A silicone polymer brush super-slippery liquid surface material and a preparation method and application thereof

Abstract

The application discloses a kind of organic silicon polymer brush super-slippery liquid surface material and its preparation method and application, belong to functional material technical field.The glycidyl ether monomer PDMS-g-POSS-G and amine curing agent PDMS-g-D-NH2 are respectively prepared, and the glycidyl ether monomer and amine curing agent are cured on extensive substrate by addition reaction, and excellent adhesion is obtained, realizes the introduction of super-slippery liquid PDMS polymer brush coating layer;The medium of precursor slurry is non-toxic or low-toxic or safe substance, and PDMS polymer brush coating layer can be formed on the surface of substrate at room temperature, which is beneficial to large-scale operation;Due to the good chemical matching of PDMS-g-POSS-G and PDMS-g-D-NH2, the slurry is thermodynamically stable, the coating flow leveling property is good, the liquid-like activity of polymer brush is strong, the transparency of coating layer is high, and the super-slippery performance is excellent.

Description

Technical Field

[0001] This invention relates to the field of functional materials technology, specifically to an organosilicon polymer brush superlubricating fluid surface material, its preparation method, and its application. Background Technology

[0002] Superhydrophilic surfaces, such as superlubricating and superhydrophobic surfaces, are special interfacial phenomena of solid materials, referring to their ability to repel liquid droplets and thus impart excellent anti-liquid adhesion. Compared to superhydrophobic surfaces (including superhydrophobic and superoleophobic surfaces), superlubricating surfaces, represented by silicone polymer brushes, have greater advantages in properties such as light transmittance, abrasion resistance, and liquid repellency spectrum. Therefore, silicone polymer brush superlubricating surfaces have more ideal functions such as antimicrobial adhesion, anti-fingerprint, anti-corrosion, anti-icing, and fluid drag reduction.

[0003] Currently, the main methods for constructing the surface of organosilicon polymer brushes with superlubricating fluid are as follows:

[0004] (1) Hydrolysis-condensation self-assembly of silane monomers: The hydrolysis-condensation self-assembly of silane monomers is usually based on the condensation self-assembly of hydrolysis products of alkyl dimethoxysilanes or alkyl dichlorosilanes to form organosilicon polymer brushes, as shown in Chinese invention patent application number: 202211226022.0 and research papers with DOIs: 10.1002 / adma.202100237 and 10.1002 / anie.201509385. In this method, the adhesion of the organosilicon polymer brush depends on the chemical interaction between the Si-OH of the hydrolysis product and the -OH of the substrate, which means that the superlubricating surface of the organosilicon polymer brush is only suitable for glass or a few metal substrates (such as aluminum and titanium), thus limiting its practical application in fields such as construction, electronics, biology, transportation, chemical industry, and medicine. In addition, the self-assembly of silanes through hydrolysis-condensation requires strict control of the reaction process and involves the use of toluene or strong acids as media or catalysts, resulting in low environmental friendliness or safety, which is not conducive to large-scale operation.

[0005] (2) Grafting of Organosilicon Polymers: Grafted organosilicon polymer brushes are achieved by co-curing polydimethylsiloxane (PDMS) with polymer (resin) monomers under the action of a curing agent (or initiator), using active groups (amino, glycidyl ether, hydroxyl, etc.) to achieve grafting. Examples include Chinese invention patent application number 202211283011.6 and research paper DOI: 10.1002 / anie.201904210. However, in this method, because PDMS is a low surface energy material while the polymer monomers and curing agent / initiator are high surface energy materials, the chemical compatibility between components is low, leading to thermodynamic instability of the slurry, poor coating leveling, and limited liquid-like mobility of the polymer brush (requiring activation). Therefore, the light transmittance and super-slippery properties of the resulting coating are inferior to the first method (hydrolytic condensation self-assembly).

[0006] In summary, there is an urgent need to provide a safe, environmentally friendly superlubricating fluid surface material that exhibits excellent adhesion on a wide range of substrates, as well as excellent light transmittance and superlubricating properties. Summary of the Invention

[0007] [Technical Issues]

[0008] The technical problem to be solved by the present invention is to provide a safe, environmentally friendly organosilicon polymer brush superlubricating fluid surface material with excellent adhesion on a wide range of substrates, as well as excellent light transmittance and superlubricating properties, and its preparation method and application.

[0009] [Technical Solution]

[0010] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0011] In a first aspect, the present invention provides a method for preparing an organosilicon polymer brush superlubricating fluid surface material, comprising the following steps:

[0012] Preparation of S1, PDMS-g-POSS-G (polydimethylsiloxane-modified glycidyl etheroxypropyl polyhedral cage-type polysilsesquioxane):

[0013] PDMS-NH2 (amino-terminated polydimethylsiloxane) and POSS-G (glycidoxypropyl polyhedral cage polysilsesquioxane) were dissolved in solvent A, heated to react, acetonitrile was added, and the upper layer was collected to obtain PDMS-g-POSS-G solution.

[0014] Preparation of S2, PDMS-gD-NH2 (polydimethylsiloxane-modified aminopropylmethylcyclosiloxane):

[0015] PDMS-G (glycidyl-terminated polydimethylsiloxane) and D-NH2 (aminopropylmethylcyclosiloxane) were dissolved in solvent B and heated to react, resulting in a reaction solution. The upper layer of the reaction solution was collected to obtain a PDMS-gD-NH2 solution.

[0016] S3. Preparation of superlubricating fluid surface materials:

[0017] The PDMS-g-POSS-G from step S1, the PDMS-gD-NH2 from step S2, and the catalyst are mixed and reacted to obtain a superlubricating fluid surface material; the catalyst includes one or more of salicylic acid, imidazole, triethylamine, methyldiethanolamine, resorcinol, and benzyltriethylammonium chloride.

[0018] In one embodiment, the PDMS-NH2 in step S1 is aminopropyl double-terminated. Optionally, the molecular weight of the PDMS-NH2 is 1000 to 15000.

[0019] In one embodiment, the concentration of PDMS-NH2 in step S1 is 2 to 40 mg / mL.

[0020] In one embodiment, the concentration of POSS-G in step S1 is 150–500 mg / mL.

[0021] In one embodiment, the cage type of POSS-G in step S1 includes T8 and T. 10 T 12 One or more of them.

[0022] In one embodiment, the ratio of the number of silicon atoms on the silicon-oxygen cage of POSS-G in step S1 to the number of glycidyl ether oxypropyl side chains is 40 to 100%.

[0023] In one embodiment, solvent A and solvent B may be the same or different. Solvent A or solvent B includes one or more of propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dimethyl carbonate, ethyl butyl ester, petroleum ether, and propylene carbonate.

[0024] In one embodiment, the heating reaction in step S1 is heating under reflux conditions with stirring.

[0025] In one embodiment, the heating reaction time in step S1 is not limited, as long as it allows the reactants to react completely. Optionally, but not limited to, the heating reaction time in step S1 is 1-5 hours. More specifically, it is 2 hours.

[0026] In one embodiment, the heating temperature in step S1 is 55–140°C.

[0027] In one embodiment, the PDMS-G mentioned in step S2 is a glycidyl etheroxypropyl single-terminated product.

[0028] In one embodiment, the molecular weight of PDMS-G in step S2 is 800 to 12000.

[0029] In one embodiment, the concentration of PDMS-G in step S2 is 80–300 mg / mL.

[0030] In one embodiment, the D-NH2 mentioned in step S2 is one or more of tetraaminopropyltetramethylcyclotetrasiloxane (D4-NH2), pentaaminopropylpentamethylcyclopentasiloxane (D5-NH2), hexaaminopropylhexamethylcyclohexasiloxane (D6-NH2), and octaaminopropyloctamethylcyclooctasiloxane (D8-NH2).

[0031] In one embodiment, the concentration of D-NH2 in step S2 is 120–350 mg / mL.

[0032] In one embodiment, the heating reaction in step S2 is heating under stirring and reflux.

[0033] In one embodiment, the heating reaction time in step S2 is not limited, as long as it allows the reactants to react completely. Optionally, but not limited to, the heating reaction time in step S2 is 1-5 hours. More specifically, it is 2 hours.

[0034] In one embodiment, the heating temperature in step S2 is 55–140°C.

[0035] In one embodiment, the mixing volume ratio of PDMS-g-POSS-G and PDMS-gD-NH2 in step S3 is 1:0.5 to 4.

[0036] In one embodiment, the concentration of the catalyst in the catalytic system is 1–25 mg / mL.

[0037] In a second aspect, the present invention also provides a superlubricating fluid surface material prepared using the method described in the first aspect.

[0038] In a third aspect, the present invention also provides the application of the method described in the first aspect or the superlubricating fluid surface material described in the second aspect in the preparation of superlubricating fluid coatings.

[0039] In one embodiment, the application includes coating the superlubricating fluid surface material onto a substrate surface and drying it to obtain a superlubricating coating.

[0040] In one embodiment, the coating method includes any one or more of spraying, brushing, scraping, roller coating, spin coating, and dip coating.

[0041] In one embodiment, the substrate includes, but is not limited to, metal, glass, plastic, ceramic, fabric, paper, or leather.

[0042] In one embodiment, the thickness of the super-slippery coating is less than 2 μm.

[0043] It should be understood that, within the scope of this invention, the above-described technical features of this invention and the technical features specifically described below (such as in the embodiments) can be combined with each other to form new or preferred technical solutions. Due to space limitations, they will not be described in detail here.

[0044] Compared with the prior art, the present invention has the following beneficial effects:

[0045] This invention prepares glycidyl ether monomer PDMS-g-POSS-G and amine curing agent PDMS-gD-NH2 respectively. The glycidyl ether monomer and amine curing agent exhibit excellent adhesion on a wide range of substrates through an addition reaction, achieving a super-lubricating PDMS polymer brush coating. The precursor slurry is a non-toxic / low-toxic or safe substance, and the PDMS polymer brush coating forms on the substrate surface by air drying at room temperature, facilitating large-scale operations. Due to the good chemical compatibility between PDMS-g-POSS-G and PDMS-gD-NH2, the slurry is thermodynamically stable, has good coating leveling properties, and the polymer brush exhibits strong liquid-like mobility, resulting in a coating with high transparency and excellent super-lubricating properties. Attached Figure Description

[0046] Figure 1 The contact angle and roll-off angle of different liquids on the PDMS polymer brush coating surface.

[0047] Figure 2 The image shows the ethylene glycol sliding effect of the PDMS polymer brush coating on the glass surface before and after 50 tape tear tests. In the image, A represents before the tape test (0s), B represents before the tape test (0.5s), C represents after the tape test (0s), and D represents after the tape test (0.5s). Detailed Implementation

[0048] The present invention will now be described in further detail with reference to specific embodiments. The given embodiments are merely illustrative of the invention and not intended to limit its scope. The embodiments provided below can serve as a guide for further improvements by those skilled in the art and do not constitute a limitation of the invention in any way.

[0049] Unless otherwise specified, the experimental methods used in the following examples are conventional methods, performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Unless otherwise specified, the materials and reagents used in the following examples are commercially available.

[0050] Example:

[0051] Example 1:

[0052] In a round-bottom flask, PDMS-NH2 (15 mg / mL) with a molecular weight of 1000 and T8-type octane POSS-G (230 mg / mL) were dissolved in 100 mL of propylene glycol monomethyl ether. The mixture was stirred and refluxed at 110 °C for 2 h. After cooling, 20 mL of acetonitrile was added, and the lower layer and sediment were removed to obtain a PDMS-g-POSS-G solution. In a round-bottom flask, single-terminated PDMS-G (125 mg / mL) with a molecular weight of 5000 and tetraaminopropyltetramethylcyclotetrasiloxane (D4-NH2, 146 mg / mL) were dissolved in 100 mL of propylene glycol monomethyl ether. The mixture was stirred and refluxed at 110 °C for 2 h. After cooling, the lower layer was removed to obtain a PDMS-g-D4-NH2 solution. 5 mL of PDMS-g-POSS-G solution was mixed with 10 mL of PDMS-g-D4-NH2 solution, and methyldiethanolamine (1 mg / mL) was added. The mixture was stirred to form a precursor slurry. The precursor slurry is sprayed onto the glass surface, and the naturally leveled liquid film is about 30 μm thick. After air drying at room temperature for 1.5 h, a PDMS polymer brush coating is formed. Figure 1 As shown, the PDMS polymer brush coating exhibits excellent superlubricating properties for low surface tension liquids (such as hexadecane and n-hexane). Figure 2 As shown, the PDMS polymer brush coating on the glass surface has high transparency, and the ethylene glycol sliding performance before and after 50 tape tear tests did not change significantly, indicating that the coating has excellent adhesion.

[0053] Example 2:

[0054] In a round-bottom flask, PDMS-NH2 (18.5 mg / mL) with a molecular weight of 1200 and T8-type eight-side-chain POSS-G (220 mg / mL) were dissolved in 100 mL of propylene glycol monomethyl ether. The mixture was stirred and refluxed at 110 °C for 2 h. After cooling, 20 mL of acetonitrile was added, and the lower layer and sediment were removed to obtain a PDMS-g-POSS-G solution. In a round-bottom flask, single-terminated PDMS-G (125 mg / mL) with a molecular weight of 5000 and D4-NH2 (146 mg / mL) were dissolved in 100 mL of propylene glycol monomethyl ether. The mixture was stirred and refluxed at 110 °C for 2 h. After cooling, the lower layer was removed to obtain a PDMS-g-D4-NH2 solution. 5 mL of the PDMS-g-POSS-G solution was mixed with 10 mL of the PDMS-g-D4-NH2 solution, and imidazole (1.5 mg / mL) was added. The mixture was stirred to form a precursor slurry. The precursor slurry was sprayed onto the stainless steel surface, and the naturally leveled liquid film was about 30 μm thick. After air drying at room temperature for 1.5 h, a PDMS polymer brush coating was formed.

[0055] Example 3:

[0056] In a round-bottom flask, PDMS-NH2 (14 mg / mL) with a molecular weight of 1000 and T12-type dodecyl side-chain POSS-G (300 mg / mL) were dissolved in 100 mL of butyl acetate. The mixture was stirred and refluxed at 90 °C for 2 h. After cooling, 20 mL of acetonitrile was added, and the lower layer and sediment were removed to obtain a PDMS-g-POSS-G solution. In a round-bottom flask, single-terminated PDMS-G (125 mg / mL) with a molecular weight of 5000 and D4-NH2 (146 mg / mL) were dissolved in 100 mL of butyl acetate. The mixture was stirred and refluxed at 90 °C for 2 h. After cooling, the lower layer was removed to obtain a PDMS-g-D4-NH2 solution. 5 mL of the PDMS-g-POSS-G solution was mixed with 10 mL of the PDMS-g-D4-NH2 solution, and methyldiethanolamine (1 mg / mL) was added. The mixture was stirred to form a precursor slurry. The precursor slurry is sprayed onto the ceramic surface, and the naturally leveled liquid film is about 30 μm thick. After air drying at room temperature for 1.5 h, a PDMS polymer brush coating is formed.

[0057] Example 4:

[0058] In a round-bottom flask, PDMS-NH2 (15 mg / mL) with a molecular weight of 1000 and T8-type octane-chain POSS-G (220 mg / mL) were dissolved in 100 mL of propylene glycol monomethyl ether. The mixture was stirred and refluxed at 110 °C for 2 h. After cooling, 20 mL of acetonitrile was added, and the lower layer and precipitate were removed to obtain a PDMS-g-POSS-G solution. In a round-bottom flask, single-terminated PDMS-G (135 mg / mL) with a molecular weight of 3000 and hexaaminopropylhexamethylcyclohexasiloxane (D6-NH2, 170 mg / mL) were dissolved in 100 mL of propylene glycol monomethyl ether. The mixture was stirred and refluxed at 110 °C for 2 h. After cooling, the lower layer was removed to obtain a PDMS-g-D6-NH2 solution. 5 mL of PDMS-g-POSS-G solution was mixed with 10 mL of PDMS-g-D6-NH2 solution, and resorcinol (1 mg / mL) was added. The mixture was stirred to form a precursor slurry. The precursor slurry was sprayed onto the surface of a PET film. The naturally leveled liquid film was approximately 30 μm thick. After air drying at room temperature for 1.5 h, a PDMS polymer brush coating was formed.

[0059] Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Anyone skilled in the art can make various modifications and alterations without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be determined by the claims.

Claims

1. A method for preparing an organosilicon polymer brush superlubricating fluid surface material, characterized in that, Includes the following steps: S1, Preparation of glycidyl ether monomer PDMS-g-POSS-G: PDMS-NH2 and POSS-G were dissolved in solvent A, heated to react, acetonitrile was added, and the supernatant was collected to obtain a PDMS-g-POSS-G solution; the PDMS-NH2 was aminopropyl double-terminated. Preparation of S2, amine curing agent PDMS-gD-NH2: PDMS-G and D-NH2 are dissolved in solvent B and heated to react, yielding a reaction solution. The supernatant of the reaction solution is collected to obtain a PDMS-gD-NH2 solution. PDMS-G is glycidyl etheroxypropyl single-terminated; D-NH2 is one or more of tetraaminopropyltetramethylcyclotetrasiloxane, pentaaminopropylpentamethylcyclopentasiloxane, hexaaminopropylhexamethylcyclohexasiloxane, and octaaminopropyloctamethylcyclooctasiloxane. S3. Preparation of superlubricating fluid surface materials: The PDMS-g-POSS-G from step S1, the PDMS-gD-NH2 from step S2, and the catalyst are mixed and reacted to obtain a superlubricating fluid surface material; the catalyst includes one or more of salicylic acid, imidazole, triethylamine, methyldiethanolamine, resorcinol, and benzyltriethylammonium chloride. The solvent A and the solvent B may be the same or different; the solvent A or solvent B includes one or more of propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dimethyl carbonate, petroleum ether, and propylene carbonate.

2. The method according to claim 1, characterized in that, The cage type of POSS-G mentioned in step S1 includes T8 and T. 10 T 12 One or more of them.

3. The method according to claim 1, characterized in that, The ratio of the number of silicon atoms on the silicon-oxygen cage of POSS-G in step S1 to the number of glycidyl ether oxypropyl side chains is 40 to 100%.

4. The superlubricating fluid surface material prepared by any one of the methods described in claims 1-3.

5. The application of the superlubricating fluid surface material obtained by any of the methods of claims 1-3 or the superlubricating fluid surface material of claim 4 in the preparation of superlubricating fluid coatings.

6. The application according to claim 5, characterized in that, The application includes coating the superlubricating fluid surface material onto the surface of a substrate and drying it to obtain a superlubricating coating.

7. The application according to claim 6, characterized in that, The substrate may include metal, glass, plastic, ceramic, fabric, paper or leather.

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