Polyurethane elastomer for wind turbine blades and preparation method and application thereof

Abstract

The application discloses a polyurethane elastomer for a wind power blade, characterized in that the polyurethane elastomer comprises an A component and a B component, and the mass ratio of the A component to the B component ranges from 5 to 25:1; wherein the A component comprises the following components in parts by weight: 70-100 parts of a hydroxyl dihydric alcohol, 1-20 parts of polysiloxane, 15-45 parts of diisocyanate, 0.01-0.5 parts of a catalyst and 1-10 parts of a silane coupling agent; wherein the B component comprises the following components in parts by weight: 5-20 parts of a small-molecule chain extender; the hydroxyl dihydric alcohol is one or more of polyether dihydric alcohol and polycarbonate dihydric alcohol, and the molecular weight of the hydroxyl dihydric alcohol is 650-3500 g / mol. The application further discloses a preparation method and application of the polyurethane elastomer. The protective film manufactured from the polyurethane elastomer can play a role in resisting sand and rain in a front edge structure of the wind power blade.

Description

Technical Field

[0001] This invention relates to the field of polyurethane elastomers, specifically to a polyurethane elastomer for wind turbine blades, its preparation method, and its application. Background Technology

[0002] Wind power, as an important renewable energy source, is of great significance in energy transition, ecological protection, energy security, economic development, and technological innovation. As the only component of a wind turbine that captures wind energy, the blades are severely corroded by sand, salt spray, and rainwater at high operating speeds. The leading edge, in particular, is directly exposed to air friction and is the most severely corroded area of ​​the entire blade. The blade leading edge is prone to wear, surface damage, and decreased aerodynamic performance due to sand and rain erosion, leading to reduced power generation efficiency, increased operating costs, and even shortened service life. Studies show that mild leading edge corrosion can cause a 5% loss in annual power generation, while severe leading edge corrosion can cause as much as 25% of the annual power generation loss, and this erosion damage intensifies over time. Therefore, when developing wind power projects, it is essential to prioritize blade leading edge protection technology and take effective measures to improve the economy and reliability of wind turbine units.

[0003] Currently, protection solutions for blade leading-edge corrosion can be broadly categorized into protective polyurethane coatings and protective polyurethane elastic films. The main problems with protective polyurethane coatings are: (1) They are highly dependent on the construction process; the protective performance of the coating is gradually established during construction, thus greatly affected by the construction process. Poor construction conditions at the blade factory will severely impact the coating's service life; (2) The protection cycle is short; the conventional protection cycle for coatings is 1-2 years, after which reconstructive work is required, significantly increasing the maintenance costs of wind turbine blade operation. Protective polyurethane elastic films are made of polyurethane elastomer, a highly elastic protective material. Utilizing its high elasticity, it absorbs or disperses the impact kinetic energy of raindrops, dust, etc., thereby reducing the destructive effect of the environment on the blade's leading-edge shell and achieving a good anti-corrosion effect.

[0004] The core technologies for protective polyurethane elastic membranes are still largely monopolized by foreign countries, and domestic research is still in its infancy. Therefore, designing a leading-edge protection material that can meet the requirements of the entire life cycle operation and does not need to be replaced is the current research focus. There is an urgent need to develop a polyurethane elastomer for wind turbine blade leading-edge protection, which requires high body strength, high elongation, and high hydrophobicity to resist the corrosion of the blade leading edge by sand and rainwater. Summary of the Invention

[0005] To address the problems existing in the prior art, the present invention aims to provide a polyurethane elastomer for the leading edge of wind turbine blades, its preparation method, and its application. The polyurethane elastomer prepared by the present invention possesses high strength, high elongation, and excellent hydrophobicity, and can be used in the leading edge of wind turbine blades to provide corrosion protection.

[0006] To achieve the objectives of this invention, the technical solution adopted is as follows:

[0007] A polyurethane elastomer for wind turbine blades includes component A and component B, wherein the mass ratio of component A to component B ranges from 5 to 25:1.

[0008] Component A, by weight, includes the following components:

[0009] 70-100 parts of hydroxydiol;

[0010] 1-20 parts of polysiloxane;

[0011] 15-45 parts of diisocyanate;

[0012] Catalyst 0.01-0.5 parts;

[0013] 1-10 parts of silane coupling agent;

[0014] Component B, by weight, includes the following components:

[0015] 5-20 parts of small molecule chain extender;

[0016] The hydroxyl diol is one or more of polyether diols and polycarbonate diols, and the molecular weight of the hydroxyl diol is 650-3500 g / mol.

[0017] The polyether diol is one or more of polypropylene glycol and polytetrahydrofuran glycol. The most preferred polytetrahydrofuran ether is PTMEG1000-3000.

[0018] The polycarbonate diol is one or more of polyhexanediol carbonate, polypentylene glycol carbonate, and polybutanediol carbonate. The most preferred polycarbonate is SYHP2000-3000.

[0019] In a preferred embodiment of the present invention, the polysiloxane is one or more of hydroxyalkyl-terminated linear polydimethylsiloxane or amino-terminated linear polydimethylsiloxane, and the molecular weight of the polysiloxane is 1000-3000 g / mol. Amino-modified polysiloxanes are preferred. Most preferably, amino silicone oil AEAPS1000-3000 is preferred.

[0020] In a preferred embodiment of the present invention, the diisocyanate is at least one of aliphatic diisocyanate, alicyclic diisocyanate or aromatic diisocyanate.

[0021] Preferably, it is at least one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, terephthalic diisocyanate, and naphthalene diisocyanate. More preferably, it is isocyanate HMDI, isocyanate MDI, or isocyanate HDI.

[0022] In a preferred embodiment of the present invention, the catalyst is one or more of dibutyltin diacetate, stannous octoate, and dibutyltin dilaurate.

[0023] The preferred catalyst is T12 dibutyltin dilaurate.

[0024] In a preferred embodiment of the present invention, the silane coupling agent is any one or more of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane.

[0025] In a preferred embodiment of the present invention, the small molecule chain extender is any one or more of aliphatic small molecule chain extenders and aromatic small molecule chain extenders.

[0026] Preferably, it is any one or more of ethylene glycol, 1,4-butanediol, 2-methyl-1,3-propanediol, 3,5-dimethylthiotoluenediamine, and 3,5-diethyltoluenediamine.

[0027] The molar ratio of isocyanate to active hydrogen in the raw materials of the present invention is 0.9 to 1.1, preferably 0.95 to 1.05.

[0028] A method for preparing a polyurethane elastomer for wind turbine blades includes the following steps:

[0029] S1: Hydroxydiol and polysiloxane are added to the reactor, heated to 100-130℃, vacuum dehydrated for 2-4 hours, then cooled to 50-60℃ and vacuuming is stopped. Diisocyanate and catalyst are added, the temperature is raised and controlled at 70-100℃, and the reaction time is 2-4 hours to obtain the first prepolymer.

[0030] S2: Cool the first prepolymer to 60-80℃, add a silane coupling agent, and react for 1-2 hours to obtain the second prepolymer;

[0031] S3: Add the small molecule chain extender to the second prepolymer, stir evenly and degas under vacuum to obtain a polyurethane mixture;

[0032] S4: Pour the polyurethane mixture into a mold for curing. After it is completely cured, place it at room temperature to obtain the polyurethane elastomer.

[0033] In a preferred embodiment of the present invention, the vacuum degree in steps S1 and S3 is -0.085 to -0.1 MPa.

[0034] In a preferred embodiment of the present invention, the stirring speed in step S3 is 1000-2000 r / min, and the stirring time is 2-5 min.

[0035] In a preferred embodiment of the present invention, the curing temperature in step S4 is 80-120°C and the curing time is 4-24 hours.

[0036] In a preferred embodiment of the present invention, the polyurethane elastomer has a tensile strength ≥30MPa, an elongation at break ≥700%, and a surface contact angle with water of 100-120°.

[0037] An application of a polyurethane elastomer for wind turbine blades, wherein the application is for manufacturing a protective film, the protective film being an outdoor protective film against sand and rain environments.

[0038] It is preferred for use in the leading edge structure of wind turbine blades as a protective film against sand and rain environments.

[0039] The beneficial effects of this invention are as follows:

[0040] First, the polyurethane elastomer provided by the present invention has a tensile strength ≥30MPa, an elongation at break ≥700%, and a surface contact angle with water of 100-120°.

[0041] Secondly, the polyurethane elastomer provided by the present invention effectively improves the hydrolysis resistance of the polyurethane elastomer by selecting polyether polyols or polycarbonate polyols with excellent hydrolysis resistance.

[0042] Third, the polyurethane elastomer provided by this invention has high bulk strength and excellent elongation because the inventors of this invention have selected appropriate types and amounts of isocyanate, hydroxy polyol and small molecule chain extender through extensive research.

[0043] Fourth, the polyurethane elastomer provided by the present invention effectively improves the hydrophobicity and anti-stick properties of the polyurethane elastomer by selecting high molecular weight linear polysiloxane and silane coupling agent and introducing organosilicon with extremely low surface energy (the range of extremely low surface energy is 20-25 mN / m).

[0044] Fifth, the raw materials used in this invention are free of solvents and fluorine, making them safe and environmentally friendly. Detailed Implementation

[0045] The preferred embodiments of the present invention will be described in detail below so that the advantages and features of the present invention can be better understood by those skilled in the art.

[0046] Example 1:

[0047] This embodiment provides a polyurethane elastomer for wind turbine blades, the raw materials of which are as follows:

[0048] Component A:

[0049] Polytetrahydrofuran ether PTMEG1000 70g;

[0050] AEAPS2000 amino silicone oil 5g;

[0051] HMDI isocyanate 35g;

[0052] Catalyst T12 0.05g;

[0053] Coupling agent KH792 1g.

[0054] Component B:

[0055] Chain extender 1,4-butanediol 5g.

[0056] The preparation method of the above-mentioned polyurethane elastomer includes the following steps:

[0057] S1: PTMEG1000 and AEAPS2000 are added to the reactor, heated to about 115°C, vacuum dehydrated for 2 hours with a vacuum degree of -0.1MPa, then cooled to 55°C and vacuuming is stopped. HMDI and T12 are added, the temperature is raised and controlled at 100°C, and the reaction time is 4 hours to obtain the first prepolymer.

[0058] S2: Cool the first prepolymer to 80℃, add KH792, and react for 2 hours to obtain the second prepolymer;

[0059] S3: Add 1,4-butanediol to the second prepolymer, stir evenly and remove bubbles under vacuum. The stirring speed is 1000 r / min, the stirring time is 5 min, and the vacuum degree is -0.1 MPa to obtain a polyurethane mixture.

[0060] S4: Pour the polyurethane mixture into a mold at 100°C and cure for 12 hours, then place it at room temperature to obtain the polyurethane elastomer.

[0061] Example 2:

[0062] This embodiment provides a polyurethane elastomer for wind turbine blades, the raw materials of which are as follows:

[0063] Component A:

[0064] Polytetrahydrofuran ether PTMEG2000 90g;

[0065] Amino silicone oil AEAPS1000 10g;

[0066] HDI isocyanate 18.5g;

[0067] Catalyst T12 0.05g;

[0068] Coupling agent KH550 2g.

[0069] Component B:

[0070] Chain extender 1,4-butanediol 5g.

[0071] The preparation method of the above-mentioned polyurethane elastomer includes the following steps:

[0072] S1: PTMEG2000 and AEAPS1000 are added to the reactor, heated to about 115°C, vacuum dehydrated for 2 hours with a vacuum degree of -0.1MPa, then cooled to 55°C and vacuuming is stopped. HDI and T12 are added, the temperature is raised and controlled at 90°C, and the reaction time is 3 hours to obtain the first prepolymer.

[0073] S2: Cool the first prepolymer to 70℃, add KH550, and react for 2 hours to obtain the second prepolymer;

[0074] S3: Add 1,4-butanediol to the second prepolymer, stir until homogeneous, and degas under vacuum. The stirring speed is 1000 r / min, the stirring time is 3 min, and the vacuum degree is -0.1 MPa to obtain a polyurethane mixture.

[0075] S4: Pour the polyurethane mixture into a mold at 100℃ and cure for 10 hours, then let it stand at room temperature to obtain the desired product.

[0076] The description of polyurethane elastomers.

[0077] Example 3:

[0078] This embodiment provides a polyurethane elastomer for wind turbine blades, the raw materials of which are as follows:

[0079] Component A:

[0080] Polytetrahydrofuran ether PTMEG3000 100g;

[0081] Amino silicone oil AEAPS1000 8g;

[0082] MDI isocyanate 25g;

[0083] Catalyst T12 0.05g;

[0084] Coupling agent KH550 2g.

[0085] Component B:

[0086] Chain extender E300 12g.

[0087] The preparation method of the above-mentioned polyurethane elastomer includes the following steps:

[0088] S1: PTMEG3000 and AEAPS1000 are added to the reactor, heated to about 115°C, vacuum dehydrated for 2 hours with a vacuum degree of -0.1MPa, then cooled to 55°C and vacuuming is stopped. MDI and T12 are added, the temperature is raised and controlled at 80°C, and the reaction time is 4 hours to obtain the first prepolymer.

[0089] S2: Cool the first prepolymer to 60℃, add KH550, and react for 2 hours to obtain the second prepolymer;

[0090] S3: Add E300 to the second prepolymer, stir evenly and degas under vacuum. The stirring speed is 1000 r / min, the stirring time is 5 min, and the vacuum degree is -0.1 MPa to obtain a polyurethane mixture.

[0091] S4: Pour the polyurethane mixture into a mold at 100°C and cure for 24 hours, then place it at room temperature to obtain the polyurethane elastomer.

[0092] Example 4:

[0093] This embodiment provides a polyurethane elastomer for wind turbine blades, the raw materials of which are as follows:

[0094] Component A:

[0095] Polycarbonate SYHP2000 90g;

[0096] Amino silicone oil AEAPS1000 10g;

[0097] HDI isocyanate 18.5g;

[0098] Catalyst T12 0.05g;

[0099] Coupling agent KH550 2g.

[0100] Component B:

[0101] Chain extender E100 10g.

[0102] The preparation method of the above-mentioned polyurethane elastomer includes the following steps:

[0103] S1: Add SYHP2000 and AEAPS1000 to the reactor, heat to about 115℃, dehydrate under vacuum for 2 hours with a vacuum degree of -0.1MPa, then cool down to 55℃ and stop vacuuming, add HDI and T12, heat up and control the reaction temperature at 90℃, and react for 3 hours to obtain the first prepolymer.

[0104] S2: Cool the first prepolymer to 70℃, add KH550, and react for 2 hours to obtain the second prepolymer;

[0105] S3: Add E100 to the second prepolymer, stir evenly and degas under vacuum. The stirring speed is 1000 r / min, the stirring time is 3 min, and the vacuum degree is -0.1 MPa to obtain a polyurethane mixture.

[0106] S4: Pour the polyurethane mixture into a mold at 100°C and cure for 12 hours, then place it at room temperature to obtain the polyurethane elastomer.

[0107] Comparative Example 1:

[0108] The difference between this comparative example and Example 1 is that amino silicone oil AEAPS2000 is not added.

[0109] Component A:

[0110] Polytetrahydrofuran ether PTMEG1000 72.5g;

[0111] HMDI isocyanate 35g;

[0112] Catalyst T12 0.05g;

[0113] Coupling agent KH792 1g.

[0114] Component B:

[0115] Chain extender 1,4-butanediol 5g.

[0116] The preparation method of the above-mentioned polyurethane elastomer includes the following steps:

[0117] S1: PTMEG1000 is added to the reactor, heated to about 115℃, vacuum dehydrated for 2 hours with a vacuum degree of -0.1MPa, then cooled to 55℃ and the vacuuming is stopped. HMDI and T12 are added, the temperature is raised and the reaction temperature is controlled at 100℃, and the reaction time is 4 hours to obtain the first prepolymer.

[0118] S2: Cool the first prepolymer to 80℃, add KH792, and react for 2 hours to obtain the second prepolymer;

[0119] S3: Add 1,4-butanediol to the second prepolymer, stir evenly and remove bubbles under vacuum. The stirring speed is 1000 r / min, the stirring time is 5 min, and the vacuum degree is -0.1 MPa to obtain a polyurethane mixture.

[0120] S4: Pour the polyurethane mixture into a mold at 100°C and cure for 12 hours, then place it at room temperature to obtain the polyurethane elastomer.

[0121] Comparative Example 2:

[0122] The difference between this comparative example and Example 3 is that it does not contain amino silicone oil AEAPS1000 and coupling agent KH550.

[0123] Component A:

[0124] Polytetrahydrofuran ether PTMEG3000 100g;

[0125] MDI isocyanate 25g;

[0126] Catalyst T12 0.05g.

[0127] Component B:

[0128] Chain extender E300 12g.

[0129] The preparation method of the above-mentioned polyurethane elastomer includes the following steps:

[0130] S1: PTMEG3000 is added to the reactor, heated to about 115℃, vacuum dehydrated for 2 hours with a vacuum degree of -0.1MPa, then cooled to 55℃ and the vacuuming is stopped. MDI and T12 are added, the temperature is raised and the reaction temperature is controlled at 80℃, and the reaction time is 4 hours to obtain the first prepolymer.

[0131] S2: Add E300 to the first prepolymer, stir evenly and degas under vacuum. The stirring speed is 1000 r / min, the stirring time is 5 min, and the vacuum degree is -0.1 MPa to obtain a polyurethane mixture.

[0132] S3: Pour the polyurethane mixture into a mold at 100°C and cure for 24 hours, then place it at room temperature to obtain the polyurethane elastomer.

[0133] Test results:

[0134] The polyurethane elastomer was tested using the following standard methods:

[0135] Tensile strength and elongation at break test methods: GB / T 528-2009;

[0136] Water contact angle: Deionized water was used. Water droplets were placed on the polyurethane elastomer and tested using a contact angle measuring instrument.

[0137] The test results of the polyurethane elastomers obtained in Examples 1-4 and Comparative Examples 1-2 are shown in Table 1:

[0138] Table 1

[0139]

[0140] As can be seen from the table above, the water contact angles of Examples 1-4 are all greater than 90°, indicating that the hydrophobic properties of the polyurethane materials in Examples 1-4 have been greatly improved.

[0141] However, the hydrophobic properties of Comparative Examples 1-2 are clearly defective.

[0142] In addition, judging from the tensile strength and elongation at break data, the polyurethane elastomer of the present invention has a tensile strength >30MPa and an elongation at break >700%, which far exceeds the mechanical properties of ordinary polyurethane elastomers.

[0143] Therefore, the polyurethane elastomer for wind turbine blades provided by this invention has excellent mechanical and hydrophobic properties, which can solve the problems of short protection period of current protective coatings and poor mechanical properties of conventional polyurethane elastomers.

[0144] This polyurethane elastic protective material can effectively reduce the pollution and corrosion of wind turbine blades by sand and rainwater during use. It has good hydrophobicity and antifouling properties and can meet the requirements of the entire life cycle operation without the need for replacement of the leading edge protection material.

[0145] The above description is merely an embodiment of the present invention, and the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the improved concept of the technical solution of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A polyurethane elastomer for wind turbine blades, characterized in that, It includes component A and component B, wherein the mass ratio of component A to component B is in the range of 5 to 25:1; Component A, by weight, includes the following components: 70-100 parts of hydroxydiol; 1-20 parts of polysiloxane; 15-45 parts of diisocyanate; Catalyst 0.01-0.5 parts; 1-10 parts of silane coupling agent; Component B, by weight, includes the following components: 5-20 parts of small molecule chain extender; The hydroxyl diol is one or more of polyether diols and polycarbonate diols, and the molecular weight of the hydroxyl diol is 650-3500 g / mol.

2. The polyurethane elastomer for wind turbine blades as described in claim 1, characterized in that, The polyether diol is one or more of polypropylene glycol and polytetrahydrofuran diol; The polycarbonate diol is one or more of polyhexanediol carbonate, polypentylene glycol carbonate, and polybutanediol carbonate; The polysiloxane is one or more of hydroxyalkyl-terminated linear polydimethylsiloxane or amino-terminated linear polydimethylsiloxane, and the molecular weight of the polysiloxane is 1000-3000 g / mol.

3. The polyurethane elastomer for wind turbine blades as described in claim 2, characterized in that, The polyether diol is polytetrahydrofuran ether PTMEG1000-3000; the polycarbonate diol is polycarbonate SYHP2000-3000; and the polysiloxane is amino-modified polysiloxane.

4. The polyurethane elastomer for wind turbine blades as described in claim 1, characterized in that, The diisocyanate is at least one of aliphatic diisocyanate, alicyclic diisocyanate or aromatic diisocyanate; The catalyst is one or more of dibutyltin diacetate, stannous octoate, and dibutyltin dilaurate; The silane coupling agent is any one or more of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane. The small molecule chain extender is any one or more of aliphatic small molecule chain extenders and aromatic small molecule chain extenders; The molar ratio of isocyanate to active hydrogen in the raw material is 0.9 to 1.

1.

5. The polyurethane elastomer for wind turbine blades as described in claim 4, characterized in that, The diisocyanate is at least one selected from toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, terephthalic diisocyanate, and naphthalene diisocyanate. The catalyst is one or more of dibutyltin diacetate, stannous octate, and dibutyltin dilaurate; The small molecule chain extender is any one or more of aliphatic small molecule chain extenders and aromatic small molecule chain extenders; The molar ratio of isocyanate to active hydrogen in the raw material is 0.95 to 1.

05.

6. The polyurethane elastomer for wind turbine blades as described in claim 5, characterized in that, The catalyst is catalyst T12 dibutyltin dilaurate.

7. A method for preparing a polyurethane elastomer for wind turbine blades according to any one of claims 1-6, characterized in that, Includes the following steps: S1: Hydroxydiol and polysiloxane are added to the reactor, heated to 100-130℃, vacuum dehydrated for 2-4 hours, then cooled to 50-60℃ and vacuuming is stopped. Diisocyanate and catalyst are added, the temperature is raised and controlled at 70-100℃, and the reaction time is 2-4 hours to obtain the first prepolymer. S2: Cool the first prepolymer to 60-80°C, add a silane coupling agent, and react for 1-2 hours to obtain the second prepolymer; S3: Add the small molecule chain extender to the second prepolymer, stir evenly and degas under vacuum to obtain a polyurethane mixture; S4: Pour the polyurethane mixture into a mold for curing. After it is completely cured, place it at room temperature to obtain the polyurethane elastomer. The polyurethane elastomer has a tensile strength ≥30MPa, an elongation at break ≥700%, and a surface contact angle with water of 100-120°.

8. The method for preparing a polyurethane elastomer for wind turbine blades as described in claim 7, characterized in that, The vacuum level in steps S1 and S3 is -0.085 to -0.1 MPa; The stirring speed in step S3 is 1000-2000 r / min, and the stirring time is 2-5 min; The curing temperature in step S4 is 80-120℃, and the curing time is 4-24h.

9. An application of a polyurethane elastomer for wind turbine blades as described in any one of claims 1-6, characterized in that, The application is for manufacturing protective films, which are outdoor protective films that resist sand and rain environments.

10. The application of the polyurethane elastomer for wind turbine blades as described in claim 9, characterized in that, The protective film is used in the leading edge structure of wind turbine blades to resist sand and rain environments.

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