Fluorine-containing alkyl silicone oil, preparation method thereof and wear-resistant hydrophobic coating

Abstract

The invention belongs to the technical field of coating protection, and particularly relates to fluorine-containing alkyl silicone oil, a preparation method thereof and a wear-resistant hydrophobic coating. The invention provides fluorine-containing alkyl silicone oil. The fluorine-containing alkyl silicone oil has a structure as shown in a formula I, wherein Rf is as follows: x is more than 5 and less than 20, y is more than 5 and less than 10, z is more than 0.5 and less than 1.5, and x, y and z are all integers. By introducing fluorinated groups (such as-CF2 and-CF3), the surface energy is remarkably reduced, and hydrophobicity and oleophobicity are realized; a silicon-oxygen-silicon main chain (-Si-O-Si-) endows the coating with flexibility and thermal stability, and vinyl (-CH = CH2) can form a three-dimensional network through cross-linking curing, so that the adhesive force and wear resistance of the coating are enhanced. Tests show that the contact angle of a coating formed by hydrosilylation of the silane containing alkenyl and fluoroalkyl and hydrogen-containing silicone oil can reach 135 degrees with water, the contact angle of the coating with oil can reach 84 degrees, and the antifouling property is excellent.

Description

Technical Field

[0001] This invention belongs to the field of coating protection technology, specifically relating to a fluorinated alkyl silicone oil and its preparation method, and a wear-resistant and hydrophobic coating. Background Technology

[0002] Fluorosilane compounds, with their unique "bifunctional" molecular structure, have become key building blocks for high-performance surface protection materials. One end of their molecules contains highly reactive functional groups (such as alkoxy, chlorine, and alkenyl groups), enabling them to chemically react with various substrates such as metals, glass, and concrete, forming stable covalent bonds and providing excellent interfacial adhesion and durability. The other end of the fluorosilane molecule is connected to perfluoroalkyl or fluoroalkyl segments. These highly fluorinated structures endow the materials with extremely low surface energy, exhibiting excellent hydrophobic and oleophobic properties. In recent years, fluorosilane hydrophobic coatings developed based on these compounds have been widely used in critical engineering fields exposed to harsh environments, such as building exteriors, bridge steel structures, and offshore platform facilities, due to their outstanding water repellency, antifouling, and self-cleaning capabilities. The core value of these coatings lies in their induced superhydrophobic and self-cleaning effects. Water droplets form a high contact angle on superhydrophobic surfaces and easily roll off, simultaneously carrying away surface contaminants such as dust and salt. This property not only significantly reduces maintenance costs but also effectively inhibits the adhesion and accumulation of contaminants such as moisture, oil, and dust on the substrate surface. This is particularly important for applications with high precision or high safety requirements. For example, in the electronics field, effectively preventing electrostatic discharge (ESD) induced by contaminants (especially conductive dust) can avoid serious accidents such as short circuits, component damage, and even fires caused by electrostatic discharge in precision electronic equipment. However, existing commercial products still have significant limitations in overall performance. For example, during use, perfluoropolyethers (PFPEs) experience chain segment rearrangement and free volume expansion, allowing oil molecules to easily penetrate and damage the fluorinated surface, resulting in insufficient wear resistance and long-term hydrophobic properties (especially resistance to oily contaminants). These bottlenecks highlight the urgency and significance of developing new high-performance fluorinated silane silicone oils. Summary of the Invention

[0003] In view of this, the present invention provides a fluorinated alkyl silicone oil and its preparation method, as well as a wear-resistant and hydrophobic coating. The coating formed by the coating containing the fluorinated alkyl silicone oil provided by the present invention has excellent waterproof properties, strong adhesion to the substrate, and is not easy to fall off, while also having good wear resistance.

[0004] To solve the above-mentioned technical problems, the present invention provides a fluorinated alkyl silicone oil having the structure shown in Formula I: Formula I; Where R f for , 5 < x < 20, 5 < y < 10, 0.5 < z < 1.5, where x, y and z are all integers.

[0005] Preferably, the fluorine content in the fluorinated alkyl silicone oil is 10-20% by mass.

[0006] The present invention also provides a method for preparing the fluorinated alkyl silicone oil described in the above technical solution, comprising the following steps: Compound 1, Compound 2, Compound 3, Compound 4 and the first catalyst were mixed and subjected to a condensation reaction to obtain the fluorinated alkyl silicone oil. Compound 1 is Compound 2 is Compound 3 is Compound 4 is .

[0007] Preferably, the first catalyst is H2PtCl6·6H2O catalysis; The molar ratio of compound 1, compound 2, compound 3 and compound 4 is 0.5~2:0.5~1:0.07~0.15:0.032.

[0008] Preferably, the condensation reaction is carried out at a temperature of 60~120℃ for a time of 20~60 min.

[0009] Preferably, the condensation reaction further includes: sequentially cooling, washing, removing low-boiling substances, adsorbing impurities, and filtering the system after the condensation reaction to obtain the fluorinated alkyl silicone oil.

[0010] Preferably, the washing liquid is a saturated sodium chloride solution; The adsorbent used for adsorption and impurity removal includes activated carbon, and the mass ratio of the adsorbent to the system after removal of low-boiling substances is 0.3~1.2:100.

[0011] Preferably, the temperature for removing the low-boiling-point substance is 150~170℃, the vacuum degree for removing the low-boiling-point substance is -0.096~-0.056MPa, and the removal time for the low-boiling-point substance is 30~90min.

[0012] The present invention also provides a wear-resistant and hydrophobic coating, comprising a fluorinated alkyl silicone oil, a hydrogen-containing silicone oil, a second catalyst, and an organic solvent; wherein the fluorinated alkyl silicone oil is the fluorinated alkyl silicone oil described in the above technical solution or the fluorinated alkyl silicone oil prepared by the preparation method described in the above technical solution; The mass ratio of the fluorinated alkyl silicone oil to the hydrogen-containing silicone oil is 5~40:1.

[0013] Preferably, the organic solvent includes toluene, xylene, or cyclohexane; The second catalyst includes a caster platinum catalyst, and the content of the second catalyst in the wear-resistant hydrophobic coating is 5~20 ppm.

[0014] This invention provides a fluorinated alkyl silicone oil having the structure shown in Formula I: Equation I; where R f for 5 < x < 20, 5 < y < 10, 0.5 < z < 1.5, where x, y, and z are all integers. This invention significantly reduces surface energy by introducing fluorinated groups (such as -CF2 and -CF3), achieving hydrophobic and oleophobic properties. The silicon-oxygen-silicon backbone (-Si-O-Si-) imparts flexibility and thermal stability to the coating, while vinyl groups (-CH=CH2) can form a three-dimensional network through cross-linking and curing, enhancing coating adhesion and abrasion resistance. Testing shows that the coating formed by the hydrosilylation reaction of alkenyl and fluoroalkyl silanes synthesized in this invention with hydrogen-containing silicone oil exhibits excellent antifouling properties, with a water contact angle of 135° and an oil contact angle of 84°. Attached Figure Description

[0015] Figure 1 The fluorinated alkyl silicone oil prepared in Example 1 1 H NMR spectrum; Figure 2 The static hydrophobic angle test results of the cured coating and the untreated substrate (cotton fabric) in Example 1 and Comparative Example 1 after 20 rubs are shown. Figure 3 The images show the oleophobic angle test results of the cured coatings and the untreated substrate (cotton fabric) in Example 1 and Comparative Example 1 after 0 rubs. Figure 4 The static hydrophobic angle test results are shown for the cured coating and the untreated circuit board in Example 1 and Comparative Example 1. Figure 5 The images show the oleophobic angle test results of the cured coating and the untreated circuit board in Example 1 and Comparative Example 1. Detailed Implementation

[0016] This invention provides a fluorinated alkyl silicone oil having the structure shown in Formula I: Formula I; Where R f for , 5 < x < 20, 5 < y < 10, 0.5 < z < 1.5, where x, y and z are all integers.

[0017] In this invention, x can specifically be 6, 8, 10, 12, 14, 16, 18 or 20, y can specifically be 6, 7, 8 or 9, and z can specifically be 1.

[0018] In this invention, the mass percentage of fluorine in the fluorinated alkyl silicone oil can be 10-20%, specifically 10%, 13%, 15%, 17% or 19%.

[0019] In this invention, the fluorinated alkyl silicone oil contains alkenyl groups at multiple sites, which can significantly increase the adhesion of the coating formed by the fluorinated alkyl silicone oil; at the same time, the presence of silicon improves the wear resistance of the coating, and by controlling the position and content of fluorine, a balance between the wear resistance and waterproof / oil-proof properties of the coating is achieved, thus giving it a broader application prospect in the field of wear-resistant and waterproof coatings.

[0020] The present invention also provides a method for preparing the fluorinated alkyl silicone oil described in the above technical solution, comprising the following steps: Compound 1, Compound 2, Compound 3, Compound 4 and the first catalyst were mixed and subjected to a condensation reaction to obtain the fluorinated alkyl silicone oil. Compound 1 is Compound 2 is Compound 3 is Compound 4 is .

[0021] In this invention, the first catalyst can be an H2PtCl6·6H2O catalyst. This invention does not have a special limitation on the amount of the first catalyst added, and the amount added can be the conventional amount in the art.

[0022] In this invention, the molar ratio of compound 1, compound 2, compound 3 and compound 4 can be 0.5~2:0.5~1:0.07~0.15:0.032, specifically 1.67:0.5:0.1:0.032.

[0023] In this invention, the temperature of the condensation reaction can be 60~120℃, specifically 60℃, 80℃, 100℃ or 120℃; the time of the condensation reaction can be 20~60min, specifically 20min, 30min, 40min, 50min or 60min. In this invention, when the temperature is below 60℃, the condensation reaction hardly occurs.

[0024] In this invention, the bond breaking positions of compounds 1 to 3 during the condensation reaction are uncertain, so the values ​​of x, y, and z in the generated fluorinated alkyl silicone oil are also uncertain. This invention ensures the range of values ​​of x, y, and z by controlling the amount of materials added.

[0025] In this invention, the equation for the condensation reaction is shown in equation a: Formula a.

[0026] In this invention, the condensation reaction may further include: sequentially cooling, washing, removing low-boiling substances, adsorbing impurities, and filtering the system after the condensation reaction to obtain the fluorinated alkyl silicone oil; the cooling temperature may be room temperature, which may be 20~35℃ or 25~30℃; this invention has no special requirements for the cooling method, and conventional cooling methods in the art can be used.

[0027] In this invention, the washing liquid can be a saturated sodium chloride solution; the temperature for removing low-boiling substances can be 150~170℃, specifically 150℃, 160℃ or 170℃; the vacuum degree for removing low-boiling substances can be -0.096~-0.056MPa, specifically -0.096MPa; the time for removing low-boiling substances can be 30~90min, specifically 30min, 60min or 90min.

[0028] In this invention, the adsorbent used for adsorption and impurity removal may include activated carbon. The mass ratio of the adsorbent to the system after removal of low-boiling substances can be 0.3~1.2:100, specifically 0.4:100, 0.5:100, 0.6:100, 0.7:100, 0.8:100, 0.9:100, 1.0:100, or 1.1:100. This invention does not impose any special limitations on the filtration process; conventional methods in the art can be used.

[0029] This invention removes impurities from the condensation reaction system through washing, removal of low-boiling substances, and adsorption to obtain a high-purity fluorinated alkyl silicone oil.

[0030] This invention utilizes a condensation reaction of hydrogen-containing silicone oil with nonafluorohexene groups in its side chains, silylene, silicone esters, and terminal alkenes. The reaction conditions are mild, with few side reactions and stable product properties. The catalyst dosage is low, no solvent is required, and it is environmentally friendly. The preparation method of this invention is simple to operate and can be industrialized. The alkenyl groups in the synthesized fluoroalkyl silicone oil can form stable chemical bonds with various substrate surfaces, providing excellent interfacial adhesion. The nonafluorohexene groups not only adjust the hydrophobic and oleophobic properties of the silicone oil but also provide good acid and alkali resistance and solvent resistance.

[0031] The present invention also provides a wear-resistant and hydrophobic coating, comprising fluorinated alkyl silicone oil, hydrogen-containing silicone oil, a second catalyst and an organic solvent; wherein the fluorinated alkyl silicone oil is the fluorinated alkyl silicone oil described in the above technical solution or the fluorinated alkyl silicone oil prepared by the preparation method described in the above technical solution.

[0032] In this invention, the mass percentage of hydrogen in the hydrogen-containing silicone oil can be 0.4-0.6%, specifically 0.5%; the mass ratio of the fluorinated alkyl silicone oil to the hydrogen-containing silicone oil is 5-40:1, and can also be 10-36.5:1.

[0033] In this invention, the organic solvent may include toluene, xylene, or cyclohexane; the mass ratio of the organic solvent to the fluorinated alkyl silicone oil may be 0.7~1:1, or 0.8~0.9:1.

[0034] In this invention, the second catalyst may include a caster platinum catalyst, and the content of the second catalyst in the wear-resistant hydrophobic coating may be 0.005~0.2%, or 0.1~0.18%.

[0035] The present invention mixes fluorinated alkyl silicone oil, hydrogen-containing silicone oil, a second catalyst and an organic solvent to obtain the wear-resistant and hydrophobic coating; the present invention has no special limitation on the mixing, as long as it can be mixed evenly.

[0036] The method for forming a wear-resistant hydrophobic coating using the wear-resistant hydrophobic coating of the present invention may include the following steps: coating the wear-resistant hydrophobic coating on the surface of a substrate and then drying and curing it to obtain the wear-resistant hydrophobic coating.

[0037] In this invention, the substrate may include cotton fabric or a circuit board. This invention does not impose any particular limitation on the coating method; any method conventional in the art may be used.

[0038] In this invention, the drying temperature can be 80~100℃, specifically 80℃, 85℃, 90℃, 95℃ or 100℃; the drying time can be 0.5~2h, specifically 0.5h, 1h, 1.5h or 2h; the curing temperature can be 145~155℃, specifically 150℃; the curing time can be 1~3h, specifically 1h, 1.5h, 2h, 2.5h or 3h.

[0039] The fluorinated alkyl silicone oil provided by this invention has excellent wear resistance, hydrophobicity and oleophobicity, which can meet the higher requirements of high-end fields such as aerospace, microelectronics packaging, and new energy equipment for long-lasting, reliable and multifunctional surface protection materials, and can improve the safety and service life of industrial equipment.

[0040] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0041] Example 1 153 g (0.167 mol) of compound 1 was added to a 500 mL three-necked flask equipped with a mechanical stirrer, thermometer, and spherical condenser. ), 17.2 g (0.05 mol) of compound 2 ( ), 2.2 g (0.01 mol) of compound 3 ( ), 0.6 g (0.0032 mol) of compound 4 ( 0.2 g of H2PtCl6·6H2O catalyst was added, stirred, and heated to 60 °C for condensation reaction for 20 min. The mixture was then cooled to room temperature (25 °C), transferred to a separatory funnel, and washed with water after adding saturated sodium chloride solution. The lower layer of sodium chloride solution was removed, and the upper layer of silicone oil was transferred to a three-necked flask. The flask was then evacuated and heated to -0.096 MPa and 150 °C for 30 min to remove low-boiling substances. After cooling to room temperature (25 °C), the mixture was transferred to a beaker, and 1.02 g of activated carbon was added and stirred for adsorption. The mixture was filtered to obtain a colorless and transparent fluorinated alkyl silicone oil with the following structural formula: .

[0042] Examples 2-16 Fluorinated alkyl silicone oils were prepared according to the scheme in Example 1, with specific differences as shown in Tables 1-2.

[0043] Table 1. Types and amounts of materials used in the preparation of fluorinated alkyl silicone oils in Examples 1-16

[0044] Table 2 Conditions for condensation reaction and removal of low-boiling substances in Examples 1-16

[0045] The fluorinated alkyl silicone oil prepared in Example 1 was subjected to... 1 H nuclear magnetic resonance detection yielded... 1 H NMR spectrum, as shown Figure 1 As shown. By Figure 1 It can be seen that the fluorinated alkyl silicone oil prepared in Example 1 has the structure shown in Formula I.

[0046] Performance Test 1 5g of the fluorinated alkyl silicone oil prepared in Example 1, 0.137g of commercially available hydrogen-containing silicone oil with a hydrogen content of 0.5%, 4g of toluene, and 0.0171g of caster platinum catalyst were mixed to obtain a wear-resistant and hydrophobic coating. Cotton fabric was immersed in the wear-resistant and hydrophobic coating for 5 minutes, then removed, dried at 80°C for 30 minutes, and then cured at 150°C for 1 hour to form a cotton fabric with a wear-resistant and hydrophobic coating.

[0047] A coating was prepared by mixing 5g of commercially available vinyl fluorosilicone oil (NFS 7300-G35), 0.107g of commercially available hydrogen-containing silicone oil with a hydrogen content of 0.5%, 4g of toluene, and 0.0171g of caster platinum catalyst. Cotton fabric was immersed in the coating for 5 minutes, then removed, dried at 80°C for 30 minutes, and then cured at 150°C for 1 hour to form a coated cotton fabric, serving as Comparative Example 1.

[0048] The hydrophobic and oleophobic properties of the modified fabric were tested as follows: weights were applied to the modified fabric (with a glass slide placed in the middle to ensure uniform force), and sandpaper was used for rubbing; then water and standard test oil ASTM NO.1 were dropped onto the surface after different rubbing cycles, and the contact angle was tested. The results are listed in Table 3.

[0049] Table 3. Hydrophobicity and oleophobicity test results of Example 1 and Comparative Example 1 after different numbers of rubbing cycles.

[0050] Figure 2 The images show the static hydrophobic angle test results of the cured coating and the untreated substrate (cotton fabric) in Example 1 and Comparative Example 1 after 20 rubs. Figure 3 The images show the oleophobic angle test results of the cured coating and the untreated substrate (cotton fabric) in Example 1 and Comparative Example 1 after 0 rubs.

[0051] From Table 3 and Figures 2-3 It can be seen that the oleophobic angle of the cotton fabric treated with the fluorinated alkyl silicone oil prepared in Example 1 without friction is 27° higher than that of Comparative Example 1 (commercial fluorinated silicone oil), and its hydrophobic angle is always higher than that of Comparative Example 1 at each number of friction cycles; at the same time, the hydrophobic angle of Example 1 only decreased by 19° (a decrease of about 14%) in 0 to 100 friction cycles, while that of Comparative Example 1 decreased by 28° (a decrease of about 26%), and the curve is flatter, proving that Example 1 has both excellent oleophobic properties and wear resistance.

[0052] Performance Test 2 Abrasion-resistant hydrophobic coatings were prepared according to the method of performance test 1. The abrasion-resistant hydrophobic coatings were evenly applied to the surface of the circuit board and dried at 80°C for 30 min, and then cured at 150°C for 1 h to form abrasion-resistant hydrophobic coating. The coating of Comparative Example 1 prepared in performance test 1 was evenly applied to the surface of the circuit board and dried at 80°C for 30 min, and then cured at 150°C for 1 h to form a coating as a comparison.

[0053] Water and standard test oil (ASTM NO.1) were added to the coating surface, and the contact angle was measured. The results are listed in Table 4.

[0054] Table 4. Hydrophobic and oleophobic test results

[0055] Figure 4 These are static hydrophobic angle test images of the cured coating and the untreated circuit board in Example 1 and Comparative Example 1. Figure 5 The images show the oleophobic angle test results of the cured coating and the untreated circuit board in Example 1 and Comparative Example 1.

[0056] Combine Table 4 and Figures 4-5 It can be seen that the circuit board treated with the fluorinated alkyl silicone oil prepared in Example 1 has better hydrophobic and oleophobic effects than commercial fluorinated silicone oil.

[0057] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A fluorinated alkyl silicone oil, characterized in that, It has the structure shown in Equation I: Formula I; Where R f for , 5 < x < 20, 5 < y < 10, 0.5 < z < 1.5, where x, y and z are all integers.

2. The fluorinated alkyl silicone oil according to claim 1, characterized in that, The fluorine content in the fluorinated alkyl silicone oil is 10-20% by mass.

3. The method for preparing the fluorinated alkyl silicone oil according to claim 1 or 2, characterized in that, Includes the following steps: Compound 1, Compound 2, Compound 3, Compound 4 and the first catalyst were mixed and subjected to a condensation reaction to obtain the fluorinated alkyl silicone oil. Compound 1 is Compound 2 is Compound 3 is Compound 4 is .

4. The preparation method according to claim 3, characterized in that, The first catalyst is H2PtCl6·6H2O catalysis; The molar ratio of compound 1, compound 2, compound 3 and compound 4 is 0.5~2:0.5~1:0.07~0.15:0.

032.

5. The preparation method according to claim 3 or 4, characterized in that, The condensation reaction is carried out at a temperature of 60~120℃ for a time of 20~60 min.

6. The preparation method according to claim 5, characterized in that, The condensation reaction is followed by: sequentially cooling, washing, removing low-boiling substances, adsorbing impurities, and filtering the system after the condensation reaction to obtain the fluorinated alkyl silicone oil.

7. The preparation method according to claim 6, characterized in that, The washing solution used for washing is a saturated sodium chloride solution; The adsorbent used for adsorption and impurity removal includes activated carbon, and the mass ratio of the adsorbent to the system after removal of low-boiling substances is 0.3~1.2:

100.

8. The preparation method according to claim 6, characterized in that, The temperature for removing the low-boiling-point substance is 150~170℃, the vacuum degree for removing the low-boiling-point substance is -0.096~-0.056MPa, and the removal time for the low-boiling-point substance is 30~90min.

9. A wear-resistant and hydrophobic coating, characterized in that, It includes fluorinated alkyl silicone oil, hydrogen-containing silicone oil, a second catalyst, and an organic solvent; the fluorinated alkyl silicone oil is the fluorinated alkyl silicone oil according to claim 1 or 2, or the fluorinated alkyl silicone oil prepared by the preparation method according to any one of claims 3 to 8; The mass ratio of the fluorinated alkyl silicone oil to the hydrogen-containing silicone oil is 5~40:

1.

10. The wear-resistant and hydrophobic coating according to claim 9, characterized in that, The organic solvent includes toluene, xylene, or cyclohexane; The second catalyst includes a caster platinum catalyst, and the content of the second catalyst in the wear-resistant hydrophobic coating is 5~20 ppm.

Images