High-transparency super-hydrophobic polypropylene blending material as well as preparation method and application thereof

Abstract

The invention provides a high-transparency super-hydrophobic polypropylene blending material as well as a preparation method and application thereof, and the high-transparency super-hydrophobic polypropylene blending material is prepared from the following raw materials in parts by mass: 100 parts of polypropylene resin, 0.3-10 parts of solid paraffin, 0.03-2.5 parts of a compatibilizer, 0.03-1.5 parts of a micro-crosslinking modifier, 0.5-5 parts of a hydrophobic modifier and 0.3-3 parts of inorganic nano powder. Under the combined action of the materials, the blended material has excellent hydrophobicity, high light transmittance and extremely low surface solution adsorption effect; no fluoride or halide is contained, so that the biosafety is higher; the contact angle of the inner surface of the pipette tip prepared from the blending material to pure water is greater than or equal to 125 degrees, the light transmittance of natural light is greater than or equal to 80%, and the surface adsorption to an ethanol solution, a 5X protein loading buffer solution and a toluidine blue solution is extremely low.

Description

Technical Field

[0001] The invention belongs to the technical field of polypropylene-based super-hydrophobic materials, and in particular relates to a highly transparent super-hydrophobic polypropylene blend material and a preparation method and application thereof, and more specifically relates to a twin-screw melt-blending extrusion preparation method and an application method of a polypropylene-based super-hydrophobic material which is mainly suitable for preparing biochemical pipette tips and has high light transmittance and is fluorine-free and halogen-free. Background Art

[0002] In recent years, with the further in-depth study of the wettability of material surfaces, the practical application value of hydrophobic surfaces and hydrophobic materials has been discovered, and their application prospects in the fields of anti-fouling and self-cleaning, oil-water separation, metal rust prevention, hull drag reduction, battery fuel, anti-fog and anti-icing, and biomedicine have gradually emerged. Scholars from various countries have successively used plasma irradiation, sol-gel method, layer-by-layer self-assembly method, etching method, vapor deposition method and other technologies to construct micro-nano composite structures on the surface of products or change their chemical composition structure to prepare artificial hydrophobic surfaces or hydrophobic materials.

[0003] Among them, surface treatment methods based on coating are commonly used methods for preparing hydrophobic materials. Although the hydrophobic materials prepared by this method have a high contact angle with water, even reaching super hydrophobicity, these methods have shortcomings such as most of the solvents used are toxic reagents, harmful to the human body, and the wastewater generated during the production process is easy to cause environmental pollution. Summary of the invention

[0004] In view of this, the object of the present invention is to provide a highly transparent super-hydrophobic polypropylene blend material and a preparation method and application thereof, wherein the blend material has excellent hydrophobic properties.

[0005] The present invention provides a highly transparent super-hydrophobic polypropylene blend material, wherein the raw materials for preparing the material include the following components in parts by mass:

[0006] 100 parts of polypropylene resin, 0.3-10 parts of solid paraffin, 0.03-2.5 parts of a compatibilizer, 0.03-1.5 parts of a micro-crosslinking modifier, 0.5-5 parts of a hydrophobic modifier and 0.3-3 parts of an inorganic nano powder.

[0007] Preferably, the melting point of the solid paraffin is 50-70°C.

[0008] Preferably, the compatibilizer is selected from at least one of ethylene propylene diene monomer rubber, ethylene propylene diene monomer rubber, polyolefin elastomer, styrene-butadiene block copolymer and hydrogenated styrene-butadiene block copolymer.

[0009] Preferably, the hydrophobic modifier is selected from at least one of stearic acid, calcium stearate, barium stearate, zinc stearate, trimethoxysilane, dodecyltrimethoxysilane, tetradecyltrimethoxysilane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane, n-hexylmercaptan, n-dodecylmercaptan, n-tetradecylmercaptan, n-hexadecylmercaptan, n-octadecylmercaptan, n-eicosylmercaptan, and n-docosylmercaptan.

[0010] The inorganic nano powder is selected from at least one of nano silicon dioxide, nano titanium dioxide, nano zinc oxide and nano calcium carbonate;

[0011] The micro-crosslinking modifier is selected from at least one of dibenzoyl peroxide, dicumyl peroxide, and azobisisobutyronitrile.

[0012] Preferably, the raw materials for preparing the highly transparent super-hydrophobic polypropylene blend material include:

[0013] 100 parts of polypropylene resin, 0.8 parts of solid paraffin, 0.05 parts of dicumyl peroxide, 0.12 parts of hydrogenated styrene-butadiene block copolymer, 1.0 parts of n-hexadecylmercaptan, 1.0 parts of octadecyltrimethoxysilane and 0.6 parts of silicon dioxide;

[0014] or 100 parts of polypropylene resin, 2.0 parts of solid paraffin, 0.05 parts of dicumyl peroxide, 0.4 parts of hydrogenated styrene-butadiene block copolymer, 1.0 parts of n-hexadecylmercaptan, 1.0 parts of octadecyltrimethoxysilane and 1.0 parts of silicon dioxide;

[0015] Or 100 parts of polypropylene resin, 2.0 parts of solid paraffin, 0.05 parts of dicumyl peroxide, 0.2 parts of hydrogenated styrene-butadiene block copolymer, 0.2 parts of polyolefin elastomer, 1.0 parts of n-hexadecyl mercaptan, 1.0 parts of octadecyltrimethoxysilane and 0.8 parts of silicon dioxide;

[0016] Or 100 parts of polypropylene resin, 1.6 parts of solid paraffin, 0.05 parts of dibenzoyl peroxide, 0.4 parts of polyolefin elastomer, 0.8 parts of n-hexadecyl mercaptan, 0.8 parts of octadecyltrimethoxysilane and 0.8 parts of silicon dioxide.

[0017] The present invention provides a method for preparing the highly transparent super-hydrophobic polypropylene blend material described in the above technical solution, comprising the following steps:

[0018] The polypropylene resin, solid paraffin, a compatibilizer, a micro-crosslinking modifier, a hydrophobic modifier and an inorganic nano-powder are mixed, discharged after 5 to 30 minutes, extruded, cooled and granulated, and dried to obtain a highly transparent and super-hydrophobic polypropylene blend material.

[0019] Preferably, the extrusion temperature is 160-250° C., and the extrusion rotation speed is 80-200 rpm.

[0020] The present invention provides a super-hydrophobic article, which is made by directly using the highly transparent super-hydrophobic polypropylene blend material described in the above technical solution through extrusion molding, injection molding, hollow molding, blow molding, compression molding, or calendering molding.

[0021] The present invention provides a highly transparent super-hydrophobic polypropylene blend material, and the raw materials for preparation include the following components by weight: 100 parts of polypropylene resin, 0.3-10 parts of solid paraffin, 0.03-2.5 parts of a compatibilizer, 0.03-1.5 parts of a micro-crosslinking modifier, 0.5-5 parts of a hydrophobic modifier, and 0.3-3 parts of an inorganic nanopowder. The present invention enables the blend material to have excellent hydrophobicity, high transmittance, and excellent surface solution adsorption effect under the joint action of the above materials. The experimental results show that the highly transparent super-hydrophobic polypropylene blend material provided by the present invention does not contain any fluoride or halide, and has higher biological safety; the inner surface of the pipette tip prepared by the above polypropylene blend material has a contact angle of ≥125° to pure water, a transmittance of ≥80% for natural light, and extremely low surface adsorption to ethanol solutions, 5X protein loading buffer, and toluidine blue solutions. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a surface SEM image of the injection molded sample of Example 1 of the present invention;

[0023] Figure 2 This is a cross-sectional SEM image of the injection-molded sample of Example 1 of the present invention;

[0024] Figure 3 This is a diagram showing the residual effect of using a pipette tip prepared using the raw material of Example 1 of the present invention to extract 5X protein loading buffer;

[0025] Figure 4 This is a diagram showing the residual effect of taking liquid from 5X protein loading buffer using a pipette tip prepared using the raw materials of Comparative Example 1 of the present invention. DETAILED DESCRIPTION

[0026] The present invention provides a highly transparent super-hydrophobic polypropylene blend material, wherein the raw materials for preparing the material include the following components in parts by mass:

[0027] 100 parts of polypropylene resin, 0.3-10 parts of solid paraffin, 0.03-2.5 parts of a compatibilizer, 0.03-1.5 parts of a micro-crosslinking modifier, 0.5-5 parts of a hydrophobic modifier and 0.3-3 parts of an inorganic nano powder.

[0028] The solid paraffin and hydrophobic modifier used in the present invention are in a dual-continuous phase structure with polypropylene in a microscopic thermodynamic phase structure under the joint action of a compatibilizer and a micro-crosslinking modifier. By constructing a dual-continuous phase structure, the present invention can avoid the formation of discontinuous phases such as sea island structures and core-shell structures by low surface energy substances during the blending process, and improve the dispersion concentration of low surface energy substances in the microscopic interface layer in the blending system; by utilizing the microfluidic channel in the dual-continuous phase structure, a melt blending grafting reaction is performed, which can not only improve the thermodynamic compatibility of the two phases in the blending system, but also further improve the dispersion concentration of low surface energy substances in the microscopic interface layer in the blending system, so that the material meets the application requirements of hydrophobicity and super-hydrophobicity.

[0029] The raw materials of the highly transparent super-hydrophobic polypropylene blend material provided by the present invention include 100 parts of polypropylene resin; in a specific embodiment, the grade of the polypropylene resin is M800E.

[0030] The raw materials of the highly transparent super-hydrophobic polypropylene blend material provided by the present invention include 0.3 to 10 parts of solid paraffin wax, and the specific amount can be 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2.0 parts, 2.1 parts, 2.2 parts, 2. 3 parts, 2.4 parts, 2.5 parts, 2.6 parts, 2.7 parts, 2.8 parts, 2.9 parts, 3.0 parts, 3.5 parts, 4.0 parts, 4.5 parts, 5.0 parts, 5.5 parts, 6.0 parts, 6.5 parts, 7.0 parts, 7.5 parts, 8.0 parts, 8.5 parts, 9.0 parts, 9.5 parts or 10.0 parts; the melting point of the solid paraffin is 50-70°C, preferably 60-70°C, and more preferably 65-70°C. The beneficial effect of the solid paraffin used in the present invention is that the main components of the solid paraffin are n-docosahexanes and n-octacosane, as a typical long-chain aliphatic hydrocarbon compound, it has a higher melting point and a lower solubility, not only has good hydrophobicity, but also has good biosafety compared with fluorine-containing compounds, more importantly, in the processing temperature range of 160-230°C, its melt viscosity is moderate, when blended with the polypropylene matrix material in the present invention, the shear field control such as the selection of the screw type of twin-screw extrusion, the control of the screw speed, the control of the injection pressure during injection molding can be realized in the microscopic phase structure. The paraffin phase exists in the form of a continuous phase in the polypropylene phase, so as to improve the content concentration of the paraffin phase with low surface energy in the interface layer, and further improve the hydrophobicity of the blend. At the same time, under the effect of the cross-linking modifiers such as dibenzoyl oxide, diisopropylbenzene peroxide, and azobisisobutyronitrile adopted in the present invention, paraffin can also further cross-link with polypropylene to improve the thermodynamic compatibility of paraffin and polypropylene.

[0031] The raw materials of the highly transparent super-hydrophobic polypropylene blend material provided by the present invention include 0.03 to 2.5 parts of a compatibilizer; the specific amount can be 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29 , 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2.0 parts, 2.1 parts, 2.2 parts, 2.3 parts, 2.4 parts or 2.5 parts; the compatibilizer is selected from at least one of ethylene propylene rubber (EPR), ethylene propylene rubber (EPDM), polyolefin elastomer (POE), styrene-butadiene block copolymer (SBS) and hydrogenated styrene-butadiene block copolymer (SEBS). The beneficial effect of the compatibilizer used in the present invention is that its molecular structure is similar to that of the polypropylene and paraffin in the main raw materials of the highly transparent super-hydrophobic polypropylene blend material provided by the present invention, while increasing the thermodynamic compatibility of polypropylene and paraffin, so as to further ensure that the paraffin phase exists in the polypropylene phase as a continuous phase during twin-screw extrusion and injection molding of the highly transparent super-hydrophobic polypropylene blend material.

[0032] The raw material of the highly transparent super-hydrophobic polypropylene blend material provided by the present invention includes 0.03 to 1.5 parts of a micro-crosslinking modifier, and the specific amount can be 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.25, 0.16, 0.17, 0.18, 0.19, 0.2, 0.2 5 parts, 0.30 parts, 0.35 parts, 0.40 parts, 0.45 parts, 0.5 parts, 0.55 parts, 0.60 parts, 0.65 parts, 0.70 parts, 0.75 parts, 0.8 parts, 0.9 parts, 1.0 parts, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts or 1.5 parts; the micro-crosslinking modifier is selected from at least one of dibenzoyl peroxide (BPO), diisopropylbenzene peroxide (DCP), and azobisisobutyronitrile (AIBN). The beneficial effect of the micro-crosslinking modifier used in the present invention is that the micro-crosslinking modifier can form a reaction activation point in the polypropylene and paraffin molecular chains, and through the crosslinking reaction between the activation points, to improve the thermodynamic compatibility of solid paraffin and polypropylene, to further ensure that the highly transparent super-hydrophobic polypropylene blend material exists in the form of a continuous phase in the polypropylene phase during twin-screw extrusion and injection molding.

[0033] The raw materials of the highly transparent super-hydrophobic polypropylene blend material provided by the present invention include 0.5 to 5 parts of a hydrophobic modifier; the specific amount can be 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2.0 parts, 2.1 parts, 2.2 parts, 2.3 parts 1, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9 or 5.0; The hydrophobic modifier is preferably selected from at least one of stearic acid, calcium stearate, barium stearate, zinc stearate, trimethoxysilane, dodecyltrimethoxysilane, tetradecyltrimethoxysilane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane, hexanethiol, dodecanethiol, tetradecylthiol, hexadecylthiol, octadecylthiol, eicosylthiol, and docosylthiol; more preferably selected from one or more of stearic acid, trimethoxysilane, tetradecyltrimethoxysilane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane, hexadecylthiol, octadecylthiol, eicosylthiol, and docosylthiol; most preferably selected from one or more of stearic acid, trimethoxysilane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane, hexadecylthiol, octadecylthiol, and eicosylthiol. In the present invention, the above-mentioned type of hydrophobic modifier used is similar to the solid paraffin molecule in the main structure of the molecular chain, and its main function is to cooperate with the solid paraffin to further improve the hydrophobic properties of the highly transparent super-hydrophobic polypropylene blend material provided by the present invention. At the same time, the refractive index is low, which can ensure the light transmittance of the final product.

[0034] The raw materials of the highly transparent super-hydrophobic polypropylene blend material provided by the present invention include 0.3-3 parts of inorganic nano powder; the dosage can be specifically 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2.0 parts, 2.1 parts, 2.2 parts, 2.3 parts, 2.4 parts, 2.5 parts, 2.6 parts, 2.7 parts, 2.8 parts, 2.9 parts or 3 parts; the inorganic nano powder is selected from at least one of nano silicon dioxide, nano titanium dioxide, nano zinc oxide and nano calcium carbonate, preferably nano silicon dioxide; the mesh number of the nano silicon dioxide is preferably 400-1000nm, more preferably 600-800nm. The effective purpose of the inorganic nanopowder used in the present invention is that the inorganic nanopowder itself has a certain hydrophobicity. During the blending process, it can synergistically act with the paraffin wax and the hydrophobic modifier used in the present invention to further improve the hydrophobic properties of the highly transparent super-hydrophobic polypropylene blend material provided by the present invention; at the same time, the inorganic nanopowder used can also act as a polypropylene nucleating agent, by further refining the grain size during the crystallization process of polypropylene, so as to further improve the light transmittance of the final product.

[0035] In a specific embodiment, the raw materials for preparing the highly transparent super-hydrophobic polypropylene blend material provided by the present invention include:

[0036] 100 parts of polypropylene resin, 0.8 parts of solid paraffin, 0.05 parts by mass of dicumyl peroxide, 0.12 parts by mass of hydrogenated styrene-butadiene block copolymer (SEBS), 1.0 parts by mass of n-hexadecylmercaptan, 1.0 parts by mass of octadecyltrimethoxysilane and 0.6 parts by mass of silicon dioxide having a particle size of 600 to 800 nm;

[0037] Or comprising 100 parts by mass of polypropylene resin, 2.0 parts by mass of solid paraffin, 0.05 parts by mass of dicumyl peroxide (DCP), 0.4 parts by mass of hydrogenated styrene-butadiene block copolymer (SEBS), 1.0 parts by mass of n-hexadecyl mercaptan, 1.0 parts by mass of octadecyltrimethoxysilane, and 1.0 parts by mass of silicon dioxide;

[0038] Or including 100 parts by mass of polypropylene resin, 2.0 parts by mass of solid paraffin, 0.05 parts by mass of dicumyl peroxide (DCP), 0.2 parts by mass of hydrogenated styrene-butadiene block copolymer (SEBS), 0.2 parts by mass of polyolefin elastomer (POE) (brand: 6102FL, origin: ExxonMobil (Huizhou) Chemical Co., Ltd.), 1.0 parts by mass of n-hexadecyl mercaptan, 1.0 parts by mass of octadecyltrimethoxysilane, and 0.8 parts by mass of silicon dioxide;

[0039] Or including 100 parts by mass of polypropylene resin, 1.6 parts by mass of solid paraffin, 0.05 parts by mass of dibenzoyl peroxide (BPO) (brand: AR, origin: Sinopharm Chemical Reagent Co., Ltd.), 0.4 parts by mass of polyolefin elastomer (POE) (brand: 6102FL, origin: ExxonMobil (Huizhou) Chemical Co., Ltd.), 0.8 parts by mass of n-hexadecyl mercaptan, 0.8 parts by mass of octadecyltrimethoxysilane, and 0.8 parts by mass of silica.

[0040] The present invention provides a method for preparing the highly transparent super-hydrophobic polypropylene blend material described in the above technical solution, comprising the following steps:

[0041] The polypropylene resin, solid paraffin, a compatibilizer, a micro-crosslinking modifier, a hydrophobic modifier and an inorganic nano-powder are mixed, discharged after 5 to 30 minutes, extruded, cooled and granulated, and dried to obtain a highly transparent and super-hydrophobic polypropylene blend material.

[0042] In the present invention, the extrusion temperature is 160-250° C., and the extrusion rotation speed is 80-200 rpm.

[0043] The highly transparent super-hydrophobic polypropylene blend material is placed in a precision injection molding machine for injection molding to obtain an injection molded product; the injection molding temperature is 215-225° C., and the injection molding pressure is 0.75-0.85 MPa; in a specific embodiment, the injection molding temperature is 220° C., and the injection molding pressure is 0.8 MPa.

[0044] The greatest beneficial effect of the present invention is that paraffin, a long-chain aliphatic hydrocarbon compound with a high melting point and low solubility, is used as the main hydrophobic modifier, and the shear field is controlled by selecting the screw type of twin-screw extrusion during the blending process, controlling the screw speed, and controlling the injection pressure during injection molding, so as to achieve the paraffin phase in the form of a continuous phase in the polypropylene phase in the microscopic phase structure, avoiding the formation of non-continuous phase structures such as sea island structures and core-shell structures by the paraffin during the blending process, so as to maximize the dispersion concentration of the paraffin phase with low surface energy in the interface layer; at the same time, a micro-crosslinking modifier is used to form reaction activation points in the molecular chains of polypropylene and paraffin, and through the crosslinking reaction between the activation points, the thermodynamic compatibility of paraffin and polypropylene is improved, so as to further ensure high transparency and super hydrophobicity. Water-based polypropylene blend material exists in the form of a continuous phase in the polypropylene phase during twin-screw extrusion and injection molding; Utilizing the synergistic effect of a hydrophobic modifier with a lower refractive index and solid paraffin, while further improving the hydrophobic properties of a high-transparent super-hydrophobic polypropylene blend material provided by the present invention, the light transmittance of the final product is ensured; Further, using an inorganic nano powder having both hydrophobicity and nucleation properties, utilizing the synergistic effect of the solid paraffin and hydrophobic modifier used in the present invention, the hydrophobic properties of a high-transparent super-hydrophobic polypropylene blend material provided by the present invention are further improved; The inorganic nano powder used simultaneously can also play the role of a polypropylene nucleating agent, by further refining the grain size in the crystallization process of polypropylene, to further improve the light transmittance of the final product. The present invention has the advantages of simple raw material production process control, strong hydrophobic durability of the obtained product, and is particularly suitable for the preparation of hydrophobic biochemical consumables with higher requirements for biosafety.

[0045] The preparation method of conventional hydrophobic material, mainly focuses on the synthesis of low surface energy material, and utilizes it to construct micron, nanometer-level rough structure in interface layer to realize, the means adopted mainly focus on the technical means such as surface coating method, surface chemical treatment, the maximum limitation of this means is that only the surface of material can be processed, it is difficult to go deep into the inside of material, therefore, the use durability of the hydrophobic material prepared by this method is not good; meanwhile, when the surface modification of material is carried out, it is necessary to have a larger, open outer surface, therefore for the relatively fine parts (such as the inner surface of ultra-small liquid transfer tip) etc. of structure, it is difficult to utilize surface modification method to carry out super-hydrophobic treatment. In the present invention, by the mode of disposable melt blending, utilizing the shearing action of twin screw extruder screw in blending process, the effect of shearing field such as injection pressure shearing during injection molding, to realize low surface energy material (paraffin, hydrophobic modifier, etc.) in microscopic phase structure in polypropylene basic phase in the form of continuous phase existence, self-construct nanometer-level rough structure. Therefore, it can be seen that the greatest advantage of the present invention is that, through the melt-blending extrusion method, the synthesis, dispersion and self-construction of nano-scale rough structures of low surface energy materials can be achieved at one time; and compared with the surface modification method that only forms a hydrophobic interface layer on the outer surface of the material, the prepared material has uniform performance in the overall composition, so the durability of the material and the stability of product performance are greatly improved.

[0046] The present invention also provides a super-hydrophobic article, which is made by directly using the highly transparent super-hydrophobic polypropylene blend material described in the above technical solution through extrusion molding, injection molding, hollow molding, blow molding, compression molding or calendering molding.

[0047] The super-hydrophobic component provided by the present invention is particularly suitable for continuous production of fine structural components requiring hydrophobic properties. The present invention preferably performs plasma sputtering treatment and / or electrostatic negative charge sputtering treatment on the surface of the super-hydrophobic component to further improve the hydrophobic properties of the component.

[0048] The highly transparent super-hydrophobic polypropylene blend material provided by the present invention has high light transmittance, is fluorine-free and halogen-free, and is suitable for preparing biochemical pipette tips.

[0049] In order to further illustrate the present invention, a highly transparent super-hydrophobic polypropylene blend material provided by the present invention and its preparation method and application are described in detail below in conjunction with embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0050] Example 1

[0051] A highly transparent super-hydrophobic polypropylene blend material comprises the following steps:

[0052] 1) Weigh 100 parts by mass of polypropylene resin (brand: M800E, origin: Sinopec Shanghai Petrochemical Co., Ltd., the same below), 1.8 parts by mass of solid paraffin (melting point: 65°C-70°C, origin: Sinopharm Chemical Reagent Co., Ltd., the same below), 0.05 parts by mass of diisopropylbenzene peroxide (DCP) (brand: AR, origin: Sinopharm Chemical Reagent Co., Ltd., the same below), 0.12 parts by mass of hydrogenated styrene-butadiene block copolymer (SEBS) (brand: G6152E, origin: Kraton Polymer Trading (Shanghai) Co., Ltd., the same below), 1.0 parts by mass of n-decyl Hexathiol (brand name: AR, origin: Sinopharm Chemical Reagent Co., Ltd., the same below), 1.0 parts by mass of octadecyltrimethoxysilane (brand name: AR, origin: Sinopharm Chemical Reagent Co., Ltd., the same below), and 0.6 parts by mass of silicon dioxide (particle size: 600-800 mesh, the same below, origin: Sinopharm Chemical Reagent Co., Ltd., the same below) were placed in a high-speed mixer (model: SHR-5, manufacturer: Zhangjiagang Huanfeng Machinery Factory, the same below), mixed for 5 minutes, and then taken out and placed in the hopper of a twin-screw extruder (model: CTE-20, manufacturer: Nanjing Coperion Co., Ltd., the same below);

[0053] 2) Setting the feeding rate of the feeder of the twin-screw extruder to 200 rpm, setting the screw temperature of the twin-screw extruder from the feed hopper to the die to 160-230° C.; setting the screw speed of the screw extruder to 140 rpm;

[0054] 3) The melt mixture of polypropylene resin / solid paraffin / compatibilizer / micro-crosslinking modifier / hydrophobic modifier / inorganic nano-powder extruded by the screw extruder is cooled and pelletized, and then dried to obtain a highly transparent super-hydrophobic polypropylene blend material described in the present invention.

[0055] The highly transparent super-hydrophobic polypropylene blend material prepared in Example 1 was used in an injection molding machine (model: Babyplast 6 / 10P, origin: Cronoplast Company, Spain, the same below), with the injection molding temperature set to 220° C. and the injection molding pressure set to 0.8 MPa, to prepare a sample with a thickness×width×length of 1 mm×40 mm×100 mm. The test results of the sample are shown in Table 1.

[0056] Figure 1 and Figure 2 The following are SEM images of the surface and cross section of the injection molded sample of Example 1 of the present invention. Figure 1It can be seen from the surface SEM image that, under the combined action of the micro-crosslinking modifier and the compatibilizer, the surface layer of the injection molded sample of the highly transparent super-hydrophobic polypropylene blend material prepared by the technical solution provided in Example 1 is dispersed in a continuous structure similar to a dendritic network, which is completely different from the common island-like discontinuous structure dispersion formed by conventional technical means; Figure 2 It can be seen from the SEM image of the cross section that the prepared highly transparent super-hydrophobic polypropylene blend material is still a uniform phase inside. The greatest advantage of the above two microstructures is that the highly transparent super-hydrophobic polypropylene blend material prepared by this technology can not only realize the synthesis and dispersion of low surface energy substances (paraffin, hydrophobic modifier), and the self-construction of nano-scale rough structures on the surface of the product at one time; but also the prepared product material has uniform performance in the overall composition, so the durability of the material and the stability of product performance are greatly improved.

[0057] Embodiment 2:

[0058] A highly transparent super-hydrophobic polypropylene blend material comprises the following steps:

[0059] 1) Weigh 100 parts by mass of polypropylene resin, 2.0 parts by mass of solid paraffin, 0.05 parts by mass of dicumyl peroxide (DCP), 0.4 parts by mass of hydrogenated styrene-butadiene block copolymer (SEBS), 1.0 parts by mass of n-hexadecylmercaptan, 1.0 parts by mass of octadecyltrimethoxysilane, and 1.0 parts by mass of silicon dioxide, place them in a high-speed mixer, mix for 5 minutes, take them out, and place them in the feeding hopper of a twin-screw extruder;

[0060] 2) Setting the feeding rate of the feeder of the twin-screw extruder to 200 rpm, setting the screw temperature of the twin-screw extruder from the feed hopper to the die to 160-230° C.; setting the screw speed of the screw extruder to 140 rpm;

[0061] 3) The melt mixture of polypropylene resin / solid paraffin / compatibilizer / micro-crosslinking modifier / hydrophobic modifier / inorganic nano powder extruded by the screw extruder is cooled, pelletized, and dried to obtain a highly transparent super-hydrophobic polypropylene blend material.

[0062] The highly transparent super-hydrophobic polypropylene blend material prepared in Example 2 was used in an injection molding machine with an injection molding temperature of 220° C. and an injection molding pressure of 0.8 MPa to prepare a sample sheet with a thickness×width×length of 1 mm×40 mm×100 mm. The test results of the sample sheet are shown in Table 1.

[0063] Embodiment 3:

[0064] A highly transparent super-hydrophobic polypropylene blend material comprises the following steps:

[0065] 1) Weigh 100 parts by mass of polypropylene resin, 2.0 parts by mass of solid paraffin, 0.05 parts by mass of dicumyl peroxide (DCP), 0.2 parts by mass of hydrogenated styrene-butadiene block copolymer (SEBS), 0.2 parts by mass of polyolefin elastomer (POE) (brand: 6102FL, origin: ExxonMobil (Huizhou) Chemical Co., Ltd., the same below), 1.0 parts by mass of n-hexadecyl mercaptan, 1.0 parts by mass of octadecyltrimethoxysilane, and 0.8 parts by mass of silicon dioxide, place them in a high-speed mixer, mix for 5 minutes, take them out, and place them in the feeding hopper of a twin-screw extruder;

[0066] 2) Setting the feeding rate of the feeder of the twin-screw extruder to 200 rpm, setting the screw temperature of the twin-screw extruder from the feed hopper to the die to 160-230° C.; setting the screw speed of the screw extruder to 140 rpm;

[0067] 3) The melt mixture of polypropylene resin / solid paraffin / compatibilizer / micro-crosslinking modifier / hydrophobic modifier / inorganic nano-powder extruded by the screw extruder is cooled, pelletized, and dried to obtain a highly transparent super-hydrophobic polypropylene blend material.

[0068] The highly transparent super-hydrophobic polypropylene blend material prepared in Example 3 was used in an injection molding machine with an injection molding temperature of 220° C. and an injection molding pressure of 0.8 MPa to prepare a sample sheet with a thickness×width×length of 1 mm×40 mm×100 mm. The test results of the sample sheet are shown in Table 1.

[0069] Embodiment 4:

[0070] A highly transparent super-hydrophobic polypropylene blend material comprises the following steps:

[0071] 1) Weigh 100 parts by mass of polypropylene resin, 1.6 parts by mass of solid paraffin, 0.05 parts by mass of dibenzoyl peroxide (BPO) (brand: AR, origin: Sinopharm Chemical Reagent Co., Ltd., the same below), 0.4 parts by mass of polyolefin elastomer (POE) (brand: 6102FL, origin: ExxonMobil (Huizhou) Chemical Co., Ltd., the same below), 0.8 parts by mass of n-hexadecyl mercaptan, 0.8 parts by mass of octadecyltrimethoxysilane, and 0.8 parts by mass of silicon dioxide, place them in a high-speed mixer, mix for 5 minutes, take them out, and place them in the feeding hopper of a twin-screw extruder;

[0072] 2) Setting the feeding rate of the feeder of the twin-screw extruder to 200 rpm, setting the screw temperature of the twin-screw extruder from the feed hopper to the die to 160-230° C.; setting the screw speed of the screw extruder to 140 rpm;

[0073] 3) The melt mixture of polypropylene resin / solid paraffin / compatibilizer / micro-crosslinking modifier / hydrophobic modifier / inorganic nano-powder extruded by the screw extruder is cooled and pelletized, and then dried to obtain a highly transparent super-hydrophobic polypropylene blend material described in the present invention.

[0074] The highly transparent super-hydrophobic polypropylene blend material prepared in Example 4 was used in an injection molding machine with an injection molding temperature of 220° C. and an injection molding pressure of 0.8 MPa to prepare a sample sheet with a thickness×width×length of 1 mm×40 mm×100 mm. The test results of the sample sheet are shown in Table 1.

[0075] The testing process and method of the samples prepared in the above embodiments are as follows:

[0076] The raw materials prepared in each embodiment were placed in a precision injection molding machine, the injection temperature was set to 220°C, the injection pressure was set to 0.8 MPa, and a sample with a thickness × width × length of 1 mm × 40 mm × 100 mm was injected. The sample was then taken out, cleaned in an ultrasonic cleaner, and dried at room temperature for later use.

[0077] Comparative Example 1:

[0078] The method for preparing the sample described in Comparative Example 1 comprises the following steps:

[0079] 100 parts by mass of polypropylene resin was weighed and placed in an injection molding machine, with the injection temperature set at 220°C and the injection pressure set at 0.8 MPa to prepare a sample with a thickness×width×length of 1 mm×40 mm×100 mm. The test results of the sample are shown in Table 1.

[0080] Comparative Example 2:

[0081] The hydrophobic polypropylene blend material described in Comparative Example 2 comprises the following steps:

[0082] 1) Weigh 100 parts by mass of polypropylene resin, 0.05 parts by mass of dicumyl peroxide (DCP), 0.12 parts by mass of hydrogenated styrene-butadiene block copolymer (SEBS), 1.0 parts by mass of n-hexadecylmercaptan, 1.0 parts by mass of octadecyltrimethoxysilane, and 0.6 parts by mass of silicon dioxide, place them in a high-speed mixer, mix for 5 minutes, take them out, and place them in the feeding hopper of a twin-screw extruder;

[0083] 2) Setting the feeding rate of the feeder of the twin-screw extruder to 200 rpm, setting the screw temperature of the twin-screw extruder from the feed hopper to the die to 160-230° C.; setting the screw speed of the screw extruder to 140 rpm;

[0084] 3) The melt mixture of polypropylene resin / compatibilizer / micro-crosslinking modifier / hydrophobic modifier / inorganic nano-powder extruded by the screw extruder is cooled, pelletized, and dried to obtain a highly transparent super-hydrophobic polypropylene blend material described in the present invention.

[0085] The highly transparent super-hydrophobic polypropylene blend material prepared in Example 1 was used in an injection molding machine with an injection molding temperature of 220° C. and an injection molding pressure of 0.8 MPa to prepare a sample sheet with a thickness×width×length of 1 mm×40 mm×100 mm. The test results of the sample sheet are shown in Table 1.

[0086] Comparative Example 3:

[0087] The hydrophobic polypropylene blend material described in Comparative Example 3 comprises the following steps:

[0088] 1) Weigh 100 parts by mass of polypropylene resin, 1.8 parts by mass of solid paraffin, 0.12 parts by mass of hydrogenated styrene-butadiene block copolymer (SEBS), 1.0 parts by mass of n-hexadecylmercaptan, 1.0 parts by mass of octadecyltrimethoxysilane, and 0.6 parts by mass of silicon dioxide, place them in a high-speed mixer, mix for 5 minutes, take them out, and place them in the feeding hopper of a twin-screw extruder;

[0089] 2) Setting the feeding rate of the feeder of the twin-screw extruder to 200 rpm, setting the screw temperature of the twin-screw extruder from the feed hopper to the die to 160-230° C.; setting the screw speed of the screw extruder to 140 rpm;

[0090] 3) The melt mixture of polypropylene resin / solid paraffin / compatibilizer / hydrophobic modifier / inorganic nano powder extruded by the screw extruder is cooled, pelletized, and dried to obtain a highly transparent super-hydrophobic polypropylene blend material described in the present invention.

[0091] The highly transparent super-hydrophobic polypropylene blend material prepared in Example 1 was used in an injection molding machine with an injection molding temperature of 220° C. and an injection molding pressure of 0.8 MPa to prepare a sample sheet with a thickness×width×length of 1 mm×40 mm×100 mm. The test results of the sample sheet are shown in Table 1.

[0092] Comparative Example 4:

[0093] The hydrophobic polypropylene blend material described in Comparative Example 4 comprises the following steps:

[0094] 1) Weigh 100 parts by mass of polypropylene resin, 1.8 parts by mass of solid paraffin, 0.05 parts by mass of dicumyl peroxide (DCP), 0.12 parts by mass of hydrogenated styrene-butadiene block copolymer (SEBS), and 0.6 parts by mass of silicon dioxide, place them in a high-speed mixer, mix for 5 minutes, then take them out and place them in the feeding hopper of a twin-screw extruder;

[0095] 2) Setting the feeding rate of the feeder of the twin-screw extruder to 200 rpm, setting the screw temperature of the twin-screw extruder from the feed hopper to the die to 160-230° C.; setting the screw speed of the screw extruder to 140 rpm;

[0096] 3) The melt mixture of polypropylene resin / solid paraffin / compatibilizer / micro-crosslinking modifier / inorganic nano-powder extruded by the screw extruder is cooled, pelletized, and dried to obtain a highly transparent super-hydrophobic polypropylene blend material described in the present invention.

[0097] The highly transparent super-hydrophobic polypropylene blend material prepared in Example 1 was used in an injection molding machine with an injection molding temperature of 220° C. and an injection molding pressure of 0.8 MPa to prepare a sample sheet with a thickness×width×length of 1 mm×40 mm×100 mm. The test results of the sample sheet are shown in Table 1.

[0098] For the test of the contact angle of the blend system: the test is carried out in accordance with GB / T 30447-2013 "Nanofilm Contact Angle Measurement Method". At room temperature, the test sample is placed horizontally under the objective lens of the contact angle meter, and the contact angle of the blend system to pure water is tested with ultrapure water.

[0099] For the test of the light transmittance of the blending system: the test is carried out in accordance with GB / T 2410-2008 "Measurement Methods for Optical Properties of Plastic Transparent Materials". At room temperature, the test sample is placed in a light transmittance / haze meter to measure the light transmittance of the blending system.

[0100] Test for the adsorption effect of the surface solution of the blend system: The test was carried out in accordance with GB / T 9264-2012 "Evaluation of Sag Resistance of Paints and Varnishes". At room temperature, after drawing a 5mm×5mm grid on the surface of the test sample, the test sample was vertically immersed in the solution to be tested (75% ethanol solution, 5X protein loading buffer, toluidine blue solution) for 1 min and then taken out. After standing for 5 s in the vertical state, a photo was taken. Using the drawn grid, the residual area ratio S of the solution on the surface of the test sample was calculated. When the residual area ratio S≤0.5%, it was judged as no residue; when 0.5%<S≤1%, it was judged as micro residue; when 1%<S≤5%, it was judged as extremely small residue; when 5%<S≤10%, it was judged as small residue; when 10%<S≤50%, it was judged as residue; when 50%<S≤85%, it was judged as large residue; when 85%<S, it was judged as complete residue.

[0101] Table 1 Test results of the sample pieces

[0102]

[0103]

[0104] The high-transparency superhydrophobic polypropylene blend materials prepared in Example 1 and Comparative Example 1 were made into pipette tips, and their adsorption of 5X protein loading buffer was tested. The test results are shown in Figure 3 and Figure 4 . By comparing Figure 3 and Figure 4 , it can be seen that: The pipette tip prepared from the high-transparency superhydrophobic polypropylene blend material prepared by the technical solution of Example 1 has a high transparency. After pipetting 5X protein loading buffer, there is only an extremely small amount of protein loading buffer residue at the tip of the pipette tip inside the pipette tip, and the pipetting accuracy is extremely high; while the pipette tip prepared by the technical solution of Comparative Example 1, although it also has a high transparency, after pipetting 5X protein loading buffer, serious wall sticking residue of the protein loading buffer appears throughout the inside of the pipette tip, and the pipetting accuracy is extremely poor.

[0105] It can be seen from the above embodiments that the present invention provides a highly transparent super-hydrophobic polypropylene blend material, and the raw materials for preparation include the following components in parts by mass: 100 parts of polypropylene resin, 0.3-10 parts of solid paraffin, 0.03-2.5 parts of a compatibilizer, 0.03-1.5 parts of a micro-crosslinking modifier, 0.5-5 parts of a hydrophobic modifier, and 0.3-3 parts of an inorganic nanopowder. The present invention makes the blend material have excellent hydrophobicity, high transmittance, and excellent surface solution adsorption effect under the joint action of the above materials. The experimental results show that the highly transparent super-hydrophobic polypropylene blend material provided by the present invention does not contain any fluoride or halide, and has higher biological safety; the inner surface of the pipette tip prepared from the above polypropylene blend material is subjected to a contact test, and the results show that the contact angle of pure water is ≥125°, the transmittance of natural light is ≥80%, and the surface adsorption of ethanol solutions, 5X protein loading buffer, and toluidine blue solutions is extremely low.

[0106] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A highly transparent super-hydrophobic polypropylene blend material, wherein the raw materials for preparation include the following components in parts by mass: 100 parts of polypropylene resin, 0.3-10 parts of solid paraffin, 0.03-2.5 parts of a compatibilizer, 0.03-1.5 parts of a micro-crosslinking modifier, 0.5-5 parts of a hydrophobic modifier and 0.3-3 parts of an inorganic nano powder.

2. The highly transparent super-hydrophobic polypropylene blend material according to claim 1, characterized in that: The melting point of the solid paraffin is 50-70°C.

3. The highly transparent super-hydrophobic polypropylene blend material according to claim 1, characterized in that: The solid paraffin is 0.8 to 2 parts.

4. The highly transparent super-hydrophobic polypropylene blend material according to claim 1, characterized in that: The compatibilizer is selected from at least one of ethylene propylene diene monomer rubber, ethylene propylene diene monomer rubber, polyolefin elastomer, styrene-butadiene block copolymer and hydrogenated styrene-butadiene block copolymer.

5. The highly transparent super-hydrophobic polypropylene blend material according to claim 1, characterized in that: The hydrophobic modifier is selected from at least one of stearic acid, calcium stearate, barium stearate, zinc stearate, trimethoxysilane, dodecyltrimethoxysilane, tetradecyltrimethoxysilane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane, n-hexylmercaptan, n-dodecylmercaptan, n-tetradecylmercaptan, n-hexadecylmercaptan, n-octadecylmercaptan, n-eicosylmercaptan, and n-docosylmercaptan.

6. The highly transparent super-hydrophobic polypropylene blend material according to claim 1, characterized in that: The inorganic nano powder is selected from at least one of nano silicon dioxide, nano titanium dioxide, nano zinc oxide and nano calcium carbonate; The micro-crosslinking modifier is selected from at least one of dibenzoyl peroxide, dicumyl peroxide, and azobisisobutyronitrile.

7. The highly transparent super-hydrophobic polypropylene blend material according to claim 1, characterized in that: The raw materials for preparing the highly transparent super-hydrophobic polypropylene blend material include: 100 parts of polypropylene resin, 0.8 parts of solid paraffin, 0.05 parts of dicumyl peroxide, 0.12 parts of hydrogenated styrene-butadiene block copolymer, 1.0 parts of n-hexadecylmercaptan, 1.0 parts of octadecyltrimethoxysilane and 0.6 parts of silicon dioxide; or 100 parts of polypropylene resin, 2.0 parts of solid paraffin, 0.05 parts of dicumyl peroxide, 0.4 parts of hydrogenated styrene-butadiene block copolymer, 1.0 parts of n-hexadecylmercaptan, 1.0 parts of octadecyltrimethoxysilane and 1.0 parts of silicon dioxide; Or 100 parts of polypropylene resin, 2.0 parts of solid paraffin, 0.05 parts of dicumyl peroxide, 0.2 parts of hydrogenated styrene-butadiene block copolymer, 0.2 parts of polyolefin elastomer, 1.0 parts of n-hexadecyl mercaptan, 1.0 parts of octadecyltrimethoxysilane and 0.8 parts of silicon dioxide; Or 100 parts of polypropylene resin, 1.6 parts of solid paraffin, 0.05 parts of dibenzoyl peroxide, 0.4 parts of polyolefin elastomer, 0.8 parts of n-hexadecyl mercaptan, 0.8 parts of octadecyltrimethoxysilane and 0.8 parts of silicon dioxide.

8. A method for preparing the highly transparent super-hydrophobic polypropylene blend material according to any one of claims 1 to 7, comprising the following steps: The polypropylene resin, solid paraffin, a compatibilizer, a micro-crosslinking modifier, a hydrophobic modifier and an inorganic nano powder are mixed, discharged after 5 to 30 minutes, extruded, cooled and granulated, and dried to obtain a highly transparent super-hydrophobic polypropylene blend material.

9. The preparation method according to claim 8, characterized in that: The extrusion temperature is 160 to 250° C., and the extrusion rotation speed is 80 to 200 rpm.

10. A super-hydrophobic article, which is made by directly using the highly transparent super-hydrophobic polypropylene blend material according to any one of claims 1 to 7 by extrusion molding, injection molding, hollow molding, blow molding, compression molding, or calendering molding.

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