A kind of fluorine silicon modified polyaspartic polyurea coating and preparation method thereof

Abstract

The present invention relates to the technical field of synthetic coatings, and in particular to a fluorosilicone modified polyaspartic acid ester polyurea coating and a preparation method thereof. First, in the synthesis stage of polyaspartic acid resin, a monofunctional perfluoro macromonomer is introduced into the main chain of a polyaspartic acid ester molecule, thereby forming a comb-shaped (side chain) long-chain fluorine-containing hydrophobic group. Secondly, a monohydroxyl-terminated polydimethylsiloxane is used to modify an aliphatic isocyanate trimer, so that the curing agent component also has a comb-shaped (side chain) long-chain siloxane hydrophobic group. The fluorosilicone modified polyaspartic acid ester polyurea coating prepared by the present invention has excellent hydrophobic properties while still maintaining the excellent material properties and chemical resistance inherent in polyaspartic acid ester coatings.

Description

Technical Field

[0001] The present invention relates to the technical field of synthetic coatings, in particular to a fluorosilicone modified polyaspartic polyurea coating and a preparation method thereof. Background Art

[0002] Aliphatic polyaspartic polyurea coatings are a new type of polyurea coating developed in recent years, known as the "third-generation polyurea." They feature high solids, low viscosity, excellent mechanical properties, and resistance to aging and corrosion. Due to the combined electronic and steric effects of their active amino groups, their reactivity is significantly reduced. This overcomes the drawbacks of traditional polyurea materials, such as short application time, poor film adhesion, and numerous surface defects, making them more suitable for industrial applications. However, in practice, aspartic polyurea coatings suffer from poor water resistance and hydrophobic properties.

[0003] To solve the above problems, the prior art usually introduces hydrophobic groups (such as fluorine, silicon, etc.) to improve the water resistance of coatings by chemical modification. The unique molecular structure and mechanism of action of siloxanes make them have good hydrophobicity. In modern technology, they are often used as hydrophobic modification agents to give other materials hydrophobic properties. Similarly, the molecular activity space of the fluorinated chain segments in fluorinated compounds is large, the surface tension is low, the polarity is small, and they are hydrophobic and oleophobic. Therefore, they are also often used as hydrophobic modification agents. The hydrophobic modification of coatings is increasingly receiving attention and research in the industry, and many related patent documents have been reported.

[0004] CN109207039 reports a method for preparing a fluorinated polyaspartate coating. Fumaryl chloride and trifluoroethanol are reacted via a substitution reaction to synthesize a fluorinated unsaturated dicarboxylic acid ester, which is then reacted with a primary amine compound via Michael addition to produce a fluorinated polyaspartic acid resin. This patent utilizes a fluorinated polyaspartic acid ester as the resin component and an isocyanate as the curing agent, resulting in a high-performance coating with excellent water resistance and anti-icing properties. However, the preparation process is complex and involves the generation of pollutants. Furthermore, the patent does not provide quantitative data related to water resistance.

[0005] CN111848950 reports a method for preparing a silicon-modified aspartic acid ester polyurea coating. A primary amine compound is reacted with a maleate compound and an organosiloxane to produce the silicon-modified aspartic acid ester polyurea, and its water resistance is tested. When immersed in water at room temperature, the coating film only showed whitening after 14 days, significantly improving water resistance. However, the patent does not mention contact angle and other related data.

[0006] CN114231142 reports a method for preparing a new fluorosilicone-modified polyurea material. A fluorosilicone-modified asparagine resin, obtained by reacting a polysiloxane primary amine compound with a fluorine-containing unsaturated dicarboxylic acid ester, is used as the resin component, and an isocyanate is used as the curing agent to produce a fluorosilicone-modified polyurea material. This patent uses a water spray classification method to test the hydrophobicity of the coating and finds that the fluorosilicone-modified polyurea coating exhibits excellent hydrophobicity. Furthermore, its weather resistance, temperature resistance, and flexibility are significantly superior to those of the comparative examples. However, this patent also suffers from complex preparation processes and high costs, making it difficult to use in industrial production.

[0007] CN114958269 reports a long-life fluorosilicone-modified polyurea sealant and its preparation method. A fluorine-modified polyaspartic acid resin obtained by reacting an aliphatic diamine, a maleate, and a fluorine-containing epoxy resin is used as the resin component; a silicon-modified aliphatic isocyanate obtained by reacting a terminal hydroxyl silane, a polyol, and an aliphatic diisocyanate is used as the curing agent to produce the fluorosilicone-modified polyurea sealant. However, the fluorine-containing epoxy resin used in the examples of this patent is actually 1,1,1-trifluoro-2,3-propylene oxide. After ring opening, the fluorine-containing side chains that form the polyaspartic acid ester are too short to effectively improve the surface properties of the coating. Similarly, the steric hindrance effect of the fluorine-containing side chains is not as strong as that of diethyl maleate, and in fact, it cannot effectively reduce the reactivity of the resulting polyaspartic acid ester. Furthermore, the terminal hydroxyl siloxane used to modify the isocyanate has a double-terminal hydroxyl structure, so the siloxane groups can only be located on the main chain rather than the side chains, thus limiting the effectiveness of improving the surface properties of the coating.

[0008] In summary, although fluorine and silicon modification is the development direction for improving the hydrophobic properties of polyurea coatings, the existing problems such as poor water resistance, reduced performance, structural design, process route and production cost are still difficult problems that need to be solved.

[0009] The patent of this invention introduces a long-chain fluorine-containing monomer as a side chain into polyaspartic acid ester, thereby giving the aspartic polyurea coating excellent hydrophobicity; at the same time, a long-chain polysiloxane is used as a side chain modified isocyanate curing agent to prepare a fluorosilicone-modified aspartic polyurea coating, which significantly reduces the surface tension of the coating and improves the hydrophobicity, and has broad application prospects. Summary of the Invention

[0010] Purpose of the Invention

[0011] The present invention relates to a fluorine-modified polyaspartic acid ester; the present invention also relates to a method for preparing a fluorine-modified polyaspartic acid resin ester; the present invention further relates to a polysiloxane-modified curing agent; the present invention further relates to a method for preparing a polysiloxane-modified curing agent; the present invention further relates to a method for preparing a fluorine-silicon-modified two-component polyaspartic polyurea coating.

[0012] Technical Solution

[0013] The present invention relates to a fluorine-modified polyaspartic acid ester, characterized in that the fluorine-modified polyaspartic acid ester has the following structure (Formula 1).

[0014]

[0015] Wherein R1 and R2 are alkyl groups with the same or different carbon atoms (such as C1-C4 alkyl); Y can be an alkylene group (such as: wherein n=0, 1, 2, ...), cycloalkylene (such as: ) or substituted cycloalkyl (such as: ), n=7 or 9.

[0016] It is any of the following structures:

[0017]

[0018]

[0019] The present invention also relates to a method for preparing a fluorine-modified polyaspartic acid ester resin. The method is characterized by adding a fluorine-containing acrylate to the polyaspartic acid ester during the synthesis process. The fluorine-containing acrylate undergoes a Michael addition reaction with the primary amino group of the primary amino compound, and the fluorine-modified polyaspartic acid ester is simultaneously synthesized with the unsaturated dicarboxylic acid ester to form the fluorine-modified polyaspartic acid ester resin. The reaction equation is shown below (Formula 8):

[0020]

[0021] wherein R1, R2, Y and n are defined the same as in Formula 1.

[0022] The above-mentioned fluorine-containing acrylates include but are not limited to perfluorodecyl acrylate, 2-perfluorodecyl ethyl acrylate, perfluorooctanol acrylate, perfluoroalkylethyl acrylate, 2-(perfluorooctyl)ethyl methacrylate, and perfluorodecyl acrylate and 2-perfluorodecyl ethyl acrylate are preferably used.

[0023] The unsaturated dicarboxylic acid ester may be a dialkyl maleate including but not limited to diethyl maleate, dipropyl maleate, dibutyl maleate, and methylpropyl maleate; or a dialkyl fumarate including but not limited to diethyl fumarate, dipropyl fumarate, dibutyl fumarate, and methylpropyl fumarate. The unsaturated dicarboxylic acids may be used alone or in any combination, preferably diethyl maleate and dipropyl maleate, and most preferably diethyl maleate.

[0024] The primary amino compounds include, but are not limited to, ethylenediamine, 1,2-propylenediamine, 2,5-dimethyl-2,5-hexanediamine, 1,11-undecyldiamine, 1,12-dodecyldiamine, 2,4'-diamino-dicyclohexylmethane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,4-toluenediamine or 2,6-toluenediamine, 2,4'-diaminodiphenylmethane or 4,4'-diaminodiphenylmethane, and mixtures thereof. The primary amino compounds also include, but are not limited to, 1,4-butanediamine, 1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 4,4'-diamino-dicyclohexylmethane, 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane, and mixtures thereof. The primary amino compound may also include, but is not limited to, polyoxypropylene, polyethylene oxide, or terminal amino compounds of ethylene oxide and propylene oxide copolymers, such as Jeffamine D230, D2000, T403, T5000, ED600, and ED900 from HUNTSMAN. The primary amino compound may be a monoamine or a polyamine, preferably a diamine. These include 1,6-hexanediamine, 4,4'-diamino-dicyclohexylmethane, and 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane. 1,6-hexanediamine and 4,4'-diamino-dicyclohexylmethane are most preferred.

[0025] The preparation method of the fluorine-modified polyaspartic acid ester resin is as follows: first, a measured amount of a primary amino compound is added to a reaction kettle, then a measured amount of a perfluoroalkyl acrylate is added dropwise, and the mixture is reacted for 30 minutes after the addition is complete. Then, an unsaturated dicarboxylic acid ester is added dropwise, and the reaction is continued until the reaction is complete, thereby obtaining the fluorine-modified polyaspartic acid ester resin.

[0026] The suitable molar ratio between the unsaturated dicarboxylic acid ester and the fluorinated acrylate is 0.98:0.02 to 0.90:0.10, the preferred molar ratio is 0.97:0.03 to 0.93:0.08, and the most preferred molar ratio is 0.96:0.04 to 0.94:0.06.

[0027] The suitable molar ratio of the sum of the moles of the unsaturated dicarboxylic acid ester and the fluorinated acrylate to the primary amino compound is 2:1.10-2:1.00, preferably 2:1.08-2:1.05, and most preferably 2:1.03-2:1.00.

[0028] The temperature for the Michael addition reaction between the unsaturated dicarboxylic acid ester and fluorine-containing acrylate and the primary amino compound is 45°C-80°C, preferably 55°C-70°C, and most preferably 60°C-65°C.

[0029] The Michael addition reaction time between the unsaturated dicarboxylic acid ester and the fluorine-containing acrylate and the primary amino compound is 6-24 hours, preferably 8-18 hours, and most preferably 10-16 hours.

[0030] The present invention further relates to a polysiloxane-modified curing agent, characterized in that the polysiloxane-modified curing agent has the following structure (Formula 9):

[0031]

[0032] Wherein, R3 is an alkylene group of isophorone diisocyanate (IPDI) or hexamethylene diisocyanate (HDI), R4 and R5 are linear or branched alkyl groups, and x and y are natural numbers such as 1, 2, 3, or 4.

[0033] The present invention further relates to a method for preparing a polysiloxane-modified curing agent, which is characterized in that a siloxane-modified isocyanate trimer is obtained by reacting a monohydroxyl-terminated long-chain polysiloxane with an aliphatic isocyanate trimer, as shown in the reaction formula (Formula 10):

[0034]

[0035] The monohydroxy-terminated long-chain polysiloxane has the following structure (Formula 11):

[0036]

[0037] Wherein, R4, R5, x, and y are defined the same as in Formula 9.

[0038] The molecular weight of the monohydroxyl-terminated long-chain polysiloxane is in the range of 500-200,0, preferably in the range of 1000-1300.

[0039] The trimer of the aliphatic isocyanate includes IPDI trimer or HDI trimer, such as commercially available Covestro Desmodur N3300, N3600, N75, etc., preferably HDI trimer.

[0040] The mol ratio of the monohydroxyl-terminated long-chain polysiloxane to the aliphatic isocyanate trimer is 0.01-0.02:1, preferably 0.013-0.015:1.

[0041] The reaction of the monohydroxyl-terminated long-chain polysiloxane and the aliphatic isocyanate trimer can be carried out using conventional synthesis methods in the polyurethane field. For example, a certain weight ratio of the monohydroxyl-terminated long-chain polysiloxane and the aliphatic isocyanate trimer are mixed in a three-necked flask, and a catalyst (0.1-0.3% by weight of the total reactants) is added. The catalyst can be a catalyst commonly used in current polyurethane synthesis technology. The mixture is then heated to 70-80°C under nitrogen with stirring for 3-4 hours, until the NCO% content reaches the theoretical value.

[0042] The present invention further relates to a method for preparing a fluorosilicone modified two-component polyaspartic polyurea coating, one of the characteristics of which is:

[0043] The resin component (component A) is composed of the fluorine-modified polyaspartic acid ester resin, wherein the fluorine-modified resin can be a single resin of the Y structure in formula 1, or a mixture of two or more resins of the Y structure, and the weight ratio of the mixed resin can be any proportion.

[0044] In addition to the fluorine-modified polyaspartic acid ester, the resin component may also contain diluents, fillers, coupling agents, dispersants, thixotropic agents, pigments, leveling agents, defoamers, ultraviolet light absorbers, antioxidants, etc. as needed.

[0045] The diluent includes but is not limited to ethyl acetate (EAc), butyl acetate (BAc), propylene glycol methyl ether acetate (PMA), ethyl 3-ethoxypropionate (EEP), etc. The amount of solvent used can account for 10-30% of the total weight of the resin component, preferably 5-15%.

[0046] The filler can be calcium carbonate, talc, titanium dioxide, silicon micropowder, barium sulfate, etc. They can be used alone or mixed in any proportion. The total amount of filler used can account for 10-50% of the total weight of the resin component.

[0047] Preferably 15-30%.

[0048] The coupling agent can be KH550, KH560, KH602, etc. The amount of coupling agent used is 0.1%-1% of the total weight of the pigment and filler in the resin component, preferably 0.1-0.5%.

[0049] The dispersant may be BYK110, BYK163, BYK180, etc. The amount of dispersant used is determined according to the supplier's recommendations.

[0050] The thixotropic agent can be fumed silica, kaolin, attapulgite, etc. The thixotropic agent can be used alone or mixed in any proportion. The total amount of the thixotropic agent used is 0-20%, preferably 0-15%.

[0051] The pigment can be carbon black, titanium dioxide, iron yellow, iron red, phthalocyanine blue, etc. The amount of pigment used depends on the color requirements of the coating.

[0052] The leveling agent can be BYK333, BYK354, etc. The leveling agent can be used alone or mixed in any proportion, and the amount used is determined according to the supplier's recommendation.

[0053] The defoaming agent can be BYK066N, BYK085, etc. The defoaming agent can be used alone or mixed in any proportion, and the amount used is determined according to the supplier's recommendation.

[0054] The ultraviolet light absorber can be BASF1130, BASF770 and BASF292, etc. The ultraviolet light absorber can be used alone or mixed in any proportion, and the amount used is determined according to the supplier's recommendation.

[0055] The antioxidant can be BASF1010, BASF B225, BASF1330, etc. The antioxidant can be used alone or mixed in any proportion, and the amount used is determined according to the supplier's recommendation.

[0056] The preparation method of the resin component can be carried out in the following order:

[0057] 1 First, weigh a certain amount of fluorine-modified polyaspartic acid and add it into a container.

[0058] 2. Add the measured amount of coupling agent, dispersant, leveling agent, defoamer, UV absorber, antioxidant and other additives, and stir thoroughly.

[0059] 3. Add diluent, filler, thixotropic agent and color paste and stir thoroughly. Then increase the stirring speed (2000 rpm) and disperse at high speed for 30 minutes. Grind until the fineness is qualified to obtain the resin component.

[0060] The present invention further relates to a method for preparing a fluorosilicone modified two-component polyaspartic polyurea coating, the second feature of which is:

[0061] The curing agent component (component B) is the polysiloxane-modified isocyanate trimer.

[0062] A diluent may be added to the curing agent component to adjust viscosity. Such diluents include, but are not limited to, ethyl acetate (EAc), butyl acetate (BAc), propylene glycol methyl ether acetate (PMA), and ethyl 3-ethoxypropionate (EEP). The amount of solvent used may be 5-30% by weight, preferably 10-20%, of the total weight of the resin component.

[0063] The preparation method of the polysiloxane-modified isocyanate curing agent component can be carried out in the following order:

[0064] 1 Weigh the polysiloxane-modified isocyanate trimer according to the proportion.

[0065] 2. Add the calculated amount of diluent and mix well to obtain the curing agent component.

[0066] The mixing ratio of the resin component (component A) and the curing agent component (component B) of the fluorosilicone modified two-component polyaspartic polyurea coating is calculated according to the ratio of the total NH equivalent in component A to the total NCO equivalent in component B [NH] / [NCO]=1:1.05.

[0067] Beneficial effects

[0068] 1. The innovations of this patent lie in: First, during the synthesis of the polyaspartic acid resin, a monofunctional perfluorinated macromonomer is introduced into the main chain of the polyaspartic acid ester molecule, thereby forming a comb-like (side chain) of long-chain fluorinated hydrophobic groups. Second, a monohydroxy-terminated polydimethylsiloxane is used to modify an aliphatic isocyanate trimer, resulting in the curing agent component also having a comb-like (side chain) of long-chain siloxane hydrophobic groups.

[0069] 2. Utilizing the aforementioned monofunctional macromonomer, side-chain hydrophobic groups are introduced into the resin component and curing agent component, respectively. This facilitates rotation and bending within the polyurea polymer structure, synergistically reducing the surface tension of the polyurea coating and imparting excellent hydrophobic properties to the polyaspartic acid ester coating. Consequently, the fluorosilicone-modified polyaspartic acid ester polyurea coating provided by this patent can achieve a water contact angle exceeding 120°, thereby producing a hydrophobic aspartic acid ester polyurea coating.

[0070] 3. By adjusting the formula of the above-mentioned resin component and curing agent component, the water contact angle of the fluorosilicone modified polyaspartic acid ester polyurea coating prepared according to the patent of the present invention can be adjusted between 100° and 110°, thereby effectively improving the water resistance of the polyaspartic acid ester polyurea coating.

[0071] 4. The fluorosilicone modified polyaspartic acid ester polyurea coating prepared according to the present invention has excellent hydrophobic properties while still maintaining the excellent material properties and chemical resistance inherent in polyaspartic acid ester coatings. BRIEF DESCRIPTION OF THE DRAWINGS

[0072] Figure 1 IR image of diethyl maleate (DM);

[0073] Figure 2 FC-016 infrared image;

[0074] Figure 3 FC-018 infrared image;

[0075] Figure 4 Initial infrared images of DM, FC-016, and PACM reactions;

[0076] Figure 5 Initial infrared images of DM, FC-016, and DMDC reactions;

[0077] Figure 6 Initial infrared images of DM, FC-018, and PACM reactions;

[0078] Figure 7 Initial infrared images of DM, FC-018, and DMDC reactions;

[0079] Figure 8 Infrared image of resin 104-FC016;

[0080] Figure 9 Infrared image of resin 105-FC016;

[0081] Figure 10 Infrared image of resin 104-FC018;

[0082] Figure 11 Infrared image of resin 105-FC018;

[0083] Figure 12 Water contact angle of F4 coating;

[0084] Figure 13 Water contact angle of FC2 coating;

[0085] Figure 14 Water contact angle of FC4 coating. DETAILED DESCRIPTION

[0086] The names and abbreviations of the main raw materials used in the synthesis of each resin are shown in Table 1

[0087] Table 1 Names and structures of main raw materials used in the synthesis of each resin

[0088]

[0089] analytical instruments

[0090] Fourier transform infrared spectrometer WAF-530 (Beijing Beifen Rayleigh Analytical Instrument Co., Ltd.)

[0091] Automatic Potentiometric Titrator AT-1 (Shanghai Hegong Scientific Instrument Co., Ltd.)

[0092] Contact Angle Meter JC2000C1 (Shanghai Zhongchen Digital Technology Equipment Co., Ltd.)

[0093] Example 1 Synthesis of Resin 104-FC016

[0094] To a 500ml four-necked flask equipped with an electric stirrer, thermometer, dropping funnel, nitrogen line, and reflux condenser, add 210.36g (1 mol) of PACM. Start stirring and replace the air in the reaction flask twice with nitrogen and maintain a nitrogen flow. Raise the temperature to approximately 45°C, then slowly add 163.57g (0.95 mol) of DM dropwise to the reaction flask, maintaining the temperature above 60°C and controlling the addition to complete over 20-40 minutes. Allow the reaction to proceed at 60-65°C for 0.5 hour, then add 25.91g (0.05 mol) of FC-016 dropwise, maintaining the temperature at 60-65°C and controlling the addition to complete over 10-30 minutes. Continue the reaction at this temperature for 16 hours. Cool to 40°C and discharge to obtain product 104-FC016. Using a potentiometric titrator, it was determined that the primary amine value of the reaction system was 187.97 mg / g at the beginning of the reaction, and the remaining primary amine value in the reaction system was 0.34 mg / g after the reaction was completed. This indicates that most of the carbon-carbon double bonds on DM and FC-016 reacted with the primary amine of PACM to form the product 104-FC016.

[0095] Figure 1 、 Figure 2 These are the infrared images of DM and FC-016 respectively. Figure 4 This is the initial infrared image of the reaction of DM, FC-016, and PACM. Figure 4 Middle at 1644cm -1 The absorption peaks are those of carbon-carbon double bonds of DM and FC-016. Figure 8 This is the infrared image of product 104-FC016. Figure 8 It can be seen that 1644cm -1 The absorption peak at has disappeared, indicating that DM and FC-016 have participated in the reaction to form product 104-FC016.

[0096] The structural formula of 104-FC016 (Formula 3):

[0097]

[0098] Example 2 Synthesis of Resin 105-FC016

[0099] To a 500ml four-necked flask equipped with an electric stirrer, thermometer, dropping funnel, nitrogen line, and reflux condenser, add 238.41g (1 mol) of DMDC. Start stirring and replace the air in the reaction flask twice with nitrogen, maintaining a nitrogen flow. Raise the temperature to approximately 45°C, then slowly add 163.57g (0.95 mol) of DMDC dropwise to the reaction flask, maintaining the temperature above 60°C and controlling the addition to complete over 20-40 minutes. Allow the reaction to proceed at 60-65°C for 0.5 hour, then add 25.91g (0.05 mol) of FC-016 dropwise, maintaining the temperature at 60-65°C and controlling the addition to complete over 10-30 minutes. Continue the reaction at this temperature for 16 hours. Cool to 40°C and discharge to obtain product 105-FC016. Using a potentiometric titrator, it was determined that the primary amine value of the reaction system was 174.73 mg / g at the beginning of the reaction, and the remaining primary amine value in the reaction system was 0.28 mg / g after the reaction was completed. This indicates that most of the carbon-carbon double bonds on DM and FC-016 reacted with the primary amine of DMDC to form product 105-FC016.

[0100] Figure 5 This is the initial infrared image of the reaction between DM and DM, FC-016, and DMDC. -1 The absorption peaks at the two locations are the carbon-carbon double bonds of DM and FC-016, respectively. Figure 9 This is the infrared image of product 105-FC016. Figure 9 It can be seen that 1644cm -1 The absorption peak at has disappeared, indicating that DM and FC-016 have participated in the reaction to form product 105-FC016.

[0101] The structural formula of 105-FC016 (Formula 4):

[0102]

[0103] Example 3 Synthesis of Resin 104-FC018

[0104] To a 500ml four-necked flask equipped with an electric stirrer, thermometer, dropping funnel, nitrogen line, and reflux condenser, add 210.36g (1 mol) of PACM. Start stirring and replace the air in the reaction flask twice with nitrogen and maintain a nitrogen flow. Raise the temperature to approximately 45°C, then slowly add 163.57g (0.95 mol) of DM dropwise to the reaction flask, maintaining the temperature above 60°C and ensuring that the addition is complete over 20-40 minutes. Allow the reaction to proceed at 60-65°C for 0.5 hour, then add 30.91g (0.05 mol) of FC-018 dropwise, maintaining the temperature at 60-65°C and ensuring that the addition is complete over 10-30 minutes. Continue the reaction at this temperature for 16 hours. Cool to 40°C and discharge to obtain product 104-FC018. Using a potentiometric titrator, it was determined that the primary amine value of the reaction system was 185.65 mg / g at the beginning of the reaction, and the remaining primary amine value in the reaction system was 0.37 mg / g after the reaction was completed. This indicates that most of the carbon-carbon double bonds on DM and FC-018 reacted with the primary amine of PACM to form product 104-FC018.

[0105] Figure 3 This is the infrared image of FC-018. Figure 6 The infrared spectra of DM, DM, FC-018 and PACM are shown in Figure 1. -1 The absorption peaks at the carbon-carbon double bonds of DM and FC-018 are respectively. Figure 10 This is the infrared image of product 104-FC018. Figure 10 It can be seen that 1644cm -1 The absorption peak at has disappeared, indicating that DM and FC-018 have participated in the reaction to form product 104-FC018.

[0106] The structural formula of 104-FC018 (Formula 6):

[0107]

[0108] Example 4 Synthesis of Resin 105-FC018

[0109] To a 500ml four-necked flask equipped with an electric stirrer, thermometer, dropping funnel, nitrogen line, and reflux condenser, add 238.41g (1 mol) of DMDC. Stirring was initiated, and the air in the reaction flask was replaced twice with nitrogen, maintaining a nitrogen flow. The temperature was raised to approximately 45°C, and then 163.57g (0.95 mol) of DMDC was slowly added dropwise to the reaction flask, maintaining the temperature above 60°C and allowing the addition to complete over 20-40 minutes. The reaction was allowed to proceed at 60-65°C for 0.5 hour, followed by the dropwise addition of 30.91g (0.05 mol) of FC-018, maintaining the temperature at 60-65°C and allowing the addition to complete over 10-30 minutes. The reaction was then continued at this temperature for 16 hours. The temperature was then lowered to 40°C and the product, 105-FC018, was obtained. Using a potentiometric titrator, it was determined that the primary amine value of the reaction system was 172.72 mg / g at the beginning of the reaction, and the remaining primary amine value in the reaction system was 0.49 mg / g after the reaction was completed. This indicates that most of the carbon-carbon double bonds on DM and FC-018 reacted with the primary amine of DMDC to form product 105-FC018.

[0110] Figure 7 The infrared spectra of DM, DM, FC-018 and DMDC are shown in Figure 1. -1 The absorption peaks at the carbon-carbon double bonds of DM and FC-018 are respectively. Figure 11 This is the infrared image of product 105-FC018. Figure 11 It can be seen that 1644cm -1 The absorption peak at has disappeared, indicating that DM and FC-018 have participated in the reaction to form product 105-FC018.

[0111] The structural formula of 105-FC018 (Formula 7):

[0112]

[0113] Table 2 shows the formulation examples of resin components A-A6 in Examples 5-10, with each component being calculated by weight.

[0114] Table 2 Formulation examples of resin components A-A6 in Examples 5-10

[0115]

[0116]

[0117] Example 5 Preparation of resin component A1

[0118] 1. Weigh the raw materials numbered 1-8 of Formulation A1 in Table 2 into a container and stir thoroughly.

[0119] 2. Weigh and add the raw materials No. 9-11 in sequence, stir thoroughly and disperse at high speed (1500 rpm) for 20 minutes, then grind into a sand mill until the fineness is less than 15 μm.

[0120] 3. Then weigh and add the raw materials numbered 12-13 in sequence, stir thoroughly and disperse at high speed (2000 rpm) for 20 minutes to obtain resin component A1.

[0121] Example 6 Preparation of resin component A2

[0122] The raw materials numbered 1 to 8 in the formulation A2 in Table 2 were weighed into a container according to the measurement, and the remaining operations were carried out in accordance with the operation flow in Example 5 to obtain the resin component A2.

[0123] Example 7 Preparation of resin component A3

[0124] The raw materials numbered 1 to 8 in the formulation A3 in Table 2 were weighed into a container according to the measurement, and the remaining operations were carried out in accordance with the operation flow in Example 5 to obtain the resin component A3.

[0125] Example 8 Preparation of resin component A4

[0126] The raw materials numbered 1 to 8 in the formulation A4 in Table 2 were weighed into a container according to the measurement, and the remaining operations were carried out in accordance with the operation flow in Example 5 to obtain the resin component A4.

[0127] Example 9 Preparation of resin component A5

[0128] The raw materials numbered 1 to 8 in the formulation A5 in Table 2 were weighed into a container according to the measurement, and the remaining operations were carried out in accordance with the operation flow in Example 5 to obtain the resin component A5.

[0129] Example 10 Preparation of resin component A6

[0130] The raw materials numbered 1 to 8 in the formulation A6 in Table 2 were weighed into a container according to the measurement, and the remaining operations were carried out according to the operation flow in Example 5 to obtain the resin component A6.

[0131] Comparative Example 1 Preparation of resin component AC1

[0132] The raw materials numbered 1 to 8 in the AC1 formula in Table 2 were weighed into a container according to the measurement, and the remaining operations were carried out in accordance with the operation flow in Example 5 to obtain the resin component AC1.

[0133] Example 11 Preparation of polysiloxane-modified isocyanate trimer S-HT300

[0134] To a 1000ml four-necked flask equipped with an electric stirrer, a thermometer, a nitrogen gas line, and a reflux condenser, 630g (1mol) of HT-300 and 25.2g (0.019mol) of IOTA8861 were added, stirred, and then 0.6g of stannous octoate was added. The air in the reaction flask was then replaced with nitrogen and maintained under nitrogen flow. The temperature was slowly raised to 70°C and stirred for 3-4 hours, until the NCO% content reached 19.1%. After cooling to room temperature, S-HT100 was obtained.

[0135] Example 12 Preparation of Curing Agent B

[0136] 1. Mix S-HT300 and compound diluent in a ratio of 9:1 to obtain curing agent B with an average NCO% of 17.2%.

[0137] Example 13 Preparation of Fluorosilicone-Modified Two-Component Polyaspartame Polyurea Coating Film F1

[0138] 1 Prepare a clean glass test panel (25×76×1 mm) for coating spraying.

[0139] 2. According to the proportions of F1 in Table 3, weigh components A and B respectively and mix them evenly. Add appropriate amount of diluent to adjust the viscosity of the mixture to within 18-21 seconds of T-4 cup.

[0140] 3 Use an air spray gun (SATA-5000 spray gun, nozzle diameter is 1.3mm) to evenly spray on the surface of the glass test plate to ensure that the wet film thickness is between 55-80μm (dry film is between 35-50μm).

[0141] 4. After the wet film is allowed to stand at room temperature for 15 minutes to level and flash dry, it is then placed at room temperature for 4 hours to cure. It can also be placed in an 80°C oven for 30 minutes to cure, to obtain the F1 coating film.

[0142] 5. After the coating has matured for 24 hours, the water contact angle can be tested.

[0143] Example 14 Preparation of Fluorosilicone-Modified Two-Component Polyaspartame Polyurea Coating Film F2

[0144] According to the formula of F2 in Table 3, components A and B were weighed respectively, and the rest of the operations were carried out according to the operating procedures of Example 13 to obtain the F2 coating film.

[0145] Example 15 Preparation of Fluorosilicone-Modified Two-Component Aspartame Polyurea Coating F3

[0146] According to the formula of F3 in Table 3, components A and B were weighed respectively, and the rest of the operations were carried out according to the operating procedures of Example 13 to obtain the F3 coating film.

[0147] Example 16 Preparation of Fluorosilicone-Modified Two-Component Aspartame Polyurea Coating F4

[0148] According to the formula of F4 in Table 3, components A and B were weighed respectively, and the rest of the operation was carried out according to the operation flow of Example 13 to obtain F4 coating film. The water contact angle was measured to be 125.6° (see Figure 12 ).

[0149] Example 17 Preparation of Fluorosilicone-Modified Two-Component Aspartame Polyurea Coating F5

[0150] According to the formula of F5 in Table 3, components A and B were weighed respectively, and the rest of the operations were carried out in accordance with the operating procedures of Example 13 to obtain the F5 coating film.

[0151] Example 18 Preparation of Fluorosilicone-Modified Two-Component Aspartame Polyurea Coating F6

[0152] According to the formula of F6 in Table 3, components A and B were weighed respectively, and the rest of the operations were carried out according to the operating procedures of Example 13 to obtain the F6 coating film.

[0153] Comparative Example 2 Preparation of Comparative Example Coating FC1

[0154] According to the FC1 formula in Table 3, components A and B were weighed respectively, and the rest of the operations were carried out according to the operating procedures of Example 13 to obtain the FC1 coating film.

[0155] Comparative Example 3 Preparation of Comparative Example Coating FC2

[0156] According to the FC2 formula in Table 3, components A and B were weighed respectively, and the rest of the operation was carried out according to the operation flow of Example 13 to obtain the FC2 coating film. The water contact angle was measured to be 99.7° (see Figure 13 ).

[0157] Comparative Example 4 Preparation of Comparative Example Coating FC3

[0158] According to the FC3 formula in Table 3, components A and B were weighed respectively, and the rest of the operations were carried out according to the operating procedures of Example 13 to obtain the FC3 coating film.

[0159] Comparative Example 5 Preparation of Comparative Example Coating FC4

[0160] According to the FC4 formula in Table 3, components A and B were weighed respectively, and the rest was carried out according to the operation flow of Example 13.

[0161] , and the FC4 coating was obtained. The water contact angle was measured to be 70.7° (see Figure 14 ).

[0162] Table 3 is a list of the formulations of the coating films in Examples 13-18 and Comparative Examples 2-5 and the test data of the corresponding water contact angles and water resistance.

[0163] Table 3 List of the formulations of the coatings in Examples 13-18 and Comparative Examples 2-5 and the test data of the corresponding water contact angles and water resistance

[0164]

[0165] As shown in Table 3, all the coatings that meet the requirements of the present invention, i.e., the coatings F1-F6 in Examples 13-18, have a water contact angle greater than 110°, and the water contact angles of F3 and F4 are greater than 120° (see Table 3). Figure 12 ) In the comparative examples 2-4, the FC1-FC3 coatings had water contact angles of only about 100° because the curing agents used were not modified with monohydroxyl-terminated silicone oil (see Figure 13 ) In the FC4 coating of comparative example 5, the polyaspartic acid ester used was not modified with long-chain fluorinated acrylate, and the curing agent was not modified with monohydroxyl-terminated silicone oil, so its water contact angle was only 70.7° (see Figure 14 Table 4 is the comprehensive performance table of fluorosilicone modified two-component aspartame polyurea coating F4

[0166] It can be seen from the data in Table 4 that the fluorosilicone modified polyaspartic acid ester polyurea coating prepared in the present invention has excellent hydrophobic properties while still maintaining the excellent material properties and chemical resistance inherent in polyaspartic acid ester coatings.

[0167] Table 4 Comprehensive performance of fluorosilicone modified two-component aspartame polyurea coating F4

[0168]

[0169]

Claims

1. A fluorosilicone modified two-component polyaspartic polyurea coating, characterized in that: It includes a resin component and a curing agent component: Wherein: the resin component is fluorine-modified polyaspartic acid ester; the fluorine-modified polyaspartic acid ester is selected from a single resin of structure Y in formula 1, or a mixture of two or more resins of structure Y, and the weight ratio of the mixture can be any proportion; The fluorine-modified polyaspartic acid ester resin has a structure as shown in Formula 1: In Formula 1, R1 and R2 are C1-C4 alkyl groups with the same or different carbon atoms; Y is an alkylene group, a cycloalkylene group or a substituted cycloalkylene group, and n=7 or 9; The curing agent component is a siloxane-modified isocyanate trimer; the siloxane-modified isocyanate trimer has the following structure: In Formula 9, R3 is an alkylene group of isophorone diisocyanate IPDI or hexamethylene diisocyanate HDI; R4 and R5 are straight-chain or branched-chain alkyl groups, and x and y are 1, 2, 3, or 4; The resin component is also added with diluent, filler, coupling agent, dispersant, thixotropic agent, pigment, leveling agent, defoamer, ultraviolet light absorber and antioxidant as required; A diluent is also added to the curing agent component as needed.

2. The fluorosilicone modified two-component polyaspartate polyurea coating according to claim 1, characterized in that: The fluorine-modified polyaspartic acid ester resin is any one of the following structures:

3. The fluorosilicone modified two-component polyaspartate polyurea coating according to claim 1, characterized in that: The fluorine-modified polyaspartic acid ester resin is prepared according to the following steps: During the synthesis of polyaspartic acid resin, fluorinated acrylate is added, and its double bond undergoes Michael addition reaction with the primary amino group on the primary amino compound, and fluorine-modified polyaspartic acid resin is synthesized simultaneously with unsaturated dicarboxylic acid ester; the reaction equation is shown in Formula 8: In formula 8, R1 and R2 are C1-C4 alkyl groups with the same or different carbon atoms; Y is an alkylene group, a cycloalkylene group or a substituted cycloalkylene group, and n=7 or 9; Fluorinated acrylates include perfluorodecyl acrylate, 2-perfluorodecyl ethyl acrylate, perfluorooctanol acrylate, perfluoroalkylethyl acrylate, or 2-(perfluorooctyl)ethyl methacrylate; The unsaturated dibasic acid carboxylic acid ester includes dialkyl maleate or dialkyl fumarate; wherein the dialkyl maleate includes diethyl maleate, dipropyl maleate, dibutyl maleate and methyl propyl maleate; the dialkyl fumarate includes diethyl fumarate, dipropyl fumarate, dibutyl fumarate and methyl propyl fumarate; the above unsaturated dicarboxylic acids are used alone or in any proportion; Primary amino compounds include ethylenediamine, 1,2-propylenediamine, 2,5-dimethyl-2,5-hexanediamine, 1,11-undecyldiamine, 1,12-dodecyldiamine, 2,4 , -Diamino-dicyclohexylmethane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,4-toluenediamine or 2,6-toluenediamine, 2,4 ， -Diaminodiphenylmethane or 4,4 ， -diaminodiphenylmethane, 1,4-butanediamine, 1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 4,4,-diamino-dicyclohexylmethane, 3,3,-dimethyl-4,4,-diamino-dicyclohexylmethane and mixtures thereof, terminal amino compounds of polypropylene oxide, polyethylene oxide or copolymers of ethylene oxide and propylene oxide, and primary amino compounds may be monoamines or polyamines; they include 1,6-hexanediamine, 4,4,-diamino-dicyclohexylmethane, 3,3,-dimethyl-4,4,-diamino-dicyclohexylmethane.

4. The fluorosilicone modified two-component polyaspartate polyurea coating according to claim 3, characterized in that: The fluorine-modified polyaspartic acid ester resin is prepared according to the following steps: First, add a measured amount of primary amino compound into a reaction kettle, then add a measured amount of perfluoroalkyl acrylate in a dropwise manner, react for 30 minutes after the dropwise addition is completed, then add an unsaturated dicarboxylic acid ester dropwise, and continue to react until the reaction is completed, thereby obtaining a fluorine-modified polyaspartic acid resin; The molar ratio between the unsaturated dicarboxylic acid ester and the fluorinated acrylate is 0.98:0.02--0.90:0.10; The suitable molar ratio of the sum of the moles of the unsaturated dicarboxylic acid ester and the fluorinated acrylate to the primary amino compound is 2:1.10--2:1.00; The temperature of the Michael addition reaction between the unsaturated dicarboxylic acid ester and the fluorinated acrylate and the primary amino compound is 45°C-80°C; The time for the Michael addition reaction between the unsaturated dicarboxylic acid ester and the fluorine-containing acrylate and the primary amino compound is 6 to 24 hours.

5. The fluorosilicone modified two-component polyaspartic polyurea coating according to claim 1, characterized in that: The siloxane-modified isocyanate trimer is prepared by the following steps: The siloxane-modified isocyanate trimer is obtained by reacting a monohydroxy-terminated long-chain polysiloxane with a trimer of aliphatic isocyanate, and the reaction is shown in Formula 10: In formula 10, R3 is an alkylene group of isophorone diisocyanate IPDI or hexamethylene diisocyanate HDI; R4 and R5 are straight-chain or branched-chain alkyl groups, and x and y are 1, 2, 3, or 4.

6. The fluorosilicone modified two-component polyaspartate polyurea coating according to claim 5, characterized in that: The siloxane-modified isocyanate trimer is prepared by the following steps: the molecular weight of the monohydroxyl-terminated long-chain polysiloxane is in the range of 500-2000; the trimer of the aliphatic isocyanate includes an IPDI trimer or an HDI trimer; and the mol ratio of the monohydroxyl-terminated long-chain polysiloxane to the aliphatic isocyanate trimer is 0.01-0.02:

1.

7. The fluorosilicone modified two-component polyaspartate polyurea coating according to claim 6, characterized in that: The siloxane-modified isocyanate trimer is prepared by the following steps: monohydroxyl-terminated long-chain polysiloxane and aliphatic isocyanate trimer are mixed in a three-necked flask, and a catalyst accounting for 0.1-0.3% by weight of the total reactants is added, and the mixture is stirred and heated to 70-80° C. under nitrogen protection for 3-4 hours until the NCO% content reaches the theoretical value.

8. The fluorosilicone modified two-component polyaspartic polyurea coating according to claim 1, characterized in that: The ratio of the total NH equivalent in the resin component to the total NCO equivalent in the curing agent component is [NH] / [NCO]=1:1.05.

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