Anti-biological erosion coating for wind turbine blades and preparation method thereof

Abstract

The present invention discloses an anti-biological erosion coating for wind turbine blades and a preparation method thereof. The preparation method uses two base materials, polyurethane and polyphosphazene, for compounding, wherein the polyurethane base material includes: diisocyanate, polyether diol, post-chain extender, hydrophilic chain extender, catalyst, neutralizer and solvent. The polyphosphazene base material includes: monomer raw materials, catalyst, promoter, solvent and detergent. The polyphosphazene base material has good light and heat stability, oxidation resistance, water resistance, solvent resistance, oil resistance, biological corrosion resistance, chemical resistance and the like. Compounding the polyurethane base material with the polyphosphazene base material can improve the anti-rain erosion performance of the leading edge of the wind turbine blade on the one hand, and enhance the anti-biological erosion performance of the leading edge of the wind turbine blade on the other hand, thereby extending the service life of the wind turbine blade.

Description

Technical Field

[0001] The invention belongs to the technical field of wind power generation, and in particular relates to an anti-biological erosion coating for wind power blades and a preparation method thereof. Background Art

[0002] Wind turbine blades are a key component of wind turbines. Blades need to work in different environments, and their performance is directly related to the power generation efficiency of the entire system. Depending on the installation location and the design of the blades, the impact of environmental factors on the corrosion of the leading edge varies greatly, but the factors that cause corrosion of the leading edge of wind turbine blades mainly include two aspects: 1) Erosion by particles in the air around the blades: including raindrops, hail, waves, salt spray, dust / sand and gravel 2) High-altitude flying insects and organisms in the wild.

[0003] Most domestic blade manufacturers use the method of coating the leading edge of the blade with a polyurethane film to protect the blade surface from rain erosion. However, polyurethane materials have disadvantages such as poor resistance to rain erosion, high and low temperature resistance, and weather resistance. In wind farms with harsh conditions, the leading edge protection material of the blade will fail after 3 to 5 years, leading to leading edge corrosion. Therefore, the development of leading edge protection materials with high protection, which can decompose the stress of rain impact and prevent biological erosion, is a problem that needs to be solved urgently. Summary of the invention

[0004] The purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art and provide an anti-biological corrosion coating for wind turbine blades and a preparation method thereof, so as to solve the problem in the prior art that the leading edge of wind turbine blades is easily corroded by rainwater.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] A method for preparing an anti-biological erosion coating for a wind turbine blade comprises the following steps:

[0007] Step 1, hexachlorocyclotriphosphazene, aminosulfonic acid, calcium sulfate dihydrate and a second solvent are placed in a container, nitrogen is introduced, and the mixture is heated and stirred for reaction, and after the reaction, the reaction liquid is used as a linear polydichlorophosphazene raw material, and the linear polydichlorophosphazene raw material is poured into a container containing a detergent, and the mixed liquid is stirred to obtain a linear polydichlorophosphazene base material;

[0008] Step 2, drying the polyether diol and placing it in a container, introducing nitrogen into the container and stirring, adding the prepared polyphosphazene base material, adding the first catalyst and diisocyanate and stirring, then adding the hydrophilic chain extender, stirring to obtain a process product, cooling the process product and adding a neutralizer to carry out a neutralization reaction, cooling the neutralization reaction product and adding a post-chain extender and a first solvent, and obtaining a polyurethane-polyphosphazene coating after the reaction;

[0009] The mass ratio of the linear polydichlorophosphazene raw material to the polyurethane base material is 1:(1-2.5), and the polyurethane base material comprises diisocyanate, polyether diol, post-chain extender, hydrophilic chain extender, a first catalyst, a neutralizer and a first solvent.

[0010] A further improvement of the present invention is:

[0011] Preferably, in the raw materials of the water-based aspartic acid ester polyurea base material, the mass proportion of diisocyanate is 20-25%, the mass proportion of polyether diol is 15-20%, the mass proportion of post-chain extender is 2.5-7.5%, the mass proportion of hydrophilic chain extender is 1-2%, the mass proportion of catalyst is 1-3.5%, the mass proportion of neutralizer is 1-3.5%, and the mass proportion of the first solvent is 50%.

[0012] Preferably, the diisocyanate is a mixture of any one or more of isophorone diisocyanate, hexamethylene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate; and the polyether diol is a mixture of one or more of polytetramethylene glycol, polyethylene glycol, and polypropylene glycol.

[0013] Preferably, the post-chain extender is sodium N-[(2-amino)-amino]ethane sulfonate; and the hydrophilic chain extender is one or a mixture of 2,2-dihydroxymethylpropionic acid and dihydroxymethylbutyric acid.

[0014] Preferably, the first catalyst is one or a mixture of dibutyltin dilaurate, stannous octoate, and dibutyltin oxide; the neutralizer is one or a mixture of triethylamine, tripropylamine, formic acid, acetic acid, and triethanolamine; and the first solvent is deionized water.

[0015] Preferably, in the raw materials of the linear polydichlorophosphazene base material, the mass proportion of hexachlorocyclotriphosphazene is 30-50%, the mass proportion of aminosulfonic acid is 3-5%, the mass proportion of calcium sulfate dihydrate is 0.2-0.6%, and the mass proportion of the second solvent is 40-45%.

[0016] Preferably, the second solvent is a mixture of one or more of 1,2,4-trichlorobenzene, tetrahydrofuran, dioxane, pyridine, ethanol, and acetone; the detergent is a mixture of one or more of n-heptane, deionized water, cyclohexane, petroleum ether, ethyl acetate, and dichloromethane.

[0017] Preferably, during the preparation of the linear polydichlorophosphazene base material, nitrogen is introduced, and the reaction is heated and stirred. After heating to 190° C., the nitrogen is turned off, the stirring speed is 100 to 200 r / min, and the stirring time is 1 to 1.5 h; based on heating and stirring, the stirring speed is 50 to 80 r / min, and the heating and stirring are stopped after heating to 200 to 210° C.

[0018] An anti-biological erosion coating prepared by any one of the preparation methods described above.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] The present invention discloses a method for preparing an anti-biological erosion coating for wind turbine blades. The method adopts two base materials, polyurethane and polyphosphazene, for compounding, wherein the polyurethane base material comprises: diisocyanate, polyether diol, post-chain extender, hydrophilic chain extender, catalyst, neutralizer and solvent. The hydrophilic chain extender makes the waterborne polyurethane base material have a certain hydrophilicity, and when raindrops wash onto the surface of the wind turbine blades, it plays a role in buffering and decomposing the impact force of raindrops; the waterborne polyurethane prepared by adding the post-chain extender has high stability, uniform emulsion dispersion, and can form a film quickly, and can effectively reduce the rain erosion hazard of the wetted surface. The polyphosphazene base material comprises: monomer raw materials, catalysts, promoters, solvents and detergents. The prepared polydichlorophosphazene not only has a P=N inorganic main chain, but also the two side groups (R1, R2) attached to each P atom can be organic groups with different characteristics (single or mixed), so as to have the characteristics of inorganic and organic polymers, and can play an anti-fouling role and produce a self-cleaning polishing effect through the continuous hydrolysis of organic chlorine in the molecular structure. Polyphosphazene base material has good light and heat stability, oxidation resistance, water resistance, solvent resistance, oil resistance, biological corrosion resistance, chemical resistance, etc. Compounding polyurethane base material with polyphosphazene base material can improve the anti-rain erosion performance of the leading edge of the fan blade on the one hand, and enhance the anti-biological erosion performance of the leading edge of the fan blade on the other hand, thereby extending the service life of the fan blade.

[0021] The present invention also discloses an anti-biological erosion coating for wind turbine blades, which is obtained by compounding two base materials, polyurethane and polyphosphazene, and is a coating material with rain erosion resistance, biocorrosion resistance, wear resistance and weather resistance. At the same time, corresponding preparation methods and applications are also provided. The preparation method is flexible and simple to operate and can be mass-produced. Among them, polyphosphazene, as one of the three types of inorganic polymers, has been vigorously developed in the field of protective coatings due to its good light and thermal stability, oxidation resistance, water resistance, solvent resistance, oil resistance, chemical resistance and good biocompatibility, radiation resistance, low temperature resistance and non-combustion. Therefore, polyurethane and polyphosphazene are compounded and sprayed on the leading edge of the fan blade, and the excellent flexibility of polyurethane can be used to disperse the stress generated during the raindrop impact process. The excellent biocorrosion resistance of polyphosphazene can effectively reduce the chemical corrosion caused by biocorrosion on the surface of the fan blade. The combination of the two significantly improves the anti-rain erosion performance, and the fan blade also has good biocorrosion resistance, wear resistance and weather resistance. The preparation method is simple, highly operable, and easy to promote on a large scale. DETAILED DESCRIPTION

[0022] The present invention is further described in detail below with reference to specific embodiments.

[0023] One of the embodiments of the present invention discloses an anti-biological corrosion coating for wind turbine blades, which includes two base materials, polyurethane and linear polydichlorophosphazene. The polyurethane base material includes: diisocyanate, polyether diol, post-chain extender, hydrophilic chain extender, first catalyst, neutralizer and first solvent. The linear polydichlorophosphazene raw material includes: monomer raw material, second catalyst, accelerator and second solvent. The ratio of polyphosphazene to polyurethane base material (the combined mass of diisocyanate, polyether diol, post-chain extender, hydrophilic chain extender, first catalyst, neutralizer and first solvent) is 1: (1-2.5).

[0024] The prepared polydichlorophosphazene not only has a P=N inorganic main chain, but also the two side groups (R1, R2) attached to each P atom can be organic groups with different characteristics (single or mixed), so it has the characteristics of inorganic and organic polymers. Through the continuous hydrolysis of organic chlorine in the molecular structure, it can play an anti-fouling role and produce a self-cleaning polishing effect. The polyphosphazene base material has good light and thermal stability, oxidation resistance, water resistance, solvent resistance, oil resistance, bio-corrosion resistance, chemical resistance and other characteristics. Compounding the polyurethane base material with the polyphosphazene base material can improve the anti-rain erosion performance of the leading edge of the fan blade on the one hand, and enhance the anti-bio-corrosion performance of the leading edge of the fan blade on the other hand, and extend the service life of the fan blade.

[0025] Specifically, the diisocyanate is a mixture of any one or more of isophorone diisocyanate (IPDI), hexamethylene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate, and the mass content thereof is 20-25% of the polyurethane base material;

[0026] Specifically, the polyether diol is a mixture of one or more of polytetramethylene glycol (PTMG), polyethylene glycol, and polypropylene glycol, and its mass content is 15-20% of the polyurethane base material;

[0027] Specifically, the post-chain extender in the polyurethane base material is sodium N-[(2-amino)-amino]ethane sulfonate (AAS), and its mass content is 2.5 to 7.5% of the polyurethane base material;

[0028] Specifically, the hydrophilic chain extender in the polyurethane base material is one or a mixture of 2,2-dimethylol propionic acid (DMPA) and dimethylol butyric acid, and its mass content is 1-2% of the polyurethane base material;

[0029] Specifically, the catalyst in the polyurethane base material is one or more of dibutyltin dilaurate (DBTDL), stannous octoate, and dibutyltin oxide, and its mass content is 1 to 3.5% of the polyurethane base material;

[0030] Specifically, the neutralizing agent in the polyurethane base material is one or more of triethylamine (TEA), tripropylamine, formic acid, acetic acid, and triethanolamine, and its mass content is 0.5-2% of the polyurethane base material.

[0031] Specifically, the first solvent in the polyurethane base material is deionized water, and its mass content is 50% of the polyurethane base material.

[0032] The raw materials of linear polydichlorophosphazene include: monomer raw material, second catalyst, promoter and second solvent. Among them, the monomer raw material is hexachlorocyclotriphosphazene (HCCP), and its mass content is 30-50%.

[0033] Specifically, the second catalyst in the polyphosphazene base material is aminosulfonic acid, and its mass content is 3-5%.

[0034] Specifically, the accelerator in the polyphosphazene base material is calcium sulfate dihydrate, and its mass content is 0.2-0.6%.

[0035] Specifically, the second solvent in the polyphosphazene base material is one or more of 1,2,4-trichlorobenzene, tetrahydrofuran, dioxane, pyridine, ethanol, and acetone, and its mass content is 44.4-66.8%. 。

[0036] Specifically, the detergent in the polyphosphazene base material is one or more of n-heptane, deionized water, cyclohexane, petroleum ether, ethyl acetate, and dichloromethane, and the amount of the detergent used is the remainder of the other raw materials.

[0037] One embodiment of the present invention discloses a method for preparing a polyurethane-ceramic composite coating, comprising the following steps:

[0038] (1) Weigh the monomer raw material, the second catalyst, the accelerator and the second solvent according to the above proportions and place them in a three-necked flask. Place the detergent in a dry beaker.

[0039] (2) Place the three-necked flask in step (1) in a constant temperature heating magnetic stirrer, introduce nitrogen, start stirring, slowly heat to 190°C, and then turn off the nitrogen. The stirring condition is 100-200 r / min for 1-1.5 h.

[0040] (3) Continue to slowly heat the three-necked flask in step (2) until the temperature reaches 200-210° C., then stop heating and stirring. The stirring condition is 50-80 r / min for 1-1.5 h.

[0041] (4) Pour the reaction solution in the three-necked flask after stopping heating in step (3) into the beaker containing detergent in step (1), place the beaker in a magnetic stirrer, stir at a speed of 20 to 30 r / min, and stir for 1 to 1.5 h to obtain a linear polydichlorophosphazene base material.

[0042] (5) Weigh diisocyanate, polyether diol, hydrophilic chain extender, neutralizer, catalyst, post-chain extender and deionized water according to the set ratio.

[0043] (6) Weigh the linear polydiphosphazene base material in step (4) according to the set ratio and place it in a constant pressure titration funnel.

[0044] (7) Dry the weighed polyether diol at 110°C for 5 h.

[0045] (8) The polyether diol dried in step (7) was added to a three-necked round-bottom flask, nitrogen was introduced into the flask, and stirring was started at 350 r / min for 20 min.

[0046] (9) Open the titration funnel in step (6) and add the linear polydiphosphazene base material to the three-necked flask in step (8) at a uniform rate for 0.5 to 1 h.

[0047] (10) Add the weighed first catalyst and diisocyanate to the flask of step (9), start stirring, and the stirring conditions are: 350 r / min, 88° C., 30 to 60 min;

[0048] (11) Add the weighed hydrophilic chain extender to the flask in step (10) and start stirring at 350 r / min, 80° C., for 2 to 3 h;

[0049] (12) The reaction product of step (11) is cooled to 50° C., and a weighed neutralizing agent is added to carry out a neutralization reaction for 30 to 40 minutes.

[0050] (13) The reaction product of step (12) is cooled to 35° C., and the weighed post-chain extender and deionized water are added, and stirring is started at 900 r / min for 30 to 40 min to finally obtain a polyurethane-polyphosphazene composite coating.

[0051] Example 1

[0052] (1) Weigh hexachlorocyclotriphosphazene, aminosulfonic acid, calcium sulfate dihydrate and 1,2,4-trichlorobenzene respectively, with the mass contents of 40%, 4%, 0.4% and 55.6% respectively, and place them in a three-necked flask. Place n-heptane in a dry beaker.

[0053] (2) Place the three-necked flask in step (1) in a constant temperature heating magnetic stirrer, introduce nitrogen, start stirring, slowly heat to 190°C, and then turn off the nitrogen. The stirring condition is 150 r / min for 1 h.

[0054] (3) Continue to slowly heat the three-necked flask in step (2) until the temperature reaches 205°C, then stop heating and stirring at a stirring speed of 70 r / min.

[0055] (4) Pour the reaction solution in the three-necked flask after stopping heating in step (3) into the beaker containing detergent in step (1), and place the beaker in a magnetic stirrer at 20 r / min for 1 h, thereby obtaining a linear polydichlorophosphazene base material.

[0056] (5) Weigh isophorone diisocyanate (IPDI), polytetramethylene glycol (PTMG), 2,2-dihydroxymethyl propionic acid (DMPA), triethylamine (TEA), dibutyltin dilaurate (DBTDL), sodium N-[(2-amino)-amino]ethane sulfonate (AAS) and deionized water, and the mass contents of each are 25%, 15%, 1%, 1.5%, 1.5%, 6% and 50%, respectively.

[0057] (6) Weigh the linear polydiphosphazene base material in step (4) according to the above ratio and place it in a constant pressure titration funnel, and the ratio of polyphosphazene to polyurethane raw materials (the combined mass of diisocyanate, polyether diol, post-chain extender, hydrophilic chain extender, first catalyst, neutralizer and first solvent) is 1:1.

[0058] (7) Dry the weighed polytetrahydrofuran diol at 110° C. for 5 h.

[0059] (8) taking out the dried polytetrahydrofuran diol in step (2) and adding it in three mouthfuls of round-bottomed flasks, nitrogen was passed through the flask, and stirring was opened, and stirring condition was: 350r / min, 20min.

[0060] (9) Open the titration funnel in step (6) and add the linear polydiphosphazene base material to the three-necked flask in step (8) at a uniform rate for 0.5 h.

[0061] (10) Add weighed dibutyltin dilaurate (DBTDL) and isophorone diisocyanate (IPDI) into the flask of step (9), start stirring, and the stirring conditions are: 350 r / min, 88° C., 30 to 60 min;

[0062] (11) Add the weighed 2,2-dihydroxymethylpropionic acid (DMPA) into the flask of step (10) and start stirring. The stirring conditions are: 350 r / min, 80° C., 2 to 3 h;

[0063] (12) The reaction product of step (11) was cooled to 50° C., and weighed triethylamine (TEA) was added to carry out a neutralization reaction for 30 min.

[0064] (13) The reaction product of step (12) is cooled to 35° C., and weighed sodium N-[(2-amino)-amino]ethane sulfonate (AAS) and deionized water are added, and stirring is started at 900 r / min for 30 to 40 min to finally obtain a polyurethane-polyphosphazene composite coating.

[0065] Example 2

[0066] (1) Weigh hexachlorocyclotriphosphazene, aminosulfonic acid, calcium sulfate dihydrate and 1,2,4-trichlorobenzene respectively.

[0067] The mass contents thereof are 30%, 3%, 0.2% and 66.8% respectively and are placed in a three-necked flask, and n-heptane is placed in a dry beaker.

[0068] (2) The three-necked flask in step (1) was placed in a constant temperature heating magnetic stirrer, nitrogen was introduced, stirring was started, and the mixture was slowly heated to 190° C., and then the nitrogen was turned off. The stirring condition was 100 r / min and the time was 1.5 h.

[0069] (3) Continue to slowly heat the three-necked flask in step (2) until the temperature reaches 200° C., then stop heating and stirring at 50 r / min.

[0070] (4) Pour the reaction solution in the three-necked flask after stopping heating in step (3) into the beaker containing n-heptane in step (1), place the beaker in a magnetic stirrer, start stirring until the dark brown mixture in the beaker turns into a light brown elastomer, and then stop stirring at 20 r / min, thereby obtaining a linear polydichlorophosphazene base material.

[0071] (5) Weigh isophorone diisocyanate (IPDI), polytetramethylene glycol (PTMG),

[0072] 2,2-Dihydroxymethylpropionic acid (DMPA), triethylamine (TEA), dibutyltin dilaurate (DBTDL), sodium N-[(2-amino)-amino]ethane sulfonate (AAS) and deionized water, with the mass contents of each being 20%, 15%, 2%, 2%, 3.5%, 7.5% and 50%, respectively.

[0073] (6) Weigh the linear polydiphosphazene base material in step (4) according to the above ratio and place it in a constant pressure titration funnel, and the ratio of polyphosphazene to polyurethane raw materials (combined mass of diisocyanate, polyether diol, post-chain extender, hydrophilic chain extender, first catalyst, neutralizer and first solvent) is 1:1.5.

[0074] (7) Dry the weighed polytetrahydrofuran diol at 110° C. for 5 h.

[0075] (8) taking out the dried polytetrahydrofuran diol in step (2) and adding it in three mouthfuls of round-bottomed flasks, nitrogen was passed through the flask, and stirring was opened, and stirring condition was: 350r / min, 20min.

[0076] (9) Open the titration funnel in step (6) and add the linear polydiphosphazene base material to step (8) at a uniform rate.

[0077] In the three-necked flask, the time is 1h.

[0078] (10) Add weighed dibutyltin dilaurate (DBTDL) and isophorone diisocyanate (IPDI) into the flask of step (3), and start stirring at 350 r / min.

[0079] 88℃, 60min;

[0080] (11) Add the weighed 2,2-dihydroxymethylpropionic acid (DMPA) into the flask of step (10) and start stirring. The stirring conditions are: 350 r / min, 80° C., 3 h;

[0081] (12) The reaction product of step (11) was cooled to 50° C., and weighed triethylamine (TEA) was added to carry out a neutralization reaction for 40 min.

[0082] (13) The reaction product of step (12) was cooled to 35° C., and weighed sodium N-[(2-amino)-amino]ethane sulfonate (AAS) and deionized water were added, and stirring was started at 900 r / min for 40 min to finally obtain a polyurethane-polyphosphazene composite coating.

[0083] Example 3

[0084] (1) Weigh hexachlorocyclotriphosphazene, aminosulfonic acid, calcium sulfate dihydrate and 1,2,4-trichlorobenzene according to the above proportions and place them in a three-necked flask. The mass contents are 50%, 5%, 0.6%, and 1,2,4-trichlorobenzene, respectively.

[0085] 44.4%, place n-heptane in a dry beaker.

[0086] (2) The three-necked flask in step (1) was placed in a constant temperature heating magnetic stirrer, nitrogen was introduced, stirring was started, and the mixture was slowly heated to 190° C., and then the nitrogen was turned off. The stirring condition was 200 r / min and the time was 1.5 h.

[0087] (3) Continue to slowly heat the three-necked flask in step (2) until the temperature reaches 210°C and then stop heating and stirring. The stirring condition is 80 r / min for 1.5 h.

[0088] (4) Pour the reaction solution in the three-necked flask after stopping heating in step (3) into the beaker containing n-heptane in step (1), place the beaker in a magnetic stirrer, start stirring until the dark brown mixture in the beaker turns into a light brown elastomer, and then stop stirring at 30 r / min, thereby obtaining a linear polydichlorophosphazene base material.

[0089] (5) Weigh isophorone diisocyanate (IPDI), polytetramethylene glycol (PTMG),

[0090] 2,2-Dihydroxymethylpropionic acid (DMPA), triethylamine (TEA), dibutyltin dilaurate (DBTDL), sodium N-[(2-amino)-amino]ethane sulfonate (AAS) and deionized water, with the mass contents of 25%, 20%, 1%, 0.5%, 1%, 2.5% and 50%, respectively.

[0091] (6) Weigh the linear polydiphosphazene base material in step (4) according to the above ratio and place it in a constant pressure titration funnel, and the ratio of polyphosphazene to polyurethane raw materials (combined mass of diisocyanate, polyether diol, post-chain extender, hydrophilic chain extender, first catalyst, neutralizer and first solvent) is 1:2.5.

[0092] (7) Dry the weighed polytetrahydrofuran diol at 110° C. for 5 h.

[0093] (8) taking out the dried polytetrahydrofuran diol in step (2) and adding it in three mouthfuls of round-bottomed flasks, nitrogen was passed through the flask, and stirring was opened, and stirring condition was: 350r / min, 20min.

[0094] (9) Open the titration funnel in step (6) and add the linear polydiphosphazene base material to step (8) at a uniform rate.

[0095] In the three-necked flask, the time is 1h.

[0096] (10) Add weighed dibutyltin dilaurate (DBTDL) and isophorone diisocyanate (IPDI) into the flask of step (9), and start stirring at 350 r / min.

[0097] 88°C, 30min;

[0098] (11) Add the weighed 2,2-dihydroxymethylpropionic acid (DMPA) into the flask of step (10) and start stirring. The stirring conditions are: 350 r / min, 80° C., 2 h;

[0099] (12) The reaction product of step (11) was cooled to 50° C., and weighed triethylamine (TEA) was added to carry out a neutralization reaction for 30 min.

[0100] (13) The reaction product of step (12) was cooled to 35° C., and weighed sodium N-[(2-amino)-amino]ethane sulfonate (AAS) and deionized water were added, and stirring was started at 900 r / min for 30 min to finally obtain a polyurethane-polyphosphazene composite coating.

[0101] Example 4

[0102] (1) Hexachlorocyclotriphosphazene, aminosulfonic acid, calcium sulfate dihydrate and tetrahydrofuran are weighed in the above proportions and placed in a three-necked flask. The mass contents are 35%, 4%, 0.3% and 60.7% respectively. Tetrahydrofuran is placed in a dry beaker.

[0103] (2) The three-necked flask in step (1) was placed in a constant temperature heating magnetic stirrer, nitrogen was introduced, stirring was started, and the mixture was slowly heated to 190° C., and then the nitrogen was turned off. The stirring condition was 120 r / min, and the time was 1.2 h.

[0104] (3) Continue to slowly heat the three-necked flask in step (2) until the temperature reaches 208°C, then stop heating and stirring at a stirring speed of 60 r / min.

[0105] (4) Pour the reaction solution in the three-necked flask after stopping heating in step (3) into the beaker containing tetrahydrofuran in step (1), and place the beaker in a magnetic stirrer at a stirring condition of 30 r / min.

[0106] Thus, a linear polydichlorophosphazene base material is obtained.

[0107] (5) Hexamethylene diisocyanate, polyethylene glycol, 2,2-dihydroxymethylpropionic acid (DMPA), formic acid, dibutyltin dilaurate (DBTDL), sodium N-[(2-amino)-amino]ethane sulfonate (AAS) and deionized water were weighed respectively, and the mass contents of each were 22%, 18%, 1.5%, 1.2%, 2%, 5.3% and 50%, respectively.

[0108] (6) Weigh the linear polydiphosphazene base material in step (4) according to the above ratio and place it in a constant pressure titration funnel, and the ratio of polyphosphazene to polyurethane raw materials (combined mass of diisocyanate, polyether diol, post-chain extender, hydrophilic chain extender, first catalyst, neutralizer and first solvent) is 1:2.5.

[0109] (7) Dry the weighed polyethylene glycol at 110°C for 5 h.

[0110] (8) Take out the polyethylene glycol diol dried in step (2) and add it into a three-necked round-bottom flask, introduce nitrogen into the flask, and start stirring. The stirring conditions are: 350 r / min, 20 min.

[0111] (9) Open the titration funnel in step (6) and add the linear polydiphosphazene base material to step (8) at a uniform rate.

[0112] In the three-necked flask, the time is 1h.

[0113] (10) Add weighed dibutyltin dilaurate (DBTDL) and hexamethylene diisocyanate into the flask of step (9), and start stirring at 350 r / min and 88° C.

[0114] 30min;

[0115] (11) Add the weighed 2,2-dihydroxymethylpropionic acid (DMPA) into the flask of step (10) and start stirring. The stirring conditions are: 350 r / min, 80° C., 2 h;

[0116] (12) The reaction product of step (11) was cooled to 50° C., and weighed formic acid was added to carry out a neutralization reaction for 30 min.

[0117] (13) The reaction product of step (12) was cooled to 35° C., and weighed sodium N-[(2-amino)-amino]ethane sulfonate (AAS) and deionized water were added, and stirring was started at 900 r / min for 30 min to finally obtain a polyurethane-polyphosphazene composite coating.

[0118] Example 5

[0119] (1) Hexachlorocyclotriphosphazene, aminosulfonic acid, calcium sulfate dihydrate and dioxane were weighed in the above proportions and placed in a three-necked flask. Their mass contents were 45%, 4%, 0.55% and 40.45% respectively. Dioxane was placed in a dry beaker.

[0120] (2) The three-necked flask in step (1) was placed in a constant temperature heating magnetic stirrer, nitrogen was introduced, stirring was started, and the mixture was slowly heated to 190° C., and then the nitrogen was turned off. The stirring condition was 200 r / min and the time was 1.5 h.

[0121] (3) Continue to slowly heat the three-necked flask in step (2) until the temperature reaches 210°C and then stop heating and stirring. The stirring condition is 80 r / min for 1.5 h.

[0122] (4) Pour the reaction solution in the three-necked flask after stopping heating in step (3) into the beaker containing dioxane in step (1), place the beaker in a magnetic stirrer, and start stirring at 30 r / min, thereby obtaining a linear polydichlorophosphazene base material.

[0123] (5) Weigh 4,4'-dicyclohexylmethane diisocyanate, polypropylene glycol, dimethylolbutyric acid, tripropylamine, stannous octoate, sodium N-[(2-amino)-amino]ethane sulfonate (AAS), and deionized water, respectively, with the mass contents of each being 23%, 17%, 1%, 1.8%, 2.5%, 4.7%, and 50%, respectively.

[0124] (6) Weigh the linear polydiphosphazene base material in step (4) according to the above ratio and place it in a constant pressure titration funnel, and the ratio of polyphosphazene to polyurethane raw materials (combined mass of diisocyanate, polyether diol, post-chain extender, hydrophilic chain extender, first catalyst, neutralizer and first solvent) is 1:2.5.

[0125] (7) Dry the weighed polypropylene glycol at 110°C for 5 h.

[0126] (8) The polypropylene glycol dried in step (2) was added to a three-necked round-bottom flask, nitrogen was introduced into the flask, and stirring was started at 350 r / min for 20 min.

[0127] (9) Open the titration funnel in step (6) and add the linear polydiphosphazene base material to step (8) at a uniform rate.

[0128] In the three-necked flask, the time is 1h.

[0129] (10) Add the weighed stannous octoate and 4,4'-dicyclohexylmethane diisocyanate to the mixture in step (9)

[0130] In a flask, start stirring, stirring conditions: 350r / min, 88℃, 30min;

[0131] (11) Add the weighed dimethylolbutyric acid into the flask of step (10) and start stirring. The stirring conditions are: 350 r / min, 80° C., 2 h;

[0132] (12) The reaction product of step (11) was cooled to 50° C., and weighed triethylamine (TEA) was added to carry out a neutralization reaction for 30 min.

[0133] (13) The reaction product of step (12) was cooled to 35° C., and weighed sodium N-[(2-amino)-amino]ethane sulfonate (AAS) and deionized water were added, and stirring was started at 900 r / min for 30 min to finally obtain a polyurethane-polyphosphazene composite coating.

[0134] Example 6

[0135] (1) Hexachlorocyclotriphosphazene, aminosulfonic acid, calcium sulfate dihydrate and pyridine are weighed in the above proportions and placed in a three-necked flask. The mass contents are 50%, 5%, 0.6% and 44.4% respectively. Pyridine is placed in a dry beaker.

[0136] (2) The three-necked flask in step (1) was placed in a constant temperature heating magnetic stirrer, nitrogen was introduced, stirring was started, and the mixture was slowly heated to 190° C., and then the nitrogen was turned off. The stirring condition was 200 r / min and the time was 1.5 h.

[0137] (3) Continue to slowly heat the three-necked flask in step (2) until the temperature reaches 210°C and then stop heating and stirring. The stirring condition is 80 r / min for 1.5 h.

[0138] (4) Pour the reaction solution in the three-necked flask after stopping heating in step (3) into the beaker containing pyridine in step (1), place the beaker in a magnetic stirrer, and start stirring at 30 r / min, thereby obtaining a linear polydichlorophosphazene base material.

[0139] (5) Hexamethylene diisocyanate, polyethylene glycol, 2,2-dihydroxymethylpropionic acid (DMPA), acetic acid, dibutyltin oxide, sodium N-[(2-amino)-amino]ethane sulfonate (AAS), and deionized water were weighed respectively, with the mass contents of each being 25%, 20%, 1%, 0.5%, 1%, 2.5%, and 50%, respectively.

[0140] (6) Weigh the linear polydiphosphazene base material in step (4) according to the above ratio and place it in a constant pressure titration funnel, and the ratio of polyphosphazene to polyurethane raw materials (combined mass of diisocyanate, polyether diol, post-chain extender, hydrophilic chain extender, first catalyst, neutralizer and first solvent) is 1:2.5.

[0141] (7) Dry the weighed polytetrahydrofuran diol at 110° C. for 5 h.

[0142] (8) taking out the dried polytetrahydrofuran diol in step (2) and adding it in three mouthfuls of round-bottomed flasks, nitrogen was passed through the flask, and stirring was opened, and stirring condition was: 350r / min, 20min.

[0143] (9) Open the titration funnel in step (6) and add the linear polydiphosphazene base material to step (8) at a uniform rate.

[0144] In the three-necked flask, the time is 1h.

[0145] (10) Add the weighed dibutyltin oxide and isophorone diisocyanate (IPDI) into the flask of step (9), start stirring, and the stirring conditions are: 350 r / min, 88° C., 30 min;

[0146] (11) Add the weighed 2,2-dihydroxymethylpropionic acid (DMPA) into the flask of step (10) and start stirring. The stirring conditions are: 350 r / min, 80° C., 2 h;

[0147] (12) The reaction product of step (11) was cooled to 50° C., and weighed triethylamine (TEA) was added to carry out a neutralization reaction for 30 min.

[0148] (13) The reaction product of step (12) was cooled to 35° C., and weighed sodium N-[(2-amino)-amino]ethane sulfonate (AAS) and deionized water were added, and stirring was started at 900 r / min for 30 min to finally obtain a polyurethane-polyphosphazene composite coating.

[0149] Example 7

[0150] (1) Hexachlorocyclotriphosphazene, aminosulfonic acid, calcium sulfate dihydrate and ethanol are weighed in the above proportions and placed in a three-necked flask. The mass contents are 50%, 5%, 0.6% and 44.4% respectively. Ethanol is placed in a dry beaker.

[0151] (2) The three-necked flask in step (1) was placed in a constant temperature heating magnetic stirrer, nitrogen was introduced, stirring was started, and the mixture was slowly heated to 190° C., and then the nitrogen was turned off. The stirring condition was 200 r / min and the time was 1.5 h.

[0152] (3) Continue to slowly heat the three-necked flask in step (2) until the temperature reaches 210°C and then stop heating and stirring. The stirring condition is 80 r / min for 1.5 h.

[0153] (4) Pour the reaction solution in the three-necked flask after stopping heating in step (3) into the beaker containing ethanol in step (1), place the beaker in a magnetic stirrer, and start stirring at 30 r / min, thereby obtaining a linear polydichlorophosphazene base material.

[0154] (5) Weigh 4,4'-dicyclohexylmethane diisocyanate, polypropylene glycol, dimethylolbutyric acid, triethanolamine, dibutyltin dilaurate (DBTDL), sodium N-[(2-amino)-amino]ethane sulfonate (AAS), and deionized water, respectively, with the mass contents of each being 25%, 20%, 1%, 0.5%, 1%, 2.5%, and 50%, respectively.

[0155] (6) Weigh the linear polydiphosphazene base material in step (4) according to the above ratio and place it in a constant pressure titration funnel, and the ratio of polyphosphazene to polyurethane raw materials (combined mass of diisocyanate, polyether diol, post-chain extender, hydrophilic chain extender, first catalyst, neutralizer and first solvent) is 1:2.5.

[0156] (7) Dry the weighed polytetrahydrofuran diol at 110° C. for 5 h.

[0157] (8) taking out the dried polytetrahydrofuran diol in step (2) and adding it in three mouthfuls of round-bottomed flasks, nitrogen was passed through the flask, and stirring was opened, and stirring condition was: 350r / min, 20min.

[0158] (9) Open the titration funnel in step (6) and add the linear polydiphosphazene base material to step (8) at a uniform rate.

[0159] In the three-necked flask, the time is 1h.

[0160] (10) Add weighed dibutyltin dilaurate (DBTDL) and isophorone diisocyanate (IPDI) into the flask of step (9), and start stirring at 350 r / min.

[0161] 88°C, 30min;

[0162] (11) Add the weighed 2,2-dihydroxymethylpropionic acid (DMPA) into the flask of step (10) and start stirring. The stirring conditions are: 350 r / min, 80° C., 2 h;

[0163] (12) The reaction product of step (11) was cooled to 50° C., and weighed triethylamine (TEA) was added to carry out a neutralization reaction for 30 min.

[0164] (13) The reaction product of step (12) was cooled to 35° C., and weighed sodium N-[(2-amino)-amino]ethane sulfonate (AAS) and deionized water were added, and stirring was started. The stirring conditions were:

[0165] 900r / min, 30min, finally the polyurethane-polyphosphazene composite coating was obtained.

[0166] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing an anti-biological erosion coating for wind turbine blades, characterized in that: The following steps are involved: Step 1, hexachlorocyclotriphosphazene, aminosulfonic acid, calcium sulfate dihydrate and a second solvent are placed in a container, nitrogen is introduced, and then heated and stirred for reaction, wherein the reaction liquid obtained after the reaction is a linear polydichlorophosphazene raw material, the linear polydichlorophosphazene raw material is poured into a container containing a detergent, and the mixed liquid is stirred to obtain a linear polydichlorophosphazene base material; Step 2, drying the polyether diol and placing it in a container, introducing nitrogen into the container and stirring, adding the prepared linear polydichlorophosphazene base material, adding the first catalyst and diisocyanate and stirring, then adding the hydrophilic chain extender, stirring to obtain a process product, cooling the process product and adding a neutralizer to carry out a neutralization reaction, cooling the neutralization reaction product and adding a post-chain extender and a first solvent, and reacting to obtain a polyurethane-polyphosphazene coating; The mass ratio of the linear polydichlorophosphazene raw material to the polyurethane base material is 1:(1-2.5), and the polyurethane base material includes diisocyanate, polyether diol, post-chain extender, hydrophilic chain extender, first catalyst, neutralizer and first solvent; In the linear polydichlorophosphazene raw material, the mass proportion of hexachlorocyclotriphosphazene is 30-50%, the mass proportion of aminosulfonic acid is 3-5%, the mass proportion of calcium sulfate dihydrate is 0.2-0.6%, the mass proportion of the second solvent is 40-45%, and the mass proportion of each raw material in the linear polydichlorophosphazene raw material is 100%; Among the raw materials of the polyurethane base material, the mass proportion of diisocyanate is 20~25%, the mass proportion of polyether diol is 15~20%, the mass proportion of post-chain extender is 2.5~7.5%, the mass proportion of hydrophilic chain extender is 1~2%, the mass proportion of catalyst is 1~3.5%, the mass proportion of neutralizer is 1~3.5%, and the mass proportion of the first solvent is 50%.

2. The method for preparing an anti-biological erosion coating for wind turbine blades according to claim 1, characterized in that: The diisocyanate is a mixture of any one or more of isophorone diisocyanate, hexamethylene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate; and the polyether diol is a mixture of any one or more of polytetramethylene glycol, polyethylene glycol, and polypropylene glycol.

3. The method for preparing an anti-biological erosion coating for wind turbine blades according to claim 1, characterized in that: The post-chain extender is sodium N-[(2-amino)-amino]ethane sulfonate; the hydrophilic chain extender is one or a mixture of 2,2-dihydroxymethylpropionic acid and dihydroxymethylbutyric acid.

4. The method for preparing an anti-biological erosion coating for wind turbine blades according to claim 1, characterized in that: The first catalyst is one or a mixture of dibutyltin dilaurate, stannous octoate, and dibutyltin oxide; the neutralizer is one or a mixture of triethylamine, tripropylamine, formic acid, acetic acid, and triethanolamine; and the first solvent is deionized water.

5. The method for preparing an anti-biological erosion coating for wind turbine blades according to claim 1, characterized in that: The second solvent is a mixture of one or more of 1,2,4-trichlorobenzene, tetrahydrofuran, dioxane, pyridine, ethanol, and acetone; the detergent is a mixture of one or more of n-heptane, deionized water, cyclohexane, petroleum ether, ethyl acetate, and dichloromethane.

6. The method for preparing an anti-biological erosion coating for wind turbine blades according to claim 1, characterized in that: During the preparation of the linear polydichlorophosphazene base material, after nitrogen is introduced, the reaction is heated and stirred. After heating to 190°C, the nitrogen is turned off, the stirring speed is 100~200r / min, and the stirring time is 1~1.5h; based on heating and stirring, the stirring speed is 50~80r / min, and the heating and stirring are stopped after heating to 200~210°C.

7. An anti-biological erosion coating prepared by the preparation method according to any one of claims 1 to 6.