.

[0026] The following describes the implementation methods of the present application through specific examples, and those skilled in the art can easily understand other advantages and effects of the present application from the contents disclosed in this specification. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. The present application can also be implemented or applied through other different specific implementation methods, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present application. It should be noted that, in the absence of conflict, the following embodiments and the features in the embodiments can be combined with each other. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in the field without making creative work belong to the scope of protection of the present application.

[0027] It should be noted that various aspects of the embodiments within the scope of protection of the present invention are described below. It should be apparent that the aspects described herein can be embodied in a wide variety of forms, and any specific structure and / or function described herein is merely illustrative. Based on the present application, it should be understood by those skilled in the art that an aspect described herein can be implemented independently of any other aspect, and two or more of these aspects can be combined in various ways. For example, any number and aspect described herein can be used to implement the device and / or practice the method. In addition, other structures and / or functionalities other than one or more of the aspects described herein can be used to implement this device and / or practice this method.

[0028] Additionally, in the following description, specific details are provided to facilitate a thorough understanding of the examples. However, it will be understood by those skilled in the art that the aspects described may be practiced without these specific details.

[0029] The embodiment of the present application provides a degradable epoxy resin composition for vacuum infusion, including component A and component B.

[0030] Component A comprises epoxy resin, epoxy resin modifier, epoxy reactive diluent and degradation aid.

[0031] The epoxy value of the epoxy resin ranges from 0.571 to 0.694 mol / 100 g, and the viscosity at 25° C. is 1500 to 5000 cps. In one embodiment, the epoxy resin is obtained by molecular distillation, and the purity is ≥90.0%.

[0032] The epoxy resin modifier is at least one of poly[(2-oxiranyl)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propylene glycol ether, cyclohexane-1,2-dicarboxylic acid di(oxiranylmethyl) ester, 4-cyclohexene-1,2-dicarboxylic acid diglycidyl ester, and 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester.

[0033] Epoxy reactive diluents refer to low molecular weight compounds with one or more epoxy groups, which can directly participate in the curing reaction of epoxy resins and become part of the cross-linked network structure of epoxy resin cured products. Epoxy reactive diluents can be monoepoxy-containing acryl glycidyl ether, phenyl glycidyl ether, or diepoxy-containing ethylene glycol diglycidyl ether, resorcinol diglycidyl ether, etc.

[0034] Prodegradants are substances that can accelerate the degradation rate of polymers. In one embodiment, photosensitive prodegradants and / or catalysts for degradation can be selected based on the mechanism of action.

[0035] Component B comprises amino-terminated polyether, aromatic amine, alicyclic amine and accelerator.

[0036] The selection criteria for amino-terminated polyethers are polymers with a molecular weight of 230-5000, at least two amino groups at the end, a polyether structure as the main chain, and an amine group as the terminal active functional group. Amino-terminated polyethers are polyamines with a polyether main chain, also known as "polyether polyamines". Polyetheramine products usually share the same CAS number (9046-10-0). Amino-terminated polyethers can be the product of amination of secondary hydroxyl-terminated polyether diols or triols (including PPG and PO-EO copolyethers). They are aliphatic polyetheramines, in which the terminal groups are mainly primary amino groups. Since the activity of amino groups with isocyanates is much higher than that of hydroxyl groups, polyether polyamines are highly active polyethers. Amino-terminated polyethers also have a small amount of polyetheramines obtained by converting amino groups to secondary amino groups. There are also special amino-terminated polyethers with PTMEG as the main chain and aromatic amino groups as the terminal groups. The CAS number of polyoxypropylenediamine is 9046-10-0, and representative products include the JeffamineD series. The CAS number of polyoxypropylenetriamChemicalbookine with glycerol as the initiator is 64852-22-8, and the representative products are T-3000 and T-5000. The CAS number of polyoxypropylenetriamine with trimethylolpropane as the initiator is 39423-51-3, and the representative products are T-403. The CAS number of polyoxyethylene-oxypropylene diamine (PPG-PEG-PPG copolyether diamine) is 65605-36-9, and the representative products are Jeffamine ED series. The CAS number of PPG-PTMEG-PPG block copolyether diamine is 796093-55-5, and the representative products are Jeffamine THF-100 and THF-140. The CAS number of polytetrahydrofuran diamine is 960525-56-8, and the typical product is Jeffamine THF-170.

[0037] The above-mentioned degradable epoxy resin composition, through the screening of epoxy resin, epoxy resin modifier and terminal amino polyether, makes the degradable epoxy resin composition have low viscosity and high fluidity, and the viscosity is low enough to meet the infusion requirements of large structural parts, and the cured product has excellent mechanical properties and heat resistance. The recycling method of the degradable epoxy resin body is simple, and there is no need to separate the degradation product from its degradation liquid. It can be 100% directly recycled and added to the epoxy resin system, and has excellent heat resistance and mechanical properties, further reducing the degradation cost.

[0038] The above-mentioned degradable epoxy resin composition can be applied to the production and manufacturing of degradable and recyclable wind turbine blades, degradable and recyclable yachts / ships, degradable and recyclable cars / high-speed trains and other land transportation vehicles, degradable and recyclable low-altitude aircraft, helicopters, and small aircraft.

[0039] In one embodiment, the epoxy resin comprises at least one of the following components: , and .

[0040] The epoxy value is 0.571 mol / 100g -0.588 mol / 100g, the viscosity at 25°C is 3000-5000cps; the total chlorine is ≤900ppm; the appearance is a colorless, transparent, easily crystallized liquid, referred to as "resin 1#" in the following examples.

[0041] The epoxy value is 0.575 mol / 100g-0.595 mol / 100g, the viscosity at 25°C is 2000-4800 cps, and the appearance is a colorless or light yellow easily crystallized liquid. In the following examples, it is referred to as "resin 2#".

[0042] The epoxy value is 0.640 mol / 100g -0.694 mol / 100g; the viscosity at 25°C is 1500-4000cps, the total chlorine is ≤900ppm; the appearance is a colorless to light yellow transparent and easily crystallized liquid. In the following examples, it is referred to as "resin 3#".

[0043] In one embodiment, the epoxy resin modifier is at least one of poly[(2-oxiranyl)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propylene glycol ether (hereinafter referred to as "modifier 1#"), cyclohexane-1,2-dicarboxylic acid di(oxiranylmethyl) ester (hereinafter referred to as "modifier 2#"), 4-cyclohexene-1,2-dicarboxylic acid diglycidyl ester (hereinafter referred to as "modifier 3#"), and 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester (hereinafter referred to as "modifier 4#") .

[0044] In one embodiment, the amino-terminated polyether is at least one of D230, MA223, D400, MA240, D2000, MA2200, T403, MA340, T5000, and MA3500.

[0045] 1. D in D230 stands for difunctionality (i.e., the molecule contains two amino functional groups), and 230 means that its average molecular weight is about 230. The main chain is polypropylene oxide with two primary amino groups at the end.

[0046] 2. MA223, MA means that the product belongs to the polyetheramine series, and 223 means that its average molecular weight is about 230. The main chain is polypropylene oxide, with two primary amino groups at the end. It is similar to D230, but may have slight differences in production process or purity.

[0047] 3. The D in D400 stands for difunctionality, and 400 means its average molecular weight is about 400. The main chain is polypropylene oxide with two amino groups at the ends.

[0048] 4. In MA240, MA stands for polyetheramine, and 240 means its average molecular weight is about 400. The main chain is polypropylene oxide, with two amino groups at the end. It is similar to D400, but may be slightly optimized in production process or performance.

[0049] 5. The D in D2000 stands for difunctionality, and 2000 means its average molecular weight is about 2000. The main chain is polypropylene oxide with two amino groups at the end.

[0050] 6. In MA2200, MA stands for polyetheramine, and 2200 means its average molecular weight is about 2000. The main chain is polypropylene oxide, with two amino groups at the end. It is similar to D2000, but the performance may be optimized during the production process.

[0051] 7.T in T403 stands for trifunctionality (i.e., the molecule contains three amino functional groups), and 403 means that its average molecular weight is about 403. The main chain is polypropylene oxide, with three amino groups at the end.

[0052] 8. In MA340, MA stands for polyetheramine, and 340 means that its average molecular weight is about 340. The main chain is polypropylene oxide, with three amino groups at the end. It has three functionalities, high reactivity, and low viscosity (50-100 mPa·s). It is similar to T403, but the performance may be optimized during the production process.

[0053] 9. T in T5000 stands for trifunctionality, and 5000 means its average molecular weight is about 5000. The main chain is polypropylene oxide with three amino groups at the end.

[0054] 10. In MA3500, MA stands for polyetheramine, and 3500 means its average molecular weight is about 3500. The main chain is polypropylene oxide, with three amino groups at the end. It is similar to T5000, but the performance may be optimized during the production process.

[0055] The amino-terminated polyether can be selected according to the specific performance parameters in the table below (AHEW active hydrogen equivalent refers to the average molecular weight of each active hydrogen atom in the compound).

[0056]

[0057] In one embodiment, the weight ratio of component A to component B is 100:29-35.

[0058] Every 100 parts of component A contain the following parts by weight: 15-45.5 parts of epoxy resin, 35-75.5 parts of epoxy resin modifier, 1-12 parts of epoxy active diluent and 0.01-1.0 parts of degradation aid.

[0059] Every 100 parts of component B contain the following parts by weight: 40-80 parts of amino-terminated polyether, 0-15 parts of aromatic amine, 5-30 parts of alicyclic amine, and 0.2-12 parts of accelerator.

[0060] In one embodiment, the epoxy-reactive diluent is at least one of 1,4-butanediol diglycidyl ether (hereinafter referred to as "diluent 1#" in the examples), ethylene glycol diglycidyl ether (hereinafter referred to as "diluent 2#" in the examples), 1,6-hexanediol diglycidyl ether (hereinafter referred to as "diluent 3#" in the examples), benzyl glycidyl ether (hereinafter referred to as "diluent 4#" in the examples), butyl glycidyl ether (hereinafter referred to as "diluent 5#" in the examples), phenyl glycidyl ether (hereinafter referred to as "diluent 6#" in the examples), and C12-C14 alkyl glycidyl ether (hereinafter referred to as "diluent 7#" in the examples).

[0061] In one embodiment, the prodegradant is at least one of N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane (hereinafter referred to as "prodegradant 1#" in the examples), 3-ureidopropyltriethoxysilane (hereinafter referred to as "prodegradant 2#"), 3-ureidopropyltrimethoxysilane (hereinafter referred to as "prodegradant 3#"), 3-ureidopropyltriethoxysilane (hereinafter referred to as "prodegradant 4#"), γ-glycidyloxypropyltrimethoxysilane (hereinafter referred to as "prodegradant 5#"), β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane (hereinafter referred to as "prodegradant 6#"), hexamethyldisilazane (hereinafter referred to as "prodegradant 7#"), hexamethylcyclotrisilazane (hereinafter referred to as "prodegradant 8#"), and trivinyltrimethylcyclotrisilazane (hereinafter referred to as "prodegradant 9#") in the examples.

[0062] In one embodiment, the aromatic amine is at least one of m-xylylenediamine, diaminodiphenylmethane (DDM), o-(β-aminoethoxy)aniline, methylaniline, 2,3-dimethylaniline, and diethyltoluenediamine.

[0063] In one embodiment, the alicyclic amine is at least one of isophoronediamine (IPDA), menthanediamine (MDA), 1,3-bis(aminomethyl)cyclohexane (13BAC), diaminodicyclohexylmethane (PACM), methylcyclohexanediamine (HMDA), cyclohexanediamine, and 4,4-diamino-dicyclohexylmethane.

[0064] In one embodiment, the promoter is at least one of 3-diethylaminopropylamine (hereinafter referred to as "promoter 1#"), aminoethylpiperazine (hereinafter referred to as "promoter 2#"), diethylenetriamine (hereinafter referred to as "promoter 3#"), 2,4,6-tris(dimethylaminomethyl)phenol (hereinafter referred to as "promoter 4#"), o-hydroxybenzoic acid (hereinafter referred to as "promoter 5#"), phthalic acid dihydrazide (hereinafter referred to as "promoter 6#"), and furan dicarboxylic acid dihydrazide (hereinafter referred to as "promoter 7#") .

[0065] The invention discloses a use of a degradable epoxy resin composition for vacuum infusion. The epoxy resin composition is used for preparing a degradable epoxy resin body or a degradable epoxy resin composite material by adopting a vacuum infusion process.

[0066] A degradable epoxy resin body is prepared by mixing and curing the above-mentioned epoxy resin composition. The preparation of the degradable epoxy resin body comprises: weighing component A and component B respectively according to set weight proportions; mixing component A and component B respectively and evenly, and then mixing to obtain a mixture; and curing the mixture after vacuum infusion to obtain the degradable epoxy resin body.

[0067] A method for recovering a degradable epoxy resin body comprises the following steps: immersing the degradable epoxy resin body in a degradation liquid, heating the temperature to 80-180°C for a degradation reaction for 4-68 hours, and obtaining a first comprehensive product after degradation; the degradation liquid is configured with a cyclic compound or a branched compound containing at least one lone pair of electrons.

[0068] Cyclic compounds or branched compounds containing lone pairs of electrons may have lone pairs of electrons introduced through the presence of heteroatoms (such as nitrogen, oxygen, sulfur, phosphorus, etc.). These lone pairs of electrons can participate in the π electron system and form hydrogen bonds. The ring structure of the cyclic compound may be a five-membered ring or a six-membered ring structure. The number of heteroatoms in the ring structure is 1 or 2, and when the number of heteroatoms is 2, the heteroatoms may be the same or different. The degradation liquid may be composed of a single cyclic compound or a branched compound, or may be composed of a plurality of cyclic compounds or branched compounds containing lone pairs of electrons. When there are a plurality of cyclic compounds or branched compounds containing lone pairs of electrons, the cyclic compounds or branched compounds in the degradation liquid may react without destroying the lone pairs of electrons. For example, the degradation liquid may be , , , , , ethylene oxide, furan, imidazole, amino compounds of ethylene dichloride, etc., or the reaction product of at least one of them.

[0069] A use of a first comprehensive product. After the first comprehensive product is mixed with epoxy resin, it is used to prepare a degradable epoxy resin body or a degradable epoxy resin composite material by adopting a vacuum infusion process.

[0070] A degradable epoxy resin composite material is prepared by mixing an epoxy resin composition, compounding it with a reinforcing material, and then curing it.

[0071] The biodegradable epoxy resin composite material (FRP material) may include but is not limited to glass fiber reinforced composite materials, carbon fiber reinforced composite materials, aramid fiber reinforced composite materials, ceramic fiber reinforced composite materials, BPO fiber reinforced composite materials, and basalt fiber reinforced composite materials.

[0072] In one embodiment, the reinforcement material is at least one of glass fiber, carbon fiber, polyester fiber and polyamide fiber.

[0073] A method for recycling a degradable epoxy resin composite material comprises the following steps: immersing the degradable epoxy resin composite material in a degradation liquid, heating it to 80-180°C for a degradation reaction for 4-68 hours, and obtaining a second comprehensive product after degradation; the degradation liquid is a cyclic compound or a branched compound containing at least one lone pair of electrons. The degradable epoxy resin composite material is completely degraded 100% in the degradation liquid, and the degraded organic product is a transparent liquid.

[0074] A use of a second comprehensive product, after the second comprehensive product is mixed with epoxy resin, is used to prepare a degradable epoxy resin composite material by adopting a vacuum infusion process.

[0075] Each component in the following examples is weighed in parts by weight.

[0076] Embodiment 1 Prepare a degradable epoxy resin composition, the weight ratio of component A to component B is 100:30. Every 100 parts of component A contains: 23.8 parts of resin 2#, 20 parts of resin 3#, 13.2 parts of modifier 1#, 35 parts of modifier 2#, 7.8 parts of diluent 1#, 0.05 parts of degradation aid 1#, and 0.15 parts of degradation aid 2#; every 100 parts of component B contains: 70 parts of amino-terminated polyether D230, 3 parts of amino-terminated polyether T403, 10 parts of aromatic amine (DDM), 10 parts of alicyclic amine (10.8 parts of IPDA, 6 parts of PACM), and 0.2 parts of accelerator 1#.

[0077] Embodiment 2 A degradable epoxy resin composition was prepared, wherein the weight ratio of component A to component B was 100:29.

[0078] Among them, for every 100 parts of component A: 30.5 parts of resin 1#, 6.4 parts of resin 2#, 32.2 parts of modifier 2#, 30.8 parts of modifier 3#, 0.09 parts of diluent 1#, 0.01 parts of degradation aid 5#; for every 100 parts of component B: 72 parts of amino-terminated polyether D230, 1 part of aromatic amine (DDM), 16 parts of alicyclic amine (HMDA, 10 parts of PACM), 0.2 parts of accelerator 3#, 0.8 parts of accelerator 4#.

[0079] Embodiment 3 A degradable epoxy resin composition was prepared, wherein the weight ratio of component A to component B was 100:34.

[0080] Every 100 parts of component A include: 22.6 parts of resin 2#, 12.4 parts of resin 3#, 23.8 parts of modifier 2#, 40.2 parts of modifier 4#, 0.7 parts of degradation aid 3#, and 0.3 parts of degradation aid 9#; every 100 parts of component B include: 74 parts of amino-terminated polyether D230, 0.1 parts of amino-terminated polyether T5000, aromatic amines (2 parts of meta-xylylenediamine, 2.8 parts of methylaniline), alicyclic amines (10 parts of IPDA, 3 parts of 13BAC, and 7.9 parts of HMDA), and 0.2 parts of accelerator 5#.

[0081] Embodiment 4 A degradable epoxy resin composition was prepared, wherein the weight ratio of component A to component B was 100:33.

[0082] Every 100 parts of component A include: 25 parts of resin 1#, 10 parts of resin 3#, 60 parts of modifier 2#, 4.8 parts of diluent 1#, 0.05 parts of degradation aid 1#, and 0.15 parts of degradation aid 2#; every 100 parts of component B include: 50 parts of amino-terminated polyether D230, 4 parts of amino-terminated polyether D400, 18 parts of amino-terminated polyether T403, aromatic amines (10 parts of DDM, 0.9 parts of o-(β-aminoethoxy) aniline, and 1.9 parts of methyl aniline), alicyclic amines (10 parts of IPDA and 7 parts of HMDA), and 0.2 parts of accelerator 7#.

[0083] Embodiment 5 A degradable epoxy resin composition is prepared, wherein the weight ratio of component A to component B is 100:35.

[0084] Every 100 parts of component A include: 35 parts of resin 1#, 5 parts of resin 3#, 33 parts of modifier 2#, 2 parts of modifier 3#, 12 parts of modifier 4#, 8 parts of diluent 1#, 4 parts of diluent 4#, 0.9 parts of degradation aid 8#, 0.1 parts of degradation aid 9#; every 100 parts of component B include: 48 parts of amino-terminated polyether D230, 22 parts of amino-terminated polyether T403, 5 parts of aromatic amine (meta-phenylenediamine), 20 parts of alicyclic amine (HMDA, 4.8 parts of PACM), and 0.2 parts of accelerator 2#.

[0085] Embodiment 6 A degradable epoxy resin composition was prepared, wherein the weight ratio of component A to component B was 100:29.

[0086] Every 100 parts of component A include: 38 parts of resin 1#, 15 parts of resin 3#, 12 parts of modifier 1#, 19 parts of modifier 4#, 15 parts of diluent 1#, 0.9 parts of degradation aid 7#, and 0.1 parts of degradation aid 9#; every 100 parts of component B include: 46 parts of amino-terminated polyether D230, 24 parts of amino-terminated polyether T403, 8 parts of aromatic amine (DDM), 15 parts of alicyclic amine (HMDA), and 7 parts of accelerator 4#.

[0087] Embodiment 7 A degradable epoxy resin composition was prepared, wherein the weight ratio of component A to component B was 100:31.

[0088] Every 100 parts of component A include: 33 parts of resin 2#, 62 parts of modifier 3#, 4 parts of diluent 5#, 0.3 parts of degradation aid 4#, 0.2 parts of degradation aid 6#, and 0.5 parts of degradation aid 8#; every 100 parts of component B include: 30 parts of amino-terminated polyether D230, 5 parts of amino-terminated polyether D400, 0.3 parts of amino-terminated polyether D2000, 38 parts of amino-terminated polyether T403, 4 parts of aromatic amine (DDM), 11 parts of alicyclic amine (HMDA), and 11.7 parts of accelerator 4#.

[0089] Embodiment 8 A degradable epoxy resin composition was prepared, wherein the weight ratio of component A to component B was 100:32.

[0090] Every 100 parts of component A include: 25 parts of resin 1#, 14 parts of resin 2#, 60 parts of modifier 2#, 0.5 parts of diluent 6#, 0.3 parts of degradation aid 5#, and 0.2 parts of degradation aid 6#; every 100 parts of component B include: 33 parts of amino-terminated polyether D230, 10 parts of amino-terminated polyether D400, 33 parts of amino-terminated polyether T403, 23.6 parts of alicyclic amine (HMDA), and 0.4 parts of accelerator 3#.

[0091] Embodiment 9 A degradable epoxy resin composition was prepared, wherein the weight ratio of component A to component B was 100:29.

[0092] Among them, every 100 parts of component A contains: 34.3 parts of resin 1#, 0.7 parts of modifier 1#, 60 parts of modifier 3#, 3.5 parts of modifier 4#, 1 part of diluent 6#, 0.3 parts of degradation aid 3#, and 0.2 parts of degradation aid 4#; every 100 parts of component B contains: 35 parts of amino-terminated polyether D230, 2 parts of amino-terminated polyether D2000, 40 parts of amino-terminated polyether T403, 1.8 parts of aromatic amine (diethyltoluenediamine), alicyclic amine (10 parts of IPDA, 11 parts of HMDA), 0.1 parts of accelerator 4#, and 0.1 parts of accelerator 6#.

[0093] Embodiment 10 A degradable epoxy resin composition was prepared, wherein the weight ratio of component A to component B was 100:33.

[0094] Every 100 parts of component A include: 30 parts of resin 1#, 3.3 parts of resin 2#, 55 parts of modifier 2#, 9.7 parts of modifier 3#, 1.8 parts of diluent 7#, 0.1 parts of degradation aid 5#, and 0.1 parts of degradation aid 7#; every 100 parts of component B include: 37 parts of amino-terminated polyether D230, 35 parts of amino-terminated polyether T403, 1 part of amino-terminated polyether T5000, 3.8 parts of aromatic amine (diethyltoluenediamine), 12 parts of alicyclic amine (IPDA, 11 parts of HMDA), 0.1 parts of accelerator 6#, and 0.1 parts of accelerator 7#.

[0095] The degradable epoxy resin composition is weighed according to the above weight proportions and applied to prepare the degradable epoxy resin body by adopting a vacuum infusion process.

[0096] The performance data of the prepared biodegradable epoxy resin body are: .

[0097] Therefore, the mixed viscosity of the biodegradable epoxy resin prepared by the above method is 100~400mpa.s@25℃, and its operating time is 100min-212min; tensile strength is 65-82MPa, tensile modulus is 3000-4000MPa, elongation at break is 2%-9%, flexural strength is 110-145MPa, flexural modulus is 3100-4100MPa, compressive strength is 80-120MPa, compression modulus is 2500-3100MPa, and glass transition temperature is 70-83℃ (the units of the performance parameters in the above table are consistent with the units of the performance parameters in this paragraph).

[0098] The above-mentioned method for recovering the degradable epoxy resin body comprises the following steps: immersing the degradable epoxy resin body in a degradation liquid, heating it to 80-180°C for a degradation reaction for 4-68 hours, obtaining a first comprehensive product after degradation, and the degradation liquid is + +NH3.H2O+ The reaction products under certain conditions are formed in proportion. The entire degradation process does not need to be carried out in a strong acid environment, which reduces the danger of the degradation process, nor does it need to add additional catalysts, which reduces the degradation cost.

[0099] The performance data of the first comprehensive product after degradation are as follows: .

[0100] The viscosity of the first comprehensive product after degradation is 10-780mpa.s@25°C, and it can be mixed with epoxy resin and reused again. The degradation product and its degradation liquid do not need to be separated, and can be 100% directly recycled and added to the epoxy resin system, and has excellent heat resistance and mechanical properties.

[0101] The first comprehensive product is directly added to the HPRTM (High Pressure Resin Transfer Molding) formula, and the test data of the degradable epoxy resin composite material prepared by the HPRTM process are as follows (the weight proportion of the first comprehensive product added to product A in the degradable epoxy resin composite material is 63.4%, the weight proportion of the first comprehensive product added to product B in the degradable epoxy resin composite material is 58.0%, and product C is a degradable epoxy resin composite material without adding the first comprehensive product, and the first comprehensive product is the first comprehensive product obtained after degradation in Example 4):

[0102] The purpose of testing the gel time is to determine the curing speed of the product. The HPRTM molding process requires a fast curing speed.

[0103] The TG test refers to placing the resin and glass fiber together in the HPRTM equipment mold, maintaining the pressure at 100°C and 1300 tons for 180 seconds to allow the degradable epoxy resin composite material to cure, and then measuring the glass transition temperature of the cured degradable epoxy resin composite material. The test equipment is DSC; the unit of Tg is ℃.

[0104] Normal temperature mechanical test refers to: resin + curing agent with 600g / m 2 The tensile strength mechanical properties of FRP (fiber reinforced polymer) made of biaxial glass fiber cloth were tested at room temperature.

[0105] 97℃ 72h mechanical test means: resin + curing agent with 600g / m 2 The FRP (fiber reinforced polymer) made of biaxial glass fiber cloth was subjected to mechanical property testing of tensile strength after heat aging at 97°C for 72h.

[0106] From the above table, it can be seen that the first comprehensive product after degradation can be directly added to the epoxy resin system to prepare a new resin product without additional separation treatment. And the performance of the prepared degradable epoxy resin composite material is not greatly affected, and it still has excellent heat resistance and mechanical properties.

[0107] In one embodiment, the method for recycling a degradable epoxy resin body or a degradable epoxy resin composite material further includes: before the degradation reaction, using ultrasound with a power of 30KW and a frequency of 50HZ for pretreatment for 4 hours, and mechanically oscillating during the degradation process.

[0108] The above is only a specific implementation of the present application, but the protection scope of the present application is not limited thereto. Any changes or substitutions that can be easily conceived by any technician familiar with the technical field within the technical scope disclosed in the present application should be covered within the protection scope of the present application.

Claims

1. A degradable epoxy resin composition for use in a vacuum infusion process, characterized in that: It includes component A and component B. Component A includes epoxy resin, epoxy resin modifier, epoxy active diluent and degradation aid. Component B contains amino-terminated polyether, aromatic amine, alicyclic amine and accelerator. The epoxy value of the epoxy resin ranges from 0.571 mol / 100 g to 0.694 mol / 100 g, and the viscosity of the epoxy resin at 25° C. ranges from 1500 cps to 5000 cps. The epoxy resin modifier is at least one of poly[(2-oxiranyl)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propylene glycol ether, cyclohexane-1,2-dicarboxylic acid di(oxiranylmethyl) ester, 4-cyclohexene-1,2-dicarboxylic acid diglycidyl ester, and 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester; The selection criteria of the amino-terminated polyether are polymers with a molecular weight of 230-5000, at least two amino-terminated groups, a main chain of a polyether structure, and an amino-terminal active functional group.

2. The degradable epoxy resin composition according to claim 1, characterized in that: The epoxy resin comprises at least one of the following components: , and , The epoxy value is 0.571mol / 100g-0.588mol / 100g, and the viscosity of epoxy resin at 25℃ is 3000cps-5000cps. The epoxy value is 0.575mol / 100g-0.595 mol / 100g, and the viscosity of the epoxy resin at 25°C is 2000cps-4800cps. The epoxy value is 0.640 mol / 100g-0.694 mol / 100g, and the viscosity of the epoxy resin at 25°C is 1500cps-4000cps.

3. The degradable epoxy resin composition according to claim 1, characterized in that: The weight ratio of component A to component B is 100:29~35. Wherein, every 100 parts of component A contains the following parts by weight: 15-45.5 parts of epoxy resin, 35-75.5 parts of epoxy resin modifier, 1-12 parts of epoxy reactive diluent and 0.01 parts to 1.0 parts of degradation aid. Every 100 parts of component B contain the following parts by weight: 40-80 parts of amino-terminated polyether, 0-15 parts of aromatic amine, 5-30 parts of alicyclic amine, and 0.2-12 parts of accelerator.

4. The degradable epoxy resin composition according to claim 1, characterized in that: The epoxy active diluent is at least one of 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, benzyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and C12-C14 alkyl glycidyl ether.

5. The degradable epoxy resin composition according to claim 1, characterized in that: The degradation aid is at least one of N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureapropyltriethoxysilane, 3-ureapropyltrimethoxysilane, 3-ureapropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, hexamethyldisilazane, hexamethylcyclotrisilazane and triethylenetrimethylcyclotrisilazane.

6. The degradable epoxy resin composition according to claim 1, characterized in that: The aromatic amine is at least one of m-phenylenediamine, diaminodiphenylmethane, o-(β-aminoethoxy)aniline, methylaniline, 2,3-dimethylaniline and diethyltoluenediamine.

7. The degradable epoxy resin composition according to claim 1, characterized in that: The alicyclic amine is at least one of isophorone diamine, menthane diamine, 1,3-bis(aminomethyl)cyclohexane, diaminodicyclohexylmethane, methylcyclohexane diamine, cyclohexane diamine, and 4,4-diamino-dicyclohexylmethane.

8. The degradable epoxy resin composition according to claim 1, characterized in that: The accelerator is at least one of 3-diethylaminopropylamine, aminoethylpiperazine, diethylenetriamine, 2,4,6-tris(dimethylaminomethyl)phenol, o-hydroxybenzoic acid, phthalic acid dihydrazide, and furandicarboxylic acid dihydrazide.

9. The degradable epoxy resin composition according to claim 1, characterized in that: The epoxy resin is obtained through molecular distillation, and has a purity of ≥90.0%.

10. A use of a degradable epoxy resin composition, characterized in that: The epoxy resin composition is used for preparing a degradable epoxy resin body or a degradable epoxy resin composite material by a vacuum infusion process. The epoxy resin composition is the epoxy resin composition according to any one of claims 1 to 9.

11. A degradable epoxy resin body, characterized in that: The preparation method of the degradable epoxy resin body is prepared by mixing and curing the epoxy resin composition according to any one of claims 1 to 9, and comprises: Weigh component A and component B according to the set weight proportions respectively; The component A and the component B are mixed evenly respectively, and then mixed to obtain a mixture; The mixed material is vacuum-infused and then cured to obtain a degradable epoxy resin body.

12. A method for recycling a degradable epoxy resin body as claimed in claim 11, characterized in that: The steps include: The degradable epoxy resin body is immersed in a degradation liquid, and the temperature is raised to 80-180° C. to perform a degradation reaction for 4-68 hours to obtain a first comprehensive product after degradation; The degradation liquid is composed of a cyclic compound or a branched chain compound containing at least one lone pair of electrons.

13. A use of the first integrated product as claimed in claim 12, characterized in that: After the first comprehensive product is mixed with epoxy resin, it is used to prepare a degradable epoxy resin body or a degradable epoxy resin composite material by adopting a vacuum infusion process.

14. A degradable epoxy resin composite material, characterized in that: The epoxy resin composition according to any one of claims 1 to 9 is mixed, compounded with a reinforcing material, and then cured to make the product.

15. A method for recycling the degradable epoxy resin composite material according to claim 14, characterized in that: The steps include: The degradable epoxy resin composite material is immersed in a degradation solution, and the temperature is raised to 80-180° C. to perform a degradation reaction for 4-68 hours to obtain a second comprehensive product after degradation; The degradation liquid is composed of a cyclic compound or a branched chain compound containing at least one lone pair of electrons.

16. A use of the second integrated product according to claim 15, characterized in that: After the second comprehensive product is mixed with epoxy resin, it is used to prepare a degradable epoxy resin composite material using a vacuum infusion process.

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