A phenol-terminated silicone polymer and a method for preparing the same

Abstract

The application belongs to the field of organic silicon material, and provides a phenol-terminated organic silicon polymer and a preparation method thereof.The preparation method of the phenol-terminated organic silicon polymer is as follows: under stirring and protection of a protective gas, an adhesion agent solution is added dropwise into an organic silicon molecule solution, and the mixture is fully reacted at 0-100 DEG C; unreacted raw materials and solvents are removed, and drying is performed, and the phenol-terminated organic silicon polymer is obtained; the adhesion agent is a compound with a hydroxyl group and an amine group on a benzene ring.Based on the phenol-terminated organic silicon polymer, a nano-coating with good liquid-repellent and anti-fouling performance can be constructed.

Description

Technical Field

[0001] This invention belongs to the field of organosilicon materials and relates to a phenol-terminated organosilicon polymer and its preparation method. Background Technology

[0002] Organosilicon is a polysiloxane composed of silicon-oxygen bonds (Si-O-Si) as its backbone. Due to its unique structure, it has excellent insulation, hydrophobicity, corrosion resistance, and high and low temperature resistance properties, and is widely used in aerospace, electronics, chemical, energy and medical industries.

[0003] Organosilicon-modified materials have wide applications in the field of hydrophobicity. CN117363159A discloses an organosilicon-modified epoxy resin waterborne superhydrophobic coating and its preparation method. This method involves mixing organosilicon-modified epoxy resin with hydrophilic / hydrophobic modified nano-inorganic particles, an organic solvent, and water in a specific ratio to obtain a waterborne superhydrophobic coating that can be applied to self-cleaning and antifouling applications. However, during the preparation of this superhydrophobic coating, it is difficult to ensure that the hydrophilic / hydrophobic modified nano-inorganic particles are uniformly dispersed in the organosilicon-modified epoxy resin, which can easily lead to poor coating uniformity and thus affect the coating's performance. CN117363135A discloses a hydrogen-bonded modified organosilicon marine antifouling coating. This antifouling coating consists of component A, containing modified organosilicon resin and pigments / fillers; component B, containing a curing agent; and component C, containing a catalyst. The modified organosilicon resin is synthesized by reacting monomers with thiourea and olefin groups, cationic monomers, acrylamide monomers, methyl vinyl MQ type silicone resin, and ethanol under the initiator condition of azobisisobutyronitrile. This antifouling coating firmly bonds to the substrate surface through hydrogen bonding between thiourea groups and quaternary ammonium salt groups, achieving its antifouling effect through the silicon-oxygen backbone structure. However, when this antifouling coating is applied to the substrate surface by brushing, spraying, or rolling and then dried and cured, the resulting antifouling coating thickness is 150–250 μm. This relatively large thickness leads to the problem of easy peeling during use and also limits its application in certain precision fields. Currently, nanoscale coatings have broad application prospects in corrosion prevention, friction reduction and heat exchange. The development of nanoscale coating technology is an inevitable trend. Therefore, it is crucial to develop materials that can be used to prepare nanoscale coatings with hydrophobic and antifouling properties. Summary of the Invention

[0004] To address the problem that existing low surface energy silicone antifouling coatings based on silicone polymers have large thicknesses and are prone to peeling off during use, making them unsuitable for precision applications, this invention provides a phenol-terminated silicone polymer and its preparation method to achieve the construction of a nano-coating with good hydrophobic and antifouling properties.

[0005] To achieve the above-mentioned objectives, the technical solution adopted by the present invention is as follows:

[0006] A method for preparing a phenol-terminated organosilicon polymer, characterized by comprising the following steps:

[0007] (1) Dissolve organosilicon molecules in dichloromethane to form an organosilicon molecule solution; dissolve an adhesive in N,N-dimethylformamide to form an adhesive solution, wherein the adhesive is a compound having hydroxyl and amine groups on a benzene ring;

[0008] (2) Under stirring and protective gas protection, the adhesive solution is added dropwise to the organosilicon molecular solution and reacted fully at 0-100℃. Unreacted raw materials and solvents are removed and dried to obtain phenol-terminated organosilicon polymer.

[0009] In the above-mentioned method for preparing phenol-terminated organosilicon polymers, the organosilicon molecules are R1-Si(CH3)2-O-Si(CH3)2-R1, R2-Si(CH3)2-O-Si-(CH3)3, and H2N(CH2)3Si[O(CH2)]. n [(CH3)3]3 or poly[dimethylsiloxane-co-(3-aminopropyl)methylsiloxane], wherein R1 is -(CH2)3NH2, -OH, -(CH2)3COOH or -CH(O)CH-, and R2 is -(CH2)3O(CH2)2OH, -(CH2)3COOH or -(CH2)3OCH2CH(O)CH.

[0010] Furthermore, in the above-mentioned method for preparing phenol-terminated organosilicon polymers, the H2N(CH2)3Si[O(CH2)]... n In (CH3)3]3, n = 0 or 1.

[0011] In step (2) of the above-mentioned method for preparing phenol-terminated organosilicon polymer, it is preferable to control the amount of organosilicon molecular solution and adhesive solution added so that the molar ratio of organosilicon molecules to adhesive is 1:(0.05~5).

[0012] In step (2) of the above-mentioned method for preparing phenol-terminated organosilicon polymer, a chain extender solution is also added dropwise to the organosilicon molecular solution. That is, in step (2), under stirring and protective gas conditions, the adhesive solution and chain extender solution are added dropwise to the organosilicon molecular solution, reacted fully at 0–100°C, unreacted raw materials and solvents are removed, and the mixture is dried to obtain the phenol-terminated organosilicon polymer. Preferably, the amount of chain extender solution added is controlled such that the molar ratio of organosilicon molecules to chain extender to adhesive is 1:(1–5).

[0013] In the above-mentioned method for preparing phenol-terminated organosilicon polymers, whether or not a chain extender is used depends mainly on the specific structure of the organosilicon molecule used. When the organosilicon molecule is R2-Si(CH3)2-O-Si-(CH3)3, a chain extender is not necessary; when the organosilicon molecule is H2N(CH2)3Si[O(CH2)3]... n When [(CH3)3]3 or poly[dimethylsiloxane-co-(3-aminopropyl)methylsiloxane] is used, a chain extender is required; when the organosilicon molecule is R1-Si(CH3)2-O-Si(CH3)2-R1, a chain extender may or may not be used. In practical applications, whether or not to add a chain extender depends on the structure of the organosilicon molecule and the specific application requirements.

[0014] Furthermore, in the above-mentioned method for preparing phenol-terminated organosilicon polymers, the chain extender is a commonly used chain extender in the prior art for preparing organosilicon polymers. For example, feasible chain extenders include one or more combinations of 4,4′-methylenebis(phenyl isocyanate), 4,4′-diisocyanate dicyclohexylmethane D, isocyclohexylimide, isophorone diisocyanate, and toluene diisocyanate.

[0015] Furthermore, in the above-mentioned method for preparing phenol-terminated organosilicon polymers, the chain extender solution is formed by dissolving the chain extender in N,N-dimethylformamide.

[0016] In the above-mentioned method for preparing phenol-terminated organosilicon polymers, the adhesive includes any one of dopamine hydrochloride, 6-hydroxydopamine, and 3-hydroxy-4-methoxyphenylethylamine.

[0017] In step (2) of the above-described method for preparing phenol-terminated organosilicon polymer, a catalyst may be added to the organosilicon molecular solution. Typically, the amount of catalyst added should be such that the molar ratio of catalyst to organosilicon molecules is 1:(2-3). Further, the catalyst includes at least one of triethylamine, 4-N,N-dimethylpyridine, trimethylamine, and dibutyltin dilaurate.

[0018] In step (2) of the above-mentioned method for preparing phenol-terminated organosilicon polymer, the reaction time at 0-100°C can be 4-8 hours.

[0019] In the above-mentioned method for preparing phenol-terminated organosilicon polymers, the protective gas is a non-reactive gas that does not react with the adhesive / organosilicon molecule system or the adhesive / organosilicon molecule / chain extender system in step (2). The protective gas can be an inert gas or nitrogen.

[0020] In the above-mentioned method for preparing phenol-terminated organosilicon polymer, after preparing the organosilicon molecular solution, it is best to remove the oxygen in the organosilicon molecular solution before proceeding with the reaction in step (2). When preparing the adhesive solution and the chain extender solution, it is best to use a solvent that has removed oxygen.

[0021] In the above-mentioned method for preparing phenol-terminated organosilicon polymers, the concentration of the organosilicon molecular solution is preferably 0.01–0.2 mmol / mL, the concentration of the adhesive solution is preferably 0.01–1 mmol / mL, and the concentration of the chain extender solution is preferably 0.1–1 mmol / mL.

[0022] The present invention also provides a phenol-terminated organosilicon polymer prepared by the above method.

[0023] The phenol-terminated organosilicon polymer provided by this invention is dissolved in an organic solvent to prepare a phenol-terminated organosilicon polymer solution of appropriate concentration. Then, a coating with a thickness in the nanometer range can be formed on a substrate by spraying, brushing, or immersion. Experiments have demonstrated that the phenol-terminated organosilicon polymer provided by this invention can form a nanometer-thickness coating on metallic, inorganic, and organic substrates, and the formed coating exhibits good hydrophobic and antifouling properties.

[0024] Compared with the prior art, the technical solution of the present invention can produce the following beneficial technical effects:

[0025] 1. This invention provides a phenol-terminated organosilicon polymer, formed by the reaction of organosilicon molecules with compounds having hydroxyl and amino groups on the benzene ring. By introducing compounds with both hydroxyl and amino groups on the benzene ring into the organosilicon polymer for end-capping, functional groups such as C=O, NH, and -OH are introduced into the organosilicon polymer molecular chain, increasing the hydrogen bond formation sites in the organosilicon polymer molecule. This allows the prepared phenol-terminated organosilicon polymer to stably bond with the substrate through multiple interactions such as hydrogen bonding, complexation, and π-π bonding to form a coating with nanoscale thickness. This not only increases the bonding stability between the coating and the substrate but also effectively reduces the coating thickness, solving the problems of excessive thickness and poor bonding stability of hydrophobic coatings formed by existing organosilicon-modified materials.

[0026] 2. The phenol-terminated organosilicon polymer provided by this invention can form a coating on organic, inorganic, or organic substrates through simple spraying, brushing, and immersion methods. The low surface energy side methyl groups in the phenol-terminated organosilicon polymer reduce the interaction force between the coating and the liquid, thus giving the coating excellent hydrophobic properties. Simultaneously, the phenol-terminated organosilicon polymer exhibits high dynamic flexibility, acting as a lubricant. The coating formed on the substrate surface effectively reduces the surface free energy of the substrate surface, thereby reducing the adhesion force between contaminants and the substrate surface, achieving anti-adhesion and anti-fouling effects. Based on these characteristics, the phenol-terminated organosilicon polymer provided by this invention can be used in the preparation of hydrophobic and anti-fouling coatings.

[0027] 3. The preparation method of the phenol-terminated organosilicon polymer and the method of forming a coating with the phenol-terminated organosilicon polymer described in this invention are very simple and conducive to their widespread application in practical scenarios. Attached Figure Description

[0028] Figure 1 This is the 1H NMR spectrum of the phenol-terminated organosilicon polymer prepared in Example 1.

[0029] Figure 2 This describes the antifouling effect of the phenol-terminated organosilicon polymer prepared in Example 2 on a metal substrate.

[0030] Figure 3 It is the thickness of the phenol-terminated organosilicon polymer coating formed on the silicon wafer in Example 4.

[0031] Figure 4 This describes the antifouling effect of the phenol-terminated organosilicon polymer prepared in Example 7 on an inorganic material substrate.

[0032] Figure 5 This is the Fourier transform infrared spectrum of the phenol-terminated organosilicon polymer prepared in Example 8.

[0033] Figure 6 This describes the antifouling effect of the phenol-terminated organosilicon polymer prepared in Example 9 on an organic material substrate. Detailed Implementation

[0034] The following examples further illustrate the phenol-terminated organosilicon polymer and its preparation method provided by the present invention. It should be noted that the following examples are only for further illustration of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made to the present invention by those skilled in the art based on the above description are still within the scope of protection of the present invention.

[0035] Example 1

[0036] In this embodiment, the preparation of the phenol-terminated organosilicon polymer is carried out through the following steps:

[0037] (1) An organosilicon molecule R1-Si(CH3)2-O-Si(CH3)2-R1 (where R1 is -(CH2)3NH2, and the organosilicon molecule is denoted as NH2-PDMS-NH2) with a molecular weight of 27000 g / mol was dissolved in dichloromethane to obtain an organosilicon molecular solution with a concentration of 0.05 mmol / mL. The organosilicon molecular solution was placed in a three-necked round-bottom flask, and nitrogen gas was bubbled through it for 10 min to remove air from the organosilicon molecular solution. At the same time, the organosilicon molecular solution was stirred using a magnetic stirrer.

[0038] Nitrogen gas was bubbled into N,N-dimethylformamide (DMF) for 10 min to expel the air. Then, the chain extender 4,4′-methylenebis(phenyl isocyanate) (MDI) was dissolved in DMF to obtain an MDI solution with a concentration of 0.33 mmol / mL.

[0039] Nitrogen gas was bubbled into the DMF for 10 minutes to expel the air. Then, dopamine hydrochloride (DOPA) was dissolved in the DMF to obtain a 0.0167 mmol / L dopamine hydrochloride solution.

[0040] (2) Under stirring, nitrogen protection and ice bath conditions, MDI solution was added dropwise to a three-necked round-bottom flask containing organosilicon molecular solution, and then dopamine hydrochloride solution was added dropwise to the three-necked round-bottom flask. After the addition was completed, the reaction was carried out for 4 hours under stirring, nitrogen protection and ice bath conditions. The resulting reaction product was repeatedly washed with deionized water, then dried by vacuum rotary evaporation at 30°C, and then placed in an oven to dry, thus obtaining the final product phenol-terminated organosilicon polymer.

[0041] In this step, the amounts of organosilicon molecular solution, MDI solution and dopamine hydrochloride solution are controlled so that the molar ratio of organosilicon molecules, MDI and dopamine hydrochloride is 1:1:0.05.

[0042] The structural formula of the phenol-terminated organosilicon polymer prepared in this embodiment is as follows:

[0043]

[0044] The 1H NMR spectrum of the phenol-terminated organosilicon polymer prepared in this embodiment is shown below. Figure 1 As shown, Figure 1In the reaction, d (δ 3.18 ppm), e (δ 1.56 ppm), f (δ 0.6 ppm), g (δ 0.25 ppm), and h (δ 0.13 ppm) belong to the organosilicon molecule NH2-PDMS-NH2, a (δ 7.36 ppm), b (δ 7.03 ppm), and c (δ 3.8 ppm) belong to the chain extender MDI, and i, j, and k (δ 6.72 ppm) belong to DOPA. This indicates that DOPA, MDI, and NH2-PDMS-NH2 participated in the reaction, and the integral ratio of MDI to DOPA was 25:1.

[0045] Example 2

[0046] In this embodiment, the preparation of the phenol-terminated organosilicon polymer is carried out through the following steps:

[0047] (1) An organosilicon molecule R1-Si(CH3)2-O-Si(CH3)2-R1 (where R1 is -OH) with a molecular weight of 10000 g / mol was dissolved in dichloromethane to obtain an organosilicon molecular solution with a concentration of 0.013 mmol / mL. The organosilicon molecular solution was placed in a three-necked round-bottom flask, and nitrogen gas was bubbled through it for 15 min to remove air from the organosilicon molecular solution. At the same time, the organosilicon molecular solution was stirred using a magnetic stirrer.

[0048] Nitrogen gas was bubbled into DMF for 15 minutes to remove air. Then, chain extender 4,4′-methylenebis(phenyl isocyanate) (MDI) and toluene diisocyanate (TDI) were dissolved in DMF to obtain an MDI-TDI mixture with an MDI concentration of 0.2 mmol / mL and a TDI concentration of 0.2 mmol / mL.

[0049] Nitrogen gas was bubbled into the DMF for 15 minutes to expel the air. Then, 6-hydroxydopamine was dissolved in the DMF to obtain a 0.04 mmol / L 6-hydroxydopamine solution.

[0050] (2) Add the MDI-TDI mixture dropwise to a three-necked round-bottom flask containing an organosilicon molecular solution, and then add the 6-hydroxydopamine solution dropwise to the three-necked round-bottom flask. After the addition is complete, add the catalyst triethylamine and dibutyltin dilaurate. React for 8 hours under nitrogen protection and reflux at 100°C. Wash the resulting reaction product repeatedly with deionized water, then dry it by vacuum rotary evaporation at 50°C, and then dry it in an oven to obtain the final product, phenol-terminated organosilicon polymer.

[0051] In this step, the amounts of organosilicon molecular solution, MDI-TDI mixture and 6-hydroxydopamine solution are controlled so that the molar ratio of organosilicon molecules, MDI, TDI and 6-hydroxydopamine is 2:1:1:0.2; the amounts of triethylamine and dibutyltin dilaurate are controlled so that the molar ratio of triethylamine, dibutyltin dilaurate and organosilicon molecules is 1:1:1.

[0052] The following tests demonstrate the antifouling effect of phenol-terminated silicone polymers on metallic substrates:

[0053] The phenol-terminated organosilicon molecules prepared in this example were dissolved in acetone to form a solution with a concentration of 30 μg / mL. The resulting solution was uniformly sprayed onto a stainless steel surface. After the solvent evaporated, it was rinsed with toluene to obtain stainless steel with a phenol-terminated organosilicon polymer coating (coated stainless steel). This coated stainless steel was fixed on an inclined stage with a 10° tilt angle, and 5 μL of hexadecane was dropped onto the coated stainless steel. The movement of the hexadecane droplets on the coated stainless steel was observed and recorded using a camera. The results are as follows: Figure 2 As shown. By Figure 2 It can be seen that the hexadecane droplet slid smoothly on the coated stainless steel surface within 3 seconds without any droplet residue, indicating that when the phenol-terminated organosilicon polymer prepared in this embodiment is used as a coating, the coating has a good anti-fouling effect.

[0054] Example 3

[0055] In this embodiment, the preparation of the phenol-terminated organosilicon polymer is carried out through the following steps:

[0056] (1) An organosilicon molecule R1-Si(CH3)2-O-Si(CH3)2-R1 (where R1 is -(CH2)3COOH) with a molecular weight of 50000 g / mol was dissolved in dichloromethane to obtain an organosilicon molecular solution with a concentration of 0.03 mmol / mL. The organosilicon molecular solution was placed in a three-necked round-bottom flask, and nitrogen gas was bubbled through it for 5 min to remove air from the organosilicon molecular solution. At the same time, the organosilicon molecular solution was stirred using a magnetic stirrer.

[0057] Nitrogen gas was bubbled into the DMF for 5 minutes to expel the air. Then, the chain extender 4,4′-diisocyanate dicyclohexylmethane (HMDI) was dissolved in the DMF to obtain an HMDI solution with a concentration of 1 mmol / mL.

[0058] Nitrogen gas was bubbled into the DMF for 5 minutes to expel the air. Then, dopamine hydrochloride was dissolved in the DMF to obtain a 0.1 mmol / L dopamine hydrochloride solution.

[0059] (2) Add HMDI solution dropwise to a three-necked round-bottom flask containing organosilicon molecular solution, then add hydrochloric acid dopamine solution dropwise to the three-necked round-bottom flask. After the addition is complete, add triethylamine catalyst and react for 6 hours under nitrogen protection and reflux at 90°C. Wash the resulting reaction product repeatedly with deionized water, then dry it by vacuum rotary evaporation at 60°C, and then dry it in an oven to obtain the final product phenol-terminated organosilicon polymer.

[0060] In this step, the amounts of organosilicon molecular solution, HMDI solution and dopamine hydrochloride solution are controlled so that the molar ratio of organosilicon molecules, HMDI and dopamine hydrochloride is 1:1:0.1; the amount of triethylamine added is controlled so that the molar ratio of triethylamine to organosilicon molecules is 1:1.5.

[0061] Example 4

[0062] In this embodiment, the preparation of the phenol-terminated organosilicon polymer is carried out through the following steps:

[0063] (1) An organosilicon molecule R1-Si(CH3)2-O-Si(CH3)2-R1 (where R1 is -CH(O)CH-) with a molecular weight of 800 g / mol was dissolved in dichloromethane to obtain an organosilicon molecular solution with a concentration of 0.1 mmol / mL. The organosilicon molecular solution was placed in a three-necked round-bottom flask, and nitrogen gas was bubbled through it for 5 min to remove air from the organosilicon molecular solution. At the same time, the organosilicon molecular solution was stirred using a magnetic stirrer.

[0064] Nitrogen gas was bubbled into DMF for 5 minutes to remove air. Then, the chain extender isophorone diisocyanate (IPDI) and 4,4′-methylenebis(phenyl isocyanate) (MDI) were dissolved in DMF to obtain an IPDI-MDI mixture with a concentration of 0.167 mmol / mL for both IPDI and MDI.

[0065] Nitrogen gas was bubbled into DMF for 5 minutes to expel the air. Then, 3-hydroxy-4-methoxyphenylethylamine was dissolved in DMF to obtain a 0.33 mmol / L 3-hydroxy-4-methoxyphenylethylamine solution.

[0066] (2) The IPDI-MDI mixture was added dropwise to a three-necked round-bottom flask containing an organosilicon molecular solution. Then, the 3-hydroxy-4-methoxyphenylethylamine solution was added dropwise to the three-necked round-bottom flask. After the addition was complete, the catalyst triethylamine was added. The reaction was carried out under nitrogen protection and reflux at 80°C for 8 hours. The resulting reaction product was repeatedly washed with deionized water, then dried by vacuum rotary evaporation at 45°C, and then dried in an oven to obtain the final product, phenol-terminated organosilicon polymer.

[0067] In this step, the amounts of organosilicon molecular solution, IPDI-MDI mixture and 3-hydroxy-4-methoxyphenylethylamine solution are controlled so that the molar ratio of organosilicon molecules, IPDI, MDI and 3-hydroxy-4-methoxyphenylethylamine is 1:0.5:0.5:0.6; the amount of triethylamine added is controlled so that the molar ratio of triethylamine to organosilicon molecules is 1:2.5.

[0068] The following tests were conducted to determine the coating thickness of phenol-terminated silicone polymers on inorganic material substrates:

[0069] The phenol-terminated organosilicon polymer prepared in this embodiment was dissolved in acetone to prepare solutions with concentrations of 5 μg / mL, 15 μg / mL, 30 μg / mL, 50 μg / mL, and 100 μg / mL. Each solution was uniformly sprayed onto the surface of a different silicon wafer. After the solvent evaporated, the wafers were rinsed with toluene to obtain multiple silicon wafers with phenol-terminated organosilicon polymer coatings (coated silicon wafers). The coating thickness on each coated silicon wafer was measured using an ellipsometry. The test results are as follows: Figure 3 As shown, by Figure 3 It can be seen that when the concentration of the phenol-terminated organosilicon polymer solution is 5–100 μg / mL, the coating thickness on the prepared coated silicon wafer is 20–25 nm, and the coating thickness is in the nanometer range.

[0070] Example 5

[0071] In this embodiment, the preparation of the phenol-terminated organosilicon polymer is carried out through the following steps:

[0072] (1) An organosilicon molecule R2-Si(CH3)2-O-Si-(CH3)3 (where R2 is -(CH2)3O(CH2)2OH) with a molecular weight of 5000 g / mol was dissolved in dichloromethane to obtain an organosilicon molecular solution with a concentration of 0.03 mmol / mL. The organosilicon molecular solution was placed in a three-necked round-bottom flask, and nitrogen gas was bubbled through it for 20 min to remove air from the organosilicon molecules. At the same time, the organosilicon molecular solution was stirred using a magnetic stirrer.

[0073] Nitrogen gas was bubbled into the DMF for 10 minutes to expel the air. Then, dopamine hydrochloride was dissolved in the DMF to obtain a 0.33 mmol / L dopamine hydrochloride solution.

[0074] (2) Add the hydrochloric acid dopamine solution dropwise into a three-necked round-bottom flask containing an organosilicon molecular solution. After the addition is complete, add the catalyst triethylamine and react for 8 hours under nitrogen protection and reflux at 80°C. Wash the resulting reaction product repeatedly with deionized water, then dry it at 40°C using a vacuum rotary evaporator, and then dry it in an oven to obtain the final product, phenol-terminated organosilicon polymer.

[0075] In this step, the amounts of organosilicon molecular solution and dopamine hydrochloride solution are controlled to make the molar ratio of organosilicon molecules to dopamine hydrochloride 1:1, and the amount of triethylamine added is controlled to make the molar ratio of triethylamine to organosilicon molecules 1:1.

[0076] Example 6

[0077] In this embodiment, the preparation of the phenol-terminated organosilicon polymer is carried out through the following steps:

[0078] (1) An organosilicon molecule R2-Si(CH3)2-O-Si-(CH3)3 (where R2 is -(CH2)3COOH) with a molecular weight of 4500 g / mol was dissolved in dichloromethane to obtain an organosilicon molecular solution with a concentration of 0.1 mmol / mL. The organosilicon molecular solution was placed in a three-necked round-bottom flask, and nitrogen gas was bubbled through it for 20 min to remove air from the organosilicon molecular solution. At the same time, the organosilicon molecular solution was stirred using a magnetic stirrer.

[0079] Nitrogen gas was bubbled into DMF for 20 minutes to expel the air. Then, 3-hydroxy-4-methoxyphenylethylamine was dissolved in DMF to obtain a 0.1 mmol / mL 3-hydroxy-4-methoxyphenylethylamine solution.

[0080] (2) 3-hydroxy-4-methoxyphenethylamine solution was added dropwise to a three-necked round-bottom flask containing organosilicon molecular solution. After the addition was complete, 4-N,N-dimethylpyridine catalyst was added. The reaction was carried out under nitrogen protection and reflux at 60°C for 6 hours. The resulting reaction product was washed repeatedly with deionized water, then dried by vacuum rotary evaporation at 45°C, and then dried in an oven to obtain the final product, phenol-terminated organosilicon polymer.

[0081] In this step, the amounts of organosilicon molecular solution and 3-hydroxy-4-methoxyphenylethylamine solution are controlled to ensure a molar ratio of organosilicon molecules to 3-hydroxy-4-methoxyphenylethylamine of 1:1; the amount of 4-N,N-dimethylpyridine added is controlled to ensure a molar ratio of 4-N,N-dimethylpyridine to organosilicon molecules of 1:3.

[0082] Example 7

[0083] In this embodiment, the preparation of the phenol-terminated organosilicon polymer is carried out through the following steps:

[0084] (1) An organosilicon molecule R2-Si(CH3)2-O-Si-(CH3)3 (where R2 is -(CH2)3OCH2CH(O)CH) with a molecular weight of 5000 g / mol was dissolved in dichloromethane to obtain an organosilicon molecular solution with a concentration of 0.1 mmol / mL. The organosilicon molecular solution was placed in a three-necked round-bottom flask, and nitrogen gas was bubbled through it for 10 min to remove air from the organosilicon molecular solution. At the same time, the organosilicon molecular solution was stirred using a magnetic stirrer.

[0085] Nitrogen gas was bubbled into the DMF for 10 minutes to expel the air. Then, 6-hydroxydopamine was dissolved in the DMF to obtain a 6-hydroxydopamine solution with a concentration of 0.67 mmol / mL.

[0086] (2) Add 6-hydroxydopamine solution dropwise to a three-necked round-bottom flask containing organosilicon molecular solution. After the addition is complete, add triethylamine catalyst and react for 8 hours under nitrogen protection and reflux at 80°C. Wash the resulting reaction product repeatedly with deionized water, then dry it at 45°C using a vacuum rotary evaporator, and then dry it in an oven to obtain the final product, phenol-terminated organosilicon polymer.

[0087] In this step, the amounts of organosilicon molecular solution and 6-hydroxydopamine solution are controlled so that the molar ratio of organosilicon molecules to 6-hydroxydopamine is 1:1; the amount of triethylamine added is controlled so that the molar ratio of triethylamine to organosilicon molecules is 1:1.5.

[0088] The following tests demonstrate the antifouling effect of phenol-terminated silicone polymers on inorganic material substrates:

[0089] The phenol-terminated organosilicon molecules prepared in this embodiment were dissolved in acetone to form a solution with a concentration of 30 μg / mL. The resulting solution was uniformly sprayed onto the surface of a glass slide. After the solvent evaporated, the slide was rinsed with toluene to obtain a glass slide with a phenol-terminated organosilicon polymer coating (coated glass slide). The slide was fixed on an inclined stage with a tilt angle of 10°, and 5 μL of hexadecane was dropped onto the coated glass slide. The movement of the hexadecane droplet on the coated glass slide was observed and recorded with a camera. The results are as follows. Figure 4 As shown. By Figure 4 It can be seen that the hexadecane droplet slid smoothly on the coated glass surface within 3 seconds without any droplet residue, indicating that when the phenol-terminated organosilicon polymer prepared in this embodiment is used as a coating, the coating has a good anti-fouling effect.

[0090] Example 8

[0091] In this embodiment, the preparation of the phenol-terminated organosilicon polymer is carried out through the following steps:

[0092] (1) Dissolve the organosilicon molecule poly[dimethylsiloxane-co-(3-aminopropyl)methylsiloxane] with a molecular weight of 209.39 g / mol in dichloromethane to obtain an organosilicon molecular solution with a concentration of 0.1 mmol / mL. Place the organosilicon molecular solution in a three-necked round-bottom flask, bubble nitrogen gas for 15 min to remove air from the organosilicon molecular solution, and stir the organosilicon molecular solution with a magnetic stirrer at the same time.

[0093] Nitrogen gas was bubbled into DMF for 15 minutes to expel the air. Then, the chain extender 4,4′-methylenebis(phenyl isocyanate) (MDI) was dissolved in DMF to obtain an MDI solution with a concentration of 1 mmol / mL.

[0094] Nitrogen gas was bubbled into the DMF for 15 minutes to expel the air. Then, dopamine hydrochloride was dissolved in the DMF to obtain a 1 mmol / L dopamine hydrochloride solution.

[0095] (2) Under stirring, nitrogen protection and ice bath conditions, MDI solution was added dropwise to a three-necked round-bottom flask containing organosilicon molecular solution, and then dopamine hydrochloride solution was added dropwise to the three-necked round-bottom flask. After the addition was completed, the reaction was carried out for 5 hours under stirring, nitrogen protection and ice bath conditions. The resulting reaction product was repeatedly washed with deionized water, then dried by vacuum rotary evaporation at 50°C, and then placed in an oven to dry, thus obtaining the final product phenol-terminated organosilicon polymer.

[0096] In this step, the amounts of organosilicon molecular solution, MDI solution and dopamine hydrochloride solution are controlled so that the molar ratio of organosilicon molecules, MDI and dopamine hydrochloride is 1:5:5.

[0097] The Fourier transform infrared spectrum of the phenol-terminated organosilicon polymer prepared in this embodiment is as follows: Figure 5 As shown, Figure 5 The assignment of the characteristic peak in the middle is: 2960 cm⁻¹ -1 (νC-H), 1259cm -1 (νSi-CH3), 1022 / 1107cm -1 (νSi-O-Si) and 806cm -1 (νSi-(CH3)2).

[0098] Example 9

[0099] In this embodiment, the preparation of the phenol-terminated organosilicon polymer is carried out through the following steps:

[0100] (1) An organosilicon molecule (3-aminopropyl)triethoxysilane (i.e., H2N(CH2)3Si(OC2H5)3) with a molecular weight of 191.34 g / mol was dissolved in dichloromethane to obtain an organosilicon molecule solution with a concentration of 0.2 mmol / mL. The organosilicon molecule solution was placed in a three-necked round-bottom flask, and nitrogen gas was bubbled through it for 10 min to remove air from the organosilicon molecule solution. At the same time, the organosilicon molecule solution was stirred using a magnetic stirrer.

[0101] Nitrogen gas was bubbled into the DMF for 10 minutes to expel the air. Then, the chain extender isophorone diisocyanate (IPDI) was dissolved in the DMF to obtain an IPDI solution with a concentration of 1 mmol / mL.

[0102] Nitrogen gas was bubbled into the DMF for 10 minutes to expel the air. Then, dopamine hydrochloride was dissolved in the DMF to obtain a 0.5 mmol / L dopamine hydrochloride solution.

[0103] (2) Under stirring, nitrogen protection and ice bath conditions, IPDI solution was added dropwise to a three-necked round-bottom flask containing organosilicon molecular solution, and then dopamine hydrochloride solution was added dropwise to the three-necked round-bottom flask. After the addition was completed, the reaction was carried out for 6 hours under stirring, nitrogen protection and ice bath conditions. The resulting reaction product was repeatedly washed with deionized water, then dried by vacuum rotary evaporation at 35°C, and then placed in an oven to dry, thus obtaining the final product phenol-terminated organosilicon polymer.

[0104] In this step, the amounts of organosilicon molecular solution, IPDI solution and dopamine hydrochloride solution are controlled so that the molar ratio of organosilicon molecules, IPDI and dopamine hydrochloride is 1:1:0.5.

[0105] The following tests demonstrate the antifouling effect of phenol-terminated silicone polymers on polymer substrates:

[0106] The phenol-terminated organosilicon molecules prepared in this embodiment were dissolved in acetone to form a solution with a concentration of 30 μg / mL. The resulting solution was uniformly sprayed onto the surface of polyurethane. After the solvent evaporated, it was rinsed with toluene to obtain a polyurethane with a phenol-terminated organosilicon polymer coating (coated polyurethane). This polyurethane was fixed on an inclined stage with a tilt angle of 10°, and 5 μL of hexadecane was dropped onto the coated polyurethane. The movement of the hexadecane droplets on the coated polyurethane was observed and recorded with a camera. The results are as follows: Figure 6 As shown. By Figure 6 It can be seen that the hexadecane droplet slid smoothly on the coated polyurethane surface within 3 seconds without any droplet retention, indicating that when the phenol-terminated organosilicon polymer prepared in this embodiment is used as a coating, the coating has a good anti-fouling effect.

[0107] Example 10

[0108] Considering that when the organosilicon molecule is R1-Si(CH3)2-O-Si(CH3)2-R1, a chain extender can be omitted when preparing phenol-terminated organosilicon polymers, this embodiment provides a method for preparing phenol-terminated organosilicon polymers without adding a chain extender, the steps of which are as follows:

[0109] (1) An organosilicon molecule R1-Si(CH3)2-O-Si(CH3)2-R1 (where R1 is -(CH2)3COOH) with a molecular weight of 50000 g / mol was dissolved in dichloromethane to obtain an organosilicon molecular solution with a concentration of 0.03 mmol / mL. The organosilicon molecular solution was placed in a three-necked round-bottom flask, and nitrogen gas was bubbled through it for 5 min to remove air from the organosilicon molecular solution. At the same time, the organosilicon molecular solution was stirred using a magnetic stirrer.

[0110] Nitrogen gas was bubbled into the DMF for 5 minutes to expel the air. Then, dopamine hydrochloride was dissolved in the DMF to obtain a 0.06 mmol / L dopamine hydrochloride solution.

[0111] (2) Add the hydrochloric acid dopamine solution dropwise into the three-necked round-bottom flask. After the addition is complete, add the catalyst triethylamine and react for 6 hours under nitrogen protection and reflux at 90°C. Wash the resulting reaction product repeatedly with deionized water, then dry it at 60°C using a vacuum rotary evaporator, and then dry it in an oven to obtain the final product, phenol-terminated organosilicon polymer.

[0112] In this step, the amounts of organosilicon molecular solution and dopamine hydrochloride solution are controlled so that the molar ratio of organosilicon molecules to dopamine hydrochloride is 1:2; the amount of triethylamine added is controlled so that the molar ratio of triethylamine to organosilicon molecules is 1:1.5.

Claims

1. Application of phenol-terminated organosilicon polymers in the preparation of coatings with thicknesses in the nanometer range, wherein the phenol-terminated organosilicon polymers are prepared by the following method: (1) Dissolve organosilicon molecules in dichloromethane to form an organosilicon molecule solution; dissolve the adhesive in... N,N An adhesive solution is formed in dimethylformamide, wherein the adhesive is a compound having hydroxyl and amine groups on a benzene ring; the adhesive includes any one of dopamine hydrochloride, 6-hydroxydopamine, and 3-hydroxy-4-methoxyphenethylamine; the concentration of the organosilicon molecule solution is 0.01~0.2 mmol / mL, and the concentration of the adhesive solution is 0.01~1 mmol / mL; (2) When the organosilicon molecule is R2-Si(CH3)2-O-Si-(CH3)3 and R2 is -(CH2)3O(CH2)2OH or -(CH2)3COOH, under stirring and protective gas protection, the adhesive solution is added dropwise to the organosilicon molecule solution. The amount of organosilicon molecule solution and adhesive solution added is controlled so that the molar ratio of organosilicon molecule to adhesive is 1:(0.05~5). The reaction is carried out at 0~100 °C. Unreacted raw materials and solvents are removed and dried to obtain phenol-terminated organosilicon polymer. When the organosilicon molecule is R1-Si(CH3)2-O-Si(CH3)2-R1 and R1 is -(CH2)3NH2, -OH or -(CH2)3COOH, under stirring and protective gas protection, the chain extender solution is added dropwise to the organosilicon molecule solution, and then the adhesive solution is added dropwise. The amount of organosilicon molecule solution and adhesive solution added is controlled so that the molar ratio of organosilicon molecule to adhesive is 1:(0.05~0.6) and the molar ratio of organosilicon molecule to chain extender is controlled to be 1:

1. The reaction is carried out at 0~100℃, the unreacted raw materials and solvents are removed, and the product is dried to obtain the phenol-terminated organosilicon polymer. When the organosilicon molecule is H2N(CH2)3Si(OC2H5)3, under stirring and protective gas protection, the chain extender solution is added dropwise to the organosilicon molecule solution, and then the adhesive solution is added dropwise. The amount of organosilicon molecule solution and adhesive solution added is controlled so that the molar ratio of organosilicon molecule to adhesive is 1: (0.05~5), and the molar ratio of organosilicon molecule to chain extender is controlled to be 1: (1~5). The reaction is carried out at 0~100℃ until it is fully reacted. Unreacted raw materials and solvents are removed, and the product is dried to obtain the phenol-terminated organosilicon polymer.

2. The application of the phenol-terminated organosilicon polymer according to claim 1 in the preparation of coatings with thicknesses in the nanometer range, characterized in that, The chain extender includes one or more of the following: 4,4′-methylenebis(phenyl isocyanate), 4,4′-diisocyanate dicyclohexylmethane, isocyclohexylimide, isophorone diisocyanate, and toluene diisocyanate.

3. The application of the phenol-terminated organosilicon polymer according to claim 1 or 2 in the preparation of coatings with thicknesses in the nanometer range, characterized in that, Step (2) also involves adding a catalyst to the organosilicon molecular solution, the catalyst comprising at least one of triethylamine, 4-N,N-dimethylpyridine, trimethylamine, and dibutyltin dilaurate.

4. The application of the phenol-terminated organosilicon polymer according to claim 1 or 2 in the preparation of coatings with thicknesses in the nanometer range, characterized in that, Step (2) involves a reaction time of 4 to 8 hours at 0 to 100 °C.

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