Epoxy resin composition for wind turbine blade as well as preparation method and application of epoxy resin composition

Abstract

The invention discloses an epoxy resin composition for a wind turbine blade, the epoxy resin composition is a two-component system, and the two-component system is formed by mixing an epoxy resin component A and a curing agent component B according to the weight ratio of 100: (22-26). The low-temperature curing agent has good fluidity and crystallization resistance in a low-temperature environment, is less affected by a low-temperature operation environment, has good infiltration on fibers, has excellent comprehensive properties such as mechanical properties, toughness, heat resistance and water resistance of a cured product, can meet practical requirements of hand lay-up manufacturing and repairing of various composite materials, and has wide application prospects. The method is particularly suitable for large-area high-strength composite materials such as wind power blades.

Description

Technical Field

[0001] This invention relates to the field of epoxy resin composition technology, specifically to an epoxy resin composition for wind turbine blades, its preparation method, and its application. Background Technology

[0002] The blade is the most fundamental and critical component of a wind turbine. Its good design, reliable quality, and superior performance are the decisive factors in ensuring the normal and stable operation of the unit. With the significant increase in installed wind power capacity in the market, more and more units are operating for more than 5 years, making blade maintenance and repair increasingly important.

[0003] The maintenance of wind turbine blades mainly involves the reinforcement and repair of the leading and trailing edges, blade tips, and blade roots.

[0004] Hand lay-up bonding is one of the traditional processes for blade repair. With the development of modern composite material technology, various resin compositions suitable for hand lay-up bonding have been developed and are now more diverse.

[0005] Existing technologies currently suffer from problems such as poor fluidity, easy crystallization, poor glass fiber wetting, and low curing speed in low-temperature environments, which seriously affect the efficiency and quality of blade maintenance in winter.

[0006] Therefore, overcoming the performance defects of conventional hand lay-up resins in low-temperature environments and improving the efficiency and quality of wind turbine blade maintenance has become an urgent problem to be solved in my country's wind power operation and maintenance market. However, there are currently very few products on the market that can overcome the challenges of low-temperature application environments while improving process stability. Summary of the Invention

[0007] One of the objectives of this invention is to provide an epoxy resin composition for wind turbine blades.

[0008] The aim is to overcome the problems of wettability, curing degree and curing speed of fiber braided layers in low temperature environment, and improve the maintenance efficiency and quality stability of hand lay-up bonding repair of wind turbine blades in winter.

[0009] The low-temperature environment referred to in this invention is a winter low-temperature environment with a temperature not exceeding 10°C.

[0010] The second objective of this invention is a method for preparing epoxy resin compositions.

[0011] The third objective of this invention is the application of an epoxy resin composition for wind turbine blades.

[0012] To achieve the objectives of this invention, the technical solution adopted is as follows: An epoxy resin composition for wind turbine blades, wherein the epoxy resin composition is a two-component system, and the two-component system is formed by mixing epoxy resin component A and curing agent component B in a weight ratio of 100:22-26; in, Component A, calculated by mass parts, comprises the following components: 40-60 parts of bisphenol F type epoxy resin; 10-20 parts of hydrogenated bisphenol A type epoxy resin; 20-40 parts reactive diluent; 0-10 parts epoxy diluent; 0.1-2 parts of auxiliary agent; Component B, calculated by mass parts, comprises the following components: 40-60 parts of fatty amine modified curing agent; 30-50 parts of phenolic amine modified curing agent; Accelerator 0-5 parts; Pigment 0.001 parts - 0.01 parts.

[0013] In a preferred embodiment of the present invention, the bisphenol F epoxy resin is a 170 type bisphenol F epoxy resin.

[0014] In a preferred embodiment of the present invention, the hydrogenated bisphenol A epoxy resin is a 518 type hydrogenated bisphenol A epoxy resin.

[0015] In a preferred embodiment of the present invention, the reactive diluent is 30-40 parts by mass.

[0016] In a preferred embodiment of the present invention, the active diluent is any one or more of 1,4-butanediol diglycidyl ether or 1,6-hexanediol diglycidyl ether.

[0017] In a preferred embodiment of the present invention, the epoxy diluent is a monofunctional epoxy diluent with an epoxy value ranging from 0.49 to 0.54 eq / 100g and a viscosity range of 5 to 10 mPa·s at 25°C.

[0018] In a preferred embodiment of the present invention, the additive is an antifoaming agent, which is a polyether-modified dimethyl polysiloxane copolymer.

[0019] In a preferred embodiment of the present invention, the fatty amine modified curing agent is any one or more of F205 type fatty amine modified curing agent and H-725 type fatty amine modified curing agent.

[0020] In a preferred embodiment of the present invention, the phenolic amine modified curing agent is any one or more of the phenolic amine modified amine epoxy curing agents LT-635A, LT-63Y or LT-3637Y.

[0021] In a preferred embodiment of the present invention, the accelerator is any one or more of the following: DMP-30 type accelerator, EP-184 type accelerator, EP-399 type accelerator, and CT-152X type accelerator.

[0022] In a preferred embodiment of the present invention, the pigment is phthalocyanine green or transparent blue.

[0023] A method for preparing an epoxy resin composition for wind turbine blades includes the following steps: Preparation steps for component A, The components were mixed and stirred according to the mass ratio, and then vacuum-heated for 3 hours. Preparation steps of component B, The components were mixed and stirred according to the mass ratio, and then vacuum-heated for 3 hours. After mixing the prepared components A and B in a certain proportion, stirring and then vacuum degassing are performed to obtain an epoxy resin composition.

[0024] In a preferred embodiment of the present invention, the epoxy resin composition has a mixing viscosity of 100-200 mPa·s at 25°C.

[0025] In a preferred embodiment of the present invention, the epoxy resin composition has a mixing viscosity of 10,000-20,000 mPa·s at -15°C.

[0026] In a preferred embodiment of the present invention, the gel time of 100g of the epoxy resin composition at 0°C is 30-60 min; the gel time of 100g of the epoxy resin composition at 0°C is 8-12 h; and the gel time of 100g of the epoxy resin composition at -10°C is 48-72 h.

[0027] An application of an epoxy resin composition for wind turbine blades, wherein the application is to bond and repair wind turbine blades using a hand lay-up process in a normal or low temperature environment.

[0028] The main technical effects of this invention are as follows: First, the present invention uses an active diluent, an epoxy diluent, and bisphenol F type epoxy resin and hydrogenated bisphenol A type epoxy resin to obtain an epoxy resin composition under a certain range. The product still has fluidity, antifreeze and anti-crystallization properties and excellent wettability to glass fiber under low temperature conditions, thus improving the efficiency of wind turbine blade maintenance. This invention uses highly reactive curing agents such as fatty amine modified curing agents and phenolic amine modified curing agents, which can achieve rapid curing in a low temperature environment of -10℃, significantly improving the curing efficiency compared with existing hand lay-up resin products.

[0029] The materials used in this invention are all low-allergenic, reducing harm to the human body, improving the construction environment, and meeting the needs of the rapid development of wind turbine blades in the future. This invention also enhances the technical and manufacturing capabilities of the wind turbine blade operation and maintenance market in terms of materials, aligning with the future rapid development needs of wind turbine blades. Detailed Implementation

[0030] The mechanism of action of the raw materials in the formulation of this invention: In this invention, bisphenol F epoxy resin and hydrogenated bisphenol A type epoxy resin are used to reduce the viscosity of the system and improve its antifreeze and anti-crystallization ability.

[0031] This invention employs reactive diluents and a combination of reactive diluents and epoxy diluents to improve viscosity reduction and glass fiber wettability.

[0032] This invention employs a rational combination of aliphatic amine modified curing agent and phenolic amine modified curing agent, which has high reactivity and can achieve rapid curing in low-temperature environments.

[0033] To further understand this invention, the following comparative analysis is conducted using test results such as viscosity, gel time, mechanical properties, and glass transition temperature, in conjunction with embodiments and comparative examples. The scope of protection of this invention is not limited to the following embodiments.

[0034] The bisphenol F type epoxy resin is type 170 bisphenol F type epoxy resin.

[0035] The hydrogenated bisphenol A type epoxy resin is type 518 hydrogenated bisphenol A type epoxy resin.

[0036] Comparative Example 1 (the epoxy resin formulation differs from the scope of this invention): A method for preparing an epoxy resin composition for wind turbine blades: a) Prepare the various raw materials for component A, with the following proportions (parts by mass): 80 parts of bisphenol F type epoxy resin; 15 parts of hydrogenated bisphenol A type epoxy resin; 5 parts of reactive diluent (1,4-butanediol diglycidyl ether); Additive (polyether-modified dimethyl polysiloxane copolymer) 0.1 parts.

[0037] Add all raw materials to the reactor, heat to 40℃-80℃, stir under vacuum for 3 hours, cool, and then pack into a container and seal for storage.

[0038] b) Prepare the various raw materials for component B, with the following proportions (parts by mass): 52 parts of fatty amine modified curing agent; The fatty amine modified curing agent is type F205 fatty amine modified curing agent.

[0039] 45 parts of phenolic amine modified curing agent; The phenolic amine modified curing agent is LT-635A, a phenolic amine modified amine epoxy curing agent.

[0040] Three parts of accelerator; the accelerator is DMP-30 type accelerator.

[0041] Phthalocyanine green pigment, 0.005 parts.

[0042] Add all raw materials to the reactor, heat to 20℃-40℃, stir under vacuum for 3 hours, cool, and then pack into a container and seal for storage.

[0043] c) Mix and stir the prepared components A and B at a mass ratio of 100:24, and then perform vacuum degassing to obtain the epoxy resin composition for wind turbine blades of Comparative Example 1.

[0044] Comparative Example 2 (the epoxy resin formulation differs from the scope of this invention): A method for preparing an epoxy resin composition for wind turbine blades: a) Prepare the various raw materials for component A, with the following proportions (parts by mass): 70 parts of bisphenol F type epoxy resin; 15 parts of hydrogenated bisphenol A type epoxy resin; 15 parts of reactive diluent (1,4-butanediol diglycidyl ether); Additive (polyether-modified dimethyl polysiloxane copolymer) 0.1 parts.

[0045] Add all raw materials to the reactor, heat to 40℃-80℃, stir under vacuum for 3 hours, cool, and then pack into a container and seal for storage.

[0046] b) Prepare the various raw materials for component B, with the following proportions (parts by mass): 52 parts of fatty amine modified curing agent; The fatty amine modified curing agent is type F205 fatty amine modified curing agent.

[0047] 45 parts of phenolic amine modified curing agent; The phenolic amine modified curing agent is LT-635A, a phenolic amine modified amine epoxy curing agent.

[0048] Three parts of accelerator; the accelerator is DMP-30 type accelerator.

[0049] Phthalocyanine green pigment, 0.005 parts.

[0050] Add all raw materials to the reactor, heat to 20℃-40℃, stir under vacuum for 3 hours, cool, and then pack into a container and seal for storage.

[0051] c) Mix and stir the prepared components A and B at a mass ratio of 100:24, and then perform vacuum degassing to obtain the epoxy resin composition for wind turbine blades of Comparative Example 2. Example 1

[0052] A method for preparing an epoxy resin composition for wind turbine blades: a) Prepare the various raw materials for component A, with the following proportions (parts by mass): 60 parts of bisphenol F type epoxy resin; 15 parts of hydrogenated bisphenol A type epoxy resin; 25 parts of reactive diluent (1,4-butanediol diglycidyl ether); Additive (polyether-modified dimethyl polysiloxane copolymer) 0.1 parts.

[0053] Add all raw materials to the reactor, heat to 40℃-80℃, stir under vacuum for 3 hours, cool, and then pack into a container and seal for storage.

[0054] b) Prepare the various raw materials for component B, with the following proportions (parts by mass): 52 parts of fatty amine modified curing agent; 45 parts of phenolic amine modified curing agent; Three parts of accelerator; the accelerator is DMP-30 type accelerator.

[0055] Phthalocyanine green pigment, 0.005 parts.

[0056] Add all raw materials to the reactor, heat to 20℃-40℃, stir under vacuum for 3 hours, cool, and then pack into a container and seal for storage.

[0057] c) Mix and stir the prepared components A and B at a mass ratio of 100:24, and then perform vacuum degassing to obtain the epoxy resin composition for wind turbine blades of Example 1.

[0058] Example 2 (Diluent Compound): A method for preparing an epoxy resin composition for wind turbine blades: a) Prepare the various raw materials for component A, with the following proportions (parts by mass): 60 parts of bisphenol F type epoxy resin; 10 parts of hydrogenated bisphenol A type epoxy resin; 25 parts of reactive diluent; 5 parts epoxy diluent (e.g., 622); Additives (defoamer XY033, etc., rheology modifier) ​​0.1 parts.

[0059] Add all raw materials to the reactor, heat to 40℃-80℃, stir under vacuum for 3 hours, cool, and then pack into a container and seal for storage.

[0060] b) Prepare the various raw materials for component B, with the following proportions (parts by mass): 52 parts of fatty amine modified curing agent; The fatty amine modified curing agent is type F205 fatty amine modified curing agent.

[0061] 45 parts of phenolic amine modified curing agent; The phenolic amine modified curing agent is LT-635A, a phenolic amine modified amine epoxy curing agent.

[0062] Three parts of accelerator; the accelerator is DMP-30 type accelerator.

[0063] Phthalocyanine green pigment, 0.005 parts.

[0064] Add all raw materials to the reactor, heat to 20℃-40℃, stir under vacuum for 3 hours, cool, and then pack into a container and seal for storage.

[0065] c) Mix and stir the prepared components A and B at a mass ratio of 100:24, and then perform vacuum degassing to obtain the epoxy resin composition for wind turbine blades of Example 2.

[0066] Comparison of existing technologies: A commercially available hand lay-up epoxy resin (LT5089) was selected as a control example for the comparative experiment.

[0067] Table 1: Results of Physicochemical Properties Tests

[0068] Table 2: Mechanical Performance Test Results

[0069] As can be seen from Tables 1 and 2, the viscosity at 25℃ in the comparative examples is relatively high, and the viscosity at -15℃ cannot be detected because it is in a non-flowing crystalline state.

[0070] The product of this invention retains its fluidity, antifreeze and anti-crystallization properties, and excellent wettability to glass fiber even in low-temperature environments, thereby improving the efficiency of wind turbine blade maintenance.

[0071] As can be seen from Tables 1 and 2, the gelation time of the present invention is significantly shortened under conditions of 5° and 0°, indicating that the system of the present invention has high reactivity and can achieve rapid curing in a low-temperature environment.

[0072] Therefore, this invention significantly reduces the impact of manual operation and temperature changes, and can be widely and conveniently used in the manufacture of epoxy composite materials, especially suitable for hand lay-up molding and repair reinforcement processes of large composite structural components such as wind turbine blades.

[0073] The foregoing has shown and illustrated the technical features, implementation methods, and outstanding advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the present invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claims. The scope of protection of the present invention is defined by the appended claims and their equivalents.

Claims

1. An epoxy resin composition for wind turbine blades, characterized in that, The epoxy resin composition is a two-component system, which is composed of epoxy resin component A and curing agent component B mixed in a weight ratio of 100:22-26. in, Component A, calculated by mass parts, comprises the following components: 40-60 parts of bisphenol F type epoxy resin; 10-20 parts of hydrogenated bisphenol A type epoxy resin; 20-40 parts reactive diluent; 0-10 parts epoxy diluent; 0.1-2 parts of auxiliary agent; Component B, calculated by mass parts, comprises the following components: 40-60 parts of fatty amine modified curing agent; 30-50 parts of phenolic amine modified curing agent; Accelerator 0-5 parts; Pigment 0.001 parts - 0.01 parts.

2. The epoxy resin composition for wind turbine blades as described in claim 1, characterized in that, The bisphenol F type epoxy resin is type 170 bisphenol F type epoxy resin.

3. The epoxy resin composition for wind turbine blades as described in claim 1, characterized in that, The hydrogenated bisphenol A type epoxy resin is type 518 hydrogenated bisphenol A type epoxy resin.

4. The epoxy resin composition for wind turbine blades as described in claim 1, characterized in that, The active diluent is 30-40 parts by weight; The active diluent is any one or more of 1,4-butanediol diglycidyl ether or 1,6-hexanediol diglycidyl ether; The epoxy diluent is a monofunctional epoxy diluent with an epoxy value ranging from 0.49 to 0.54 eq / 100g and a viscosity range of 5 to 10 mPa·s at 25°C.

5. The epoxy resin composition for wind turbine blades as described in claim 1, characterized in that, The additive is an antifoaming agent, which is a polyether-modified dimethyl polysiloxane copolymer.

6. The epoxy resin composition for wind turbine blades as described in claim 1, characterized in that, The fatty amine modified curing agent is any one or more of the F205 type fatty amine modified curing agent and the H-725 type fatty amine modified curing agent.

7. The epoxy resin composition for wind turbine blades as described in claim 1, characterized in that, The phenolic amine modified curing agent is any one or more of the phenolic amine modified amine epoxy curing agents LT-635A, LT-63Y or LT-3637Y.

8. The epoxy resin composition for wind turbine blades as described in claim 1, characterized in that, The accelerator is any one or more of the following: DMP-30 type accelerator, EP-184 type accelerator, EP-399 type accelerator, and CT-152X type accelerator; The pigment is phthalocyanine green or transparent blue.

9. A method for preparing an epoxy resin composition for wind turbine blades according to any one of claims 1-8, characterized in that, Includes the following steps: Preparation steps for component A, The components were mixed and stirred according to the mass ratio, and then vacuum-heated for 3 hours. Preparation steps of component B, The components were mixed and stirred according to the mass ratio, and then vacuum-heated for 3 hours. After mixing the prepared components A and B in a certain proportion, stirring and then vacuum degassing are performed to obtain an epoxy resin composition.

10. The application of the epoxy resin composition for wind turbine blades as described in any one of claims 1-8, characterized in that, The application involves using a hand lay-up process to bond and repair wind turbine blades in normal or low-temperature environments.

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