Composite Adhesive Material with Self-Healing Function and Its Application on Wind Energy Blades

Abstract

The present invention discloses a composite adhesive material with self-healing function and its application on wind energy blades. The composite adhesive material comprises polyurethane microcapsules, epoxy resin and composite polyetheramine. Among them, the mass ratio of the polyurethane microcapsules, the epoxy resin and the composite polyetheramine is (1-9):100:(26-45). Fix the profile of the wind energy blade within a mold, close the mold and evacuate to -0.095 to -0.100 MPa, pour the composite adhesive material according to any one of claims 1-9 into the mold, and cure for 12 h to obtain an epoxy wind energy blade with self-healing function. The present invention adopts a single-component microcapsule. After cracks occur in the blade, the microcapsules crack due to greater stress, and the epoxy resin in the microcapsules reacts with the excessive unreacted composite polyetheramine in the blade to complete the self-healing process.

Description

Technical Field

[0001] The present invention belongs to the technical field of new materials for new energy, and relates to a composite adhesive material with self-healing function and its application on wind energy blades. Background Art

[0002] Wind turbines operate in harsh natural environments, and it is inevitable that particles such as sand grains, raindrops, hailstones, and insects scour the surface of the blades, resulting in wear on the surface of the wind energy blades, especially severe wear on the leading edge. This will cause a significant increase in the resistance of the wind turbine and a significant decrease in the output power of the wind turbine, with a decrease amplitude of up to 25%, and pose potential safety hazards in operation. As the input end of the wind power generation unit, the material properties of the blades directly determine the output power and maintenance cost of the wind power generation device.

[0003] The master's thesis "Research on Composite Blade Repair Technology" by Meijie Lin of Wuhan University of Technology first selected an alkali-free glass fiber square cloth / epoxy resin system to prepare plates. Defect specimens were prepared by pre-embedding defects, mainly including air bubbles, uneven infiltration, dry spots, etc. For different defects, several different repair methods were used for repair, such as patch hand lay-up process, injection resin method, filling and perfusion resin method, etc. After the specimens were repaired and cured, mechanical property tests were carried out to study the repair effects of various methods and summarize the repair methods suitable for different defects. The results showed that no matter which defect occurred, it would affect the mechanical properties of the products; hand lay-up repair was more suitable for repairing air bubbles on the surface and not good for repairing internal defects; injection resin, filling and perfusion resin were more suitable for repairing internal damage and uneven infiltration defects. All the above repair methods were manual active repairs, with relatively high costs.

[0004] The master's thesis "Rapid Self-Healing System Based on Thiourea-Modified Polyamine Microcapsules and Epoxy Resin Microcapsules" by Junjie Peng of South China University of Technology synthesized modified polyetheramine (TU-T403) by the chemical reaction of polyetheramine and thiourea, and encapsulated them with epoxy resin by electrostatic spraying-interfacial polymerization respectively. Then, the two microcapsules were blended in a certain proportion to obtain an epoxy resin self-healing sample. This idea has relatively difficult-to-control chemical reactions of polyetheramine and thiourea, and processes such as electrostatic spraying-interfacial polymerization, with complex processes and high costs.

[0005] Xiao Chunping, Wan Liying et al. in "Study on the Self-healing Performance of Monocomponent Microcapsule-filled Epoxy-based Composites" and "Preparation and Self-healing Performance of Epoxy Resin-urea Formaldehyde Resin@2-methylimidazole Microcapsule / Epoxy Resin Composites" introduced the preparation of E-51-UF microcapsules with epoxy resin (E-51) as the core material and urea formaldehyde resin (UF) as the wall material by one-step in-situ polymerization. The microcapsules are filled inside the composite resin, and the maximum repair rate exceeds 90%. However, Xiao Chunping, Wan Liying et al. confirmed in "Aging Performance of Composite Microcapsule-filled Epoxy Resin Self-healing Composites" that the microcapsules have poor resistance to humidity, heat, acid, alkali and ultraviolet aging.

[0006] Xiao Yang, Wan Liying et al. synthesized self-healing siloxane epoxy resin (EP-DA) containing Diels-Alder (DA) bonds in "Study on the Performance of Self-healing Siloxane Epoxy Resin Containing DA Bonds". Patent CN112210070A discloses a novel self-healing epoxy resin curing agent and its preparation method and application. However, the temperature required for the DA bond reaction in the paper and the patent is 87°C or even 130 - 150°C, and the reaction conditions are harsh, and the repair effect cannot be guaranteed at low and normal temperatures.

[0007] Patent CN110791053A discloses an epoxy resin composition containing a microcapsule curing agent, its prepreg and composite material, including a microcapsule curing agent, an epoxy resin and a resin. The weight parts of each component are: 80 - 100 parts of epoxy resin, 15 - 30 parts of microcapsule curing agent, 10 - 20 parts of resin. The microcapsule curing agent is composed of a thermoplastic shell and an epoxy resin curing agent, and the epoxy resin curing agent is wrapped inside the thermoplastic shell. The particle size of the microcapsule curing agent is 3 - 20μm. This invention overcomes the following problems in the prior art: (1) When simply using rubber or elastomer to toughen epoxy resin, usually a dosage of 20% is required to play a toughening role; (2) When using inorganic rigid particles for toughening, strict requirements are imposed on the size of the rigid particles. Both too large and too small are not conducive to toughening. In addition, the rigid particles need to have a suitable elastic modulus and good interfacial compatibility with the epoxy resin matrix, which requires modification of the rigid particles, resulting in a decline in processability and an increase in cost; (3) The pot life of existing prepregs at normal temperature is generally 30 days. Usually, prepregs need to be stored frozen at -18°C. Users of prepregs need to be equipped with cold storage or freezing equipment, increasing the usage cost. Moreover, the thermoplastic shell of the microcapsule curing agent in this invention gradually collapses under the action of heat and resin, and the epoxy resin curing agent flows out of the thermoplastic shell or the epoxy resin penetrates into the thermoplastic shell to participate in the reaction, and it cannot actively repair the damaged part when the material cracks.

[0008] Patent CN109971125A discloses a carbon fiber / epoxy resin composite material with self-healing function, its preparation method and application. In the present invention, furan groups are introduced on the surface of carbon fibers, and maleimide groups are introduced into the epoxy resin matrix, and chemical bonding is formed through a reversible Diels-Alder reaction. After the interface of the carbon fiber / epoxy resin matrix is damaged, the forward and reverse reactions of the reaction can be controlled under mild conditions to achieve efficient and multiple self-healing of the interface. This invention does not require external capsules or hollow glass fibers, reducing the processing difficulty. However, the repair condition requires heating, which is not suitable for the self-healing of wind turbine blades.

[0009] Patent CN114230749A discloses a rapidly self-healing epoxy resin cured product, its preparation method and application. When repairing, this method requires heat treatment of the substrate, and the treatment temperature is 100-200 °C, which is not suitable for the self-healing of wind turbine blades.

[0010] Patents CN108973185A and CN208867611U disclose a self-healing intelligent wind turbine blade. The blade is cast by a vacuum infusion process using a glass fiber or carbon fiber reinforced epoxy resin composite material. In the epoxy resin composite material, a first hollow glass tube and a second hollow glass tube arranged side by side are embedded. The first hollow glass tube is filled with degassed epoxy resin, and the second hollow glass tube is filled with an epoxy resin curing agent. The first and second hollow glass tubes are arranged on the spar or trailing edge spar of the blade; the laying directions of the first and second hollow glass tubes are the same as the laying direction of the fibers in the epoxy resin composite material. The lengths of the first and second hollow glass tubes are 0.5-1 m, the outer diameters are 0.8-1.2 mm, and the inner diameters are 0.5-1.0 mm. The self-healing intelligent wind turbine blade of the present invention realizes rapid repair of cracks by setting two kinds of hollow glass tubes. When cracks appear in the blade matrix, the repair agents in the two kinds of hollow glass tubes flow out, mix, and cure at room temperature, reducing the fatigue source of the blade and improving the service life of the blade. Due to the laying problem of the hollow glass tubes, this invention has a good repair effect on the spar and trailing edge spar of the blade, but does not have the same repair effect on the whole blade.

[0011] Therefore, it can be seen that there are still a series of problems with epoxy wind energy blades with self-healing functions, such as the need for high temperature for self-healing, narrow self-healing range, short shelf life, and high cost. Summary of the Invention

[0012] The technical problems to be solved by the present invention are: to provide a composite adhesive material with self-healing function and a preparation method of an epoxy wind energy blade with self-healing function. So that the whole epoxy wind energy blade has self-healing function and can quickly achieve self-healing at room temperature, thereby improving the service life of the blade and the safety performance of the blade operation.

[0013] The technical solution of the present invention is: a composite adhesive material with self-repairing function, the composite adhesive material comprises polyurethane microcapsules, epoxy resin and composite polyether amine; wherein the mass ratio of the polyurethane microcapsules, epoxy resin and composite polyether amine is (1-9):100:(26-45).

[0014] The synthesis method of the polyurethane microcapsule comprises the following steps:

[0015] 1) Preparation of polyurethane microporous foam white material and black material: polyether polyol, catalyst, surfactant and cross-linking agent are mixed in a mass ratio of 100: (1-3): (0.1-2): (1-5) to prepare white material, and isocyanate is set as black material.

[0016] 2) Preparation of microporous foam containing epoxy resin: epoxy resin, white material and black material are fully mixed in a mass ratio of 20-40:100:(30-55), and micro-foamed to obtain microporous foam containing epoxy resin.

[0017] 3) Preparation of polyurethane microcapsules: The microporous foam containing epoxy resin obtained in step 2) is crushed into small particles with a particle size of 0.05-5 mm, the epoxy resin on the surface of the particles is washed off with methanol, and the particles are dried at 80° C. for 2-3 h to obtain polyurethane microcapsules containing epoxy resin in the core.

[0018] Furthermore, the polyether polyol described in step 1) is a polyether polyol of grades 330, 330N, 310, 305, etc., which is obtained by grafting ethylene oxide, propylene oxide, or a mixture of ethylene oxide and propylene oxide with glycerol and trimethylolpropane as initiators. The present invention uses glycerol and trimethylolpropane as initiators, and the functionality of the polyether is 3, so that the polyurethane microporous elastomer formed in this way has higher strength and density.

[0019] Furthermore, the catalyst described in step 1) is one or a mixture of dimethylethanolamine, dimethylcyclohexylamine, dimethylbenzylamine, triethylenediamine, pentamethyldiethylenetriamine, potassium acetate, potassium octoate, potassium oleate, stannous octoate, dibutyltin dilaurate, etc.

[0020] Furthermore, the surfactant in step 1) is one or a mixture of polyether-modified polysiloxanes such as CGY-1, CGY-6885, etc.

[0021] Furthermore, the crosslinking agent in step 1) is one or a mixture of ethylene glycol, propylene glycol, 1,4-butanediol, and glycerol. Since most of the hydroxyl groups of the crosslinking agent are primary hydroxyl groups, the activity of reacting with isocyanate is much faster than that of secondary hydroxyl groups, which will form a certain number of short chains during the synthesis of the polyurethane elastomer and increase the strength of the microporous elastomer.

[0022] Further, the isocyanate described in step 1) is one or a mixture of toluene diisocyanate, diphenylmethane diisocyanate, and polyphenyl polymethylene polyisocyanate.

[0023] Further, the particle size of the microcellular foam described in step 3) is 0.1 - 2 mm.

[0024] Further, the epoxy resin is one or a mixture of glycidyl ether epoxy resins such as XY - 690, XY - 686, XY - 693, XY - 205, and XY - 636, bisphenol A epoxy resins such as E44 and E51, or bisphenol F epoxy resins such as 170, 175, and 176.

[0025] Further, the composite polyetheramine is a mixture of high - performance polyetheramines CAD200 and CAM2000 produced by a continuous process in a mass ratio of (13 - 23):(13 - 23).

[0026] Further, the production method of high - performance polyetheramine CAD200 is as follows: Propylene glycol propylene oxide polyether with a molecular weight of 200, hydrogen, and ammonia are continuously fed into a reactor. Under the action of a nickel - ruthenium catalyst in the reactor, a hydroamination reaction is carried out at a temperature of 120 - 125 °C and a pressure of 3.9 - 4.4 MPa to obtain high - performance polyetheramine CAD200. The molar ratio of propylene glycol propylene oxide polyether to ammonia is 1:43, and the volume concentration of hydrogen in the system is maintained at 15%.

[0027] Further, the production method of high - performance polyetheramine CAM2000 is as follows: Propylene glycol propylene oxide polyether with a molecular weight of 2000, hydrogen, and ammonia are continuously fed into a reactor. Under the action of a nickel - based catalyst in the reactor, a hydroamination reaction is carried out at a temperature of 125 - 130 °C and a pressure of 4.3 - 4.8 MPa to obtain high - performance polyetheramine CAM2000. The molar ratio of propylene glycol propylene oxide polyether to ammonia is 1:45, and the volume concentration of hydrogen in the system is maintained at 16%.

[0028] Among them, the primary amine content of high - performance polyetheramines CAD200 and CAM2000 produced by the continuous process is ≥99.5%, and the content of dimethylmorpholine is <0.10%.

[0029] A preparation method of an epoxy wind energy blade with self-healing function, fixing the wind energy blade profile (including but not limited to accessories such as reinforcing fibers, balsa wood core, foam core, bolt sleeves, flanges, support steel frames, stiffeners, webs, lightning rods, etc.) within a mold, closing the mold and evacuating to -0.095~-0.100 MPa, pouring the composite adhesive material of the present invention (after uniformly mixing polyurethane microcapsules and epoxy resin and then mixing with composite polyetheramine) into the mold, and curing for 12 h to obtain an epoxy wind energy blade with self-healing function.

[0030] Furthermore, the wind energy blade profile includes reinforcing fibers, and the mass ratio of reinforcing fibers∶polyurethane microcapsules∶epoxy resin∶composite polyetheramine is (5~30):(1~9):100:(26~45).

[0031] Furthermore, the reinforcing fibers are one or a mixture of glass fibers, asbestos fibers, carbon fibers, nylon fibers, aramid fibers, polypropylene fibers, etc. Fibers can increase the strength of the blade.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] 1. Traditional microcapsules are all two-component microcapsules. The epoxy material and the curing agent are stored in the microcapsules respectively, and then the whole is put into epoxy resin in a certain proportion. There are certain problems with the adhesion between the epoxy resin formed by self-healing and the substrate, thus affecting the overall structural strength of the blade. However, the present invention adopts a single-component microcapsule. After the blade generates cracks, the microcapsules crack due to greater stress, and the epoxy resin in the microcapsules reacts with the excessive unreacted composite polyetheramine in the blade to complete the self-healing process;

[0034] 2. A slightly excessive amount of composite polyetheramine is evenly dispersed in the blade. Some groups of the composite polyetheramine have participated in the epoxy curing reaction, so the unreacted groups will not migrate or overflow. After the unreacted amino groups react with the epoxy resin in the capsule, they will form a high polymer with the substrate, and the structure is more firm;

[0035] 3. The primary amine content of commercially available polyetheramine D230 is generally 90~95%, and the content of impurity dimethylmorpholine is generally 0.20~0.50%. However, the high-performance polyetheramine produced by the continuous process has a high primary amine content and a very low impurity content. The primary amine content ≥99.5%, and the dimethylmorpholine content ≤0.10%. The product has more ideal denseness when synthesizing the blade. The high-performance polyetheramine CAD200 has a small molecular weight. The more it accounts for, the faster the reaction, and the greater the hardness of the product. The high-performance polyetheramine CAM2000 has a large molecular weight. The more it accounts for, the better the toughness of the product. By adjusting the ratio of the two polyetheramine products, the quality requirements of different-length blades can be met.

[0036] 4. The microcapsules are evenly dispersed in various places of the epoxy wind energy blades, which can play a good role in cracking in various places of the blades;

[0037] 5. The purpose of using polyurethane microporous foam as microcapsule is that polyurethane microporous foam contains more polyether chains, and composite polyether amine also has more polyether segments. According to the theory of chemical similarity, the compatibility of the two materials is very good, and the microcapsule has no shelling phenomenon. DETAILED DESCRIPTION

[0038] The experimental methods in the following examples are conventional methods unless otherwise specified. The experimental materials used in the following examples are purchased from commercial channels unless otherwise specified.

[0039] Example 1

[0040] 1. Preparation of polyurethane microcapsules

[0041] 100 kg of polyether polyol 330N, 1 kg of catalyst dimethylethanolamine, 0.1 kg of surfactant CGY-1 and 1 kg of cross-linking agent ethylene glycol were mixed evenly to form a white material, and toluene diisocyanate was used as a black material.

[0042] 20 kg of bisphenol A epoxy resin E44, 100 kg of white material and 30 kg of black material were fully mixed and micro-foamed to obtain microporous foam containing epoxy resin. The microporous foam was crushed into small particles with a particle size of 0.05 mm, and the epoxy resin on the surface of the particles was washed with methanol. After drying at 80°C for 2 hours, polyurethane microcapsules containing epoxy resin in the core were obtained.

[0043] 2. Preparation of self-repairing epoxy wind blades

[0044] 5 kg of reinforced glass fiber and balsa core material, foam core material, bolt sleeve, flange, supporting steel frame, stiffener, web, lightning rod and other accessories are fixed in the mold, the mold is closed and evacuated to -0.095 MPa, 1 kg of polyurethane microcapsules and 100 kg of bisphenol A epoxy resin E44 are evenly mixed, and then mixed with 13 kg of high-performance polyetheramine CAD200 produced by a continuous process and 13 kg of high-performance polyetheramine CAM2000 produced by a continuous process, and then poured into the mold, and molded and cured for 12 hours to obtain the blade of the present invention.

[0045] The production method of high-performance polyetheramine CAD200 is as follows: Continuously input propylene glycol propylene oxide polyether with a molecular weight of 200, hydrogen, and ammonia into a reactor. Under the action of a nickel-ruthenium catalyst in the reactor, carry out a hydroamination reaction at a temperature of 120 - 125°C and a pressure of 3.9 - 4.4 MPa to obtain high-performance polyetheramine CAD200. The molar ratio of propylene glycol propylene oxide polyether to ammonia is 1:43, and the volume concentration of hydrogen in the system is maintained at 15%.

[0046] The production method of high-performance polyetheramine CAM2000 is as follows: Continuously input propylene glycol propylene oxide polyether with a molecular weight of 2000, hydrogen, and ammonia into a reactor. Under the action of a nickel-based catalyst in the reactor, carry out a hydroamination reaction at a temperature of 125 - 130°C and a pressure of 4.3 - 4.8 MPa to obtain high-performance polyetheramine CAM2000. The molar ratio of propylene glycol propylene oxide polyether to ammonia is 1:45, and the volume concentration of hydrogen in the system is maintained at 16%.

[0047] Example 2

[0048] 1. Preparation of polyurethane microcapsules

[0049] Mix 100 kg of polyether polyol 330N, 1.2 kg of catalyst dimethylcyclohexylamine, 0.2 kg of surfactant CGY - 6885, and 1.4 kg of crosslinking agent ethylene glycol evenly as the white material. Use toluene diisocyanate as the black material.

[0050] Fully mix 23 kg of bisphenol A epoxy resin E44, 100 kg of the white material, and 33 kg of the black material, and through micro-foaming, obtain a microporous foam containing epoxy resin. Crush the microporous foam into small particles with a particle size of 0.56 mm, wash the epoxy resin on the surface of the particles with methanol, and after drying at 80°C for 2.5 h, obtain polyurethane microcapsules with epoxy resin contained in the core.

[0051] 2. Preparation of a self-healing functional epoxy wind turbine blade

[0052] Fix 9 kg of reinforced fiberglass and accessories such as balsa wood core material, foam core material, bolt sleeves, flanges, support steel frames, stiffeners, webs, lightning rods, etc. in a mold, close the mold and evacuate to -0.095 MPa. After mixing 1.6 kg of polyurethane microcapsules evenly with 100 kg of bisphenol A epoxy resin E44, then mix with 14 kg of high-performance polyetheramine CAD200 produced by a continuous process and 15 kg of high-performance polyetheramine CAM2000 produced by a continuous process, and pour the mixture into the mold. After molding and curing for 12 h, obtain the blade of the present invention.

[0053] The production method of high-performance polyetheramine CAD200 is as follows: Continuously input propylene glycol propylene oxide polyether with a molecular weight of 200, hydrogen, and ammonia into a reactor. Under the action of a nickel-ruthenium catalyst in the reactor, carry out a hydroamination reaction at a temperature of 120 - 125°C and a pressure of 3.9 - 4.4 MPa to obtain high-performance polyetheramine CAD200. The molar ratio of propylene glycol propylene oxide polyether to ammonia is 1:43, and the volume concentration of hydrogen in the system is maintained at 15%.

[0054] The production method of high-performance polyetheramine CAM2000 is as follows: Continuously input propylene glycol propylene oxide polyether with a molecular weight of 2000, hydrogen, and ammonia into a reactor. Under the action of a nickel-based catalyst in the reactor, carry out a hydroamination reaction at a temperature of 125 - 130°C and a pressure of 4.3 - 4.8 MPa to obtain high-performance polyetheramine CAM2000. The molar ratio of propylene glycol propylene oxide polyether to ammonia is 1:45, and the volume concentration of hydrogen in the system is maintained at 16%.

[0055] Example 3

[0056] 1. Preparation of polyurethane microcapsules

[0057] Mix 100 kg of polyether polyol 330N, 1.5 kg of catalyst dimethylcyclohexylamine, 0.4 kg of surfactant CGY-1, and 1.7 kg of crosslinking agent ethylene glycol evenly as the white material. Use toluene diisocyanate as the black material.

[0058] Fully mix 25 kg of bisphenol A epoxy resin E51, 100 kg of the white material, and 36 kg of the black material, and through micro-foaming, obtain a microporous foam containing epoxy resin. Crush the microporous foam into small particles with a particle size of 1.07 mm, wash the surface of the particles with methanol, and dry at 80°C for 3 h to obtain polyurethane microcapsules with epoxy resin contained in the core.

[0059] 2. Preparation of self-healing functional epoxy wind turbine blade

[0060] Fix 11 kg of reinforced asbestos fiber and accessories such as balsa wood core material, foam core material, bolt sleeve, flange, support steel frame, stiffener, web, lightning rod, etc. in a mold, close the mold and evacuate to -0.096 MPa. After mixing 2.3 kg of polyurethane microcapsules evenly with 100 kg of bisphenol A epoxy resin E51, then mix with 16 kg of high-performance polyetheramine CAD200 produced by the continuous process and 15 kg of high-performance polyetheramine CAM2000 produced by the continuous process, and pour the mixture into the mold. After molding and curing for 12 h, obtain the blade of the present invention.

[0061] The production method of high-performance polyetheramine CAD200 is as follows: Continuously input propylene glycol propylene oxide polyether with a molecular weight of 200, hydrogen, and ammonia into a reactor. Under the action of a nickel-ruthenium catalyst in the reactor, carry out a hydroamination reaction at a temperature of 120 - 125 °C and a pressure of 3.9 - 4.4 MPa to obtain high-performance polyetheramine CAD200. The molar ratio of propylene glycol propylene oxide polyether to ammonia is 1:43, and the volume concentration of hydrogen in the system is maintained at 15%.

[0062] The production method of high-performance polyetheramine CAM2000 is as follows: Continuously input propylene glycol propylene oxide polyether with a molecular weight of 2000, hydrogen, and ammonia into a reactor. Under the action of a nickel-based catalyst in the reactor, carry out a hydroamination reaction at a temperature of 125 - 130 °C and a pressure of 4.3 - 4.8 MPa to obtain high-performance polyetheramine CAM2000. The molar ratio of propylene glycol propylene oxide polyether to ammonia is 1:45, and the volume concentration of hydrogen in the system is maintained at 16%.

[0063] Example 4

[0064] 1. Preparation of polyurethane microcapsules

[0065] Mix 100 kg of polyether polyol 330, 1.6 kg of catalyst triethylenediamine, 0.6 kg of surfactant CGY - 6885, and 2.3 kg of crosslinking agent propylene glycol evenly as the white material. Use diphenylmethane diisocyanate as the black material.

[0066] Fully mix 27 kg of bisphenol A epoxy resin E51, 100 kg of the white material, and 40 kg of the black material, and through micro - foaming, obtain a microporous foam containing epoxy resin. Crush the microporous foam into small particles with a particle size of 2.18 mm, wash the epoxy resin on the surface of the particles with methanol, and after drying at 80 °C for 2 h, obtain polyurethane microcapsules with epoxy resin contained in the core.

[0067] 2. Preparation of self - healing functional epoxy wind turbine blade

[0068] Fix 15 kg of reinforced asbestos fiber and accessories such as balsa wood core material, foam core material, bolt sleeve, flange, support steel frame, stiffener, web, lightning rod, etc. in a mold, close the mold and evacuate to - 0.096 MPa. After mixing 3.5 kg of polyurethane microcapsules and 100 kg of bisphenol A epoxy resin E51 evenly, then mix with 16 kg of high - performance polyetheramine CAD200 produced by the continuous process and 16 kg of high - performance polyetheramine CAM2000 produced by the continuous process, and pour the mixture into the mold, and cure for 12 h to obtain the blade of the present invention.

[0069] The production method of high-performance polyetheramine CAD200 is as follows: Continuously input propylene glycol propylene oxide polyether with a molecular weight of 200, hydrogen, and ammonia into a reactor. Under the action of a nickel-ruthenium catalyst in the reactor, carry out a hydroamination reaction at a temperature of 120 - 125°C and a pressure of 3.9 - 4.4 MPa to obtain high-performance polyetheramine CAD200. The molar ratio of propylene glycol propylene oxide polyether to ammonia is 1:43, and the volume concentration of hydrogen in the system is maintained at 15%.

[0070] The production method of high-performance polyetheramine CAM2000 is as follows: Continuously input propylene glycol propylene oxide polyether with a molecular weight of 2000, hydrogen, and ammonia into a reactor. Under the action of a nickel-based catalyst in the reactor, carry out a hydroamination reaction at a temperature of 125 - 130°C and a pressure of 4.3 - 4.8 MPa to obtain high-performance polyetheramine CAM2000. The molar ratio of propylene glycol propylene oxide polyether to ammonia is 1:45, and the volume concentration of hydrogen in the system is maintained at 16%.

[0071] Example 5

[0072] 1. Preparation of polyurethane microcapsules

[0073] Mix 100 kg of polyether polyol 330, 1.8 kg of catalyst pentamethyldiethylenetriamine, 0.7 kg of surfactant CGY - 1, and 2.8 kg of crosslinker propylene glycol evenly as the white material. Use diphenylmethane diisocyanate as the black material.

[0074] Fully mix 29 kg of glycidyl ether epoxy resin XY - 690, 100 kg of the white material, and 42 kg of the black material, and through micro - foaming, obtain a microporous foam containing epoxy resin. Crush the microporous foam into small particles with a particle size of 2.93 mm, wash the surface of the particles with methanol, and after drying at 80°C for 2.5 h, obtain polyurethane microcapsules with epoxy resin contained in the core.

[0075] 2. Preparation of self - healing functional epoxy wind turbine blade

[0076] Fix 18 kg of reinforced carbon fiber and accessories such as balsa wood core, foam core, bolt sleeve, flange, support steel frame, stiffener, web, lightning rod, etc. in a mold, close the mold and evacuate to - 0.097 MPa. After mixing 4.1 kg of polyurethane microcapsules and 100 kg of glycidyl ether epoxy resin XY - 690 evenly, then mix with 16 kg of high - performance polyetheramine CAD200 produced by the continuous process and 18 kg of high - performance polyetheramine CAM2000 produced by the continuous process, and then pour the mixture into the mold and cure for 12 h to obtain the blade of the present invention.

[0077] The production method of high-performance polyetheramine CAD200 is as follows: Continuously input propylene glycol propylene oxide polyether with a molecular weight of 200, hydrogen, and ammonia into a reactor. Under the action of a nickel-ruthenium catalyst in the reactor, carry out a hydroamination reaction at a temperature of 120 - 125 °C and a pressure of 3.9 - 4.4 MPa to obtain high-performance polyetheramine CAD200. The molar ratio of propylene glycol propylene oxide polyether to ammonia is 1:43, and the volume concentration of hydrogen in the system is maintained at 15%.

[0078] The production method of high-performance polyetheramine CAM2000 is as follows: Continuously input propylene glycol propylene oxide polyether with a molecular weight of 2000, hydrogen, and ammonia into a reactor. Under the action of a nickel-based catalyst in the reactor, carry out a hydroamination reaction at a temperature of 125 - 130 °C and a pressure of 4.3 - 4.8 MPa to obtain high-performance polyetheramine CAM2000. The molar ratio of propylene glycol propylene oxide polyether to ammonia is 1:45, and the volume concentration of hydrogen in the system is maintained at 16%.

[0079] Example 6

[0080] 1. Preparation of polyurethane microcapsules

[0081] Mix 100 kg of polyether polyol 330, 2 kg of catalyst dimethylbenzylamine, 0.9 kg of surfactant CGY - 6885, and 3.1 kg of crosslinking agent propylene glycol evenly as the white material. Use diphenylmethane diisocyanate as the black material.

[0082] Fully mix 30 kg of glycidyl ether epoxy resin XY - 686, 100 kg of the white material, and 45 kg of the black material, and through micro - foaming, obtain a microporous foam containing epoxy resin. Crush the microporous foam into small particles with a particle size of 3.16 mm, wash the epoxy resin on the surface of the particles with methanol, and dry at 80 °C for 3 h to obtain polyurethane microcapsules with epoxy resin contained in the core.

[0083] 2. Preparation of a self - healing functional epoxy wind turbine blade

[0084] Fix 20 kg of reinforced carbon fiber and accessories such as balsa wood core, foam core, bolt sleeve, flange, support steel frame, stiffener, web, lightning rod, etc. in a mold, close the mold and evacuate to - 0.097 MPa. After mixing 5.2 kg of polyurethane microcapsules evenly with 100 kg of glycidyl ether epoxy resin XY - 686, then mix it with 18 kg of high - performance polyetheramine CAD200 produced by the continuous process and 17 kg of high - performance polyetheramine CAM2000 produced by the continuous process, and pour the mixture into the mold and cure for 12 h to obtain the blade of the present invention.

[0085] The production method of high-performance polyetheramine CAD200 is as follows: Continuously input propylene glycol propylene oxide polyether with a molecular weight of 200, hydrogen, and ammonia into a reactor. Under the action of a nickel-ruthenium catalyst in the reactor, carry out a hydroamination reaction at a temperature of 120 - 125 °C and a pressure of 3.9 - 4.4 MPa to obtain high-performance polyetheramine CAD200. The molar ratio of propylene glycol propylene oxide polyether to ammonia is 1:43, and the volume concentration of hydrogen in the system is maintained at 15%.

[0086] The production method of high-performance polyetheramine CAM2000 is as follows: Continuously input propylene glycol propylene oxide polyether with a molecular weight of 2000, hydrogen, and ammonia into a reactor. Under the action of a nickel-based catalyst in the reactor, carry out a hydroamination reaction at a temperature of 125 - 130 °C and a pressure of 4.3 - 4.8 MPa to obtain high-performance polyetheramine CAM2000. The molar ratio of propylene glycol propylene oxide polyether to ammonia is 1:45, and the volume concentration of hydrogen in the system is maintained at 16%.

[0087] Example 7

[0088] 1. Preparation of polyurethane microcapsules

[0089] Mix 100 kg of polyether polyol 310, 2.1 kg of catalyst potassium acetate, 1 kg of surfactant CGY-1, and 3.4 kg of crosslinking agent 1,4-butanediol evenly as the white material. Use polyphenyl polymethylene polyisocyanate as the black material.

[0090] Fully mix 32 kg of glycidyl ether epoxy resin XY-693, 100 kg of the white material, and 47 kg of the black material, and through micro-foaming, obtain a microporous foam containing epoxy resin. Crush the microporous foam into small particles with a particle size of 3.53 mm, wash the surface of the particles with methanol, and dry them at 80 °C for 3 h to obtain polyurethane microcapsules with epoxy resin contained in the core.

[0091] 2. Preparation of a self-healing epoxy wind turbine blade

[0092] Fix 22 kg of reinforced nylon fiber and accessories such as balsa wood core material, foam core material, bolt sleeve, flange, support steel frame, stiffener, web, and lightning rod in a mold, close the mold and evacuate to -0.098 MPa. After mixing 5.8 kg of polyurethane microcapsules and 100 kg of glycidyl ether epoxy resin XY-693 evenly, then mix them with 18 kg of high-performance polyetheramine CAD200 produced by a continuous process and 19 kg of high-performance polyetheramine CAM2000 produced by a continuous process, and pour the mixture into the mold. After molding and curing for 12 h, obtain the blade of the present invention.

[0093] The production method of high-performance polyetheramine CAD200 is as follows: Continuously input propylene glycol propylene oxide polyether with a molecular weight of 200, hydrogen, and ammonia into a reactor. Under the action of a nickel-ruthenium catalyst in the reactor, carry out a hydroamination reaction at a temperature of 120 - 125 °C and a pressure of 3.9 - 4.4 MPa to obtain high-performance polyetheramine CAD200. The molar ratio of propylene glycol propylene oxide polyether to ammonia is 1:43, and the volume concentration of hydrogen in the system is maintained at 15%.

[0094] The production method of high-performance polyetheramine CAM2000 is as follows: Continuously input propylene glycol propylene oxide polyether with a molecular weight of 2000, hydrogen, and ammonia into a reactor. Under the action of a nickel-based catalyst in the reactor, carry out a hydroamination reaction at a temperature of 125 - 130 °C and a pressure of 4.3 - 4.8 MPa to obtain high-performance polyetheramine CAM2000. The molar ratio of propylene glycol propylene oxide polyether to ammonia is 1:45, and the volume concentration of hydrogen in the system is maintained at 16%.

[0095] Example 8

[0096] 1. Preparation of polyurethane microcapsules

[0097] Mix 100 kg of polyether polyol 310, 2.3 kg of potassium octoate catalyst, 1.2 kg of surfactant CGY - 6885, and 3.9 kg of crosslinking agent 1,4 - butanediol evenly as the white material. Use polyphenyl polymethylene polyisocyanate as the black material.

[0098] Fully mix 34 kg of glycidyl ether epoxy resin XY - 205, 100 kg of the white material, and 49 kg of the black material, and through micro - foaming, obtain a microporous foam containing epoxy resin. Crush the microporous foam into small particles with a particle size of 3.92 mm, wash the epoxy resin on the surface of the particles with methanol, and dry at 80 °C for 2 h to obtain polyurethane microcapsules with epoxy resin contained in the core.

[0099] 2. Preparation of a self - healing functional epoxy wind turbine blade

[0100] Fix 23 kg of reinforced nylon fiber and accessories such as balsa wood core, foam core, bolt sleeve, flange, support steel frame, stiffener, web, lightning rod, etc. in a mold, close the mold and evacuate to - 0.098 MPa. After evenly mixing 6.3 kg of polyurethane microcapsules with 100 kg of glycidyl ether epoxy resin XY - 205, then mix with 20 kg of high - performance polyetheramine CAD200 produced by the continuous process and 20 kg of high - performance polyetheramine CAM2000 produced by the continuous process, and pour the mixture into the mold, and cure for 12 h to obtain the blade of the present invention.

[0101] The production method of high-performance polyetheramine CAD200 is as follows: Continuously input propylene glycol propylene oxide polyether with a molecular weight of 200, hydrogen, and ammonia into a reactor. Under the action of a nickel-ruthenium catalyst in the reactor, carry out a hydroamination reaction at a temperature of 120 - 125 °C and a pressure of 3.9 - 4.4 MPa to obtain high-performance polyetheramine CAD200. The molar ratio of propylene glycol propylene oxide polyether to ammonia is 1:43, and the volume concentration of hydrogen in the system is maintained at 15%.

[0102] The production method of high-performance polyetheramine CAM2000 is as follows: Continuously input propylene glycol propylene oxide polyether with a molecular weight of 2000, hydrogen, and ammonia into a reactor. Under the action of a nickel-based catalyst in the reactor, carry out a hydroamination reaction at a temperature of 125 - 130 °C and a pressure of 4.3 - 4.8 MPa to obtain high-performance polyetheramine CAM2000. The molar ratio of propylene glycol propylene oxide polyether to ammonia is 1:45, and the volume concentration of hydrogen in the system is maintained at 16%.

[0103] Example 9

[0104] 1. Preparation of polyurethane microcapsules

[0105] Mix 100 kg of polyether polyol 310, 2.4 kg of catalyst oleate, 1.5 kg of surfactant CGY-1, and 4.1 kg of crosslinking agent 1,4-butanediol evenly as the white material. Use polyphenyl polymethylene polyisocyanate as the black material.

[0106] Fully mix 35 kg of glycidyl ether epoxy resin XY-636, 100 kg of the white material, and 50 kg of the black material, and through micro-foaming, obtain a microporous foam containing epoxy resin. Crush the microporous foam into small particles with a particle size of 4.08 mm, wash the epoxy resin on the surface of the particles with methanol, and after drying at 80 °C for 2.5 h, obtain polyurethane microcapsules with epoxy resin contained in the core.

[0107] 2. Preparation of self-healing functional epoxy wind turbine blades

[0108] Fix 25 kg of reinforced aramid fiber and accessories such as balsa wood core material, foam core material, bolt sleeve, flange, support steel frame, stiffener, web, lightning rod, etc. in a mold, close the mold and evacuate to -0.099 MPa. After mixing 6.7 kg of polyurethane microcapsules and 100 kg of glycidyl ether epoxy resin XY-636 evenly, then mix with 20 kg of high-performance polyetheramine CAD200 produced by the continuous process and 22 kg of high-performance polyetheramine CAM2000 produced by the continuous process, and pour the mixture into the mold and cure for 12 h to obtain the blade of the present invention.

[0109] The production method of high-performance polyetheramine CAD200 is as follows: Continuously input propylene glycol propylene oxide polyether with a molecular weight of 200, hydrogen, and ammonia into a reactor. Under the action of a nickel ruthenium catalyst in the reactor, carry out a hydroamination reaction at a temperature of 120 - 125 °C and a pressure of 3.9 - 4.4 MPa to obtain high-performance polyetheramine CAD200. The molar ratio of propylene glycol propylene oxide polyether to ammonia is 1:43, and the volume concentration of hydrogen in the system is maintained at 15%.

[0110] The production method of high-performance polyetheramine CAM2000 is as follows: Continuously input propylene glycol propylene oxide polyether with a molecular weight of 2000, hydrogen, and ammonia into a reactor. Under the action of a nickel-based catalyst in the reactor, carry out a hydroamination reaction at a temperature of 125 - 130 °C and a pressure of 4.3 - 4.8 MPa to obtain high-performance polyetheramine CAM2000. The molar ratio of propylene glycol propylene oxide polyether to ammonia is 1:45, and the volume concentration of hydrogen in the system is maintained at 16%.

[0111] Example 10

[0112] 1. Preparation of polyurethane microcapsules

[0113] Mix 100 kg of polyether polyol 305, 2.7 kg of catalyst stannous octoate, 1.7 kg of surfactant CGY - 6885, and 4.4 kg of crosslinking agent glycerol evenly as the white material. Mix toluene diisocyanate and diphenylmethane diisocyanate in a mass ratio of 3:1 as the black material.

[0114] Fully mix 37 kg of bisphenol F epoxy resin 170, 100 kg of the white material, and 52 kg of the black material, and through micro - foaming, obtain a microporous foam containing epoxy resin. Crush the microporous foam into small particles with a particle size of 4.56 mm, wash the epoxy resin on the surface of the particles with methanol, and dry at 80 °C for 2 h to obtain polyurethane microcapsules with epoxy resin contained in the core.

[0115] 2. Preparation of self - healing functional epoxy wind turbine blade

[0116] Fix 27 kg of reinforced aramid fiber and accessories such as balsa wood core, foam core, bolt sleeve, flange, support steel frame, stiffener, web, lightning rod, etc. in a mold, close the mold and evacuate to - 0.099 MPa. After evenly mixing 7.5 kg of polyurethane microcapsules with 100 kg of bisphenol F epoxy resin 170, then mix it with 22 kg of high - performance polyetheramine CAD200 produced by the continuous process and 21 kg of high - performance polyetheramine CAM2000 produced by the continuous process, and pour the mixture into the mold, and cure for 12 h to obtain the blade of the present invention.

[0117] The production method of high-performance polyetheramine CAD200 is as follows: Continuously input propylene glycol propylene oxide polyether with a molecular weight of 200, hydrogen, and ammonia into a reactor. Under the action of a nickel ruthenium catalyst in the reactor, carry out a hydroamination reaction at a temperature of 120 - 125°C and a pressure of 3.9 - 4.4 MPa to obtain high-performance polyetheramine CAD200. The molar ratio of propylene glycol propylene oxide polyether to ammonia is 1:43, and the volume concentration of hydrogen in the system is maintained at 15%.

[0118] The production method of high-performance polyetheramine CAM2000 is as follows: Continuously input propylene glycol propylene oxide polyether with a molecular weight of 2000, hydrogen, and ammonia into a reactor. Under the action of a nickel-based catalyst in the reactor, carry out a hydroamination reaction at a temperature of 125 - 130°C and a pressure of 4.3 - 4.8 MPa to obtain high-performance polyetheramine CAM2000. The molar ratio of propylene glycol propylene oxide polyether to ammonia is 1:45, and the volume concentration of hydrogen in the system is maintained at 16%.

[0119] Example 11

[0120] 1. Preparation of polyurethane microcapsules

[0121] Mix 100 kg of polyether polyol 305, 2.9 kg of catalyst dibutyltin dilaurate, 1.8 kg of surfactant CGY-1, and 4.8 kg of crosslinking agent glycerol evenly as the white material. Mix toluene diisocyanate and polyphenyl polymethylene polyisocyanate in a mass ratio of 3:1 as the black material.

[0122] Fully mix 39 kg of bisphenol F epoxy resin 175, 100 kg of the white material, and 54 kg of the black material, and through micro-foaming, obtain a microporous foam containing epoxy resin. Crush the microporous foam into small particles with a particle size of 4.83 mm, wash the surface of the particles with methanol, and dry at 80°C for 3 h to obtain polyurethane microcapsules with epoxy resin contained in the core.

[0123] 2. Preparation of a self-healing functional epoxy wind turbine blade

[0124] Fix 29 kg of reinforced polypropylene fiber and accessories such as balsa wood core material, foam core material, bolt sleeve, flange, support steel frame, stiffener, web, lightning rod, etc. in a mold, close the mold and evacuate to -0.100 MPa. After mixing 8.8 kg of polyurethane microcapsules evenly with 100 kg of bisphenol F epoxy resin 175, then mix with 22 kg of high-performance polyetheramine CAD200 produced by a continuous process and 22 kg of high-performance polyetheramine CAM2000 produced by a continuous process, and pour the mixture into the mold, and cure for 12 h to obtain the blade of the present invention.

[0125] The production method of high-performance polyetheramine CAD200 is as follows: Continuously input propylene glycol propylene oxide polyether with a molecular weight of 200, hydrogen, and ammonia into a reactor. Under the action of a nickel-ruthenium catalyst in the reactor, carry out a hydroamination reaction at a temperature of 120 - 125 °C and a pressure of 3.9 - 4.4 MPa to obtain high-performance polyetheramine CAD200. The molar ratio of propylene glycol propylene oxide polyether to ammonia is 1:43, and the volume concentration of hydrogen in the system is maintained at 15%.

[0126] The production method of high-performance polyetheramine CAM2000 is as follows: Continuously input propylene glycol propylene oxide polyether with a molecular weight of 2000, hydrogen, and ammonia into a reactor. Under the action of a nickel-based catalyst in the reactor, carry out a hydroamination reaction at a temperature of 125 - 130 °C and a pressure of 4.3 - 4.8 MPa to obtain high-performance polyetheramine CAM2000. The molar ratio of propylene glycol propylene oxide polyether to ammonia is 1:45, and the volume concentration of hydrogen in the system is maintained at 16%.

[0127] Example 12

[0128] 1. Preparation of polyurethane microcapsules

[0129] Mix 100 kg of polyether polyol 305, 3 kg of catalyst dimethylbenzylamine, 2 kg of surfactant CGY - 6885, and 5 kg of crosslinking agent glycerol evenly as the white material. Mix diphenylmethane diisocyanate and polyphenyl polymethylene polyisocyanate in a mass ratio of 3:1 as the black material.

[0130] Fully mix 40 kg of bisphenol F epoxy resin 176, 100 kg of the white material, and 55 kg of the black material, and through micro-foaming, obtain a microporous foam containing epoxy resin. Crush the microporous foam into small particles with a particle size of 5 mm, wash the epoxy resin on the surface of the particles with methanol, and dry at 80 °C for 2 h to obtain polyurethane microcapsules with epoxy resin contained in the core.

[0131] 2. Preparation of a self-healing functional epoxy wind turbine blade

[0132] Fix 30 kg of reinforced polypropylene fiber and accessories such as balsa wood core material, foam core material, bolt sleeve, flange, support steel frame, stiffener, web, and lightning rod in a mold, close the mold and evacuate to -0.100 MPa. After mixing 9 kg of polyurethane microcapsules and 100 kg of bisphenol F epoxy resin 176 evenly, then mix with 22 kg of high-performance polyetheramine CAD200 produced by the continuous process and 23 kg of high-performance polyetheramine CAM2000 produced by the continuous process, and pour the mixture into the mold, and cure for 12 h to obtain the blade of the present invention.

[0133] The production method of high-performance polyetheramine CAD200 is as follows: Continuously input propylene glycol propylene oxide polyether with a molecular weight of 200, hydrogen, and ammonia into a reactor, and under the action of a nickel-ruthenium catalyst in the reactor, carry out a hydroamination reaction at a temperature of 120 - 125 °C and a pressure of 3.9 - 4.4 MPa to obtain high-performance polyetheramine CAD200. The molar ratio of propylene glycol propylene oxide polyether to ammonia is 1:43, and the volume concentration of hydrogen in the system is maintained at 15%.

[0134] The production method of high-performance polyetheramine CAM2000 is as follows: Continuously input propylene glycol propylene oxide polyether with a molecular weight of 2000, hydrogen, and ammonia into a reactor, and under the action of a nickel-based catalyst in the reactor, carry out a hydroamination reaction at a temperature of 125 - 130 °C and a pressure of 4.3 - 4.8 MPa to obtain high-performance polyetheramine CAM2000. The molar ratio of propylene glycol propylene oxide polyether to ammonia is 1:45, and the volume concentration of hydrogen in the system is maintained at 16%.

[0135] Comparative Example

[0136] 1. Preparation of polyurethane microcapsules

[0137] Mix 100 kg of polyether polyol 330N, 1 kg of catalyst dimethylethanolamine, 0.1 kg of surfactant CGY-1, and 1 kg of crosslinking agent ethylene glycol evenly as the white material. Use toluene diisocyanate as the black material.

[0138] Fully mix 20 kg of bisphenol A epoxy resin E44, 100 kg of the white material, and 30 kg of the black material, and through micro-foaming, obtain a microporous foam containing epoxy resin. Crush the microporous foam into small particles with a particle size of 0.05 mm, wash the surface of the particles with methanol, and dry at 80 °C for 2 h to obtain polyurethane microcapsules with epoxy resin contained in the core.

[0139] 2. Preparation of self-healing functional epoxy wind turbine blades

[0140] Fix 5 kg of reinforced glass fiber and accessories such as balsa wood core material, foam core material, bolt sleeve, flange, support steel frame, stiffener, web, lightning rod, etc. in a mold, close the mold and evacuate to -0.095 MPa. After mixing 1 kg of polyurethane microcapsules and 100 kg of bisphenol A epoxy resin E44 evenly, then mix with 26 kg of commercially available D230 polyetheramine and pour it into the mold, and cure for 12 h to obtain the blade of the present invention.

[0141] The performance tests of the epoxy resin cut blocks of the wind turbine blades provided in the comparative example and Examples 1 - 12 of the present invention are shown in the following table:

[0142] Project Comparative Example Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 General Design Requirements Shear Strength / MPa 0.78 0.82 0.88 0.85 0.73 0.85 0.85 ＞0.65 Shear Strength after 5 Years / MPa 0.66 0.81 0.88 0.84 0.73 0.84 0.84 ＞0.65 Shear Modulus / MPa 33.5 34.2 35.5 34.5 31.6 35.2 34.7 ＞20 Compressive Strength / MPa 1.40 1.55 1.44 1.53 1.08 1.45 1.55 ＞0.88 Compressive Strength after 5 Years / MPa 1.29 1.54 1.43 1.52 1.08 1.45 1.55 ＞0.88 Compressive Modulus / MPa 195.0 198.5 195.2 196.5 165.3 197.9 197.0 ＞59

[0143] Project Comparative Example Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 General Design Requirements Shear Strength / MPa 0.78 0.90 0.87 0.83 0.78 0.87 0.92 ＞0.65 Shear Strength after 5 Years / MPa 0.66 0.88 0.87 0.82 0.77 0.87 0.91 ＞0.65 Shear Modulus / MPa 33.5 34.0 35.3 34.7 30.6 35.2 36.7 ＞20 Compressive Strength / MPa 1.40 1.64 1.54 1.55 1.38 1.45 1.65 ＞0.88 Compressive Strength after 5 Years / MPa 1.29 1.62 1.53 1.53 1.37 1.44 1.64 ＞0.88 Compressive Modulus / MPa 195.0 198.3 197.1 197.5 175.5 196.8 198.0 ＞59

[0144] As can be seen from the above table, the shear strength and compressive strength of the present invention basically remain unchanged after 5 years, while the shear strength and compressive strength of the comparative example change significantly after 5 years.

[0145] The above are only the embodiments of the present invention, and do not limit the patent scope of the present invention accordingly. Any equivalent transformation made by using the content of the specification of the present invention, directly or indirectly applied in other related fields, shall fall within the scope of patent protection of the present invention.

Claims

1. A composite adhesive material with self-repairing function, It is characterized in that The composite adhesive material comprises polyurethane microcapsules, epoxy resin and composite polyetheramine; wherein the mass ratio of the polyurethane microcapsules, epoxy resin and composite polyetheramine is (1-9):100:(26-45); The synthesis method of the polyurethane microcapsule comprises the following steps: 1) Preparation of polyurethane microporous foam white material and black material: polyether polyol, catalyst, surfactant and cross-linking agent are mixed in a mass ratio of 100: (1-3): (0.1-2): (1-5) to prepare white material, and isocyanate is used as black material; 2) Preparation of microporous foam containing epoxy resin: epoxy resin, white material and black material are fully mixed in a mass ratio of (20-40) : 100 : (30-55), and micro-foamed to obtain microporous foam containing epoxy resin; 3) Preparation of polyurethane microcapsules: The microporous foam containing epoxy resin obtained in step 2) was crushed into small particles with a particle size of 0.05 to 5 mm, the epoxy resin on the surface of the particles was washed off with methanol, and dried at 80°C for 2 to 3 hours to obtain polyurethane microcapsules containing epoxy resin in the core; The composite polyetheramine is composed of polyetheramine CAD200 and CAM2000 produced by a continuous process in a mass ratio of (13-23): (13-23); The primary amine content of polyetheramine CAD200 and CAM2000 is ≥99.5%, and the dimethylmorpholine content is <0.10%; The production method of polyetheramine CAD200 is as follows: propylene glycol oxypropylene polyether with a molecular weight of 200, hydrogen and ammonia are continuously introduced into a reactor, and under the action of a nickel ruthenium catalyst in the reactor, a hydrogen amination reaction is carried out at a temperature of 120-125°C and a pressure of 3.9-4.4MPa to obtain polyetheramine CAD200, wherein the molar ratio of propylene glycol oxypropylene polyether to ammonia is 1:43, and the volume concentration of hydrogen in the system is maintained at 15%; The production method of polyetheramine CAM2000 is as follows: propylene glycol oxypropylene polyether with a molecular weight of 2000, hydrogen and ammonia are continuously introduced into a reactor, and under the action of a nickel-based catalyst in the reactor, a hydrogen amination reaction is carried out at a temperature of 125-130°C and a pressure of 4.3-4.8MPa to obtain polyetheramine CAM2000, wherein the molar ratio of propylene glycol oxypropylene polyether to ammonia is 1:45, and the volume concentration of hydrogen in the system is maintained at 16%.

2. The composite adhesive material according to claim 1, It is characterized in that The polyether polyol described in step 1) is a polyether polyol obtained by grafting ethylene oxide, propylene oxide or a mixture of ethylene oxide and propylene oxide with glycerol and trimethylolpropane as initiators.

3. The composite adhesive material according to claim 1, It is characterized in that The catalyst in step 1) is one of dimethylethanolamine, dimethylcyclohexylamine, dimethylbenzylamine, triethylenediamine, pentamethyldiethylenetriamine, potassium acetate, potassium octoate, potassium oleate, stannous octoate or dibutyltin dilaurate, or any mixture thereof.

4. The composite adhesive material according to claim 1, wherein, the surfactant described in step 1) is a polyether-modified polysiloxane.

5. The composite adhesive material according to claim 1, wherein, the crosslinking agent described in step 1) is one of ethylene glycol, propylene glycol, 1,4-butanediol or glycerol or any mixture thereof.

6. The composite adhesive material according to claim 1, wherein, the isocyanate described in step 1) is one of toluene diisocyanate, diphenylmethane diisocyanate or polyphenyl polymethylene polyisocyanate or any mixture thereof.

7. The composite adhesive material according to claim 1, wherein, the particle size of the microporous foam described in step 3) is 0.1 - 2 mm.

8. The composite adhesive material according to claim 1, wherein, the epoxy resin is one of glycidyl ether epoxy resins, bisphenol A epoxy resins or bisphenol F epoxy resins or any mixture thereof.

9. A preparation method of an epoxy wind energy blade with a self-healing function, wherein, fix the profile of the wind energy blade within a mold, close the mold and evacuate to -0.095 to -0.100 MPa, pour the composite adhesive material according to any one of claims 1 - 8 into the mold, and cure for 12 h to obtain an epoxy wind energy blade with a self-healing function.