CN109897216B

CN109897216B - Recycling method of waste thermosetting resin and composite material thereof

Info

Publication number: CN109897216B
Application number: CN201910195846.8A
Authority: CN
Inventors: 徐世美; 赵旭; 王雄雷; 田飞; 安文丽; 王玉忠
Original assignee: Sichuan University
Current assignee: Sichuan University
Priority date: 2019-03-15
Filing date: 2019-03-15
Publication date: 2021-02-09
Anticipated expiration: 2039-03-15
Also published as: CN109897216A

Abstract

The invention discloses a method for recycling waste thermosetting resin and composite material thereof, which comprises the steps of pretreating the waste thermosetting resin and the composite material thereof, mixing the pretreated material with polyamine or a mixture of the polyamine and an organic solvent, and heating and degrading to obtain a degradation product. The method has mild reaction conditions, and the degradation product is directly used for preparing epoxy resin in an epoxy curing system without separation and purification, or oleogel capable of adsorbing organic matters is obtained after separation and purification.

Description

Recycling method of waste thermosetting resin and composite material thereof

Technical Field

The invention relates to the technical field of chemical recovery of waste high polymer materials, in particular to a method for recycling waste thermosetting resin and a composite material thereof.

Background

The thermosetting resin and the composite material thereof have the performances of corrosion resistance, insulation, good thermal stability, excellent adhesion and the like, and are widely applied to the fields of aerospace, ship industry, electronic and electric appliances, coatings and the like. The products can produce a plurality of leftover materials and defective products in the production and processing processes, or form a large amount of waste after the life cycle is reached, thereby not only harming the environment, but also causing the loss of resources. The resin waste materials formed by curing have a stable three-dimensional network structure, so that the recycling difficulty is high. At present, simple incineration, landfill and mechanical crushing are mainly used, but the treatment method has great environmental hidden danger. The burning method can release a large amount of toxic gas, thereby seriously polluting the environment; in addition, the waste epoxy resin and the composite material thereof contain a large amount of resources with high added value, and direct incineration causes a large amount of resource waste. The landfill method is also a treatment method which is widely applied, and because the waste epoxy resin and the composite material thereof have stable structures, the waste epoxy resin and the composite material thereof cannot be naturally degraded when buried underground, but can pollute the soil environment and underground water resources. The mechanical crushing method is to crush waste thermosetting resin and composite material thereof and then to process and mold, and although the method can recover a certain amount of waste thermosetting resin and composite material thereof, the application of the method has great limitation and is only simple and low-efficiency recycling. In contrast, chemical recovery is the most promising method of recycling because useful chemicals are available, and thus has attracted general attention.

At present, the chemical recovery work of waste thermosetting resins and composite materials thereof mainly focuses on recovering reinforcing materials from the composite materials, and the decomposed resin products are not utilized. This is because the degradation methods used are mostly carried out at high temperatures (>200 ℃) and under high pressure using strongly corrosive acids (i.e. nitric acid, sulfuric acid) or bases as catalyst systems, and these harsh degradation conditions lead to decomposition of the polymer into complex mixtures of gaseous, liquid and solid states, which makes its reuse very difficult. The existing recycling technology generally has the defects of harsh recycling condition, incomplete recycling, large resource waste and the like. Therefore, the development of a mild recycling method for efficiently recycling the degradation products has important application value.

Disclosure of Invention

The invention aims to provide a recycling method of waste thermosetting resin and a composite material thereof, and aims to solve the problems of harsh reaction conditions, incomplete recycling and resource waste of the existing recycling method. The recycling method has simple process and mild conditions; meanwhile, the invention can completely convert the raw materials into products, realizes complete recovery, generates no by-products, realizes clean, efficient and high-value recovery and reutilization of waste thermosetting resin, saves energy, and has low production cost.

The technical scheme for solving the technical problems is as follows:

a method for recycling waste thermosetting resin and composite material thereof comprises the following steps: firstly, the waste thermosetting resin and the composite material thereof are pretreated, the pretreated material is mixed with polyamine or a mixture of polyamine and an organic solvent, and the mixture is heated and degraded to obtain a degradation product which can be further utilized.

Further, in a preferred embodiment of the present invention, the pretreatment method includes: mechanically pulverizing or soaking in polyhalogen substituted alkane or organic amine, wherein polyhalogen substituted alkane comprises one or more of dichloromethane, trichloromethane, dichloroethane, trichloroethane, dichloropropane and dichlorobutane; the organic amine comprises one or more of ethylenediamine, diethylenetriamine, ethanolamine and amide.

According to the invention, the waste thermosetting resin and the composite material thereof are subjected to soaking pretreatment by using polyhalogen substituted alkane or organic amine, so that the material is loosened, the subsequent degradation process is facilitated, the degradation speed is accelerated, and the degradation efficiency is improved.

The invention utilizes polyamine to recover waste thermosetting resin and composite material thereof, and polyamine is used as a degradation reagent to carry out aminolysis reaction with thermosetting resin under the heating condition. After the thermosetting resin is completely degraded, the degradation liquid does not need to be further purified and separated, and the degraded product and the unreacted polyamine can be directly added into an uncured epoxy resin system as a reactive cross-linking agent at the same time, so that a curing reaction is carried out to form new epoxy resin. The polyamine has the capability of selectively catalyzing and cracking ester bond crosslinking points, is used as a degradation solvent, can react with ester bonds under the conditions of normal pressure and low temperature, and can efficiently and quickly obtain degradation products; meanwhile, the degradation product and the unreacted solvent polyamine can be used as a curing agent of a new epoxy resin synthesis system.

In addition, as another way of the recycling method, the organic solvent is added into the degradation solvent, and the organic solvent does not participate in the reaction and plays a role in swelling, so that the polyamine is brought into the resin in the reaction process, the inside and the outside of the resin are simultaneously degraded to form a solid-phase product, and the porous gel is obtained by filtering. Because the thermosetting resin has oleophylic and hydrophobic properties, the obtained gel is an oil gel material, can adsorb organic matters and is used for sewage treatment. The liquid phase product generated during the degradation process can be used for preparing epoxy resin by a re-curing system containing epoxy-anhydride or epoxy-amine, or used as a hydrophobic modifier for carrying out surface modification on cotton cloth, filter paper and metal nets to prepare surface hydrophobic materials. The invention can conveniently obtain oil gel materials and other degradation products by selectively adding organic solvents, thereby expanding the application field and range of products.

Further, in a preferred embodiment of the present invention, the polyamine is one or a combination of more of ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine; the organic solvent is one or more of N-methyl pyrrolidone, dimethyl sulfoxide, acetamide, hexamethylphosphoric triamide, N-dimethylformamide, N-dimethylacetamide, butyrolactone, decalin, tetrahydronaphthalene, cyclohexanol, ethylene glycol and polyethylene glycol.

Further, in the preferred embodiment of the present invention, the degradation products obtained when the polyamine is used for degradation can be directly added as a reactive crosslinking agent to an epoxy curing system to prepare a new epoxy resin again. The degradation solvent is polyamine, and the degradation product obtained after the reaction is directly used as a reactive cross-linking agent to be added into an epoxy resin system to prepare the epoxy resin.

Further, in a preferred embodiment of the present invention, the mass ratio of the waste thermosetting resin and the composite material thereof to the polyamine is 1: (1-100), the reaction temperature is 40-220 ℃, and the reaction time is 0.1-12 h.

Further, in a preferred embodiment of the present invention, the mass ratio of the waste thermosetting resin and the composite material thereof to the polyamine is 1: (2-20), the reaction temperature is 50-200 ℃, and the reaction time is 0.5-2 h. Preferably, the mass ratio of the waste thermosetting resin and the composite material thereof to the polyamine is 1: 2. 1:10 or 1: 20. Preferably, the reaction temperature is 50 ℃, 130 ℃ or 200 ℃. Preferably, the reaction time is 0.5h, 1h or 2 h.

Further, in a preferred embodiment of the present invention, the degradation products obtained when the degradation is carried out using a mixture of polyamine and organic solvent include solid phase products and liquid phase products; wherein the solid phase product is oleogel which can be applied to the adsorption of organic matters; the liquid phase product can be used for preparing epoxy resin by a re-curing system containing epoxy-anhydride or epoxy-amine, or used as a hydrophobic modifier for carrying out surface modification on cotton cloth, filter paper and metal nets to prepare surface hydrophobic materials.

The degradation solvent comprises polyamine and an organic solvent, and the degradation product comprises a solid-phase product and a liquid-phase product; separating and purifying the solid phase product to obtain oil gel; and separating and purifying the liquid phase product to obtain a degradation product. The oleogel obtained from the solid-phase product is used for adsorbing organic matters; the degradation products obtained from the liquid phase products are used in resolidification systems containing epoxy-anhydrides or epoxy-amines, or for the hydrophobic modification of cotton or stainless steel fabrics.

Further, in a preferred embodiment of the present invention, the method for separating and purifying the solid phase product comprises: filtering, soaking in organic cleaning agent, washing and drying; the method for separating and purifying the liquid phase product comprises the following steps: separated by precipitation with water or by distillation under reduced pressure.

Further, in a preferred embodiment of the present invention, the mass ratio of the polyamine to the organic solvent is 1: (0.1-10), the reaction temperature of the waste thermosetting epoxy resin and the composite material thereof, the mixture of polyamine and organic solvent is 60-200 ℃, and the reaction time is 0.5-12 h.

Preferably, the mass ratio of the polyamine to the organic solvent is 1: 1. 1:5 or 1: 10. Preferably, the reaction temperature of the waste thermosetting resin and the composite material thereof with the mixture of the polyamine and the organic solvent is 100 ℃, 130 ℃ or 150 ℃. Preferably, the reaction time is 0.5h, 5h or 8 h.

Further, in the preferred embodiment of the present invention, the heating manner is microwave heating and conventional heating.

The waste thermosetting resin and the composite material thereof comprise: one or more of waste epoxy resin, waste polyurethane, waste phenolic resin, waste unsaturated polyester, waste carbon fiber reinforced epoxy resin, waste glass fiber reinforced epoxy resin, waste carbon fiber reinforced polyurethane, waste glass fiber reinforced polyurethane, waste carbon fiber reinforced phenolic resin, waste glass fiber reinforced phenolic resin, waste carbon fiber reinforced unsaturated polyester and waste glass fiber unsaturated polyester.

Further, in a preferred embodiment of the present invention, the waste thermosetting resin and the composite material thereof are mainly waste epoxy resin containing ester bonds and the composite material thereof.

Preferably, the waste epoxy resin containing ester bonds and the composite material thereof are anhydride-cured epoxy resin and the composite material thereof or carboxylic acid-cured epoxy resin and the composite material thereof.

The present invention includes, but is not limited to, the above-mentioned anhydride-cured epoxy resin and its composite material or carboxylic acid-cured epoxy resin and its composite material, and may also be other epoxy resins and their composite materials containing ester bonds, such as modified anhydride and carboxylic acid curing agent and ester bonds obtained by other reaction forms.

The invention has the following beneficial effects:

the invention degrades the waste thermosetting resin and the composite material thereof into a product with multiple functional groups, so that the waste thermosetting resin and the composite material thereof can be more widely reused. Most importantly, the decomposition product of the resin matrix and the polyamine serving as the reaction reagent can be directly and further recycled without further separation and purification, so that the separation cost is greatly reduced, the resource waste is avoided, and higher economic value is created, thereby having important application value.

The reaction conditions adopted by the invention are mild, the degraded epoxy composite material can be recycled to obtain high-strength fiber and high value-added oleogel material, and expensive corrosion-resistant equipment is avoided; the adopted reaction solvents have low toxicity and less pollution; the whole reaction process is simple, the degradation speed is high, the degradation efficiency is high, and the method has the advantages of high efficiency and economy.

Drawings

FIG. 1 is an FTIR spectrum before and after degradation of a waste anhydride cured epoxy resin;

FIG. 2 is an SEM image of an oleogel made according to an example of the invention;

FIG. 3 is a block diagram of an oleogel made according to an example of the invention.

Detailed Description

The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

It is worth mentioning that:

1) the parts of materials used in the following examples and application examples are parts by weight;

2) the resin degradation rates given in the following examples and application examples were calculated by the following formula:

or

3) In the oil absorption experiment of the following application example, 1 part of xerogel is soaked in 50 parts of organic solvent for a certain time and then taken out for weighing, and the oil absorption multiplying power of the organic solvent is calculated by the following formula:

example 1

Mechanically crushing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (the diameter is 0.45-0.9mm), weighing 2 parts of crushed resin, mixing with 5 parts of diethylenetriamine, heating to 130 ℃ by using 300W microwave, keeping for 60min to obtain degradation products, filtering the degradation products to respectively obtain degradation liquid and degraded resin residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The resin degradation rate of this example was 5.8%.

Example 2

20 parts of waste anhydride curing epoxy resin is soaked in 50 parts of dichloromethane for 48 hours, washed by ethanol and water respectively, and dried. Weighing 2 parts of dried resin, mixing with 5 parts of diethylenetriamine, heating to 130 ℃ by using 300W microwave, keeping for 60min to obtain a degradation product, filtering the degradation product to respectively obtain a degradation liquid and degraded resin residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The resin degradation rate of this example was 90.8%.

Example 3

20 parts of waste anhydride curing epoxy resin is soaked in 50 parts of chloroform for 48 hours, washed by ethanol and water respectively, and dried. Weighing 2 parts of dried resin, mixing with 5 parts of diethylenetriamine, heating to 130 ℃ by using 300W microwave, keeping for 60min to obtain a degradation product, filtering the degradation product to respectively obtain a degradation liquid and degraded resin residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The resin degradation rate of this example was 80.8%.

Example 4

20 parts of waste anhydride curing epoxy resin is soaked in 50 parts of diethylenetriamine for 48 hours, washed by ethanol and water respectively and dried. Weighing 2 parts of dried resin, mixing with 5 parts of diethylenetriamine, heating to 130 ℃ by using 300W microwave, keeping for 60min to obtain a degradation product, filtering the degradation product to respectively obtain a degradation liquid and degraded resin residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The resin degradation rate of this example was 60.3%.

Example 5

20 parts of waste anhydride curing epoxy resin is soaked in 50 parts of ethanolamine for 48 hours, washed by ethanol and water respectively, and dried. Weighing 2 parts of dried resin, mixing with 5 parts of diethylenetriamine, heating to 130 ℃ by using 300W microwave, keeping for 60min to obtain a degradation product, filtering the degradation product to respectively obtain a degradation liquid and degraded resin residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The resin degradation rate of this example was 50.3%.

Example 6

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. Weighing 2 parts of dried resin, mixing with 5 parts of diethylenetriamine, heating to 130 ℃ by using 300W microwave, keeping for 90min to obtain degradation products, filtering the degradation products to respectively obtain degradation liquid and degraded resin residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The resin degradation rate of this example was 100%.

Example 7

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of chloroform for 48h, washing with ethanol and water respectively, and oven drying. Weighing 2 parts of dried resin, mixing with 5 parts of diethylenetriamine, heating to 130 ℃ by using 300W microwave, keeping for 60min to obtain a degradation product, filtering the degradation product to respectively obtain a degradation liquid and degraded resin residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The resin degradation rate of this example was 80.7%.

Example 8

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of diethylenetriamine for 48h, washing with ethanol and water, and oven drying. Weighing 2 parts of dried resin, mixing with 5 parts of diethylenetriamine, heating to 130 ℃ by using 300W microwave, keeping for 60min to obtain a degradation product, filtering the degradation product to respectively obtain a degradation liquid and degraded resin residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The resin degradation rate of this example was 80.4%.

Example 9

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of ethanolamine for 48h, washing with ethanol and water respectively, and oven drying. Weighing 2 parts of dried resin, mixing with 5 parts of diethylenetriamine, heating to 130 ℃ by using 300W microwave, keeping for 60min to obtain a degradation product, filtering the degradation product to respectively obtain a degradation liquid and degraded resin residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The resin degradation rate of this example was 65.1%.

Example 10

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. Weighing 2 parts of dried resin, mixing with 5 parts of diethylenetriamine, heating to 50 ℃ by using 300W microwave, keeping for 60min to obtain a degradation product, filtering the degradation product to respectively obtain a degradation liquid and degraded resin residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The resin degradation rate of this example was 13.3%.

Example 11

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. Weighing 1 part of dried resin, mixing with 1 part of diethylenetriamine, heating to 130 ℃ by using 300W microwave, keeping for 60min to obtain a degradation product, filtering the degradation product to respectively obtain a degradation liquid and degraded resin residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The resin degradation rate of this example was 80.3%.

Example 12

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. Weighing 1 part of dried resin, mixing with 20 parts of diethylenetriamine, heating to 130 ℃ by using 300W microwave, keeping for 60min to obtain a degradation product, filtering the degradation product to respectively obtain a degradation liquid and degraded resin residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The resin degradation rate of this example was 100%.

Example 13

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. Weighing 2 parts of dried resin, mixing with 5 parts of diethylenetriamine, heating to 200 ℃ by using 300W microwave, keeping for 60min to obtain a degradation product, filtering the degradation product to respectively obtain a degradation liquid and degraded resin residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The resin degradation rate of this example was 100%.

Example 14

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. Weighing 2 parts of dried resin, mixing with 5 parts of triethylene tetramine, heating to 130 ℃ by using 300W microwave, keeping for 90min to obtain degradation products, filtering the degradation products to respectively obtain degradation liquid and degraded resin residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The resin degradation rate of this example was 34.5%.

Example 15

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. Weighing 2 parts of dried resin, mixing with 5 parts of tetraethylenepentamine, heating to 130 ℃ by using 300W microwave, keeping for 90min to obtain degradation products, filtering the degradation products to respectively obtain degradation liquid and degraded resin residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The resin degradation rate of this example was 36.9%.

Example 16

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. Weighing 2 parts of dried resin, mixing with 5 parts of polyethylene polyamine, heating to 130 ℃ by using 300W microwave, keeping for 90min to obtain degradation products, filtering the degradation products to respectively obtain degradation liquid and degraded resin residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The resin degradation rate of this example was 36.2%.

Example 17

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. Weighing 2 parts of dried resin, mixing with 5 parts of ethylenediamine, heating to 130 ℃ by using 300W microwave, keeping for 90min to obtain degradation products, filtering the degradation products to respectively obtain degradation liquid and degraded resin residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The resin degradation rate of this example was 100%.

Example 18

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. Weighing 2 parts of dried resin, mixing with 5 parts of diethylenetriamine, heating to 220 ℃ by using 300W microwave, keeping for 60min to obtain a degradation product, filtering the degradation product to respectively obtain a degradation liquid and degraded resin residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The resin degradation rate of this example was 100%.

Example 19

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. Weighing 2 parts of dried resin, mixing with 5 parts of diethylenetriamine, heating to 130 ℃ by using 300W microwave, keeping for 60min to obtain a degradation product, filtering the degradation product to respectively obtain a degradation liquid and degraded resin residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The resin degradation rate of this example was 100%.

Example 20

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. Weighing 2 parts of dried resin, mixing with 5 parts of diethylenetriamine, conventionally heating to 50 ℃, keeping for 60min to obtain degradation products, filtering the degradation products to respectively obtain degradation liquid and degraded resin residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The resin degradation rate of this example was 50.1%.

Example 21

Mechanically pulverizing 20 parts of waste carboxylic acid cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water, and oven drying. Weighing 2 parts of dried resin, mixing with 5 parts of diethylenetriamine, heating to 130 ℃ by using 300W microwave, keeping for 60min to obtain a degradation product, filtering the degradation product to respectively obtain a degradation liquid and degraded resin residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The resin degradation rate of this example was 100%.

Example 22

Mechanically pulverizing 20 parts of waste styrene-maleic anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. Weighing 2 parts of dried resin, mixing with 5 parts of diethylenetriamine, heating to 130 ℃ by using 300W microwave, keeping for 60min to obtain a degradation product, filtering the degradation product to respectively obtain a degradation liquid and degraded resin residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The resin degradation rate of this example was 100%.

Example 23

Mechanically pulverizing 20 parts of waste liquid polyurethane cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. Weighing 2 parts of dried resin, mixing with 5 parts of diethylenetriamine, heating to 130 ℃ by using 300W microwave, keeping for 60min to obtain a degradation product, filtering the degradation product to respectively obtain a degradation liquid and degraded resin residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The resin degradation rate of this example was 100%.

Example 24

20 parts of waste anhydride cured epoxy composite material is soaked in 50 parts of dichloromethane for 48 hours, washed by ethanol and water respectively and dried. Weighing 2 parts of dried resin, mixing with 5 parts of diethylenetriamine, heating to 130 ℃ by using 300W microwave, keeping for 30min, filtering out solids from the mixed solution, separating to obtain epoxy resin residues, fibers and the like, cleaning and drying the residues, weighing and calculating the degradation rate. The composite material of this example had a degradation rate of 78.9%.

Example 25

20 parts of waste anhydride cured epoxy composite material is soaked in 50 parts of dichloromethane for 48 hours, washed by ethanol and water respectively and dried. Weighing 2 parts of dried resin, mixing with 5 parts of diethylenetriamine, heating to 130 ℃ by using 300W microwave, keeping for 90min, completely degrading the epoxy resin, filtering to obtain recycled fiber, washing, drying and weighing. The degradation rate of the composite material of this example was 100%.

Example 26

20 parts of waste amine cured epoxy resin is soaked in 50 parts of dichloromethane for 48 hours, washed by ethanol and water respectively, and dried. Weighing 2 parts of dried resin, mixing with 5 parts of ethylenediamine, heating to 180 ℃ by using 300W microwave, keeping for 2 hours to obtain degradation products, filtering the degradation products to respectively obtain degradation liquid and degraded resin residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The resin degradation rate of this example was 29.3%.

Example 27

Mechanically pulverizing 20 parts of waste polyurethane to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water, and oven drying. Weighing 2 parts of dried resin, mixing with 5 parts of diethylenetriamine, heating to 100 ℃ by using 300W microwave, and keeping for 2 hours until the polyurethane is completely degraded. The resin degradation rate of this example was 100%.

Example 28

Mechanically pulverizing 20 parts of waste phenolic resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water, and oven drying. Weighing 2 parts of dried resin, mixing with 5 parts of diethylenetriamine, heating to 160 ℃ by using 300W microwave, keeping for 3h to obtain a degradation product, filtering the degradation product to respectively obtain a degradation liquid and degraded resin residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The resin degradation rate of this example was 40.6%.

Example 29

Mechanically pulverizing 20 parts of waste unsaturated polyester to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water, and oven drying. Weighing 2 parts of dried resin, mixing with 5 parts of diethylenetriamine, heating to 150 ℃ by using 300W microwave, and keeping for 3h to completely degrade unsaturated polyester. The resin degradation rate of this example was 100%.

Example 30

Mechanically pulverizing 20 parts of waste circuit board to 20-40 mesh (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water, and oven drying. Weighing 2 parts of dried resin, mixing with 5 parts of diethylenetriamine, heating to 150 ℃ in an oil bath, keeping for 2 hours, separating the reinforcing material, filtering to obtain a degradation liquid and degraded residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The degradation rate of the composite material of this example was 43.9%.

Example 31

Mechanically pulverizing 20 parts of waste epoxy terrace to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and drying. Weighing 2 parts of dried resin, mixing with 5 parts of diethylenetriamine, heating to 150 ℃ by using 300W microwave, keeping for 2h, separating the reinforced material, filtering to obtain a degradation liquid and degraded resin residues, cleaning and drying the residues, and weighing to calculate the degradation rate. The degradation rate of the composite material of this example was 40.1%.

Example 32

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (the diameter is 0.45-0.9mm), weighing 1 part of the pulverized resin, mixing with 10 parts of solvent (diethylenetriamine/N-methylpyrrolidone ═ 1/1), heating to 130 ℃ by using 300W microwave, keeping for 2 hours, filtering after the reaction is finished, soaking, cleaning and drying the solid-phase product by using ethanol, and weighing. The oleogel yield of this example was 37.7%.

Example 33

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (the diameter is 0.45-0.9mm), weighing 1 part of the pulverized resin, mixing with 10 parts of solvent (diethylenetriamine/dimethylsulfoxide 1/1), heating to 130 ℃ by using 300W microwave, keeping for 2 hours, filtering after the reaction is finished, soaking and cleaning a solid-phase product by using ethanol, drying, and weighing. The oleogel yield of this example was 39.1%.

Example 34

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (the diameter is 0.45-0.9mm), weighing 1 part of the pulverized resin, mixing with 10 parts of solvent (diethylenetriamine/acetamide ═ 1/1), heating to 130 ℃ by using 300W microwave, keeping for 2 hours, filtering after the reaction is finished, soaking, cleaning and drying the solid-phase product by using ethanol, and weighing. The oleogel yield of this example was 32.7%.

Example 35

Mechanically crushing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (the diameter is 0.45-0.9mm), weighing 1 part of crushed resin, mixing with 10 parts of solvent (diethylenetriamine/hexamethylphosphoric triamide is 1/1), heating to 130 ℃ by using 300W microwave, keeping for 2 hours, soaking, cleaning and drying a filtered solid-phase product after the reaction is finished, and weighing. The oleogel yield of this example was 30.5%.

Example 36

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (the diameter is 0.45-0.9mm), weighing 1 part of pulverized resin, mixing with 10 parts of solvent (diethylenetriamine/N, N-dimethylformamide ═ 1/1), heating to 130 ℃ by using 300W microwave, keeping for 2 hours, filtering after the reaction is finished, soaking, cleaning and drying the solid-phase product by using ethanol, and weighing. The oleogel yield of this example was 39.7%.

Example 37

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (the diameter is 0.45-0.9mm), weighing 1 part of the pulverized resin, mixing with 10 parts of solvent (diethylenetriamine/N, N-dimethylacetamide ═ 1/1), heating to 130 ℃ by using 300W microwave, keeping for 2 hours, filtering after the reaction is finished, soaking, cleaning and drying the solid-phase product by using ethanol, and weighing. The oleogel yield of this example was 38.8%.

Example 38

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (the diameter is 0.45-0.9mm), weighing 1 part of the pulverized resin, mixing with 10 parts of solvent (diethylenetriamine/butyrolactone: 1/1), heating to 130 ℃ by using 300W microwave, keeping for 2h, filtering after the reaction is finished, soaking, cleaning and drying the solid-phase product by using ethanol, and weighing. The oleogel yield of this example was 36.8%.

Example 39

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (the diameter is 0.45-0.9mm), weighing 1 part of the pulverized resin, mixing with 10 parts of solvent (diethylenetriamine/decalin: 1/1), heating to 130 ℃ by using 300W microwave, keeping for 2h, filtering after the reaction is finished, soaking and cleaning a solid-phase product by using ethanol, drying, and weighing. The oleogel yield of this example was 32.4%.

Example 40

Mechanically crushing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (the diameter is 0.45-0.9mm), weighing 1 part of crushed resin, mixing with 10 parts of solvent (diethylenetriamine/tetralin 1/1), heating to 130 ℃ by using 300W microwave, keeping for 2 hours, filtering after the reaction is finished, soaking, cleaning and drying the solid-phase product by using ethanol, and weighing. The oleogel yield of this example was 32.5%.

EXAMPLE 41

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (the diameter is 0.45-0.9mm), weighing 1 part of the pulverized resin, mixing with 10 parts of solvent (diethylenetriamine/cyclohexanol: 1/1), heating to 130 ℃ by using 300W microwave, keeping for 2h, filtering after the reaction is finished, soaking, cleaning and drying the solid-phase product by using ethanol, and weighing. The oleogel yield of this example was 30.0%.

Example 42

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (the diameter is 0.45-0.9mm), weighing 1 part of the pulverized resin, mixing with 10 parts of solvent (diethylenetriamine/ethylene glycol: 1/1), heating to 130 ℃ by using 300W microwave, keeping for 2h, filtering after the reaction is finished, soaking and cleaning a solid-phase product by using ethanol, drying, and weighing. The oleogel yield of this example was 34.2%.

Example 43

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter is 0.45-0.9mm), weighing 1 part of pulverized resin, mixing with 10 parts of solvent (diethylenetriamine/polyethylene glycol: 1/1), heating to 130 ℃ with 300W microwave, keeping for 2h, filtering after the reaction is finished, soaking, cleaning and drying the solid-phase product with ethanol, and weighing. The oleogel yield of this example was 40.1%.

Example 44

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. Weighing 1 part of dried resin, mixing with 10 parts of solvent (diethylenetriamine/N-methyl pyrrolidone ═ 1/1), heating to 130 ℃ by using 300W microwave, keeping for 1h, filtering after the reaction is finished, soaking, cleaning and drying the solid-phase product by using ethanol, and weighing. The oleogel yield of this example was 70.8%.

Example 45

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (the diameter is 0.45-0.9mm), weighing 1 part of the pulverized resin, mixing with 10 parts of solvent (diethylenetriamine/N-methylpyrrolidone ═ 1/1), heating to 60 ℃ by using 300W microwave, keeping for 6h, filtering after the reaction is finished, soaking, cleaning and drying the solid-phase product by using ethanol, and weighing. The oleogel yield of this example was 80.5%.

Example 46

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (the diameter is 0.45-0.9mm), weighing 1 part of pulverized resin, mixing with 10 parts of solvent (diethylenetriamine/N-methylpyrrolidone ═ 1/1), heating to 220 ℃ by using 300W microwave, keeping for 1h, filtering after the reaction is finished, soaking, cleaning and drying the solid-phase product by using ethanol, and weighing. The oleogel yield of this example was 47.9%.

Example 47

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter is 0.45-0.9mm), weighing 1 part of pulverized resin, mixing with 10 parts of solvent (diethylenetriamine/N-methylpyrrolidone ═ 1/1), heating to 130 ℃ with 300W microwave, keeping for 0.5h, filtering after the reaction is finished, soaking, cleaning and drying the solid-phase product with ethanol, and weighing. The oleogel yield of this example was 88.2%.

Example 48

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (the diameter is 0.45-0.9mm), weighing 1 part of the pulverized resin, mixing with 10 parts of solvent (diethylenetriamine/N-methylpyrrolidone ═ 1/1), heating to 130 ℃ by using 300W microwave, keeping for 8h, filtering after the reaction is finished, soaking, cleaning and drying the solid-phase product by using ethanol, and weighing. The oleogel yield of this example was 10.9%.

Example 49

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (the diameter is 0.45-0.9mm), weighing 1 part of pulverized resin, mixing with 10 parts of solvent (diethylenetriamine/N-methyl pyrrolidone is 1/0.5), heating to 130 ℃ by using 300W microwave, keeping for 2 hours, filtering after the reaction is finished, soaking, cleaning and drying a solid-phase product by using ethanol, and weighing. The oleogel yield of this example was 20.0%.

Example 50

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (the diameter is 0.45-0.9mm), weighing 1 part of the pulverized resin, mixing with 10 parts of solvent (diethylenetriamine/N-methylpyrrolidone ═ 1/20), heating to 130 ℃ by using 300W microwave, keeping for 2 hours, filtering after the reaction is finished, soaking, cleaning and drying the solid-phase product by using ethanol, and weighing. The oleogel yield of this example was 78.6%.

Example 51

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter is 0.45-0.9mm), weighing 1 part of pulverized resin, mixing with 0.5 part of solvent (diethylenetriamine/N-methyl pyrrolidone ═ 1/1), heating to 130 ℃ with 300W microwave, keeping for 1h, filtering after the reaction is finished, soaking, cleaning and drying the solid-phase product with ethanol, and weighing. The oleogel yield of this example was 65.5%.

Example 52

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (the diameter is 0.45-0.9mm), weighing 1 part of the pulverized resin, mixing with 50 parts of a solvent (diethylenetriamine/N-methylpyrrolidone ═ 1/1), heating to 130 ℃ by using 300W microwaves, keeping for 2 hours, filtering after the reaction is finished, soaking, cleaning and drying the solid-phase product by using ethanol, and weighing. The oleogel yield of this example was 75.8%.

In order to examine the performance of the degradation liquid obtained by degrading the waste resin in the invention for re-solidifying the resin, the degradation product liquids of the above examples are respectively used in the recycled resin of the following application examples, and the dynamic thermo-mechanical performance of the recycled resin is tested. Meanwhile, in order to investigate the oleogel obtained by degrading the waste resin, the degradation products of the above embodiments are applied to an organic solvent absorption experiment, and the oil absorption multiplying power of the experiment is tested.

Application example 1

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. Weighing 3 parts of dried resin, mixing with 2 parts of diethylenetriamine, heating to 130 ℃ by using 300W microwave, and keeping for 60min to obtain the degradation liquid. Mixing the degradation liquid and the uncured epoxy resin according to the ratio of 1:10, adding 0.1g of catalyst (3-dimethylaminophenol), pouring into a mold, heating for 2 hours at 70 ℃ and heating for 2 hours at 110 ℃ in an oven to obtain the cured resin. The glass transition temperature is 139.4 ℃; storage modulus 1929MPa at 25 ℃.

Application example 2

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. Weighing 3 parts of dried resin, mixing with 3 parts of diethylenetriamine, heating to 130 ℃ by using 300W microwave, and keeping for 60min to obtain the degradation liquid. Mixing the degradation liquid and the uncured epoxy resin according to the ratio of 1:10, adding 0.1g of catalyst (3-dimethylaminophenol), pouring into a mold, heating for 2 hours at 70 ℃ and heating for 2 hours at 110 ℃ in an oven to obtain the cured resin. The glass transition temperature is 144.1 ℃; the storage modulus is 1888MPa at 25 ℃.

Application example 3

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. Weighing 3 parts of dried resin, mixing with 4 parts of diethylenetriamine, heating to 130 ℃ by using 300W microwave, and keeping for 60min to obtain the degradation liquid. Mixing the degradation liquid and the uncured epoxy resin according to the ratio of 1:10, adding 0.1g of catalyst (3-dimethylaminophenol), pouring into a mold, heating for 2 hours at 70 ℃ and heating for 2 hours at 110 ℃ in an oven to obtain the cured resin. The glass transition temperature is 143.1 ℃; at 25 ℃, the storage modulus is 1666 MPa.

Application example 4

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. Weighing 3 parts of dried resin, mixing with 5 parts of diethylenetriamine, heating to 130 ℃ by using 300W microwave, and keeping for 60min to obtain the degradation liquid. Mixing the degradation liquid and the uncured epoxy resin according to the ratio of 1:10, adding 0.1g of catalyst (3-dimethylaminophenol), pouring into a mold, heating for 2 hours at 70 ℃ and heating for 2 hours at 110 ℃ in an oven to obtain the cured resin. The glass transition temperature is 145.9 ℃; the storage modulus is 1884MPa at 25 ℃.

Application example 5

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. 3 parts of dried resin and 2 parts of diethylenetriamine are weighed, heated to 130 ℃ by using a conventional oil bath and then kept for 60min to obtain the degradation liquid. Mixing the degradation liquid and the uncured epoxy resin according to the ratio of 1:10, adding 0.1g of catalyst (3-dimethylaminophenol), pouring into a mold, heating for 2 hours at 70 ℃ and heating for 2 hours at 110 ℃ in an oven to obtain the cured resin. The glass transition temperature is 136.5 ℃; the storage modulus is 2523MPa at 25 ℃.

Application example 6

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. 3 parts of dried resin and 3 parts of diethylenetriamine are weighed, heated to 130 ℃ by using a conventional oil bath and then kept for 60min to obtain the degradation liquid. Mixing the degradation liquid and the uncured epoxy resin according to the ratio of 1:10, adding 0.1g of catalyst (3-dimethylaminophenol), pouring into a mold, heating for 2 hours at 70 ℃ and heating for 2 hours at 110 ℃ in an oven to obtain the cured resin. The glass transition temperature is 150.8 ℃; the storage modulus is 2525MPa at 25 ℃.

Application example 7

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. 3 parts of dried resin and 4 parts of diethylenetriamine are weighed, heated to 130 ℃ by using a conventional oil bath and then kept for 60min to obtain the degradation liquid. Mixing the degradation liquid and the uncured epoxy resin according to the ratio of 1:10, adding 0.1g of catalyst (3-dimethylaminophenol), pouring into a mold, heating for 2 hours at 70 ℃ and heating for 2 hours at 110 ℃ in an oven to obtain the cured resin. The glass transition temperature is 144.3 ℃; storage modulus 1825MPa at 25 ℃.

Application example 8

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. 3 parts of dried resin and 5 parts of diethylenetriamine are weighed, heated to 130 ℃ by using a conventional oil bath and then kept for 60min to obtain the degradation liquid. Mixing the degradation liquid and the uncured epoxy resin according to the ratio of 1:10, adding 0.1g of catalyst (3-dimethylaminophenol), pouring into a mold, heating for 2 hours at 70 ℃ and heating for 2 hours at 110 ℃ in an oven to obtain the cured resin. The glass transition temperature is 142.1 ℃; the storage modulus is 1387MPa at 25 ℃.

Application example 9

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. Weighing 3 parts of dried resin and 3 parts of diethylenetriamine, heating to 130 ℃ by using a microwave of 300W, and keeping for 60min to obtain the degradation liquid. Mixing the degradation liquid and the uncured epoxy resin according to the ratio of 2:10, adding 0.1g of catalyst (3-dimethylaminophenol), pouring into a mould, heating for 2 hours at 70 ℃ and 2 hours at 110 ℃ in an oven to obtain the cured resin. The glass transition temperature is 144.6 ℃; storage modulus 2425MPa at 25 ℃.

Application example 10

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. Weighing 3 parts of dried resin and 3 parts of diethylenetriamine, heating to 130 ℃ by using a microwave of 300W, and keeping for 60min to obtain the degradation liquid. Mixing the degradation liquid and the uncured epoxy resin according to the ratio of 3:10, adding 0.1g of catalyst (3-dimethylaminophenol), pouring into a mould, and heating in an oven at 70 ℃ for 2h and 110 ℃ for 2h to obtain the cured resin. The glass transition temperature is 145.4 ℃; the storage modulus is 1854MPa at 25 ℃.

Application example 11

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. 3 parts of dried resin and 4 parts of diethylenetriamine are weighed, heated to 130 ℃ by using microwave 300W and then kept for 60min to obtain degradation liquid. Mixing the degradation liquid and the uncured epoxy resin according to the ratio of 3:7, adding 0.1g of catalyst (3-dimethylaminophenol), pouring into a mould, and heating in an oven at 70 ℃ for 2h and 110 ℃ for 2h to obtain the cured resin. The glass transition temperature is 146.4 ℃; the storage modulus is 2398MPa at 25 ℃.

Application example 12

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. 3 parts of dried resin and 5 parts of diethylenetriamine are weighed, heated to 130 ℃ by using microwave 300W and then kept for 60min to obtain degradation liquid. Mixing the degradation liquid and the uncured epoxy resin according to the ratio of 4:6, adding 0.1g of catalyst (3-dimethylaminophenol), pouring into a mould, and heating in an oven at 70 ℃ for 2h and 110 ℃ for 2h to obtain the cured resin. The glass transition temperature is 108.3 ℃; the storage modulus is 1588MPa at 25 ℃.

Application example 13

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. 3 parts of dried resin and 3 parts of diethylenetriamine are weighed, heated to 130 ℃ by using a conventional oil bath and then kept for 60min to obtain the degradation liquid. Mixing the degradation liquid and the uncured epoxy resin according to the ratio of 2:10, adding 0.1g of catalyst (3-dimethylaminophenol), pouring into a mould, heating for 2 hours at 70 ℃ and 2 hours at 110 ℃ in an oven to obtain the cured resin. The glass transition temperature is 145.9 ℃; the storage modulus is 2523MPa at 25 ℃.

Application example 14

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. 3 parts of dried resin and 4 parts of diethylenetriamine are weighed, heated to 130 ℃ by using a conventional oil bath and then kept for 60min to obtain the degradation liquid. Mixing the degradation liquid and the uncured epoxy resin according to the ratio of 3:10, adding 0.1g of catalyst (3-dimethylaminophenol), pouring into a mould, and heating in an oven at 70 ℃ for 2h and 110 ℃ for 2h to obtain the cured resin. The glass transition temperature is 145.8 ℃; storage modulus 1901MPa at 25 ℃.

Application example 15

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. 3 parts of dried resin and 5 parts of diethylenetriamine are weighed, heated to 130 ℃ by using a conventional oil bath and then kept for 60min to obtain the degradation liquid. Mixing the degradation liquid and the uncured epoxy resin according to the ratio of 3:7, adding 0.1g of catalyst (3-dimethylaminophenol), pouring into a mould, and heating in an oven at 70 ℃ for 2h and 110 ℃ for 2h to obtain the cured resin. The glass transition temperature is 146.5 ℃; the storage modulus is 2349MPa at 25 ℃.

Application example 16

Mechanically pulverizing 20 parts of waste anhydride cured epoxy resin to 20-40 meshes (diameter of 0.45-0.9mm), soaking in 50 parts of dichloromethane for 48h, washing with ethanol and water respectively, and oven drying. 3 parts of dried resin and 5 parts of diethylenetriamine are weighed, heated to 130 ℃ by using a conventional oil bath and then kept for 60min to obtain the degradation liquid. Mixing the degradation liquid and the uncured epoxy resin according to the ratio of 4:6, adding 0.1g of catalyst (3-dimethylaminophenol), pouring into a mould, and heating in an oven at 70 ℃ for 2h and 110 ℃ for 2h to obtain the cured resin. The glass transition temperature is 115.1 ℃; at 25 ℃, the storage modulus is 2041 MPa.

Application example 17

In this application example, the oil absorption test was performed on the oil gel obtained after the reaction in example 26 was completed. The oil absorption multiplying power of the oil gel to the trichloromethane is 10.9 times within 5 s; the oil absorption multiplying power to dichloromethane is 8.7 times; the oil absorption multiplying power of the N-methyl pyrrolidone is 7.9 times;

application example 18

In this application example, the oil absorption test was performed on the oil gel obtained after the reaction in example 36 was completed. The oil absorption multiplying power of the oil gel to the trichloromethane is 10.9 times within 5 s; the oil absorption multiplying power to dichloromethane is 9.0 times; the oil absorption capacity for tetrahydrofuran was 8.7 times.

Application example 19

In this application example, the oil absorption test was performed on the oil gel obtained after the reaction in example 38 was completed. The oil gel is within 5s, and the oil absorption multiplying power of the oil gel to the trichloromethane is 12.2 times; the oil absorption multiplying power to dichloromethane is 10.1 times; the oil absorption magnification for N, N-dimethylformamide was 9.5 times.

Application example 20

In this application example, the oil absorption test was performed on the oil gel obtained after the reaction in example 41 was completed. The oil gel is within 5s, and the oil absorption multiplying power of the oil gel to the trichloromethane is 13.5 times; the oil absorption multiplying power to dichloromethane is 11.1 times; the oil absorption capacity for tetrahydrofuran was 9.8 times.

FIG. 1 is an FTIR spectrum before and after degradation of waste epoxy resin containing ester bonds. As can be seen from FIG. 1, at 1735cm^-1The stretching vibration peak of the ester group C ═ O is weakened, which indicates that the ester bond of the resin is broken during the degradation process. At 3450cm^-1A significant increase was exhibited indicating the production of hydroxyl groups. In addition 1654cm^-1A new peak which is obvious and is characteristic of amide appears. Meanwhile, it corresponds to a benzene skeleton (1510 cm)^-1And 1610cm^-1) And an ether bond (1180 cm)^-1And 1248cm^-1) The peak of (a) did not change significantly after degradation, indicating that these structures were not degraded. The FTIR results indicated that only the ester bond was degraded by the DETA catalytic system and that the amide and hydroxyl groups were generated due to aminolysis of the ester bond.

FIG. 2 is an SEM image of an epoxy resin prepared oleogel. It can be seen that the oleogel has a porous structure, and in addition, the resin has an oleophilic and hydrophobic skeleton, and thus has a rapid absorption capacity for organic solvents.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims

1. A method for recycling waste thermosetting resin and composite material thereof is characterized by comprising the following steps: the method comprises the following steps: firstly, pretreating waste thermosetting resin and a composite material thereof, mixing the pretreated material with polyamine or a mixture of polyamine and an organic solvent, and heating for degradation to obtain a degradation product capable of being further utilized;

when the degradation product obtained by degrading polyamine can be directly used as a reactive cross-linking agent to be added into an epoxy curing system, and new epoxy resin is prepared again;

when the mixture of polyamine and organic solvent is used for degradation, the obtained degradation product comprises a solid-phase product and a liquid-phase product; wherein the solid phase product is oleogel which can be applied to the adsorption of organic matters; the liquid phase product can be used for preparing epoxy resin by a re-curing system containing epoxy-anhydride or epoxy-amine, or used as a hydrophobic modifier for carrying out surface modification on cotton cloth, filter paper and metal nets to prepare a surface hydrophobic material;

the waste thermosetting resin and the composite material thereof are one or more of waste epoxy resin, waste polyurethane, waste carbon fiber reinforced epoxy resin, waste glass fiber reinforced epoxy resin, waste carbon fiber polyurethane and waste glass polyurethane.

2. The recycling method of the waste thermosetting resin and the composite material thereof according to claim 1, characterized in that: the pretreatment method comprises the steps of mechanically crushing or soaking in polyhalogen substituted alkane or organic amine; wherein the polyhalogenated substituted alkane comprises one or more of dichloromethane, trichloromethane, dichloroethane, trichloroethane, dichloropropane and dichlorobutane; the organic amine comprises one or more of ethylenediamine, diethylenetriamine, ethanolamine and amide.

3. The recycling method of the waste thermosetting resin and the composite material thereof according to claim 1, characterized in that: the polyamine is one or a combination of more of ethylenediamine, diethylenetriamine, triethylene tetramine and tetraethylene pentamine; the organic solvent is one or more of N-methyl pyrrolidone, dimethyl sulfoxide, acetamide, hexamethylphosphoric triamide, N-dimethylformamide, N-dimethylacetamide, butyrolactone, decalin, tetrahydronaphthalene, cyclohexanol, ethylene glycol and polyethylene glycol.

4. The recycling method of the waste thermosetting resin and the composite material thereof according to claim 1, characterized in that: the mass ratio of the waste thermosetting resin and the composite material thereof to the polyamine is 1:1 to 100 ℃, the reaction temperature is 40 to 220 ℃, and the reaction time is 0.1 to 12 hours.

5. The recycling method of the waste thermosetting resin and the composite material thereof according to claim 1, characterized in that: the mass ratio of the polyamine to the organic solvent is 1: 0.1-10 ℃, the reaction temperature of the waste thermosetting epoxy resin and the composite material thereof, the mixture of polyamine and organic solvent is 60-200 ℃, and the reaction time is 0.5-12 h.

6. The recycling method of the waste thermosetting resin and the composite material thereof according to any one of claims 1 to 5, characterized in that: the heating mode used in the method is microwave heating and conventional heating.