A silane compound, its preparation method and uses

Abstract

The present invention provides a silane compound, a preparation method and a use thereof. The silane compound is formed by addition of raw material components, and the raw material components include: 1) at least one cyclic hydrogen-containing silane, which includes one or two of the compounds of formula I and the compounds of formula II; 2) at least one α-olefin oligomer; the molar amount of the Si-H bond in the cyclic hydrogen-containing silane is greater than the molar amount of the α-olefin oligomer. The silane compound can be used for preparing a waterborne hydrophobic coating, which has extremely strong hydrophobicity compared with traditional waterborne coatings, can effectively prevent water penetration, reduce the water absorption and cracking of the paint film, improve the scrub resistance and aging resistance of the paint film, and achieve a long-lasting hydrophobic effect.

Description

Technical Field

[0001] The present invention relates to the technical field of fine chemical engineering, and particularly to a silane compound, a preparation method and a use thereof. Background Art

[0002] With the increasing enhancement of human environmental protection awareness, various countries have successively formulated strict laws and regulations to limit the emission of VOCs. It is an irresistible trend to carry out "oil-to-water conversion" in the field of coating application. In recent years, waterborne coatings have developed rapidly due to their advantages of safety and environmental protection. However, the waterborne resins in waterborne coatings usually need to be stably dispersed in water with the help of surfactants such as emulsifiers. After the latex particles form a film, they are affected by hydrophilic surfactants such as emulsifiers and wetting agents. Therefore, waterborne hydrophobic coatings have obvious defects in water resistance, alkali resistance and weather resistance, which affects their applications in fields such as anti-fouling, anti-fogging, anti-icing, corrosion resistance, oil-water separation and biomedicine. In addition, scrub resistance is also a problem that hydrophobic coatings need to face in practical applications. Traditional hydrophobic coatings have a certain dependence on the structure of the hydrophobic coatings themselves. After external forces such as repeated scrubbing, the hydrophobic performance of the coatings decreases significantly, and the water contact angle decreases significantly, making it difficult to achieve a long-lasting hydrophobic effect. For example, the prior art usually uses particle filling methods (CN102051120A, US9708527B2, US20180030282A1), phase separation methods (Hao L, et al. Colloids and Surfaces A: Physico-chemical and Engineering Aspects, 2012, 396: 83-89), sol-gel methods (US9688866B2, Wen X F, et al. Applied Surface Science, 2011, 258(3): 991-998) to construct hierarchical rough structures to achieve hydrophobic effects through the rough structures. However, such waterborne hydrophobic coatings have the defect of low mechanical strength of the coatings. Under external forces such as scrubbing, the rough structures are easily damaged, resulting in a decrease in the hydrophobic effect of the coatings. Therefore, such waterborne hydrophobic coatings are difficult to be widely applied.

[0003] For the solution to low scrub resistance, the prior art (US9630224B2, US20180147604A1, CN102030990A, Preston D J, et al. ACS applied materials & interfaces, 2017, 9(48):42383 - 42392) proposes a "super - lubricant liquid layer structure surface (SLIPS)" without structural dependence, that is, injecting lubricant after the hydrophobic coating forms a film. However, this method is rather cumbersome in the actual application process, and the lubricant itself does not form a cross - linked structure with the hydrophobic coating itself, and is extremely easy to lose under external forces such as scrubbing, which is also not conducive to maintaining the long - term hydrophobic effect. Therefore, it is of great significance to develop an aqueous hydrophobic coating with a simple industrial preparation method, inexpensive and easily available raw materials, excellent scrub resistance performance, and long - term hydrophobic effect. Summary of the Invention

[0004] In view of the above - mentioned disadvantages of the prior art, the purpose of the present invention is to provide a silane compound, its preparation method and use, for solving the problems in the prior art.

[0005] To achieve the above - mentioned purpose and other related purposes, the present invention is obtained through the following technical solutions.

[0006] One of the purposes of the present invention is to disclose a silane compound, which is formed by adding raw material components, and the raw material components include:

[0007] 1) At least one cyclic hydrogen - containing silane, and the cyclic hydrogen - containing silane includes one or both of the compound of formula Ⅰ and the compound of formula Ⅱ:

[0008]

[0009] Among them, both a and b are positive integers, and the sum of a and b is 3 - 12, R a 、R b 、R c 、R d 、R e and R f are branched chains connected to the main chain of the cyclic structure by Si - C bonds;

[0010] 2) At least one α - olefin oligomer;

[0011] The molar amount of Si - H bonds in the cyclic hydrogen - containing silane is greater than the molar amount of the α - olefin oligomer.

[0012] The sum of a and b can be 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12. Preferably, the sum of a and b is 4 - 8.

[0013] Preferably, the Ra and R b and R c and R d and R e and R f contain one or more of alkyl, alkylene, phenyl, aromatic condensed ring group, aromatic heterocyclic group, oxy group, thio group, carbonyl group, -NH-.

[0014] Preferably, R a and R b and R c and R d and R e and R f are independently selected from methyl or phenyl.

[0015] Preferably, the cyclic hydrogen-containing silane includes:

[0016]

[0017] Preferably, the cyclic hydrogen-containing silane further includes a cyclic hydrogen-containing silane with a three-dimensional structure, such as cage-type hydrogen silsesquioxane, tetrafunctional silicon hydride-functionalized cage-type silsesquioxane,

[0018]

[0019] Preferably, the α-olefin oligomer includes one or more of the following structural formulas:

[0020]

[0021] Among them, n is an integer of ≥1. Considering the reactivity, too high n leads to too large steric hindrance, which is not conducive to the hydrosilylation reaction and it is also difficult to separate from the product by means such as vacuum distillation. n is preferably 1-8, more preferably 1-4.

[0022] C m is a straight-chain or branched-chain alkyl group with the number of carbon atoms m = 2-18. m can be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18. Since too many carbon atoms will lead to too large steric hindrance and is not conducive to the hydrosilylation reaction, C m is preferably a straight-chain or branched-chain alkyl group with the number of carbon atoms m = 2-12. More preferably, C m is a straight-chain alkyl group with the number of carbon atoms m = 2-12.

[0023] Preferably, the α-olefin oligomer includes hexene oligomer, octene oligomer, decene oligomer.

[0024] Preferably, the molar ratio of the Si-H bond of the cyclic hydrogen-containing silane to the α-olefin oligomer is (2 to 15):1. For example, it can be 2:1, 8:3, 3:1, 16:5, 4:1, 9:2, 6:1, 32:5, 36:5, 8:1, 10:1, 12:1, 14:1 or 15:1.

[0025] More preferably, the molar ratio of the Si-H bond of the cyclic hydrogen-containing silane to the unsaturated α-olefin oligomer is (2 to 10):1.

[0026] Preferably, the raw material components further include a catalyst, and the catalyst is a Pt-containing catalyst. More preferably, the Pt-containing catalyst is one or more selected from an alcohol solution of chloroplatinic acid, a Pt-vinylbenzene complex, a Karstedt catalyst or a Pt-carbene complex. Further preferably, the Pt-containing catalyst is a Karstedt catalyst.

[0027] More preferably, the dosage of the Pt-containing catalyst is 0.1 to 0.5% (m / m) of the dosage of the α-olefin oligomer. For example, it can be 0.1%, 0.2%, 0.3%, 0.4% or 0.5%.

[0028] Preferably, the raw material components further include a polymerization inhibitor, and the polymerization inhibitor is p-methoxyphenol. The polymerization inhibitor is used to avoid free radical polymerization reactions between the double bonds of the α-olefin oligomer.

[0029] More preferably, the dosage of the polymerization inhibitor is 0.1 to 0.5% (m / m) of the dosage of the α-olefin oligomer.

[0030] Preferably, the raw material components further include a solvent, and the solvent is one or two selected from toluene and xylene.

[0031] The second object of the present invention is to disclose a preparation method of the silane compound as described above, in which an unsaturated α-olefin oligomer and a cyclic hydrogen-containing silane are subjected to a hydrosilylation reaction.

[0032] Preferably, the specific preparation method is: the cyclic hydrogen-containing silane and the α-olefin oligomer are reacted at a certain temperature, and then distilled after cooling to a certain temperature.

[0033] Preferably, the preparation method is specifically: after rising to the reaction temperature, the cyclic hydrogen-containing silane and the α-olefin oligomer are added to the reaction vessel, and after the addition is completed, the temperature is raised and kept warm for a period of time, and then distilled after cooling to a certain temperature.

[0034] It should be noted that since the hydrosilylation reaction has addition products following Markovnikov's rule and anti-Markovnikov's rule (see: Silicon in Organic, Organometallic, and Polymer Chemistry, Michael A. Brook, John Wiley & Sons, New York, 2000, pp401 - 458), it will result in at least two isomers of the addition product. All isomers obtained by the hydrosilylation of the unsaturated α-olefin oligomers with different double bond positions and the cyclic hydrogen-containing silane are within the scope of this invention application.

[0035] Preferably, the temperature of the hydrosilylation reaction is 70 - 120 °C.

[0036] Preferably, the time of the hydrosilylation reaction is 2 - 4 h.

[0037] Preferably, the holding temperature is 80 - 120 °C.

[0038] Preferably, the holding time is 1 - 3 h.

[0039] Preferably, the distillation is carried out under reduced pressure at 40 - 80 °C; further, the vacuum degree of the reduced pressure distillation is 0.5 torr.

[0040] The third object of the present invention is to disclose the use of the silane compound as described above as a water repellent.

[0041] The fourth object of the present invention is to disclose an aqueous hydrophobic coating, and the aqueous hydrophobic coating comprises the following raw materials in parts by weight:

[0042]

[0043] The water repellent is the silane compound as described above.

[0044] The dosage of the silicone-acrylic emulsion can be 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 66 parts by weight or 70 parts by weight.

[0045] The dosage of the silane water repellent can be 1 part by weight, 2 parts by weight, 2.2 parts by weight, 2.4 parts by weight, 2.5 parts by weight, 2.9 parts by weight or 3 parts by weight.

[0046] The dosage of the auxiliary agent can be 1 part by weight, 2 parts by weight, 2.8 parts by weight, 3 parts by weight, 4.2 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight or 10 parts by weight.

[0047] The amount of water can be 1 part by weight, 10 parts by weight, 14.7 parts by weight, 20 parts by weight, 26.2 parts by weight, 26.6 parts by weight, 26.9 parts by weight, 27.1 parts by weight, 30 parts by weight, 40 parts by weight or 50 parts by weight.

[0048] Preferably, the pH of the silicone-acrylic emulsion is 7-9.

[0049] Preferably, the auxiliary agent is selected from one or more of a wetting agent, a defoaming agent, a thickening agent, a film-forming auxiliary agent, an antifreezing agent or a bactericide.

[0050] More preferably, the auxiliary agent comprises the following components in parts by weight:

[0051]

[0052] The wetting agent can be 0.1 part by weight, 0.5 part by weight, 0.7 part by weight, 1.0 part by weight, 1.5 part by weight or 2.0 parts by weight.

[0053] The defoaming agent can be 0.1 part by weight, 0.2 part by weight, 0.3 part by weight, 0.4 part by weight or 0.5 part by weight.

[0054] The thickening agent can be 0.1 part by weight, 0.3 part by weight, 0.4 part by weight, 0.5 part by weight, 0.7 part by weight, 0.9 part by weight or 1.0 part by weight.

[0055] The film-forming auxiliary agent can be 0.5 part by weight, 1.0 part by weight, 1.3 part by weight, 2.0 parts by weight, 2.2 parts by weight, 3.0 parts by weight, 4.0 parts by weight or 5.0 parts by weight.

[0056] The antifreezing agent can be 0.1 part by weight, 0.3 part by weight, 0.4 part by weight, 0.5 part by weight, 0.7 part by weight, 0.9 part by weight or 1.0 part by weight.

[0057] The bactericide can be 0.1 part by weight, 0.2 part by weight, 0.3 part by weight, 0.4 part by weight or 0.5 part by weight.

[0058] More preferably, the wetting agent is BD-405.

[0059] More preferably, the defoaming agent is

[0060] More preferably, the thickening agent is ASE-60 or ASE-80.

[0061] More preferably, the film-forming auxiliary agent is Texanol ester alcohol, propylene glycol monobutyl ether (DPNB), ethylene glycol monobutyl ether (EB), diethylene glycol monobutyl ether (DEB) or dipropylene glycol monomethyl ether (DPM).

[0062] More preferably, the antifreeze is ethylene glycol, propylene glycol or glycerol.

[0063] More preferably, the bactericide is LX150.

[0064] Preferably, to reduce the cost of the coating and improve the surface hardness and covering power of the coating, the raw materials of the water-based hydrophobic coating further include inert fillers, and the inert fillers are one or more selected from titanium dioxide, talc powder, mica powder, kaolin, heavy calcium, silica, montmorillonite, bentonite or diatomaceous earth.

[0065] More preferably, the dosage of the inert filler does not exceed 50 parts by weight. For example, it can be 50 parts by weight, 40 parts by weight, 30

[0066] parts by weight.

[0067] The fifth object of the present invention is to disclose a preparation method of a water-based hydrophobic coating. By uniformly mixing the raw materials of the water-based hydrophobic coating, the water-based hydrophobic coating can be obtained.

[0068] Preferably, the preparation method of the water-based hydrophobic coating is as follows: after the silicone-acrylic emulsion and the silane hydrophobizing agent undergo a cross-linking reaction, additives and inert fillers are added, and after stirring evenly, the water-based hydrophobic coating can be obtained.

[0069] More preferably, during the cross-linking reaction, the pH of the system is 7.0-9.0, and the temperature is 40-60 °C.

[0070] More preferably, when adding the additives and inert fillers, the temperature of the system is at room temperature.

[0071] The sixth object of the present invention is to disclose a water-based hydrophobic coating formed by using the above water-based hydrophobic coating.

[0072] The seventh object of the present invention is to disclose a preparation method of a water-based hydrophobic coating. Using the above water-based hydrophobic coating, it is applied to a substrate and after drying treatment, a water-based hydrophobic coating is obtained.

[0073] Preferably, the substrate can be made of materials including: glass, ceramic, wood, stone, polyester, iron, cement, etc.

[0074] Preferably, the coating methods include conventional methods in the art such as scraping, rolling, spraying or pouring, and a suitable coating method can be selected according to the actual situation of the substrate to be coated.

[0075] Preferably, the drying treatment is to first make the surface of the coating dry, and then continue to completely dry it.

[0076] More preferably, the complete drying is to thermally dry or naturally dry the surface-dried coating. The thermal drying is to dry at 60 °C for 0.5-1

[0077] h. Natural drying is natural drying at room temperature for 1 - 7 days.

[0078] The present invention discloses a silane compound, which is prepared by hydrosilylation reaction of an α-olefin oligomer containing an unsaturated double bond with a cyclic hydrogen-containing silane. It can be used to prepare a waterborne hydrophobic coating. Compared with traditional waterborne coatings, it has extremely strong hydrophobicity, can effectively prevent water penetration, reduce the water absorption and cracking of the paint film, improve the scrub resistance and aging resistance of the paint film, and achieve a long-lasting hydrophobic effect. Description of the Drawings

[0079] Figure 1 It is the infrared spectrum of the silane hydrophobic agent prepared in Example 5. Detailed Embodiments

[0080] The following specific embodiments illustrate the implementation manners of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification.

[0081] Before further describing the specific implementation manners of the present invention, it should be understood that the protection scope of the present invention is not limited to the following specific implementation manners; it should also be understood that the terms used in the embodiments of the present invention are for describing specific implementation manners, rather than for limiting the protection scope of the present invention. The test methods without specific conditions noted in the following embodiments are generally carried out under conventional conditions or according to the conditions recommended by each manufacturer.

[0082] When the embodiments give a numerical range, it should be understood that unless otherwise specified in the present invention, any value at both ends of each numerical range and any value between the two ends can be selected. Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as commonly understood by those skilled in the art of this technology. In addition to the specific methods, equipment, and materials used in the embodiments, according to the knowledge of those skilled in the art of this technology and the description of the present invention, any methods, equipment, and materials similar to or equivalent to the methods, equipment, and materials described in the embodiments of the present invention can also be used to implement the present invention.

[0083] In specific embodiments, the α-olefin monomer undergoes a polymerization reaction to obtain an α-olefin oligomer, and the synthesis route is as follows:

[0084]

[0085] In specific embodiments, the preparation method of the α-olefin oligomer is as follows:

[0086] First, heat the polymerization reactor to above 100 °C, evacuate and bake it for 1 - 2 h, and displace it with high-purity nitrogen multiple times during this period to remove water and oxygen impurities in the reactor. Subsequently, adjust the temperature of the reactor to the reaction temperature of 40 - 120 °C through the jacket cooling water circulation, add the refined α-olefin and part of the cocatalyst, stir for 10 - 60 min, then add the metallocene compound dissolved in an inert solvent such as toluene and the remaining cocatalyst to the polymerization reactor. The concentration of the metallocene compound in the reaction system is 0.01 - 1 mmol / L (calculated based on the transition metal), and the molar ratio of the metal ion in the cocatalyst to the transition metal contained in the metallocene compound is 1 - 1000:1. Open the nitrogen valve to charge nitrogen to a pressure of 0.1 - 1.0 MPa for the reaction. During the reaction, the pressure in the reactor is kept constant by adding nitrogen, and the reaction temperature is coordinately controlled by the jacket heat transfer oil and the coil cooling water in the reactor. After the polymerization reaction is completed, open the vent pipe to relieve the pressure, discharge the crude product from the polymerization reactor, add acidified ethanol to the crude product to terminate the reaction, add 3 wt% activated clay to the obtained product to adsorb and remove the catalyst residues, then filter under pressure to obtain the filtrate. The obtained filtrate is distilled under reduced pressure to remove the solvent and unreacted monomers, and the fractions of polymers with different degrees of polymerization are collected at a certain vacuum degree and different temperatures, thereby obtaining an α-olefin oligomer containing unsaturated double bonds.

[0087] Example 1

[0088] This example provides a specific preparation method of a silane compound.

[0089] (1) Preparation of unsaturated α-olefin oligomer:

[0090] In this preparation method, the main catalyst is a metallocene compound, and the structural formula is:

[0091]

[0092] The α-olefin is 1-hexene (C6), the cocatalyst is methylaluminoxane, the solvent is toluene, the concentration of the metallocene compound in the reaction system is 0.3 mmol / L (calculated based on Zr), the concentration of methylaluminoxane in the reaction system is 45 mmol / L, the mass ratio of Al to Zr is 150:1, the addition amount of 1-hexene is 600 mL, the addition amount of toluene is 200 mL, the reaction temperature is 80 °C, and the reaction pressure is 0.5 MPa. After reacting for 0.5 h, the reaction is terminated, and the corresponding fractions of dimers, trimers, tetramers, and pentamers are collected by distillation under reduced pressure of the obtained filtrate. The fraction collection conditions are shown in the following table.

[0093]

[0094] (2) Preparation of silane compound:

[0095] Add 60 g of toluene solvent to a four-necked flask. Add 0.16 g of the polymerization inhibitor p-methoxyphenol and 0.20 g of Karstedt catalyst to the four-necked flask. Start stirring and heat up to 85 °C, then add dropwise to the flask the mixed 8.4 g (0.05 mol) of C6 dimer C 12 H 24 , 37.8 g (0.15 mol) of C6 trimer C 18 H 36 , 33.6 g (0.1 mol) of C6 tetramer C 24 H 48 , 48 g (0.2 mol) of 1,3,5,7-tetramethylcyclotetrasiloxane (D4H) and 60 g of toluene solvent. After dropping for 2 h, heat up to 95 °C and keep warm for 1.5 h. After the heat preservation is over, cool down to 60 °C and then distill off the solvent and unreacted monomers under a vacuum of 0.5 torr. Finally, 119.4 g of the residue in the flask is the silane compound, and the yield is 93.4%.

[0096] The structure characterization data of the silane compound are as follows: FTIR: 2967 cm -1 (v as -CH3), 2922 cm -1 (v as -CH2-), 2123 cm -1 (vSi-H), 1458 cm -1 (δ-CH2-), 1263 cm -1 (δSi-C), 1084 cm -1 (v Si-O-Si), 825 cm -1 (vSi-C).

[0097] Example 2

[0098] This example provides a specific preparation method of a silane compound.

[0099] The difference between this example and Example 1 is that the unsaturated α-olefin oligomer uses 25.2 g (0.1 mol) of C6 trimer C 18 H 36 , 33.6 g (0.1 mol) of C6 tetramer C 24 H 48 , 21 g (0.05 mol) of C60 pentamer C 30 H 60 , the heat preservation temperature is 105 °C, and the vacuum distillation temperature is 80 °C. 121.6 g of the residue in the flask is the silane compound, and the yield is 95.1%. The structure characterization data of the silane compound are as follows: FTIR: 2965 cm -1 (v as-CH3), 2924 cm -1 (v as -CH2-), 2126 cm -1 (vSi-H), 1456 cm -1 (δ-CH2-), 1265 cm -1 (δSi-C), 1085 cm -1 (vSi-O-Si), 827 cm -1 (vSi-C).

[0100] Example 3

[0101] This example provides a specific preparation method of a silane compound.

[0102] (1) Preparation of unsaturated α-olefin oligomers:

[0103] In this preparation method, the main catalyst is a metallocene compound with the structural formula:

[0104]

[0105] In this preparation method, the α-olefin is 1-octene (C8), the co-catalyst is methylaluminoxane, the solvent is toluene, the concentration of the metallocene compound in the reaction system is 0.3 mmol / L (calculated as Zr), the concentration of methylaluminoxane in the reaction system is 60 mmol / L, the mass ratio of Al to Zr is 200:1, the addition amount of 1-octene is 600 mL, the addition amount of toluene is 200 mL, the reaction temperature is 80 °C, and the reaction pressure is 0.1 MPa. After reacting for 0.5 h, the reaction is terminated, and the obtained filtrate is subjected to vacuum distillation to collect the fractions of the corresponding dimers, trimers, tetramers, and pentamers. The fraction collection conditions are shown in the following table.

[0106]

[0107] (2) Preparation of silane compound:

[0108] Add 60 g of toluene solvent to a four-necked flask, add 0.30 g of inhibitor p-methoxyphenol and 0.35 g of Karstedt catalyst to the four-necked flask, start stirring, and after heating to 85 °C, add 67.2 g (0.3 mol) of C8 dimer C 16 H 32 、33.6 g (0.1 mol) of C8 trimer C 24 H 48 、44.8 g (0.1 mol) of C8 tetramer C 32 H 64, 90 g (0.375 mol) of 1,3,5,7 - tetramethylcyclotetrasiloxane (D4H) and 60 g of toluene solvent were added. After dropping over 2 h, the temperature was raised to 95 °C and kept for 1.5 h. After the holding was completed, the temperature was lowered to 60 °C, and the solvent and unreacted monomers were removed by vacuum distillation under a vacuum of 0.5 torr. Finally, 221.9 g of the residue in the flask was the silane compound, and the yield was 94.2%.

[0109] The structural characterization data of the silane compound are as follows: FTIR: 2965 cm -1 (v as -CH3), 2925 cm -1 (v as -CH2-), 2124 cm -1 (vSi-H), 1455 cm -1 (δ-CH2-), 1263 cm -1 (δSi-C), 1083 cm -1 (v Si-O-Si), 828 cm -1 (vSi-C).

[0110] Example 4

[0111] This example provides a specific method for preparing a silane compound.

[0112] The difference between this example and Example 3 is that the amount of the polymerization inhibitor p - methoxyphenol is 0.32 g, the amount of the Karstedt catalyst is 0.4 g, and the unsaturated α - olefin oligomer uses 67.2 g (0.2 mol) of C8 trimer C 24 H 48 , 67.2 g (0.15

[0113] mol) of C8 tetramer C 32 H 64 , 28 g (0.05 mol) of C8 pentamer C 40 H 80 . The amount of 1,3,5,7 - tetramethylcyclotetrasiloxane (D4H) is 96 g (0.4 mol), the holding temperature is 105 °C, and the vacuum distillation temperature is 80 °C. 236.3 g of the residue in the flask was the silane compound, and the yield was 91.4%.

[0114] The structural characterization data of the silane compound are as follows: FTIR: 2964 cm -1 (v as -CH3), 2926 cm -1 (v as -CH2-), 2126 cm -1 (vSi-H), 1454 cm -1(δ-CH2-), 1264 cm -1 (δSi-C), 1082 cm -1 (v Si-O-Si), 826 cm -1 (vSi-C).

[0115] Example 5

[0116] This example provides a specific preparation method of a silane compound.

[0117] (1) Preparation of unsaturated α-olefin oligomers:

[0118] In this preparation method, the main catalyst is a metallocene compound with the structural formula:

[0119]

[0120] The α-olefin is 1-decene (C10), the cocatalyst is methylaluminoxane, the solvent is toluene, the concentration of the metallocene compound in the reaction system is 0.3 mmol / L (calculated as Zr), the concentration of methylaluminoxane in the reaction system is 90 mmol / L, the mass ratio of Al to Zr is 300:1, the addition amount of 1-decene is 600 mL, the addition amount of toluene is 200 mL, the reaction temperature is 80 °C, and the reaction pressure is 0.1 MPa. After reacting for 0.5 h, the reaction is terminated, and the corresponding fractions of dimers, trimers, tetramers, and pentamers are collected by vacuum distillation of the obtained filtrate. The fraction collection conditions are shown in the following table.

[0121]

[0122] (2) Preparation of silane compound:

[0123] Add 60 g of toluene solvent to a four-necked flask, add 0.5 g of the inhibitor p-hydroxyanisole and 0.64 g of Karstedt catalyst to the four-necked flask, start stirring, heat up to 85 °C, and then dropwise add 210 g (0.75 mol) of C10 dimer C 20 H 40 , 63 g (0.15 mol) of C10 trimer C 30 H 60 , 108 g (0.45 mol) of 1,3,5,7-tetramethylcyclotetrasiloxane (D4H), and 80 g of toluene solvent. After dropping for 2 h, heat up to 105 °C and keep warm for 1.5 h. After the heat preservation is over, cool down to 50 °C and distill off the solvent and unreacted monomers under a vacuum of 0.8 torr. The residue in the flask is 359.3 g of the silane compound, and the yield is 94.3%.

[0124] The structural characterization data of the silane compound are as follows: FTIR: 2966 cm-1 (v as -CH3), 2924 cm -1 (v as -CH2-), 2126 cm -1 (v Si-H), 1456 cm -1 (δ-CH2-), 1262 cm -1 (δSi-C), 1084 cm -1 (v Si-O-Si), 824 cm -1 (v Si-C).

[0125] The infrared characterization of the silane hydrophobizing agent prepared in Example 5 is as Figure 1 shown.

[0126] Example 6

[0127] This example provides a specific preparation method of a silane compound.

[0128] The difference between this example and Example 5 is that the amount of the polymerization inhibitor p-methoxyphenol is 0.35 g, the amount of the Karstedt catalyst is 0.45 g, and the unsaturated α-olefin oligomer uses 84 g (0.2 mol) of C10 trimer C 30 H 60 , 84 g (0.15

[0129] mol) of C10 tetramer C 40 H 80 , 35 g (0.05 mol) of C10 pentamer C 50 H 100 , and the vacuum distillation temperature is 80 °C. The residue of 294.8 g in the flask is the silane compound, and the yield is 94.8%.

[0130] The structural characterization data of the silane hydrophobizing agent are as follows: FTIR: 2965 cm -1 (v as -CH3), 2925 cm -1 (v as -CH2-), 2125 cm -1 (vSi-H), 1454 cm -1 (δ-CH2-), 1265 cm -1 (δSi-C), 1082 cm -1 (v Si-O-Si), 826 cm -1 (vSi-C).

[0131] Example 7

[0132] This embodiment provides a specific waterborne hydrophobic coating, and the formula is shown in the following table:

[0133] Raw material Remarks Dosage (g) Deionized water 60 Silicone-acrylic emulsion RS-3799A Film-forming resin 150 Silane compound prepared in Example 1 Silane water repellent 5.5 BD-405 Wetting agent 1.5 KEPERPOL-3300W Defoaming agent 0.5 Glycerol Antifreeze 1.0 ASE-60 Thickening agent 1.0 Texanol Film-forming aid 5.0 LX150 Bactericide 0.5 Total 225

[0134] Preparation method of the waterborne hydrophobic coating: Adjust the pH value of the silicon-acrylic emulsion to 8.0, raise the temperature to 50 °C, stir for 60 min, then add the silane compound prepared in Example 1, stir for 30 min, and after cooling to room temperature, continue to add other additives and stir for 15 min to obtain the waterborne hydrophobic coating.

[0135] Example 8

[0136] This embodiment provides a specific waterborne hydrophobic coating, and the formula is shown in the following table:

[0137] Raw material Remarks Dosage (g) Deionized water 61 Silicone-acrylic emulsion RS-3799A Film-forming resin 150 Silane compound prepared in Example 2 Silane water repellent 4.5 BD-405 Wetting agent 1.5 KEPERPOL-3300W Defoaming agent 0.5 Glycerol Antifreeze 1.0 ASE-80 Thickening agent 1.0 Texanol Film-forming aid 5.0 LX150 Bactericide 0.5 Total 225

[0138] The preparation method of the waterborne hydrophobic coating is the same as that of Example 7.

[0139] Example 9

[0140] This embodiment provides a specific waterborne hydrophobic coating, and the formula is shown in the following table:

[0141] Raw material Remarks Dosage (g) Deionized water 59 Silicone-acrylic emulsion RS-3799A Film-forming resin 150 Silane compound prepared in Example 3 Silane water repellent 6.5 BD-405 Wetting agent 1.5 KEPERPOL-3300W Defoaming agent 0.5 Ethylene glycol Antifreeze 1.0 ASE-60 Thickening agent 1.0 Texanol Film-forming aid 5.0 LX150 Bactericide 0.5 Total 225

[0142] The difference between the preparation method of the waterborne hydrophobic coating provided in this embodiment and that of Example 7 is that the temperature for adding the silane compound is 60 °C, and it is stirred for 10 min after adding other additives.

[0143] Example 10

[0144] This embodiment provides a specific waterborne hydrophobic coating, and the formula is shown in the following table:

[0145] Raw material Remarks Dosage (g) Deionized water 60 Silicone-acrylic emulsion RS-3799A Film-forming resin 150 Silane compound prepared in Example 4 Silane water repellent 5.5 BD-405 Wetting agent 1.5 KEPERPOL-3300W Defoaming agent 0.5 Propylene glycol Antifreeze 1.0 ASE-80 Thickening agent 1.0 Texanol Film-forming aid 5.0 LX150 Bactericide 0.5 Total 225

[0146] The difference between the preparation method of the waterborne hydrophobic coating provided in this embodiment and that of Example 7 is that the temperature for adding the silane compound is 60 °C, and it is stirred for 10 min after adding other additives.

[0147] Example 11

[0148] This embodiment provides a specific waterborne hydrophobic coating, and the formula is shown in the following table:

[0149] Raw material Remarks Dosage (g) Deionized water 61 Silicone-acrylic emulsion RS-3799A Film-forming resin 150 Silane compound prepared in Example 5 Silane water repellent 5.0 BD-405 Wetting agent 1.5 KEPERPOL-3300W Defoaming agent 0.5 Glycerol Antifreeze 1.0 ASE-60 Thickening agent 1.0 Texanol Film-forming aid 5.0 LX150 Bactericide 0.5 Total 225

[0150] The difference between the preparation method of the waterborne hydrophobic coating provided in this embodiment and that of Example 7 is that the temperature for adding the silane compound is 40 °C, and it is stirred for 10 min after adding other additives.

[0151] Example 12

[0152] This example provides a specific waterborne hydrophobic coating, and the formula is shown in the following table:

[0153] Raw material Remarks Dosage (g) Deionized water 60 Silicone-acrylic emulsion RS-3799A Film-forming resin 150 Silane compound prepared in Example 6 Silane water repellent 4.5 BD-405 Wetting agent 1.5 KEPERPOL-3300W Defoaming agent 0.5 Propylene glycol Antifreeze 1.0 ASE-60 Thickening agent 1.0 Texanol Film-forming aid 5.0 LX150 Bactericide 0.5 Total 225

[0154] The difference between the preparation method of the waterborne hydrophobic coating provided in this example and that of Example 7 is that the temperature for adding the silane compound is 40 °C, and after adding other additives, it is stirred for 10 min.

[0155] Example 13

[0156] This example provides a specific waterborne hydrophobic coating, and the formula is shown in the following table:

[0157]

[0158]

[0159] The difference between the preparation method of the waterborne hydrophobic coating provided in this example and that of Example 7 is that after adding other additives, it is stirred for 20 min.

[0160] Example 14

[0161] This example provides a specific waterborne hydrophobic coating, and the formula is shown in the following table:

[0162] Raw material Remarks Dosage (g) Deionized water 55 Silicone-acrylic emulsion ROSF-9907 Film-forming resin 150 Silane compound prepared in Example 3 Silane water repellent 9.5 BD-405 Wetting agent 2.5 KEPERPOL-3300W Defoaming agent 0.5 Propylene glycol Antifreeze 1.0 ASE-60 Thickening agent 1.0 DPM Film-forming aid 2.5 DPNB Film-forming aid 2.5 LX150 Bactericide 0.5 Kaolin Inert filler 75 Rutile titanium dioxide Inert filler 5.0 Heavy calcium carbonate Inert filler 70 Total 375

[0163] The difference between the preparation method of the waterborne hydrophobic coating provided in this example and that of Example 7 is that the temperature for adding the silane compound is 60 °C, and after adding other additives, it is stirred for 20 min.

[0164] Example 15

[0165] This example provides a specific waterborne hydrophobic coating, and the formula is shown in the following table:

[0166]

[0167]

[0168] The difference between the preparation method of the waterborne hydrophobic coating provided in this example and that of Example 7 is that the temperature for adding the silane compound is 40 °C, and after adding other additives, it is stirred for 20 min.

[0169] Comparative Example 1

[0170] Comparative Example 1 is the comparative example of Example 10. The difference is that the silane hydrophobe is polydimethylsiloxane.

[0171] Comparative Example 2

[0172] Comparative Example 2 is a comparative example of Example 15, except that KH-305 (n-octyltriethoxysilane) is used as the silane hydrophobic agent.

[0173] The water-based hydrophobic coatings prepared in Examples 7 to 15 and Comparative Examples 1 to 2 are used to prepare water-based hydrophobic coatings. The material of the substrate is one or more of a glass plate, a tinplate sheet, and an asbestos fiber cement board. The coating method is spraying.

[0174] The prepared water-based hydrophobic coating was subjected to the following performance tests, and the test results are shown in Tables 1 and 2. The test methods or standards are as follows:

[0175] Alkali resistance: Tested according to the method of GB / T 9265-2009 for 96 hours. No discoloration, bubbles, peeling, powdering and softening are considered normal.

[0176] Water resistance: Tested according to the immersion test method in GB / T1733-1993, the test time is 168h.

[0177] Scrub resistance: Tested according to the method of GB / T9266-2009, the dry film thickness is 23±2μm, and the number of times the coating is washed until it is damaged and the substrate is exposed is recorded.

[0178] Acid rain resistance: Tested according to the immersion method in GB / T 9274-1988, the test liquid is an acidic aqueous solution, pH 3.5-4.5, the test time is 48h, the dry film thickness is 23±2μm, the immersion depth is 2 / 3 immersion, no aeration stirring or circulation, no volume maintenance, the cover is added during the test, and the water evaporation is not obvious. Normal means that the contact part between the coating and the liquid phase has not changed.

[0179] Artificial weathering: Tested according to the method of GB / T 1865-2009.

[0180] The material of the substrate is a test-grade tinplate sheet of 100*200*0.28mm, the dry film thickness of the paint film is 23±2μm, and the paint film is dried naturally for 7 days under constant temperature and humidity conditions of 23±5℃ and 50±5% after spraying. The test equipment is a Ci5000 xenon lamp artificial weathering tester, using method 1, and the test conditions are: irradiance (340nm) 0.51W / m 2 , relative humidity 50%, the wetting cycle adopts cycle A, and the black standard temperature is set to 65±2℃.

[0181] The artificial weathering resistance was evaluated according to GB / T 1766-2008, and the ratings of color change grade, cracking grade, blistering grade, and peeling grade were carried out. The degree and quantity of damage were rated with a numerical scale from 0 to 5. Among them, grades 0, 1, 2, 3, 4, and 5 represent: none, very few, few, medium, many, severe or dense, respectively.

[0182] Thermal storage stability: The aqueous hydrophobic coating was placed in an oven at 60 ± 1 °C for 7 days, and the fluidity and whether there was stratification were observed. If the coating could flow normally without caking, stratification, or coagulation, it was considered normal.

[0183] Contact angle with water: The contact angle of the paint film before and after the scrub resistance test was measured using a CA200 contact angle measuring instrument. Among them, the scrub resistance test was uniformly carried out for 30 minutes, and each paint film sample was scrubbed about 1110 times.

[0184] Table 1

[0185]

[0186]

[0187] Table 2

[0188]

[0189] It can be seen from Table 1 and Table 2 that compared with Example 10, in Comparative Example 1, polydimethylsiloxane was used as the silane hydrophobic agent, lacking the reactive groups for crosslinking with the silicone-acrylic emulsion. Therefore, its compatibility with the silicone-acrylic emulsion decreased, and the waterproofness, scrub resistance, and aging resistance of the aqueous hydrophobic coating prepared in Comparative Example 1 were all reduced.

[0190] Compared with Example 15, in Comparative Example 2, n-octyltriethoxysilane was used as the silane hydrophobic agent. n-Octyltriethoxysilane can react with the silicone-acrylic emulsion and graft onto the film-forming resin. However, because its crosslinking density is not as good as that of the silane hydrophobic agent prepared in the present invention, and the volume of the hydrophobic group of n-octyltriethoxysilane is also not as large as that of the α-olefin oligomer with a branched structure, there is still a gap in the scrub resistance and aging resistance of the aqueous hydrophobic coating prepared in Comparative Example 2 compared with Example 15. Specifically, it is reflected in the contact angle with water before and after scrubbing. The difference in the contact angle with water before and after scrubbing of the aqueous hydrophobic coating prepared in Example 15 is not obvious, while the difference in the contact angle with water before and after scrubbing of the aqueous hydrophobic coating prepared in Comparative Example 2 is obvious. This shows that using the silane hydrophobic agent prepared in this application in combination with the silicone-acrylic emulsion can significantly reduce the impact of scrubbing on the hydrophobicity of the aqueous hydrophobic coating, achieve a long-lasting hydrophobic effect, and have a wider range of applications.

[0191] The above embodiments are only illustrative of the principles and effects of the present invention and are not intended to limit the present invention. Any person familiar with this technology can modify or change the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or changes made by those with ordinary knowledge in the technical field without departing from the spirit and technical idea disclosed by the present invention should still be covered by the claims of the present invention.

Claims

1. A silane compound, characterized in that, The silane compound is formed by a hydrosilylation reaction of raw material components, and the raw material components include: 1) At least one cyclic hydrogen-containing silane, and the cyclic hydrogen-containing silane includes one or both of the compound of formula I and the compound of formula II: ； Among them, both a and b are positive integers, and the sum of a and b is 4 to 8; R a , R b , R c , R d , R e , and R f are independently selected from methyl or phenyl; 2) At least one α-olefin oligomer; The molar amount of Si-H bonds in the cyclic hydrogen-containing silane is greater than the molar amount of the α-olefin oligomer; The α-olefin oligomer includes one or more of the following structural formulas: 、 、 、 ； Among them, n is from 1 to 8, and C m is a straight-chain or branched-chain alkyl group with m carbon atoms, where m is from 2 to 18.

2. The silane compound according to claim 1, wherein The molar ratio of the Si-H bond of the cyclic hydrogen-containing silane to the unsaturated α-olefin oligomer is (2-15):1; and / or, a catalyst is further included in the raw material components, and the catalyst is a Pt-containing catalyst; and / or, an inhibitor is further included in the raw material components, and the inhibitor is p-methoxyphenol; and / or, a solvent is further included in the raw material components, and the solvent is one or both selected from toluene and xylene.

3. A method for preparing a silane compound according to any one of claims 1 to 2, characterized in that, The unsaturated α-olefin oligomer and the cyclic hydrogen-containing silane carry out a hydrosilylation reaction.

4. The preparation method according to claim 3, characterized in that, The temperature of the hydrosilylation reaction is 70-120 °C.

5. Use of the silane compound according to any one of claims 1-2 as a water repellent.

6. An aqueous hydrophobic coating, characterized in that, The aqueous hydrophobic coating includes the following raw materials in parts by weight: Silicone-acrylic emulsion 30-70 parts by weight; Water repellent 1-3 parts by weight; Auxiliary agent 1-10 parts by weight; Water 1-50 parts by weight; The water repellent is the silane compound according to any one of claims 1-2.

7. The aqueous hydrophobic coating according to claim 6, characterized in that, The auxiliary agent is selected from one or more of a wetting agent, a defoaming agent, a thickening agent, a film-forming auxiliary agent, an antifreezing agent or a bactericide; and / or, an inert filler is further included in the raw materials of the aqueous hydrophobic coating, and the inert filler is one or more selected from titanium dioxide, talc powder, mica powder, kaolin, heavy calcium, silica, montmorillonite, bentonite or diatomaceous earth.

8. A method for preparing an aqueous hydrophobic coating according to any one of claims 6 to 7, characterized in that, Mix the raw materials of the aqueous hydrophobic coating evenly to obtain the aqueous hydrophobic coating.

9. A water-based hydrophobic coating, characterized in that, Formed by using the aqueous hydrophobic coating according to any one of claims 6-7.

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