A kind of organic silicon modified polyurethane compound rubber for wind turbine blade leading edge protection and preparation method thereof

Abstract

The present invention belongs to the field of new materials, and specifically relates to a silicone-modified polyurethane compound for protecting the leading edge of a wind turbine blade and a preparation method thereof. The Si-O-Si structure in the terminal hydroxyl silicone oil prepared by the present invention firstly gives the material excellent weather resistance and low surface energy; the phenyl group of the side group can increase the polarity of the polysiloxane, thereby improving its compatibility with the polyurethane raw rubber; the vinyl group of the side group can undergo a cross-linking reaction with the polyurethane rubber in the presence of a peroxide vulcanizer, further improving the compatibility of the silicone with the polyurethane; the terminal group is a hydroxyl hydrocarbon group, which can react with isocyanate; secondly, the polar urethane bond in the prepared raw rubber can further enhance the compatibility with the polyurethane raw rubber; finally, the silicone-modified polyurethane compound obtained by blending has excellent mechanical properties, hydrophobicity and UV resistance.

Description

Technical Field

[0001] The invention belongs to the field of new materials, and specifically relates to an organosilicon-modified polyurethane compound rubber for protecting the leading edge of a wind turbine blade and a preparation method thereof. Background Art

[0002] As a clean and renewable energy source, wind energy has received widespread attention worldwide and has great application potential. my country has large wind energy reserves and wide distribution, but most of the wind farms are located in harsh environments such as the northwest with strong winds and sand, the northeast with high cold, and the east China coastal areas with high salt fog. They are often subject to atmospheric corrosion, ultraviolet rays, sand and dust, lightning, rainstorms, ice and snow erosion. In order to make wind power equipment produce higher benefits, it is necessary to protect the surface of the wind turbine blades. The traditional protection method is generally to apply a layer of protective coating on the leading edge of the blade to protect it from external erosion and increase the service life of the wind turbine.

[0003] With the rapid development of wind turbine blade technology, wind turbine blades are getting longer and longer, and their blade tip speeds are getting faster and faster. The performance of traditional protective coatings is increasingly unable to meet the needs of new blade leading edge protection. Polyurethane rubber has excellent mechanical strength, wear resistance, flexibility, impact resistance, salt spray resistance, and moisture and heat resistance. In recent years, it has been increasingly used to replace traditional coatings as a protective material for blade leading edge protection. However, due to its own molecular structure characteristics, polyurethane rubber has poor anti-icing and UV resistance. Wind farms are often built on cold mountains or at sea. At low temperatures, the icing phenomenon of blades becomes more and more prominent, and the ultraviolet radiation on mountains and sea is also stronger. Therefore, how to improve the anti-icing and UV resistance of polyurethane rubber is the focus of current research.

[0004] There are no unsaturated bonds in the main chain structure of silicone rubber molecules, and the bond energy of the silicon-oxygen bond is greater than the bond energy of the carbon-carbon single bond. Therefore, the silicon-oxygen-silicon bond is very stable to ozone and ultraviolet rays, and has excellent weather resistance. In addition, silicone has a low surface energy and very good hydrophobic properties, which can effectively prevent water from freezing on the surface of the material at low temperatures. Since the polarity of polyurethane and silicone is too different, their compatibility is also very poor. It is often difficult to vulcanize and mold polyurethane raw rubber and silicone raw rubber simply. Even if they are molded, the performance is very poor. Therefore, it is of great significance to combine polyurethane and silicone and use their respective characteristics to develop a rubber that has both the excellent mechanical properties and wear resistance of polyurethane and the excellent UV resistance and hydrophobicity of silicone.

[0005] Therefore, based on this, the technical solution of the present invention is proposed. Summary of the invention

[0006] In order to solve the problems existing in the prior art, the present invention provides a method for preparing a silicone-modified polyurethane compound for protecting the leading edge of a wind turbine blade, the preparation method comprising the following steps:

[0007] (I) Preparation of hydroxyl-terminated silicone oil:

[0008] (I-1) mixing a dimethylsiloxane ring body, a phenylsiloxane ring body, tetramethyltetravinylcyclotetrasiloxane and a capping agent and heating the mixture to obtain a premix;

[0009] (I-2) adding a first catalyst to the premix to react, then adding a neutralizing agent to make the pH of the system neutral, and finally filtering and removing low-boiling substances by reduced pressure distillation to obtain a hydroxy-terminated silicone oil;

[0010] (II) Preparation of silicone-modified polyurethane raw rubber:

[0011] Dehydrating the terminal hydroxyl silicone oil, and then mixing and aging with diisocyanate and a second catalyst to obtain a silicone-modified polyurethane raw rubber (in the form of a colorless to light yellow transparent viscous liquid or semisolid);

[0012] (III) Preparation of silicone-modified polyurethane compound:

[0013] The organosilicon-modified polyurethane raw rubber and polyurethane raw rubber are plasticized, and then fillers, stearic acid, crosslinking agent, antioxidant, ultraviolet absorber, polycarbodiimide and vulcanizing agent are added in sequence for vulcanization to obtain the organosilicon-modified polyurethane mixed rubber.

[0014] Preferably, in step (I), the dimethylsiloxane ring body is one of octamethylcyclotetrasiloxane and dimethylsiloxane mixed ring body DMC;

[0015] And / or, the phenylsiloxane ring body is one of tetramethyltetraphenylcyclotetrasiloxane, methylphenylsiloxane mixed ring body, and octaphenylcyclotetrasiloxane;

[0016] and / or, the end-capping agent is one of 1,3-bis(3-hydroxypropyl)-1,1,3,3-tetramethyldisiloxane and 1,3-bis(4-hydroxybutyl)-1,1,3,3-tetramethyldisiloxane;

[0017] And / or, the first catalyst is one of concentrated sulfuric acid, trifluoromethanesulfonic acid, acidic clay, and acidic ion exchange resin;

[0018] And / or, the neutralizing agent is one of potassium carbonate, sodium carbonate, potassium bicarbonate, and sodium bicarbonate.

[0019] Preferably, in step (I), the mass ratio of the dimethylsiloxane ring body, the phenylsiloxane ring body, the tetramethyltetravinylcyclotetrasiloxane, the first catalyst, the end-capping agent, and the neutralizing agent is: 60-90:10-40:0.01-2:0.5-20:5-20:2-20.

[0020] Preferably, in step (I-1), the heating is performed to 30-60°C;

[0021] And / or, in step (I-2), the reaction is carried out for 3 to 10 hours.

[0022] Preferably, in step (II), the terminal hydroxyl silicone oil is heated to 110° C. under stirring, dehydrated at a vacuum of 50 mbar for 1 to 3 hours, then N2 is introduced to normal pressure and the temperature is lowered to 60 to 80° C., and then diisocyanate and a second catalyst are added, stirred at 60 to 100° C. for 1 to 2 minutes, and finally aged at 80 to 120° C. for 2 to 4 hours to obtain a silicone-modified polyurethane raw rubber.

[0023] Preferably, in step (II), the mass ratio of the terminal hydroxyl silicone oil, the diisocyanate, and the second catalyst is: 60-90:10-40:0-0.1;

[0024] And / or, the diisocyanate is one or a combination of two or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, and 1,4-dicyclohexylmethane diisocyanate;

[0025] And / or, the second catalyst is one or a combination of two or more of dibutyltin dilaurate, stannous octoate, and an organic bismuth catalyst.

[0026] Preferably, in step (III), the organosilicon-modified polyurethane raw rubber and polyurethane raw rubber are added on a double-roll rubber mixer for plasticization, and then filler, stearic acid, crosslinking agent, antioxidant, ultraviolet absorber, polycarbodiimide and vulcanizing agent are added in sequence. After being thinned for 5 times, the sheet is unrolled and vulcanized on a flat vulcanizing press at a vulcanization condition of 170°C×5MPa×10min to obtain an organosilicon-modified polyurethane mixed rubber.

[0027] Preferably, in step (III), the mass ratio of the organosilicon-modified polyurethane rubber, polyurethane rubber, filler, stearic acid, crosslinking agent, antioxidant, ultraviolet absorber, polycarbodiimide and vulcanizing agent is:

[0028] 30~70:30~70:5~30:0.3~1:0~1:0.2~1:1~5:1~3:1.5~4.

[0029] Preferably, in step (III), the polyurethane raw rubber is mainly MDI type polyurethane raw rubber, which can be MDI / polyether type polyurethane raw rubber or MDI / polyester type polyurethane raw rubber, because the methylene groups between MDI molecules can be crosslinked by vulcanization. More specifically, it can be one or a combination of two or more of MDI / polytetrahydrofuran polyurethane raw rubber, MDI / polypropylene oxide polyurethane raw rubber, MDI / polyethylene oxide polyurethane raw rubber, MDI / polyethylene adipate polyurethane raw rubber, MDI / polybutylene adipate polyurethane raw rubber, MDI / polyethylene adipate raw rubber, and MDI / polycaprolactone raw rubber;

[0030] And / or, the filler is one or a combination of two or more of nano titanium dioxide, nano zinc oxide, fumed silica, polytetrafluoroethylene powder, and nano calcium carbonate;

[0031] And / or, the cross-linking agent is one or a combination of two or more of triallyl isocyanurate, trimethylolpropane trimethacrylate, glycerol trimethacrylate, and pentaerythritol trimethacrylate;

[0032] and / or, the antioxidant is one or a combination of two or more of antioxidant 1010, antioxidant 168, antioxidant 245, antioxidant 1035, antioxidant 1076, antioxidant 5057, antioxidant 1135, and antioxidant 1024;

[0033] And / or, the ultraviolet absorber is one or a combination of two or more of UV-1, UV-320, UV-328, UV-1130, UV-234, light stabilizer 292, light stabilizer 622, and light stabilizer 770;

[0034] And / or, the vulcanizing agent is one of cumene peroxide, tert-butyl cumene peroxide, benzoyl peroxide, and dodecyl peroxide.

[0035] Based on the same technical concept, the present invention further provides a silicone-modified polyurethane compound for protecting the leading edge of a wind turbine blade obtained by the above preparation method.

[0036] To facilitate understanding of the present invention, the present invention is explained more intuitively:

[0037] (I) When preparing hydroxy-terminated silicone oil, the synthetic route is as follows Figure 1 As shown, when Figure 1 When d=3, the corresponding compound is 1,3-bis(3-hydroxypropyl)-1,1,3,3-tetramethyldisiloxane; Figure 1 When d=4, the corresponding compound is 1,3-bis(4-hydroxybutyl)-1,1,3,3-tetramethyldisiloxane.

[0038] (ii) When preparing silicone-modified polyurethane raw rubber, the synthetic route is as follows: Figure 2 As shown, Figure 2 R represents an alkyl group; the values ​​of a, b, c, d, and m can be: a is 3 to 100, b is 1 to 10, c is 1 to 4, d is 3 or 4, and m is 1 to 100.

[0039] The beneficial effects of the present invention are:

[0040] The preparation method of the present invention first prepares a polysiloxane with a Si-O-Si structure as the main chain and a hydroxyl hydrocarbon group as the terminal group (i.e., terminal hydroxyl silicone oil), wherein the Si-O-Si structure of the main chain gives the material excellent weather resistance and low surface energy; the phenyl group of the side group can improve the polarity of the polysiloxane, thereby improving its compatibility with polyurethane rubber; the vinyl group of the side group can undergo a cross-linking reaction with polyurethane rubber in the presence of a peroxide vulcanizer, thereby further improving the compatibility of the organosilicon with polyurethane; the terminal group is a hydroxyl hydrocarbon group, which can react with isocyanate; secondly, the organosilicon-modified polyurethane rubber with a hydroxyl terminal group is reacted with diisocyanate to generate a organosilicon-modified polyurethane rubber with a hydroxyl terminal group, wherein the polar urethane bond can further enhance the compatibility with the polyurethane rubber; and finally, the organosilicon-modified polyurethane mixed rubber obtained by blending has excellent mechanical properties, hydrophobicity and UV resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0042] Figure 1 This is a synthetic route diagram for preparing terminal hydroxyl silicone oil.

[0043] Figure 2 It is a synthetic route diagram for preparing silicone-modified polyurethane raw rubber. DETAILED DESCRIPTION

[0044] To make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be described in detail below. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other implementation methods obtained by ordinary technicians in this field without creative work belong to the scope of protection of the present invention.

[0045] Example 1

[0046] This embodiment provides a method for preparing terminal hydroxyl silicone oil, and the details of each raw material are shown in Table 1.

[0047] Table 1

[0048]

[0049] The preparation method is as follows: octamethylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane and 1,3-bis(3-hydroxypropyl)-1,1,3,3-tetramethyldisiloxane are added to a reaction kettle, heated to 45°C, and then trifluoromethanesulfonic acid is added to carry out a balancing reaction for 8 hours, sodium bicarbonate is added to make the pH of the system neutral, and low-boiling substances are removed by filtering and distillation under reduced pressure to obtain terminal hydroxyl silicone oil.

[0050] Example 2

[0051] This embodiment provides a method for preparing terminal hydroxyl silicone oil, and the details of each raw material are shown in Table 2.

[0052] Table 2

[0053]

[0054] The preparation method is as follows: add a dimethylsiloxane mixed ring body, a methylphenylsiloxane mixed ring body, tetramethyltetravinylcyclotetrasiloxane and 1,3-bis(3-hydroxypropyl)-1,1,3,3-tetramethyldisiloxane into a reaction kettle, heat to 50°C, then add trifluoromethanesulfonic acid, carry out equilibration reaction for 7 hours, add sodium carbonate to make the pH of the system neutral, filter, and remove low-boiling substances by reduced pressure distillation to obtain terminal hydroxyl silicone oil.

[0055] Example 3

[0056] This embodiment provides a method for preparing terminal hydroxyl silicone oil, and the details of each raw material are shown in Table 3.

[0057] Table 3

[0058]

[0059] The preparation method is as follows: add a dimethylsiloxane mixed ring body, octaphenylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane and 1,3-bis(3-hydroxypropyl)-1,1,3,3-tetramethyldisiloxane into a reaction kettle, heat to 40°C, then add concentrated sulfuric acid, carry out equilibration reaction for 10 hours, add sodium bicarbonate to make the pH of the system neutral, filter, and remove low-boiling substances by reduced pressure distillation to obtain terminal hydroxyl silicone oil.

[0060] Example 4

[0061] This embodiment provides a method for preparing terminal hydroxyl silicone oil, and the details of each raw material are shown in Table 4.

[0062] Table 4

[0063]

[0064] The preparation method is as follows: octamethylcyclotetrasiloxane, methylphenylsiloxane mixed ring body, tetramethyltetravinylcyclotetrasiloxane and 1,3-bis(3-hydroxypropyl)-1,1,3,3-tetramethyldisiloxane are added into a reaction kettle, heated to 55°C, then acidic white clay is added, and a balancing reaction is carried out for 6 hours. Low boiling substances are removed by filtering and reduced pressure distillation to obtain terminal hydroxyl silicone oil.

[0065] Example 5

[0066] This embodiment provides a method for preparing a silicone-modified polyurethane raw rubber. The details of each raw material are shown in Table 5.

[0067] Table 5

[0068]

[0069] The preparation method is as follows: add the silicone oil of Example 1 into a four-mouth reaction vessel with an open lid, heat it to 110°C under mechanical stirring, and remove water for 1 hour at a vacuum of 50 mbar; pass N2 to normal pressure, cool it to 60°C, then add toluene diisocyanate and dibutyltin dilaurate, and stir rapidly for 2 minutes at 80°C; then pour it into a tray and mature it at 80°C for 4 hours to obtain a silicone-modified polyurethane raw rubber in a light yellow transparent semi-solid state.

[0070] Example 6

[0071] This embodiment provides a method for preparing a silicone-modified polyurethane raw rubber. The details of each raw material are shown in Table 6.

[0072] Table 6

[0073]

[0074] The preparation method is as follows: add the silicone oil of Example 2 to a four-mouth reaction vessel with an open lid, heat it to 110°C under mechanical stirring, and remove water for 2 hours at a vacuum of 50 mbar; pass N2 to normal pressure, cool it to 70°C, then add diphenylmethane diisocyanate, and stir rapidly for 1 minute at 60°C; then pour it into a tray and mature it at 120°C for 2 hours to obtain a silicone-modified polyurethane raw rubber in a colorless, transparent, semi-solid state.

[0075] Example 7

[0076] This embodiment provides a method for preparing a silicone-modified polyurethane raw rubber. The details of each raw material are shown in Table 7.

[0077] Table 7

[0078]

[0079] The preparation method is as follows: add the silicone oil of Example 3 to a four-mouth reaction vessel with an open lid, heat it to 110°C under mechanical stirring, and remove water for 3 hours at a vacuum of 50 mbar; pass N2 to normal pressure, cool it to 80°C, then add diphenylmethane diisocyanate, and stir rapidly at 90°C for 1 minute; then pour it into a tray and mature it at 100°C for 3 hours to obtain a silicone-modified polyurethane raw rubber in the form of a colorless, transparent, viscous liquid.

[0080] Example 8

[0081] This embodiment provides a method for preparing a silicone-modified polyurethane raw rubber. The details of each raw material are shown in Table 8.

[0082] Table 8

[0083]

[0084] The preparation method is as follows: add the silicone oil of Example 4 to a four-mouth reaction vessel with an open lid, heat the vessel to 110°C under mechanical stirring, and remove water for 3 hours at a vacuum of 50 mbar; pass N2 to normal pressure, cool the vessel to 80°C, then add isophorone diisocyanate, and stir rapidly at 90°C for 1 minute; then pour the vessel into a tray and mature at 100°C for 3 hours to obtain a silicone-modified polyurethane raw rubber in a colorless, transparent, semi-solid state.

[0085] Example 9

[0086] This embodiment provides a method for preparing a silicone-modified polyurethane compound rubber. Details of the raw materials are shown in Table 9.

[0087] Table 9

[0088]

[0089] The preparation method is as follows: the organosilicon-modified polyurethane raw rubber obtained in Example 5 and the MDI type polyurethane raw rubber (molecular weight 30,000) are added to a double-roll rubber mixer for plasticizing, and then R974, stearic acid, triallyl isocyanurate, antioxidant 1010, light stabilizer 292, polycarbodiimide and isopropylbenzene peroxide are added in sequence, and the sheet is removed after being thinned through 5 times, and vulcanized on a flat vulcanizer under the vulcanization conditions of 170°C×5MPa×10min. After the vulcanization is completed, the organosilicon-modified polyurethane mixed rubber is obtained, and the performance test can be subsequently performed.

[0090] Example 10

[0091] This embodiment provides a method for preparing a silicone-modified polyurethane compound rubber. Details of the raw materials are shown in Table 10.

[0092] Table 10

[0093]

[0094] The preparation method is as follows: the organosilicon-modified polyurethane raw rubber obtained in Example 6 and the MDI type polyurethane raw rubber (molecular weight 30,000) are added to a double-roll rubber mixer for plasticizing, and then R974, stearic acid, triallyl isocyanurate, antioxidant 1010, light stabilizer 292, polycarbodiimide and isopropylbenzene peroxide are added in sequence, and the sheet is removed after being thinned through 5 times, and vulcanized on a flat vulcanizer under the vulcanization conditions of 170°C×5MPa×10min. After the vulcanization is completed, the organosilicon-modified polyurethane mixed rubber is obtained, and the performance test can be subsequently performed.

[0095] Embodiment 11

[0096] This embodiment provides a method for preparing a silicone-modified polyurethane compound rubber. Details of the raw materials are shown in Table 11.

[0097] Table 11

[0098]

[0099] The preparation method is as follows: the organosilicon-modified polyurethane raw rubber obtained in Example 6 and the MDI type polyurethane raw rubber (molecular weight 30,000) are added to a double-roll rubber mixer for plasticizing, and then R974, stearic acid, triallyl isocyanurate, antioxidant 1010, light stabilizer 292, polycarbodiimide and isopropylbenzene peroxide are added in sequence, and the sheet is removed after being thinned through 5 times, and vulcanized on a flat vulcanizer under the vulcanization conditions of 170°C×5MPa×10min. After the vulcanization is completed, the organosilicon-modified polyurethane mixed rubber is obtained, and the performance test can be subsequently performed.

[0100] Example 12

[0101] This embodiment provides a method for preparing a silicone-modified polyurethane compound rubber. Details of the raw materials are shown in Table 12.

[0102] Table 12

[0103]

[0104] The preparation method is as follows: the organosilicon-modified polyurethane raw rubber obtained in Example 6 and the MDI type polyurethane raw rubber (molecular weight 30,000) are added to a double-roll rubber mixer for plasticizing, and then R974, stearic acid, triallyl isocyanurate, antioxidant 1010, light stabilizer 292, polycarbodiimide and isopropylbenzene peroxide are added in sequence, and the sheet is removed after being thinned through 5 times, and vulcanized on a flat vulcanizer under the vulcanization conditions of 170°C×5MPa×10min. After the vulcanization is completed, the organosilicon-modified polyurethane mixed rubber is obtained, and the performance test can be subsequently performed.

[0105] Example 13

[0106] This embodiment provides a method for preparing a silicone-modified polyurethane compound rubber. Details of the raw materials are shown in Table 13.

[0107] Table 13

[0108]

[0109] The preparation method is as follows: the organosilicon-modified polyurethane raw rubber obtained in Example 8 and MDI type polyurethane raw rubber (molecular weight 30,000) are added to a double-roll rubber mixer for plasticizing, and then R974, stearic acid, triallyl isocyanurate, antioxidant 1010, light stabilizer 292, polycarbodiimide and isopropylbenzene peroxide are added in sequence, and the sheet is removed after being thinned through 5 times, and vulcanized on a flat vulcanizer under the vulcanization conditions of 170°C×5MPa×10min. After the vulcanization is completed, the organosilicon-modified polyurethane mixed rubber is obtained, and the performance test can be subsequently performed.

[0110] Comparative Example 1

[0111] This comparative example provides a method for preparing a polyurethane compound rubber, and the details of each raw material are shown in Table 14.

[0112] Table 14

[0113]

[0114] The preparation method is as follows: add MDI type polyurethane raw rubber (molecular weight 30,000) on a double-roll rubber mixer for plasticization, and then add R974, stearic acid, triallyl isocyanurate, antioxidant 1010, light stabilizer 292, polycarbodiimide and isopropylbenzene peroxide in sequence, pass through it 5 times and then take it off the sheet, vulcanize it on a flat vulcanizer, and the vulcanization conditions are 170°C×5MPa×10min. After the vulcanization is completed, the polyurethane mixed rubber is obtained, and then the performance test can be carried out.

[0115] Verification Example

[0116] The products obtained from Examples 9 to 13 and Comparative Example 1 were tested, and their performances are shown in Table 15.

[0117] Table 15

[0118]

[0119] Table 15 (Continued)

[0120]

[0121] As shown in Table 15, the organosilicon-modified polyurethane rubber of the present invention is not added to Comparative Example 1, while organosilicon-modified polyurethane rubber is added to Examples 9 to 13. It can be seen that after adding the organosilicon-modified polyurethane rubber, its tensile strength is slightly reduced, and the elongation at break and abrasion change little; however, the water contact angle is significantly increased from 82° to 115°, and it can be seen from Examples 10, 11 and 12 that with the increase in the amount of organosilicon-modified polyurethane rubber added, the water contact angle of the mixed rubber gradually increases, indicating that after the organosilicon-modified polyurethane rubber is introduced into the polyurethane mixed rubber, its hydrophobicity is significantly enhanced. From the tensile strength retention rate after ultraviolet aging, after adding the organosilicon-modified polyurethane rubber, the tensile strength retention rate after aging is greatly improved, from 68.4% to 93.6%, and with the increase in the organosilicon content, its strength retention rate after ultraviolet aging will also increase, indicating that after the organosilicon-modified polyurethane rubber is introduced into the polyurethane mixed rubber, its anti-ultraviolet ability is significantly enhanced.

[0122] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed by the present invention, which should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A method for preparing a silicone-modified polyurethane compound for protecting the leading edge of a wind turbine blade, characterized in that: The preparation method comprises the following steps: (I) Preparation of hydroxyl-terminated silicone oil: (I-1) mixing a dimethylsiloxane ring body, a phenylsiloxane ring body, tetramethyltetravinylcyclotetrasiloxane and a capping agent and heating the mixture to obtain a premix; (I-2) adding a first catalyst to the premix to react, then adding a neutralizing agent to make the pH of the system neutral, and finally filtering and removing low-boiling substances by reduced pressure distillation to obtain a hydroxy-terminated silicone oil; Wherein: the dimethylsiloxane ring body is one of octamethylcyclotetrasiloxane and dimethylsiloxane mixed ring body DMC; And / or, the phenylsiloxane ring body is one of tetramethyltetraphenylcyclotetrasiloxane, methylphenylsiloxane mixed ring body, and octaphenylcyclotetrasiloxane; and / or, the end-capping agent is one of 1,3-bis(3-hydroxypropyl)-1,1,3,3-tetramethyldisiloxane and 1,3-bis(4-hydroxybutyl)-1,1,3,3-tetramethyldisiloxane; And / or, the first catalyst is one of concentrated sulfuric acid, trifluoromethanesulfonic acid, acidic clay, and acidic ion exchange resin; And / or, the neutralizing agent is one of potassium carbonate, sodium carbonate, potassium bicarbonate, and sodium bicarbonate; The mass ratio of dimethylsiloxane ring body, phenylsiloxane ring body, tetramethyltetravinylcyclotetrasiloxane, the first catalyst, the end-capping agent, and the neutralizing agent is: 60-90:10-40:0.01-2:0.5-20:5-20:2-20; (II) Preparation of silicone-modified polyurethane raw rubber: Dehydrating the terminal hydroxyl silicone oil, and then mixing and aging with diisocyanate and a second catalyst to obtain a silicone-modified polyurethane raw rubber; (III) Preparation of silicone-modified polyurethane compound: The organosilicon-modified polyurethane raw rubber and polyurethane raw rubber are plasticized, and then fillers, stearic acid, crosslinking agent, antioxidant, ultraviolet absorber, polycarbodiimide and vulcanizing agent are added in sequence for vulcanization to obtain the organosilicon-modified polyurethane mixed rubber.

2. The preparation method according to claim 1, characterized in that: In step (I-1), the heating is to 30-60°C; And / or, in step (I-2), the reaction is carried out for 3 to 10 hours.

3. The preparation method according to claim 1, characterized in that: In step (II), the terminal hydroxyl silicone oil is heated to 110° C. under stirring, dehydrated at a vacuum of 50 mbar for 1 to 3 hours, then N2 is introduced to normal pressure and the temperature is lowered to 60 to 80° C., and then diisocyanate and a second catalyst are added, stirred at 60 to 100° C. for 1 to 2 minutes, and finally aged at 80 to 120° C. for 2 to 4 hours to obtain a silicone-modified polyurethane raw rubber.

4. The preparation method according to claim 1, characterized in that: In step (II), the mass ratio of the terminal hydroxyl silicone oil, the diisocyanate, and the second catalyst is: 60-90:10-40:0-0.1; And / or, the diisocyanate is one or a combination of two or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, and 1,4-dicyclohexylmethane diisocyanate; And / or, the second catalyst is one or a combination of two or more of dibutyltin dilaurate, stannous octoate, and an organic bismuth catalyst.

5. The preparation method according to claim 1, characterized in that: In step (III), the organosilicon-modified polyurethane raw rubber and polyurethane raw rubber are added to a double-roll rubber mixer for plasticization, and then fillers, stearic acid, crosslinking agents, antioxidants, ultraviolet absorbers, polycarbodiimide and vulcanizing agents are added in sequence. After being thinned for 5 times, the sheets are unrolled and vulcanized on a flat vulcanizing press at a vulcanization condition of 170° C.×5 MPa×10 min to obtain an organosilicon-modified polyurethane mixed rubber.

6. The preparation method according to claim 1, characterized in that: In step (III), the mass ratio of the organosilicon-modified polyurethane rubber, polyurethane rubber, filler, stearic acid, crosslinking agent, antioxidant, ultraviolet absorber, polycarbodiimide and vulcanizing agent is: 30~70:30~70:5~30:0.3~1:0~1:0.2~1:1~5:1~3:1.5~4.

7. The preparation method according to claim 1, characterized in that: In step (III), the polyurethane raw rubber is one or a combination of two or more of MDI / polytetrahydrofuran polyurethane raw rubber, MDI / polypropylene oxide polyurethane raw rubber, MDI / polyethylene oxide polyurethane raw rubber, MDI / polyethylene adipate polyurethane raw rubber, MDI / polybutylene adipate polyurethane raw rubber, MDI / polyethylene adipate raw rubber, and MDI / polycaprolactone raw rubber; And / or, the filler is one or a combination of two or more of nano titanium dioxide, nano zinc oxide, fumed silica, polytetrafluoroethylene powder, and nano calcium carbonate; And / or, the cross-linking agent is one or a combination of two or more of triallyl isocyanurate, trimethylolpropane trimethacrylate, glycerol trimethacrylate, and pentaerythritol trimethacrylate; and / or, the antioxidant is one or a combination of two or more of antioxidant 1010, antioxidant 168, antioxidant 245, antioxidant 1035, antioxidant 1076, antioxidant 5057, antioxidant 1135, and antioxidant 1024; And / or, the ultraviolet absorber is one or a combination of two or more of UV-1, UV-320, UV-328, UV-1130, UV-234, light stabilizer 292, light stabilizer 622, and light stabilizer 770; And / or, the vulcanizing agent is one of cumene peroxide, tert-butyl cumene peroxide, benzoyl peroxide, and dodecyl peroxide.

8. The organosilicon-modified polyurethane compound for protecting the leading edge of a wind turbine blade obtained by the preparation method according to any one of claims 1 to 7.

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