Polyurethane foam filling material for wind power generation blade as well as preparation method and application of polyurethane foam filling material

Abstract

The invention belongs to the technical field of wind power generation blade filling materials, and particularly relates to a polyurethane foam filling material for a wind power generation blade and a preparation method and application of the polyurethane foam filling material. Wherein the component A comprises the following components: polyether polyol a, polyether polyol b, polyether polyol c, polyester polyol d, a viscosity reducer, a cross-linking agent, a foam stabilizer, a catalyst, chemical foaming agent water and an auxiliary agent; the component B is polymethylene polyphenyl polyisocyanate; the polyether polyol a is polyether polyol prepared by taking enzymatic hydrolysis lignin, pentaerythritol, trihydroxymethyl melamine and propylene glycol as initiators and carrying out a reaction; the polyether polyol b is polyether polyol which is prepared by taking bisphenol A and trimethylolpropane as initiators; the filling material prepared by the invention is safe, green and environment-friendly, has the advantages of low density, high strength, better process adaptability and excellent dimensional stability, and also can provide good weather resistance.

Description

Technical Field

[0001] The present invention belongs to the technical field of filling materials for wind power generation blades, and particularly relates to a polyurethane foam filling material for wind power generation blades, a preparation method thereof, and an application thereof. Background Art

[0002] With the development of wind power technology, the length of blades has been continuously increasing, and most of them need to reach more than 80 meters to capture more wind energy. Traditional core materials such as PVC foam and balsa wood face problems such as insufficient mechanical properties and large weight in ultra-large blades, and there is an urgent need for higher-strength and lighter alternative materials. Especially in the marine environment, the requirements for blades are higher, and the extreme climate from -30°C to +60°C needs to be strengthened. Traditional core materials are easy to absorb moisture and have poor durability. Polyurethane has become an ideal choice due to its hydrophobicity and high weather resistance.

[0003] Patent CN101402791A discloses a low-density and high-strength nano-polyurethane wind turbine blade composite material, which includes component A and component B. By weight, component A: polyester polyol 20-50; polyether polyol 10-60; vegetable oil 10-25; inorganic nano material 10-20; catalyst 0.01-1; antioxidant 0.01-1; fiber reinforcement material 10-30; component B: polydiphenyl diisocyanate, toluene diisocyanate or isocyanate prepolymer; the weight ratio of component A to component B except for the fiber reinforcement material is A:B = 1:1-1.5. It overcomes the problems of high density, low temperature resistance, and easy aging of existing unsaturated resin and epoxy resin materials. It is made by compounding nano materials with glass fiber and volcanic rock fiber as reinforcement materials with polyurethane, and has special properties such as low density, high tensile, shear strength, low temperature resistance, and corrosion resistance, and is suitable for the application of wind turbine blades and engineering structure materials in wind power generation. Although this patent has a lower density compared with unsaturated resin and epoxy resin, this product is a non-foaming product and still has a relatively high density, and the achieved strength is not mentioned either.

[0004] Patent CN103339375A discloses a reinforced polyurethane foam and its uses as a load-bearing and rigid planar element inside a blade or wing, and as a thermal insulation material for a liquefied natural gas tank. The reinforced polyurethane foam is obtained by the following method: mixing (a) polyisocyanate with (b) a compound having isocyanate-reactive groups, (c) a blowing agent containing water, and optionally (d) a catalyst and (e) other additives to form a reaction mixture and curing the reaction mixture, wherein the reaction mixture to be cured contains 1 wt% - 40 wt% of hollow microspheres and / or a porous reinforcing agent (f) capable of forming a two-dimensional or three-dimensional network structure in the polyurethane foam. The compound (b) having isocyanate-reactive groups contains a polyether polyol (b1), a polyester polyol (b2), a chain extender (b3), and optionally a crosslinking agent (b4) and an aromatic polyether diol (b5), and the polyester polyol (b2), the chain extender (b3), and the aromatic polyether diol (b5) contained in component (b) are at least 50 wt% based on the total weight of component (b). Although this patent is for a reinforced polyurethane foam with relatively excellent performance, the reinforcing effect is achieved by the layered form of hollow glass microspheres and the reinforcing agent, and it is difficult to achieve a uniform distribution of solids and liquids, i.e., a uniform distribution with polyurethane, which requires high production control.

[0005] Traditional polyurethane filling materials rely on petroleum-based polyether / polyester polyols, while bio-based alternatives can reduce the carbon footprint and meet the industry's low-carbon environmental protection requirements. At the same time as taking into account the low-carbon environmental protection characteristics, improving their application performance as the core material of wind turbine blades is a difficult problem in the industry today. Therefore, a low-density, high-modulus, green and environmentally friendly polyurethane foam filling material suitable for wind turbine blades has become a trend in the industry's development. Summary of the Invention

[0006] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a polyurethane foam filling material for wind turbine blades, which has low density, high strength, good process adaptability, and excellent dimensional stability, and can provide good weather resistance.

[0007] The present invention also provides a preparation method thereof, which is simple and easy to operate and suitable for large-scale production.

[0008] The present invention also provides its application, which can replace traditional materials and optimize its performance as a filling material for wind turbine blades.

[0009] The polyurethane foam filling material for wind turbine blades described in the present invention is composed of component A and component B with a mass ratio of 1: (0.9 - 1.1), wherein: Component A contains the following components and parts by weight: Polyether polyol a: 55 - 65 parts; Polyether polyol b: 20 - 30 parts; Polyether polyol c: 10 - 15 parts; Polyester polyol d: 5 - 10 parts; Crosslinking agent: 3 - 5 parts; Viscosity reducer: 5 - 7 parts; Foam stabilizer: 2 - 2.5 parts; Catalyst: 0.8 - 1.2 parts; Chemical blowing agent water: 0.8 - 1.1 parts; Auxiliary agent: 4 - 8.4 parts; Component B is polymethylene polyphenyl polyisocyanate; The polyether polyol a is a special bio - based polyether polyol, which is obtained by using enzymatically hydrolyzed lignin, pentaerythritol, trimethylolmelamine, and propylene glycol as initiators, reacting with propylene oxide under the catalysis of KOH, removing propylene oxide monomer, and undergoing post - treatment. The average hydroxyl value of polyether polyol a is 280 mgKOH / g, and the functionality is 3.32; The polyether polyol b is a special polyether polyol, which is a polyether polyol prepared by using bisphenol A and trimethylolpropane as initiators and reacting with propylene oxide under the catalysis of KOH. The average hydroxyl value of polyether polyol b is 360 mgKOH / g, and the functionality is 2.71; The polyether polyol c has a functionality of 7.25 and an average hydroxyl value of 370 mgKOH / g. INOVOL R8037 from Shandong Yinuowei New Materials Co., Ltd. is preferred; The polyester polyol d has a functionality of 2.4 and an average hydroxyl value of 295 mgKOH / g. PS - 3158 from Stepan (Nanjing) Chemical Co., Ltd. is preferred.

[0010] The indicators of the enzymatically hydrolyzed lignin are number - average molecular weight of 800 - 1500, functionality of 3 - 3.5. Number - average molecular weight of 1000 and functionality of 3.3 are preferred.

[0011] The preparation method of the polyether polyol a includes the following steps: Step 1: Put enzymatically hydrolyzed lignin, pentaerythritol, trimethylolmelamine, and propylene glycol into the polymerization kettle, and at the same time add solid potassium hydroxide in a proportion of 0.25 - 0.3% of the system. After pressurizing for leak detection and nitrogen replacement, evacuate to a pressure in the polymerization kettle of - 0.09 to - 0.1 MPa, heat up to a temperature in the polymerization kettle of 80 - 85 °C, continuously dropwise add propylene oxide monomer (accounting for 40% of the total mass of propylene oxide), and control the feeding speed so that the pressure in the kettle is 0 - 0.2 MPa. After the dropping is completed, cure for 0.5 - 1 h; Step 2: Adjust the temperature to 90 - 110°C, continuously dropwise add propylene oxide monomer (60% of the total mass of propylene oxide), ensure that the pressure is controlled below 0.2 MPa during the process, until all the propylene oxide is added dropwise, and cure for 3 - 5 h to obtain crude polyether; Step 3: Control the temperature in the polymerization kettle at 100 - 120°C, evacuate to control the pressure in the polymerization kettle at -0.08 to -0.09 MPa to remove unreacted propylene oxide; lower the temperature in the polymerization kettle to 75 - 85°C, add phosphoric acid and water, stir for 1 h, add magnesium silicate, raise the temperature to 100 - 110°C, evacuate to dehydrate and control the pressure in the kettle at -0.08 to -0.09 MPa, detect that the moisture is less than 0.1%, discharge and filter by suction to obtain polyether polyol a, with an average hydroxyl value of 280 mg KOH / g and a functionality of 3.32.

[0012] The molar ratio of the enzymatically hydrolyzed lignin, pentaerythritol, trimethylolmelamine, and propylene glycol is 1:1:0.5:1.515.

[0013] The cross-linking agent is one or both of glycerol and triethanolamine.

[0014] The viscosity reducer is one or both of 2,2,4 - trimethyl - 1,3 - pentanediol diisobutyrate, dibutyl phthalate, and propylene carbonate.

[0015] The foam stabilizer is one or both of B84813 (Evonik Specialties (Shanghai) Co., Ltd.) and H3565 (Zhongshan Dongjun Chemical Co., Ltd.), preferably B84813.

[0016] The catalyst is one or more of triethylenediamine, N,N - dimethylcyclohexylamine, benzylamine, delayed - type quaternary ammonium salt catalyst TMR - 2, 1,3,5 - tris(dimethylaminopropyl)hexahydro - s - triazine, or 2,4,6 - tris(dimethylaminomethyl)phenol.

[0017] The auxiliary agent is dimethyl carbonate.

[0018] The polyurethane foam filling material for wind power generation blades has the following properties: Density ≥ 80 kg / m 3 ; Compressive strength ≥ 1.8 MPa; High - low temperature dimensional stability ≤ 0.3%; Water absorption rate ≤ 1%.

[0019] The preparation method of the polyurethane foam filling material for wind power generation blades according to the present invention includes the following steps: (1) Preparation of Component A: Polyether polyol a, polyether polyol b, polyether polyol c, polyester polyol d, crosslinking agent, viscosity reducer, foam stabilizer, catalyst, chemical blowing agent water and additives are added into a reaction kettle, stirred and mixed evenly at room temperature to obtain Component A, which is then sealed and stored; (2) Preparation of Component B: Polymethylene polyphenyl polyisocyanate is taken as Component B, preferably PM200 of Wanhua Chemical Group Co., Ltd.; (3) During use, Component A and Component B are mixed evenly according to a mass ratio of 1.0: (0.9 - 1.1), and then injected into a mold. After molding and curing, the polyurethane foam filling material for wind turbine blades is obtained.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) For the polyurethane foam filling material for wind turbine blades of the present invention, the polyether polyol a used is a special bio - based polyether polyol. By screening a specific enzymatically hydrolyzed lignin initiator, it provides a high - rigidity ring in an environmentally friendly manner. Trihydroxymethyl melamine introduces a triazine structure to increase the nitrogen - containing rigid group. When paired with pentaerythritol, the regular structure and cross - linking degree of pentaerythritol ensure excellent rigidity and mechanical properties in the application of the prepared polyether polyol product, and at the same time ensure the isotropy of the prepared product, avoiding uneven distribution of the filling material in local areas.

[0021] (2) Through the selection of the initiator and control of the index range of polyether polyol b, polyether polyol with low viscosity and high strength is synthesized. Polyol b uses bisphenol A as the initiator and trimethylolpropane as the initiator, avoiding the problems of difficult mixing caused by the high viscosity of traditional polyethers initiated by high - functionality sucrose and sorbitol and incompatibility with viscosity reducers. When paired with high - functionality polyether polyol c, it maximizes the strength of the product while ensuring regular chain segments and low viscosity.

[0022] (3) The small - molecule dimethyl carbonate added in the present invention is effectively paired with the physical blowing agent. During the foaming process, its relatively fast evaporation rate can buffer heat, effectively inhibiting the escape of the physical blowing agent during the reaction, making the foam structure more stable, significantly improving the foam strength, and enhancing the dimensional stability of the product.

[0023] (4) The chemical blowing agent of the present invention is water, and no physical blowing agent is added, which is green, environmentally friendly and pollution - free.

[0024] (5) The polyurethane foam filling material for wind turbine blades of the present invention is safe, green and environmentally friendly. It not only has the advantages of low density, high strength, good process adaptability, excellent dimensional stability, but also can provide good weather resistance. Detailed implementation mode

[0025] The present invention will be further described below in conjunction with embodiments.

[0026] All raw materials used in the examples are commercially available unless otherwise specified.

[0027] INOVOL R8037 is purchased from Yinuowei New Materials Co., Ltd., using sucrose and glycerol as initiators, with a functionality of 7.25 and an average hydroxyl value of 370 mgKOH / g; PS-3158 is purchased from Stepan (Nanjing) Chemical Co., Ltd.; B84813 is purchased from Evonik Specialty Chemicals (Shanghai) Co., Ltd.; H3565 is purchased from Zhongshan Dongjun Chemical Co., Ltd.; The number-average molecular weight of the enzymatically hydrolyzed lignin is 1000 and the functionality is 3.3. It is purchased from Shandong Longli Biotechnology Co., Ltd.; INOVOL R4110 is purchased from Yinuowei New Materials Co., Ltd., using sucrose and diethylene glycol as initiators, with an average hydroxyl value of 430 mgKOH / g and a functionality of 4.1; INOVOL R8345 is purchased from Yinuowei New Materials Co., Ltd., using sucrose and glycerol as initiators, with an average hydroxyl value of 45 mgKOH / g and a functionality of 4.6; INOVOL R8243 is purchased from Yinuowei New Materials Co., Ltd., using sucrose and diethylene glycol as initiators, with an average hydroxyl value of 430 mgKOH / g and a functionality of 4.0.

[0028] Preparation of the polyether polyol a: Step 1: Put 1000 g of enzymatically hydrolyzed lignin, 136.17 g of pentaerythritol, 108 g of trimethylolmelamine, and 115.3 g of propylene glycol into a polymerization kettle. At the same time, add 7.2 g of solid potassium hydroxide, pressurize for leak testing, and after nitrogen replacement, evacuate to a pressure of -0.1 MPa in the polymerization kettle. Heat up to a temperature of 83 °C in the polymerization kettle, and continuously dropwise add 524.54 g of propylene oxide monomer. Control the pressure in the kettle within 0.2 MPa during the feeding speed. After the dropping is completed, cure for 1 h; Step 2: Adjust the temperature to 105 °C, and continuously dropwise add 786.81 g of propylene oxide monomer, ensuring that the pressure is controlled below 0.2 MPa during the process until all the propylene oxide is added. Cure for 4 h to obtain a crude polyether; Step 3: Control the temperature in the polymerization kettle at 110°C, evacuate to control the pressure in the polymerization kettle at -0.09 MPa, and remove unreacted propylene oxide. Lower the temperature in the polymerization kettle to 80°C, add 16.13 g of phosphoric acid and 134 g of water, stir for 1 h, add 2.7 g of magnesium silicate, raise the temperature to 105°C, evacuate to dehydrate and control the pressure in the kettle at -0.09 MPa, detect that the moisture content is lower than 0.1%, discharge and filter to obtain polyether polyol a, with an average hydroxyl value of 280 mg KOH / g and a functionality of 3.32.

[0029] Preparation of the polyether polyol b: Step 1: Charge 335 g of trimethylolpropane and 228 g of bisphenol A into the polymerization kettle. At the same time, add 4.5 g of solid potassium hydroxide, pressurize to test for leaks, and after nitrogen replacement, evacuate to make the pressure in the polymerization kettle reach -0.1 MPa. Raise the temperature in the polymerization kettle to 83°C, continuously dropwise add 220 g of propylene oxide monomer, and control the pressure in the kettle within 0.2 MPa by the feeding speed. After the dropping is completed, age for 1 h; Step 2: Adjust the temperature to 105°C, continuously dropwise add 693 g of propylene oxide monomer, ensure that the pressure is controlled below 0.2 MPa during the process until all the propylene oxide is dropped, and age for 4 h to obtain crude polyether; Step 3: Control the temperature in the polymerization kettle at 110°C, evacuate to control the pressure in the polymerization kettle at -0.09 MPa, and remove unreacted propylene oxide. Lower the temperature in the polymerization kettle to 80°C, add 10.1 g of phosphoric acid and 73.8 g of water, stir for 1 h, add 1.5 g of magnesium silicate, raise the temperature to 105°C, evacuate to dehydrate and control the pressure in the kettle at -0.09 MPa, detect that the moisture content is lower than 0.1%, discharge and filter to obtain polyether polyol b, with an average hydroxyl value of 360 mg KOH / g and a functionality of 2.71.

[0030] Example 1 The polyurethane foam filling material for wind power generation blades is composed of component A and component B with a mass ratio of 1:1.1, where: Component A is composed of the following components in parts by mass: Polyether polyol a: 550 kg; Polyether polyol b: 300 kg; INOVOL R8037: 150 kg; PS-3158: 50 kg; Triethanolamine (TEA): 30 kg; 2,2,4-Trimethyl-1,3-pentanediol diisobutyrate: 70 kg; B84813: 22.5 kg; Triethylenediamine: 2 kg; Benzylamine: 8 kg; 1,3,5 - Tris(dimethylaminopropyl)hexahydro - 1,3,5 - triazine: 2 kg; Water: 8 kg; Dimethyl carbonate: 84 kg; Component B: PM200 1000 kg; The preparation method of the polyurethane foam filling material for wind turbine blades: (1) Weigh the polyether polyol a, polyether polyol b, polyether polyol INOVOL R8037, PS - 3158, 2,2,4 - trimethyl - 1,3 - pentanediol diisobutyrate, TEA, B84813, triethylenediamine, benzylamine, 1,3,5 - tris(dimethylaminopropyl)hexahydro - 1,3,5 - triazine, water, and dimethyl carbonate, and add them to the reaction kettle in sequence. Stir and mix at room temperature for 1.5 h to obtain Component A, and store it sealed; (2) Store PM200 under nitrogen sealing.

[0031] Application of the polyurethane foam filling material for wind turbine blades: Mix Component A and Component B in a mass ratio of 1:1.1, pour and mold them in a mold, and take them out after curing to obtain the polyurethane foam filling material for wind turbine blades.

[0032] Example 2 The described polyurethane foam filling material for wind turbine blades is composed of Component A and Component B with a mass ratio of 1:1.0, where Component A is composed of the following components in parts by mass: Polyether polyol a: 600 kg; Polyether polyol b: 250 kg; INOVOL R8037: 125 kg; PS - 3158: 75 kg; Glycerol: 50 kg; Propylene carbonate 50 kg; H3565: 25 kg; N,N - dimethylcyclohexylamine: 3 kg; Benzylamine: 3 kg; 1,3,5 - Tris(dimethylaminopropyl)hexahydro - 1,3,5 - triazine: 2 kg; Water: 10 kg; Dimethyl carbonate: 60 kg; Component B: PM200 1000 kg; The preparation method of the polyurethane foam filling material for wind turbine blades: (1) Add the weighed polyether polyol a, polyether polyol b, polyether polyol INOVOL R8037, PS-3158, propylene carbonate, glycerol, H3565, N,N-dimethylcyclohexylamine, benzylamine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, water, and dimethyl carbonate into the reaction kettle in sequence, and stir and mix at room temperature for 1.5 h to obtain Component A, which is stored in a sealed manner; (2) Store PM200 under nitrogen filling and sealing.

[0033] Application of the polyurethane foam filling material for wind power generation blades: Mix Components A and B in a ratio of 1:1.0, pour and mold them in a mold, and take them out after curing to obtain the polyurethane foam filling material for wind power generation blades.

[0034] Example 3 The polyurethane foam filling material for wind power generation blades is composed of Component A and Component B with a mass ratio of 1:0.9, wherein Component A is composed of the following mass parts: Polyether polyol a: 650 kg; Polyether polyol b: 200 kg; INOVOL R8037: 100 kg; PS-3158: 100 kg; Glycerol: 40 kg; Dibutyl phthalate: 60 kg; B84813: 20 kg; N,N-dimethylcyclohexylamine: 3 kg; Benzylamine: 5 kg; 2,4,6-tris(dimethylaminomethyl)phenol: 2 kg; Water: 11 kg; Dimethyl carbonate: 40 kg; Component B PM200: 1000 kg; Preparation method of the polyurethane foam filling material for wind power generation blades: (1) Add the weighed polyether polyol a, polyether polyol b, polyether polyol INOVOL R8037, PS-3158, dibutyl phthalate, glycerol, B84813, N,N-dimethylcyclohexylamine, benzylamine, 2,4,6-tris(dimethylaminomethyl)phenol, water, and dimethyl carbonate into the reaction kettle in sequence, and stir and mix at room temperature for 1.5 h to obtain Component A, which is stored in a sealed manner; (2) Store PM200 under nitrogen filling and sealing.

[0035] Application of the polyurethane foam filling material for wind power generation blades: Mix component A and component B in a ratio of 1:0.9, pour and mold them in a mold, and take them out after curing to obtain the polyurethane foam filling material for wind turbine blades.

[0036] Comparative Example 1 The polyurethane foam filling material for wind turbine blades is composed of component A and component B with a mass ratio of 1:1.1, where: Component A is composed of the following components in parts by mass: INOVOL R4110: 550 kg; Polyether polyol b: 300 kg; INOVOL R8037: 150 kg; PS-3158: 50 kg; Triethanolamine (TEA): 30 kg; 2,2,4-Trimethyl-1,3-pentanediol diisobutyrate 70 kg; B84813: 22.5 kg; Triethylenediamine: 2 kg; Benzylamine: 8 kg; 1,3,5-Tris(dimethylaminopropyl)hexahydrotriazine: 2 kg; Water: 8 kg; Dimethyl carbonate: 84 kg; Component B PM200 1000 kg; Preparation method of the polyurethane foam filling material for wind turbine blades: (2) Add the weighed INOVOL R4110, polyether polyol b, polyether polyol INOVOL R8037, PS-3158, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, TEA, B84813, triethylenediamine, benzylamine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, water, and dimethyl carbonate into the reaction kettle in sequence, stir and mix at room temperature for 1.5 h to obtain component A, and store it sealed; (2) Store PM200 under nitrogen and seal it.

[0037] Application of the polyurethane foam filling material for wind turbine blades: Mix component A and component B in a ratio of 1:1.1, pour and mold them in a mold, and take them out after curing to obtain the polyurethane foam filling material for wind turbine blades.

[0038] Comparative Example 2 The polyurethane foam filling material for wind turbine blades is composed of component A and component B with a mass ratio of 1:1.0, where: Component A is composed of the following parts by mass: Polyether polyol a: 600 kg; INOVOL R8345: 250 kg; INOVOL R8037: 125 kg; PS - 3158: 75 kg; Glycerol: 50 kg; Propylene carbonate: 50 kg; H3565: 25 kg; N,N - Dimethylcyclohexylamine: 3 kg; Benzylamine: 3 kg; 1,3,5 - Tris(dimethylaminopropyl)hexahydro - s - triazine: 2 kg; Water: 10 kg; Dimethyl carbonate: 60 kg; Component B PM200 1000 kg; Preparation method of the polyurethane foam filling material for wind power generation blades: (1) Sequentially add the weighed polyether polyol a, INOVOL R8345, polyether polyol INOVOL R8037, PS - 3158, propylene carbonate, glycerol, H3565, N,N - dimethylcyclohexylamine, benzylamine, 1,3,5 - tris(dimethylaminopropyl)hexahydro - s - triazine, water, and dimethyl carbonate into the reaction kettle, stir and mix at room temperature for 1.5 h to obtain Component A, and store it sealed; (2) Store PM200 sealed with nitrogen.

[0039] Application of the polyurethane foam filling material for wind power generation blades: Mix Component A and Component B in a ratio of 1:1.0, pour and mold in a mold, and take it out after curing to obtain the polyurethane foam filling material for wind power generation blades.

[0040] Comparative Example 3 The described polyurethane foam filling material for wind power generation blades is composed of Component A and Component B with a mass ratio of 1:0.9, where Component A consists of the following mass parts: Polyether polyol a: 650 kg; Polyether polyol b: 200 kg; INOVOL R8243: 100 kg; PS - 3158: 100 kg; Glycerol: 40 kg; Dibutyl phthalate: 60 kg; B84813: 20 kg; N,N - Dimethylcyclohexylamine: 3 kg; Benzylamine: 5 kg; 2,4,6-Tris(dimethylaminomethyl)phenol: 2 kg; Water: 11 kg; Dimethyl carbonate: 40 kg; Component B PM200 1000 kg; Preparation method of the polyurethane foam filling material for wind power generation blades: (1) Weigh the polyether polyol a, polyether polyol b, polyether polyol INOVOL R8243, PS-3158, dibutyl phthalate, glycerol, B84813, N,N-dimethylcyclohexylamine, benzylamine, 2,4,6-tris(dimethylaminomethyl)phenol, water, and dimethyl carbonate, and add them to the reaction kettle in sequence. Stir and mix at room temperature for 1.5 h to obtain Component A, and store it sealed; (2) Store PM200 sealed with nitrogen.

[0041] Application of the polyurethane foam filling material for wind power generation blades: Mix Component A and Component B in a ratio of 1:0.9, pour and mold them in a mold, and take them out after curing to obtain the polyurethane foam filling material for wind power generation blades.

[0042] Comparative Example 4 The polyurethane foam filling material for wind power generation blades is composed of Component A and Component B with a mass ratio of 1:1.0, where Component A consists of the following mass parts: Polyether polyol a: 600 kg; Polyether polyol b: 250 kg; INOVOL R8037: 125 kg; PS-3158: 75 kg; Glycerol: 50 kg; Propylene carbonate 50 kg; H3565: 25 kg; N,N-Dimethylcyclohexylamine: 3 kg; Benzylamine: 3 kg; 1,3,5-Tris(dimethylaminopropyl)hexahydrotriazine: 2 kg; Water: 18 kg; Component B PM200 1000 kg; Preparation method of the polyurethane foam filling material for wind power generation blades: (1) Weigh the polyether polyol a, polyether polyol b, INOVOL R8037, PS-3158, propylene carbonate, glycerol, H3565, N,N-dimethylcyclohexylamine, benzylamine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, and water in sequence and add them into the reaction kettle. Stir and mix them at room temperature for 1.5 h to obtain Component A, which is sealed and stored. (2) PM200 is stored in a nitrogen-filled and sealed manner.

[0043] Application of the polyurethane foam filling material for wind power generation blades: Mix Components A and B in a ratio of 1:1.0 and cast them in a mold. After curing, take them out to obtain the polyurethane foam filling material for wind power generation blades.

[0044] Comparative Example 5 The polyurethane foam filling material for wind power generation blades is composed of Component A and Component B with a mass ratio of 1:1.0. Among them, Component A is composed of the following components in parts by mass: Polyether polyol a1: 600 kg; Polyether polyol b: 250 kg; INOVOL R8037: 125 kg; PS-3158: 75 kg; Glycerol: 50 kg; Propylene carbonate: 50 kg; H3565: 25 kg; N,N-dimethylcyclohexylamine: 3 kg; Benzylamine: 3 kg; 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine: 2 kg; Water: 10 kg; Dimethyl carbonate: 60 kg; Component B: PM200: 1000 kg; Preparation of the polyether polyol a1: Step 1: Put 136.17 g of pentaerythritol, 108 g of trimethylolmelamine, and 116.4 g of propylene glycol into the polymerization kettle. At the same time, add 5.44 g of solid potassium hydroxide, conduct a pressure test for leakage, and after nitrogen replacement, evacuate to a pressure of -0.1 MPa in the polymerization kettle. Heat up to a temperature of 83 °C in the polymerization kettle, continuously dropwise add 662 g of propylene oxide monomer, and control the pressure in the kettle within 0.2 MPa during the feeding speed. After the dropping is completed, cure for 1 h. Step 2: Adjust the temperature to 105 °C and continuously dropwise add 993 g of propylene oxide monomer, ensuring that the pressure is controlled below 0.2 MPa during the process until all the propylene oxide is added. Cure for 4 h to obtain the crude polyether. Step 3: Control the temperature in the polymerization kettle at 110 °C, evacuate to control the pressure in the polymerization kettle at -0.09 MPa, and remove unreacted propylene oxide. Lower the temperature in the polymerization kettle to 80 °C, add 12.18 g of phosphoric acid and 101 g of water, stir for 1 h, add 2.0 g of magnesium silicate, raise the temperature to 105 °C, evacuate to dehydrate and control the pressure in the kettle at -0.09 MPa. When the water content is detected to be lower than 0.1%, discharge and filter to obtain polyether polyol a1 with an average hydroxyl value of 280 mg KOH / g and a functionality of 3.32.

[0045] Preparation method of the polyurethane foam filling material for wind power generation blades: (1) Sequentially add the weighed polyether polyol a1, polyether polyol b, polyether polyol INOVOL R8037, PS-3158, propylene carbonate, glycerol, H3565, N,N-dimethylcyclohexylamine, benzylamine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, water, and dimethyl carbonate into the reaction kettle, and stir and mix at room temperature for 1.5 h to obtain Component A, which is sealed and stored; (2) PM200 is filled with nitrogen and sealed for storage.

[0046] Application of the polyurethane foam filling material for wind power generation blades: Mix Components A and B in a ratio of 1:1.0, pour and mold in a mold, and take it out after curing to obtain the polyurethane foam filling material for wind power generation blades.

[0047] Comparative Example 6 The described polyurethane foam filling material for wind power generation blades is composed of Component A and Component B with a mass ratio of 1:1.0, wherein: Component A is composed of the following components in parts by mass: Polyether polyol a2: 600 kg; Polyether polyol b: 250 kg; INOVOL R8037: 125 kg; PS-3158: 75 kg; Glycerol: 50 kg; Propylene carbonate 50 kg; H3565: 25 kg; N,N-dimethylcyclohexylamine: 3 kg; Benzylamine: 3 kg; 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine: 2 kg; Water: 10 kg; Dimethyl carbonate: 60 kg; Component B: PM200 1000 kg; Preparation of the polyether polyol a2: Step 1: Put 1000 g of enzymatically hydrolyzed lignin, 136.17 g of pentaerythritol, and 38.06 g of propylene glycol into a polymerization kettle and stir. At the same time, add 4.5 g of solid potassium hydroxide, pressurize for leak detection. After nitrogen replacement, evacuate to a pressure of -0.1 MPa in the polymerization kettle, heat up to a temperature of 83 °C in the polymerization kettle, continuously dropwise add 195.5 g of propylene oxide monomer, and control the pressure in the kettle within 0.2 MPa during the feeding speed. After the dropping is completed, cure for 1 h until the pressure in the polymerization kettle is below 0 MPa; Step 2: Adjust the temperature to 105 °C, continuously dropwise add 293.2 g of propylene oxide monomer, ensure that the pressure is controlled below 0.2 MPa during the process until all the propylene oxide is dropped, and cure for 4 h to obtain a crude polyether; Step 3: Control the temperature in the polymerization kettle at 110 °C, evacuate to control the pressure in the polymerization kettle at -0.09 MPa, and remove the unreacted propylene oxide. Lower the temperature in the polymerization kettle to 80 °C, add 10.08 g of phosphoric acid and 83.15 g of water, stir for 1 h, add 1.66 g of magnesium silicate, heat up to 105 °C, evacuate and dehydrate to control the pressure in the kettle at -0.09 MPa, detect that the water content is lower than 0.1%, discharge and filter to obtain polyether polyol a2, with an average hydroxyl value of 280 mg KOH / g and a functionality of 3.32.

[0048] Preparation method of the polyurethane foam filling material for wind power generation blades: (1) Add the weighed polyether polyol a2, polyether polyol b, polyether polyol INOVOL R8037, PS-3158, propylene carbonate, glycerol, H3565, N,N-dimethylcyclohexylamine, benzylamine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, water, and dimethyl carbonate into the reaction kettle in sequence, stir and mix at room temperature for 1.5 h to obtain Component A, and store it sealed; (2) PM200 is stored sealed under nitrogen.

[0049] Application of the polyurethane foam filling material for wind power generation blades: Mix Components A and B in a ratio of 1:1.0 and pour and mold in a mold. After curing, take it out to obtain the polyurethane foam filling material for wind power generation blades.

[0050] Comparative Example 7 The described polyurethane foam filling material for wind power generation blades is composed of Component A and Component B with a mass ratio of 1:1.0, wherein: Component A is composed of the following components in parts by mass: Polyether polyol a3: 600 kg; Polyether polyol b: 250 kg; INOVOL R8037: 125 kg; PS - 3158: 75 kg; Glycerol: 50 kg; Propylene carbonate: 50 kg; H3565: 25 kg; N,N - Dimethylcyclohexylamine: 3 kg; Benzylamine: 3 kg; 1,3,5 - Tris(dimethylaminopropyl)hexahydro - 1,3,5 - triazine: 2 kg; Water: 10 kg; Dimethyl carbonate: 60 kg; Component B: PM200: 1000 kg; Preparation of the polyether polyol a3: Step 1: Put 1000 g of enzymatically hydrolyzed lignin, 216 g of trimethylolmelamine, and 153.7 g of propylene glycol into the polymerization kettle and stir. At the same time, add 7.2 g of solid potassium hydroxide, pressurize for leak testing. After nitrogen replacement, evacuate to a pressure of -0.1 MPa in the polymerization kettle, raise the temperature to 83 °C in the polymerization kettle, continuously dropwise add 521.2 g of propylene oxide monomer, control the feeding speed so that the pressure in the kettle is within 0.2 MPa. After dropping, cure for 1 h until the pressure in the polymerization kettle is below 0 MPa; Step 2: Adjust the temperature to 105 °C, continuously dropwise add 781.8 g of propylene oxide monomer, ensure that the pressure is controlled below 0.2 MPa during the process until all the propylene oxide is dropped, and cure for 4 h to obtain the crude polyether; Step 3: Control the temperature in the polymerization kettle at 110 °C, evacuate to control the pressure in the polymerization kettle at -0.09 MPa to remove the unreacted propylene oxide. Lower the temperature in the polymerization kettle to 80 °C, add 16.1 g of phosphoric acid and 133.6 g of water, stir for 1 h, add 2.7 g of magnesium silicate, raise the temperature to 105 °C, evacuate to dehydrate and control the pressure in the kettle at -0.09 MPa. Detect that the water content is lower than 0.1%, discharge and filter to obtain the polyether polyol a3, with an average hydroxyl value of 280 mg KOH / g and a functionality of 3.32.

[0051] Preparation method of the polyurethane foam filling material for wind power generation blades: (1) Sequentially add the weighed polyether polyol a3, polyether polyol b, polyether polyol INOVOL R8037, PS - 3158, propylene carbonate, glycerol, H3565, N,N - dimethylcyclohexylamine, benzylamine, 1,3,5 - tris(dimethylaminopropyl)hexahydro - 1,3,5 - triazine, water, and dimethyl carbonate into the reaction kettle, stir and mix at room temperature for 1.5 h to obtain Component A, and store it sealed; (2) Store PM200 under nitrogen and sealed.

[0052] Application of polyurethane foam filling material for wind power generation blades: Mix components A and B in a ratio of 1:1.0, pour and mold them in a mold, and take them out after curing to obtain the polyurethane foam filling material for wind power generation blades.

[0053] Perform performance tests on the products prepared in Examples 1-3 and Comparative Examples 1-7, and the results are shown in Table 1.

[0054] Table 1 shows the performance test results of the products prepared in Examples 1-3 and Comparative Examples 1-7:

[0055] As can be seen from Examples 1-3 in Table 1, the polyurethane foam filling material for wind power generation blades prepared by the present invention can achieve a density ≥ 80 kg / m 3 ; compressive strength ≥ 1.8 MPa; shear strength ≥ 1.8 MPa; dimensional stability ≤ 0.3%; water absorption rate ≤ 1%. Compared with Example 1, in Comparative Example 1, INOVOL R4110 is used instead of polyether polyol a, and the compressive strength and shear strength of the material are significantly worse, and the water absorption rate is significantly increased; compared with Example 2, in Comparative Example 2, INOVOL R8345 is used instead of polyether polyol b, and the compressive strength and shear strength of the material are also affected, and the water absorption rate is significantly increased; compared with Example 3, in Comparative Example 3, INOVOL R8243 is used instead of INOVOL R8037, the crosslinking of the system is weakened, and the high and low temperature dimensional stability of the material is significantly affected; compared with Example 2, in Comparative Example 4, dimethyl carbonate is not used, and only water is used as the foaming agent, the dimensional stability becomes worse and the water absorption rate increases, and the use effect is affected; compared with Example 2, in Comparative Examples 5 and 6, the initiator of polyether polyol a1 does not contain lignin, and the initiator of polyether polyol a2 does not contain trimethylolmelamine, the compressive strength and shear strength of the material are affected, and at the same time the water absorption rate increases; compared with Example 2, in Comparative Example 7, the initiator of polyether polyol does not contain pentaerythritol. Although the overall strength of the foam is not much different, the density difference at different positions of the foam is large at high temperature, and the dimensional stability at high temperature is poor, and the dimensional stability is affected.

Claims

1. A polyurethane foam filling material for a wind power generation blade, characterized in that It is composed of component A and component B with a mass ratio of 1:(0.9 - 1.1), where: Component A contains the following components and parts by weight: Polyether polyol a: 55 - 65 parts; Polyether polyol b: 20 - 30 parts; Polyether polyol c: 10 - 15 parts; Polyester polyol d: 5 - 10 parts; Crosslinking agent: 3 - 5 parts; Viscosity reducer: 5 - 7 parts; Foam stabilizer: 2 - 2.5 parts; Catalyst: 0.8 - 1.2 parts; Chemical blowing agent water: 0.8 - 1.1 parts; Auxiliary agent: 4 - 8.4 parts; Component B is polymethylene polyphenylene polyisocyanate; The polyether polyol a is a bio - based polyether polyol, which is a polyether polyol prepared by reacting with propylene oxide using enzymatically hydrolyzed lignin, pentaerythritol, trimethylolmelamine, and propylene glycol as initiators; the average hydroxyl value of polyether polyol a is 280 mgKOH / g, and the functionality is 3.32; The polyether polyol b is a polyether polyol, which is a polyether polyol prepared by reacting with propylene oxide using bisphenol A and trimethylolpropane as initiators, the average hydroxyl value of polyether polyol b is 360 mgKOH / g, and the functionality is 2.71; The polyether polyol c has a functionality of 7.25 and an average hydroxyl value of 370 mgKOH / g; The polyester polyol d has a functionality of 2.4 and an average hydroxyl value of 295 mgKOH / g.

2. The polyurethane foam filling material for a wind power generation blade according to claim 1, wherein The preparation method of the polyether polyol a includes the following steps: Step 1: Put enzymatically hydrolyzed lignin, pentaerythritol, trimethylolmelamine, and propylene glycol into a polymerization kettle, add a catalyst at the same time, after nitrogen replacement, evacuate, raise the temperature, continuously drop - add propylene oxide monomer, and after dropping, cure; Step 2: Raise the temperature, continuously drop - add propylene oxide monomer, ensure that the pressure is controlled below 0.2 MPa during the process until all propylene oxide is dropped, and cure to obtain crude polyether; Step 3: Remove the unreacted propylene oxide, lower the temperature, add phosphoric acid and water, stir, add magnesium silicate, raise the temperature and evacuate to dehydrate, discharge and filter to obtain polyether polyol a.

3. The polyurethane foam filling material for a wind power generation blade according to claim 2, wherein, The molar ratio of the enzymatically hydrolyzed lignin, pentaerythritol, trimethylolmelamine, and propylene glycol is 1:1:0.5:1.

515.

4. The polyurethane foam filling material for a wind power generation blade according to claim 1, wherein The crosslinking agent is one or two of glycerol and triethanolamine.

5. The polyurethane foam filling material for a wind power generation blade according to claim 1, characterized in that, The viscosity reducer is one or two of 2,2,4 - trimethyl - 1,3 - pentanediol diisobutyrate, dibutyl phthalate, and propylene carbonate.

6. The polyurethane foam filling material for a wind power generation blade according to claim 1, wherein, The foam stabilizer is one or two of B84813 and H3565.

7. The polyurethane foam filling material for a wind power generation blade according to claim 1, characterized in that, The catalyst is one or more of triethylenediamine, N,N - dimethylcyclohexylamine, benzylamine, delayed - type quaternary ammonium salt catalyst TMR - 2, 1,3,5 - tris(dimethylaminopropyl)hexahydro - s - triazine, or 2,4,6 - tris(dimethylaminomethyl)phenol.

8. The polyurethane foam filling material for a wind power generation blade according to claim 1, characterized in that, The auxiliary agent is dimethyl carbonate.

9. A preparation method of the polyurethane foam filling material for a wind power generation blade according to any one of claims 1 to 8, characterized in that, It includes the following steps: (1) Preparation of component A: Add polyether polyol a, polyether polyol b, polyether polyol c, polyester polyol d, crosslinking agent, viscosity reducer, foam stabilizer, catalyst, chemical blowing agent water, and auxiliary agent into a reaction kettle, and stir and mix evenly at room temperature to obtain component A; (2)Preparation of Component B: Take polymethylene polyphenyl polyisocyanate as Component B; (3)During use, after uniformly mixing Component A and Component B, inject them into a mold, and through forming and curing, the polyurethane foam filling material for wind turbine blades can be obtained.

10. Application of the polyurethane foam filling material for wind power generation blades according to any one of claims 1 to 8, characterized in that, It is used as a filling material inside wind turbine blades.

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