WO2024078496A1 - Thermoplastic polymer, preparation method therefor, and use thereof - Google Patents

Thermoplastic polymer, preparation method therefor, and use thereof Download PDF

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Publication number
WO2024078496A1
WO2024078496A1 PCT/CN2023/123782 CN2023123782W WO2024078496A1 WO 2024078496 A1 WO2024078496 A1 WO 2024078496A1 CN 2023123782 W CN2023123782 W CN 2023123782W WO 2024078496 A1 WO2024078496 A1 WO 2024078496A1
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WIPO (PCT)
Prior art keywords
thermoplastic polymer
cone structure
micron
flexible screen
polymer
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PCT/CN2023/123782
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French (fr)
Chinese (zh)
Inventor
谢恒�
杨友强
杜宇
魏金刚
丁超
陈平绪
卢翔
李成
杨方强
李振华
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金发科技股份有限公司
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Publication of WO2024078496A1 publication Critical patent/WO2024078496A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

  • the present invention relates to the technical field of super-hydrophobic polymer materials, and more specifically, to a thermoplastic polymer and a preparation method and application thereof.
  • a water droplet with a contact angle of less than 90° is called a hydrophilic surface
  • a contact angle greater than 90° is called a hydrophobic surface
  • a contact angle of 150° or more is called a super-hydrophobic surface.
  • the air cushion can effectively reduce the contact area between the water droplet and the surface, so that the water droplet cannot penetrate into the surface microstructure, but is "supported" on the super-hydrophobic surface. Therefore, super-hydrophobic surfaces are widely used in raindrop power generation, anti-fouling, anti-corrosion, self-cleaning, anti-adhesion, and resistance reduction.
  • Superhydrophobic surfaces with robust dynamic wetting stability perform well in application scenarios that focus on capturing the potential energy of water droplets, and the motion behavior of water droplets after rebounding is crucial for energy collection and device design.
  • the repellency of existing superhydrophobic surfaces to water droplets can enable high-speed water droplets to rebound without residue to achieve energy conversion and long-term operation, the rebound motion of water droplets after falling is irregular and uncontrollable, thus causing many inconveniences for the directional collection and discharge of falling water droplets. Therefore, superhydrophobic surfaces that can control the directional motion of rebounding water droplets are a problem that needs to be overcome in the current application of superhydrophobic surfaces.
  • the prior art discloses a method for controlling the direction of droplet bouncing, which specifically comprises the following steps: dividing the substrate surface into several regions, constructing a micron-scale columnar structure with a regular array in each region, and constructing micron-scale columnar structures with different densities in each region by adjusting process parameters, ensuring that the density of micron-scale columnar structures in adjacent regions is different or that the density of micron-scale columnar structures in each region decreases or increases in sequence as required, thereby obtaining the effect of droplets bouncing toward regions with sparse micron-scale columnar structures.
  • the preparation of the surface for controlling droplet bouncing is relatively complex, and can only achieve regional displacement of droplets, but cannot achieve precise directional displacement.
  • the purpose of the present invention is to overcome the defects and shortcomings of existing super-hydrophobic surfaces that cannot achieve directional deviation of rebounding water droplets while being super-hydrophobic, and to provide a thermoplastic polymer that achieves directional deviation of rebounding water droplets through a microstructure of directional deviation of rebounding water droplets on the polymer surface, thereby obtaining a polymer material that is both hydrophobic and can control the directional deviation of rebounding water droplets.
  • Another object of the present invention is to provide a method for preparing a thermoplastic polymer.
  • Another object of the present invention is to provide an application of a thermoplastic polymer in the preparation of a water droplet potential energy capture device surface, a fluid directional and efficient transport device surface, a drug release control device surface, a drag reduction device surface and a microfluidic device surface.
  • thermoplastic polymer has a surface with an inclined micron cone structure, the inclined micron cone structure array is distributed on the polymer surface, the inclined angle ⁇ of the inclined micron cone structure is 0° ⁇ 90°, and the vertical height H is 0 ⁇ H ⁇ 900 ⁇ m.
  • test method of the tilt angle ⁇ and the vertical height H of the tilted micro-cone structure of the present invention is as follows:
  • the prepared inclined micron cone sheet was cut with a cutter, and the cut surface was placed perpendicular to the scanning electron microscope lens.
  • the cross-sectional microscopic morphology was observed through a microscope and the original photo was obtained.
  • mapping software With the help of mapping software, the inclination angle and height of the inclined micron cone structure in different regions were measured, and the data were statistically analyzed to obtain the average value, and finally the inclination angle and height of the inclined micron cone were obtained.
  • the surface of the thermoplastic polymer of the present invention has an inclined micron cone structure, which can effectively prevent the infiltration of water droplets and drive the water droplets to move in a directional direction of the inclined structure when they rebound.
  • the thermoplastic polymer surface of the present invention has an inclined micron cone structure.
  • the vertical height of the inclined micron cone structure is 0 ⁇ H ⁇ 900 ⁇ m. As the vertical height increases, the water repellency of the sample surface increases.
  • the tilted micron cone structure array distribution of the present invention can be an array distribution of tilted micron cone structures with constant height and equal spacing, or can be an array distribution of tilted micron cone structures with different heights and variable spacing.
  • the bottom surface of the inclined micro-cone structure on the surface of the thermoplastic polymer of the present invention can be of any shape, preferably an ellipse.
  • the inclined micro-cone structure has an inclination angle ⁇ of 20° ⁇ 70°, and a vertical height H of 100 ⁇ H ⁇ 500 ⁇ m.
  • the tilt angle ⁇ of the tilted micro-cone structure is 30° ⁇ 45°, and the vertical height H is 130 ⁇ H ⁇ 450 ⁇ m.
  • the density of the inclined micro-cone structures is preferably 9000 to 11000 per square inch.
  • the density of the inclined micro-cone structure is determined as follows:
  • the surface of the prepared polymer surface was observed by means of a scanning electron microscope: the prepared surface was placed under the lens of the scanning electron microscope, and an original photo was directly observed and obtained, and the density of the inclined microcones was counted.
  • thermoplastic polymer of the present invention is one or more of polyethylene, polypropylene, polycaprolactone, and ABS.
  • the present invention also specifically protects a method for preparing a thermoplastic polymer, comprising the following steps:
  • thermoplastic polymer melt into a mold cavity having a flexible screen placed at the bottom, and cooling and shaping the thermoplastic polymer melt after completely filling the micropores of the flexible screen to obtain a polymer sheet having a flexible screen on the surface;
  • the flexible screen of the polymer sheet with the flexible screen and the polymer sheet are clamped separately, and the flexible screen is peeled off from the surface of the thermoplastic polymer sheet under external traction, and an inclined micron cone structure is formed on the surface of the polymer sheet during the peeling process, and the thermoplastic polymer is obtained after cooling and shaping.
  • the peeling temperature in S2 is 25-200°C
  • the pulling angle is ⁇ , 0° ⁇ 90°
  • the pulling speed is 1-100 mm/min.
  • the inclination angle ⁇ and vertical height H of the inclined micron-cone structure on the surface of the thermoplastic polymer of the present invention are mainly controlled by the peeling process.
  • the pulling speed and peeling temperature affect the length of the inclined micron-cone structure, which in turn affects the height of the structure.
  • the pulling angle will also affect the final inclination angle.
  • the present invention controls the peeling temperature to make the polymer sheet form a viscous flow state, and effectively controls the peeling temperature in the viscous flow state.
  • the pulling angle is controlled so that the inclined micron cone structure of the present invention is formed on the surface of the polymer sheet. If the peeling temperature is too low, the peeling and stretching cannot be effectively achieved, and the specific inclined micron cone structure cannot be formed.
  • the flexible screen has densely distributed micropores, which serves as a flexible template with an inclined micron-cone structure for controlling the directional rebound of water droplets. It is fixed to the bottom surface of the mold cavity after drying and cutting, and the thermoplastic polymer melt is injected into the mold cavity with the flexible template placed on the bottom surface. Through the action of the mold compression force or the filling pressure, the thermoplastic polymer polymer melt can be completely filled into the densely distributed micropores of the flexible template. After cooling and shaping, a thermoplastic polymer sheet with a flexible template on the surface can be obtained.
  • thermoplastic polymer sheet having a flexible screen on its surface can be fixed on a tensile test fixture of a universal testing machine, wherein one end of the fixture clamps the flexible screen and the other end clamps the thermoplastic polymer sheet. Subsequently, the flexible screen is peeled off from the surface of the thermoplastic polymer sheet at about the glass transition temperature of the thermoplastic polymer under the traction of the fixture.
  • the surface microstructure of the polymer sheet is tilted at a certain angle during the demolding process, and after cooling and shaping, a regularly arranged directional offset structure with a certain inclination angle, i.e., an inclined micron cone structure, is formed, thereby obtaining a thermoplastic polymer having a surface with hydrophobicity and directional offset characteristics of rebounding water droplets.
  • the melt filling depth can be different by controlling the molding or injection molding process parameters in the filling process, and the inclination angle and stretching ratio of the surface inclined micron cone structure can be changed by the coordination of the traction angle and the traction speed in the stripping process.
  • the overall process synergistically acts to prepare an inclined micron cone structure having the inclination angle and vertical height of the present invention, thereby obtaining the thermoplastic polymer of the present invention.
  • the peeling temperature is 40-150°C
  • the pulling angle ⁇ is 20°-70°
  • the pulling speed is 20-50 mm/min.
  • thermoplastic polymer melt is completely filled into the micropores of the flexible screen by molding or injection molding.
  • melt filling of different depths can be achieved, and then surface inclined micron cone structures of different vertical heights can be obtained by peeling.
  • the specific process parameter control of compression molding or injection molding of the present invention includes melt temperature, mold temperature, molding pressure, etc., specifically: melt temperature range is 25-250°C, compression molding pressure is 5-20MPa, and mold temperature is 25-260°C.
  • the flexible screen of the present invention can be one or more of plain, twill or mat-shaped woven wire screens.
  • the average diameter of the metal wire is 15 to 800 ⁇ m, preferably 15 to 25 ⁇ m.
  • the average hole diameter of the metal wire mesh is 10 to 50 ⁇ m, preferably 20 ⁇ 30 ⁇ m.
  • the metal wire can be a non-ferrous metal wire such as stainless steel wire, iron wire, black steel wire, white steel wire, brass wire, copper wire, etc.
  • the preferred limitation of the wire diameter, weaving method (mat weave, plain weave, twill weave, etc.), and average hole diameter can be more conducive to determining the morphology, spacing, and diameter of the inclined micron-cone structure, thereby being more conducive to obtaining the final surface inclined micron-cone structure.
  • thermoplastic polymer of the present invention can also be prepared by other methods, for example, 3D printing technology that can be quickly molded.
  • the required inclined micron cone structure morphology is drawn with the help of three-dimensional software and converted into a digital model file, and the required inclined micron cone structure surface is constructed by layer-by-layer printing using adhesive materials such as powder plastics, but this method has low processing efficiency and is difficult to efficiently prepare the inclined micron cone structure surface.
  • the thermoplastic polymer of the present invention has a super-hydrophobic surface that can control the directional rebound of water droplets, and can be widely used in the preparation of hydrophobic polymer products. It is widely used in raindrop power generation, anti-fouling, anti-corrosion, self-cleaning, anti-adhesion, and resistance reduction. For example, it can be used to prepare the surface of water droplet potential energy capture equipment, the surface of fluid directional and efficient transportation equipment, the surface of drug release control equipment, the surface of drag reduction equipment, and the surface of microfluidic equipment.
  • the present invention has the following beneficial effects:
  • the surface of the thermoplastic polymer of the present invention has an array-distributed inclined micron-cone structure, which can effectively prevent the infiltration of water droplets and drive the water droplets to move in the direction of the inclined structure when they rebound. It can be widely used in raindrop power generation, anti-fouling, anti-corrosion, self-cleaning, anti-adhesion, resistance reduction and other aspects.
  • the preparation method of the thermoplastic polymer of the present invention comprises filling a flexible template with a thermoplastic polymer melt, and then forming a thermoplastic polymer sheet glass with a flexible screen on the surface to obtain a thermoplastic polymer with an inclined micron cone structure on the surface. High-precision replication of the inclined micron cone structure can be achieved, and the flexible template can be used repeatedly to achieve batch and low-cost manufacturing.
  • FIG1 is a schematic diagram of the peeling process of a thermoplastic polymer having an inclined micro-cone structure.
  • FIG. 2 is a scanning electron microscope photograph of the flexible screen.
  • FIG. 3 is a scanning electron microscope photograph of the inclined micro-cone structure on the surface of the thermoplastic polymer of Example 1.
  • FIG. 4 is a diagram showing the wetting state of a 4 ⁇ L water droplet on the surface of the thermoplastic polymer of Example 1.
  • Figure 5 shows a 4 ⁇ L water droplet on a thermoplastic polymer without an inclined micro-cone structure in Comparative Example 1.
  • (a) is a video screenshot of the rebound motion state of a 4 ⁇ L water droplet on the surface of a thermoplastic polymer with an inclined micro-cone structure of Example 1 of the present invention.
  • FIG. 6 is a scanning electron microscope photograph of the inclined micro-cone structure on the surface of the thermoplastic polymer of Example 2.
  • FIG. 7 is a scanning electron microscope photograph of the inclined micro-cone structure on the surface of the thermoplastic polymer of Example 4.
  • FIG. 8 is a scanning electron microscope photograph of the inclined micro-cone structure on the surface of the thermoplastic polymer of Example 5.
  • FIG. 9 is a scanning electron microscope photograph of the inclined micro-cone structure on the surface of the thermoplastic polymer of Example 6.
  • FIG. 10 is a scanning electron microscope photograph of the surface of the thermoplastic polymer of Comparative Example 1.
  • FIG. 11 is a diagram showing the wetting state of a 4 ⁇ L water droplet on the surface of the thermoplastic polymer of Comparative Example 1.
  • the present invention is further described below in conjunction with specific embodiments, but the embodiments do not limit the present invention in any form.
  • the raw materials and reagents used in the embodiments of the present invention are conventionally purchased raw materials and reagents.
  • the raw material information of the present invention is as follows:
  • Polypropylene PP T30S, Fujian Zhongjing Petrochemical Co., Ltd.;
  • Polycaprolactone PCL Capa 6800, Solvay, USA;
  • Polyethylene PE FL8008, Fujian United Petrochemical Co., Ltd.;
  • thermoplastic polymer the surface of the thermoplastic polymer has an inclined micron-cone structure (as shown in FIG. 3 ), the inclined micron-cone structure array is distributed on the polymer surface, the inclination angle ⁇ of the inclined micron-cone structure is 30°, the vertical height H is 100 ⁇ m, the thermoplastic polymer is PP, and the density of the inclined micron-cone structure is 10,000 per square inch.
  • thermoplastic polymer The specific preparation method of the thermoplastic polymer is as follows:
  • the flexible mesh 2 with an average hole diameter of 25 ⁇ m and an average wire diameter of 20 ⁇ m is immersed in anhydrous ethanol for ultrasonic cleaning for 20 minutes and then placed in an oven for drying.
  • thermoplastic polymer sheet with a flexible screen on the surface is obtained 3;
  • thermoplastic polymer sheet with a flexible screen on the surface on the upper and lower traction clamps 1 respectively (the traction angle ⁇ is 30°), turn on the constant temperature heating box 4 to stabilize its peeling temperature at 100°C and keep it warm for 30 minutes, set the traction speed V to 20mm/min, and when the flexible screen is peeled off, a micro-cone structure with a certain inclination angle is formed on the polymer surface, and finally a thermoplastic polymer 5 with an inclined micron-cone structure is obtained.
  • thermoplastic polymer having the inclined micro-cone structure The peeling process of the thermoplastic polymer having the inclined micro-cone structure is shown in FIG1 .
  • FIG2 is a scanning electron microscope photograph of the flexible screen, which shows that it has regularly and closely distributed micropores with a diameter of about 25 ⁇ m.
  • Figure 3 is a scanning electron microscope photo of the inclined micro-cone structure on the surface of the thermoplastic polymer. It can be seen that the angle between the inclined micro-cone structure on the surface of the thermoplastic polymer and the vertical direction is about 30°, and the height of the inclined micro-cone structure is about 100 ⁇ m.
  • Figure 4 is a photograph of the wetting state of a 4 ⁇ L water droplet on the surface of the thermoplastic polymer of the present invention. It can be seen that the microstructure on the surface of the product can prevent the water droplet from further infiltrating, thereby forming a solid-liquid-gas three-phase composite wetting interface on the top. This composite wetting state reduces the solid-liquid contact area, thereby presenting a larger contact angle.
  • thermoplastic polymer has a surface with an inclined micron cone structure, an array of the inclined micron cone structures is distributed on the polymer surface, an inclination angle ⁇ of the inclined micron cone structure is 80°, a vertical height H is 100 ⁇ m, the thermoplastic polymer is PP, and a density of the inclined micron cone structures is 10,000 per square inch.
  • thermoplastic polymer The specific preparation method of the thermoplastic polymer is as follows:
  • the flexible mesh 2 with an average hole diameter of 25 ⁇ m and an average wire diameter of 20 ⁇ m is immersed in anhydrous ethanol for ultrasonic cleaning for 20 minutes and then placed in an oven for drying.
  • the flexible screen is fixed in the mold cavity of the molding machine, the mold is heated, the PP is melted and plasticized into a melt, and under the action of the compression force, the PP melt is pressed into the micropores of the flexible screen, and after cooling and shaping, a thermoplastic polymer sheet with a flexible screen on the surface is obtained 3;
  • thermoplastic polymer sheet with a flexible screen on the surface on the upper and lower traction clamps 1 respectively (the traction angle ⁇ is 80°), turn on the constant temperature heating box 4 to stabilize its peeling temperature at 130°C and keep it warm for 30 minutes, set the traction speed V to 20 mm/min, and when the flexible screen is peeled off, a micro-cone structure with a certain inclination angle is formed on the polymer surface, and finally a thermoplastic polymer 5 with an inclined micron-cone structure is obtained.
  • Figure 6 is a scanning electron microscope photograph of the inclined micro-cone structure on the surface of the thermoplastic polymer. It can be seen that the angle ⁇ between the inclined micro-cone structure on the surface of the thermoplastic polymer and the vertical direction is 80°, and the height of the inclined micro-cone structure is about 100 ⁇ m.
  • thermoplastic polymer the surface of the thermoplastic polymer has an inclined micron cone structure, the inclined micron cone structure array is distributed on the polymer surface, the inclined angle ⁇ of the inclined micron cone structure is 10°, the vertical height H is 40 ⁇ m, the thermoplastic polymer is PP, and the density of the inclined micron cone structure is 1000 per square inch.
  • thermoplastic polymer The specific preparation method of the thermoplastic polymer is as follows:
  • the flexible mesh 2 with an average hole diameter of 50 ⁇ m and an average wire diameter of 800 ⁇ m is immersed in anhydrous ethanol for ultrasonic cleaning for 20 minutes and then placed in an oven for drying.
  • the flexible screen is fixed in the mold cavity of the molding machine, the mold is heated, the PP is melted and plasticized into a melt, and under the action of the compression force, the PP melt is pressed into the micropores of the flexible screen, and after cooling and shaping, a thermoplastic polymer sheet with a flexible screen on the surface is obtained 3;
  • thermoplastic polymer sheet with a flexible screen on the surface on the upper and lower traction clamps 1 respectively (the traction angle ⁇ is 10°), turn on the constant temperature heating box 4 to stabilize its peeling temperature at 25°C and keep it warm for 30 minutes, set the traction speed V to 5mm/min, and when the flexible screen is peeled off, a micro-cone structure with a certain inclination angle is formed on the polymer surface, and finally a thermoplastic polymer 5 with an inclined micron-cone structure is obtained.
  • thermoplastic polymer the surface of the thermoplastic polymer has an inclined micron cone structure, the inclined micron cone structure array is distributed on the polymer surface, the inclined angle ⁇ of the inclined micron cone structure is 45°, the vertical height H is 450 ⁇ m, the thermoplastic polymer is PP, and the density of the inclined micron cone structure is 10,000 per square inch.
  • thermoplastic polymer The specific preparation method of the thermoplastic polymer is as follows:
  • the flexible mesh 2 with an average hole diameter of 25 ⁇ m and an average wire diameter of 20 ⁇ m is immersed in anhydrous ethanol for ultrasonic cleaning for 20 minutes and then placed in an oven for drying.
  • the flexible screen is fixed in the mold cavity of the molding machine, the mold is heated, the PP is melted and plasticized into a melt, and under the action of the compression force, the PP melt is pressed into the micropores of the flexible screen, and after cooling and shaping, a thermoplastic polymer sheet with a flexible screen on the surface is obtained 3;
  • thermoplastic polymer sheet with a flexible screen on the surface to the upper and lower traction fixtures 1 respectively (the traction angle ⁇ is 45°), turn on the constant temperature heating box 4 to stabilize the peeling temperature at 150°C and keep it warm for 30 minutes, set the traction speed V to 50mm/min, and when the flexible screen is peeled off, the polymer surface A micro-cone structure with a certain inclination angle is formed, and finally a thermoplastic polymer 5 with an inclined micro-cone structure is obtained.
  • thermoplastic polymer the surface of the thermoplastic polymer has an inclined micron cone structure, the inclined micron cone structure array is distributed on the polymer surface, the inclined angle ⁇ of the inclined micron cone structure is 30°, the vertical height H is 130 ⁇ m, the thermoplastic polymer is PP, and the density of the inclined micron cone structure is 10,000 per square inch.
  • thermoplastic polymer The specific preparation method of the thermoplastic polymer is as follows:
  • the flexible mesh 2 with an average hole diameter of 25 ⁇ m and an average wire diameter of 20 ⁇ m is immersed in anhydrous ethanol for ultrasonic cleaning for 20 minutes and then placed in an oven for drying.
  • the flexible screen is fixed in the mold cavity of the molding machine, the mold is heated, the PP is melted and plasticized into a melt, and under the action of the compression force, the PP melt is pressed into the micropores in the flexible screen, and after cooling and shaping, a thermoplastic polymer sheet with a flexible screen on the surface is obtained 3;
  • thermoplastic polymer sheet with a flexible screen on the surface on the upper and lower traction clamps 1 respectively (the traction angle ⁇ is 30°), turn on the constant temperature heating box 4 to stabilize its peeling temperature at 40°C and keep it warm for 30 minutes, set the traction speed V to 25mm/min, and when the flexible screen is peeled off, a micro-cone structure with a certain inclination angle is formed on the polymer surface, and finally a thermoplastic polymer 5 with an inclined micron-cone structure is obtained.
  • thermoplastic polymer the surface of the thermoplastic polymer has an inclined micron cone structure, the inclined micron cone structure array is distributed on the polymer surface, the inclined angle ⁇ of the inclined micron cone structure is 20 degrees, the vertical height H is 900 ⁇ m, the thermoplastic polymer is ABS, and the density of the inclined micron cone structure is 10,000 per square inch.
  • thermoplastic polymer The specific preparation method of the thermoplastic polymer is as follows:
  • the flexible mesh 2 with an average hole diameter of 25 ⁇ m and an average wire diameter of 20 ⁇ m is immersed in anhydrous ethanol for ultrasonic cleaning for 20 minutes and then placed in an oven for drying.
  • the flexible screen is fixed in the mold cavity of the molding machine, the mold is heated, the PP is melted and plasticized into a melt, and under the action of the compression force, the PP melt is pressed into the micropores of the flexible screen, and after cooling and shaping, a thermoplastic polymer sheet with a flexible screen on the surface is obtained 3;
  • thermoplastic polymer sheet with a flexible screen on the surface on the upper and lower traction clamps 1 respectively (the traction angle ⁇ is 20°), turn on the constant temperature heating box 4 to stabilize its peeling temperature at 200°C and keep it warm for 30 minutes, set the traction speed V to 100 mm/min, and when the flexible screen is peeled off, a micro-cone structure with a certain inclination angle is formed on the polymer surface, and finally a thermoplastic polymer 5 with an inclined micron-cone structure is obtained.
  • thermoplastic polymer the surface of the thermoplastic polymer has an inclined micron-cone structure (as shown in FIG. 3 ), the inclined micron-cone structure array is distributed on the polymer surface, the inclination angle ⁇ of the inclined micron-cone structure is 30°, the vertical height H is 20 ⁇ m, the thermoplastic polymer is PP, and the density of the inclined micron-cone structure is 10,000 per square inch.
  • thermoplastic polymer The specific preparation method of the thermoplastic polymer is as follows:
  • the flexible mesh 2 with an average hole diameter of 25 ⁇ m and an average wire diameter of 20 ⁇ m is immersed in anhydrous ethanol for ultrasonic cleaning for 20 minutes and then placed in an oven for drying.
  • the flexible screen is fixed in the mold cavity of the molding machine, the mold is heated, the PP is melted and plasticized into a melt, and under the action of the compression force, the PP melt is pressed into the micropores of the flexible screen, and after cooling and shaping, a thermoplastic polymer sheet with a flexible screen on the surface is obtained 3;
  • thermoplastic polymer sheet with a flexible screen on the surface on the upper and lower traction clamps 1 respectively (the traction angle ⁇ is 30°), turn on the constant temperature heating box 4 to stabilize its peeling temperature at 100°C and keep it warm for 30 minutes, set the traction speed V to 1mm/min, and when the flexible screen is peeled off, a micro-cone structure with a certain inclination angle is formed on the polymer surface, and finally a thermoplastic polymer 5 with an inclined micron-cone structure is obtained.
  • thermoplastic polymer the surface of the thermoplastic polymer has an inclined micron cone structure, the inclined micron cone structure array is distributed on the polymer surface, the inclined angle ⁇ of the inclined micron cone structure is 20°, the vertical height H is 150 ⁇ m, the thermoplastic polymer is PCL, and the density of the inclined micron cone structure is 9000 per square inch.
  • thermoplastic polymer The specific preparation method of the thermoplastic polymer is the same as that of Example 1, wherein the average hole diameter of the flexible screen is 35 ⁇ m, and the average diameter of the metal wire is 30 ⁇ m.
  • the pulling angle ⁇ was 20°
  • the pulling speed V was 30 mm/min
  • the peeling temperature was 100°C.
  • the inclined micro-cone structure of the thermoplastic polymer surface is specifically formed as shown in FIG7 .
  • thermoplastic polymer the surface of the thermoplastic polymer has an inclined micron cone structure, the inclined micron cone structure array is distributed on the polymer surface, the inclined angle ⁇ of the inclined micron cone structure is 70°, the vertical height H is 250 ⁇ m, the thermoplastic polymer is PE, and the density of the inclined micron cone structure is 11000 per square inch.
  • thermoplastic polymer The specific preparation method of the thermoplastic polymer is the same as that of Example 1, wherein the average hole diameter of the flexible screen is 10 ⁇ m, and the average diameter of the metal wire is 15 ⁇ m.
  • the pulling angle ⁇ was 70°
  • the pulling speed V was 40 mm/min
  • the peeling temperature was 100°C.
  • thermoplastic polymer surface formed specifically is shown in FIG8 .
  • thermoplastic polymer the surface of the thermoplastic polymer has an inclined micron cone structure, the inclined micron cone structure array is distributed on the polymer surface, the inclined angle ⁇ of the inclined micron cone structure is 3°, the vertical height H is 20 ⁇ m, the thermoplastic polymer is ABS, and the density of the inclined micron cone structure is 5000 per square inch.
  • thermoplastic polymer The specific preparation method of the thermoplastic polymer is the same as that in Example 1.
  • the inclined micro-cone structure of the thermoplastic polymer surface is shown in FIG9 , wherein the average hole diameter of the flexible mesh is 45 ⁇ m, and the average diameter of the metal wire is 50 ⁇ m.
  • the pulling angle ⁇ was 3°
  • the pulling speed V was 1 mm/min
  • the peeling temperature was 200°C.
  • thermoplastic polymer the specific preparation method is as follows:
  • thermoplastic polymer sheet 3 is obtained;
  • thermoplastic polymer surface of Examples 1 to 6 was measured, and the specific measurement method was as follows:
  • the hydrophobicity is expressed by the contact angle, and the larger the contact angle, the better the hydrophobicity of the material.
  • the contact angle of the sample surface was measured using a contact angle meter (JC2000, Shanghai Zhongchen Co., Ltd., China).
  • the volume of the water droplet was 5 ⁇ L. Five locations of the same sample were tested and the average value was calculated.
  • the microstructure on the surface of the thermoplastic polymer of the present invention can prevent further infiltration of water droplets, thereby forming a solid-liquid-gas three-phase composite wetting interface on the top.
  • This composite wetting state reduces the solid-liquid contact area, thereby presenting a larger contact angle.
  • the directional rebound accuracy of a water droplet is detected by using a motion video of a 4 ⁇ L water droplet bouncing off a thermoplastic polymer surface with an inclined micro-cone structure.
  • thermoplastic polymer with an inclined micron-cone structure of the present invention can achieve directional rebound of water droplets.
  • Figure 5(a) is a video screenshot of the rebound motion state of a 4 ⁇ L water drop on the thermoplastic polymer surface without the inclined micro-cone structure of Comparative Example 1;
  • Figure 5(b) is a video screenshot of the rebound and deflection motion state of a 4 ⁇ L water drop on the thermoplastic polymer surface with the inclined micro-cone structure of Example 1 of the present invention. It can be seen that the 4 ⁇ L water drop produced an obvious deflection motion after the drop bounced, and the motion direction was consistent with the structural tilt direction, indicating that the thermoplastic polymer with the inclined micro-cone structure of the present invention can achieve directional rebound of the water drop.
  • thermoplastic polymer of Comparative Example 1 The surface of the thermoplastic polymer of Comparative Example 1 is shown in FIG10 , and it can be seen that it is a flat plane and no relevant surface microstructure is formed.
  • FIG11 is a wetting state diagram of the thermoplastic polymer of Comparative Example 1 in a water contact angle test. Combining FIG10 and FIG11 , it can be seen that the thermoplastic polymer of Comparative Example 1 cannot form a micro-surface structure with an inclined micro-cone structure, the water repellency is deteriorated, and the directional rebound of water droplets cannot be achieved.

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Abstract

The present invention relates to the technical field of superhydrophobic polymer materials. Disclosed are a thermoplastic polymer, a preparation method therefor, and a use thereof. The surface of the thermoplastic polymer of the present invention is provided with inclined micro-cone structures. The inclined micro-cone structures are distributed on the surface of the polymer in an array. The inclined micro-cone structures have an inclination angle λ satisfying that 0°<λ<90°, and a vertical height H satisfying that 0<H≤900 µm. The surface of the thermoplastic polymer of the present invention is provided with inclined micro-cone structures distributed in an array, and the inclined micro-cone structures can effectively prevent the infiltration of water drops and can drive the water drops to directionally move in the inclination direction of the structures when the water drops rebound. The present invention can be widely applied to aspects such as raindrop power generation, fouling prevention, corrosion prevention, self-cleaning, adhesion prevention, and resistance reduction.

Description

一种热塑性聚合物及其制备方法和应用A thermoplastic polymer and its preparation method and application 技术领域Technical Field
本发明涉及超疏水聚合物材料技术领域，更具体地，涉及一种热塑性聚合物及其制备方法和应用。The present invention relates to the technical field of super-hydrophobic polymer materials, and more specifically, to a thermoplastic polymer and a preparation method and application thereof.
背景技术Background technique
固体表面与水接触时，水滴接触角小于90°的称为亲水表面，接触角大于90°的称为疏水表面；特别地，接触角达到150°及以上的称为超疏水表面。当水滴滴落在超疏水表面上时，由于水滴与超疏水表面间存在一层空气垫，空气垫可有效减小水滴与表面的接触面积，使水滴无法浸入表面微观结构中，而被“支撑”在超疏水表面上，因而超疏水表面在雨滴发电、防污、防腐、自清洁、防附着、减少阻力等方面被广泛应用。When a solid surface comes into contact with water, a water droplet with a contact angle of less than 90° is called a hydrophilic surface, and a contact angle greater than 90° is called a hydrophobic surface; in particular, a contact angle of 150° or more is called a super-hydrophobic surface. When a water droplet falls on a super-hydrophobic surface, there is a layer of air cushion between the water droplet and the super-hydrophobic surface. The air cushion can effectively reduce the contact area between the water droplet and the surface, so that the water droplet cannot penetrate into the surface microstructure, but is "supported" on the super-hydrophobic surface. Therefore, super-hydrophobic surfaces are widely used in raindrop power generation, anti-fouling, anti-corrosion, self-cleaning, anti-adhesion, and resistance reduction.
具有稳健动态润湿稳定性的超疏水表面在以水滴势能捕捉为主的应用场景中表现优异，而水滴反弹后的运动行为对于能量的收集和器件设计至关重要。虽然现有超疏水表面对水滴的排斥性可以使高速水滴无残留的反弹以实现能量转换和长效工作，但是水滴滴落后的反弹运动是无规则和不可控的，因此为滴落水滴的定向收集和排出带来诸多不便。因此，能够控制反弹水滴定向运动的超疏水表面是目前超疏水表面应用需要着重克服的问题。虽然激光刻蚀、3D打印、注塑成型、纳米压印等现有的超疏水表面制备技术已经实现了表面润湿行为和结构形态的高度调控，但如何制备高动态润湿稳定性超疏水表面，尤其是具有反弹水滴定向偏移微结构的表面仍是难以攻克的技术难点。Superhydrophobic surfaces with robust dynamic wetting stability perform well in application scenarios that focus on capturing the potential energy of water droplets, and the motion behavior of water droplets after rebounding is crucial for energy collection and device design. Although the repellency of existing superhydrophobic surfaces to water droplets can enable high-speed water droplets to rebound without residue to achieve energy conversion and long-term operation, the rebound motion of water droplets after falling is irregular and uncontrollable, thus causing many inconveniences for the directional collection and discharge of falling water droplets. Therefore, superhydrophobic surfaces that can control the directional motion of rebounding water droplets are a problem that needs to be overcome in the current application of superhydrophobic surfaces. Although existing superhydrophobic surface preparation technologies such as laser etching, 3D printing, injection molding, and nanoimprinting have achieved a high degree of regulation of surface wetting behavior and structural morphology, how to prepare superhydrophobic surfaces with high dynamic wetting stability, especially surfaces with directional offset microstructures of rebounding water droplets, is still a technical difficulty that is difficult to overcome.
现有技术公开了控制液滴弹跳方向的方法，其具体操作为：将基体表面划分为若干区域，每一个区域构造规则阵列分布微米级柱状结构，通过调节工艺参数，在每一区域内构造出不同密集程度的微米级柱状结构，保证相邻区域的微米级柱状结构密集程度不同或者根据需要各个区域内的微米级柱状结构密度依次减小或者依次增大，即可获得液滴向微米级柱状结构稀疏区域反弹的效果。该控制液滴弹跳表面制备较为复杂，且只能实现液滴的区域偏移，无法实现精准的定向偏移。 The prior art discloses a method for controlling the direction of droplet bouncing, which specifically comprises the following steps: dividing the substrate surface into several regions, constructing a micron-scale columnar structure with a regular array in each region, and constructing micron-scale columnar structures with different densities in each region by adjusting process parameters, ensuring that the density of micron-scale columnar structures in adjacent regions is different or that the density of micron-scale columnar structures in each region decreases or increases in sequence as required, thereby obtaining the effect of droplets bouncing toward regions with sparse micron-scale columnar structures. The preparation of the surface for controlling droplet bouncing is relatively complex, and can only achieve regional displacement of droplets, but cannot achieve precise directional displacement.
发明内容Summary of the invention
本发明的目的是克服现有超疏水表面无法在超疏水的同时实现反弹水滴定向偏移的缺陷和不足，提供一种热塑性聚合物，通过聚合物表面的反弹水滴定向偏移微结构来实现反弹水滴的定向偏移，从而得到即可疏水又可以控制反弹水滴定向偏移的聚合物材料。The purpose of the present invention is to overcome the defects and shortcomings of existing super-hydrophobic surfaces that cannot achieve directional deviation of rebounding water droplets while being super-hydrophobic, and to provide a thermoplastic polymer that achieves directional deviation of rebounding water droplets through a microstructure of directional deviation of rebounding water droplets on the polymer surface, thereby obtaining a polymer material that is both hydrophobic and can control the directional deviation of rebounding water droplets.
本发明的再一目的在于提供一种热塑性聚合物的制备方法。Another object of the present invention is to provide a method for preparing a thermoplastic polymer.
本发明的又一目的在于提供一种热塑性聚合物在制备水滴势能捕捉设备表面、流体定向高效输送设备表面、药物释放控制设备表面、减阻设备表面和微流控设备表面中的应用。Another object of the present invention is to provide an application of a thermoplastic polymer in the preparation of a water droplet potential energy capture device surface, a fluid directional and efficient transport device surface, a drug release control device surface, a drag reduction device surface and a microfluidic device surface.
本发明上述目的通过以下技术方案实现：The above-mentioned purpose of the present invention is achieved through the following technical solutions:
一种热塑性聚合物，所述热塑性聚合物的表面具有倾斜微米锥结构，所述倾斜微米锥结构阵列分布在聚合物表面，所述倾斜微米锥结构的倾斜角λ，0°<λ<90°，垂直高度H为0<H≤900μm。A thermoplastic polymer has a surface with an inclined micron cone structure, the inclined micron cone structure array is distributed on the polymer surface, the inclined angle λ of the inclined micron cone structure is 0°<λ<90°, and the vertical height H is 0<H≤900μm.
其中，需要说明的是：Among them, it should be noted that:
本发明的倾斜微米锥结构的倾斜角λ和垂直高度H的测试方法如下：The test method of the tilt angle λ and the vertical height H of the tilted micro-cone structure of the present invention is as follows:
利用裁刀将所制备的倾斜微米锥片材截开，截开面与扫描电子显微镜镜头垂直放置，通过显微镜观察截面微观形貌并获取原始照片。借助测绘软件，测量不同区域的倾斜微米锥结构的倾斜角度和高度，并进行数据统计，求取平均值，最终得到倾斜微米锥的倾斜角度和高度。The prepared inclined micron cone sheet was cut with a cutter, and the cut surface was placed perpendicular to the scanning electron microscope lens. The cross-sectional microscopic morphology was observed through a microscope and the original photo was obtained. With the help of mapping software, the inclination angle and height of the inclined micron cone structure in different regions were measured, and the data were statistically analyzed to obtain the average value, and finally the inclination angle and height of the inclined micron cone were obtained.
本发明的热塑性聚合物的表面具有倾斜微米锥结构，通过倾斜微米锥结构可以有效防止水滴的浸润，并在水滴反弹时驱动其向着结构倾斜的方向定向运动。The surface of the thermoplastic polymer of the present invention has an inclined micron cone structure, which can effectively prevent the infiltration of water droplets and drive the water droplets to move in a directional direction of the inclined structure when they rebound.
在本发明的热塑性聚合物表面具有倾斜微米锥结构，水滴在接触倾斜微米锥结构表面时，通过表面倾斜微米锥结构所构成微纳米结构之间的空间结构产生的气穴可以有效防止水滴的渗入，因此，表面呈现出优异的拒水性能。倾斜微米锥结构垂直高度0<H≤900μm，垂直高度增加，样品表面拒水性增加。The thermoplastic polymer surface of the present invention has an inclined micron cone structure. When a water drop contacts the inclined micron cone structure surface, the air pockets generated by the space structure between the micro-nano structures formed by the inclined micron cone structure on the surface can effectively prevent the water drop from penetrating. Therefore, the surface exhibits excellent water repellency. The vertical height of the inclined micron cone structure is 0<H≤900μm. As the vertical height increases, the water repellency of the sample surface increases.
当水滴碰撞到表面时发生反弹，同样通过特定的表面倾斜微米锥结构的倾斜角度和垂直高度控制，水滴在脱离倾斜结构表面过程中受到倾斜微米锥结构所致的非平衡表面张力的驱动，因而产生定向反弹。When a water droplet collides with the surface, it rebounds. The inclination angle and vertical height of the specific surface inclined microcone structure are also controlled. In the process of detaching from the inclined structure surface, the water droplet is driven by the non-equilibrium surface tension caused by the inclined microcone structure, thus producing a directional rebound.
本发明的倾斜微米锥结构阵列分布可以为高度不变的倾斜微米锥结构等间距阵列分布，也可以是高度不同的倾斜微米锥结构的变间距阵列分布。 The tilted micron cone structure array distribution of the present invention can be an array distribution of tilted micron cone structures with constant height and equal spacing, or can be an array distribution of tilted micron cone structures with different heights and variable spacing.
在具体实施方式中，本发明的热塑性聚合物的表面的倾斜微米锥结构的底面可以为任意形状，优选为椭圆形。In a specific embodiment, the bottom surface of the inclined micro-cone structure on the surface of the thermoplastic polymer of the present invention can be of any shape, preferably an ellipse.
优选地，所述倾斜微米锥结构的倾斜角λ为20°≤λ≤70°，垂直高度H为100≤H≤500μm。Preferably, the inclined micro-cone structure has an inclination angle λ of 20°≤λ≤70°, and a vertical height H of 100≤H≤500 μm.
进一步优选地，所述倾斜微米锥结构的倾斜角λ为30°≤λ≤45°，垂直高度H为130≤H≤450μm。Further preferably, the tilt angle λ of the tilted micro-cone structure is 30°≤λ≤45°, and the vertical height H is 130≤H≤450 μm.
在具体实施方式中，优选所述倾斜微米锥结构的密度为9000～11000个/平方英寸。In a specific embodiment, the density of the inclined micro-cone structures is preferably 9000 to 11000 per square inch.
其中，需要说明的是：Among them, it should be noted that:
倾斜微米锥结构的密度的测定方法如下：The density of the inclined micro-cone structure is determined as follows:
借助扫描电子显微镜，观察所制备聚合物表面的表面：将所制备表面置于扫描电子显微镜镜头下方，直接观察并获取原始照片，计数得到倾斜微米锥的密度。The surface of the prepared polymer surface was observed by means of a scanning electron microscope: the prepared surface was placed under the lens of the scanning electron microscope, and an original photo was directly observed and obtained, and the density of the inclined microcones was counted.
在具体实施方式中，本发明的热塑性聚合物为所述热塑性聚合物为聚乙烯、聚丙烯、聚己内酯、ABS中的一种或多种。In a specific embodiment, the thermoplastic polymer of the present invention is one or more of polyethylene, polypropylene, polycaprolactone, and ABS.
本发明还具体保护一种热塑性聚合物的制备方法，包括如下步骤：The present invention also specifically protects a method for preparing a thermoplastic polymer, comprising the following steps:
S1.将热塑性聚合物熔体注入底部放置有柔性筛网的模具腔内，热塑性聚合物熔体完全填充柔性筛网的微孔后冷却定型得到表面具有柔性筛网的聚合物板材；S1. injecting a thermoplastic polymer melt into a mold cavity having a flexible screen placed at the bottom, and cooling and shaping the thermoplastic polymer melt after completely filling the micropores of the flexible screen to obtain a polymer sheet having a flexible screen on the surface;
S2.将具有柔性筛网的聚合物板材的柔性筛网和聚合物板材分别夹持，在外力牵引下将柔性筛网从热塑性聚合物板材表面剥离，聚合物板材表面在剥离过程中形成倾斜微米锥结构，冷却定型后得到所述热塑性聚合物，S2. The flexible screen of the polymer sheet with the flexible screen and the polymer sheet are clamped separately, and the flexible screen is peeled off from the surface of the thermoplastic polymer sheet under external traction, and an inclined micron cone structure is formed on the surface of the polymer sheet during the peeling process, and the thermoplastic polymer is obtained after cooling and shaping.
其中，S2中剥离温度为25～200℃，牵引角度为θ，0°<θ≤90°，牵引速度为1～100mm/min。Among them, the peeling temperature in S2 is 25-200°C, the pulling angle is θ, 0°<θ≤90°, and the pulling speed is 1-100 mm/min.
其中，需要说明的是：Among them, it should be noted that:
本发明的热塑性聚合物表面的倾斜微米锥结构的倾斜角λ和垂直高度H主要通过剥离工艺控制，牵引速度和剥离温度对倾斜微米锥结构的长度有影响，进而会影响结构的高度，牵引角度也会影响最终的倾斜角度，通过控制本发明的剥离温度、牵引角度和牵引速度可以综合实现最终表面形成的热塑性聚合物表面的倾斜微米锥结构的倾斜角λ和垂直高度H。The inclination angle λ and vertical height H of the inclined micron-cone structure on the surface of the thermoplastic polymer of the present invention are mainly controlled by the peeling process. The pulling speed and peeling temperature affect the length of the inclined micron-cone structure, which in turn affects the height of the structure. The pulling angle will also affect the final inclination angle. By controlling the peeling temperature, pulling angle and pulling speed of the present invention, the inclination angle λ and vertical height H of the inclined micron-cone structure on the surface of the thermoplastic polymer formed on the final surface can be comprehensively achieved.
本发明控制剥离温度可以使聚合物板材形成粘流态，在粘流态下通过有效控 制牵引角度使得聚合物板材表面形成本发明的倾斜微米锥结构。剥离温度过低，无法有效实现剥离拉伸，也无法形成特定的倾斜微米锥结构。The present invention controls the peeling temperature to make the polymer sheet form a viscous flow state, and effectively controls the peeling temperature in the viscous flow state. The pulling angle is controlled so that the inclined micron cone structure of the present invention is formed on the surface of the polymer sheet. If the peeling temperature is too low, the peeling and stretching cannot be effectively achieved, and the specific inclined micron cone structure cannot be formed.
在本发明的制备方法中，柔性筛网具有密集分布微孔洞，作为控制水滴定向反弹的倾斜微米锥结构的柔性模板，通过烘干、分切后固定于模具型腔底面，将热塑性聚合物熔体注入底面放置有柔性模板的模具型腔内，通过模具压缩力或充模压力的作用，热塑性聚合物高分子熔体即可完全填充至柔性模板密集分布的微孔洞中，冷却定型即可获得表面具有柔性模板的热塑性聚合物板材。In the preparation method of the present invention, the flexible screen has densely distributed micropores, which serves as a flexible template with an inclined micron-cone structure for controlling the directional rebound of water droplets. It is fixed to the bottom surface of the mold cavity after drying and cutting, and the thermoplastic polymer melt is injected into the mold cavity with the flexible template placed on the bottom surface. Through the action of the mold compression force or the filling pressure, the thermoplastic polymer polymer melt can be completely filled into the densely distributed micropores of the flexible template. After cooling and shaping, a thermoplastic polymer sheet with a flexible template on the surface can be obtained.
在具体实施方式中，S2步骤中可以将表面具有柔性筛网的热塑性聚合物板材在万能实验机的拉伸测试夹具上进行固定，其中，夹具的一端夹持柔性筛网，另一端夹持热塑性聚合物板材，随后在夹具牵引下将柔性筛网在热塑性聚合物的玻璃化转变温度左右从热塑性聚合物板材表面剥离，聚合物板材表面微结构在脱模过程中形成一定角度的倾斜，冷却定型后形成规整排列且具有一定倾角的定向偏移结构，即倾斜微米锥结构，从而获得表面具有疏水和反弹水滴定向偏移特性的热塑性聚合物。In a specific embodiment, in step S2, a thermoplastic polymer sheet having a flexible screen on its surface can be fixed on a tensile test fixture of a universal testing machine, wherein one end of the fixture clamps the flexible screen and the other end clamps the thermoplastic polymer sheet. Subsequently, the flexible screen is peeled off from the surface of the thermoplastic polymer sheet at about the glass transition temperature of the thermoplastic polymer under the traction of the fixture. The surface microstructure of the polymer sheet is tilted at a certain angle during the demolding process, and after cooling and shaping, a regularly arranged directional offset structure with a certain inclination angle, i.e., an inclined micron cone structure, is formed, thereby obtaining a thermoplastic polymer having a surface with hydrophobicity and directional offset characteristics of rebounding water droplets.
其中，在具体制备方法中，通过填充工艺中控制模压或注塑工艺参数可使熔体填充深度不同，通过剥离工艺中牵引角度和牵引速度的协同可以改变表面倾斜微米锥结构的倾角和拉伸倍率，整体工艺协同作用即可制备得到具有本发明的倾斜角度和垂直高度的倾斜微米锥结构，进而得到本发明的热塑性聚合物。Among them, in the specific preparation method, the melt filling depth can be different by controlling the molding or injection molding process parameters in the filling process, and the inclination angle and stretching ratio of the surface inclined micron cone structure can be changed by the coordination of the traction angle and the traction speed in the stripping process. The overall process synergistically acts to prepare an inclined micron cone structure having the inclination angle and vertical height of the present invention, thereby obtaining the thermoplastic polymer of the present invention.
优选地，S2中剥离温度为40～150℃，牵引角度为θ为20°～70°，牵引速度为20～50mm/minPreferably, in S2, the peeling temperature is 40-150°C, the pulling angle θ is 20°-70°, and the pulling speed is 20-50 mm/min.
在具体实施方式中，S1中通过模压或注塑成型方法将热塑性聚合物熔体完全填充柔性筛网的微孔中。通过调节模压或注塑成型的工艺参数即可实现不同深度的熔体填充，进而剥离得到不同垂直高度的表面倾斜微米锥结构。In a specific embodiment, in S1, the thermoplastic polymer melt is completely filled into the micropores of the flexible screen by molding or injection molding. By adjusting the molding or injection molding process parameters, melt filling of different depths can be achieved, and then surface inclined micron cone structures of different vertical heights can be obtained by peeling.
在具体实施方式中，本发明具体的模压或注塑成型的工艺参数控制包括熔体温度，模具温度，成型压力等，具体分别为：熔体温度范围为25～250℃，模压成型压力为5～20MPa，模具温度为25～260℃。In a specific embodiment, the specific process parameter control of compression molding or injection molding of the present invention includes melt temperature, mold temperature, molding pressure, etc., specifically: melt temperature range is 25-250°C, compression molding pressure is 5-20MPa, and mold temperature is 25-260°C.
在具体实施方式中，本发明的柔性筛网可以为平纹、斜纹或席形编织的金属丝筛网中的一种或几种。In a specific embodiment, the flexible screen of the present invention can be one or more of plain, twill or mat-shaped woven wire screens.
进一步优选地，所述金属丝的平均直径为15～800μm，优选为15～25μm。More preferably, the average diameter of the metal wire is 15 to 800 μm, preferably 15 to 25 μm.
进一步优选地，所述金属丝筛网的平均孔洞直径为10～50μm，优选为 20～30μm。More preferably, the average hole diameter of the metal wire mesh is 10 to 50 μm, preferably 20～30μm.
在具体实施方式中，金属丝可以为不锈钢丝、铁丝、黑钢丝、白钢丝、黄铜丝、紫铜丝等有色金属丝。In a specific implementation, the metal wire can be a non-ferrous metal wire such as stainless steel wire, iron wire, black steel wire, white steel wire, brass wire, copper wire, etc.
通过金属丝的直径、编织方式(席型编织、平纹编织、斜纹编织等)、平均孔洞直径的优选限定可以更有利于确定倾斜微米锥结构形态、间距，直径，从而更有利于得到最终的表面倾斜微米锥结构。The preferred limitation of the wire diameter, weaving method (mat weave, plain weave, twill weave, etc.), and average hole diameter can be more conducive to determining the morphology, spacing, and diameter of the inclined micron-cone structure, thereby being more conducive to obtaining the final surface inclined micron-cone structure.
本发明的热塑性聚合物还可通过其他方式制备，例如，可快速成型的3D打印技术。将所需要的倾斜微米锥结构形态借助三维软件绘制后转为数字模型文件，运用粉末塑料等可粘合材料，通过逐层打印的方式构造所需求倾斜微米锥结构表面，但该方法加工效率低，难以高效制备制备倾斜微米锥结构表面。The thermoplastic polymer of the present invention can also be prepared by other methods, for example, 3D printing technology that can be quickly molded. The required inclined micron cone structure morphology is drawn with the help of three-dimensional software and converted into a digital model file, and the required inclined micron cone structure surface is constructed by layer-by-layer printing using adhesive materials such as powder plastics, but this method has low processing efficiency and is difficult to efficiently prepare the inclined micron cone structure surface.
本发明的热塑性聚合物具有可以控制水滴定向反弹的超疏水表面，可以广泛应用于制备疏水高分子制品，在雨滴发电、防污、防腐、自清洁、防附着、减少阻力等方面被广泛应用，例如用于制备水滴势能捕捉设备表面、流体定向高效输送设备表面、药物释放控制设备表面、减阻设备表面和微流控设备表面等。The thermoplastic polymer of the present invention has a super-hydrophobic surface that can control the directional rebound of water droplets, and can be widely used in the preparation of hydrophobic polymer products. It is widely used in raindrop power generation, anti-fouling, anti-corrosion, self-cleaning, anti-adhesion, and resistance reduction. For example, it can be used to prepare the surface of water droplet potential energy capture equipment, the surface of fluid directional and efficient transportation equipment, the surface of drug release control equipment, the surface of drag reduction equipment, and the surface of microfluidic equipment.
与现有技术相比，本发明的有益效果是：Compared with the prior art, the present invention has the following beneficial effects:
本发明的热塑性聚合物表面具有阵列分布的倾斜微米锥结构，通过倾斜微米锥结构可以有效防止水滴的浸润，并在水滴反弹时驱动其向着结构倾斜的方向定向运动，可以广泛应用于雨滴发电、防污、防腐、自清洁、防附着、减少阻力等方面。The surface of the thermoplastic polymer of the present invention has an array-distributed inclined micron-cone structure, which can effectively prevent the infiltration of water droplets and drive the water droplets to move in the direction of the inclined structure when they rebound. It can be widely used in raindrop power generation, anti-fouling, anti-corrosion, self-cleaning, anti-adhesion, resistance reduction and other aspects.
本发明的热塑性聚合物的制备方法将热塑性聚合物熔体填充柔性模板，再将表面具有柔性筛网的热塑性聚合物板材玻璃即可制备得到表面具有倾斜微米锥结构的热塑性聚合物，可以实现倾斜微米锥结构的高精度复制重复，且柔性模板可反复使用可实现批量、低成本制造。The preparation method of the thermoplastic polymer of the present invention comprises filling a flexible template with a thermoplastic polymer melt, and then forming a thermoplastic polymer sheet glass with a flexible screen on the surface to obtain a thermoplastic polymer with an inclined micron cone structure on the surface. High-precision replication of the inclined micron cone structure can be achieved, and the flexible template can be used repeatedly to achieve batch and low-cost manufacturing.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为具有倾斜微米锥结构的热塑性聚合物的剥离过程示意图。FIG1 is a schematic diagram of the peeling process of a thermoplastic polymer having an inclined micro-cone structure.
图2为柔性筛网的扫描电子显微镜照片。FIG. 2 is a scanning electron microscope photograph of the flexible screen.
图3为实施例1的热塑性聚合物表面倾斜微米锥结构的扫描电子显微镜照片。FIG. 3 is a scanning electron microscope photograph of the inclined micro-cone structure on the surface of the thermoplastic polymer of Example 1.
图4为4μL水滴在实施例1的热塑性聚合物表面表面上的润湿状态图。FIG. 4 is a diagram showing the wetting state of a 4 μL water droplet on the surface of the thermoplastic polymer of Example 1.
图5中(a)为4μL水滴在对比例1的不具有倾斜微米锥结构的热塑性聚合 物表面的反弹运动状态视频截图；(b)为4μL水滴在本发明实施例1的倾斜微米锥结构的热塑性聚合物表面上的反弹偏移的运动状态视频截图。Figure 5 (a) shows a 4 μL water droplet on a thermoplastic polymer without an inclined micro-cone structure in Comparative Example 1. (a) is a video screenshot of the rebound motion state of a 4 μL water droplet on the surface of a thermoplastic polymer with an inclined micro-cone structure of Example 1 of the present invention.
图6为实施例2的热塑性聚合物表面倾斜微米锥结构的扫描电子显微镜照片。FIG. 6 is a scanning electron microscope photograph of the inclined micro-cone structure on the surface of the thermoplastic polymer of Example 2.
图7为实施例4的热塑性聚合物表面倾斜微米锥结构的扫描电子显微镜照片。FIG. 7 is a scanning electron microscope photograph of the inclined micro-cone structure on the surface of the thermoplastic polymer of Example 4.
图8为实施例5的热塑性聚合物表面倾斜微米锥结构的扫描电子显微镜照片。FIG. 8 is a scanning electron microscope photograph of the inclined micro-cone structure on the surface of the thermoplastic polymer of Example 5.
图9为实施例6的热塑性聚合物表面倾斜微米锥结构的扫描电子显微镜照片。FIG. 9 is a scanning electron microscope photograph of the inclined micro-cone structure on the surface of the thermoplastic polymer of Example 6.
图10为对比例1的热塑性聚合物表面的扫描电子显微镜照片。FIG. 10 is a scanning electron microscope photograph of the surface of the thermoplastic polymer of Comparative Example 1.
图11为4μL水滴在对比例1的热塑性聚合物表面表面上的润湿状态图。FIG. 11 is a diagram showing the wetting state of a 4 μL water droplet on the surface of the thermoplastic polymer of Comparative Example 1.
具体实施方式Detailed ways
下面结合具体实施方式对本发明作进一步的说明，但实施例并不对本发明做任何形式的限定。除非另有说明，本发明实施例采用的原料试剂为常规购买的原料试剂。The present invention is further described below in conjunction with specific embodiments, but the embodiments do not limit the present invention in any form. Unless otherwise specified, the raw materials and reagents used in the embodiments of the present invention are conventionally purchased raw materials and reagents.
其中，本发明的原料信息如下：Among them, the raw material information of the present invention is as follows:
聚丙烯PP：T30S，福建中景石化有限公司；Polypropylene PP: T30S, Fujian Zhongjing Petrochemical Co., Ltd.;
聚己内酯PCL：Capa 6800，美国苏威公司；Polycaprolactone PCL: Capa 6800, Solvay, USA;
聚乙烯PE：FL8008，福建联合石油化工有限公司；Polyethylene PE: FL8008, Fujian United Petrochemical Co., Ltd.;
ABS：PA-757，台湾奇美。ABS: PA-757, Chimei, Taiwan.
实施例1Example 1
一种热塑性聚合物，热塑性聚合物的表面具有倾斜微米锥结构(如图3所示)，倾斜微米锥结构阵列分布在聚合物表面，倾斜微米锥结构的倾斜角λ为30°，垂直高度H为100μm，热塑性聚合物为PP，倾斜微米锥结构的密度为10000个/平方英寸。A thermoplastic polymer, the surface of the thermoplastic polymer has an inclined micron-cone structure (as shown in FIG. 3 ), the inclined micron-cone structure array is distributed on the polymer surface, the inclination angle λ of the inclined micron-cone structure is 30°, the vertical height H is 100 μm, the thermoplastic polymer is PP, and the density of the inclined micron-cone structure is 10,000 per square inch.
热塑性聚合物的具体制备方法如下：The specific preparation method of the thermoplastic polymer is as follows:
S1.将平均孔洞直径为25μm、金属丝的平均直径为20μm的柔性筛网2浸入无水乙醇中超声清洗20min后，置于烘箱中干燥。S1. The flexible mesh 2 with an average hole diameter of 25 μm and an average wire diameter of 20 μm is immersed in anhydrous ethanol for ultrasonic cleaning for 20 minutes and then placed in an oven for drying.
将柔性筛网固定在模压机模腔内，加热模具，将PP熔融、塑化成熔体，在 压缩力的作用下，PP熔体被压入柔性筛网的微孔中，冷却定型后，获得表面具有柔性筛网的热塑性聚合物板材3；Fix the flexible screen in the mold cavity of the molding machine, heat the mold, melt and plasticize the PP into a melt, and then Under the action of the compression force, the PP melt is pressed into the micropores of the flexible screen, and after cooling and shaping, a thermoplastic polymer sheet with a flexible screen on the surface is obtained 3;
S2.将表面具有柔性筛网的热塑性聚合物板材两端分别固定在上、下牵引夹具1上(牵引角度θ为30°)，开启恒温加热箱4使其剥离温度稳定在100℃并保温30min，设定牵引速度V为20mm/min，当柔性筛网被剥离时聚合物表面形成具有一定倾角的微锥结构，最后获得具有倾斜微米锥结构的热塑性聚合物5。S2. Fix the two ends of the thermoplastic polymer sheet with a flexible screen on the surface on the upper and lower traction clamps 1 respectively (the traction angle θ is 30°), turn on the constant temperature heating box 4 to stabilize its peeling temperature at 100°C and keep it warm for 30 minutes, set the traction speed V to 20mm/min, and when the flexible screen is peeled off, a micro-cone structure with a certain inclination angle is formed on the polymer surface, and finally a thermoplastic polymer 5 with an inclined micron-cone structure is obtained.
其中具有倾斜微米锥结构的热塑性聚合物的剥离过程如图1所示。The peeling process of the thermoplastic polymer having the inclined micro-cone structure is shown in FIG1 .
图2为柔性筛网的扫描电子显微镜照片，可以看出其具有规整、紧密分布的微孔洞，其直径约为25μm。FIG2 is a scanning electron microscope photograph of the flexible screen, which shows that it has regularly and closely distributed micropores with a diameter of about 25 μm.
图3为热塑性聚合物表面倾斜微米锥结构的扫描电子显微镜照片。可见，热塑性聚合物表面的倾斜微米锥结构和垂直方向的夹角约为30°，倾斜微米锥结构的高度约为100μm。Figure 3 is a scanning electron microscope photo of the inclined micro-cone structure on the surface of the thermoplastic polymer. It can be seen that the angle between the inclined micro-cone structure on the surface of the thermoplastic polymer and the vertical direction is about 30°, and the height of the inclined micro-cone structure is about 100 μm.
图4为4μL水滴在本发明的热塑性聚合物表面润湿状态的照片。可见，制品表面上的微米结构可阻止水滴的进一步浸润，从而在顶部形成固-液-气三相复合润湿界面，这种复合润湿状态减少了固-液接触面积，从而呈现较大接触角。Figure 4 is a photograph of the wetting state of a 4 μL water droplet on the surface of the thermoplastic polymer of the present invention. It can be seen that the microstructure on the surface of the product can prevent the water droplet from further infiltrating, thereby forming a solid-liquid-gas three-phase composite wetting interface on the top. This composite wetting state reduces the solid-liquid contact area, thereby presenting a larger contact angle.
实施例2Example 2
一种热塑性聚合物，热塑性聚合物的表面具有倾斜微米锥结构，倾斜微米锥结构阵列分布在聚合物表面，倾斜微米锥结构的倾斜角λ为80°，垂直高度H为100μm，热塑性聚合物为PP，倾斜微米锥结构的密度为10000个/平方英寸。A thermoplastic polymer has a surface with an inclined micron cone structure, an array of the inclined micron cone structures is distributed on the polymer surface, an inclination angle λ of the inclined micron cone structure is 80°, a vertical height H is 100 μm, the thermoplastic polymer is PP, and a density of the inclined micron cone structures is 10,000 per square inch.
热塑性聚合物的具体制备方法如下：The specific preparation method of the thermoplastic polymer is as follows:
S1.将平均孔洞直径为25μm、金属丝的平均直径为20μm的柔性筛网2浸入无水乙醇中超声清洗20min后，置于烘箱中干燥。S1. The flexible mesh 2 with an average hole diameter of 25 μm and an average wire diameter of 20 μm is immersed in anhydrous ethanol for ultrasonic cleaning for 20 minutes and then placed in an oven for drying.
将柔性筛网固定在模压机模腔内，加热模具，将PP熔融、塑化成熔体，在压缩力的作用下，PP熔体被压入柔性筛网的微孔中，冷却定型后，获得表面具有柔性筛网的热塑性聚合物板材3；The flexible screen is fixed in the mold cavity of the molding machine, the mold is heated, the PP is melted and plasticized into a melt, and under the action of the compression force, the PP melt is pressed into the micropores of the flexible screen, and after cooling and shaping, a thermoplastic polymer sheet with a flexible screen on the surface is obtained 3;
S2.将表面具有柔性筛网的热塑性聚合物板材两端分别固定在上、下牵引夹具1上(牵引角度θ为80°)，开启恒温加热箱4使其剥离温度稳定在130℃并保温30min，设定牵引速度V为20mm/min，当柔性筛网被剥离时聚合物表面形成具有一定倾角的微锥结构，最后获得具有倾斜微米锥结构的热塑性聚合物5。 S2. Fix the two ends of the thermoplastic polymer sheet with a flexible screen on the surface on the upper and lower traction clamps 1 respectively (the traction angle θ is 80°), turn on the constant temperature heating box 4 to stabilize its peeling temperature at 130°C and keep it warm for 30 minutes, set the traction speed V to 20 mm/min, and when the flexible screen is peeled off, a micro-cone structure with a certain inclination angle is formed on the polymer surface, and finally a thermoplastic polymer 5 with an inclined micron-cone structure is obtained.
图6为热塑性聚合物表面倾斜微米锥结构的扫描电子显微镜照片。可见，热塑性聚合物表面的倾斜微米锥结构和垂直方向的夹角倾斜角λ为80°，倾斜微米锥结构的高度约为100μm。Figure 6 is a scanning electron microscope photograph of the inclined micro-cone structure on the surface of the thermoplastic polymer. It can be seen that the angle λ between the inclined micro-cone structure on the surface of the thermoplastic polymer and the vertical direction is 80°, and the height of the inclined micro-cone structure is about 100 μm.
实施例3Example 3
一种热塑性聚合物，热塑性聚合物的表面具有倾斜微米锥结构，倾斜微米锥结构阵列分布在聚合物表面，倾斜微米锥结构的倾斜角λ为10°，垂直高度H为40μm，热塑性聚合物为PP，倾斜微米锥结构的密度为1000个/平方英寸。A thermoplastic polymer, the surface of the thermoplastic polymer has an inclined micron cone structure, the inclined micron cone structure array is distributed on the polymer surface, the inclined angle λ of the inclined micron cone structure is 10°, the vertical height H is 40μm, the thermoplastic polymer is PP, and the density of the inclined micron cone structure is 1000 per square inch.
热塑性聚合物的具体制备方法如下：The specific preparation method of the thermoplastic polymer is as follows:
S1.将平均孔洞直径为50μm、金属丝的平均直径为800μm的柔性筛网2浸入无水乙醇中超声清洗20min后，置于烘箱中干燥。S1. The flexible mesh 2 with an average hole diameter of 50 μm and an average wire diameter of 800 μm is immersed in anhydrous ethanol for ultrasonic cleaning for 20 minutes and then placed in an oven for drying.
将柔性筛网固定在模压机模腔内，加热模具，将PP熔融、塑化成熔体，在压缩力的作用下，PP熔体被压入柔性筛网的微孔中，冷却定型后，获得表面具有柔性筛网的热塑性聚合物板材3；The flexible screen is fixed in the mold cavity of the molding machine, the mold is heated, the PP is melted and plasticized into a melt, and under the action of the compression force, the PP melt is pressed into the micropores of the flexible screen, and after cooling and shaping, a thermoplastic polymer sheet with a flexible screen on the surface is obtained 3;
S2.将表面具有柔性筛网的热塑性聚合物板材两端分别固定在上、下牵引夹具1上(牵引角度θ为10°)，开启恒温加热箱4使其剥离温度稳定在25℃并保温30min，设定牵引速度V为5mm/min，当柔性筛网被剥离时聚合物表面形成具有一定倾角的微锥结构，最后获得具有倾斜微米锥结构的热塑性聚合物5。S2. Fix the two ends of the thermoplastic polymer sheet with a flexible screen on the surface on the upper and lower traction clamps 1 respectively (the traction angle θ is 10°), turn on the constant temperature heating box 4 to stabilize its peeling temperature at 25°C and keep it warm for 30 minutes, set the traction speed V to 5mm/min, and when the flexible screen is peeled off, a micro-cone structure with a certain inclination angle is formed on the polymer surface, and finally a thermoplastic polymer 5 with an inclined micron-cone structure is obtained.
实施例4Example 4
一种热塑性聚合物，热塑性聚合物的表面具有倾斜微米锥结构，倾斜微米锥结构阵列分布在聚合物表面，倾斜微米锥结构的倾斜角λ为45°，垂直高度H为450μm，热塑性聚合物为PP，倾斜微米锥结构的密度为10000个/平方英寸。A thermoplastic polymer, the surface of the thermoplastic polymer has an inclined micron cone structure, the inclined micron cone structure array is distributed on the polymer surface, the inclined angle λ of the inclined micron cone structure is 45°, the vertical height H is 450μm, the thermoplastic polymer is PP, and the density of the inclined micron cone structure is 10,000 per square inch.
热塑性聚合物的具体制备方法如下：The specific preparation method of the thermoplastic polymer is as follows:
S1.将平均孔洞直径为25μm、金属丝的平均直径为20μm的柔性筛网2浸入无水乙醇中超声清洗20min后，置于烘箱中干燥。S1. The flexible mesh 2 with an average hole diameter of 25 μm and an average wire diameter of 20 μm is immersed in anhydrous ethanol for ultrasonic cleaning for 20 minutes and then placed in an oven for drying.
将柔性筛网固定在模压机模腔内，加热模具，将PP熔融、塑化成熔体，在压缩力的作用下，PP熔体被压入柔性筛网的微孔中，冷却定型后，获得表面具有柔性筛网的热塑性聚合物板材3；The flexible screen is fixed in the mold cavity of the molding machine, the mold is heated, the PP is melted and plasticized into a melt, and under the action of the compression force, the PP melt is pressed into the micropores of the flexible screen, and after cooling and shaping, a thermoplastic polymer sheet with a flexible screen on the surface is obtained 3;
S2.将表面具有柔性筛网的热塑性聚合物板材两端分别固定在上、下牵引夹具1上(牵引角度θ为45°)，开启恒温加热箱4使其剥离温度稳定在150℃并保温30min，设定牵引速度V为50mm/min，当柔性筛网被剥离时聚合物表面 形成具有一定倾角的微锥结构，最后获得具有倾斜微米锥结构的热塑性聚合物5。S2. Fix the two ends of the thermoplastic polymer sheet with a flexible screen on the surface to the upper and lower traction fixtures 1 respectively (the traction angle θ is 45°), turn on the constant temperature heating box 4 to stabilize the peeling temperature at 150°C and keep it warm for 30 minutes, set the traction speed V to 50mm/min, and when the flexible screen is peeled off, the polymer surface A micro-cone structure with a certain inclination angle is formed, and finally a thermoplastic polymer 5 with an inclined micro-cone structure is obtained.
实施例5Example 5
一种热塑性聚合物，热塑性聚合物的表面具有倾斜微米锥结构，倾斜微米锥结构阵列分布在聚合物表面，倾斜微米锥结构的倾斜角λ为30°，垂直高度H为130μm，热塑性聚合物为PP，倾斜微米锥结构的密度为10000个/平方英寸。A thermoplastic polymer, the surface of the thermoplastic polymer has an inclined micron cone structure, the inclined micron cone structure array is distributed on the polymer surface, the inclined angle λ of the inclined micron cone structure is 30°, the vertical height H is 130μm, the thermoplastic polymer is PP, and the density of the inclined micron cone structure is 10,000 per square inch.
热塑性聚合物的具体制备方法如下：The specific preparation method of the thermoplastic polymer is as follows:
S1.将平均孔洞直径为25μm、金属丝的平均直径为20μm的柔性筛网2浸入无水乙醇中超声清洗20min后，置于烘箱中干燥。S1. The flexible mesh 2 with an average hole diameter of 25 μm and an average wire diameter of 20 μm is immersed in anhydrous ethanol for ultrasonic cleaning for 20 minutes and then placed in an oven for drying.
将柔性筛网固定在模压机模腔内，加热模具，将PP熔融、塑化成熔体，在压缩力的作用下，PP熔体被压入柔性筛网中的微孔中，冷却定型后，获得表面具有柔性筛网的热塑性聚合物板材3；The flexible screen is fixed in the mold cavity of the molding machine, the mold is heated, the PP is melted and plasticized into a melt, and under the action of the compression force, the PP melt is pressed into the micropores in the flexible screen, and after cooling and shaping, a thermoplastic polymer sheet with a flexible screen on the surface is obtained 3;
S2.将表面具有柔性筛网的热塑性聚合物板材两端分别固定在上、下牵引夹具1上(牵引角度θ为30°)，开启恒温加热箱4使其剥离温度稳定在40℃并保温30min，设定牵引速度V为25mm/min，当柔性筛网被剥离时聚合物表面形成具有一定倾角的微锥结构，最后获得具有倾斜微米锥结构的热塑性聚合物5。S2. Fix the two ends of the thermoplastic polymer sheet with a flexible screen on the surface on the upper and lower traction clamps 1 respectively (the traction angle θ is 30°), turn on the constant temperature heating box 4 to stabilize its peeling temperature at 40°C and keep it warm for 30 minutes, set the traction speed V to 25mm/min, and when the flexible screen is peeled off, a micro-cone structure with a certain inclination angle is formed on the polymer surface, and finally a thermoplastic polymer 5 with an inclined micron-cone structure is obtained.
实施例6Example 6
一种热塑性聚合物，热塑性聚合物的表面具有倾斜微米锥结构，倾斜微米锥结构阵列分布在聚合物表面，倾斜微米锥结构的倾斜角λ为20°，垂直高度H为900μm，热塑性聚合物为ABS，倾斜微米锥结构的密度为10000个/平方英寸。A thermoplastic polymer, the surface of the thermoplastic polymer has an inclined micron cone structure, the inclined micron cone structure array is distributed on the polymer surface, the inclined angle λ of the inclined micron cone structure is 20 degrees, the vertical height H is 900μm, the thermoplastic polymer is ABS, and the density of the inclined micron cone structure is 10,000 per square inch.
热塑性聚合物的具体制备方法如下：The specific preparation method of the thermoplastic polymer is as follows:
S1.将平均孔洞直径为25μm、金属丝的平均直径为20μm的柔性筛网2浸入无水乙醇中超声清洗20min后，置于烘箱中干燥。S1. The flexible mesh 2 with an average hole diameter of 25 μm and an average wire diameter of 20 μm is immersed in anhydrous ethanol for ultrasonic cleaning for 20 minutes and then placed in an oven for drying.
将柔性筛网固定在模压机模腔内，加热模具，将PP熔融、塑化成熔体，在压缩力的作用下，PP熔体被压入柔性筛网的微孔中，冷却定型后，获得表面具有柔性筛网的热塑性聚合物板材3；The flexible screen is fixed in the mold cavity of the molding machine, the mold is heated, the PP is melted and plasticized into a melt, and under the action of the compression force, the PP melt is pressed into the micropores of the flexible screen, and after cooling and shaping, a thermoplastic polymer sheet with a flexible screen on the surface is obtained 3;
S2.将表面具有柔性筛网的热塑性聚合物板材两端分别固定在上、下牵引夹具1上(牵引角度θ为20°)，开启恒温加热箱4使其剥离温度稳定在200℃并保温30min，设定牵引速度V为100mm/min，当柔性筛网被剥离时聚合物表面形成具有一定倾角的微锥结构，最后获得具有倾斜微米锥结构的热塑性聚合物5。 S2. Fix the two ends of the thermoplastic polymer sheet with a flexible screen on the surface on the upper and lower traction clamps 1 respectively (the traction angle θ is 20°), turn on the constant temperature heating box 4 to stabilize its peeling temperature at 200°C and keep it warm for 30 minutes, set the traction speed V to 100 mm/min, and when the flexible screen is peeled off, a micro-cone structure with a certain inclination angle is formed on the polymer surface, and finally a thermoplastic polymer 5 with an inclined micron-cone structure is obtained.
实施例7Example 7
一种热塑性聚合物，热塑性聚合物的表面具有倾斜微米锥结构(如图3所示)，倾斜微米锥结构阵列分布在聚合物表面，倾斜微米锥结构的倾斜角λ为30°，垂直高度H为20μm，热塑性聚合物为PP，倾斜微米锥结构的密度为10000个/平方英寸。A thermoplastic polymer, the surface of the thermoplastic polymer has an inclined micron-cone structure (as shown in FIG. 3 ), the inclined micron-cone structure array is distributed on the polymer surface, the inclination angle λ of the inclined micron-cone structure is 30°, the vertical height H is 20 μm, the thermoplastic polymer is PP, and the density of the inclined micron-cone structure is 10,000 per square inch.
热塑性聚合物的具体制备方法如下：The specific preparation method of the thermoplastic polymer is as follows:
S1.将平均孔洞直径为25μm、金属丝的平均直径为20μm的柔性筛网2浸入无水乙醇中超声清洗20min后，置于烘箱中干燥。S1. The flexible mesh 2 with an average hole diameter of 25 μm and an average wire diameter of 20 μm is immersed in anhydrous ethanol for ultrasonic cleaning for 20 minutes and then placed in an oven for drying.
将柔性筛网固定在模压机模腔内，加热模具，将PP熔融、塑化成熔体，在压缩力的作用下，PP熔体被压入柔性筛网的微孔中，冷却定型后，获得表面具有柔性筛网的热塑性聚合物板材3；The flexible screen is fixed in the mold cavity of the molding machine, the mold is heated, the PP is melted and plasticized into a melt, and under the action of the compression force, the PP melt is pressed into the micropores of the flexible screen, and after cooling and shaping, a thermoplastic polymer sheet with a flexible screen on the surface is obtained 3;
S2.将表面具有柔性筛网的热塑性聚合物板材两端分别固定在上、下牵引夹具1上(牵引角度θ为30°)，开启恒温加热箱4使其剥离温度稳定在100℃并保温30min，设定牵引速度V为1mm/min，当柔性筛网被剥离时聚合物表面形成具有一定倾角的微锥结构，最后获得具有倾斜微米锥结构的热塑性聚合物5。S2. Fix the two ends of the thermoplastic polymer sheet with a flexible screen on the surface on the upper and lower traction clamps 1 respectively (the traction angle θ is 30°), turn on the constant temperature heating box 4 to stabilize its peeling temperature at 100°C and keep it warm for 30 minutes, set the traction speed V to 1mm/min, and when the flexible screen is peeled off, a micro-cone structure with a certain inclination angle is formed on the polymer surface, and finally a thermoplastic polymer 5 with an inclined micron-cone structure is obtained.
实施例8Example 8
一种热塑性聚合物，热塑性聚合物的表面具有倾斜微米锥结构，倾斜微米锥结构阵列分布在聚合物表面，倾斜微米锥结构的倾斜角λ为20°，垂直高度H为150μm，热塑性聚合物为PCL，倾斜微米锥结构的密度为9000个/平方英寸。A thermoplastic polymer, the surface of the thermoplastic polymer has an inclined micron cone structure, the inclined micron cone structure array is distributed on the polymer surface, the inclined angle λ of the inclined micron cone structure is 20°, the vertical height H is 150μm, the thermoplastic polymer is PCL, and the density of the inclined micron cone structure is 9000 per square inch.
热塑性聚合物的具体制备方法同实施例1，其中柔性筛网的平均孔洞直径为35μm、金属丝的平均直径为30μm，The specific preparation method of the thermoplastic polymer is the same as that of Example 1, wherein the average hole diameter of the flexible screen is 35 μm, and the average diameter of the metal wire is 30 μm.
牵引角度θ为20°，牵引速度V为30mm/min，剥离温度100℃。The pulling angle θ was 20°, the pulling speed V was 30 mm/min, and the peeling temperature was 100°C.
具体形成的热塑性聚合物的表面的倾斜微米锥结构如图7所示。The inclined micro-cone structure of the thermoplastic polymer surface is specifically formed as shown in FIG7 .
实施例9Example 9
一种热塑性聚合物，热塑性聚合物的表面具有倾斜微米锥结构，倾斜微米锥结构阵列分布在聚合物表面，倾斜微米锥结构的倾斜角λ为70°，垂直高度H为250μm，热塑性聚合物为PE，倾斜微米锥结构的密度为11000个/平方英寸。A thermoplastic polymer, the surface of the thermoplastic polymer has an inclined micron cone structure, the inclined micron cone structure array is distributed on the polymer surface, the inclined angle λ of the inclined micron cone structure is 70°, the vertical height H is 250μm, the thermoplastic polymer is PE, and the density of the inclined micron cone structure is 11000 per square inch.
热塑性聚合物的具体制备方法同实施例1，其中柔性筛网的平均孔洞直径为10μm、金属丝的平均直径为15μm，The specific preparation method of the thermoplastic polymer is the same as that of Example 1, wherein the average hole diameter of the flexible screen is 10 μm, and the average diameter of the metal wire is 15 μm.
牵引角度θ为70°，牵引速度V为40mm/min，剥离温度100℃。 The pulling angle θ was 70°, the pulling speed V was 40 mm/min, and the peeling temperature was 100°C.
具体形成的热塑性聚合物的表面的倾斜微米锥结构如图8所示。The inclined micro-cone structure of the thermoplastic polymer surface formed specifically is shown in FIG8 .
实施例10Example 10
一种热塑性聚合物，热塑性聚合物的表面具有倾斜微米锥结构，倾斜微米锥结构阵列分布在聚合物表面，倾斜微米锥结构的倾斜角λ为3°，垂直高度H为20μm，热塑性聚合物为ABS，倾斜微米锥结构的密度为5000个/平方英寸。A thermoplastic polymer, the surface of the thermoplastic polymer has an inclined micron cone structure, the inclined micron cone structure array is distributed on the polymer surface, the inclined angle λ of the inclined micron cone structure is 3°, the vertical height H is 20μm, the thermoplastic polymer is ABS, and the density of the inclined micron cone structure is 5000 per square inch.
热塑性聚合物的具体制备方法同实施例1。The specific preparation method of the thermoplastic polymer is the same as that in Example 1.
具体形成的热塑性聚合物的表面的倾斜微米锥结构如图9所示，其中柔性筛网的平均孔洞直径为45μm、金属丝的平均直径为50μm，The inclined micro-cone structure of the thermoplastic polymer surface is shown in FIG9 , wherein the average hole diameter of the flexible mesh is 45 μm, and the average diameter of the metal wire is 50 μm.
牵引角度θ为3°，牵引速度V为1mm/min，剥离温度200℃。The pulling angle θ was 3°, the pulling speed V was 1 mm/min, and the peeling temperature was 200°C.
对比例1Comparative Example 1
一种热塑性聚合物，具体制备方法如下：A thermoplastic polymer, the specific preparation method is as follows:
S1.将PP熔融、塑化成熔体，在压缩力的作用下，PP熔体被压入模具中，冷却定型后，获得热塑性聚合物板材3；S1. The PP is melted and plasticized into a melt. Under the action of a compressive force, the PP melt is pressed into a mold, and after cooling and shaping, a thermoplastic polymer sheet 3 is obtained;
S2.将热塑性聚合物板材两端分别固定在上、下牵引夹具1上(牵引角度θ为180°)，开启恒温加热箱4使其剥离温度稳定在100℃并保温30min，设定牵引速度V为1mm/s，最后获得拉伸后的热塑性聚合物5。S2. Fix the two ends of the thermoplastic polymer sheet on the upper and lower traction clamps 1 respectively (the traction angle θ is 180°), turn on the constant temperature heating box 4 to stabilize its peeling temperature at 100°C and keep it warm for 30 minutes, set the traction speed V to 1mm/s, and finally obtain the stretched thermoplastic polymer 5.
结果检测Results
(1)疏水性检测(1) Hydrophobicity test
对实施例1～6的热塑性聚合物表面的疏水性进行测定，具体测定方法为：The hydrophobicity of the thermoplastic polymer surface of Examples 1 to 6 was measured, and the specific measurement method was as follows:
疏水性通过接触角表示，接触角越大则材料的疏水性能越好。The hydrophobicity is expressed by the contact angle, and the larger the contact angle, the better the hydrophobicity of the material.
接触角的具体测定方法如下：The specific method for measuring the contact angle is as follows:
采用接触角测量仪(JC2000，上海中晨有限公司，中国)测试样品表面的接触角，所用水滴体积为5μL，对同一个样品的五个位置进行测试，并求其平均值。The contact angle of the sample surface was measured using a contact angle meter (JC2000, Shanghai Zhongchen Co., Ltd., China). The volume of the water droplet was 5 μL. Five locations of the same sample were tested and the average value was calculated.
结果如下表1所示：

The results are shown in Table 1 below:

上述结果可以看出，本发明的热塑性聚合物表面上的微米结构可阻止水滴的进一步浸润，从而在顶部形成固-液-气三相复合润湿界面，这种复合润湿状态减少了固-液接触面积，从而呈现较大接触角。It can be seen from the above results that the microstructure on the surface of the thermoplastic polymer of the present invention can prevent further infiltration of water droplets, thereby forming a solid-liquid-gas three-phase composite wetting interface on the top. This composite wetting state reduces the solid-liquid contact area, thereby presenting a larger contact angle.
(2)水滴定向反弹检测(2) Water drop directional rebound detection
通过4μL水滴在具有倾斜微米锥结构的热塑性聚合物表面上的反弹偏移的运动状态视频来检测水滴的定向反弹精准性。The directional rebound accuracy of a water droplet is detected by using a motion video of a 4μL water droplet bouncing off a thermoplastic polymer surface with an inclined micro-cone structure.
从图5可以看出4μL水滴在实施例1～8的倾斜微米锥结构的热塑性聚合物表面上滴落反弹后产生了明显偏移运动，且运动方向和结构倾斜方向一致，说明本发明的具有倾斜微米锥结构的热塑性聚合物可以实现水滴的定向反弹。It can be seen from Figure 5 that a 4 μL water droplet produced an obvious deviation movement after being dropped and rebounded on the thermoplastic polymer surface with an inclined micron-cone structure in Examples 1 to 8, and the movement direction was consistent with the inclination direction of the structure, indicating that the thermoplastic polymer with an inclined micron-cone structure of the present invention can achieve directional rebound of water droplets.
图5(a)为4μL水滴在对比例1的不具有倾斜微米锥结构的热塑性聚合物表面的反弹运动状态视频截图；图5(b)是4μL水滴在本发明实施例1的倾斜微米锥结构的热塑性聚合物表面上的反弹偏移的运动状态视频截图。可见，4μL水滴在滴落反弹后产生了明显偏移运动，且运动方向和结构倾斜方向一致，说明本发明的具有倾斜微米锥结构的热塑性聚合物可以实现水滴的定向反弹。Figure 5(a) is a video screenshot of the rebound motion state of a 4μL water drop on the thermoplastic polymer surface without the inclined micro-cone structure of Comparative Example 1; Figure 5(b) is a video screenshot of the rebound and deflection motion state of a 4μL water drop on the thermoplastic polymer surface with the inclined micro-cone structure of Example 1 of the present invention. It can be seen that the 4μL water drop produced an obvious deflection motion after the drop bounced, and the motion direction was consistent with the structural tilt direction, indicating that the thermoplastic polymer with the inclined micro-cone structure of the present invention can achieve directional rebound of the water drop.
对比例1的热塑性聚合物的表面如图10所示，可以看出，其为平整的平面，并未形成相关的表面微结构。图11为对比例1的热塑性聚合物的水接触角测试润湿状态图，结合图10和图11可以看出，对比例1的热塑性聚合物并不能形成具有倾斜微米锥结构的微表面结构，拒水性变差，且无法实现水滴的定向反弹。The surface of the thermoplastic polymer of Comparative Example 1 is shown in FIG10 , and it can be seen that it is a flat plane and no relevant surface microstructure is formed. FIG11 is a wetting state diagram of the thermoplastic polymer of Comparative Example 1 in a water contact angle test. Combining FIG10 and FIG11 , it can be seen that the thermoplastic polymer of Comparative Example 1 cannot form a micro-surface structure with an inclined micro-cone structure, the water repellency is deteriorated, and the directional rebound of water droplets cannot be achieved.
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。 Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the embodiments here. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

  1. 一种热塑性聚合物，其特征在于，所述热塑性聚合物的表面具有倾斜微米锥结构，所述倾斜微米锥结构阵列分布在聚合物表面，所述倾斜微米锥结构的倾斜角λ，0°<λ<90°，垂直高度H为0<H≤900μm。A thermoplastic polymer, characterized in that the surface of the thermoplastic polymer has an inclined micron-cone structure, the inclined micron-cone structure array is distributed on the polymer surface, the inclined angle λ of the inclined micron-cone structure is 0°<λ<90°, and the vertical height H is 0<H≤900μm.
  2. 如权利要求1所述热塑性聚合物，其特征在于，所述倾斜微米锥结构的倾斜角λ为20°≤λ≤70°，垂直高度H为100≤H≤500μm。The thermoplastic polymer according to claim 1 is characterized in that the inclination angle λ of the inclined micron-cone structure is 20°≤λ≤70°, and the vertical height H is 100≤H≤500μm.
  3. 如权利要求1所述热塑性聚合物，其特征在于，所述倾斜微米锥结构的密度为9000～11000个/平方英寸。The thermoplastic polymer according to claim 1, characterized in that the density of the inclined micro-cone structure is 9000 to 11000 per square inch.
  4. 如权利要求1所述热塑性聚合物，其特征在于，所述热塑性聚合物为聚乙烯、聚丙烯、聚己内酯、ABS中的一种或多种。The thermoplastic polymer according to claim 1, characterized in that the thermoplastic polymer is one or more of polyethylene, polypropylene, polycaprolactone, and ABS.
  5. 一种权利要求1～4任意一项所述热塑性聚合物的制备方法，其特征在于，包括如下步骤：A method for preparing a thermoplastic polymer according to any one of claims 1 to 4, characterized in that it comprises the following steps:
    S1.将热塑性聚合物熔体注入底部放置有柔性筛网的模具腔内，热塑性聚合物熔体完全填充柔性筛网的微孔后冷却定型得到表面具有柔性筛网的聚合物板材；S1. injecting a thermoplastic polymer melt into a mold cavity having a flexible screen placed at the bottom, and cooling and shaping the thermoplastic polymer melt after completely filling the micropores of the flexible screen to obtain a polymer sheet having a flexible screen on the surface;
    S2.将具有柔性筛网的聚合物板材的柔性筛网和聚合物板材分别夹持，在外力牵引下将柔性筛网从热塑性聚合物板材表面剥离，聚合物板材表面在剥离过程中形成倾斜微米锥结构，冷却定型后得到所述热塑性聚合物，S2. The flexible screen of the polymer sheet with the flexible screen and the polymer sheet are clamped separately, and the flexible screen is peeled off from the surface of the thermoplastic polymer sheet under external traction, and an inclined micron cone structure is formed on the surface of the polymer sheet during the peeling process, and the thermoplastic polymer is obtained after cooling and shaping.
    其中，S2中剥离温度为25～200℃，牵引角度为θ，0°<θ≤90°，牵引速度为1～100mm/min。Among them, the peeling temperature in S2 is 25-200°C, the pulling angle is θ, 0°<θ≤90°, and the pulling speed is 1-100 mm/min.
  6. 如权利要求5所述热塑性聚合物的制备方法，其特征在于，S2中剥离温度为40～150℃，牵引角度为θ为20°～70°，牵引速度为20～50mm/min。The method for preparing a thermoplastic polymer as claimed in claim 5, characterized in that the peeling temperature in S2 is 40 to 150°C, the pulling angle θ is 20° to 70°, and the pulling speed is 20 to 50 mm/min.
  7. 如权利要求5所述热塑性聚合物的制备方法，其特征在于，S1中所述柔性筛网为平纹、斜纹或席形编织的金属丝筛网中的一种或几种。The method for preparing a thermoplastic polymer as claimed in claim 5, characterized in that the flexible screen in S1 is one or more of a plain, twill or mat-shaped woven wire screen.
  8. 如权利要求7所述热塑性聚合物的制备方法，其特征在于，所述金属丝的平均直径为15～800μm。The method for preparing a thermoplastic polymer as claimed in claim 7, characterized in that the average diameter of the metal wire is 15 to 800 μm.
  9. 如权利要求7所述热塑性聚合物的制备方法，其特征在于，所述金属丝筛网的平均孔洞直径为10～50μm。 The method for preparing a thermoplastic polymer as claimed in claim 7, characterized in that the average hole diameter of the metal wire mesh is 10 to 50 μm.
  10. 一种权利要求1～4任意一项所述热塑性聚合物在制备水滴势能捕捉设备表面、流体定向高效输送设备表面、药物释放控制设备表面、减阻设备表面和微流控设备表面中的应用。 A use of the thermoplastic polymer described in any one of claims 1 to 4 in preparing the surface of a water droplet potential energy capture device, a fluid directional and efficient delivery device, a drug release control device, a drag reduction device, and a microfluidic device.
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