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

Abstract

The invention belongs to the technical field of recoverable epoxy resin, and relates to a degradable epoxy resin system material and application thereof, a body, a composite material and a recovery method thereof. The degradable epoxy resin system material comprises a first component and a second component, the first component comprises first epoxy resin and second epoxy resin, and the second component comprises a first curing agent, a second curing agent and an accelerant; the first epoxy resin is a mixture of one or more of glycidyl ether epoxy resin and glycidyl amine epoxy resin and accounts for 15-35% of the first component by mass, the second epoxy resin is selected from one or more of epoxy resin with the structure containing # imgabs0 #, and the second epoxy resin accounts for 60-80% of the first component by mass; the first curing agent is one or a mixture of more of alicyclic amines and accounts for 40%-60% of the second component by mass, the second curing agent is one or a mixture of more of polyether amines and accounts for 40%-60% of the second component by mass, and the accelerant accounts for 0.5%-3% of the second component by mass. The requirement for vacuum infusion of the wind power blade can be met.

Description

Technical Field

[0001] The invention belongs to the technical field of recyclable epoxy resins, and in particular relates to a degradable epoxy resin system material and its use, a body, a composite material and a recycling method thereof. Background Art

[0002] Wind energy is a typical natural clean energy. By converting wind energy into electrical energy through wind turbines, wind energy can be effectively utilized, the use of fossil energy can be reduced, and it plays a very important role in achieving the goal of carbon neutrality. my country's mass installation of wind power generation began in 2004 and reached its peak in 2020. The design life of wind turbines is generally 20-25 years, which means that from 2024, a large number of wind turbines will be replaced. Among them, how to reasonably and scientifically recycle and reuse the composite materials of retired wind turbine blades has become a key issue in the development of the wind power renewable energy industry.

[0003] At present, the methods for recycling and reusing retired wind turbine blades mainly include mechanical crushing, thermal cracking and chemical degradation. The mechanical crushing method is to cut and grind the composite materials of wind turbine blades into powder and then apply them to building materials, composite materials products and other directions. However, due to the immature technology and low efficiency of recycling equipment, the quality of recycled fiber cannot meet the application requirements of downstream products, as well as serious dust emissions and noise pollution, it is impossible to achieve sustainable development. The thermal cracking method is a method of opening the thermosetting resin molecular chain of the organic component in the wind turbine blade composite material by heating to form a multi-component small molecule gas or liquid, and separating and recycling the fiber, filler, etc. However, the cost of the pyrolysis production line is relatively high, and the recycling of reinforcing materials such as glass fiber is difficult to generate high benefit value. The thermal cracking method is mainly used for carbon fiber reinforced composite materials with high residual value. The chemical degradation method is a method of opening the polymer at a specific bond position through solvents, temperature and / or pressure to form a long-chain monomer or resin raw material. This method can simultaneously recover reinforcing materials and resin components, with little damage to the fiber, and is a true realization of circular economy.

[0004] Introducing dynamic covalent bonds into the resin structure is the most direct and effective method to achieve chemical degradation. However, existing solutions all synthesize / modify epoxy resins or curing agents and then add them to the formula. For example, CN114195984A discloses a bisphenol A type epoxy curing agent containing dynamic enamine bonds and a degradable epoxy resin and methods for preparing, reshaping, and degrading the same. A bisphenol A type epoxy curing agent containing dynamic enamine bonds is synthesized, and the degradation of the resin is achieved by breaking the enamine bonds under acidic conditions. However, the molecular weight and viscosity of the curing agent are large, and the enamine bonds are unstable and sensitive to acid. Acidic conditions are very common in the natural environment, and the performance of the cured product in actual use is difficult to directly meet the requirements; CN106832767B discloses a fiber-reinforced vacuum infusion The degradable epoxy resin composition uses a degradable fatty amine curing agent ACV-1001 and a degradable alicyclic amine curing agent ACV-1005 as a curing agent, and degradation is achieved by utilizing the rupture of the ketal structure under acidic conditions. Like the enamine bond, the structure is unstable and very sensitive to acid, and the performance of the cured product in actual use is difficult to meet the requirements; CN115594949A discloses a recyclable epoxy wind turbine blade material and a preparation method and a recycling method thereof. The curing agent uses an aromatic curing agent containing a disulfide bond, and the blade material is recycled by utilizing the rupture of the disulfide bond. However, the aromatic curing agent used in this method is solid and is difficult to disperse in the resin. It requires the use of a solvent, and the process is complicated. In addition, the curing temperature of the aromatic curing agent is higher than that of the existing wind turbine blades.

[0005] In summary, the existing technical routes are generally complex processes and high costs. The modified epoxy resin or curing agent will have a relatively large impact on the performance of the blade. In addition, the modified resin system is also difficult to meet the requirements of vacuum infusion during the preparation of wind turbine blade composite materials. There are problems such as the resin system viscosity is too high or the low-temperature viscosity increases too fast, the fiber wetting performance is poor during the infusion process, and the post-curing temperature is high. Summary of the invention

[0006] The purpose of the present invention is to provide a degradable epoxy resin system material and its use, main body, composite material and recycling method to solve the above problems, which can meet the requirements of low viscosity, slow reaction speed and high glass transition temperature of cured product for vacuum infusion of wind turbine blades, and the degradation conditions are mild, without causing obvious damage to the performance of the recycled materials.

[0007] In a first aspect, the present invention provides a degradable epoxy resin system material, comprising a first component and a second component, wherein the first component comprises a first epoxy resin and a second epoxy resin, and the second component comprises a first curing agent, a second curing agent and an accelerator; The first epoxy resin is one or a mixture of glycidyl ether epoxy resin and glycidyl amine epoxy resin, and the mass content accounts for 15%-35% of the first component; The second epoxy resin is selected from one or more structures comprising The epoxy resin, wherein R is one or more structures selected from a C1-C18 aliphatic carbon chain, a benzene ring and its derivatives, and a heterocyclic structure containing oxygen, nitrogen, silicon, phosphorus, sulfur or selenium and its derivatives, R1 is selected from at least one structure selected from a methylene group and a cyclohexyl group, R2 and R3 are each independently a hydrogen atom, a C1-C18 aliphatic carbon chain, a benzene ring and its derivatives, and one or more structures selected from a carboxyl group, a hydroxyl group, an aldehyde group or an epoxy group, and the mass content of the second epoxy resin accounts for 60%-80% of the first component; The first curing agent is one or a mixture of alicyclic amines, and its mass content accounts for 40%-60% of the second component; The second curing agent is one or a mixture of polyetheramines, and its mass content accounts for 40%-60% of the second component; The mass content of the accelerator accounts for 0.5%-3% of the second component.

[0008] Optionally, at least one of the following features: The mass ratio of the first component to the second component is 100:(25-45); The glycidyl ether epoxy resin includes one or more selected from bisphenol A epoxy resin, bisphenol F epoxy resin and bisphenol S epoxy resin; The glycidylamine epoxy resin includes one or more selected from diglycidyl aniline, N,N,N',N'-tetraepoxypropyl-4,4'-diaminodiphenylmethane, N,N,N',N'-tetra(oxiranylmethyl)-1,3-phenylenediamine, N-(2-methylphenyl)-N-(1,2-epoxypropyl)-oxiranylmethylamine and triglycidyl p-aminophenol; The second epoxy resin comprises one or more selected from diglycidyl hexahydrophthalate, diglycidyl 4,5-epoxytetrahydrophthalate and diglycidyl phthalate; The alicyclic amine includes one or more selected from 4,4-diaminodicyclohexylmethane, isophoronediamine, 3,3'-dimethyl-4,4-diaminodicyclohexylmethane, N-aminoethylpiperazine, methylbenzenediamine and hydrogenated diaminodiphenylmethane; The polyetheramine includes one or two selected from D230 and D400; The accelerator is one or a mixture of 2,4,6-tris(dimethylaminomethyl)phenol, benzyldimethylamine, 1,8-diaza-bicyclo(5,4,0)-7-undecene, N-aminoethylpiperazine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and organic metal salts.

[0009] Optionally, the first component further includes a toughening agent, which is a mixture of one or more of inorganic nanoparticles, polysulfide rubber, PU prepolymer and polyether polyol, and its mass content accounts for 0%-10% of the first component.

[0010] Optionally, the degradable epoxy resin system material has at least one of the following characteristics: The initial mixed viscosity at 25°C is 100-300 mPa·s; At 40°C, the time for the viscosity to increase to 1000 mPa·s is 100-200 min; Curing at 65-80℃ for 4-10h, the reaction degree is above 95%; The glass transition temperature of the fully cured resin is above 85°C.

[0011] In a second aspect, the present invention proposes a use of the above-mentioned degradable epoxy resin system material, wherein the degradable epoxy resin system material is used to prepare a degradable epoxy resin body or a degradable epoxy resin composite material by a vacuum infusion process.

[0012] In a third aspect, the present invention provides a degradable epoxy resin body, which is prepared by mixing and curing the degradable epoxy resin system material as described above. The preparation of the degradable epoxy resin body includes: Weigh the first component and the second component respectively according to the set mass ratio; The first component and the second component are mixed and then subjected to vacuum stirring and degassing to obtain a mixed material; The mixed material is poured into a mold coated with a release agent and then cured to obtain a degradable epoxy resin body.

[0013] Optionally, the step of pouring the mixture into a mold coated with a release agent and then curing the mixture comprises: Heat to 65-80℃ and keep warm for 6-12h; Alternatively, first heat to 30-40°C for pre-reaction for 0-4h, then heat to 65-80°C, and heat and cure for 6-10h.

[0014] In a fourth aspect, the present invention provides a method for recycling the biodegradable epoxy resin body as described above, comprising the following steps: The degradable epoxy resin body is immersed in a degradation liquid; Raising the temperature to 80-120° C. to perform a degradation reaction until the degradable epoxy resin body is completely dissolved to obtain a dissolving solution; The dissolved solution is subjected to reduced pressure distillation to separate and obtain a recovered degradation solution and a recovered degradation resin; The degradation liquid comprises one or a mixture of several of amine compounds and alcohol compounds, and an organic amine catalyst.

[0015] Optionally, at least one of the following features: The mass proportion of amine compounds in the degradation liquid is 0-96%, the mass proportion of alcohol compounds is 0-97%, and the mass proportion of organic amine catalysts is 1%-5%; The amine compound includes one or more selected from ethylenediamine, butanediamine, hexamethylenediamine, meta-xylene diamine, isophoronediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine; The alcohol compound includes one or more selected from methanol, ethanol, ethylene glycol, glycerol, isopropanol and benzyl alcohol; The organic amine catalyst is one or a mixture of 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diaza-bicyclo(5,4,0)-7-undecene, N-aminoethylpiperazine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, a modified product of 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and a complex of amine and metal.

[0016] In a fifth aspect, the present invention provides a degradable epoxy resin composite material, which is prepared by mixing the degradable epoxy resin system material as described above, compounding with a reinforcing material, and then curing.

[0017] Optionally, the reinforcing material is one or a mixture of glass fiber, carbon fiber, polyester fiber and polyamide fiber.

[0018] Optionally, the reinforcing material and the degradable epoxy resin system material are prepared by a vacuum infusion method to obtain the degradable epoxy resin composite material.

[0019] Optionally, the preparation steps of the degradable epoxy resin composite material include: Weigh the first component and the second component respectively according to the set mass ratio; The first component and the second component are mixed and then subjected to vacuum stirring and degassing to obtain a mixed material; The mixture is vacuumed and then solidified after being soaked in the laid reinforcement material to obtain a degradable epoxy resin composite material.

[0020] Optionally, the step of curing the mixed material after impregnating the laid reinforcement material includes: Heat to 65-80℃ and keep warm for 6-12h; Alternatively, first heat to 30-40°C for pre-reaction for 0-4h, then heat to 65-80°C, and heat and cure for 6-10h.

[0021] In a sixth aspect, the present invention provides a method for recycling the biodegradable epoxy resin composite material as described above, comprising the following steps: The degradable epoxy resin composite material is immersed in a degradation liquid; Raise the temperature to 80-120°C to carry out degradation reaction for 10-48h to obtain a dissolving solution and recover the reinforcing material; Fish out the recovered reinforcement material, wash it with water and dry it; The dissolved solution is subjected to reduced pressure distillation to separate and obtain a recovered degradation solution and a recovered degradation resin; The degradation liquid comprises one or a mixture of several of amine compounds and alcohol compounds, and an organic amine catalyst.

[0022] Optionally, at least one of the following features: The mass proportion of amine compounds in the degradation liquid is 0-96%, the mass proportion of alcohol compounds is 0-97%, and the mass proportion of organic amine catalysts is 1%-5%; The amine compound includes one or more selected from ethylenediamine, butanediamine, hexamethylenediamine, meta-xylene diamine, isophoronediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine; The alcohol compound includes one or more selected from methanol, ethanol, ethylene glycol, glycerol, isopropanol and benzyl alcohol; The organic amine catalyst is one or a mixture of 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diaza-bicyclo(5,4,0)-7-undecene, N-aminoethylpiperazine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, a modified product of 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and a complex of amine and metal.

[0023] Compared with the prior art, the degradable epoxy resin system material and its use, body, composite material and recycling method of the present invention have the following beneficial effects: 1) The present invention uses commercial epoxy resin and curing agent, and uses glycidyl ester epoxy resin containing ester bonds as functional raw materials. Through formula design, the degradable epoxy resin system material, epoxy resin body, and epoxy resin composite material can meet the requirements of low viscosity, slow reaction speed and high glass transition temperature of cured product for vacuum infusion of wind turbine blades, which is beneficial to the vacuum infusion operation process. At the same time, the resin and reinforcing material have good wettability, which can reduce production defects. The structure of the ester bond is more stable than that of the imine bond, ketal bond, etc. After reacting with the curing agent, the performance of the cured product is less affected under natural conditions and has good stability under normal use conditions. The prepared fiber-reinforced composite material has mechanical properties comparable to or even better than those of existing wind turbine blade products, and meets all process performance and use performance requirements for the production and use of existing wind turbine blades.

[0024] 2) The recycling method of the present invention can make the epoxy resin body and the composite material degrade rapidly at a relatively low temperature. The degradation conditions are relatively mild and can be achieved at normal pressure and 80-120°C. The equipment is simple and no waste is discharged during the degradation process. The resin and the reinforcing material are recovered at the same time. The degradation and recycling process does not cause obvious damage to the performance of the recovered reinforcing material. The recovered reinforcing material can be directly fished out, washed, dried, and then recycled and reused. The degraded resin can be directly reused after being separated from the degradation liquid by reduced pressure distillation. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 The figure is a schematic flow chart of a method for recycling a degradable epoxy resin body according to an embodiment of the present invention; Figure 2 A schematic diagram of a process for recycling a degradable epoxy resin composite material according to an embodiment of the present invention; Figure 3 This is the gel permeation chromatogram of the recovered degraded resin of Example 1. DETAILED DESCRIPTION

[0026] The present invention provides a degradable epoxy resin system material, comprising a first component and a second component. The first component comprises a first epoxy resin and a second epoxy resin, and the second component comprises a first curing agent, a second curing agent and an accelerator. The first epoxy resin is a mixture of one or more of a glycidyl ether epoxy resin and a glycidyl amine epoxy resin, and the mass content accounts for 15%-35% of the first component. The second epoxy resin is a functional epoxy resin selected from one or more of the structures containing The epoxy resin, wherein R is one or more structures selected from aliphatic carbon chains of C1-C18, benzene rings and their derivatives, and heterocyclic structures and their derivatives containing elements such as oxygen, nitrogen, silicon, phosphorus, sulfur and / or selenium, R1 is selected from at least one structure selected from methylene and cyclohexyl, R2 and R3 are each independently a group connected to the R structure, which may be a short aliphatic carbon chain of C1-C18 such as hydrogen atom, methylethyl, benzene rings and their derivatives, and one or more structures selected from structures containing carboxyl, hydroxyl, aldehyde or epoxy groups. In the above chemical formula, the structures of R2 and R3 may be the same or different, and may be selected from the above structures; two R1s of the same structure are symmetrically arranged. The mass content of the second epoxy resin accounts for 60%-80% of the first component. The first curing agent is a mixture of one or more alicyclic amines, and the mass content accounts for 40%-60% of the second component. The second curing agent is a mixture of one or more polyetheramines, and the mass content accounts for 40%-60% of the second component. The mass content of the accelerator accounts for 0.5%-3% of the second component.

[0027] Among them, the glycidyl ether epoxy resin includes one or more selected from bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, etc. The glycidyl amine epoxy resin includes one or more selected from diglycidyl aniline, N,N,N',N'-tetraepoxypropyl-4,4'-diaminodiphenylmethane, N,N,N',N'-tetra(oxiranylmethyl)-1,3-phenylenediamine, N-(2-methylphenyl)-N-(1,2-epoxypropyl)-oxiranylmethylamine, triglycidyl p-aminophenol, etc. The second epoxy resin includes one or more selected from hexahydrophthalic acid diglycidyl ester, 4,5-epoxytetrahydrophthalic acid diglycidyl ester, phthalic acid diglycidyl ester, etc. The alicyclic amine includes one or more selected from 4,4-diaminodicyclohexylmethane, isophoronediamine, 3,3'-dimethyl-4,4-diaminodicyclohexylmethane, N-aminoethylpiperazine, methylbenzenediamine, hydrogenated diaminodiphenylmethane, etc. The polyetheramine includes one or more selected from D230, D400, etc. The accelerator is one or more selected from 2,4,6-tris(dimethylaminomethyl)phenol, benzyldimethylamine, 1,8-diaza-bicyclo(5,4,0)-7-undecene, N-aminoethylpiperazine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and an organic metal salt.

[0028] In some embodiments of the present invention, the mass ratio of the first component to the second component is 100:(25-45).

[0029] In some embodiments of the present invention, the first component further includes a toughening agent, which is a mixture of one or more of inorganic nanoparticles, polysulfide rubber, PU prepolymer and polyether polyol, and its mass content accounts for 0%-10% of the first component.

[0030] The degradable epoxy resin system material of some embodiments of the present invention has at least one of the following characteristics: The initial mixed viscosity at 25°C is 100-300 mPa·s; At 40°C, the time for the viscosity to increase to 1000 mPa·s is 100-200 min; Curing at 65-80℃ for 4-10h, the reaction degree is above 95%; The glass transition temperature of the fully cured resin is above 85°C.

[0031] Specifically, the first component and the second component of the degradable epoxy resin system are mixed, and at the curing temperature, the epoxy groups of the epoxy resin interact with the active groups of the curing agent to gradually cross-link. The above-mentioned "reaction degree", which can also be referred to as the curing degree, refers to the proportion of epoxy groups that have participated in the cross-linking chemical reaction during the mixing and curing process of the first component and the second component of the degradable epoxy resin system, to the total number of initial epoxy groups.

[0032] The present invention also proposes a use of the above-mentioned degradable epoxy resin system material, wherein the degradable epoxy resin system material can be used to prepare a degradable epoxy resin body or a degradable epoxy resin composite material by adopting a vacuum infusion process.

[0033] The present invention also provides a degradable epoxy resin body, which is prepared by mixing and curing the above-mentioned degradable epoxy resin system material, and the preparation steps include: Weigh the first component and the second component respectively according to the set mass ratio; The first component and the second component are mixed and then subjected to vacuum stirring and degassing to obtain a mixed material; The mixed material is poured into a mold coated with a release agent and then placed in an oven for curing to obtain a degradable epoxy resin body.

[0034] In some embodiments of the present invention, the step of pouring the mixture into a mold coated with a release agent and then curing the mixture comprises: Heat to 65-80℃ and keep warm for 6-12h; Alternatively, first heat to 30-40°C for pre-reaction for 0-4h, then heat to 65-80°C, and heat and cure for 6-10h.

[0035] The present invention also proposes a method for recycling a biodegradable epoxy resin body, see Figure 1 , including the following steps: Step S101, immersing the degradable epoxy resin body in a degradation liquid; Step S102, heating to 80-120°C for reflux degradation reaction for 10-48h, until the degradable epoxy resin body is completely dissolved to obtain a dissolving solution, at which point the degradable epoxy resin body is degraded into small molecular oligomers dissolved in the degradation solution; Step S103, performing reduced pressure distillation on the dissolved liquid at 40° C.-190° C. to separate and obtain the recovered degradation liquid and the recovered degradation resin.

[0036] Before immersing the degradable epoxy resin body in the degradation liquid, the degradable epoxy resin body is also broken into a smaller size to accelerate degradation. 100g of the degradation liquid can generally recycle and degrade 0-70g of the degradable epoxy resin body. The time for complete degradation is generally 10-48h. The degradation is carried out in a closed container with a condensing device so that it can be continuously refluxed during the degradation process.

[0037] The degradation liquid includes a mixture of one or more of amine compounds and alcohol compounds, and an organic amine catalyst. In some embodiments of the present invention, the mass proportion of amine compounds in the degradation liquid is 0-96%, the mass proportion of alcohol compounds is 0-97%, and the mass proportion of organic amine catalysts is 1%-5%. Amine compounds include one or more selected from ethylenediamine, butanediamine, hexamethylenediamine, meta-xylene diamine, isophoronediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc. Alcohol compounds include one or more selected from methanol, ethanol, ethylene glycol, glycerol, isopropanol, benzyl alcohol, etc. The organic amine catalyst is one or a mixture of 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diaza-bicyclo(5,4,0)-7-undecene, N-aminoethylpiperazine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, a modified product of 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and a complex of amine and metal.

[0038] The present invention also provides a degradable epoxy resin composite material, which is prepared by mixing the above-mentioned degradable epoxy resin system material, compounding with a reinforcing material, and then curing.

[0039] The reinforcing material is one or a mixture of glass fiber, carbon fiber, polyester fiber and polyamide fiber.

[0040] In one embodiment of the present invention, the reinforcing material and the degradable epoxy resin system material are prepared by vacuum infusion to obtain a degradable epoxy resin composite material, and the preparation steps include: Weigh the first component and the second component respectively according to the set mass ratio; The first component and the second component are mixed and then subjected to vacuum stirring and degassing to obtain a mixed material; The mixture is vacuumed and then solidified after being soaked in the laid reinforcement material to obtain a degradable epoxy resin composite material.

[0041] In some embodiments of the present invention, the step of curing the mixed material after impregnating the laid reinforcement material comprises: Heat to 65-80℃ and keep warm for 6-12h; Alternatively, first heat to 30-40°C for pre-reaction for 0-4h, then heat to 65-80°C, and heat and cure for 6-10h.

[0042] The present invention also proposes a method for recycling a degradable epoxy resin composite material, see Figure 2 , including the following steps: Step S201, immersing the degradable epoxy resin composite material in a degradation liquid; Step S202, heating to 80-120°C for reflux degradation reaction for 10-48h to obtain a dissolving solution and recover the reinforcing material. At this time, the degradable epoxy resin system material is degraded into small molecular oligomers dissolved in the degradation solution; Step S203, taking out the recovered reinforcement material, washing and drying it with water, washing it with water three times, and drying it in an oven at 120° C. for 2 hours; Step S204, performing reduced pressure distillation on the dissolved liquid at 40° C.-190° C. to separate and obtain the recovered degradation liquid and the recovered degradation resin.

[0043] Before the degradable epoxy resin composite material is immersed in the degradation liquid, the degradable epoxy resin composite material is also broken into a smaller size to accelerate degradation. 100g of the degradation liquid can generally recycle and degrade 0-180g of the degradable epoxy resin composite material. The degradation is carried out in a closed container with a condensing device so that it can be continuously refluxed during the degradation process.

[0044] The degradation liquid includes a mixture of one or more of amine compounds and alcohol compounds, and an organic amine catalyst. In some embodiments of the present invention, the mass proportion of amine compounds in the degradation liquid is 0-96%, the mass proportion of alcohol compounds is 0-97%, and the mass proportion of organic amine catalysts is 1%-5%. Amine compounds include one or more selected from ethylenediamine, butanediamine, hexamethylenediamine, meta-xylene diamine, isophoronediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc. Alcohol compounds include one or more selected from methanol, ethanol, ethylene glycol, glycerol, isopropanol, benzyl alcohol, etc. The organic amine catalyst is one or a mixture of 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diaza-bicyclo(5,4,0)-7-undecene, N-aminoethylpiperazine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, a modified product of 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and a complex of amine and metal.

[0045] The degradable epoxy resin system material of the present invention can be used as a raw material to prepare a degradable epoxy resin body, and can also be compounded with a reinforcing material (such as fiber, fabric, etc.) to prepare a degradable epoxy resin composite material. In addition, the degradable epoxy resin body or the composite material can be made by a vacuum infusion system.

[0046] It should be noted that in this application, all features defined in the form of numerical ranges or percentage ranges, such as values, quantities, contents and concentrations, are only for simplicity and convenience. Accordingly, the description of numerical ranges or percentage ranges should be deemed to have covered and specifically disclosed all possible secondary ranges and individual values ​​within the range (including integers and fractions). In order to make the description concise, all possible combinations of various technical features in various embodiments or examples are not described. Therefore, as long as there is no contradiction in the combination of these technical features, the various technical features in various embodiments or examples can be combined arbitrarily, and all possible combinations should be considered to be the scope recorded in this specification. In the present invention, the sum of the percentage content of each component contained in the composition is 100%.

[0047] In order to make the purpose, technical scheme and advantages of the present invention more understandable, the present invention is further described in detail below in conjunction with specific embodiments, and the described embodiments are part of the embodiments of the present invention, rather than all the embodiments. It should be noted here that these embodiments describe many specific details in order to fully understand the present invention, but the present invention can also be implemented in other ways different from those described herein, and those skilled in the art can make similar generalizations without violating the connotation of the present invention. Therefore, these specific embodiments do not constitute any form of any limitation on the actual protection scope of the present invention, and the present invention is not limited by the specific embodiments disclosed below.

[0048] In all the following embodiments and comparative examples, unless otherwise specified, the "parts" related to the amount of components are all parts by weight. In engineering, the first component is more often referred to as component A, and the second component is referred to as component B, so the following embodiments follow the engineering designation. The degradable epoxy resin composite materials in the following embodiments are all prepared by vacuum infusion of reinforcing materials and degradable epoxy resin system materials. The infusion process determines that the content of reinforcing materials in the degradable epoxy resin composite materials is basically about 75%, and the changes between the embodiments are very small, so the ratio of degradable epoxy resin system materials to reinforcing materials in the degradable epoxy resin composite materials will not be described in detail. And for different reinforcing materials, due to the difference in fiber density, the mass ratio will be very different, so the mass ratio of degradable epoxy resin system materials to reinforcing materials in the degradable epoxy resin composite materials is also non-fixed.

[0049] Embodiment 1

[0050] Prepare biodegradable epoxy resin system materials: Component A: 33 parts of diglycidyl aniline, 62 parts of diglycidyl hexahydrophthalate, 5 parts of polyether polyol; Component B: 42 parts of isophorone diamine, 57 parts of polyetheramine D230, 1 part of 2,4,6-tris(dimethylaminomethyl)phenol.

[0051] Preparation of degradable epoxy resin body: Based on the above-mentioned degradable epoxy resin system material, component A: component B are mixed evenly in a mass ratio of 100:33, vacuum stirred and degassed, and then poured into a mold, first heated to 40°C for pre-reaction for 3 hours, and then heated to 80°C for insulation and curing for 7 hours to obtain a degradable epoxy resin body.

[0052] Recycling of degradable epoxy resin body: first weigh 97 parts of anhydrous ethanol and 3 parts of 1,5,7-triazabicyclo[4.4.0]dec-5-ene, stir until completely dissolved to obtain a degradation solution; cut the degradable epoxy resin body into 1×1×0.2cm sample blocks, weigh 10g and put it into a round-bottom flask; pour 50ml of the degradation solution, heat to 100℃ and stir to react for 40h, the epoxy resin body is completely degraded into small molecular oligomers dissolved in the degradation solution to obtain a dissolving solution; distill the dissolving solution under reduced pressure at 40℃ to separate the recovered degradation solution and the recovered degradation resin. The recovery rate of the resin can reach 100%.

[0053] Preparation of degradable epoxy resin composite materials: Based on the above-mentioned degradable epoxy resin system material, component A: component B are evenly mixed in a mass ratio of 100:33, and vacuum stirring and degassing are performed to obtain a mixture, which is then introduced into the glass fiber cloth by vacuum, first heated to 40°C for pre-reaction for 3 hours, and then heated to 80°C for insulation and curing for 7 hours to prepare a degradable epoxy resin composite material.

[0054] Recycling of degradable epoxy resin composite material: first weigh 97 parts of anhydrous ethanol and 3 parts of 1,5,7-triazabicyclo[4.4.0]dec-5-ene, stir until completely dissolved to obtain a degradation solution; cut the degradable epoxy resin composite material into 2×2×0.2cm-sized samples, weigh 20g and put them into a round-bottom flask; pour 50ml of the degradation solution, heat to 100℃ and stir to react for 30h, the resin is completely degraded into small molecular oligomers dissolved in the degradation solution, separated from the reinforcing fiber, and a dissolving solution and a recovered reinforcing material are obtained; the recovered reinforcing fiber is removed from the dissolving solution, rinsed with water three times, and placed in an oven at 120℃ for 2h; the dissolving solution is subjected to reduced pressure distillation at 40℃ to separate the recovered degradation solution and the recovered degradation resin. The recovery rate of the reinforcing fiber and the resin can reach 100%.

[0055] Embodiment 2

[0056] Prepare biodegradable epoxy resin system materials: Component A: 33 parts of diglycidyl aniline, 43 parts of diglycidyl phthalate, 19 parts of diglycidyl hexahydrophthalate, 5 parts of polyether polyol; Component B: 42 parts of isophorone diamine, 57 parts of polyetheramine D230, 1 part of 2,4,6-tris(dimethylaminomethyl)phenol.

[0057] Preparation of degradable epoxy resin body: Based on the above-mentioned degradable epoxy resin system material, component A: component B are mixed evenly in a mass ratio of 100:38, vacuum stirred and degassed, and then poured into a mold, heated to 70°C and cured for 10 hours to obtain a degradable epoxy resin body.

[0058] Recycling of degradable epoxy resin body: first weigh 96 parts of anhydrous ethanol and 4 parts of 1,5,7-triazabicyclo[4.4.0]dec-5-ene, stir until completely dissolved to obtain a degradation solution; cut the degradable epoxy resin body into 1×1×0.2cm sample blocks, weigh 10g and put them into a round-bottom flask; pour 50ml of the degradation solution, heat to 90℃ and stir to react for 48h, the epoxy resin body is completely degraded into small molecular oligomers dissolved in the degradation solution to obtain a dissolving solution; distill the dissolving solution under reduced pressure at 40℃ to separate the recovered degradation solution and the recovered degradation resin. The recovery rate of the resin can reach 100%.

[0059] Preparation of degradable epoxy resin composite materials: Based on the above-mentioned degradable epoxy resin system material, component A: component B are evenly mixed in a mass ratio of 100:38, and vacuum stirring and degassing are performed to obtain a mixture, which is then introduced into a glass fiber cloth by vacuum, heated to 70°C and cured for 10 hours to prepare a degradable epoxy resin composite material.

[0060] Recycling of degradable epoxy resin composite material: first weigh 96 parts of anhydrous ethanol and 4 parts of 1,5,7-triazabicyclo[4.4.0]dec-5-ene, stir until completely dissolved to obtain a degradation solution; cut the degradable epoxy resin composite material into 2×2×0.2cm sample blocks, weigh 20g and put them into a round-bottom flask; pour 50ml of the degradation solution, heat to 90℃ and stir to react for 36h, the resin is completely degraded into small molecular oligomers dissolved in the degradation solution, separated from the reinforcing fiber, and a dissolving solution and a recovered reinforcing material are obtained; the recovered reinforcing fiber is removed from the dissolving solution, rinsed with water three times, and placed in an oven at 120℃ for 2h; the dissolving solution is subjected to reduced pressure distillation at 40℃ to separate the recovered degradation solution and the recovered degradation resin. The recovery rate of the reinforcing fiber and the resin can reach 100%.

[0061] Embodiment 3

[0062] Prepare biodegradable epoxy resin system materials: Component A: 20 parts of triglycidyl p-aminophenol, 80 parts of diglycidyl hexahydrophthalate; Component B: 58 parts of 3,3'-dimethyl-4,4-diaminodicyclohexylmethane, 41 parts of polyetheramine D230, and 1 part of 2,4,6-tris(dimethylaminomethyl)phenol.

[0063] Preparation of degradable epoxy resin body: Based on the above-mentioned degradable epoxy resin system material, component A: component B are mixed evenly in a mass ratio of 100:41, vacuum stirred and degassed, and then poured into a mold, heated to 70°C and cured for 10 hours to obtain a degradable epoxy resin body.

[0064] Recycling of degradable epoxy resin bulk: first weigh 96 parts of diethylenetriamine and 4 parts of 1,8-diaza-bicyclo (5,4,0)-7-undecene, stir and dissolve evenly to obtain a degradation solution; cut the degradable epoxy resin bulk into 1×1×0.2cm sample blocks, weigh 10g and put them into a round-bottom flask; pour 50ml of the degradation solution, heat to 90℃ and stir to react for 24h, the epoxy resin bulk is completely degraded into small molecular oligomers dissolved in the degradation solution to obtain a dissolving solution; distill the dissolving solution under reduced pressure at 190℃ to separate the recovered degradation solution and the recovered degradation resin. The recovery rate of the resin can reach 100%.

[0065] Preparation of degradable epoxy resin composite materials: Based on the above-mentioned degradable epoxy resin system material, component A: component B are evenly mixed in a mass ratio of 100:41, and vacuum stirring and degassing are performed to obtain a mixture, which is then introduced into a glass fiber cloth by vacuum, heated to 70°C and cured for 10 hours to prepare a degradable epoxy resin composite material.

[0066] Recycling of degradable epoxy resin composite material: first weigh 96 parts of diethylenetriamine and 4 parts of 1,8-diaza-bicyclo (5,4,0)-7-undecene, stir and dissolve evenly to obtain degradation solution; cut the degradable epoxy resin composite material into 2×2×0.2cm sample blocks, weigh 20g and put them into a round-bottom flask; pour 50ml of degradation solution, heat to 90℃ and stir to react for 13h, the resin is completely degraded into small molecular oligomers dissolved in the degradation solution, separated from the reinforcing fiber, and the dissolving solution and the recovered reinforcing material are obtained; the recovered reinforcing fiber is removed from the dissolving solution, rinsed with water three times, and placed in an oven at 120℃ for 2h; the dissolving solution is subjected to reduced pressure distillation at 190℃ to separate the recovered degradation solution and the recovered degradation resin. The recovery rate of the reinforcing fiber and the resin can reach 100%.

[0067] Embodiment 4

[0068] Prepare biodegradable epoxy resin system materials: Component A: 9 parts of triglycidyl p-aminophenol, 24 parts of diglycidyl aniline, 62 parts of diglycidyl phthalate, 5 parts of polyether polyol; Component B: 45 parts of isophorone diamine, 54 parts of polyetheramine D230, 1 part of 2,4,6-tris(dimethylaminomethyl)phenol.

[0069] Preparation of degradable epoxy resin body: Based on the above-mentioned degradable epoxy resin system material, mix component A: component B in a mass ratio of 100:35, stir and degas in vacuum, then pour into a mold, first heat to 30°C for pre-reaction for 4 hours, then heat to 70°C for insulation and curing for 10 hours to obtain a degradable epoxy resin body.

[0070] Recycling of degradable epoxy resin body: first weigh 49 parts of anhydrous ethanol, 49 parts of hexamethylenediamine, and 2 parts of 1,5,7-triazabicyclo[4.4.0]dec-5-ene, stir until completely dissolved to obtain a degradation solution; cut the degradable epoxy resin body into 1×1×0.2 cm sample blocks, weigh 10 g and put them into a round-bottom flask; pour 50 ml of the degradation solution, heat to 100°C and stir to react for 21 hours, the epoxy resin body is completely degraded into small molecular oligomers dissolved in the degradation solution, and a dissolving solution is obtained; the dissolving solution is subjected to reduced pressure distillation at 40°C and 180°C to separate the recovered degradation solution and the recovered degradation resin. The recovery rate of the resin can reach 100%.

[0071] Preparation of degradable epoxy resin composite materials: Based on the above-mentioned degradable epoxy resin system material, component A: component B are evenly mixed in a mass ratio of 100:35, and vacuum stirring and degassing are performed to obtain a mixture, which is then introduced into the glass fiber cloth by vacuum, first heated to 30°C for pre-reaction for 4 hours, and then heated to 70°C for insulation and curing for 10 hours to prepare a degradable epoxy resin composite material.

[0072] Recycling of degradable epoxy resin composite material: first weigh 49 parts of anhydrous ethanol, 49 parts of hexamethylenediamine, and 2 parts of 1,5,7-triazabicyclo[4.4.0]dec-5-ene, stir until completely dissolved, and obtain a degradation solution; cut the degradable epoxy resin composite material into 2×2×0.2cm-sized samples, weigh 20g and put them into a round-bottom flask; pour 50ml of the degradation solution, heat to 100℃ and stir for 10h, the resin is completely degraded into small molecular oligomers dissolved in the degradation solution, separated from the reinforcing fiber, and a dissolving solution and a recovered reinforcing material are obtained; the recovered reinforcing fiber is removed from the dissolving solution, rinsed with water three times, and placed in an oven at 120℃ for 2h; the dissolving solution is subjected to reduced pressure distillation at 40℃ and 180℃ to separate the recovered degradation solution and the recovered degradation resin. The recovery rate of the reinforcing fiber and the resin can reach 100%.

[0073] Comparative Example

[0074] Taking the epoxy resin system material that is currently widely used and has better performance on the market as an example, it was purchased from Daosheng Tianhe Materials Technology (Shanghai) Co., Ltd., with the brand name TECHSTORM190 / 195, a two-component material, TS190 as epoxy resin and TS195 as curing agent.

[0075] Preparation of epoxy resin body: mix Daosheng Tianhe TS190 epoxy resin and Daosheng Tianhe TS195 curing agent in a ratio of 100:28, pour into a mold after vacuum stirring and degassing, first heat to 30°C for pre-reaction for 4 hours, then heat to 70°C for insulation and curing for 10 hours to obtain the epoxy resin body.

[0076] A recovery test was conducted on the epoxy resin body: first, 96 parts of hexamethylenediamine and 4 parts of 1,5,7-triazabicyclo[4.4.0]dec-5-ene were weighed and stirred until completely dissolved to obtain a degradation solution; the epoxy resin body was cut into samples of 1×1×0.2 cm in size, 10 g was weighed and put into a round-bottom flask; 50 ml of the degradation solution was poured in, the temperature was raised to 100°C, and the reaction was stirred for 48 hours. The sample did not change at all and was non-degradable.

[0077] Preparation of epoxy resin composite materials: Daosheng Tianhe TS190 epoxy resin and Daosheng Tianhe TS195 curing agent were mixed evenly in a ratio of 100:28, and vacuum stirred and degassed to obtain a mixture, which was then introduced into a glass fiber cloth by vacuum, first heated to 30°C for pre-reaction for 4 hours, and then heated to 70°C for heat preservation and curing for 10 hours to prepare an epoxy resin composite material.

[0078] A recovery test was conducted on the epoxy resin composite material: first, 96 parts of hexamethylenediamine and 4 parts of 1,5,7-triazabicyclo[4.4.0]dec-5-ene were weighed and stirred until completely dissolved to obtain a degradation solution; the epoxy resin composite material was cut into samples of 2×2×0.2 cm in size, and 20 g was weighed and put into a round-bottom flask; 50 ml of the degradation solution was poured in, the temperature was raised to 100°C, and the reaction was stirred for 48 hours. The sample did not change at all and was non-degradable.

[0079] The epoxy resin system materials, the main body and the composite materials of the above-mentioned embodiments and comparative examples were tested respectively to characterize the performance of the epoxy resin system materials, the main body and the composite materials of the present invention.

[0080] According to the standard DIN 53019, the epoxy resin system materials and each component of each embodiment and comparative example were tested for viscosity and viscosity growth, and the test results are shown in the following Table 1. As can be seen from Table 1, the initial mixed viscosity of the degradable epoxy resin system material used for vacuum infusion of wind turbine blades is 100-300 mPa·s (25°C), and the time for the viscosity to increase to 1000 mPa·s is 100-200 min (40°C). The epoxy resin system material in the present invention has a low viscosity and a slow viscosity growth rate. It has high operability when used for vacuum infusion of wind turbine blades, which is conducive to good infiltration of the resin into the reinforcing material and the bonding between the resin and the reinforcing material.

[0081] Table 1: Viscosity and viscosity growth test results of epoxy resin system materials and components of Examples 1 to 4 and Comparative Examples .

[0082] According to the standard ISO 11357, the epoxy resin bodies of the embodiments and comparative examples were tested for glass transition temperature (Tg), according to the standard ISO 527-2, the epoxy resin bodies of the embodiments and comparative examples were tested for tensile properties, according to the standard ISO 178, the epoxy resin bodies of the embodiments and comparative examples were tested for bending properties, and according to the standard ISO527-5, the epoxy resin composite materials of the embodiments and comparative examples were tested for tensile properties, and the test results are shown in Table 2 below. As can be seen from Table 2, the Tg of the epoxy resin body of the present invention is higher than 85°C, the curing temperature of the resin is lower than 80°C, and it is suitable for existing wind turbine blade production equipment; the tensile strength, tensile modulus, and bending strength and bending modulus of the epoxy resin body and vacuum infusion composite material of the present invention are higher than those of the commercialized product TS 190 / 195; the epoxy resin body and vacuum infusion composite material of the present invention are degradable at a relatively low temperature, and the reinforcing fiber and resin can be recycled at the same time.

[0083] Table 2: Test results of glass transition temperature, tensile properties and bending properties of epoxy resin bodies and composite materials of Examples 1 to 4 and Comparative Examples .

[0084] In summary, the degradable epoxy resin system material, epoxy resin body and epoxy resin composite material of the present invention can meet the requirements of low viscosity, slow reaction speed and high glass transition temperature of cured product for vacuum infusion of wind turbine blades, which is beneficial to the vacuum infusion operation process; they have good stability under normal use conditions, and their mechanical properties are comparable to or even better than those of existing conventional wind turbine blade products, and can meet all process performance and use performance requirements for the production and use of existing wind turbine blades.

[0085] Taking the GPC (gel permeation chromatography) test of the recycled degradable resin in Example 1 as an example, the performance of the recycled degradable resin is analyzed. Figure 3 As shown. Figure 3 It can be seen that the molecular weight of the recycled degraded resin is relatively small, mainly between 200-1300, which is conducive to the reuse of the degraded product. Subsequent use verification shows that the strength of the recycled reinforcing fiber of the present invention can be maintained at more than 95% of the original fiber, and the degraded resin can be directly reused as a raw material such as a curing agent or a toughening agent.

[0086] It should be noted that "one embodiment" or "an embodiment" in this application refers to specific features, structures or characteristics that can be included in at least one implementation of the present invention. "In one embodiment" and "an embodiment" appearing in different places in this specification do not all refer to the same embodiment, nor are they separate or selective embodiments that are mutually exclusive with other embodiments. The words "including" and "comprising" indicate the presence of the claimed features, but do not exclude the presence of one or more other features. The term "and / or" used in this application includes any and all combinations of one or more of the relevant listed items. The terms "first" and "second" are used for descriptive purposes only and are not to be understood as indicating or implying relative importance.

[0087] The present invention has the following beneficial effects: 1) The present invention uses commercial epoxy resin and curing agent, and uses glycidyl ester epoxy resin containing ester bonds as functional raw materials. Through formula design, the degradable epoxy resin system material, epoxy resin body, and epoxy resin composite material can meet the requirements of low viscosity, slow reaction speed and high glass transition temperature of cured product for vacuum infusion of wind turbine blades, which is beneficial to the vacuum infusion operation process. At the same time, the resin and reinforcing material have good wettability, which can reduce production defects. The structure of the ester bond is more stable than that of the imine bond, ketal bond, etc. After reacting with the curing agent, the performance of the cured product is less affected under natural conditions and has good stability under normal use conditions. The prepared fiber-reinforced composite material has mechanical properties comparable to or even better than those of existing wind turbine blade products, and meets all process performance and use performance requirements for the production and use of existing wind turbine blades.

[0088] 2) The recycling method of the present invention can make the epoxy resin body and the composite material degrade rapidly at a relatively low temperature. The degradation conditions are relatively mild and can be achieved at normal pressure and 80-120°C. The equipment is simple and no waste is discharged during the degradation process. The resin and the reinforcing material are recovered at the same time. The degradation and recycling process does not cause obvious damage to the performance of the recovered reinforcing material. The recovered reinforcing material can be directly fished out, washed, dried, and then recycled and reused. The degraded resin can be directly reused after being separated from the degradation liquid by reduced pressure distillation.

[0089] Although the above methods are illustrated and described as a series of actions for simplicity of explanation, it should be understood and appreciated that these methods are not limited by the order of the actions, because according to one or more embodiments, some actions may occur in a different order and / or concurrently with other actions from those illustrated and described herein or not illustrated and described herein but understandable to those skilled in the art.

[0090] The method steps of the present application shown in a plurality of different exemplary embodiments are only exemplary. Although only a few embodiments are described in detail in this disclosure, it should be readily understood by those who refer to this disclosure that many modifications are possible (e.g., parameter values, use of materials, etc.) without substantially departing from the novel teachings and advantages of the subject matter described in this application. Therefore, all such modifications are intended to be included within the scope of the present invention. The order or sequence of any process or method steps can be changed or reordered according to alternative embodiments. Without departing from the spirit of the present invention and its essence, those skilled in the art may make various corresponding modifications and changes according to the present invention, but these corresponding modifications and changes should all fall within the scope of protection of the present invention.

Claims

1. A degradable epoxy resin system material, characterized in that: The method comprises a first component and a second component, wherein the first component comprises a first epoxy resin and a second epoxy resin, and the second component comprises a first curing agent, a second curing agent and an accelerator; The first epoxy resin is one or a mixture of glycidyl ether epoxy resin and glycidyl amine epoxy resin, and the mass content accounts for 15%-35% of the first component; The second epoxy resin is selected from one or more structures comprising The epoxy resin, wherein R is one or more structures selected from a C1-C18 aliphatic carbon chain, a benzene ring and its derivatives, and a heterocyclic structure containing oxygen, nitrogen, silicon, phosphorus, sulfur or selenium and its derivatives, R1 is selected from at least one structure selected from a methylene group and a cyclohexyl group, R2 and R3 are each independently a hydrogen atom, a C1-C18 aliphatic carbon chain, a benzene ring and its derivatives, and one or more structures selected from a carboxyl group, a hydroxyl group, an aldehyde group or an epoxy group, and the mass content of the second epoxy resin accounts for 60%-80% of the first component; The first curing agent is one or a mixture of alicyclic amines, and its mass content accounts for 40%-60% of the second component; The second curing agent is one or a mixture of polyetheramines, and its mass content accounts for 40%-60% of the second component; The mass content of the accelerator accounts for 0.5%-3% of the second component.

2. The degradable epoxy resin system material according to claim 1, characterized in that: Have at least one of the following characteristics: The mass ratio of the first component to the second component is 100:(25-45); The glycidyl ether epoxy resin includes one or more selected from bisphenol A epoxy resin, bisphenol F epoxy resin and bisphenol S epoxy resin; The glycidylamine epoxy resin includes one or more selected from diglycidyl aniline, N,N,N',N'-tetraepoxypropyl-4,4'-diaminodiphenylmethane, N,N,N',N'-tetra(oxiranylmethyl)-1,3-phenylenediamine, N-(2-methylphenyl)-N-(1,2-epoxypropyl)-oxiranylmethylamine and triglycidyl p-aminophenol; The second epoxy resin comprises one or more selected from diglycidyl hexahydrophthalate, diglycidyl 4,5-epoxytetrahydrophthalate and diglycidyl phthalate; The alicyclic amine includes one or more selected from 4,4-diaminodicyclohexylmethane, isophoronediamine, 3,3'-dimethyl-4,4-diaminodicyclohexylmethane, N-aminoethylpiperazine, methylbenzenediamine and hydrogenated diaminodiphenylmethane; The polyetheramine includes one or two selected from D230 and D400; The accelerator is one or a mixture of 2,4,6-tris(dimethylaminomethyl)phenol, benzyldimethylamine, 1,8-diaza-bicyclo(5,4,0)-7-undecene, N-aminoethylpiperazine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and organic metal salts.

3. The degradable epoxy resin system material according to claim 1, characterized in that: The first component also includes a toughening agent, which is a mixture of one or more of inorganic nanoparticles, polysulfide rubber, PU prepolymer and polyether polyol, and its mass content accounts for 0%-10% of the first component.

4. A use of the degradable epoxy resin system material as claimed in any one of claims 1 to 3, characterized in that: The degradable epoxy resin system material is used for preparing a degradable epoxy resin body or a degradable epoxy resin composite material by adopting a vacuum infusion process.

5. A degradable epoxy resin body, characterized in that: The biodegradable epoxy resin system is mixed and cured according to any one of claims 1 to 3, and the preparation of the biodegradable epoxy resin body includes: Weigh the first component and the second component respectively according to the set mass ratio; The first component and the second component are mixed and then subjected to vacuum stirring and degassing to obtain a mixed material; The mixed material is poured into a mold coated with a release agent and then cured to obtain a degradable epoxy resin body.

6. The degradable epoxy resin body according to claim 5, characterized in that: The steps of pouring the mixture into a mold coated with a release agent and then curing the mixture include: Heat to 65-80℃ and keep warm for 6-12h; Alternatively, first heat to 30-40°C for pre-reaction for 0-4h, then heat to 65-80°C, and heat and cure for 6-10h.

7. A method for recycling a degradable epoxy resin body as claimed in claim 5, characterized in that: The steps include: The degradable epoxy resin body is immersed in a degradation liquid; Raising the temperature to 80-120° C. to perform a degradation reaction until the degradable epoxy resin body is completely dissolved to obtain a dissolving solution; The dissolved solution is subjected to reduced pressure distillation to separate and obtain a recovered degradation solution and a recovered degradation resin; The degradation liquid comprises one or a mixture of several of amine compounds and alcohol compounds, and an organic amine catalyst.

8. The method for recycling a degradable epoxy resin body according to claim 7, characterized in that: Have at least one of the following characteristics: The mass proportion of amine compounds in the degradation liquid is 0-96%, the mass proportion of alcohol compounds is 0-97%, and the mass proportion of organic amine catalysts is 1%-5%; The amine compound includes one or more selected from ethylenediamine, butanediamine, hexamethylenediamine, meta-xylene diamine, isophoronediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine; The alcohol compound includes one or more selected from methanol, ethanol, ethylene glycol, glycerol, isopropanol and benzyl alcohol; The organic amine catalyst is one or a mixture of 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diaza-bicyclo(5,4,0)-7-undecene, N-aminoethylpiperazine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, a modified product of 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and a complex of amine and metal.

9. A degradable epoxy resin composite material, characterized in that: The degradable epoxy resin system material according to any one of claims 1 to 3 is mixed, compounded with a reinforcing material, and then cured to make the product.

10. The degradable epoxy resin composite material according to claim 9, characterized in that: The reinforcing material is one or a mixture of glass fiber, carbon fiber, polyester fiber and polyamide fiber.

11. The degradable epoxy resin composite material according to claim 9, characterized in that: The reinforcing material and the degradable epoxy resin system material are prepared by a vacuum infusion method to obtain the degradable epoxy resin composite material.

12. The degradable epoxy resin composite material according to claim 11, characterized in that: The preparation steps of the degradable epoxy resin composite material include: Weigh the first component and the second component respectively according to the set mass ratio; The first component and the second component are mixed and then subjected to vacuum stirring and degassing to obtain a mixed material; The mixture is vacuumed and then solidified after being soaked in the laid reinforcement material to obtain a degradable epoxy resin composite material.

13. The degradable epoxy resin composite material according to claim 12, characterized in that: The step of curing the mixed material after impregnating the laid reinforcement material comprises: Heat to 65-80℃ and keep warm for 6-12h; Alternatively, first heat to 30-40°C for pre-reaction for 0-4h, then heat to 65-80°C, and heat and cure for 6-10h.

14. A method for recycling the degradable epoxy resin composite material as claimed in claim 9, characterized in that: The steps include: The degradable epoxy resin composite material is immersed in a degradation liquid; Raise the temperature to 80-120°C to carry out degradation reaction for 10-48h to obtain a dissolving solution and recover the reinforcing material; Take out the recovered reinforcement material, wash it with water and dry it; The dissolved solution is subjected to reduced pressure distillation to separate and obtain a recovered degradation solution and a recovered degradation resin; The degradation liquid comprises one or a mixture of several of amine compounds and alcohol compounds, and an organic amine catalyst.

15. The method for recycling the degradable epoxy resin composite material according to claim 14, characterized in that: Have at least one of the following characteristics: The mass proportion of amine compounds in the degradation liquid is 0-96%, the mass proportion of alcohol compounds is 0-97%, and the mass proportion of organic amine catalysts is 1%-5%; The amine compound includes one or more selected from ethylenediamine, butanediamine, hexamethylenediamine, meta-xylene diamine, isophoronediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine; The alcohol compound includes one or more selected from methanol, ethanol, ethylene glycol, glycerol, isopropanol and benzyl alcohol; The organic amine catalyst is one or a mixture of 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diaza-bicyclo(5,4,0)-7-undecene, N-aminoethylpiperazine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, a modified product of 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and a complex of amine and metal.

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