Composite asparaginic acid ester resin, asparaginic acid polyurea coating composition and application of composite asparaginic acid ester resin and asparaginic acid polyurea coating composition to wind turbine blades

Abstract

The invention provides composite asparaginic acid ester resin, an asparaginic acid polyurea coating composition and application of the asparaginic acid polyurea coating composition to wind turbine blades, and relates to the technical field of asparaginic acid polyurea. The composite aspartic acid ester resin is prepared from aspartic acid ester resin and aspartic acid ester modified graphene oxide, the aspartic acid ester modified graphene oxide is double-end aspartic acid ester polysiloxane modified graphene oxide; the double-end aspartate polysiloxane is a product obtained by carrying out a Michael addition reaction on double-end amino polysiloxane and maleate. The composite asparaginic acid ester resin is adopted in the asparaginic acid polyurea coating composition, the characteristics of graphene oxide can be exerted, and the corrosion resistance, weather resistance, high and low temperature resistance and other performance of an asparaginic acid polyurea coating are improved.

Description

Technical Field

[0001] The invention belongs to the technical field of aspartic acid ester resin and aspartic acid polyurea coating composition and the application of the aspartic acid polyurea coating composition on wind turbine blades. Background Art

[0002] Wind power generation is a clean energy source. Wind turbines are usually deployed on mountains or at sea, where the wind is strong and the sunshine is abundant and strong. Moreover, if they are at sea or near the sea, they also need to withstand high temperature, high humidity and high salt environment. Therefore, wind turbine blades need better protection. At present, the main way to protect wind turbine blades is to apply protective coatings on their surfaces, mainly polyurethane protective coatings, polyurea protective coatings and silicone-fluorine protective coatings. Polyurethane protective coatings have better adhesion, but poor weather resistance. Silicone-fluorine protective coatings have better weather resistance and hydrophobicity, but poor adhesion. Polyurea protective coatings have better adhesion and weather resistance, and better impact resistance.

[0003] Graphene is a layered nanomaterial that can be added to coatings to improve the coating's protective and anti-corrosion properties. Chinese patent CN107987274A discloses an asparagine polyurea anti-corrosion coating, which is grafted onto polyaspartic acid ester resin by subjecting aminosilane-modified graphene oxide and dibasic primary amine to Michael addition reaction with maleate, thereby improving the dispersion of graphene oxide in the coating, improving the hardness, wear resistance and weather resistance of the coating, and improving the antistatic and anti-corrosion properties of the coating film.

[0004] The applicant believes that the above method can be further improved to further enhance the anti-corrosion performance of the aspartame polyurea coating. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides a composite aspartic acid ester resin, aspartic acid polyurea coating composition and application thereof on wind turbine blades.

[0006] The technical solution of the present invention is as follows:

[0007] A composite aspartic acid ester resin, consisting of aspartic acid ester resin and aspartic acid ester modified graphene oxide;

[0008] The aspartic acid ester modified graphene oxide is double-terminated aspartic acid ester polysiloxane modified graphene oxide;

[0009] The double-terminal aspartic acid ester polysiloxane is a product of Michael addition reaction between double-terminal amino polysiloxane and maleate.

[0010] Preferably, the weight ratio of the aspartic acid ester resin to the aspartic acid ester-modified graphene oxide is 100:1-20.

[0011] Preferably, the terminal group of the dual-terminal amino polysiloxane is a primary amino group, and the side chain is chemically bonded to a grafted alkoxysilyl group.

[0012] More preferably, the proportion of the number of the alkoxysilyl groups in the degree of polymerization of the dual-terminated amino-polysiloxane is not less than 8% and not more than 30%.

[0013] More preferably, the structure of the dual-terminated amino polysiloxane is as shown in the following formula (1):

[0014] NH 2 R 1 SiMe 2 O(SiOMe 2 ) x (SiOMeR 2 ) y (SiOMeR 3 ) z SiMe 2 R 1 NH 2 (1)

[0015] Among them, R 1 is selected from C2-C8 alkylene, substituted C3-C8 alkylene or C6-C12 cycloalkylene, Me is methyl, R 2 For -(CH 2 ) n Si(OR 4 ) 3 , R 3 is selected from C1-C18 alkyl, F-substituted C3-C10 alkyl or aromatic group, R 4 Selected from C1-C4 alkyl, x≥10, y≥3, z≥0, 0.08≤y / (x+y+z)≤0.3, n=2-6.

[0016] Preferably, the structure of the maleate is as shown in the following formula (2):

[0017] R 5 OOC=COOR 6 (2)

[0018] Among them, R 5 and R 6 Independently selected from C1-C4 alkyl.

[0019] An asparagus polyurea coating composition, consisting of component A and component B;

[0020] The raw material components of component A include, by weight, 100 parts of the composite aspartic acid ester resin described in any one of the above embodiments, 0-80 parts of pigments and fillers, and 1-5 parts of additives;

[0021] The B component is an isocyanate curing agent.

[0022] Preferably, the isocyanate curing agent is a polyester-modified isocyanate curing agent, and the NCO content in the polyester-modified isocyanate curing agent is 2-6 wt %.

[0023] More preferably, the preparation method of the polyester modified isocyanate curing agent is: reacting polyester polyol with diisocyanate compound and then adding chain extender to extend the chain to obtain the polyester modified isocyanate curing agent.

[0024] An application of the asparagus polyurea coating composition described in any of the above embodiments is applied as a protective coating on wind turbine blades.

[0025] The beneficial effects of the present invention are:

[0026] (1) In order to improve the protective effect of the asparagine polyurea coating, the present invention adds graphene oxide GO to the asparagine polyurea, and the GO with a lamellar structure can significantly improve the anti-corrosion and weather resistance of the asparagine polyurea. The present invention uses a polysiloxane with a double-terminal aspartic acid ester structure to modify GO, which can improve the dispersibility of GO in the asparagine polyurea coating composition, and the terminal aspartic acid ester structure can also participate in the curing of the asparagine polyurea coating composition, so that GO can participate in the cross-linked curing network structure of the asparagine polyurea coating, further improving the dispersion stability of GO in the asparagine polyurea and the anti-corrosion properties of the asparagine polyurea.

[0027] (2) GO is modified with a double-terminal aspartic acid ester structure of polysiloxane. The polysiloxane structure on the surface of the aspartic acid polyurea coating can migrate and precipitate on the surface of the coating, thereby improving the hydrophobicity and weather resistance of the coating, and further improving the anti-corrosion and weather resistance of the aspartic acid polyurea coating. The polysiloxane structure inside the coating participates in the cross-linking structure of the aspartic acid polyurea, which can play a role in toughening the aspartic acid polyurea coating and improving its high and low temperature resistance.

[0028] (3) By using polysiloxane with side chain bonded alkoxysilyl groups, the alkoxysilyl groups can react with GO and chemically bond the double-terminated aspartic acid ester polysiloxane to GO, achieving good modification of GO. DETAILED DESCRIPTION

[0029] The technical solution of the present invention is further illustrated and described below through specific implementation methods.

[0030] In order to further improve the protective performance of aspartic acid polyurea coating, on the one hand, the present invention provides a composite aspartic acid ester resin, which is composed of aspartic acid ester resin and aspartic acid ester modified graphene oxide;

[0031] The aspartic acid ester modified graphene oxide is double-terminated aspartic acid ester polysiloxane modified graphene oxide;

[0032] The double-terminal aspartic acid ester polysiloxane is the product of Michael addition reaction between double-terminal amino polysiloxane and maleic acid ester.

[0033] In the present invention, aspartic acid ester modified graphene oxide is added to aspartic acid ester resin, and the aspartic acid ester modified graphene oxide mainly consists of three structural parts: (1) graphene oxide GO, which can improve the anti-corrosion performance of the coating; (2) polysiloxane structure, which has the characteristics of hydrophobicity, high and low temperature resistance, good flexibility, good weather resistance, etc., and can improve the waterproof, anti-corrosion, impact resistance, high and low temperature resistance, weather resistance and other properties of the coating; (3) terminal aspartic acid ester structure (structure of terminal amino group and maleic acid ester reaction), which can improve the compatibility with aspartic acid ester resin, and provide secondary amino groups participating in the cross-linking of aspartic acid ester resin, so as to bring into play the performance characteristics of polysiloxane structure.

[0034] The preparation method of the above-mentioned double-terminal aspartic acid ester polysiloxane modified graphene oxide can be as follows: disperse graphene oxide GO in an organic solvent, add double-terminal aspartic acid ester polysiloxane (the weight of double-terminal aspartic acid ester polysiloxane can be 0.5-10 times the weight of GO), react at a certain temperature, separate the solid after the reaction is complete, and then wash the solid with an organic solvent and dry it to obtain.

[0035] In the present invention, the aspartic acid ester resin is a Michael addition reaction product of a diamine compound (such as 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane) and a maleate (such as diethyl maleate), and is not particularly limited. It can be F420, F520, F421, F220, F330, etc. produced by Feiyang Junyan Company, or NH1420, NH1520, etc. produced by Bayer Company.

[0036] In a preferred embodiment of the present invention, the weight ratio of aspartic acid resin and aspartic acid modified graphene oxide is 100: 1-20. For example, the weight ratio of aspartic acid resin and aspartic acid modified graphene oxide can be any value of 100: 1, 100: 3, 100: 5, 100: 6, 100: 8, 100: 10, 100: 12, 100: 13, 100: 15, 100: 16, 100: 18, 100: 20, etc., without special restrictions. Preferably, the weight ratio of aspartic acid resin and aspartic acid modified graphene oxide can be 100: 3-20. When the weight ratio of aspartic acid resin and aspartic acid modified graphene oxide is lower than 100: 3 (such as 100: 1, 100: 2, etc.), due to the introduction of less polysiloxane structure, the high and low temperature resistance of aspartic polyurea coating is less improved. When the weight ratio is not less than 100:3 (such as 100:4, 100:5, etc.), the high and low temperature resistance of the aspartame polyurea coating is significantly improved.

[0037] In a preferred embodiment of the present invention, the terminal group of the double-terminated amino polysiloxane is a primary amino group, and the side chain is chemically bonded with an alkoxysilyl group. The terminal group of the double-terminated amino polysiloxane is a primary amino group, which can react with maleate to form an aspartic acid ester structure at the terminal group of the polysiloxane, and provide a secondary amino group to participate in the cross-linking of the aspartic polyurea coating; the alkoxysilyl group of the side chain can react with the hydroxyl group on the surface of GO, etc., to connect the polysiloxane structure and GO through chemical bonding.

[0038] More preferably, the proportion of the number of alkoxysilyl groups in the degree of polymerization of the double-terminated amino polysiloxane is not less than 8% and not more than 30%. If the number of alkoxysilyl groups is too small or the ratio is too low, the number of active groups is small, the reaction activity with GO is low, and the reaction efficiency is slow. If the number of active groups is too large or the ratio is too high, the stability of the double-terminated amino polysiloxane will be poor, and even some adjacent active groups will compete with each other, resulting in more active groups remaining, affecting the stability of aspartic acid ester modified graphene oxide and / or composite aspartic acid ester resin. For example, the proportion of the number of alkoxysilyl groups in the degree of polymerization of the double-terminated amino polysiloxane can be 8%, 10%, 12%, 13%, 15%, 17%, 18%, 20%, 22%, 25%, 27%, 28%, 30%, etc., without special restrictions. Further preferably, the proportion of the number of alkoxysilyl groups in the degree of polymerization of the double-terminated amino polysiloxane is not less than 8% and not more than 20%.

[0039] More preferably, the structure of the dual-terminated amino polysiloxane is as shown in the following formula (1):

[0040] NH 2 R 1 SiMe 2 O(SiOMe2 ) x (SiOMeR 2 ) y (SiOMeR 3 ) z SiMe 2 R 1 NH 2 (1)

[0041] Among them, R 1 is selected from C2-C8 alkylene, substituted C3-C8 alkylene or C6-C12 cycloalkylene, Me is methyl, R 2 For -(CH 2 ) n Si(OR 4 ) 3 , R 3 is selected from C1-C18 alkyl, F-substituted C3-C10 alkyl or aromatic group, R 4 Selected from C1-C4 alkyl, x≥10, y≥3, z≥0, 0.08≤y / (x+y+z)≤0.3, n=2-6.

[0042] In the structure of the double-terminal amino polysiloxane shown in the above formula (1), y / (x+y+z) is the ratio of the number of the above-mentioned alkoxysilyl groups to the degree of polymerization of the double-terminal amino polysiloxane, y is the number of alkoxysilyl groups, and x+y+z is the degree of polymerization of the double-terminal amino polysiloxane. The preparation method of the double-terminal amino polysiloxane shown in formula (1) is well known to those skilled in the art, for example, it can be prepared from the corresponding double-terminal amino hydrogen polysiloxane NH 2 R 1 SiMe 2 O(SiOMe 2 ) x (SiOMeH) y (SiOMeR 3 ) z SiMe 2 R 1 NH 2 With vinyl silane coupling agent CH 2 =CH(CH 2 ) n-2 Si(OR 4 ) 3 It can also be obtained by the corresponding double-terminal amino alkenyl polysiloxane NH 2 R 1 SiMe 2 O(SiOMe 2 ) x (SiOMeR 7 ) y (SiOMeR3 ) z SiMe 2 R 1 NH 2 With hydrogen-containing silane coupling agent HSi(OR 4 ) 3 The hydrosilylation reaction is carried out to obtain R 7 For -(CH 2 ) n-2 CH=CH 2 For example, taking double-terminal amino vinyl polysiloxane as an example, a method for carrying out a hydrosilylation reaction of double-terminal amino vinyl polysiloxane and a hydrogen-containing silane coupling agent is as follows: 1 mol of double-terminal amino vinyl polysiloxane as shown in formula (1) and (1-2) ymol of hydrogen-containing silane coupling agent are added to a reaction container, the temperature is raised to 80-90° C., a Pt catalyst (such as a Karstedt catalyst, the amount added is 10-500 ppm based on the amount of Pt) is added, the temperature is maintained at 120-135° C. for reaction for 2-5 hours, and then the excess hydrogen-containing silane coupling agent is removed by reducing the pressure, and the temperature is lowered to obtain the double-terminal amino polysiloxane.

[0043] The preparation methods of the above-mentioned double-terminated amino hydrogen polysiloxane and double-terminated amino alkenyl polysiloxane are also well known to those skilled in the art. For example, the double-terminated amino hydrogen polysiloxane and double-terminated amino alkenyl polysiloxane can be prepared by using an amino-terminated agent NH 2 R 1 Me 2 SiOSiMe 2 R 1 NH 2 It is obtained by ring-opening reaction with a siloxane ring body (such as octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, etc.) and / or a dialkoxysilane under an acidic catalyst or a basic catalyst. Taking double-terminated amino vinyl polysiloxane as an example, a preparation method can be as follows: 1 mol of amino end-capping agent NH 2 (CH 2 ) 3 Me 2 SiOSiMe 2 (CH 2 ) 3 NH 2 , 20 mol octamethylcyclotetrasiloxane, (2-4) mol tetramethyltetravinylcyclotetrasiloxane and (70-150) g ​​tetramethylammonium hydroxide alkali glue (1 wt% concentration), heat to 110-120°C to react for 1-3h, heat to 135-140°C and under a negative pressure of -0.05 to -0.08MPa to destroy the catalyst for 0.5-0.8h, then heat to 150-155°C and under -0.099MPa to remove low boiling points, cool to room temperature to obtain double-terminal amino vinyl polysiloxane.

[0044] In a preferred embodiment of the present invention, the structure of the maleate is shown in the following formula (2):

[0045] R 5 OOC=COOR 6 (2)

[0046] Among them, R 5 and R 6 Independently selected from C1-C4 alkyl.

[0047] For example, the maleate may be dimethyl maleate, dimethyl fumarate, diethyl fumarate, diethyl maleate, dibutyl maleate, etc., such as the commonly used diethyl maleate.

[0048] On the other hand, the present invention provides an asparagine polyurea coating composition, which consists of a component A and a component B;

[0049] Component A comprises, by weight, 100 parts of the composite aspartic acid ester resin described in any one of the above embodiments, 0-80 parts of pigments and fillers, and 1-5 parts of additives;

[0050] Component B is an isocyanate curing agent.

[0051] The component A of the aspartic acid ester modified graphene oxide in the aspartic acid ester coating composition of the present invention can synergistically exert the characteristics of GO, polysiloxane segments and aspartic acid ester structures, thereby improving the hydrophobicity, corrosion resistance, weather resistance, high and low temperature resistance, impact resistance and other properties of the aspartic acid ester coating.

[0052] The mixing ratio of component A and component B is well known to those skilled in the art. For example, the amino groups in component A and the NCO groups in component B are mixed at a molar ratio of 1:1-1.1.

[0053] There is no particular limitation on the pigments and fillers. The pigments may be commonly used inorganic pigments or organic pigments, such as titanium dioxide, phthalocyanine blue, carbon black, phthalocyanine green, chrome green, chrome yellow, molybdenum chrome red, cadmium yellow, cadmium red, cobalt blue, bismuth yellow, titanium nickel yellow, cerium red, etc. The amount of the pigment may be selected as needed. The fillers may be inorganic fillers or organic fillers, such as wollastonite, talc, kaolin, glass microbeads, heavy calcium carbonate, light calcium carbonate, alumina, polytetrafluoroethylene micropowder, polyethylene micropowder, etc. The amount of the fillers may be selected as needed.

[0054] There is no particular limitation on the above-mentioned auxiliary agents, which may be wetting agents, leveling agents, defoaming agents, anti-ultraviolet agents, anti-yellowing agents, dispersing aids, water absorbents, and the like.

[0055] In a preferred embodiment of the present invention, the isocyanate curing agent is a polyester-modified isocyanate curing agent, and the NCO content in the polyester-modified isocyanate curing agent is 2-6 wt %.

[0056] Generally, for asparagine, the NCO content in the isocyanate curing agent is more suitable at 15-20wt%. However, the present invention finds that the use of polyester modified isocyanate curing agent with an NCO content of 2-6wt% has a better cross-linking and curing effect, and the obtained asparagine coating has better performance, especially better bonding strength and impact strength. For example, the NCO content in the polyester modified isocyanate curing agent can be any value of 2wt%, 2.3wt%, 2.5wt%, 2.7wt%, 3wt%, 3.2wt%, 3.3wt%, 3.5wt%, 3.7wt%, 3.8wt%, 4wt%, 4.2wt%, 4.3wt%, 4.5wt%, 4.7wt%, 4.8wt%, 5.0wt%, 5.2wt%, 5.3wt%, 5.5wt%, 5.7wt%, 5.8wt%, 6.0wt%, etc., without special restrictions.

[0057] More preferably, the preparation method of the polyester modified isocyanate curing agent is: reacting a polyester polyol with a diisocyanate compound and then adding a chain extender to extend the chain. The polyester diol is not particularly limited, and can be a conventional polyester polyol, a polycarbonate polyol, a polycaprolactone polyol, etc. The diisocyanate compound is also not particularly limited, and can be IPDI, HMDI, TDI, MDI, etc. The molar ratio of the hydroxyl group in the polyester polyol to the NCO in the diisocyanate compound can be 1:1.1-1.4. The chain extender can be ethylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.

[0058] In another aspect, the present invention provides an application of the asparagine polyurea coating composition described in any of the above embodiments as a protective coating applied to a wind turbine blade. The asparagine polyurea coating composition of the present invention is applied to a wind turbine blade as a protective coating to improve the anti-corrosion performance and weather resistance of the wind turbine blade, and extend the life of the wind turbine blade.

[0059] The technical solution of the present invention is further described and illustrated according to various embodiments below.

[0060] Example 1-5 Preparation of composite aspartic acid ester resin

[0061] Example 1

[0062] Double-terminated amino polysiloxane NH 2 (CH 2 ) 3 SiMe 2 O(SiOMe 2 ) 78.2 (SiOMeR 2 ) 7.5 SiMe2 (CH 2 ) 3 NH 2 , R 2 -CH 2 CH 2 Si(OCH 3 ) 3 .

[0063] 1 mol of the above-mentioned double-terminated amino polysiloxane and 2.3 mol of diethyl maleate were added to a reaction container, the temperature was raised to 90°C for reaction for 96 hours, the pressure was reduced to below -0.099 MPa, the temperature was raised to 180-185°C to remove unreacted diethyl maleate, and the temperature was lowered to obtain double-terminated aspartic acid ester polysiloxane.

[0064] 10 g of Hummers GO was ultrasonically dispersed in 1000 g of anhydrous ethanol, 15 g of the above-mentioned double-terminated aspartic acid ester polysiloxane was added, and the mixture was stirred at room temperature for 2 h. The mixture was heated to 70 °C and the reaction was continued for 2 h. The solid was collected by centrifugation, washed twice with anhydrous ethanol, and dried at 60 °C overnight to obtain aspartic acid ester-modified GO.

[0065] The composite aspartic acid ester resin is composed of F420 of Feiyang Junyan Company and the above-mentioned aspartic acid ester modified GO in a weight ratio of 100:1.

[0066] Example 2

[0067] The difference between this embodiment and embodiment 1 is that the composite aspartic acid ester resin is adjusted to be composed of F420 and aspartic acid ester modified GO in a weight ratio of 100:10.

[0068] Example 3

[0069] The difference between this embodiment and embodiment 1 is that the composite aspartic acid ester resin is adjusted to be composed of F420 and aspartic acid ester-modified GO in a weight ratio of 100:20.

[0070] Example 4

[0071] The difference between this embodiment and embodiment 2 is that the double-terminal amino polysiloxane is adjusted to NH 2 (CH 2 ) 3 SiMe 2 O(SiOMe 2 ) 40.6 (SiOMeR 2 ) 10.2 SiMe 2 (CH 2 ) 3 NH 2 , R 2 -CH 2CH 2 Si(OCH 3 ) 3 .

[0072] Example 5

[0073] The difference between this embodiment and embodiment 2 is that the double-terminal amino polysiloxane is adjusted to NH 2 (CH 2 ) 3 SiMe 2 O(SiOMe 2 ) 51.4 (SiOMeR 2 ) 7.8 (SiOMeR f ) 6.2 SiMe 2 (CH 2 ) 3 NH 2 , R 2 -CH 2 CH 2 Si(OCH 3 ) 3 , R f It is perfluorohexylethyl.

[0074] Example 6-13 Preparation of asparagus polyurea coating composition

[0075] Example 6

[0076] The aspartame polyurea coating composition is composed of component A and component B in a molar ratio of amino group to NCO group of 1:1.05;

[0077] The raw material components of component A include: 1000g of the composite aspartic acid ester resin of Example 1, 200g of titanium dioxide, 300g of wollastonite, 6g of silicone-modified polyether wetting agent Tego 4100, 5g of silicone defoaming agent BYK-077, 6g of anti-ultraviolet agent UV-328, and 20g of 3A molecular sieve;

[0078] Component B is an isocyanate curing agent.

[0079] The isocyanate curing agent is a polycarbonate modified isocyanate curing agent, and the NCO content is 16.3 wt %. The polycarbonate modified isocyanate curing agent is obtained by reacting polycarbonate polyol (average molecular weight 1000) and IPDI.

[0080] Example 7

[0081] The difference between this example and Example 6 is that in Example 6, the composite aspartic acid ester resin of Example 1 is replaced by 1000 g of the composite aspartic acid ester resin of Example 2. The other steps remain unchanged.

[0082] Example 8

[0083] The difference between this example and Example 6 is that in Example 6, the composite aspartic acid ester resin of Example 1 is replaced by 1000 g of the composite aspartic acid ester resin of Example 3. The other steps remain unchanged.

[0084] Example 9

[0085] The difference between this embodiment and embodiment 7 is that in embodiment 7, the NCO content of the isocyanate curing agent is adjusted to 5.8wt%. The preparation method of the isocyanate curing agent is as follows: polycarbonate polyol (average molecular weight 1000) and IPDI are added to a reaction container at a molar ratio of hydroxyl group to NCO group of 1:1.3, stirred and reacted at room temperature for 2 hours, then heated to 60°C for 2 hours, a certain amount of chain extender 1,4-butanediol is added, stirred and reacted at a constant temperature for 2 hours, then heated to 95°C for stirring and reacting until the NCO group content remains unchanged, and cooled to obtain the isocyanate curing agent.

[0086] Example 10

[0087] The difference between this embodiment and embodiment 9 is that in embodiment 9, the amount of chain extender 1,4-butanediol added is adjusted so that the NCO content of the isocyanate curing agent is 2.3 wt %. The other steps remain unchanged.

[0088] Embodiment 11

[0089] The aspartame polyurea coating composition is composed of component A and component B in a molar ratio of amino group to NCO group of 1:1.08;

[0090] The raw material components of component A include: 1000g of the composite aspartic acid ester resin of Example 2, 300g of titanium dioxide, 200g of wollastonite, 10g of phthalocyanine blue, 5g of organosilicon-modified polyether wetting agent Tego 4100, 5g of organosilicon defoaming agent BYK-077, 6g of anti-ultraviolet agent UV-328, 5g of dispersing aid BYK-2009, and 20g of 3A molecular sieve;

[0091] Component B is an isocyanate curing agent.

[0092] The isocyanate curing agent is a polycarbonate modified isocyanate curing agent, and the NCO content is 4.5wt%. The preparation method of the isocyanate curing agent is as follows: polycarbonate polyol (average molecular weight 1000) and IPDI are added to a reaction container at a molar ratio of hydroxyl group to NCO group of 1:1.4, stirred and reacted at room temperature for 2 hours, then heated to 60°C for 2 hours, a certain amount of chain extender 1,6-hexanediol is added, stirred and reacted at a constant temperature for 2 hours, then heated to 95°C for stirring and reacting until the NCO group content remains unchanged, cooled, and the isocyanate curing agent is obtained.

[0093] Example 12

[0094] The difference between this example and Example 11 is that in Example 11, the composite aspartic acid ester resin of Example 2 is replaced by 1000 g of the composite aspartic acid ester resin of Example 4. The other steps remain unchanged.

[0095] Embodiment 13

[0096] The difference between this example and Example 11 is that in Example 11, the composite aspartic acid ester resin of Example 2 is replaced by 1000 g of the composite aspartic acid ester resin of Example 5. The other steps remain unchanged.

[0097] Comparative Example 1

[0098] The difference between this comparative example and Example 11 is that in Example 11, the composite aspartic acid ester resin in Example 2 is replaced by 1000g of F420. The other steps remain unchanged.

[0099] Comparative Example 2

[0100] The difference between this comparative example and Example 11 is that in Example 11, the aspartic acid ester-modified GO in the composite aspartic acid ester resin is prepared as follows. The remaining steps remain unchanged.

[0101] Preparation method of modified GO:

[0102] 10 g of Hummers GO was ultrasonically dispersed in 1000 g of anhydrous ethanol, 15 g of 3-aminopropyltrimethoxysilane was added, and the mixture was stirred at room temperature for 2 h. The temperature was raised to 70 °C and the reaction was continued for 2 h. The solid was collected by centrifugation, washed twice with anhydrous ethanol, and dried at 60 °C overnight to obtain amino-modified GO.

[0103] The above amino-modified GO (amino group is 1 mol) and 1.2 mol diethyl maleate were added to a reaction vessel, heated to 90°C for reaction for 96 hours, reduced pressure to below -0.099 MPa, heated to 180-185°C to remove unreacted diethyl maleate, cooled to obtain modified GO.

[0104] Performance Testing

[0105] Component A and component B of the asparagus polyurea coating composition of Examples 6-13 and Comparative Examples 1-2 were mixed evenly and then coated on the surface of a clean wind turbine blade with a film thickness of 200 μm and dried at room temperature for 7 days.

[0106] Adhesion strength: tested according to the method of GB / T 23446-2009.

[0107] Impact strength: tested according to ASTM D2794.

[0108] Radiation aging resistance: tested according to the method of GB / T 1865-2009, and the retention rate of bonding strength was tested after 2000h of UVB irradiation.

[0109] Salt spray resistance: According to the method of GB / T 1771-2007, the neutral salt spray test film layer shows abnormal time such as blistering, shedding, edge warping, etc.

[0110] High temperature resistance: The retention rate of bonding strength is tested after the sample is placed in a 200°C environment for 120 hours.

[0111] High and low temperature alternating stability: 80℃×30min+-40×30min is one high and low temperature cycle. Test 20 cycles to observe whether there are any abnormalities such as shedding, edge warping, bubbling, etc.

[0112] Water contact angle: tested using a water drop angle tester.

[0113] The results are shown in Table 1 below.

[0114] Table 1

[0115]

[0116]

[0117] It can be seen from the data results in Table 1 above that the aspartic acid polyurea coating composition of the present invention adopts composite aspartic acid ester and contains polysiloxane-modified GO, which can significantly improve the protective performance of aspartic acid polyurea on wind turbine blades.

[0118] As described above, the basic principles, main features and advantages of the present invention are shown and described. Those skilled in the art should understand that the present invention is not limited by the above embodiments, which are only preferred embodiments of the present invention and cannot be used to limit the scope of the present invention. That is, equivalent changes and modifications made according to the scope of the present invention and the content of the specification should still be within the scope of the present invention. The scope of protection required by the present invention is defined by the attached claims and their equivalents.

Claims

1. A composite aspartic acid ester resin, characterized in that: It is composed of aspartic acid ester resin and aspartic acid ester modified graphene oxide; The aspartic acid ester modified graphene oxide is double-terminated aspartic acid ester polysiloxane modified graphene oxide; The double-terminal aspartic acid ester polysiloxane is a product of Michael addition reaction between double-terminal amino polysiloxane and maleate.

2. The composite aspartic acid ester resin according to claim 1, characterized in that The weight ratio of the aspartic acid ester resin to the aspartic acid ester-modified graphene oxide is 100:1-20.

3. The composite aspartic acid ester resin according to claim 1, characterized in that: The terminal group of the double-terminal amino polysiloxane is a primary amino group, and the side chain is chemically bonded to a grafted alkoxysilyl group.

4. The composite aspartic acid ester resin according to claim 3, characterized in that: The proportion of the number of the alkoxysilyl groups in the polymerization degree of the dual-terminated amino polysiloxane is not less than 8% and not more than 30%.

5. The composite aspartic acid ester resin according to claim 3, characterized in that: The structure of the dual-terminal amino polysiloxane is shown in the following formula (1): NH2R 1 SiMe2O(SiOMe2) x (SiOMeR 2 ) y (SiOMeR 3 ) z SiMe2R 1 NH2(1) where R 1 is selected from C2-C8 alkylene, substituted C3-C8 alkylene or C6-C12 cycloalkylene, Me is methyl, R 2 -(CH2) n Si(OR 4 )3, R 3 is selected from C1-C18 alkyl, F-substituted C3-C10 alkyl or aromatic group, R 4 Selected from C1-C4 alkyl, x≥10, y≥3, z≥0, 0.08≤y / (x+y+z)≤0.3, n=2-6.

6. The composite aspartic acid ester resin according to claim 1, characterized in that: The structure of the maleate is shown in the following formula (2): R 5 OOC=COOR 6 (2) Among them, R 5 and R 6 Independently selected from C1-C4 alkyl.

7. An aspartame polyurea coating composition, characterized in that It is composed of component A and component B; The raw material components of component A include, by weight, 100 parts of the composite aspartic acid ester resin according to any one of claims 1 to 6, 0 to 80 parts of pigments and fillers, and 1 to 5 parts of additives; The B component is an isocyanate curing agent.

8. The asparagine polyurea coating composition according to claim 7, characterized in that: The isocyanate curing agent is a polyester modified isocyanate curing agent, and the content of NCO in the polyester modified isocyanate curing agent is 2-6wt%.

9. The asparagine polyurea coating composition according to claim 8, characterized in that: The preparation method of the polyester modified isocyanate curing agent is as follows: polyester polyol is reacted with a diisocyanate compound and then a chain extender is added to perform chain extension to obtain the curing agent.

10. An application of the asparagine polyurea coating composition according to any one of claims 7 to 9, characterized in that: Used as a protective coating on wind turbine blades.

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