A fluorine-containing aminopolysiloxane resin and a method for producing the same, an epoxy resin coating

Abstract

The application discloses a fluorine-containing aminopolysiloxane resin and a preparation method and an epoxy resin coating thereof; the fluorine-containing aminopolysiloxane resin is brand-new, can be used as a curing agent of an epoxy resin, and enables the prepared epoxy resin coating to have low-temperature or room-temperature curing capability; meanwhile, the prepared epoxy resin coating also has corrosion resistance, heat resistance, wear resistance and other performances.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a fluorinated amino polysiloxane resin and its preparation method, and epoxy resin coatings. Background Technology

[0002] Epoxy resins are widely used in coatings, adhesives, encapsulation, and composite materials due to their excellent mechanical, chemical, and electrical insulation properties, low shrinkage, and strong adhesion to various substrates. As a coating, epoxy resins play a crucial role in shipbuilding, aerospace, weaponry, transportation, and chemical pipelines. In practical applications, epoxy resins typically undergo a chemical reaction with a suitable curing agent to solidify and form a network-like three-dimensional polymer. Cured epoxy resins exhibit high strength, excellent adhesion, chemical resistance, heat resistance, electrical insulation, low shrinkage, low volatility, and good fatigue resistance. The type of curing agent significantly influences the properties of the cured product.

[0003] Currently, there are various types of epoxy resin curing agents, among which amine curing agents are the most commonly used. Amine curing agents include aliphatic amines, alicyclic amines, aromatic amines, etc., but epoxy resin coatings prepared using these organic amines as curing agents are difficult to simultaneously meet the requirements of room temperature curing, corrosion resistance, and heat resistance. Summary of the Invention

[0004] This application provides a fluorinated amino polysiloxane resin and its preparation method, as well as an epoxy resin coating, which can be used as a curing agent for epoxy resin. This allows the prepared epoxy resin coating to have the ability to cure at low temperature or room temperature. At the same time, it also enables the prepared epoxy resin coating to have properties such as corrosion resistance, heat resistance, and wear resistance.

[0005] In a first aspect, embodiments of this application provide a fluorinated amino polysiloxane resin, the chemical structural formula of which is shown in formula (I):

[0006]

[0007] Wherein, R is methyl or ethyl; R1 is phenyl; R2 is methyl or ethyl; R f G is trifluoropropyl; G is aminoalkyl.

[0008] In some embodiments, the aminoalkyl group is -R a NH2 or -R a NHR b NH2, of which R a R is a hydrocarbon group containing 2-4 carbon atoms. b It contains a hydrocarbon group having 2-4 carbon atoms.

[0009] In some embodiments, the fluorinated amino polysiloxane resin has a viscosity of 200-500 mPa·s and an amine value of 2.20-3.30 mmol / g.

[0010] Secondly, embodiments of this application provide a method for preparing a fluorinated amino polysiloxane resin, characterized by comprising the following steps:

[0011] (1) Mix the first monomer and the second monomer evenly, then add water to react and obtain reaction mixture A;

[0012] (2) A third monomer and water are added to the reaction mixture A, and the reaction mixture B is obtained after the reaction.

[0013] (3) The reaction mixture B is subjected to a polycondensation reaction under vacuum conditions, while removing the reaction byproducts, to obtain a fluorinated amino polysiloxane resin.

[0014] The chemical structural formula of the first monomer is shown in formula (II):

[0015]

[0016] The chemical structural formula of the second monomer is shown in formula (III):

[0017]

[0018] The chemical structural formula of the third monomer is shown in formula (IV):

[0019]

[0020] R is methyl or ethyl; R1 is phenyl; R2 is methyl or ethyl; R f G is trifluoropropyl; G is aminoalkyl.

[0021] In some embodiments, in step (1), the molar ratio of the first monomer, the second monomer and water is (1.00-3.00):1.00:(1.80-5.40), and in step (2), the molar ratio of the third monomer and water is 1.00:(0.50-1.00).

[0022] In some embodiments, in step (1), the molar ratio of the first monomer to the second monomer is (1.00-1.20):1.00.

[0023] In some embodiments, the molar ratio of the third monomer to the second monomer is 1.00:(0.50-2.50).

[0024] In some embodiments, in step (1), the first monomer and the second monomer are mixed evenly, and water is added at 10-30°C for hydrolysis reaction for 0.2-1.0 h to obtain the reaction mixture A; in step (2), a third monomer and water are added to the reaction mixture A, and the reaction is continued at 10-30°C for 0.5-1.0 h, and then the temperature is raised to 60-80°C for 3.0-6.0 h to obtain the reaction mixture B; in step (3), the reaction mixture B is subjected to polycondensation reaction under vacuum conditions at 60-90°C for 4.0-7.0 h, while removing reaction byproducts to obtain the fluorinated amino polysiloxane resin.

[0025] Thirdly, this application provides an epoxy resin coating, characterized in that it comprises: epoxy resin and fluorinated amino polysiloxane resin, wherein the molar ratio of epoxy groups in the epoxy resin to amino hydrogens in the fluorinated amino polysiloxane resin is 1.00:(0.80-1.00).

[0026] In some embodiments, the epoxy resin includes at least one of alicyclic epoxy resin and aromatic epoxy resin.

[0027] As can be seen from the above technical solutions, this specification provides a novel fluorinated amino polysiloxane resin, which can be used as a curing agent for epoxy resin, enabling the prepared epoxy resin coating to have low-temperature or room-temperature curing ability. At the same time, it can also enable the prepared epoxy resin coating to have properties such as corrosion resistance, heat resistance, and wear resistance. Attached Figure Description

[0028] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0029] Figure 1 The chemical reaction equations for the preparation process of the fluorinated amino polysiloxane resin provided in this application are shown;

[0030] Figure 2 The results of the neutral salt spray test on the epoxy resin coating provided in this application are shown. Detailed Implementation

[0031] To facilitate understanding of this specification, a more complete description will be provided below with reference to the accompanying drawings. Preferred embodiments of this specification are shown in the drawings. However, this specification can be implemented in many different forms without departing from the core spirit of this specification and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this specification.

[0032] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this specification belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of this specification. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0033] In a first aspect, embodiments of this application provide a fluorinated amino polysiloxane resin, characterized in that the chemical structural formula of the fluorinated amino polysiloxane resin is as shown in formula (I):

[0034]

[0035] Wherein, R is methyl or ethyl; R1 is phenyl; R2 is methyl or ethyl; R f G is trifluoropropyl; G is aminoalkyl. This application provides a novel fluorinated aminopolysiloxane resin, which can be used as a curing agent for epoxy resins, enabling the prepared epoxy resin coatings to cure at low or room temperature. Simultaneously, it also imparts properties such as corrosion resistance, heat resistance, and abrasion resistance to the prepared epoxy resin coatings.

[0036] In some embodiments of this application, the aminoalkyl group is -R a NH2 or -R a NHR b NH2, of which R a R is a hydrocarbon group containing 2-4 carbon atoms. b It consists of a hydrocarbon group having 2-4 carbon atoms. For example, R a It can be ethyl, propyl, or butyl, R b It can also be ethyl, propyl, or butyl. In the same aminoalkyl group, R... a and R b They can be the same or different.

[0037] Specifically, aminoalkyl groups can include -CH2CH2NH2, -CH2CH2CH2NH2, -CH2CH2CH2CH2NH2, -CH2CH2NHCH2CH2NH2, -CH2CH2CH2NHCH2CH2NH2, -CH2CH2NHCH2CH2NH2, -CH2CH2NHCH2CH2CH2NH2, etc.

[0038] In some embodiments of this application, the viscosity of the fluorinated amino polysiloxane resin is 200-500 mPa·s, and the amine value is 2.20-3.30 mmol / g. The fluorinated amino polysiloxane resin provided in the embodiments of this application is a low-viscosity resin, and its viscosity value can be 200 mPa·s, 220 mPa·s, 250 mPa·s, 280 mPa·s, 300 mPa·s, 320 mPa·s, 350 mPa·s, 400 mPa·s, 500 mPa·s, or any viscosity value between any two of the above viscosity values. Furthermore, the viscosity value of the fluorinated amino polysiloxane resin provided in the embodiments of this application can be 200 mPa·s, 220 mPa·s, 240 mPa·s, 260 mPa·s, 280 mPa·s, 300 mPa·s, 320 mPa·s, 340 mPa·s, 350 mPa·s, or any viscosity value between any two of the above viscosity values.

[0039] The amine value of the fluorinated amino polysiloxane resin provided in the embodiments of this application can be 2.20 mmol / g, 2.40 mmol / g, 2.60 mmol / g, 2.80 mmol / g, 3.00 mmol / g, 3.30 mmol / g, or any amine value between any two of the above-mentioned amine values. Further, the amine value of the fluorinated amino polysiloxane resin provided in the embodiments of this application can be 2.30 mmol / g, 2.40 mmol / g, 2.50 mmol / g, 2.60 mmol / g, 2.70 mmol / g, 2.80 mmol / g, 2.90 mmol / g, 3.00 mmol / g, 3.10 mmol / g, or any amine value between any two of the above-mentioned amine values.

[0040] Secondly, embodiments of this application provide a method for preparing a fluorinated amino polysiloxane resin, characterized by comprising the following steps:

[0041] (1) Mix the first monomer and the second monomer evenly, then add water to react and obtain reaction mixture A;

[0042] (2) Add the third monomer and water to reaction mixture A, and reaction mixture B is obtained after the reaction.

[0043] (3) The reaction mixture B was subjected to a polycondensation reaction under vacuum conditions, while the reaction byproducts were removed, to obtain a fluorinated amino polysiloxane resin.

[0044] The chemical structural formula of the first monomer is shown in formula (II):

[0045]

[0046] The chemical structural formula of the second monomer is shown in formula (III):

[0047]

[0048] The chemical structural formula of the third monomer is shown in formula (IV):

[0049]

[0050] R is methyl or ethyl; R1 is phenyl; R2 is methyl or ethyl; R f G is trifluoropropyl; G is aminoalkyl.

[0051] Figure 1 The chemical reaction equations for the preparation process of the fluorinated amino polysiloxane resin provided in this application are shown. In the embodiments of this application, trifunctional siloxanes and aminosiloxanes are used as raw materials, and trifluoropropyl groups are introduced. Through the organic combination of hydrolysis and condensation reactions, a novel fluorinated amino polysiloxane resin can be obtained. The synthesis reaction process is atom-economical and environmentally friendly.

[0052] In some embodiments of this application, in step (1), the molar ratio of the first monomer, the second monomer and water is (1.00-3.00):1.00:(1.80-5.40), and in step (2), the molar ratio of the third monomer and water is 1.00:(0.50-1.00).

[0053] Extensive experiments revealed that the molar ratio of the first monomer, the second monomer, and water plays a crucial role in the successful synthesis of fluorinated amino polysiloxane resins. Furthermore, the molar ratio of the third monomer and water also plays a critical role. By controlling the molar ratio of the first monomer, the second monomer, and water within the range of (1.00-3.00):1.00:(1.80-5.40), and the molar ratio of the third monomer and water within the range of 1.00:(0.50-1.00), fluorinated amino polysiloxane resins can be successfully prepared. When used as a curing agent, the resulting epoxy resin coating exhibits excellent curing, corrosion resistance, wear resistance, and heat resistance properties.

[0054] In some embodiments of this application, in step (1), the molar ratio of the first monomer and the second monomer is (1.00-1.20):1.00. As mentioned above, by controlling the molar ratio of the first monomer, the second monomer, and water within the range of (1.00-3.00):1.00:(1.80-5.40) (i.e., the molar ratio of the first monomer to the second monomer is (1.00-3.00):1.00), fluorinated amino polysiloxane resin can be successfully prepared. Based on this, the inventors discovered through numerous experiments that, within the above molar ratio range, different molar ratios between the first monomer and the second monomer result in different performance characteristics of the epoxy resin coatings obtained when the fluorinated amino polysiloxane resin is used as a curing agent.

[0055] By controlling the molar ratio of the first monomer to the second monomer within the range of (1.00-1.20):1.00, for example, controlling the molar ratio of the first monomer to the second monomer to 1.00:1.00, the prepared epoxy resin coating not only has low-temperature or room-temperature curing ability, but also improves the corrosion resistance, heat resistance, and wear resistance of the epoxy resin coating. With the increase of fluorine content, the various properties of the epoxy resin coating improve accordingly.

[0056] In some embodiments of this application, the molar ratio of the third monomer to the second monomer is 1.00:(0.50-2.50). For example, the molar ratio of the third monomer to the second monomer can be 1.00:0.50, 1.00:1.00, 1.00:1.50, 1.00:2.00, 1.00:2.50, or any molar ratio between any two of the above molar ratios.

[0057] In some embodiments of this application, in step (1), the first monomer and the second monomer are mixed evenly, and water is added at 10-30°C for hydrolysis reaction for 0.2-1.0 h to obtain reaction mixture A; in step (2), the third monomer and water are added to reaction mixture A, and the reaction is continued at 10-30°C for 0.5-1.0 h, and then the temperature is raised to 60-80°C for 3.0-6.0 h to obtain reaction mixture B; in step (3), reaction mixture B is subjected to polycondensation reaction under vacuum conditions at 60-90°C for 4.0-7.0 h, while removing reaction byproducts to obtain fluorinated amino polysiloxane resin.

[0058] Thirdly, embodiments of this application provide an epoxy resin coating, comprising: an epoxy resin and a fluorinated amino polysiloxane resin, wherein the molar ratio of epoxy groups in the epoxy resin to amino hydrogen in the fluorinated amino polysiloxane resin is 1.00:(0.80-1.00). The fluorinated amino polysiloxane resin provided in this application embodiment can be used as a curing agent for the epoxy resin. An epoxy resin coating can be obtained by mixing the epoxy resin and the fluorinated amino polysiloxane resin in a specific ratio. During the mixing process, the molar ratio of epoxy groups in the epoxy resin to amino hydrogen in the fluorinated amino polysiloxane resin can be controlled within the range of 1.00:(0.80-1.00). For example, the molar ratio of epoxy groups in epoxy resin and amino hydrogen in fluorinated amino polysiloxane resin can be controlled to be 1.00:0.80, 1.00:0.85, 1.00:0.90, 1.00:0.95, 1.00:1.00, or any molar ratio between any two of the above molar ratios.

[0059] The epoxy resin coating provided in this application embodiment can be prepared and tested according to the following method:

[0060] (1) Fluorinated amino polysiloxane resin and epoxy resin are mixed evenly, and the molar ratio of amino hydrogen to epoxy group is controlled to be (0.80-1.00):1.00 to obtain curable epoxy resin coating.

[0061] (2) Apply epoxy resin coating evenly to tinplate or Q235 steel plate, let it stand at room temperature for 0.5h, and then cure it directly at 50℃ for 4.0-6.0h (or cure it by curing at room temperature for 7 days). Alternatively, the curing process can be accelerated by using 40-50℃ / 2h or 80-100℃ / 2h to obtain epoxy resin coating, so as to conduct performance testing on epoxy resin coating.

[0062] The epoxy resin coating prepared by the above method has excellent thermal stability and a low thermal decomposition temperature (T). d5 It can withstand temperatures up to 320℃; it has strong adhesion and good corrosion resistance and wear resistance. It can be used as a high-performance coating and has a wide range of application prospects. For example, it can be widely used as a high-performance coating in aerospace, shipbuilding and marine fields.

[0063] In some embodiments of this application, the epoxy resin includes at least one of alicyclic epoxy resin and aromatic epoxy resin. For example, the epoxy resin may be hydrogenated bisphenol A epoxy resin, E51 bisphenol A epoxy resin, AFG-90H epoxy resin, AG-80 epoxy resin, TDE-85 epoxy resin, etc.

[0064] The following are specific preparation examples related to the above-described contents of this disclosure. It should be clarified that the following examples are merely illustrative of the fluorinated amino polysiloxane resin and its preparation method disclosed above, as well as the epoxy resin coating. The specific implementation methods and parameters used are only one or more of the numerous processes and methods described above. Those skilled in the art can use other parameters to prepare the fluorinated amino polysiloxane resin and epoxy resin coating according to the above methods based on the content described in this specification, without departing from the core spirit of the application.

[0065] Example 1

[0066] This embodiment prepares a fluorinated amino polysiloxane resin. The preparation process is carried out in a flask filled with dry nitrogen and includes the following steps:

[0067] (1) In a 250 mL four-necked flask equipped with a stirrer, reflux condenser and thermometer, add phenyltrimethoxysilane (59.49 g, 0.30 mol) and (3,3,3-trifluoropropyl)trimethoxysilane (65.40 g, 0.30 mol) in sequence, and slowly add water (11.34 g, 0.63 mol) while stirring, and react at 30 °C for 15 min;

[0068] (2) Add 3-(2-aminoethylamino)propylmethyldimethoxysilane (30.97 g, 0.15 mol), then slowly add water (1.89 g, 0.11 mol), continue the reaction for 45 min, and then heat to 75 °C and reflux for 4.0 h;

[0069] (3) The reaction was carried out at 75℃ and -0.005MPa for 4.0h, while removing byproducts such as methanol. After cooling, a colorless and transparent liquid product was obtained.

[0070] The colorless and transparent liquid product was analyzed by proton NMR spectroscopy, and the results were as follows: 1 H-NMR (CDCl3, TMS), δ (ppm): 6.66-7.85 (Ar-H), 2.85-3.60 (O-CH3), 2.18-2.77 (CH2NHCH2CH2), 1.55-2.16 (CH2CH2C F3), 1.26-1.55 (Si-CH2CH2CH2NHCH2CH2), 0.19-0.93 (Si-CH2CH2CH2NHCH2CH2 and CH2CH2CF3), -0.38-0.19 (Si-CH3).

[0071] Fourier transform infrared spectroscopy analysis was performed on the colorless and transparent liquid product, and the results were as follows: FT-IR (KBr, cm⁻¹) -1): 3460-3280(NH), 2980-2900(Si-CH3), 2840(SiO-CH3), 3100-3000(Ar-H), 1360(CF3), 1130-1052(Si-O-Si).

[0072] The colorless and transparent liquid product was determined to be a fluorinated amino polysiloxane resin.

[0073] In step (1) of this embodiment, the molar ratio of phenyltrimethoxysilane (0.30 mol) to (3,3,3-trifluoropropyl)trimethoxysilane (0.30 mol) is 0.30:0.30 = 1.00:1.00. For ease of distinction, the fluorinated amino polysiloxane resin prepared in this embodiment is designated as HBPSi-2Ph2F. Furthermore, for ease of distinction from the fluorinated amino polysiloxane resins provided in Examples 2-5, the fluorinated amino polysiloxane resin of this embodiment can be designated as HBPSi-2Ph2F-1.

[0074] Example 2

[0075] In this embodiment, a fluorinated amino polysiloxane resin is prepared. The preparation method is basically the same as that in Example 1, except that: in step (2), 3-aminopropylmethyldimethoxysilane (48.99g, 0.30mol) is added, and then water (3.78g, 0.21mol) is slowly added. The reaction continues for 45min, and then the temperature is raised to 75℃ and refluxed for 4.0h.

[0076] The product prepared in this embodiment was subjected to proton NMR and Fourier transform infrared spectroscopy analysis. The results showed that the colorless and transparent liquid product was a fluorinated amino polysiloxane resin.

[0077] The fluorinated amino polysiloxane resin prepared in this embodiment can also be represented as HBPSi-2Ph2F. Furthermore, to easily distinguish it from the fluorinated amino polysiloxane resins provided in Examples 1 and 3-5, the fluorinated amino polysiloxane resin of this embodiment can be represented as HBPSi-2Ph2F-2.

[0078] Example 3

[0079] This embodiment prepares a fluorinated amino polysiloxane resin. The preparation method is basically the same as that in Example 1, except that: in step (2), 3-(2-aminoethylamino)propylmethyldimethoxysilane (30.97g, 0.15mol) is added, and then water (1.89g, 0.11mol) is slowly added. The reaction continues for 45min, and then the temperature is raised to 75℃ and refluxed for 4.0h.

[0080] The product prepared in this embodiment was subjected to proton NMR and Fourier transform infrared spectroscopy analysis. The results showed that the colorless and transparent liquid product was a fluorinated amino polysiloxane resin.

[0081] The fluorinated amino polysiloxane resin prepared in this embodiment can also be represented as HBPSi-2Ph2F. Furthermore, to easily distinguish it from the fluorinated amino polysiloxane resins provided in Examples 1-2 and 4-5, the fluorinated amino polysiloxane resin of this embodiment can be represented as HBPSi-2Ph2F-3.

[0082] Example 4

[0083] In this embodiment, a fluorinated amino polysiloxane resin is prepared. The preparation method is basically the same as that in Example 1, except that in step (3), the reaction is carried out at 75°C and -0.010MPa for 3.0h, while removing byproducts such as methanol. After cooling, a colorless and transparent liquid product is obtained.

[0084] The product prepared in this embodiment was subjected to proton NMR and Fourier transform infrared spectroscopy analysis. The results showed that the colorless and transparent liquid product was a fluorinated amino polysiloxane resin.

[0085] The fluorinated amino polysiloxane resin prepared in this embodiment can also be represented as HBPSi-2Ph2F. Furthermore, to easily distinguish it from the fluorinated amino polysiloxane resins provided in Examples 1-3 and 5, the fluorinated amino polysiloxane resin of this embodiment can be represented as HBPSi-2Ph2F-4.

[0086] Example 5

[0087] In this embodiment, a fluorinated amino polysiloxane resin is prepared. The preparation method is basically the same as that in Example 1, except that: in step (2), the temperature is raised to 75°C and refluxed for 5.0 h; and in step (3), the reaction is carried out at 75°C and -0.005 MPa for 3.0 h, while removing byproducts such as methanol. After cooling, a colorless and transparent liquid product is obtained.

[0088] The product prepared in this embodiment was subjected to proton NMR and Fourier transform infrared spectroscopy analysis. The results showed that the colorless and transparent liquid product was a fluorinated amino polysiloxane resin.

[0089] The fluorinated amino polysiloxane resin prepared in this embodiment can also be represented as HBPSi-2Ph2F. Furthermore, to easily distinguish it from the fluorinated amino polysiloxane resins provided in Examples 1-4, the fluorinated amino polysiloxane resin of this embodiment can be represented as HBPSi-2Ph2F-5.

[0090] Example 6

[0091] This embodiment prepares a fluorinated amino polysiloxane resin. The preparation process is carried out in a flask filled with dry nitrogen and includes the following steps:

[0092] (1) In a 250 mL four-necked flask equipped with a stirrer, reflux condenser and thermometer, add phenyltrimethoxysilane (75.35 g, 0.38 mol) and (3,3,3-trifluoropropyl)trimethoxysilane (50.15 g, 0.23 mol) in sequence, and slowly add water (11.53 g, 0.64 mol) while stirring, and react at 30 °C for 15 min;

[0093] (2) Add 3-(2-aminoethylamino)propylmethyldimethoxysilane (30.97 g, 0.15 mol), then slowly add water (1.89 g, 0.11 mol), continue the reaction for 45 min, and then heat to 75 °C and reflux for 4.0 h;

[0094] (3) The reaction was carried out at 75℃ and -0.005MPa for 4.0h, while removing byproducts such as methanol. After cooling, a colorless and transparent liquid product was obtained.

[0095] The colorless and transparent liquid product was analyzed by proton NMR and Fourier transform infrared spectroscopy. The results showed that the colorless and transparent liquid product was a fluorinated amino polysiloxane resin.

[0096] In step (1) of this embodiment, the molar ratio of phenyltrimethoxysilane (0.38 mol) to (3,3,3-trifluoropropyl)trimethoxysilane (0.23 mol) is 0.38:0.23≈2.50:1.50. For ease of distinction, the fluorinated amino polysiloxane resin prepared in this embodiment is represented as HBPSi-2.5Ph1.5F.

[0097] Example 7

[0098] This embodiment prepares a fluorinated amino polysiloxane resin. The preparation process is carried out in a flask filled with dry nitrogen and includes the following steps:

[0099] (1) In a 250 mL four-necked flask equipped with a stirrer, reflux condenser and thermometer, add phenyltrimethoxysilane (89.23 g, 0.45 mol) and (3,3,3-trifluoropropyl)trimethoxysilane (32.71 g, 0.15 mol) in sequence, and slowly add water (11.34 g, 0.63 mol) while stirring, and react at 30 °C for 15 min;

[0100] (2) Add 3-(2-aminoethylamino)propylmethyldimethoxysilane (30.95 g, 0.15 mol), then slowly add water (1.89 g, 0.11 mol), continue the reaction for 45 min, and then heat to 75 °C and reflux for 4.0 h;

[0101] (3) The reaction was carried out at 75℃ and -0.005MPa for 3.0h, while removing byproducts such as methanol. After cooling, a colorless and transparent liquid product was obtained.

[0102] The colorless and transparent liquid product was analyzed by proton NMR and Fourier transform infrared spectroscopy. The results showed that the colorless and transparent liquid product was a fluorinated amino polysiloxane resin.

[0103] In step (1) of this embodiment, the molar ratio of phenyltrimethoxysilane (0.45 mol) to (3,3,3-trifluoropropyl)trimethoxysilane (0.15 mol) is 0.45:0.15 = 3.00:1.00. For ease of distinction, the fluorinated amino polysiloxane resin prepared in this embodiment is referred to as HBPSi-3Ph1F.

[0104] Comparative Example 1

[0105] This comparative example prepares an amino-polysiloxane resin. The preparation process is carried out in a flask filled with dry nitrogen and includes the following steps:

[0106] (1) In a 250 mL four-necked flask equipped with a stirrer, reflux condenser and thermometer, add phenyltrimethoxysilane (79.37 g, 0.40 mol) and methyltrimethoxysilane (54.44 g, 0.40 mol) in sequence, and slowly add water (15.12 g, 0.84 mol) while stirring, and react at 30 °C for 15 min;

[0107] (2) Add 3-(2-aminoethylamino)propylmethyldimethoxysilane (41.28 g, 0.20 mol), then slowly add water (2.52 g, 0.14 mol), continue the reaction for 45 min, and then heat to 75 °C and reflux for 4.0 h;

[0108] (3) The reaction was carried out at 75℃ and -0.005MPa for 5.0h, while removing byproducts such as methanol. After cooling, a colorless and transparent liquid product was obtained.

[0109] The colorless and transparent liquid product was analyzed by proton NMR spectroscopy, and the results were as follows: 1H-NMR (CDCl3, TMS), δ (ppm): 6.69-7.86 (Ar-H), 2.87-3.65 (O-CH3), 2.18-2.76 (CH2NHCH2CH2), 1 .28-1.61(Si-CH2CH2CH2NHCH2CH2), 0.24-0.66(Si-CH2CH2CH2NHCH2CH2), -0.55-0.23(Si-CH3).

[0110] Fourier transform infrared spectroscopy analysis was performed on the colorless and transparent liquid product, and the results were as follows: FT-IR (KBr, cm⁻¹) -1 ): 3460-3280(NH), 2980-2900(Si-CH3), 2840(SiO-CH3), 3100-3000(Ar-H), 1130-1052(Si-O-Si).

[0111] The colorless and transparent liquid product was determined to be an amino polysiloxane resin.

[0112] In step (1) of this embodiment, the molar ratio of phenyltrimethoxysilane (0.30 mol) to methyltrimethoxysilane (0.40 mol) is 0.40:0.40 = 1.00:1.00. For ease of distinction, the amino polysiloxane resin prepared in this embodiment is represented as HBPSi-2Ph2CH3.

[0113] Comparative Example 2

[0114] This comparative example prepares an amino-polysiloxane resin. The preparation process is carried out in a flask filled with dry nitrogen and includes the following steps:

[0115] (1) In a 250 mL four-necked flask equipped with a stirrer, reflux condenser and thermometer, add phenyltrimethoxysilane (99.15 g, 0.50 mol) and methyltrimethoxysilane (40.82 g, 0.30 mol) in sequence, and slowly add water (15.12 g, 0.84 mol) while stirring, and react at 30 °C for 15 min;

[0116] (2) Add 3-(2-aminoethylamino)propylmethyldimethoxysilane (41.27 g, 0.20 mol), then slowly add water (2.52 g, 0.14 mol), continue the reaction for 45 min, and then heat to 75 °C and reflux for 4.0 h;

[0117] (3) The reaction was carried out at 75℃ and -0.005MPa for 5.0h, while removing byproducts such as methanol. After cooling, a colorless and transparent liquid product was obtained.

[0118] The colorless and transparent liquid product was analyzed by proton NMR and Fourier transform infrared spectroscopy. The results showed that the colorless and transparent liquid product was an amino polysiloxane resin.

[0119] In step (1) of this embodiment, the molar ratio of phenyltrimethoxysilane (0.50 mol) and methyltrimethoxysilane (0.30 mol) is 0.50:0.30≈2.50:1.50. For ease of distinction, the amino polysiloxane resin prepared in this embodiment is represented as HBPSi-2.5Ph1.5CH3.

[0120] Comparative Example 3

[0121] This comparative example prepares an amino-polysiloxane resin. The preparation process is carried out in a flask filled with dry nitrogen and includes the following steps:

[0122] (1) In a 250 mL four-necked flask equipped with a stirrer, reflux condenser and thermometer, add phenyltrimethoxysilane (118.98 g, 0.60 mol) and methyltrimethoxysilane (27.22 g, 0.20 mol) in sequence, and slowly add water (15.12 g, 0.84 mol) while stirring, and react at 30 °C for 15 min;

[0123] (2) Add 3-(2-aminoethylamino)propylmethyldimethoxysilane (41.27 g, 0.20 mol), then slowly add water (2.52 g, 0.14 mol), continue the reaction for 45 min, and then heat to 75 °C and reflux for 4.0 h;

[0124] (3) The reaction was carried out at 75℃ and -0.005MPa for 5.0h, while removing byproducts such as methanol. After cooling, a colorless and transparent liquid product was obtained.

[0125] The colorless and transparent liquid product was analyzed by proton NMR and Fourier transform infrared spectroscopy. The results showed that the colorless and transparent liquid product was an amino polysiloxane resin.

[0126] In step (1) of this embodiment, the molar ratio of phenyltrimethoxysilane (0.60 mol) to methyltrimethoxysilane (0.20 mol) is 0.60:0.20 = 3.00:1.00. For ease of distinction, the amino polysiloxane resin prepared in this embodiment is referred to as HBPSi-3PhCH3.

[0127] Comparative Example 4

[0128] (1) In a 250 mL four-necked flask equipped with a stirrer, reflux condenser and thermometer, add phenyltrimethoxysilane (39.658 g, 0.20 mol) and (3,3,3-trifluoropropyl)trimethoxysilane (130.836 g, 0.60 mol) in sequence, and slowly add water (15.12 g, 0.84 mol) while stirring, and react at 30 °C for 15 min;

[0129] (2) Add 3-(2-aminoethylamino)propylmethyldimethoxysilane (41.28 g, 0.20 mol), then slowly add water (2.52 g, 0.14 mol), continue the reaction for 45 min, and then heat to 75 °C and reflux for 4.0 h;

[0130] (3) Finally, the reaction was carried out at 75℃ and -0.005MPa for 4.0h, while removing byproducts such as methanol. After cooling, a colorless and transparent liquid product was obtained.

[0131] The colorless and transparent liquid product was analyzed by proton NMR and Fourier transform infrared spectroscopy. The results showed that the colorless and transparent liquid product was a fluorinated amino polysiloxane resin.

[0132] In step (1) of this embodiment, the molar ratio of phenyltrimethoxysilane (0.20 mol) to (3,3,3-trifluoropropyl)trimethoxysilane (0.60 mol) is 0.20:0.60 = 1.00:3.00. For ease of distinction, the fluorinated amino polysiloxane resin prepared in this embodiment is referred to as HBPSi-Ph3F.

[0133] Test Example 1

[0134] The physicochemical properties of the products prepared in the above examples and comparative examples were tested according to the following methods.

[0135] 1. Viscosity testing method

[0136] Measuring instrument: Brookfield DV2TLV viscometer (USA);

[0137] Test method: Weigh 15g of sample into a sample container, place the rotor in the container and ensure that the rotor is completely submerged in the liquid, then measure the viscosity at 30℃ for 10min and record the viscosity data.

[0138] 2. Amine value test method

[0139] Weigh 0.100-0.300g of sample into an Erlenmeyer flask, add 50ml of o-nitrotoluene-glacial acetic acid mixed solvent, shake constantly to completely dissolve the sample, add 2-3 drops of methyl violet indicator, and then titrate with 0.1mol / L perchloric acid-glacial acetic acid standard solution until the color turns bright and striking green and remains unchanged for 30s, which is the endpoint.

[0140]

[0141] Where V is the volume of perchloric acid-glacial acetic acid standard solution consumed in the titration, in ml;

[0142] V0—The volume of perchloric acid-glacial acetic acid standard solution consumed in the blank experiment, in ml;

[0143] M – Mass of the sample, in grams.

[0144] The test results obtained using the above method are shown in Table 1 below.

[0145] Table 1. Physicochemical property test results of the examples and comparative examples

[0146] Serial Number product Viscosity (mPa·s) Amine value (mmol / g) Example 1 HBPSi-2Ph2F-1 300 2.40 Example 2 HBPSi-2Ph2F-2 321 2.47 Example 3 HBPSi-2Ph2F-3 310 2.44 Example 4 HBPSi-2Ph2F-4 288 2.42 Example 5 HBPSi-2Ph2F-5 305 2.43 Example 6 HBPSi-2.5Ph1.5F 240 2.49 Example 7 HBPSi-3Ph1F 277 2.52 Comparative Example 1 <![CDATA[HBPSi-2Ph2CH3]]> 268 3.07 Comparative Example 2 <![CDATA[HBPSi-2.5Ph1.5CH3]]> 285 2.86 Comparative Example 3 <![CDATA[HBPSi-3PhCH3]]> 332 2.81 Comparative Example 4 HBPSi-Ph3F 267 2.48

[0147] Test Example 2

[0148] The products obtained in the above examples and comparative examples were mixed evenly with epoxy resin to obtain epoxy resin coatings. The molar ratio of epoxy groups in the epoxy resin to amino hydrogen in the fluorinated amino polysiloxane resin was controlled to be 1.00:1.00. The molar ratio of epoxy groups and amino hydrogen was the same in all examples and comparative examples. The gel time of the epoxy resin coatings at different temperatures was tested. The test results are shown in Table 2 below.

[0149] Table 2. Gel time of epoxy resin coatings at different temperatures

[0150]

[0151]

[0152] As shown in Table 2, the epoxy resin coatings provided in the embodiments and comparative examples of this application not only have a long gel time window at room temperature (25°C) (i.e., good room temperature curing ability), but also have good curing ability at low temperature (0°C).

[0153] Test Example 3

[0154] The epoxy resin coating in Test Example 2 was degassed in a vacuum drying oven at 40°C for 15 minutes to eliminate air bubbles; then the epoxy resin coating was applied to different substrates using a coating rod (different metal substrates, such as tinplate or Q235, were used for each test according to the test standard). The coating was first placed at room temperature for 0.5 hours, and then cured at 50°C for 4.0-6.0 hours to obtain an epoxy resin coating, which is also a fluorinated amino polysiloxane-epoxy resin coating.

[0155] The physical and chemical properties of various epoxy resin coatings were tested according to the following method.

[0156] 1. Glass transition temperature (Tg)

[0157] Measuring instrument: DMA-I dynamic thermomechanical analyzer from Mettler Toledo, Switzerland;

[0158] Test conditions and methods: The casting specimen (30×6×2mm) was used. 3 The device is fixed in place in a heating furnace with a clamp and carried out in an N2 atmosphere. The three-point bending method is used, the heating rate is 5℃ / min, the vibration frequency is 1.0Hz, and the temperature range is 30-150℃.

[0159] 2. Thermal decomposition temperature (T) d5 )

[0160] Measuring instrument: TGA / DSC-1 thermogravimetric analyzer from Mettler Toledo, Switzerland;

[0161] Test conditions and methods: Weigh 5-8 mg of sample into a crucible and conduct the test in a N2 atmosphere with a gas flow rate of 60 mL / min. The test temperature range is 40-800℃, and the heating rate is 10℃ / min.

[0162] 3. Pencil hardness

[0163] Measuring instrument: QHQ-A type pencil hardness tester;

[0164] Test method: Pencil hardness was tested according to GB / T 6739-2022. Tinplate was used as the substrate, sanded with 400-grit sandpaper, wiped with ethanol, and then a coating with a thickness of 20μm was applied. The hardness of the coating was determined by the hardest pencil that did not show scratches of 3mm or more.

[0165] 4. Bending toughness

[0166] Measuring instrument: BGD 563 cylindrical bending tester from Guangzhou Biaogeda Instruments;

[0167] Test method: Bending toughness was tested according to GB / T 1731-199, using tinplate as the substrate. The substrate was sanded with 400-grit sandpaper, wiped with ethanol, and then coated with a 20μm thick layer. The test plate was bent on a shaft of a certain diameter, and the bending toughness was represented by the smallest shaft diameter that did not cause damage to the coating after bending.

[0168] 5. Impact toughness

[0169] Measuring instrument: BGD 302 paint film impactor from Guangzhou Biaogeda Instruments;

[0170] Test method: Impact toughness was tested according to GB / T 1732-202, using tinplate as the substrate. After sanding with 400-grit sandpaper and wiping with ethanol, a coating with a thickness of 20μm was applied. A heavy hammer of a certain mass was dropped onto the coating, and the maximum height to which the coating underwent elongation deformation without breaking was used to represent the impact toughness.

[0171] 6. Salt spray resistance

[0172] Measuring instrument: TMJ-9703A salt spray test chamber from Temujin Electronic Technology Co., Ltd.;

[0173] Test method: Neutral salt spray resistance was tested according to GB / T 1771-2007, using Q235 steel plate as the substrate. The plate was polished with 400-grit sandpaper, wiped with ethanol, and then coated with a 120μm thick layer. The test plate with a scratch was placed in a salt spray chamber, and a sodium chloride solution containing 50g / L was sprayed onto the test plate. The corrosion status of the coating surface was monitored and observed at regular intervals.

[0174] The test results obtained using the above method are shown in Table 3 below. Figure 2 The results of the neutral salt spray test on the epoxy resin coating are shown.

[0175] Table 3. Test results of the physicochemical properties of epoxy resin coatings

[0176]

[0177] Combined with Table 3 and Figure 2 It can be seen that the epoxy resin coatings prepared using fluorinated amino polysiloxane resin as a curing agent in Examples 1, 6, and 7 exhibit good corrosion resistance, weather resistance, and wear resistance. Among them, HBPSi-2Ph2F showed the best corrosion resistance; after a 20-day salt spray test, no blistering, peeling, rusting, or cracking occurred at the marked areas of the coating. In contrast, the fluorine-free epoxy resin coating showed blistering and metal sheet corrosion (rust color) after 5 days of storage.

[0178] Furthermore, in Examples 1, 6, and 7, as the fluorine content in the fluorinated amino polysiloxane resin increased, the corrosion resistance of the corresponding epoxy resin coating also improved. However, it should be noted that although fluorinated amino polysiloxane resin was also used as a curing agent in Comparative Example 4 to prepare the epoxy resin coating, a uniform epoxy resin coating could not be prepared using the curing agent of Comparative Example 4. This is because the fluorinated amino polysiloxane resin in Comparative Example 4 had too low a phenyl content on its surface, leading to a decrease in the compatibility between the curing agent and the epoxy resin, resulting in a whitening of the coating, an uneven surface, and defects such as pinholes.

[0179] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0180] The above-described embodiments are merely illustrative of several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. It should be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided by the present invention through logical analysis, reasoning, or limited experimentation are all within the protection scope of the appended claims. Therefore, the protection scope of this invention patent should be determined by the appended claims, and the specification and drawings can be used to interpret the content of the claims.

Claims

1. A fluorinated amino polysiloxane resin, characterized in that, The chemical structural formula of the fluorinated amino polysiloxane resin is shown in formula (I): Wherein, R is methyl or ethyl; R1 is phenyl; R2 is methyl or ethyl; R f G is trifluoropropyl; G is aminoalkyl.

2. The fluorinated amino polysiloxane resin according to claim 1, characterized in that, The aminoalkyl group is -R a NH2 or -R a NHR b NH2, of which R a R is a hydrocarbon group containing 2-4 carbon atoms. b It contains a hydrocarbon group having 2-4 carbon atoms.

3. The fluorinated amino polysiloxane resin as described in claim 1, characterized in that, The fluorinated amino polysiloxane resin has a viscosity of 200-500 mPa·s and an amine value of 2.20-3.30 mmol / g.

4. A method for preparing the fluorinated amino polysiloxane resin as described in claim 1, characterized in that, Includes the following steps: (1) Mix the first monomer and the second monomer evenly, then add water to react and obtain reaction mixture A; (2) A third monomer and water are added to the reaction mixture A, and the reaction mixture B is obtained after the reaction. (3) The reaction mixture B is subjected to a polycondensation reaction under vacuum conditions, while removing the reaction byproducts, to obtain a fluorinated amino polysiloxane resin, wherein the chemical structural formula of the first monomer is shown in formula (II): The chemical structural formula of the second monomer is shown in formula (III): The chemical structural formula of the third monomer is shown in formula (IV): R is methyl or ethyl; R1 is phenyl; R2 is methyl or ethyl; R f G is trifluoropropyl; G is aminoalkyl.

5. The method for preparing the fluorinated amino polysiloxane resin as described in claim 4, characterized in that, In step (1), the molar ratio of the first monomer, the second monomer and water is (1.00-3.00):1.00:(1.80-5.40), and in step (2), the molar ratio of the third monomer and water is 1.00:(0.50-1.00).

6. The method for preparing the fluorinated amino polysiloxane resin as described in claim 5, characterized in that, In step (1), the molar ratio of the first monomer to the second monomer is (1.00-1.20):1.

00.

7. The method for preparing the fluorinated amino polysiloxane resin according to claim 4, characterized in that, The molar ratio of the third monomer to the second monomer is 1.00:(0.50-2.50).

8. The method for preparing the fluorinated amino polysiloxane resin as described in claim 4, characterized in that, In step (1), the first monomer and the second monomer are mixed evenly, and water is added at 10-30°C. The hydrolysis reaction is carried out for 0.2-1.0 h to obtain the reaction mixture A. In step (2), a third monomer and water are added to the reaction mixture A. The reaction is carried out at 10-30°C for 0.5-1.0 h, and then the temperature is raised to 60-80°C for 3.0-6.0 h to obtain the reaction mixture B. In step (3), the reaction mixture B is subjected to a polycondensation reaction under vacuum conditions at 60-90°C for 4.0-7.0 h, while removing reaction byproducts to obtain the fluorinated amino polysiloxane resin.

9. An epoxy resin coating, characterized in that, include: The epoxy resin and the fluorinated amino polysiloxane resin as described in claim 1, wherein the molar ratio of the epoxy group in the epoxy resin to the amino hydrogen in the fluorinated amino polysiloxane resin is 1.00:(0.80-1.00).

10. The epoxy resin coating as described in claim 9, characterized in that, The epoxy resin includes at least one of alicyclic epoxy resin and aromatic epoxy resin.

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