Degradable epoxy resin composition and its uses, body, composite material and its recycling method, and use of the product

Abstract

The present invention provides a degradable epoxy resin composition and its uses, body, composite material, and its recycling method and product uses, belonging to the technical field of recyclable epoxy resins. Specifically, component A includes epoxy resin, epoxy resin modifier, epoxy active diluent, and degradation aid, and component B includes terminal amino 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, the viscosity of the epoxy resin at 25 °C is 1500 cps to 5000 cps, and the selection criteria for the terminal amino polyether are polymers with a molecular weight of 230 to 5000, having at least two terminal amino groups, a polyether structure as the main chain, and amine groups as the terminal active functional groups. The degradable epoxy resin composition of the present application has low viscosity, high fluidity, low degradation cost, and excellent mechanical properties and heat resistance of the cured product.

Description

Technical Field

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

[0002] Epoxy resins have a wide range of application fields. For example, they can be used in large wind turbine blades, GIS (gas-insulated switch) insulation parts, battery cases, lightweight vehicle body parts, aircraft structural parts, etc. However, epoxy resin products will age with the change of service life. For example, under 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) insulation parts, battery cases, lightweight vehicle body parts, aircraft structural parts, etc. need to be updated. How to reasonably and scientifically recycle and reuse various retired epoxy resin products has become a difficult problem in the field of epoxy resins.

[0003] Driven by environmental protection policies, degradable epoxy resins have become a key direction. Such resins can still maintain high strength after vacuum infusion, but after retirement, it is still necessary to chemically decompose to recover fibers and monomers to reduce waste pollution. Moreover, degradable resins rely on specific conditions (such as strong acid degradation solutions), with high degradation energy consumption and expensive catalysts (such as ruthenium-based catalysts). Summary of the Invention

[0004] Therefore, in order to overcome the above-mentioned disadvantages of the prior art, the present invention provides a degradable epoxy resin composition and its uses, a body, a composite material, its recycling method, and the use of the product. 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. The cured product has excellent mechanical properties and heat resistance. The recycling method of the degradable epoxy resin body is simple, without the need to separately separate the degradation products from their degradation solutions, and can be directly recycled into the epoxy resin system by 100%, and has excellent heat resistance and mechanical properties, further reducing the degradation cost.

[0005] To achieve the above object, the present invention provides a degradable epoxy resin composition for vacuum infusion process, which comprises component A and component B. Component A contains epoxy resin, epoxy resin modifier, epoxy active diluent and degradation aid, and component B contains terminal amino polyether, aromatic amine, alicyclic amine and accelerator. The epoxy value of the epoxy resin ranges from 0.571 to 0.694 mol / 100g, and the viscosity at 25°C is 1500 - 5000 cps. The epoxy resin modifier is at least one of poly[(2-oxiranylmethyl)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether, 1,2-cyclohexanedicarboxylic acid bis(2-oxiranylmethyl) ester, 4-cyclohexene-1,2-dicarboxylic acid diglycidyl ester, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester; the selection criterion for the terminal amino polyether is a polymer with a molecular weight of 230 - 5000, having at least two terminal amino groups, a polyether structure as the main chain, and amine groups as the terminal active functional groups.

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

[0007] In one embodiment, the epoxy resin modifier is at least one of poly[(2-oxiranylmethyl)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether, 1,2-cyclohexanedicarboxylic acid bis(2-oxiranylmethyl) ester, 4-cyclohexene-1,2-dicarboxylic acid diglycidyl ester, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester.

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

[0009] In one embodiment, the weight ratio of component A to component B is 100:29 to 35. Among them, 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 active diluent, and 0.01 part - 1.0 part of degradation aid; 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, 0.2 part - 12 parts of accelerator.

[0010] In one embodiment, 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, C12 - C14 alkyl glycidyl ether.

[0011] In one embodiment, the degradation aid is at least one of N-(2 - aminoethyl)-3 - aminopropylmethyldimethoxysilane, 3 - ureidopropyltriethoxysilane, 3 - ureidopropyltrimethoxysilane, 3 - ureidopropyltriethoxysilane, γ - glycidoxypropyltrimethoxysilane, β-(3,4 - epoxycyclohexyl)-ethyltrimethoxysilane, hexamethyldisilazane, hexamethylcyclotrisilazane, trivinyltrimethylcyclotrisilazane.

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

[0013] In one embodiment, the alicyclic amine is at least one of isophoronediamine, menthanediamine, 1,3 - bis(aminomethyl)cyclohexane, diaminodicyclohexylmethane, methylcyclohexanediamine, cyclohexanediamine, 4,4 - diaminodicyclohexylmethane.

[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 dihydrazide, furandicarboxylic dihydrazide.

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

[0016] Use of a degradable epoxy resin composition, wherein the epoxy resin composition is applied to prepare a degradable epoxy resin body or a degradable epoxy resin composite material by a vacuum infusion process, and the epoxy resin composition is the above - mentioned epoxy resin composition.

[0017] A degradable epoxy resin body is made by mixing and curing with the epoxy resin composition as described above. The preparation method of the degradable epoxy resin body includes: weighing component A and component B according to set weight parts; after uniformly mixing the component A and the component B respectively, mixing them again to obtain a mixture; vacuum-injecting and curing the mixture to obtain a degradable epoxy resin body.

[0018] A recycling method of the above-mentioned degradable epoxy resin body includes the following steps: soaking the degradable epoxy resin body in a degradation liquid, heating to 80 - 180 °C for a degradation reaction for 4 - 68 h to obtain a first comprehensive product after degradation; the degradation liquid is prepared from a cyclic compound or a branched compound containing at least one pair of lone electrons.

[0019] A use of the above-mentioned first comprehensive product. After the first comprehensive product and epoxy resin are mixed, they are applied to prepare a degradable epoxy resin body or a degradable epoxy resin composite material by a vacuum-injection process.

[0020] A degradable epoxy resin composite material is made by mixing the above-mentioned 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 recycling method of the above-mentioned degradable epoxy resin composite material includes the following steps: soaking the degradable epoxy resin composite material in a degradation liquid, heating to 80 - 180 °C for a degradation reaction for 4 - 68 h to obtain a second comprehensive product after degradation; the degradation liquid is prepared from a cyclic compound or a branched compound containing at least one pair of lone electrons.

[0023] A use of the above-mentioned second comprehensive product. After the second comprehensive product and epoxy resin are mixed, they are applied to prepare a degradable epoxy resin composite material by a vacuum-injection process.

[0024] Compared with the prior art, the advantages of the present invention are as follows: Through the screening of epoxy resin, epoxy resin modifier, and terminal amino polyether, the degradable epoxy resin composition has low viscosity and high fluidity, and the viscosity is low enough to meet the perfusion 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, does not require additional separation of the degradation product and its degradation liquid, can be directly recycled into the epoxy resin system by 100%, and has excellent heat resistance and mechanical properties, further reducing the degradation cost. Detailed Embodiments

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

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

[0027] It should be noted that the following describes various aspects of embodiments within the protection scope of the present invention. It should be obvious that the aspects described herein can be embodied in a wide variety of forms, and any specific structure and / or function described herein is only illustrative. Based on the present application, those skilled in the art should understand that one 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 aspects described herein can be used to implement the device and / or practice the method. Additionally, this device and / or this method can be implemented using other structures and / or functions in addition to one or more of the aspects described herein.

[0028] In addition, in the following description, specific details are provided to facilitate a thorough understanding of the examples. However, those skilled in the art will understand that the described aspects can 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 contains epoxy resin, epoxy resin modifier, epoxy active 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 - 5000 cps. In one embodiment, the epoxy resin is obtained by molecular distillation and has a purity ≥ 90.0%.

[0032] The epoxy resin modifier is at least one of poly[(2 - epoxyethyl)-1,2 - cyclohexanediol] 2 - ethyl - 2 - (hydroxymethyl)-1,3 - propanediol ether, cyclohexane - 1,2 - dicarboxylic acid bis(epoxyethylmethyl) ester, 4 - cyclohexene - 1,2 - dicarboxylic acid diglycidyl ester, 4,5 - epoxycyclohexane - 1,2 - dicarboxylic acid diglycidyl ester.

[0033] Epoxy active diluents refer to low-molecular compounds with one or more epoxy groups. They can directly participate in the curing reaction of epoxy resins and become part of the cross-linked network structure of the cured epoxy resin. Epoxy active diluents can be mono-epoxy allyl glycidyl ether, phenyl glycidyl ether, or bis-epoxy ethylene glycol diglycidyl ether, resorcinol diglycidyl ether, etc.

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

[0035] Component B contains terminal amino polyethers, aromatic amines, alicyclic amines, and accelerators.

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

[0037] For the above - mentioned degradable epoxy resin composition, through the screening of epoxy resins, epoxy resin modifiers, and terminal amino polyethers, the degradable epoxy resin composition has low viscosity, high fluidity, and the viscosity is low enough to meet the perfusion requirements of large - scale structural parts. The cured product has excellent mechanical properties and heat resistance. The recovery method of the degradable epoxy resin body is simple, without the need for additional separation of degradation products from their degradation solutions, and can be directly recycled 100% 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, land vehicles such as degradable and recyclable cars / high-speed trains, 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:

[0040] 、 and .

[0041] The epoxy value is 0.571 mol / 100g - 0.588 mol / 100g, the viscosity at 25°C is 3000 - 5000 cps; the total chlorine ≤ 900 ppm; the appearance is a colorless, transparent and easily crystallizable liquid, hereinafter referred to as "Resin 1#" in the following examples.

[0042] 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 crystallizable liquid. Hereinafter referred to as "Resin 2#" in the following examples.

[0043] The epoxy value is 0.640 mol / 100g - 0.694 mol / 100g; the viscosity at 25°C is 1500 - 4000 cps, the total chlorine ≤ 900 ppm; the appearance is a colorless to light yellow transparent and easily crystallizable liquid. Hereinafter referred to as "Resin 3#" in the following examples.

[0044] In one embodiment, the epoxy resin modifier is at least one of poly[(2 - epoxyethyl)-1,2 - cyclohexanediol] 2 - ethyl - 2 - (hydroxymethyl)-1,3 - propanediol ether (hereinafter referred to as "Modifier 1#" in the following examples), bis(2 - epoxyethylmethyl) cyclohexane - 1,2 - dicarboxylate (hereinafter referred to as "Modifier 2#" in the following examples), diglycidyl 4 - cyclohexene - 1,2 - dicarboxylate (hereinafter referred to as "Modifier 3#" in the following examples), diglycidyl 4,5 - epoxycyclohexane - 1,2 - dicarboxylate (hereinafter referred to as "Modifier 4#" in the following examples).

[0045] In one embodiment, the terminal amino polyether is at least one of D230, MA223, D400, MA240, D2000, MA2200, T403, MA340, T5000, MA3500.

[0046] 1. In D230, D represents difunctionality (i.e., the molecule contains two amino functional groups), and 230 represents its average molecular weight of approximately 230. The main chain is polypropylene oxide, with two primary amino groups at the ends.

[0047] 2. In MA223, MA indicates that this product belongs to the polyetheramine series, and 223 represents its average molecular weight of approximately 230. The main chain is polypropylene oxide, with two primary amino groups at the ends. It is similar to D230, but may have slight differences in production process or purity.

[0048] 3. In D400, D represents difunctionality, and 400 represents its average molecular weight of approximately 400. The main chain is polypropylene oxide, with two amino groups at the ends.

[0049] 4. In MA240, MA represents polyetheramine, and 240 represents its average molecular weight of approximately 400. The main chain is polypropylene oxide, with two amino groups at the ends. It is similar to D400, but may have slight optimizations in production process or performance.

[0050] 5. In D2000, D represents difunctionality, and 2000 represents its average molecular weight of approximately 2000. The main chain is polypropylene oxide, with two amino groups at the ends.

[0051] 6. In MA2200, MA represents polyetheramine, and 2200 represents its average molecular weight of approximately 2000. The main chain is polypropylene oxide, with two amino groups at the ends. It is similar to D2000, but may have optimized performance during the production process.

[0052] 7. In T403, T represents trifunctionality (i.e., the molecule contains three amino functional groups), and 403 represents its average molecular weight of approximately 403. The main chain is polypropylene oxide, with three amino groups at the ends.

[0053] 8. In MA340, MA represents polyetheramine, and 340 represents its average molecular weight of approximately 340. The main chain is polypropylene oxide, with three amino groups at the ends. It has trifunctionality, high reactivity, and relatively low viscosity (50 - 100 mPa·s). It is similar to T403, but may have optimized performance during the production process.

[0054] 9. In T5000, T represents trifunctionality, and 5000 represents its average molecular weight of approximately 5000. The main chain is polypropylene oxide, with three amino groups at the ends.

[0055] 10. In MA3500, MA represents polyetheramine, and 3500 represents its average molecular weight of approximately 3500. The main chain is polypropylene oxide, with three amino groups at the ends. It is similar to T5000, but may have optimized performance during the production process.

[0056] The amino-terminated polyether can be selected according to the specific performance parameters in the following table (the AHEW active hydrogen equivalent refers to the average molecular weight of each active hydrogen atom in the compound).

[0057]

[0058] In one embodiment, the weight ratio of component A to component B is 100:29 - 35.

[0059] 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 active diluent, and 0.01 part - 1.0 part of degradation aid.

[0060] 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, 0.2 part - 12 parts of accelerator.

[0061] In one embodiment, the epoxy active diluent is at least one of 1,4-butanediol diglycidyl ether (referred to as "diluent 1#" in the following examples), ethylene glycol diglycidyl ether (referred to as "diluent 2#" in the following examples), 1,6-hexanediol diglycidyl ether (referred to as "diluent 3#" in the following examples), benzyl glycidyl ether (referred to as "diluent 4#" in the following examples), butyl glycidyl ether (referred to as "diluent 5#" in the following examples), phenyl glycidyl ether (referred to as "diluent 6#" in the following examples), C12-C14 alkyl glycidyl ether (referred to as "diluent 7#" in the following examples).

[0062] In one embodiment, the degradation aid is at least one of N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane (referred to as "degradation aid 1#" in the following examples), 3-ureidopropyltriethoxysilane (referred to as "degradation aid 2#" in the following examples), 3-ureidopropyltrimethoxysilane (referred to as "degradation aid 3#" in the following examples), 3-ureidopropyltriethoxysilane (referred to as "degradation aid 4#" in the following examples), γ-glycidoxypropyltrimethoxysilane (referred to as "degradation aid 5#" in the following examples), β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane (referred to as "degradation aid 6#" in the following examples), hexamethyldisilazane (referred to as "degradation aid 7#" in the following examples), hexamethylcyclotrisilazane (referred to as "degradation aid 8#" in the following examples), triethylenetrimethylcyclotrisilazane (referred to as "degradation aid 9#" in the following examples).

[0063] In one embodiment, the aromatic amine is at least one of m-phenylenediamine, diaminodiphenylmethane (DDM), o-(β-aminoethoxy)aniline, methylaniline, 2,3-dimethylaniline, diethyltoluenediamine.

[0064] In one embodiment, the alicyclic amine is at least one of isophorone diamine (IPDA), menthane diamine (MDA), 1,3-bis(aminomethyl)cyclohexane (13BAC), diaminodicyclohexylmethane (PACM), methylcyclohexanediamine (HMDA), cyclohexanediamine, and 4,4-diamino-dicyclohexylmethane.

[0065] In one embodiment, the accelerator is at least one of 3-diethylaminopropylamine (referred to as "accelerator 1#" in the following examples), aminoethylpiperazine (referred to as "accelerator 2#" in the following examples), diethylenetriamine (referred to as "accelerator 3#" in the following examples), 2,4,6-tris(dimethylaminomethyl)phenol (referred to as "accelerator 4#" in the following examples), o-hydroxybenzoic acid (referred to as "accelerator 5#" in the following examples), phthalic dihydrazide (referred to as "accelerator 6#" in the following examples), and furan dicarboxylic dihydrazide (referred to as "accelerator 7#" in the following examples).

[0066] Use of a degradable epoxy resin composition for vacuum infusion, where the epoxy resin composition is applied to prepare a degradable epoxy resin body or a degradable epoxy resin composite material by a vacuum infusion process.

[0067] A degradable epoxy resin body is made by mixing and curing the above-mentioned epoxy resin composition. The preparation of the degradable epoxy resin body includes: weighing component A and component B according to set weight parts; after mixing component A and component B evenly respectively, mixing them again to obtain a mixture; vacuum infusing the mixture and then curing it to obtain the degradable epoxy resin body.

[0068] A recovery method of a degradable epoxy resin body includes the following steps: soaking the degradable epoxy resin body in a degradation liquid, heating to 80 - 180 °C for a degradation reaction for 4 - 68 h to obtain a first comprehensive product after degradation; the degradation liquid is prepared from a cyclic compound or a branched compound containing at least one pair of lone pairs of electrons.

[0069] The cyclic compound or the branched compound containing lone pairs of electrons can introduce lone pairs of electrons 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 can be a five-membered ring or a six-membered ring structure. The number of heteroatoms on the ring structure is 1 or 2, and when the number of heteroatoms is 2, the heteroatoms can be the same or different. The degradation liquid can be prepared from a single cyclic compound or a branched compound, or can be prepared from a variety of cyclic compounds or branched compounds containing lone pairs of electrons. When there are a variety of cyclic compounds or branched compounds containing lone pairs of electrons, the cyclic compounds or branched compounds in the degradation liquid can undergo reactions that do not destroy the lone pair electrons. For example, the degradation liquid can be , , , , , ethylene oxide, furan, imidazole, amino compounds of ethylene dichloride, etc., or the reaction product of at least one of them.

[0070] 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.

[0071] A degradable epoxy resin composite material is prepared by mixing an epoxy resin composition, compounding it with a reinforcing material, and then curing it.

[0072] 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.

[0073] In one embodiment, the reinforcement material is at least one of glass fiber, carbon fiber, polyester fiber and polyamide fiber.

[0074] 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.

[0075] 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.

[0076] Each component in the following examples is weighed in parts by weight.

[0077] Embodiment 1

[0078] Prepare a degradable epoxy resin composition, and the weight ratio of component A to component B is 100:30. Among them, 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 terminal amino polyether D230, 3 parts of terminal amino polyether T403, 10 parts of aromatic amine (DDM), alicyclic amine (10.8 parts of IPDA, 6 parts of PACM), and 0.2 parts of Accelerator 1#.

[0079] Example 2

[0080] Prepare a degradable epoxy resin composition, and the weight ratio of component A to component B is 100:29.

[0081] Among them, 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#, and 0.01 parts of Degradation Aid 5#; every 100 parts of component B: 72 parts of terminal amino polyether D230, 1 part of aromatic amine (DDM), alicyclic amine (16 parts of HMDA, 10 parts of PACM), 0.2 parts of Accelerator 3#, and 0.8 parts of Accelerator 4#.

[0082] Example 3

[0083] Prepare a degradable epoxy resin composition, and the weight ratio of component A to component B is 100:34.

[0084] Among them, every 100 parts of component A contains: 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 contains: 74 parts of terminal amino polyether D230, 0.1 part of terminal amino polyether T5000, aromatic amine (2 parts of m-xylene diamine, 2.8 parts of methylaniline), alicyclic amine (10 parts of IPDA, 3 parts of 13BAC, 7.9 parts of HMDA), and 0.2 parts of Accelerator 5#.

[0085] Example 4

[0086] Prepare a degradable epoxy resin composition, and the weight ratio of component A to component B is 100:33.

[0087] Among every 100 parts of Component A, it contains: Resin 1# weighing 25 parts, Resin 3# weighing 10 parts, Modifier 2# weighing 60 parts, Diluent 1# weighing 4.8 parts, Degradation Aid 1# weighing 0.05 parts, Degradation Aid 2# weighing 0.15 parts; among every 100 parts of Component B, it contains: Amino-terminated polyether D230 weighing 50 parts, Amino-terminated polyether D400 weighing 4 parts, Amino-terminated polyether T403 weighing 18 parts, Aromatic amine (DDM weighing 10 parts, o-(β-aminoethoxy)aniline weighing 0.9 parts, Methylaniline 1.9 parts), Alicyclic amine (IPDA weighing 10 parts, HMDA weighing 7 parts), Accelerator 7# weighing 0.2 parts.

[0088] Example Five

[0089] Prepare a degradable epoxy resin composition, and the weight ratio of Component A to Component B is 100:35.

[0090] Among every 100 parts of Component A, it contains: Resin 1# weighing 35 parts, Resin 3# weighing 5 parts, Modifier 2# weighing 33 parts, Modifier 3# weighing 2 parts, Modifier 4# weighing 12 parts, Diluent 1# weighing 8 parts, Diluent 4# weighing 4 parts, Degradation Aid 8# weighing 0.9 parts, Degradation Aid 9# weighing 0.1 parts; among every 100 parts of Component B, it contains: Amino-terminated polyether D230 weighing 48 parts, Amino-terminated polyether T403 weighing 22 parts, Aromatic amine (m-Xylylenediamine) 5 parts, Alicyclic amine (HMDA weighing 20 parts, PACM weighing 4.8 parts), Accelerator 2# weighing 0.2 parts.

[0091] Example Six

[0092] Prepare a degradable epoxy resin composition, and the weight ratio of Component A to Component B is 100:29.

[0093] Among every 100 parts of Component A, it contains: Resin 1# weighing 38 parts, Resin 3# weighing 15 parts, Modifier 1# weighing 12 parts, Modifier 4# weighing 19 parts, Diluent 1# weighing 15 parts, Degradation Aid 7# weighing 0.9 parts, Degradation Aid 9# weighing 0.1 parts; among every 100 parts of Component B, it contains: Amino-terminated polyether D230 weighing 46 parts, Amino-terminated polyether T403 weighing 24 parts, Aromatic amine (DDM) 8 parts, Alicyclic amine (HMDA) weighing 15 parts, Accelerator 4# weighing 7 parts.

[0094] Example Seven

[0095] Prepare a degradable epoxy resin composition, and the weight ratio of Component A to Component B is 100:31.

[0096] Among every 100 parts of component A, it contains: 33 parts of resin 2#, 62 parts of modifier 3#, 4 parts of diluent 5#, 0.3 part of degradation aid 4#, 0.2 part of degradation aid 6#, 0.5 part of degradation aid 8#; among every 100 parts of component B, it contains: 30 parts of terminal amino polyether D230, 5 parts of terminal amino polyether D400, 0.3 part of terminal amino polyether D2000, 38 parts of terminal amino polyether T403, 4 parts of aromatic amine (DDM), 11 parts of alicyclic amine (HMDA), 11.7 parts of accelerator 4#.

[0097] Example VIII

[0098] Prepare a degradable epoxy resin composition, and the weight ratio of component A to component B is 100:32.

[0099] Among every 100 parts of component A, it contains: 25 parts of resin 1#, 14 parts of resin 2#, 60 parts of modifier 2#, 0.5 part of diluent 6#, 0.3 part of degradation aid 5#, 0.2 part of degradation aid 6#; among every 100 parts of component B, it contains: 33 parts of terminal amino polyether D230, 10 parts of terminal amino polyether D400, 33 parts of terminal amino polyether T403, 23.6 parts of alicyclic amine (HMDA), 0.4 part of accelerator 3#.

[0100] Example IX

[0101] Prepare a degradable epoxy resin composition, and the weight ratio of component A to component B is 100:29.

[0102] Among every 100 parts of component A, it contains: 34.3 parts of resin 1#, 0.7 part of modifier 1#, 60 parts of modifier 3#, 3.5 parts of modifier 4#, 1 part of diluent 6#, 0.3 part of degradation aid 3#, 0.2 part of degradation aid 4#; among every 100 parts of component B, it contains: 35 parts of terminal amino polyether D230, 2 parts of terminal amino polyether D2000, 40 parts of terminal amino polyether T403, 1.8 parts of aromatic amine (diethyltoluenediamine), 10 parts of alicyclic amine (IPDA), 11 parts of HMDA, 0.1 part of accelerator 4#, 0.1 part of accelerator 6#.

[0103] Example X

[0104] Prepare a degradable epoxy resin composition, and the weight ratio of component A to component B is 100:33.

[0105] Among every 100 parts of component A, it contains: 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 part of degradation aid #5, 0.1 part of degradation aid #7; among every 100 parts of component B, it contains: 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), alicyclic amine (12 parts of IPDA and 11 parts of HMDA), 0.1 part of accelerator #6, 0.1 part of accelerator #7.

[0106] Weigh the degradable epoxy resin composition according to the above weight parts, and apply it to prepare a degradable epoxy resin body by vacuum infusion process.

[0107] The performance data of the prepared degradable epoxy resin body are respectively:

[0108] 。

[0109] Therefore, the mixing viscosity of the degradable epoxy resin body prepared by the above method is 100 - 400 mPa·s @ 25°C, and its operable time reaches 100 min - 212 min; the tensile strength is 65 - 82 MPa, the tensile modulus is 3000 - 4000 MPa, the elongation at break is 2% - 9%, the flexural strength is 110 - 145 MPa, the flexural modulus is 3100 - 4100 MPa, the compressive strength is 80 - 120 MPa, the compressive modulus is 2500 - 3100 MPa, and the glass transition temperature is 70 - 83°C (the units of each performance parameter in the above table are the same as those in this paragraph).

[0110] The recycling method of the above-mentioned degradable epoxy resin body includes the following steps: soaking the degradable epoxy resin body in a degradation solution, heating it to 80 - 180°C for a degradation reaction for 4 - 68 h to obtain a first comprehensive product after degradation, and the degradation solution is

[0111] + +NH3.H2O+ The reaction product in proportion under certain conditions. The whole degradation process neither needs to be carried out in a strong acid environment, reducing the danger of the degradation process, nor needs to add an additional catalyst, reducing the degradation cost.

[0112] The performance data of the first comprehensive product after degradation are as follows in the table:

[0113] 。

[0114] The product viscosity of the above-mentioned first composite product after degradation is 10-780 mPa·s at 25°C. It can be mixed with epoxy resin again and used. The degradation product and its degradation liquid do not need to be separated and can be directly recycled 100% and added to the epoxy resin system, and it has excellent heat resistance and mechanical properties.

[0115] The first composite 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 ratio of the first composite product added to product A in the degradable epoxy resin composite material is 63.4%, and the weight ratio of the first composite product added to product B in the degradable epoxy resin composite material is 58.0%. Product C is a degradable epoxy resin composite material without adding the first composite product. The first composite product is the first composite product obtained after degradation in Example 4):

[0116]

[0117] The test gel time is to determine the curing speed of the product, and the HPRTM molding process requires a fast curing speed.

[0118] The TG test means that the resin and glass fiber are placed together in the mold of the HPRTM equipment, and the pressure is maintained at 1300 tons at a temperature of 100°C for 180 s to cure the degradable epoxy resin composite material. After curing, the glass transition temperature test of the cured degradable epoxy resin composite material is measured. The test equipment is DSC; the unit of Tg is °C.

[0119] The room temperature mechanical test means: for the FRP (fiber reinforced polymer) made of biaxial glass fiber cloth with a resin + curing agent ratio of 600 g / m 2 The mechanical properties test of the tensile strength is carried out at room temperature.

[0120] The 97°C 72h mechanical test means: for the FRP (fiber reinforced polymer) made of biaxial glass fiber cloth with a resin + curing agent ratio of 600 g / m 2 After 72h of thermal aging at 97°C, the mechanical properties test of the tensile strength is carried out.

[0121] From the above table, it can be seen that the first composite product after degradation can be directly added to the epoxy resin system in its entirety without additional separation treatment to prepare a new resin product. 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.

[0122] In one embodiment, the method for recycling a degradable epoxy resin body or the method for recycling a degradable epoxy resin composite further includes: before the degradation reaction, ultrasonic waves with a power of 30 KW and a frequency of 50 HZ are used for pretreatment for 4 h, and mechanical oscillation is carried out during the degradation process.

[0123] As described above, the above are only specific embodiments 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 those skilled in the art within the technical scope disclosed by the present application should be covered within the protection scope of the present application.

Claims

1. A degradable epoxy resin composition for vacuum infusion process, characterized in that, It includes Component A and Component B. Among them, Component A contains epoxy resin, epoxy resin modifier, epoxy active diluent and degradation aid. Component B contains terminal amino polyether, aromatic amine, alicyclic amine and accelerator. The epoxy resin contains at least one of the following components: , and , The epoxy value is 0.571 mol / 100 g - 0.588 mol / 100 g, and the viscosity of the epoxy resin at 25°C is 3000 cps - 5000 cps. The epoxy value is 0.575 mol / 100 g - 0.595 mol / 100 g, and the viscosity of the epoxy resin at 25 °C is 2000 cps - 4800 cps. The epoxy value is 0.640 mol / 100 g - 0.694 mol / 100 g, and the viscosity of the epoxy resin at 25°C is 1500 cps - 4000 cps; The epoxy resin modifier is at least one of poly[(2 - epoxyethyl)-1,2 - cyclohexanediol] 2 - ethyl - 2 - (hydroxymethyl)-1,3 - propanediol ether, cyclohexane - 1,2 - dicarboxylic acid bis(epoxyethylmethyl) ester, 4 - cyclohexene - 1,2 - dicarboxylic acid diglycidyl ester, 4,5 - epoxycyclohexane - 1,2 - dicarboxylic acid diglycidyl ester. The selection criterion for the terminal amino polyether is a polymer with a molecular weight of 230 - 5000, having at least two terminal amino groups, a polyether structure as the main chain, and an amine group as the terminal active functional group.

2. The degradable epoxy resin composition according to claim 1, wherein The weight ratio of Component A to Component B is 100:29 - 35. Among them, 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 active diluent and 0.01 part - 1.0 part of degradation aid. Every 100 parts of Component B contains the following parts by weight: 40 parts - 80 parts of terminal amino polyether, 0 - 15 parts of aromatic amine, 5 parts - 30 parts of alicyclic amine, 0.2 parts - 12 parts of accelerator.

3. The biodegradable epoxy resin composition according to claim 1, wherein 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, C12 - C14 alkyl glycidyl ether.

4. The degradable epoxy resin composition according to claim 1, wherein The degradation aid is at least one of N-(2 - aminoethyl)-3 - aminopropylmethyldimethoxysilane, 3 - ureidopropyltriethoxysilane, 3 - ureidopropyltrimethoxysilane, 3 - ureidopropyltriethoxysilane, γ - glycidyletheroxypropyltrimethoxysilane, β-(3,4 - epoxycyclohexyl)-ethyltrimethoxysilane, hexamethyldisilazane, hexamethylcyclotrisilazane, trivinyltrimethylcyclotrisilazane.

5. The degradable epoxy resin composition according to claim 1, wherein The aromatic amine is at least one of m - xylylenediamine, diaminodiphenylmethane, o-(β - aminoethoxy)aniline, methylaniline, 2,3 - dimethylaniline, diethyltoluenediamine.

6. The degradable epoxy resin composition according to claim 1, characterized in that, The alicyclic amine is at least one of isophoronediamine, menthanediamine, 1,3 - bis(aminomethyl)cyclohexane, diaminodicyclohexylmethane, methylcyclohexanediamine, cyclohexanediamine, 4,4 - diaminodicyclohexylmethane.

7. 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 dihydrazide, furandicarboxylic dihydrazide.

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

9. Use of a degradable epoxy resin composition, characterized in that, The epoxy resin composition is applied to prepare 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 described in any one of claims 1 - 8.

10. A degradable epoxy resin body, characterized in that, It is made by mixing and curing the epoxy resin composition according to any one of claims 1-8. The preparation method of the degradable epoxy resin body includes: Weigh the component A and the component B respectively according to the set weight parts; After uniformly mixing the component A and the component B respectively, mix them again to obtain a mixed material; Vacuum infuse and cure the mixed material to obtain a degradable epoxy resin body.

11. A method for recycling a degradable epoxy resin body as described in claim 10, characterized in that, It includes the following steps: Immerse the degradable epoxy resin body in a degradation solution, heat it to 80-180 °C for a degradation reaction for 4-68 h to obtain a first comprehensive product after degradation; The degradation liquid is prepared from a cyclic compound or a branched compound containing at least one pair of lone electrons; the degradation liquid is , , , , , at least one of amino compounds of ethylene oxide, furan, imidazole, dichloroethane or a reaction product of at least one of them.

12. Use of a first integrated product as described in claim 11, characterized in that, After mixing the first comprehensive product and epoxy resin, it is applied to prepare a degradable epoxy resin body or a degradable epoxy resin composite material by a vacuum infusion process.

13. A degradable epoxy resin composite material, characterized in that, It is made by mixing the epoxy resin composition according to any one of claims 1-8, compounding with a reinforcing material, and then curing.

14. A method for recycling the degradable epoxy resin composite material according to claim 13, characterized in that, It includes the following steps: Immerse the degradable epoxy resin composite material in a degradation solution, heat it to 80-180 °C for a degradation reaction for 4-68 h to obtain a second comprehensive product after degradation; The degradation liquid is prepared from a cyclic compound or a branched compound containing at least one pair of lone electrons; the degradation liquid is , , , , , at least one of amino compounds of ethylene oxide, furan, imidazole, and dichloroethane, or a reaction product of at least one of them.

15. Use of a second composite product as described in claim 14, characterized in that, After mixing the second comprehensive product and epoxy resin, it is applied to prepare a degradable epoxy resin composite material by a vacuum infusion process.

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