CN115850861A - A kind of polypropylene hydrophobic material and its preparation method and application - Google Patents

Abstract

The invention belongs to the field of polymer materials, in particular to a polypropylene hydrophobic material and its preparation method and application. The polypropylene hydrophobic material provided by the present invention is made of raw materials through melt blending and extrusion, and the raw materials include: 100 parts of polypropylene resin base material, 0.5-30 parts of polypropylene-fluorocarbon resin , 0.1 to 20 parts of a diffusing agent, 0.1 to 10 parts of a hydrophobic stabilizer, 5 to 20 parts of a hydrophobic graft modifier, and 0.1 to 5 parts of a hydrophobic graft compatibilizer; the polypropylene in the polypropylene-fluorocarbon resin Resin and fluorocarbon resin are bicontinuous phase structures in microscopic thermodynamic phase structure. The polypropylene hydrophobic material provided by the invention is obtained through a melt blending extrusion process, the process is simple, continuous production can be realized, the internal and external structure and performance of the material are uniform, and it is especially suitable for the production of fine structural parts.

Description

A kind of polypropylene hydrophobic material and its preparation method and application

technical field

The invention belongs to the field of polymer materials, in particular to a polypropylene hydrophobic material and its preparation method and application.

Background technique

The hydrophobicity of solid materials is the special wettability of solid materials to liquids. Generally, water droplets are spherical on the solid surface, with a contact angle greater than 120 degrees and a roll angle less than 10 degrees. Because water droplets can carry away pollutants when they roll off the surface of hydrophobic materials, the surface of the material is kept clean. Therefore, the hydrophobic material has multiple characteristics such as waterproof, anti-corrosion, anti-icing and anti-adhesion. Scholars from various countries have successively studied the properties of hydrophobic materials through wet chemical methods, plasma irradiation, sol-gel methods, layer-by-layer self-assembly methods, etching methods, chemical vapor deposition methods, physical vapor deposition methods, hydrothermal methods, and template methods. composition and structure.

Polypropylene (PP) is one of the five general-purpose resins. Due to its good processability and high bending and tensile strength, it is widely used in packaging production, home appliance manufacturing, and daily necessities. Research and preparation of hydrophobic polypropylene is an important aspect of functional modification of polypropylene. Coating method and surface treatment method are common methods to prepare highly hydrophobic polypropylene materials, but these methods have many disadvantages, such as complex process, harsh modification conditions, etc.; solution coating modification, most of the solvents used are toxic reagents, Harmful to the human body, and the waste water produced is easy to cause environmental pollution; the reagents used for coating are expensive, and the production cost is also high, so it cannot meet the needs of industrialized mass production; the surface treatment method is to etch on the surface of polypropylene materials Micro-nano rough structure, while grafting long-chain polymers with low surface energy, although the contact angle of the prepared sheet is very high, even reaching super-hydrophobicity, but the complicated process limits its development.

Contents of the invention

In view of this, the object of the present invention is to provide a polypropylene hydrophobic material and its preparation method and application. The polypropylene hydrophobic material provided by the present invention is obtained through a melt blending extrusion process. The process is simple and continuous production can be realized. , The internal and external structure and performance of the material are uniform, especially suitable for the production of fine structural parts.

The invention provides a polypropylene hydrophobic material, which is made of raw materials through melt blending and extrusion, and in parts by mass, the raw materials include:

The polypropylene resin in the polypropylene-fluorocarbon resin and the fluorocarbon resin are bicontinuous phase structures on the microscopic thermodynamic phase structure; the mass ratio of the polypropylene resin in the polypropylene-fluorocarbon resin to the fluorocarbon resin is 100: (80-150).

Preferably, the fluorocarbon resin is polyvinylidene fluoride and tetrafluoroethylene-hexafluoropropylene copolymer; the mass ratio of polyvinylidene fluoride and tetrafluoroethylene-hexafluoropropylene copolymer is 1:(0.5～2 ).

Preferably, the diffusing agent is one or more of polyvinyl chloride, chlorinated polyethylene and chlorosulfonated polyethylene.

Preferably, the hydrophobic stabilizer is polydimethylsiloxane, triisopropylsilane, trifluoropropylmethyldimethoxysilane, polyperfluoroalkylsiloxane, fluoroalkylsilane, One or more of heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltriethoxysilane.

Preferably, the hydrophobic graft modifier is 2-(trifluoromethyl)acrylic acid, perfluoroalkyl ethyl methacrylic acid, polymethacrylic acid (N-perfluorocycloalkyl)amide ester, polyacrylic acid One or more of perfluorooctyl methyl ester and fluorinated isocyanate.

Preferably, the hydrophobic graft compatibilizer is maleic anhydride grafted polyethylene resin, maleic anhydride grafted polypropylene resin, maleic anhydride grafted chlorinated polyethylene resin and maleic anhydride grafted chlorinated polypropylene One or more of the resins.

The present invention provides a kind of preparation method of polypropylene hydrophobic material described in above-mentioned technical scheme, comprises the following steps:

The polypropylene resin base material, polypropylene-fluorocarbon resin, diffusing agent, hydrophobic stabilizer, hydrophobic graft modifier and hydrophobic graft compatibilizer are melt-blended in a screw extruder and then extruded to obtain a polymer Acrylic hydrophobic material.

Preferably, the screw extruder is sequentially provided with a main feeding port, a first feeding port and a second feeding port along the material extrusion direction; during the preparation process, the polypropylene resin base material, polypropylene-fluorocarbon Resin, diffusion agent and hydrophobic graft compatibilizer are added into the screw extruder through the main feed port, the hydrophobic graft modifier is added through the first feed port, and the hydrophobic stabilizer is fed through the The second feeding port is added.

The present invention provides a hydrophobic product, and the material of the hydrophobic product is the polypropylene hydrophobic material described in the above technical solution.

Preferably, the surface of the hydrophobic article is treated by plasma sputtering and/or electrostatic negative charge sputtering.

Compared with the prior art, the invention provides a polypropylene hydrophobic material and its preparation method and application. The polypropylene hydrophobic material provided by the present invention is made of raw materials through melt blending and extrusion, and the raw materials include: 100 parts of polypropylene resin base material, 0.5-30 parts of polypropylene-fluorocarbon resin , 0.1 to 20 parts of a diffusing agent, 0.1 to 10 parts of a hydrophobic stabilizer, 5 to 20 parts of a hydrophobic graft modifier, and 0.1 to 5 parts of a hydrophobic graft compatibilizer; the polypropylene in the polypropylene-fluorocarbon resin The resin and the fluorocarbon resin have a bicontinuous phase structure on the microscopic thermodynamic phase structure; the mass ratio of the polypropylene resin to the fluorocarbon resin in the polypropylene-fluorocarbon resin is 100:(80-150). The present invention can avoid discontinuous phases such as sea-island structure and core-shell structure formed by low surface energy substances in the blending process by constructing a double continuous phase structure, and improve the dispersion concentration of low surface energy substances in the microscopic interface layer in the blending system; by using The microfluidic channel in the bicontinuous phase structure, and the melt blending grafting reaction can not only improve the thermodynamic compatibility of the two phases in the blend system, but also further improve the low surface energy substances in the blend system at the micro interface. The dispersion concentration of the layer can make the material meet the application requirements of hydrophobic and superhydrophobic. In addition, the polypropylene hydrophobic material provided by the present invention can be directly prepared into finished parts by processes such as extrusion molding, injection molding, hollow molding, blow molding, compression molding, calendering, etc., and is especially suitable for fine structural parts that require hydrophobic properties Continuous production. In addition, in the preferred technical solution provided by the present invention, plasma sputtering treatment and/or electrostatic negative charge sputtering treatment can also be performed on the surface of the workpiece, so as to further improve the hydrophobic performance of the workpiece. Experimental results show that: the water contact angle of the polypropylene hydrophobic material provided by the present invention is more than or equal to 118°, and the water contact angle of the surface-treated workpiece can reach up to 135°.

Description of drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only It is an embodiment of the present invention, and those skilled in the art can also obtain other drawings according to the provided drawings without creative work.

Fig. 1 is the surface SEM image of the injection molded product provided by Example 1 of the present invention at room temperature;

Fig. 2 is a SEM image of the surface of the injection molded product provided in Comparative Example 1 of the present invention at room temperature.

Detailed ways

The following clearly and completely describes the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

The invention provides a polypropylene hydrophobic material, which is made of raw materials through melt blending and extrusion, and in parts by mass, the raw materials include:

In the polypropylene hydrophobic material provided by the present invention, the polypropylene resin base material is preferably a polypropylene resin with a grade of M800E, and the polypropylene resin of the above grade is provided by Sinopec Shanghai Petrochemical Co., Ltd.

In the polypropylene hydrophobic material provided by the present invention, the polypropylene-fluorocarbon resin is made of polypropylene resin and fluorocarbon resin through melt blending and extrusion, and the polypropylene resin and fluorocarbon resin in the polypropylene-fluorocarbon resin Fluorocarbon resin is a bicontinuous phase structure in the microscopic thermodynamic phase structure.

In the polypropylene hydrophobic material provided by the present invention, the specific grade of the polypropylene resin in the polypropylene-fluorocarbon resin is preferably consistent with the polypropylene resin base material introduced above.

In the polypropylene hydrophobic material provided by the present invention, the fluorocarbon resin in the polypropylene-fluorocarbon resin is preferably polyvinylidene fluoride and tetrafluoroethylene-hexafluoropropylene copolymer; the grade of the polyvinylidene fluoride is preferably 710, the polyvinylidene fluoride of the above-mentioned brand is provided by France Arkema; The mass ratio of the repeating unit corresponding to the tetrafluoroethylene structure and the repeating unit corresponding to the hexafluoropropylene structure in the tetrafluoroethylene-hexafluoropropylene copolymer is (95:5)～(70:30), more preferably (90:10)～(80:20); the grade of the tetrafluoroethylene-hexafluoropropylene copolymer is preferably 6100, and the tetrafluoroethylene of the above grade - Hexafluoropropylene copolymer is provided by DuPont of the United States; the mass ratio of polyvinylidene fluoride and tetrafluoroethylene-hexafluoropropylene copolymer is preferably 1: (0.5～2), specifically 1:0.5, 1:0.6 , 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1 :1.9 or 1:2.

In the polypropylene hydrophobic material provided by the present invention, the mass ratio of the polypropylene resin in the polypropylene-fluorocarbon resin to the fluorocarbon resin is 100:(80-150), specifically 100:80, 100:85 , 100:90, 100:95, 100:100, 100:105, 100:110, 100:115, 100:120, 100:125, 100:130, 100:135, 100:140, 100:145, or 100 :150.

In the polypropylene hydrophobic material provided by the present invention, based on 100 parts by mass of the polypropylene resin base material in the raw material, the content of the polypropylene-fluorocarbon resin in the raw material can specifically be 0.5 parts by mass, 1 part by mass, 2 parts by mass, 3 parts by mass, 4 parts by mass, 5 parts by mass, 6 parts by mass, 7 parts by mass, 8 parts by mass, 9 parts by mass, 10 parts by mass, 11 parts by mass, 12 parts by mass, 13 parts by mass Parts, 14 parts by mass, 15 parts by mass, 16 parts by mass, 17 parts by mass, 18 parts by mass, 19 parts by mass, 20 parts by mass, 21 parts by mass, 22 parts by mass, 23 parts by mass, 24 parts by mass, 25 parts by mass, 26 parts by mass, 27 parts by mass, 28 parts by mass, 29 parts by mass or 30 parts by mass.

In the polypropylene hydrophobic material provided by the present invention, the diffusing agent is preferably one or more of polyvinyl chloride, chlorinated polyethylene and chlorosulfonated polyethylene, more preferably polyvinyl chloride and chlorinated polyethylene The trade mark of described polyvinyl chloride is preferably SG-5, and the polyvinyl chloride of above-mentioned trade mark is provided by Xinjiang Tianye Group Co., Ltd.; The trade mark of described chlorinated polyethylene is preferably CPE 135A, and the chlorinated polyethylene of above-mentioned trade mark is provided by Shandong Chengshun Chemical Technology Co., Ltd.; the mass ratio of polyvinyl chloride and chlorinated polyethylene is preferably 1: (0.5～2), specifically 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, or 1:2.

In the polypropylene hydrophobic material provided by the present invention, based on 100 parts by mass of the polypropylene resin base material in the raw material, the content of the diffusing agent in the raw material can specifically be 0.1, 0.5, 1 part by mass, 1.5 parts by mass, 2 parts by mass, 3 parts by mass, 4 parts by mass, 5 parts by mass, 6 parts by mass, 7 parts by mass, 8 parts by mass, 9 parts by mass, 10 parts by mass, 11 parts by mass, 12 parts by mass parts by mass, 13 parts by mass, 14 parts by mass, 15 parts by mass, 16 parts by mass, 17 parts by mass, 18 parts by mass, 19 parts by mass or 20 parts by mass.

In the polypropylene hydrophobic material provided by the present invention, the hydrophobic stabilizer is preferably polydimethylsiloxane, triisopropylsilane, trifluoropropylmethyldimethoxysilane, polyperfluoroalkylsilane One or more of oxane, fluoroalkylsilane, heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltriethoxysilane; the molecular weight of the polydimethylsiloxane is preferably 400-1000, specifically 400, 500, 600, 700, 800, 900 or 1000.

In the polypropylene hydrophobic material provided by the present invention, based on 100 parts by mass of the polypropylene resin base material in the raw material, the content of the hydrophobic stabilizer in the raw material can be specifically 0.1 parts by mass, 0.5 parts by mass , 1 part by mass, 1.5 parts by mass, 2 parts by mass, 2.5 parts by mass, 3 parts by mass, 3.5 parts by mass, 4 parts by mass, 4.5 parts by mass, 5 parts by mass, 5.5 parts by mass, 6 parts by mass, 6.5 parts by mass, 7 parts by mass Parts by mass, 7.5 parts by mass, 8 parts by mass, 8.5 parts by mass, 9 parts by mass, 9.5 parts by mass or 10 parts by mass.

In the polypropylene hydrophobic material provided by the present invention, the hydrophobic graft modifier is preferably 2-(trifluoromethyl)acrylic acid, perfluoroalkyl ethyl methacrylic acid, polymethacrylic acid (N-perfluoromethacrylic acid) One or more of cycloalkyl)amide ester, polyperfluorooctylmethyl acrylate and fluorinated isocyanate.

In the polypropylene hydrophobic material provided by the present invention, based on 100 parts by mass of the polypropylene resin base material in the raw material, the content of the hydrophobic graft modifier in the raw material can specifically be 5 parts by mass, 6 parts by mass, 7 parts by mass, 8 parts by mass, 9 parts by mass, 10 parts by mass, 11 parts by mass, 12 parts by mass, 13 parts by mass, 14 parts by mass, 15 parts by mass, 16 parts by mass, 17 parts by mass, 18 parts by mass parts, 19 parts by mass or 20 parts by mass.

In the polypropylene hydrophobic material provided by the present invention, the hydrophobic graft compatibilizer is preferably maleic anhydride grafted polyethylene resin, maleic anhydride grafted polypropylene resin, maleic anhydride grafted chlorinated polyethylene resin and One or more of the maleic anhydride grafted chlorinated polypropylene resins; the maleic anhydride graft rate in the hydrophobic graft compatibilizer is preferably 0.3-4%, more preferably 1.5-2%. In the present invention, the hydrophobic grafting compatibilizer can specifically choose the maleic anhydride grafted polypropylene resin of the grade 50E803, and the maleic anhydride grafted polypropylene resin of the above grade is provided by DuPont of the United States.

In the polypropylene hydrophobic material provided by the present invention, based on 100 parts by mass of the polypropylene resin base material in the raw material, the content of the hydrophobic graft compatibilizer in the raw material can specifically be 0.1 parts by mass, 0.25 parts by mass, 0.5 parts by mass, 0.75 parts by mass, 1 part by mass, 1.25 parts by mass, 1.5 parts by mass, 1.75 parts by mass, 2 parts by mass, 2.25 parts by mass, 2.5 parts by mass, 2.75 parts by mass, 3 parts by mass, 3.25 parts by mass 3.5 parts by mass, 3.75 parts by mass, 4 parts by mass, 4.25 parts by mass, 4.5 parts by mass, 4.75 parts by mass or 5 parts by mass.

The present invention also provides a method for preparing the polypropylene hydrophobic material described in the above technical solution, comprising the following steps:

The polypropylene resin base material, polypropylene-fluorocarbon resin, diffusing agent, hydrophobic stabilizer, hydrophobic graft modifier and hydrophobic graft compatibilizer are melt-blended in a screw extruder and then extruded to obtain a polymer Acrylic hydrophobic material.

In the preparation method provided by the present invention, the raw material information and dosage formulation of the polypropylene resin base material, polypropylene-fluorocarbon resin, diffusing agent, hydrophobic stabilizer, hydrophobic graft modifier and hydrophobic graft compatibilizer It has been introduced in the previous article and will not be repeated here.

In the preparation method provided by the present invention, the polypropylene-fluorocarbon resin used is preferably prepared according to the following steps: the polypropylene resin and the fluorocarbon resin are melt-blended in a screw extruder and then extruded, and the polypropylene-fluorocarbon resin is extruded. Fluorocarbon resin. Wherein, the raw material information and dosage ratio of the polypropylene resin and the fluorocarbon resin have been introduced above, and will not be repeated here; before the polypropylene resin and the fluorocarbon resin are added to the screw extruder, preferably First premix evenly; the extrusion temperature of the screw extruder (that is, the temperature from the hopper to the die) is preferably 150 to 350°C, more preferably 180 to 330°C; the screw speed of the screw extruder It is preferably 120-300rpm, specifically 120rpm, 130rpm, 140rpm, 150rpm, 160rpm, 180rpm, 200rpm, 250rpm or 300rpm; after extrusion, it is preferably cooled and pelletized to obtain polypropylene-fluorocarbon resin masterbatch.

In the preparation method provided by the present invention, the screw extruder used to prepare the polypropylene hydrophobic material is preferably sequentially provided with a main feeding port, a first feeding port and a second feeding port along the extrusion direction of the material; the preparation process Among them, the polypropylene resin base material, polypropylene-fluorocarbon resin, diffusing agent and hydrophobic graft compatibilizer are preferably added to the screw extruder through the main feeding port, and the hydrophobic graft modifier is preferably passed through The first feeding port is added, and the hydrophobic stabilizer is preferably added through the second feeding port. Wherein, the polypropylene resin base material, polypropylene-fluorocarbon resin, diffusing agent and hydrophobic graft compatibilizer are preferably pre-mixed uniformly before being added to the screw extruder.

In the preparation method provided by the present invention, during the preparation of the polypropylene hydrophobic material, the extrusion temperature of the screw extruder (that is, the temperature from the feeding hopper to the die opening) is preferably 150-250° C., more preferably 150° C. ~230°C; the screw speed of the screw extruder is preferably 80~200rpm, specifically 80rpm, 100rpm, 120rpm, 130rpm, 140rpm, 160rpm, 180rpm or 200rpm; after extrusion, it is preferably cooled and pelletized to obtain Polypropylene hydrophobic pellets.

The present invention also provides a hydrophobic product, the material of which is the polypropylene hydrophobic material described in the above technical solution. The hydrophobic article provided by the present invention is made of the polypropylene hydrophobic material through a molding process, which includes but not limited to extrusion molding, injection molding, hollow molding, blow molding, compression molding, calendering molding and the like. In the present invention, in order to further improve the hydrophobic performance of the workpiece, the surface of the hydrophobic workpiece is preferably treated by plasma sputtering and/or electrostatic negative charge sputtering; wherein, the sputtering of the plasma sputtering treatment The gas temperature is preferably 15-35°C, specifically 25°C (room temperature), and the DC voltage applied by sputtering is preferably 500-1000V; the sputtering gas temperature for the electrostatic negative charge sputtering treatment is preferably 15-35°C, Specifically, it may be 25°C (room temperature), and the DC voltage applied to sputtering is preferably 500-1000V.

The present invention can avoid discontinuous phases such as sea-island structure and core-shell structure formed by low surface energy substances in the blending process by constructing a double continuous phase structure, and improve the dispersion concentration of low surface energy substances in the microscopic interface layer in the blending system; by using The microfluidic channel in the bicontinuous phase structure, and the melt blending grafting reaction can not only improve the thermodynamic compatibility of the two phases in the blend system, but also further improve the low surface energy substances in the blend system at the micro interface. The dispersion concentration of the layer can make the material meet the application requirements of hydrophobic and superhydrophobic. In addition, the polypropylene hydrophobic material provided by the present invention can be directly prepared into finished parts by processes such as extrusion molding, injection molding, hollow molding, blow molding, compression molding, calendering, etc., and is especially suitable for fine structural parts that require hydrophobic properties Continuous production. In addition, in the preferred technical solution provided by the present invention, plasma sputtering treatment and/or electrostatic negative charge sputtering treatment can also be performed on the surface of the workpiece, so as to further improve the hydrophobic performance of the workpiece. Experimental results show that: the water contact angle of the polypropylene hydrophobic material provided by the present invention is more than or equal to 118°, and the water contact angle of the surface-treated workpiece can reach up to 135°.

For more clarity, the following examples and comparative examples are described in detail below.

Example 1

A kind of preparation of polypropylene hydrophobic material, comprises the following steps:

1) Weigh 100 parts by mass of polypropylene resin (brand: M800E, place of origin: Sinopec Shanghai Petrochemical Co., Ltd., the same below), 50 parts by mass of vinylidene fluoride resin (brand: 710, place of origin: Arkema, France , the same below), 50 parts by mass of tetrafluoroethylene-hexafluoropropylene copolymer (brand: 6100, place of origin: DuPont, the United States, the same below), placed in a high-speed mixer (model: SHR-5, manufacturer: Zhangjiagang City Huan Feng Machinery Factory, the same below), take it out after mixing for 5min, and place it in the hopper of a twin-screw extruder (model: CTE-20, manufacturer: Nanjing Coperion Co., Ltd., the same below);

2) Set the feeding rate of the feeder of the twin-screw extruder to 200rpm, set the screw temperature of the twin-screw extruder to 180-330°C from the feeding hopper to the die opening; set the screw speed of the screw extruder to 140rpm;

3) After cooling, pelletizing and drying the resin melt mixture extruded by the screw extruder, a polypropylene-fluorocarbon resin masterbatch with a dual continuous phase structure is prepared for use;

4) Weigh 100 parts by mass of polypropylene resin, 20 parts by mass of polypropylene-fluorocarbon resin masterbatch, 1.5 parts by mass of polyvinyl chloride (brand: SG-5, place of origin: Xinjiang Tianye Group Co., Ltd., the same below ), 1.5 parts by mass of chlorinated polyethylene (brand: CPE 135A, place of origin: Shandong Chengshun Chemical Technology Co., Ltd., the same below), 0.75 parts by mass of maleic anhydride grafted polypropylene resin (brand: 50E803, place of origin: U.S. DuPont, the same below), placed in a high-speed mixer, took out after mixing for 5min, and placed in the hopper of a twin-screw extruder;

5) Put perfluoroalkyl ethyl methacrylic acid (place of origin: Zhengzhou Alpha Chemical Co., Ltd., the same below) in a drip feeding device, through the first feeding port above the barrel of the screw extruder Carry out dropwise, with the consumption of polypropylene resin being 100 mass parts, the dripping amount of perfluoroalkyl ethyl methacrylic acid is 10 mass parts;

6) Put polydimethylsiloxane (molecular weight: 800, place of origin: Shandong Ruihongde Chemical Technology Co., Ltd., the same below) in another drop feeding device, and set it above the barrel of the screw extruder The second feed port of the feeder is added dropwise, and the amount of polydimethylsiloxane added dropwise is 5 parts by mass based on 100 parts by mass of the polypropylene resin; in the present embodiment, the feed hopper, the first branch The arrangement order of the feeding port, the second feeding port, and the die opening of the screw extruder on the screw extruder is: feeding hopper → the first feeding port → the second feeding port → the screw extruder die opening (the same below) ;

7) Set the feeding rate of the feeder of the twin-screw extruder to 200rpm, set the screw temperature of the twin-screw extruder to 150-230°C from the feed hopper to the die opening; set the screw speed of the screw extruder to 120rpm;

8) The melt mixture extruded by the screw extruder is cooled and pelletized, and then dried to obtain a polypropylene hydrophobic material.

The polypropylene hydrophobic material prepared in this example was prepared by using an injection molding machine (model: Babyplast 6/10P, place of origin: Cronop last company in Spain, the same below) to prepare an injection molded product, and its surface microscopic appearance is shown in Figure 1 As shown, the contact angle to water at room temperature is 120 degrees; after the surface sputtering treatment (sputtering gas temperature is room temperature, and sputtering applied DC voltage is 500V, the same below) is performed on the injection molded product separately, the The contact angle of water at room temperature is 128 degrees; after the surface electrostatic negative charge sputtering treatment is performed on the injection molded product (the temperature of the sputtering gas is room temperature, and the DC voltage applied to sputtering is 500V, the same below), the water is treated at room temperature. The contact angle of the injection molded product is 125 degrees; after the surface sputtering treatment and the surface electrostatic negative charge sputtering treatment are carried out on the injection molded product in sequence, the contact angle to water at room temperature is 135 degrees.

Example 2

A kind of preparation of polypropylene hydrophobic material, comprises the following steps:

1) Weigh 100 parts by mass of polypropylene resin, 60 parts by mass of vinylidene fluoride resin, and 40 parts by mass of tetrafluoroethylene-hexafluoropropylene copolymer, place them in a high-speed mixer, take them out after mixing for 5 minutes, and place them in double In the hopper of the screw extruder;

2) Set the feeding rate of the feeder of the twin-screw extruder to 200rpm, set the screw temperature of the twin-screw extruder to 180-330°C from the feeding hopper to the die opening; set the screw speed of the screw extruder to 140rpm;

3) After cooling, pelletizing and drying the melt mixture extruded by the screw extruder, a polypropylene-fluorocarbon resin masterbatch with a dual continuous phase structure is prepared for subsequent use;

4) take by weighing the polypropylene resin of 100 mass parts, the polypropylene-fluorocarbon resin masterbatch of 20 mass parts, the polyvinyl chloride of 2.0 mass parts, the chlorinated polyethylene of 1.0 mass parts, the maleic anhydride of 1.0 mass parts A polypropylene resin is placed in a high-speed mixer, taken out after mixing for 5min, and placed in the hopper of a twin-screw extruder;

5) Perfluoroalkyl ethyl methacrylic acid is placed in a drop feeding device, and is added dropwise through the first feeding port above the barrel of the screw extruder, with the amount of polypropylene resin being 100 In parts by mass, the dripping amount of perfluoroalkyl ethyl methacrylic acid is 12 parts by mass;

6) Put polydimethylsiloxane (molecular weight: 600, place of origin: Shandong Ruihongde Chemical Technology Co., Ltd., the same below) in another drop feeding device, and set it above the barrel of the screw extruder The second feeding port of the second branch is added dropwise, and the consumption of polypropylene resin is 100 mass parts, and the dripping amount of polydimethylsiloxane is 5 mass parts;

7) Set the feeding rate of the feeder of the twin-screw extruder to 200rpm, set the screw temperature of the twin-screw extruder to 150-230°C from the feed hopper to the die opening; set the screw speed of the screw extruder to 120rpm;

8) The melt mixture extruded by the screw extruder is cooled and pelletized, and then dried to obtain a polypropylene hydrophobic material.

Using the polypropylene hydrophobic material prepared in this example, using the injection molding machine process, the injection molded product prepared has a contact angle of 118 degrees to water at room temperature; the injection molded product is subjected to plasma sputtering treatment alone Finally, the contact angle to water at room temperature is 128 degrees; after the surface electrostatic negative charge sputtering treatment is performed on the injection molded product separately, the contact angle to water at room temperature is 125 degrees; the surface sputtering of the injection molded product is carried out in turn After treatment and surface electrostatic negative charge sputtering treatment, the contact angle to water at room temperature is 133 degrees.

Example 3

A kind of preparation of polypropylene hydrophobic material, comprises the following steps:

1) Weigh 100 parts by mass of polypropylene resin, 50 parts by mass of vinylidene fluoride resin, and 50 parts by mass of tetrafluoroethylene-hexafluoropropylene copolymer, place them in a high-speed mixer, take them out after mixing for 5 minutes, and place them in double In the hopper of the screw extruder;

2) Set the feeding rate of the feeder of the twin-screw extruder to 200rpm, set the screw temperature of the twin-screw extruder to 180-330°C from the feeding hopper to the die opening; set the screw speed of the screw extruder to 140rpm;

3) After cooling, pelletizing and drying the melt mixture extruded by the screw extruder, a polypropylene-fluorocarbon resin masterbatch with a dual continuous phase structure is prepared for subsequent use;

4) The polypropylene resin of 100 mass parts, the polypropylene-fluorocarbon resin masterbatch of 15 mass parts, the polyvinyl chloride of 1.5 mass parts, the maleic anhydride grafted polypropylene resin of 4.5 mass parts, place high-speed mixing In the machine, take it out after mixing for 5 minutes, and place it in the feeding hopper of the twin-screw extruder;

5) Perfluoroalkyl ethyl methacrylic acid is placed in a drop feeding device, and is added dropwise through the first feeding port above the barrel of the screw extruder, with the amount of polypropylene resin being 100 In parts by mass, the dripping amount of perfluoroalkyl ethyl methacrylic acid is 10 parts by mass;

6) Place trifluoropropylmethyldimethoxysilane (Origin: Hubei Dongcao Chemical Technology Co., Ltd.) in another drop feeding device, and pass through the second branch above the barrel of the screw extruder. The feeding port is added dropwise, with the amount of polypropylene resin being 100 parts by mass, the amount of trifluoropropylmethyldimethoxysilane added dropwise is 6 parts by mass;

7) Set the feeding rate of the feeder of the twin-screw extruder to 200rpm, set the screw temperature of the twin-screw extruder to 150-230°C from the feed hopper to the die opening; set the screw speed of the screw extruder to 120rpm;

8) The melt mixture extruded by the screw extruder is cooled and pelletized, and then dried to obtain a polypropylene hydrophobic material.

Using the polypropylene hydrophobic material prepared in this example, using the injection molding machine process, the injection molded product prepared has a contact angle of 121 degrees to water at room temperature; the injection molded product is subjected to plasma sputtering treatment alone Finally, the contact angle to water at room temperature is 129 degrees; after the surface electrostatic negative charge sputtering treatment is carried out separately on the injection molded product, the contact angle to water at room temperature is 127 degrees; the injection molded product is subjected to surface sputtering in turn After treatment and surface electrostatic negative charge sputtering treatment, the contact angle to water at room temperature is 135 degrees.

Comparative example 1

1) Weigh the polypropylene resin of 100 mass parts, the vinylidene fluoride resin of 5 mass parts, the tetrafluoroethylene-hexafluoropropylene copolymer of 5 mass parts, the polyvinyl chloride of 1.5 mass parts, the chlorinated polyvinyl chloride of 1.5 mass parts Ethylene, the maleic anhydride grafted polypropylene resin of 0.75 mass parts, place in the high-speed mixer, take out after mixing 5min, place in the hopper of twin-screw extruder;

2) Set the feeding rate of the feeder of the twin-screw extruder to 200rpm, set the screw temperature of the twin-screw extruder to 180-330°C from the feeding hopper to the die opening; set the screw speed of the screw extruder to 140rpm;

3) After the melt mixture extruded by the screw extruder is cooled and pelletized, and then dried, the polypropylene hydrophobic material prepared in this comparative example can be obtained.

The polypropylene hydrophobic material prepared in this comparative example was used to prepare an injection molded product by using an injection molding machine process. The surface microscopic appearance is shown in Figure 2, and the contact angle to water at room temperature is 95 degrees.

Comparing the test results of Example 1 of the present invention and Comparative Example 1, it can be seen that: for the surface SEM image of the injection molded product at room temperature, it is not difficult to find out that in Comparative Example 1, on the surface of the injection molded product, the low surface energy substance is in the matrix PP resin is dispersed in sea-island structure, and the dispersion concentration and dispersion specific surface area of low surface energy substances in the interface layer are small. Therefore, when water infiltrates the surface of injection molded products, low surface energy substances can only be dispersed independently The dotted position resists the infiltration of water, while in other positions where there is no low surface energy substance, water can still infiltrate the surface of the injection molded product; and in Example 1, on the surface of the injection molded product, the low surface energy substance and matrix The PP resin is dispersed in a dual continuous phase structure, and the low surface energy material exhibits a dendritic dispersion structure under mechanical shear force during the twin-screw blending/injection molding process. The biggest beneficial effect of this structure is that it is low Surface energy substances can exist on the surface of injection molded products in a continuous structure, which can further increase the dispersion concentration and dispersion specific surface area of low surface energy substances in the interface layer of injection molded products. Therefore, when water infiltrates on the surface of injection molded products, low Surface energy substances will have a larger area of action against water infiltration; at the same time, the dendritic dispersed structure of low surface energy substances can also form a three-dimensional micro/nano structure on the interface layer, which can further improve the hydrophobicity of injection molded products. sex. At the same time, if the surface of the injection molded product is further treated by plasma sputtering, the micro/nano structure in the three-dimensional space of the surface of the injection molded product can be further optimized; when further electrostatic negative charge sputtering treatment is performed, the surface of the injection molded product can be further optimized Electrostatic repulsion, when water infiltrates the surface of the injection molded product, can further improve the ability to resist water infiltration on the surface of the injection molded product, so as to further enhance the hydrophobic effect of the injection molded product.

Each raw material listed in the present invention (such as: polypropylene, tetrafluoroethylene, hexafluoropropylene, tetrafluoroethylene/hexafluoropropylene copolymer, vinylidene fluoride resin, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene - Perfluoroalkoxy vinyl ether copolymer, polyperfluoroalkoxy resin, polydimethylsiloxane, triisopropylsilane, trifluoropropylmethyldimethoxysilane, polyperfluoroalkane fluoroalkylsilane, heptadecylfluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, 2-(trifluoromethyl)acrylic acid, perfluoroalkylethylmethyl Acrylic acid, poly(N-perfluorocycloalkyl)amide polymethacrylate, polyperfluorooctylmethyl acrylate, fluorinated isocyanate, maleic anhydride grafted polyethylene resin, maleic anhydride grafted polypropylene resin, maleic anhydride grafted polypropylene resin, chlorinated polyethylene resin grafted with maleic anhydride, chlorinated polypropylene resin grafted with maleic anhydride), and the upper and lower limits and interval values of each raw material of the present invention, and the upper and lower limits and intervals of process parameters (such as temperature, time, etc.) Values can be used to realize the present invention, and the embodiments are not listed one by one here.

In this description, the application of specific embodiments has been described to the present invention, which is only the preferred implementation mode of the present invention. It should be pointed out that for those of ordinary skill in the art, the idea of the present invention may be implemented in the specific implementation mode and application scope. There will be changes in . Therefore, the contents described in this specification should not be understood as limiting the present invention.

Claims (10)

1. The polypropylene hydrophobic material is characterized by being prepared by melt blending and extruding raw materials, wherein the raw materials comprise the following components in parts by mass:

the polypropylene resin and the fluorocarbon resin in the polypropylene-fluorocarbon resin are in a bicontinuous phase structure on the microscopic thermodynamic phase structure; the mass ratio of the polypropylene resin to the fluorocarbon resin in the polypropylene-fluorocarbon resin is 100: (80-150).

2. The polypropylene hydrophobic material according to claim 1, wherein the fluorocarbon resin is polyvinylidene fluoride and tetrafluoroethylene-hexafluoropropylene copolymer; the mass ratio of the polyvinylidene fluoride to the tetrafluoroethylene-hexafluoropropylene copolymer is 1: (0.5-2).

3. The polypropylene hydrophobic material of claim 1, wherein the dispersing agent is one or more of polyvinyl chloride, chlorinated polyethylene and chlorosulfonated polyethylene.

4. The polypropylene hydrophobing material of claim 1, wherein the hydrophobic stabiliser is one or more of polydimethylsiloxane, triisopropylsilane, trifluoropropylmethyldimethoxysilane, polyperfluoroalkylsiloxane, fluoroalkylsilane, heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltriethoxysilane.

5. The polypropylene hydrophobic material of claim 1, wherein the hydrophobic graft modifier is one or more of 2- (trifluoromethyl) acrylic acid, perfluoroalkylethyl methacrylic acid, poly (N-perfluorocycloalkyl) amide esters, poly (perfluorooctyl methyl acrylate), and fluorinated isocyanates.

6. The polypropylene hydrophobic material according to claim 1, wherein the hydrophobic grafting compatibilizer is one or more of maleic anhydride grafted polyethylene resin, maleic anhydride grafted polypropylene resin, maleic anhydride grafted chlorinated polyethylene resin, and maleic anhydride grafted chlorinated polypropylene resin.

7. A method for preparing the polypropylene hydrophobic material as defined in any one of claims 1 to 6, comprising the steps of:

and melting and blending the polypropylene resin base material, the polypropylene-fluorocarbon resin, the dispersing agent, the hydrophobic stabilizing agent, the hydrophobic grafting modifying agent and the hydrophobic grafting compatibilizer in a screw extruder, and then extruding to obtain the polypropylene hydrophobic material.

8. The preparation method according to claim 7, wherein the screw extruder is provided with a main feed port, a first branch feed port and a second branch feed port in the material extrusion direction in this order; in the preparation process, the polypropylene resin base material, the polypropylene-fluorocarbon resin, the dispersing agent and the hydrophobic grafting compatibilizer are added into the screw extruder through the main feed inlet, the hydrophobic grafting modifier is added through the first branch feed inlet, and the hydrophobic stabilizer is added through the second branch feed inlet.

9. Hydrophobic article, characterized in that the material of the hydrophobic article is a polypropylene hydrophobic material according to any of claims 1 to 6.

10. The hydrophobic article of claim 9 wherein the surface of the hydrophobic article has been subjected to a plasma sputtering process and/or an electrostatic negative charge sputtering process.

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