CN109251412B - Super-hydrophobic polytetrafluoroethylene/high polymer material composite microporous foam and preparation method thereof - Google Patents
Super-hydrophobic polytetrafluoroethylene/high polymer material composite microporous foam and preparation method thereof Download PDFInfo
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Abstract
The invention discloses super-hydrophobic polytetrafluoroethylene/high polymer material composite microporous foam and a preparation method thereof. The invention adopts micrometer-scale and nanometer-scale polytetrafluoroethylene powder, and prepares the composite microporous foam material with a high polymer material through melt extrusion and supercritical fluid foaming processes. In the extrusion process, the micron-scale polytetrafluoroethylene powder can be subjected to in-situ fiber formation to form a nanofiber network structure in the polymer matrix, and the polytetrafluoroethylene nanoparticles are uniformly dispersed in the polymer material. And furthermore, microporous foaming is carried out through the supercritical fluid, a 10-50 mu m cellular structure can be formed in the composite material, and meanwhile, the polytetrafluoroethylene nanofiber network and the nano particles are exposed on the surface of material cells, so that the obtained foam material has good superhydrophobic performance. The preparation method is simple and easy to operate, and the prepared composite microporous foam has a water contact angle of more than 150 degrees and good stability.
Description
Technical Field
The invention relates to the technical field of hydrophobic materials, in particular to super-hydrophobic polytetrafluoroethylene/high polymer material composite microporous foam and a preparation method thereof.
Background
In recent years, with the improvement of energy conservation and emission reduction requirements, the microporous foam material has attracted wide attention in different fields. The polymer material with the microporous structure can greatly reduce the requirements of raw materials and the weight of products, can keep good mechanical property and appearance size, and is particularly suitable for light weight of the products and special applications of sound insulation and heat insulation. The preparation of the high-molecular microporous foam material by the supercritical fluid is a green, low-cost and mass production process, and is widely popularized in actual production in recent years.
With the increasing severity of the problems of oil leakage and water pollution, higher market demands are made on high-performance superhydrophobic foams. The macromolecular microporous foam with super-hydrophobic property not only has the properties of water resistance, corrosion resistance and self-cleaning, but also can selectively absorb oil stains from water, thereby realizing the purification of water and the recovery of the oil stains.
However, the traditional oil-absorbing material has poor hydrophobic property, poor oil-water separation efficiency and low adsorption rate, and the currently developed super-hydrophobic modified foam or carbonized aerogel has the super-hydrophobic property, but the preparation process is complex, the cost is high, the performance stability is poor, and the method is not suitable for batch and large-scale production.
Disclosure of Invention
The invention aims to solve the technical problems of the prior art that the performance of a hydrophobic material and the preparation process are complex, and provides super-hydrophobic polytetrafluoroethylene/high polymer material composite microporous foam and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
the super-hydrophobic polytetrafluoroethylene/high polymer material composite microporous foam has an inner surface and an outer surface covered with multi-level rough polytetrafluoroethylene networks and particles, and is prepared by the following steps:
s1, sufficiently drying micron-sized polytetrafluoroethylene, nano-sized polytetrafluoroethylene and high polymer materials;
s2, uniformly mixing the micron-sized polytetrafluoroethylene, the nano-sized polytetrafluoroethylene and the high polymer material in the step S1;
s3, granulating the mixed material obtained in the step S2 through an extruder;
s4, foaming the granules obtained in the step S3 to prepare the super-hydrophobic polytetrafluoroethylene/polymer composite microporous foam.
Further, in the step S1, the diameter of the micron-sized polytetrafluoroethylene is 5-100 μm, and the diameter of the nano-sized polytetrafluoroethylene is 10-100 nm.
Further, the polymer material in step S1 includes one or more of polyethylene, polypropylene, polyurethane, polylactic acid, ABS, and polystyrene.
Furthermore, the addition amount of the micron-sized polytetrafluoroethylene is 2-10% of the mass of the high polymer material, and the addition amount of the nano-sized polytetrafluoroethylene is 1-5% of the mass of the high polymer material.
Further, step S2 may add one or more of an antioxidant, a thermal stabilizer, a reinforcing agent, a toughening agent, and a coupling agent.
Further, the extrusion granulation in step S3 adopts a twin-screw or multi-screw extruder. The temperature of the extruder is set to 150 to 250 ℃ according to the polymer, and the screw rotation speed is 80 to 150 rpm.
Further, the foaming method in step S4 is a supercritical fluid extrusion foaming method or a batch foaming method.
Further, the supercritical fluid is nitrogen or carbon dioxide.
Furthermore, the extrusion temperature in the supercritical fluid extrusion foaming process is set to be 150-250 ℃ according to the polymer, the single-screw or double-screw supercritical fluid can be adopted for extrusion foaming, and the pressure in the charging basket is 5-15 MPa.
Furthermore, the intermittent foaming temperature is 150-200 ℃, the pressure is 8-20 MPa, the soaking time of the supercritical fluid is 2-5 h, and a one-step pressure relief method is adopted for foaming.
Furthermore, the prepared super-hydrophobic polytetrafluoroethylene/polymer composite microporous foam has foam pores of 10-50 microns.
Superhydrophobic generally refers to a material surface having a water contact angle of more than 150 °, and there are two main reasons for the formation of superhydrophobic properties: firstly, the surface material has low surface energy, and secondly, the surface has a multi-level rough structure. The polytetrafluoroethylene has excellent chemical stability, corrosion resistance and high lubrication non-stick property, and is a low surface energy material, so that the polytetrafluoroethylene/high polymer composite material can achieve super-hydrophobicity only by constructing a rough surface without modifying. According to the invention, micron-scale and nano-scale polytetrafluoroethylene are added into a high polymer material, the micron-scale polytetrafluoroethylene particles can form a nanofiber network in situ in a twin-screw extrusion process, and a multi-level rough structure with low surface energy is formed on the surface of the porous foam material by combining the polytetrafluoroethylene nanoparticles and a micron-scale cellular structure, so that the foam material is endowed with super-hydrophobic performance. Further preferably, the diameter of the micron-sized polytetrafluoroethylene is 50 μm, and the diameter of the nano-sized polytetrafluoroethylene is 50 nm.
The invention adopts micrometer-scale and nanometer-scale polytetrafluoroethylene powder to prepare the composite material with the high polymer material through a double-screw extrusion process. Under the action of high temperature and strong shearing in the mixing and extruding process, the micron-scale polytetrafluoroethylene powder is subjected to in-situ fiber formation to form a nanofiber network structure in a polymer matrix, and the nano-scale polytetrafluoroethylene particles are uniformly dispersed in the polymer material. More preferably, the addition amount of the micron-sized polytetrafluoroethylene is 10% of the mass of the high polymer material, and the addition amount of the nano-sized polytetrafluoroethylene is 5% of the mass of the high polymer material.
The supercritical fluid continuous extrusion foaming is a foaming technology combining a green foaming agent and direct extrusion processing, and has the advantages of being green, efficient, continuous and the like in the aspect of polymer foaming. Meanwhile, the supercritical fluid is a green medium, has the characteristics of mass transfer of liquid and diffusion of gas, can reduce the viscosity and the processing temperature of the polymer, and has the advantages of reducing energy consumption and emission when being used for processing the polymer. The supercritical fluid extrusion foaming process mixes the molten high polymer material and supercritical nitrogen or carbon dioxide fluid in a charging barrel to form single-phase fluid, and forms the microporous foaming material with the cell size of 10-50 mu m due to pressure drop after being extruded from a neck mold. Preferably, the temperature and the pressure in the supercritical fluid extrusion foaming process are 150-250 ℃ and 5-15 MPa respectively.
The intermittent foaming molding has high nucleation rate, the intermittent characteristic in the process ensures that the supercritical gas has sufficient time to permeate into the composite material, the supercritical gas and the composite material can be fully mixed to form a high-quality homogeneous system, and a large amount of foam cell nucleuses can be instantly generated after the supercritical gas is transferred to a low-pressure environment from high pressure. The intermittent foaming molding can conveniently control the diameter and the density of the foam holes. Preferably, the intermittent foaming temperature is 150-200 ℃, the pressure is 8-20 MPa, the soaking time of the supercritical fluid is 2-5 h, and a one-step pressure relief method is adopted for foaming.
The high polymer material comprises one or more of polyethylene, polypropylene, polyurethane, polylactic acid, ABS and polystyrene. The high polymer materials have certain hydrophobicity, and the polytetrafluoroethylene/high polymer material composite microporous foam material obtained by supercritical fluid foaming has a micron-sized porous structure, and the surface of a pore has a low-surface-energy multi-layer coarse structure formed by a polytetrafluoroethylene nanofiber network and nanoparticles, so that the porous composite material has the super-hydrophobic property. According to the difference of the polymer material matrix, the polymer material is processed by selecting proper temperature.
The supercritical fluid extrusion foaming and intermittent foaming process enables a large number of micropores to be generated in the composite material, on one hand, the requirements of raw materials and the weight of a product can be reduced to a great extent, and good mechanical performance and appearance size can be kept, on the other hand, the composite material is in a three-dimensional porous structure, the micropores in the composite material can adsorb a large number of oily substances, compared with a membrane structure, the oil absorption rate and the oil absorption speed of the microporous foam structure are higher and faster, and the pollution control efficiency is effectively improved.
Compared with the prior art, the beneficial effects are:
the invention creatively uses micron-scale polytetrafluoroethylene, nano-scale polytetrafluoroethylene and high polymer materials to prepare the composite porous foam with super-hydrophobic property through high-shear screw extrusion and supercritical fluid microcellular foaming processes. In the screw extrusion process, the micron-sized polytetrafluoroethylene particles can form a nanofiber network in situ, and a multi-level rough structure with low surface energy is formed on the surface of the porous foam material by combining the polytetrafluoroethylene nanoparticles and the micron-sized cellular structure, so that the foam material is endowed with super-hydrophobic performance.
The composite microporous foam prepared by the method has the advantages that the polytetrafluoroethylene nanofiber network and the nano particles are arranged on the surface and inside of the foam pores, so that the inner surface and the outer surface have super-hydrophobic performance, and in addition, after the foam material is randomly cut or brittle-broken, the section still has the super-hydrophobic performance. The present invention uses extrusion and foaming processes, so that the composite microporous foam board or block can be produced in batch.
The preparation method of the super-hydrophobic polytetrafluoroethylene/high polymer material composite microporous foam has the advantages of feasible process, simple operation and stable quality. The water contact angle of the surface and the section of the super-hydrophobic polytetrafluoroethylene/polymer composite microporous foam prepared by the method is more than 150 degrees, so that the super-hydrophobic property is realized.
Drawings
FIG. 1 is a scanning electron microscope photomicrograph of a polytetrafluoroethylene/polypropylene composite microcellular foam prepared using micron and nanoscale polytetrafluoroethylene;
FIG. 2 is a scanning electron microscope photomicrograph of a polytetrafluoroethylene/polypropylene composite microcellular foam prepared using micron and nanoscale polytetrafluoroethylene;
FIG. 3 is a scanning electron microscope photomicrograph of a polytetrafluoroethylene/polypropylene composite microcellular foam prepared using microscale polytetrafluoroethylene;
FIG. 4 is a scanning electron microscope photomicrograph of a polytetrafluoroethylene/polypropylene composite microcellular foam prepared using microscale polytetrafluoroethylene;
FIG. 5 is a scanning electron microscope photograph of a PTFE/PP composite microporous foam section prepared from a micrometer and nanometer-scale PTFE after 500 times of abrasive paper rubbing;
FIG. 6 is a scanning electron microscope photograph of a PTFE/PP composite microporous foam section prepared from a micrometer and nanometer-scale PTFE after 500 times of abrasive paper rubbing;
FIG. 7 shows water contact angles of sections of PTFE/PP composite microcellular foams prepared using micron and nano-scale PTFE;
FIG. 8 is a water contact angle of a brittle section of a polytetrafluoroethylene/polypropylene composite microporous foam prepared by using micron and nanometer-scale polytetrafluoroethylene;
FIG. 9 shows the water contact angle of the section of the PTFE/PP composite microcellular foam prepared from the micron-sized PTFE;
FIG. 10 shows the water contact angle of the PTFE/PP composite microporous foam section prepared from the micrometer and nanometer polytetrafluoroethylene after 500 times of abrasive paper rubbing;
FIG. 11 shows the results of absorption rate tests of PTFE/PP composite microporous foams prepared with micron and nano-scale PTFE for different organic solvents and oil stains.
Detailed Description
The following examples are further explained and illustrated, but the present invention is not limited in any way by the specific examples. Unless otherwise indicated, the methods and equipment used in the examples are conventional in the art and all materials used are conventional commercially available materials.
The invention utilizes micron-scale and nano-scale polytetrafluoroethylene and high polymer materials to prepare the composite porous foam with super-hydrophobic property by a double-screw extrusion and supercritical fluid microcellular foaming process. And by combining the polytetrafluoroethylene nano particles and the micron-sized cellular structure, a low-surface-energy multi-level rough structure is formed on the surface of the porous foam material, so that the foam material is endowed with super-hydrophobic performance. A super-hydrophobic polytetrafluoroethylene/polymer composite microporous foam is prepared by the following steps:
s1, fully drying polytetrafluoroethylene and a high polymer material;
s2, uniformly mixing the polytetrafluoroethylene and the high polymer material obtained in the step S1 through a high-speed mixer;
s3, granulating the mixed material obtained in the step S2 through an extruder;
s4, foaming the granules obtained in the step S3 to prepare the super-hydrophobic polytetrafluoroethylene/polymer composite microporous foam.
Further, in step S1, the ptfe includes micron-sized ptfe and nano-sized ptfe; the diameter of the micron-sized polytetrafluoroethylene is 5-100 mu m, and the diameter of the nano-sized polytetrafluoroethylene is 10-100 nm.
Further, the polymer material in step S1 includes one or more of polyethylene, polypropylene, polyurethane, polylactic acid, ABS, and polystyrene.
Furthermore, the addition amount of the micron-sized polytetrafluoroethylene is 2-10% of the mass of the high polymer material, and the addition amount of the nano-sized polytetrafluoroethylene is 1-5% of the mass of the high polymer material.
Further, the extrusion granulation in step S3 adopts a twin-screw or multi-screw extruder. The temperature of the extruder is 150-250 ℃, and the rotation speed of the screw is 80-150 rpm.
Further, the foaming method in step S4 is a supercritical fluid extrusion foaming or batch foaming process.
Further, the supercritical fluid is nitrogen or carbon dioxide.
Furthermore, the extrusion temperature in the supercritical fluid extrusion foaming process is 150-250 ℃, single-screw or double-screw supercritical fluid extrusion foaming can be adopted, and the pressure in the charging basket is 5-15 MPa; the intermittent foaming temperature is 150-200 ℃, the pressure is 8-20 MPa, the soaking time of the supercritical fluid is 2-5 h, and a one-step pressure relief method is adopted for foaming.
Furthermore, the prepared super-hydrophobic polytetrafluoroethylene/polymer composite microporous foam has foam pores of 10-50 microns.
Example 1
In this embodiment, the preparation method of the super-hydrophobic polytetrafluoroethylene/polymer composite microporous foam using polypropylene as a matrix material comprises the following steps:
s1, drying 50-micron polytetrafluoroethylene, 50-nm polytetrafluoroethylene and polypropylene granules at 60 ℃ for 24 hours;
s2, uniformly mixing 100g of dried 50-micron polytetrafluoroethylene and 50g of 50-nm polytetrafluoroethylene in the step S1 with 1kg of polypropylene granules;
s3, granulating the mixed material obtained in the step S2 through a double-screw extruder, wherein the temperature of the extruder is set to be 170 ℃, 210 ℃, 200 ℃, 190 ℃, and the screw rotating speed of the extruder is 100 rpm;
and S4, carrying out microcellular foaming on the granules obtained in the step S3 through a supercritical fluid extruder, setting the temperature of the supercritical fluid extruder to be 170 ℃, 210 ℃, 200 ℃, 190 ℃ and 190 ℃, controlling the pressure in the charging basket to be about 10MPa, and extruding to obtain the polytetrafluoroethylene/polypropylene composite microcellular foam.
Example 2
In this embodiment, the preparation method of the super-hydrophobic polytetrafluoroethylene/polymer composite microporous foam using polypropylene as a matrix material comprises the following steps:
s1, drying polytetrafluoroethylene with the particle size of 5 microns, polytetrafluoroethylene with the particle size of 10nm and polypropylene particles at the temperature of 60 ℃ for 24 hours;
s2, uniformly mixing 100g of dried 5-micron polytetrafluoroethylene and 50g of 10-nm polytetrafluoroethylene in the step S1 with 1kg of polypropylene granules;
s3, granulating the mixed material obtained in the step S2 through an extruder, wherein the temperature of the extruder is set to be 170 ℃, 210 ℃, 200 ℃, 200 ℃ and 190 ℃, and the screw rotating speed of the extruder is 80 rpm;
and S4, carrying out microcellular foaming on the granules obtained in the step S3 through a supercritical fluid extruder, setting the temperature of the supercritical fluid extruder to be 190 ℃, controlling the pressure in the charging basket to be about 15MPa, and extruding to obtain the polytetrafluoroethylene/polypropylene composite microcellular foam.
Example 3
In this embodiment, the preparation method of the super-hydrophobic polytetrafluoroethylene/polymer composite microporous foam using polypropylene as a matrix material comprises the following steps:
s1, drying 100 mu m of polytetrafluoroethylene, 100nm of polytetrafluoroethylene and polypropylene granules at 60 ℃ for 24 hours;
s2, uniformly mixing 20g of dried 100-micron polytetrafluoroethylene and 10g of 100-nm polytetrafluoroethylene in the step S1 with 1kg of polypropylene granules;
s3, granulating the mixed material obtained in the step S2 through an extruder, wherein the temperature of the extruder is set to be 170 ℃, 210 ℃, 200 ℃, 200 ℃ and 190 ℃, and the rotating speed of a screw of the extruder is 150 rpm;
and S4, carrying out microcellular foaming on the granules obtained in the step S3 through a supercritical fluid extruder, setting the temperature of the supercritical fluid extruder to be 170 ℃, 210 ℃, 200 ℃, 200 ℃ and 190 ℃, controlling the pressure in the charging basket to be about 10MPa, and extruding to obtain the polytetrafluoroethylene/polypropylene composite microcellular foam.
Example 4
In this embodiment, the preparation method of the super-hydrophobic polytetrafluoroethylene/polymer composite microporous foam using polypropylene as a matrix material comprises the following steps:
s1, drying 50-micron polytetrafluoroethylene, 50-nm polytetrafluoroethylene and polypropylene granules at 60 ℃ for 24 hours;
s2, uniformly mixing 100g of dried 50-micron polytetrafluoroethylene and 50g of 50-nm polytetrafluoroethylene in the step S1 with 1kg of polypropylene granules;
s3, granulating the mixed material obtained in the step S2 through a double-screw extruder, wherein the temperature of the extruder is set to be 170 ℃, 210 ℃, 200 ℃, and 190 ℃;
and S4, intermittently foaming the granules obtained in the step S3 through a high-pressure kettle, releasing pressure to foam at the temperature of 180 ℃ and the pressure in the kettle of 15MPa for 3 hours to obtain the polytetrafluoroethylene/polypropylene composite microporous foam.
Example 5
In this embodiment, the polyurethane is used as a matrix material to provide a super-hydrophobic polytetrafluoroethylene/polymer composite microporous foam, and the preparation steps are as follows:
s1, drying 50-micron polytetrafluoroethylene, 50-nm polytetrafluoroethylene and polypropylene granules at 60 ℃ for 24 hours;
s2, uniformly mixing 100g of dried 50-micron polytetrafluoroethylene and 50g of 50-nm polytetrafluoroethylene in the step S1 with 1kg of polyurethane granules;
s3, granulating the mixed material obtained in the step S2 through an extruder, wherein the temperature of the extruder is set to be 180 ℃, 190 ℃, 200 ℃, 210 ℃ and 200 ℃, and the screw rotating speed of the extruder is 80 rpm;
and S4, carrying out microcellular foaming on the granules obtained in the step S3 through a supercritical fluid extruder, setting the temperature of the supercritical fluid extruder to be 180 ℃, 190 ℃, 200 ℃, 210 ℃ and 200 ℃, and controlling the pressure in the charging basket to be about 15MPa, so as to obtain the polytetrafluoroethylene/polyurethane composite microcellular foam through extrusion.
Example 6
In this embodiment, the polyurethane is used as a matrix material to provide a super-hydrophobic polytetrafluoroethylene/polymer composite microporous foam, and the preparation steps are as follows:
s1, drying 50-micron polytetrafluoroethylene, 50-nm polytetrafluoroethylene and polypropylene granules at 60 ℃ for 24 hours;
s2, uniformly mixing 100g of dried 50-micron polytetrafluoroethylene and 50g of 50-nm polytetrafluoroethylene in the step S1 with 1kg of polyurethane granules;
s3, granulating the mixed material obtained in the step S2 through an extruder, wherein the temperature of the extruder is set to be 180 ℃, 190 ℃, 200 ℃, 210 ℃ and 200 ℃, and the screw rotating speed of the extruder is 100 rpm;
and S4, intermittently foaming the granules obtained in the step S3 through a high-pressure kettle, releasing pressure and foaming to obtain the polytetrafluoroethylene/polyurethane composite microporous foam, wherein the temperature of a foaming kettle is 180 ℃, the pressure in the kettle is 15MPa, the soaking time of the supercritical fluid is 3 hours.
Example 7
In this embodiment, the polyurethane is used as a matrix material to provide a super-hydrophobic polytetrafluoroethylene/polymer composite microporous foam, and the preparation steps are as follows:
s1, drying 100 mu m of polytetrafluoroethylene, 100nm of polytetrafluoroethylene and polypropylene granules at 60 ℃ for 24 hours;
s2, uniformly mixing 100g of dried 100-micron polytetrafluoroethylene and 50g of 100-nm polytetrafluoroethylene in the step S1 with 1kg of polyurethane granules;
s3, granulating the mixed material obtained in the step S2 through an extruder, wherein the temperature of the extruder is set to be 180 ℃, 190 ℃, 200 ℃, 210 ℃ and 200 ℃, and the screw rotating speed of the extruder is 100 rpm;
and S4, intermittently foaming the granules obtained in the step S3 through a high-pressure kettle, releasing pressure and foaming to obtain the polytetrafluoroethylene/polyurethane composite microporous foam, wherein the temperature of a foaming kettle is 190 ℃, the pressure in the kettle is 15MPa, the soaking time of the supercritical fluid is 5 hours.
Example 8
In this embodiment, the polyurethane is used as a matrix material to provide a super-hydrophobic polytetrafluoroethylene/polymer composite microporous foam, and the preparation steps are as follows:
s1, drying 50-micron polytetrafluoroethylene, 50-nm polytetrafluoroethylene and polypropylene granules at 60 ℃ for 24 hours;
s2, uniformly mixing 100g of dried 50-micron polytetrafluoroethylene and 50g of 50-nm polytetrafluoroethylene in the step S1 with 1kg of polyurethane granules;
s3, granulating the mixed material obtained in the step S2 through a double-screw extruder, wherein the temperature of the extruder is set to be 180 ℃, 190 ℃, 200 ℃, 210 ℃ and 200 ℃, and the screw rotating speed of the extruder is 100 rpm;
and S4, intermittently foaming the granules obtained in the step S3 through a high-pressure kettle, releasing pressure and foaming to obtain the polytetrafluoroethylene/polyurethane composite microporous foam, wherein the temperature of a foaming kettle is 200 ℃, the pressure in the kettle is 15MPa, the soaking time of the supercritical fluid is 2 hours.
Example 9
In this embodiment, a super-hydrophobic polytetrafluoroethylene/polymer composite microporous foam is provided by using polyethylene as a matrix material, and the preparation steps are as follows:
s1, drying 50-micron polytetrafluoroethylene, 50-nm polytetrafluoroethylene and polypropylene granules at 60 ℃ for 24 hours;
s2, uniformly mixing 100g of dried 50-micron polytetrafluoroethylene and 50g of 50-nm polytetrafluoroethylene in the step S1 with 1kg of polyethylene granules;
s3, granulating the mixed material obtained in the step S2 through a double-screw extruder, wherein the temperature of the extruder is set to be 150 ℃, 170 ℃, 200 ℃, 170 ℃, and the screw rotating speed of the extruder is 100 rpm;
and S4, carrying out microcellular foaming on the granules obtained in the step S3 through a supercritical fluid extruder, setting the temperature of the supercritical fluid extruder to be 150 ℃, 170 ℃, 200 ℃, 200 ℃ and 170 ℃, and controlling the pressure in the charging basket to be about 5MPa, and extruding to obtain the polytetrafluoroethylene/polyethylene composite microcellular foam.
Example 10
In this embodiment, a super-hydrophobic polytetrafluoroethylene/polymer composite microporous foam is provided by using polyethylene as a matrix material, and the preparation steps are as follows:
s1, drying 100 mu m of polytetrafluoroethylene, 100nm of polytetrafluoroethylene and polypropylene granules at 60 ℃ for 24 hours;
s2, uniformly mixing 100g of dried 100-micron polytetrafluoroethylene and 50g of 100-nm polytetrafluoroethylene in the step S1 with 1kg of polyethylene granules;
s3, granulating the mixed material obtained in the step S2 through an extruder, wherein the temperature of the extruder is set to be 150 ℃, 170 ℃, 200 ℃, 200 ℃ and 170 ℃, and the screw rotating speed of the extruder is 80 rpm;
and S4, intermittently foaming the granules obtained in the step S3 through a high-pressure kettle, releasing pressure and foaming to obtain the polytetrafluoroethylene/polyethylene composite microporous foam, wherein the temperature of a foaming kettle is 150 ℃, the pressure in the kettle is 8MPa, the soaking time of the supercritical fluid is 3 hours.
Example 11
In this embodiment, a super-hydrophobic polytetrafluoroethylene/polymer composite microporous foam is provided by using polystyrene as a matrix material, and the preparation steps are as follows:
s1, drying 50-micron polytetrafluoroethylene, 50-nm polytetrafluoroethylene and polypropylene granules at 60 ℃ for 24 hours;
s2, uniformly mixing 100g of dried 50-micron polytetrafluoroethylene and 50g of 50-nm polytetrafluoroethylene in the step S1 with 1kg of polystyrene granules;
s3, granulating the mixed material obtained in the step S2 through a double-screw extruder, wherein the temperature of the extruder is set to be 180 ℃, 220 ℃, 230 ℃, 250 ℃ and 240 ℃, and the screw rotating speed of the extruder is 100 rpm;
and S4, carrying out microcellular foaming on the granules obtained in the step S3 through a supercritical fluid extruder, setting the temperature of the supercritical fluid extruder to be 180 ℃, 220 ℃, 230 ℃, 250 ℃ and 240 ℃, and controlling the pressure in a charging basket to be about 10MPa, so as to obtain the polytetrafluoroethylene/polystyrene composite microcellular foam through extrusion.
Example 12
In this embodiment, a super-hydrophobic polytetrafluoroethylene/polymer composite microporous foam is provided by using polystyrene as a matrix material, and the preparation steps are as follows:
s1, drying 100 mu m of polytetrafluoroethylene, 100nm of polytetrafluoroethylene and polypropylene granules at 60 ℃ for 24 hours;
s2, uniformly mixing 100g of dried 100-micron polytetrafluoroethylene and 50g of 100-nm polytetrafluoroethylene in the step S1 with 1kg of polystyrene granules;
s3, granulating the mixed material obtained in the step S2 through an extruder, wherein the temperature of the extruder is set to be 180 ℃, 220 ℃, 230 ℃, 250 ℃ and 240 ℃, and the screw rotating speed of the extruder is 100 rpm;
and S4, intermittently foaming the granules obtained in the step S3 through a high-pressure kettle, releasing pressure and foaming to obtain the polytetrafluoroethylene/polystyrene composite microporous foam, wherein the temperature of a foaming kettle is 200 ℃, the pressure in the kettle is 20MPa, the soaking time of the supercritical fluid is 2 hours.
Comparative example 1
S1, drying polytetrafluoroethylene and polypropylene granules with the particle size of 50 microns at the temperature of 60 ℃ for 24 hours;
s2, uniformly mixing 100g of the dried 50-micron polytetrafluoroethylene obtained in the step S1 with 1kg of polypropylene granules;
s3, granulating the mixed material obtained in the step S2 through a double-screw extruder, wherein the temperature of the extruder is set to be 170 ℃, 210 ℃, 200 ℃, 190 ℃, and the screw rotating speed of the extruder is 100 rpm;
and S4, carrying out microcellular foaming on the granules obtained in the step S3 through a supercritical fluid extruder, setting the temperature of the supercritical fluid extruder to be 170 ℃, 210 ℃, 200 ℃, 190 ℃ and 190 ℃, controlling the pressure in the charging basket to be about 10MPa, and extruding to obtain the polytetrafluoroethylene/polypropylene composite microcellular foam.
The invention utilizes micron-scale and nano-scale polytetrafluoroethylene and high polymer materials to prepare the super-hydrophobic composite foam material through extrusion and super-fluid foaming processes, micron-scale polytetrafluoroethylene is utilized to form fibers in situ, and the nano-scale polytetrafluoroethylene and the micron-scale polytetrafluoroethylene form a multi-layer coarse structure, thereby achieving the super-hydrophobicity of the composite foam material. The invention has the advantages of single raw material and low cost. The preparation process is simple, the super-hydrophobic composite microporous foam material can be prepared by only extrusion and super-fluid foaming processes, and the composite microporous foam plate or block can be produced in large scale.
Through the comparison of fig. 1 and fig. 2 with fig. 3 and fig. 4, the surface of the microporous foam material to which the micrometer-scale and nanometer-scale polytetrafluoroethylene is added is rougher, so that a multistage rough structure is formed, and the hydrophobic property of the material is facilitated. From fig. 7-9, it is seen that the polytetrafluoroethylene/polypropylene composite microporous foam prepared by adopting the micron-scale polytetrafluoroethylene and the nano-scale polytetrafluoroethylene has super-hydrophobic performance, the water contact angle is larger than 150 degrees, and the hydrophobic performance is better than that of the polytetrafluoroethylene/polypropylene composite microporous foam prepared by adopting the micron-scale polytetrafluoroethylene. It can be seen from fig. 5, fig. 6 and fig. 10 that the polytetrafluoroethylene/polypropylene composite microporous foam after 500 times of grinding still has better hydrophobic property. As can be seen from FIG. 11, the PTFE/PP syntactic microcellular foam prepared according to the present invention can adsorb various organic substances well. Therefore, the polytetrafluoroethylene/high polymer material composite microporous foam prepared by the method has the effects of super-hydrophobicity, high adsorption and strong practicability.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (8)
1. A preparation method of super-hydrophobic polytetrafluoroethylene/high polymer material composite microporous foam is characterized in that the inner and outer surfaces of the super-hydrophobic polytetrafluoroethylene/high polymer material composite microporous foam are covered with multi-level rough polytetrafluoroethylene networks and particles, and the preparation method comprises the following steps:
s1, drying micron-sized polytetrafluoroethylene, nano-sized polytetrafluoroethylene and high polymer materials;
s2, uniformly mixing the micron-sized polytetrafluoroethylene, the nano-sized polytetrafluoroethylene and the high polymer material in the step S1;
s3, granulating the mixed material obtained in the step S2 through an extruder;
s4, foaming the granules obtained in the step S3 to prepare the super-hydrophobic polytetrafluoroethylene/polymer composite microporous foam;
s1, the diameter of the micron-sized polytetrafluoroethylene is 5-100 mu m, and the diameter of the nano-sized polytetrafluoroethylene is 10-100 nm; the polymer material in step S1 includes one or more of polyethylene, polypropylene, polyurethane, polylactic acid, ABS, and polystyrene.
2. The preparation method of the superhydrophobic polytetrafluoroethylene/high polymer material composite microcellular foam according to claim 1, wherein the addition amount of the micron-sized polytetrafluoroethylene is 2-10% of the mass of the high polymer material, and the addition amount of the nano-sized polytetrafluoroethylene is 1-5% of the mass of the high polymer material.
3. The method of claim 1, wherein step S2 further comprises adding one or more of an antioxidant, a thermal stabilizer, a reinforcing agent, a toughening agent, and a coupling agent.
4. The method for preparing the superhydrophobic polytetrafluoroethylene/high polymer material composite microcellular foam according to claim 1, wherein the extrusion granulation in the step S3 adopts a twin-screw extruder or a multi-screw extruder, the temperature of the extruder is 150-250 ℃, and the screw rotation speed is 80-150 rpm.
5. The method for preparing the superhydrophobic polytetrafluoroethylene/polymer composite microcellular foam according to claim 1, wherein the foaming method in step S4 is a supercritical fluid extrusion foaming method or a batch foaming method.
6. The method for preparing the superhydrophobic polytetrafluoroethylene/high polymer material composite microcellular foam according to claim 5, wherein the supercritical fluid in the supercritical fluid extrusion foaming method is nitrogen or carbon dioxide.
7. The preparation method of the superhydrophobic polytetrafluoroethylene/high polymer material composite microcellular foam according to claim 5, wherein the extrusion temperature in the extrusion foaming process of the supercritical fluid is 150-250 ℃, the extrusion foaming is carried out by adopting the single-screw or double-screw supercritical fluid, and the pressure in a charging basket is 5-15 MPa; the intermittent foaming temperature is 150-200 ℃, the pressure is 8-20 MPa, the soaking time of the supercritical fluid is 2-5 h, and a one-step pressure relief method is adopted for foaming.
8. The preparation method of the superhydrophobic polytetrafluoroethylene/high polymer material composite microcellular foam according to claim 1, wherein the cells of the prepared superhydrophobic polytetrafluoroethylene/high polymer composite microcellular foam are 10-50 μm.
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| EP3838972A1 (en) * | 2019-12-20 | 2021-06-23 | SHPP Global Technologies B.V. | Foamed polymer compositions including a nanostructured fluoropolymer |
| CN112457592A (en) * | 2020-11-30 | 2021-03-09 | 上海普利特复合材料股份有限公司 | Long-acting stain-resistant, sticky-resistant and illumination-resistant polypropylene composite material for vehicles and preparation method thereof |
| CN113580520B (en) * | 2021-07-23 | 2023-04-18 | 浙江赛迅环保科技有限公司 | Polytetrafluoroethylene plate and preparation process thereof |
| CN114316452B (en) * | 2022-01-04 | 2024-04-23 | 苏州浩纳新材料科技有限公司 | Super-hydrophobic foamed polypropylene and preparation method thereof |
| CN115124801B (en) * | 2022-07-12 | 2024-02-13 | 浙江巨化新材料研究院有限公司 | FEP (fluorinated ethylene propylene) physically foamed cable insulating layer material for signal transmission and preparation method thereof |
| CN115403815B (en) * | 2022-10-08 | 2023-05-12 | 郑州大学 | Preparation method of microporous foam material with oriented cells |
| CN115418047A (en) * | 2022-11-03 | 2022-12-02 | 无锡会通轻质材料股份有限公司 | Low-friction-coefficient foaming material and preparation method and application thereof |
| CN115975373A (en) * | 2023-01-30 | 2023-04-18 | 江苏司达瑞新材料科技有限公司 | Thermoplastic foaming particle, preparation method thereof and foaming particle forming body |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102239224A (en) * | 2008-07-02 | 2011-11-09 | 微粉公司 | Compositions and processes for producing durable hydrophobic and/or olephobic surfaces |
| CN106009014A (en) * | 2016-07-04 | 2016-10-12 | 杨得全 | Method for producing super-hydrophobic polytetrafluoroethylene films through glass template process |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US6528574B1 (en) * | 1999-03-11 | 2003-03-04 | E. I. Du Pont De Nemours And Company | Blends of aqueous dispersions of fluoropolymers and aqueous dispersions of ethylene/acid or ionomeric copolymers |
| CN101474895A (en) * | 2009-01-21 | 2009-07-08 | 重庆大学 | Ultra-hydrophobic film of thermoplastic substrate |
| US20120261182A1 (en) * | 2010-06-09 | 2012-10-18 | The Board Of Trustees Of The University Of Illinois | Liquid-repellent, large-area, electrically-conducting polymer composite coatings |
| US10266636B2 (en) * | 2014-03-11 | 2019-04-23 | Mitsui Chemicals, Inc. | Process for producing episulfide compound for optical material, episulfide-containing composition, and polymerizable composition for optical material including the same composition |
| CN105237792B (en) * | 2015-10-16 | 2018-06-29 | 青岛科技大学 | A kind of preparation method of polytetrafluoroethylene (PTFE) super-hydrophobic coat |
-
2018
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106009014A (en) * | 2016-07-04 | 2016-10-12 | 杨得全 | Method for producing super-hydrophobic polytetrafluoroethylene films through glass template process |
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