CN116622117B - Fluorine-based network intercommunicating porous structure composite material and preparation method thereof - Google Patents

Fluorine-based network intercommunicating porous structure composite material and preparation method thereof Download PDF

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CN116622117B
CN116622117B CN202310824834.3A CN202310824834A CN116622117B CN 116622117 B CN116622117 B CN 116622117B CN 202310824834 A CN202310824834 A CN 202310824834A CN 116622117 B CN116622117 B CN 116622117B
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fluorine
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porous structure
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CN116622117A (en
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李肖鹏
于呈呈
李磊
祁羽
李小磊
伍德民
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Ji Hua Laboratory
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    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
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    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
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Abstract

The invention discloses a fluorine-based network intercommunication porous structure composite material and a preparation method thereof, belonging to the field of high polymer materials, wherein the preparation steps comprise: uniformly mixing raw materials comprising a pore-forming agent, a melt penetrating agent, an intercalation agent and fluorine-based resin; cold pressing the raw materials to obtain a preform; sintering the preform, and removing the pore-forming agent to obtain the fluorine-based network intercommunication porous structure composite material; the melt penetrating agent is sucrose or maltose; the intercalation agent is a fiber material, the decomposition temperature of the intercalation agent is lower than the temperature required by sintering the preform, and the fusion penetrating agent forms a radiation three-dimensional pore structure taking the hole as the center; the intercalation agent utilizes the larger length-diameter ratio to alternate the radial pore structure into a network structure, and the pore-forming agent is easier to remove, so that the storage capacity of the material is increased, the material has larger specific surface area and porosity, and the intercalation agent can meet certain adsorption and liquid storage functions while endowing the material with better mechanical properties, is suitable for various micro-nano storage and adsorption working conditions, and greatly widens the application scene of the material.

Description

Fluorine-based network intercommunicating porous structure composite material and preparation method thereof
Technical Field
The invention relates to a fluorine-based network intercommunication porous structure composite material and a preparation method thereof, belonging to the field of high polymer materials.
Background
The fluorine-based material has strong C-F bond energy, so that the fluorine-based material has strong corrosion resistance, strong acid and alkali resistance, high and low temperature resistance, high lubrication, electric insulation and other excellent performances, and is widely applied to the working conditions of sound insulation, heat insulation, lubrication, electromagnetic insulation, adsorption, filtration and the like.
Compared with the traditional physical filling modification, the porous structure fluorine-based material has more excellent elasticity and flexibility, and can meet the requirements of more lubrication working conditions on the fluorine-based material. The traditional preparation principle of the porous fluorine-based material is that a solid pore-forming agent and a fluorine-containing material are mixed and molded into a blank body, so that the pore-forming agent occupies a certain space in the material, and after the porous fluorine-based material is molded, the pore-forming agent is dissolved by washing or decomposed at high temperature to form a certain gap structure, so that the porous fluorine-based material is obtained.
However, the material obtained by the traditional preparation method has more closed spaces inside, and on one hand, the closed spaces can reduce the specific surface area and the storage space; on the other hand, part of pore-forming agent exists in the closed space, solvent can not wash the pore-forming agent in the closed space, and the pore-forming agent decomposed at high temperature can not volatilize from the closed space, so that more pore-forming agent can not be removed in the porous fluorine-based material prepared by the traditional method, and the specific surface area and the storage space are further reduced.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a fluorine-based network intercommunicating porous structure composite material and a preparation method thereof, which have little closed space and larger specific surface area and storage space.
The technical scheme adopted for solving the technical problems is as follows:
In a first aspect, the application provides a method for preparing a fluorine-based network interworking porous structure composite material, which comprises the following steps: uniformly mixing raw materials comprising a pore-forming agent, a melt penetrating agent, an intercalation agent and fluorine-based resin; cold pressing the raw materials to obtain a preform; sintering the preform, and removing the pore-forming agent to obtain the fluorine-based network intercommunication porous structure composite material; the melt penetrating agent is sucrose or maltose; the intercalating agent is a fibrous material and has a decomposition temperature lower than the temperature required to sinter the preform.
The preparation method of the fluorine-based network intercommunicating porous structure composite material provided by the application is used for pore-forming agents, and also comprises the steps of using a melting penetrating agent and an intercalation agent, wherein the melting penetrating agent is sucrose or maltose, the melting point is low, the melt index is high, the melting penetrating agent is melted and flows into various gaps in a preform in the sintering heating process, particularly gaps between the pore-forming agent and fluorine-based resin, the pore-forming agent is carbonized in the sintering high temperature to form a radial pore carbon structure, the intercalation agent serving as strip fibers is contacted with the pore-forming agent in the preform and also contacted with the melting penetrating agent, and is bridged between the pore-forming agent and the pore-forming agent, between the pore-forming agent and the melting penetrating agent and between the melting penetrating agent and the melting penetrating agent, so that the intercalation agent is decomposed in the sintering high temperature, various holes are communicated, and the pore-forming agent penetrating into the material also has a channel leading to the surface of the material, thereby being beneficial to fully removing the pore-forming agent, and increasing the specific surface area and storage space.
Further, the raw materials comprise 40-90% of fluorine-based resin, 4-30% of pore-forming agent, 1-10% of melt penetrating agent and 5-20% of intercalation agent by mass. The melting point of the melt penetrant is low, the melt index is high, and the melt penetrant is favorable for flowing in the heating process of sintering, however, the content of the melt penetrant is not excessive, otherwise, the radial structure is increased, but the liquid component is excessive in the sintering process, and the preform is easy to deform after sintering. The intercalation agent is used for communicating various holes, the content of the intercalation agent is not too high, otherwise, the connection between fluorine-based resins is not strong enough, and the strength of the sintered material is not enough easily.
Further, the technological requirements during sintering are that the temperature is raised from room temperature to 200-240 ℃ at the temperature raising speed of 150-200 ℃/h, the temperature is kept for 20-60 min, then the temperature is raised to 320-385 ℃ at the temperature raising speed of 50-70 ℃/h, the temperature is kept for 1-4 h, the temperature is lowered to 200-240 ℃ at the temperature lowering speed of 30-80 ℃/h, and the temperature is kept for 1-3 h and then the temperature is naturally cooled to the room temperature.
The sintering process enables the molten penetrant to flow in the material at a proper temperature and for a sufficient time between molten and carbonized states, is favorable for making a sufficient radial structure by using a small amount of the molten penetrant, and avoids deformation of the preform after sintering caused by using too much molten penetrant; the sintering process takes into account the annealing after the sintering of the fluorine-based resin and the time of the decomposition of the intercalation agent and the carbonization of the melt infiltration agent, so that the finished product material has enough strength and pores.
Further, the fluorine-based resin is selected from polytetrafluoroethylene, perfluoroethylene propylene or ethylene-tetrafluoroethylene copolymer.
Further, the fluorine-based resin is molding powder or dispersing powder, and the particle size is 90nm-3000 mu m. If the particle diameter of the fluorine-based resin is too large, it is difficult for the pore-forming agent, the melt-penetrating agent, and the intercalating agent to be uniformly distributed in the material.
Further, the pore-forming agent is selected from citric acid, agarose, polystyrene powder, polyvinyl alcohol, polymethyl methacrylate, hydroxyethyl cellulose, urea, naphthalene or sodium chloride.
For example, agarose starts to decompose at about 250 ℃, polystyrene powder starts to decompose at about 300 ℃, polyvinyl alcohol starts to decompose at about 200 ℃, polymethyl methacrylate starts to decompose at about 270 ℃, hydroxyethyl cellulose starts to decompose at about 208 ℃, citric acid, urea, sodium chloride, polyvinyl alcohol are soluble in water, and naphthalene sublimates at 145 ℃.
Further, the particle size of the pore-forming agent ranges from 80nm to 2000 μm.
Further, the particle size of the melt penetrant ranges from 80nm to 1000 μm. Although the melt infiltrant is quickly brought into a molten state during sintering, the primary particle size at the time of mixing is still important, and the primary particle size is related to the size of the holes left after the melt infiltrant is melted, the flow range at the time of melting and the size of the radial structure formed after carbonization.
Further, the intercalating agent is in a carbonised form at the decomposition temperature. The intercalation agent bridges between pore-forming agent and pore-forming agent, between pore-forming agent and molten penetrating agent, between molten penetrating agent and molten penetrating agent, span is large, if intercalation agent material can be completely converted into gas when sintered and dissipated, although the connectivity between various pores is stronger, pore-forming agent is easier to remove from material, but many positions between fluorine-based resin in the material are overhead, which can result in lower material strength. When the intercalation agent is carbonized in its decomposed form, the fibers form "porous carbon bridges" after carbonization, which connect the pores made by the pore-forming agent and the pores left by the melted infiltrant, and compensate for the strength of the material to some extent.
Further, the intercalating agent is selected from low temperature decomposable fiber materials such as ramie fibers, flax fibers, jute fibers, polyethylene fibers or polyvinyl chloride fibers.
Still further, the intercalating agent has an aspect ratio of 500-2000.
Under the condition of larger length-diameter ratio, the intercalating agent can spontaneously curl and twist to form a more complex connected network, so that the specific surface area of the material can be further improved.
In a second aspect, the application provides a fluorine-based network interconnected porous structure composite material prepared by the preparation method in the first aspect. The material takes fluorine-based resin as a base, holes made by pore formers, holes formed by flowing the molten penetrant to other places, radial pore carbon structures formed by flowing the molten penetrant to the periphery and channels formed by decomposing an intercalation agent are distributed in the material, and the channels are communicated with the holes, so that the pore formers are easier to remove, and the specific surface area and the storage capacity of the material are increased.
The beneficial effects of the invention are as follows: besides pore-forming agent used in general method, the invention also uses molten penetrating agent and intercalation agent, the molten penetrating agent is sucrose or maltose, melting point is low, melt index is high, in the course of raising temperature of sintering, it is melted and flowed into various gaps in the preformed body, in particular into gaps between pore-forming agent and fluorine-based resin, and continuously carbonized in high temperature of sintering to form pore-carbon structure with radial form, and the intercalation agent as strip-shaped fibre is contacted with both pore-forming agent and molten penetrating agent in preformed body, and is bridged between pore-forming agent and pore-forming agent, between pore-forming agent and molten penetrating agent, and between molten penetrating agent and molten penetrating agent, and intercalation agent is decomposed in high temperature of sintering, so that various holes are communicated, pore-forming agent deep into material also has channel leading to surface of material, so that it is favorable for fully removing pore-forming agent, and increasing specific surface area and storage space.
Additional features and advantages of the application will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the application. The objectives and other advantages of the application may be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
Fig. 1 is a schematic diagram of the principle of action of a porous structure composite material interconnected by a fluorine-based network according to an embodiment of the present application.
Fig. 2 is a mirror morphology diagram of a fluorine-based network interworking porous structure composite material provided in embodiment 1 of the present application.
Fig. 3 is a physical diagram of a porous structure composite material with fluorine-based network intercommunication provided in embodiment 3 of the present application.
Detailed Description
The following disclosure provides many different embodiments, or examples, for implementing different features of the invention. In order to simplify the present disclosure, components and arrangements of specific examples are described below. They are, of course, merely examples and are not intended to limit the invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples, which are for the purpose of brevity and clarity, and which do not themselves indicate the relationship between the various embodiments and/or arrangements discussed.
The porous structure fluorine-based material prepared by the prior art has more closed spaces, if the pore-forming principle of the pore-forming agent is that the solvent washes away the pore-forming agent to leave holes, the pore-forming agent in the closed spaces cannot be contacted with the solvent, and the holes cannot be formed in the material all the time; if the pore-forming principle of the pore-forming agent is that the pore-forming agent is decomposed to leave holes, the holes cannot be communicated although gas generated in the decomposition process of the pore-forming agent leaves holes, and the overall storage capacity of the material is low.
Aiming at the problem, the invention provides a preparation method of a fluorine-based network intercommunicating porous structure composite material, and the intercommunicating porous material prepared by the method can be applied to working condition occasions such as sound insulation, heat insulation, lubrication, sealing, electromagnetic insulation, adsorption, filtration and the like. The method is realized by the following steps:
S1: uniformly mixing raw materials comprising a pore-forming agent, a melt penetrating agent, an intercalation agent and fluorine-based resin.
S2: cold pressing the raw materials to obtain a preform.
S3: sintering the preform, and removing the pore-forming agent to obtain the fluorine-based network intercommunication porous structure composite material.
The melt penetrant is sucrose or maltose, the melting point is low, the melt index is high, the melt penetrant is melted and flows into various gaps in the preform in the sintering heating process, particularly gaps between the pore-forming agent and the fluorine-based resin, as shown in figure 1, the carbonization is continued in the sintering high temperature to form a radial pore carbon structure, the intercalation agent serving as strip fiber is contacted with the pore-forming agent in the preform and also contacted with the melt penetrant, and bridges between the pore-forming agent and the pore-forming agent, between the pore-forming agent and the melt penetrant and between the melt penetrant, and the intercalation agent is decomposed in the sintering high temperature, so that various holes are communicated, and the pore-forming agent penetrating into the material is provided with a channel leading to the surface of the material, so that the pore-forming agent is favorable for sufficiently removing the pore-forming agent, and the specific surface area and the storage space are increased.
If the pore-forming principle of the pore-forming agent is that the pore-forming agent is decomposed to leave holes, the heating in the sintering process of the step S3 synchronously realizes the removal of the pore-forming agent because the intercalation agent is communicated with various holes; if the pore-forming principle of the pore-forming agent is that the solvent washes away the pore-forming agent to leave holes, the step S3 is specifically that the solvent is used for washing and drying after sintering and cooling.
The prepared material takes fluorine-based resin as a base, holes made by pore formers, holes formed by flowing the molten penetrant to other places, radial pore carbon structures formed by flowing the molten penetrant to the periphery and channels formed by decomposing an intercalation agent are distributed in the material, and the channels are communicated with the holes, so that the pore formers are easier to remove, and the specific surface area and the storage capacity of the material are increased.
The dosage of each raw material is as follows by mass: 40-90% of fluorine-based resin, 4-30% of pore-forming agent, 1-10% of melt penetrating agent and 5-20% of intercalation agent. The intercalation agent is used for communicating various holes, the content of the intercalation agent is not too high, otherwise, the connection between fluorine-based resins is not strong enough, and the strength of the sintered material is not enough easily. The melting point of the melt penetrant is low, the melt index is high, and the melt penetrant is favorable for flowing in the heating process of sintering, however, the content of the melt penetrant is not excessive, otherwise, the radial structure is increased, but the liquid component is excessive in the sintering process, and the preform is easy to deform after sintering.
How to use less melt penetrating agent to ensure that the material is not deformed and collapsed after sintering, and how to effectively increase the porosity of the material by using the melt penetrating agent is a difficulty of research. For this reason, preferably, the process requirements during sintering are that the temperature is raised from room temperature to 200-240 ℃ at a heating rate of 150-200 ℃/h, the temperature is kept for 20-60 min, then the temperature is raised to 320-385 ℃ at a heating rate of 50-70 ℃/h, the temperature is kept for 1-4 h, the temperature is lowered to 200-240 ℃ at a cooling rate of 30-80 ℃/h, and the temperature is kept for 1-3 h and then the temperature is naturally cooled to room temperature.
The sintering process allows sufficient time and temperature for the melt infiltrant to flow in the material between the molten and carbonized state, facilitating the use of a small amount of melt infiltrant to make enough radial structure to avoid excessive melt infiltrant to cause deformation of the preform after sintering. In addition, the sintering process takes into account the annealing after the fluorine-based resin is sintered and the time for the intercalation agent to decompose and the melt infiltration agent to carbonize, so that the finished product material has enough strength and pores.
Preferably, the intercalating agent is selected from natural fibers such as ramie fibers, flax fibers, jute fibers, etc., synthetic fibers such as polyethylene fibers or polyvinyl chloride fibers, etc. The selection of the fibers has the following advantages: first, the decomposition temperature of the fibers is lower than the sintering temperature of the fluorine-based resin and higher than the melting temperature of the melt penetrant, so that the premature communication of various holes is avoided, the melt penetrant flows downwards to accumulate, the fibers are decomposed only in the carbonization stage of the melt penetrant, and the melt penetrant can only flow in a gap nearby the melt penetrant and expand under heating, so that a radial structure is formed. Second, the fibers are carbonized in their decomposed form, which forms "porous carbon bridges" that connect the pores made by the pore-forming agent and the pores left by the melted infiltrant, and compensate for the strength of the material to some extent. Thirdly, these fiber transactions achieve an aspect ratio of 500-2000 at which the intercalating agent spontaneously coils and entangles, forming a more complex connected network, which can further increase the specific surface area of the material.
Example 1
90 Parts of polytetrafluoroethylene, 4 parts of polystyrene powder, 1 part of maltose and 5 parts of flax fiber with an aspect ratio of 500 are weighed, the components are dried at 80 ℃ for 24 hours, and then are uniformly mixed by shaking, and the powder is obtained for standby after sieving. Pouring the powder into a mould, pressing for 30 minutes under the pressure of 100 MPa, demoulding, and putting the formed material into a sintering furnace for sintering. The sintering temperature is raised to 220 ℃ from room temperature at 150 ℃/h, then the temperature is raised to 375 ℃ at 60 ℃/h, the temperature is kept for 2 hours, and after the sintering is finished, the temperature is lowered to 220 ℃ at 40 ℃/h, the temperature is kept for 2 hours, and then the composite material with the polytetrafluoroethylene network intercommunication porous structure is obtained by natural cooling.
The obtained material sample is observed under a light microscope, the morphology of the material sample is shown as figure 2, and it can be seen that besides the holes left by the common pore-forming agent, the abnormal holes formed by the flowing of the molten penetrating agent are radial, and also pore carbon structures formed by carbonizing the molten penetrating agent are formed, and channels communicated with the holes are left at the positions of the intercalation agent.
Example 2
40 Parts of perfluoroethylene propylene, 30 parts of hydroxyethyl cellulose, 10 parts of sucrose and 20 parts of jute fiber with the length-diameter ratio of 600 are weighed, all the components are dried at 80 ℃ for 24 h, and then are vibrated and uniformly mixed, and the powder is obtained for standby after sieving. Pouring the powder into a mould, pressing for 20 minutes under the pressure of 120 MPa, demoulding, and putting the formed material into a sintering furnace for sintering. The sintering temperature is raised to 200 ℃ from room temperature at 160 ℃/h, then the temperature is kept for 20 minutes, then the temperature is raised to 320 ℃ at the speed of 50 ℃/h, the temperature is kept for 1 hour, and after the sintering is finished, the temperature is lowered to 240 ℃ at the speed of 30 ℃/h, the temperature is kept for 1 hour, and then the porous structure composite material with the network intercommunication of the poly (perfluoroethylene-propylene) is obtained.
Example 3
Weighing 60 parts of polytetrafluoroethylene, 20 parts of sodium chloride, 10 parts of sucrose and 10 parts of jute fiber with the length-diameter ratio of 700, drying the components at 80 ℃ for 24 hours, vibrating and uniformly mixing, and sieving to obtain powder for later use. Pouring the powder into a mould, pressing for 45 minutes under the pressure of 130 MPa, demoulding, and putting the formed material into a sintering furnace for sintering. The sintering temperature is raised to 230 ℃ from room temperature at 170 ℃/h, then is kept for 60 minutes, is raised to 385 ℃ at the rate of 70 ℃/h, is kept for 3 hours, is cooled to 200 ℃ at the rate of 80 ℃/h after the sintering is finished, and is kept for 3 hours, and then is naturally cooled. Filtering the sintered material in tap water to remove soluble sodium chloride, and drying to obtain the polytetrafluoroethylene network interconnected porous composite material.
The obtained material object is shown in fig. 3, and has the same size as the pressed compact, the diameter of 20mm and the height of 5mm, and no deformation and collapse after sintering.
Example 4
Weighing 80 parts of ethylene-tetrafluoroethylene copolymer, 5 parts of polyvinyl alcohol, 10 parts of maltose and 5 parts of polyethylene fiber with the length-diameter ratio of 2000, drying the components at 80 ℃ for 24 h, vibrating and uniformly mixing, and sieving to obtain powder for later use. Pouring the powder into a mould, pressing for 5 minutes under the pressure of 150 MPa, demoulding, and putting the formed material into a sintering furnace for sintering. The sintering temperature is raised to 240 ℃ from room temperature at 200 ℃/h, then the temperature is kept for 60 minutes, then the temperature is raised to 330 ℃ at the speed of 65 ℃/h, the temperature is kept for 4 hours, and after the sintering is finished, the temperature is lowered to 230 ℃ at 60 ℃/h, the temperature is kept for 2 hours, and then the temperature is naturally cooled, so that the ethylene-tetrafluoroethylene copolymer network intercommunication porous structure composite material is obtained.
Comparative example 1
Weighing 95 parts of polytetrafluoroethylene and 4 parts of polystyrene powder, drying the components at 80 ℃ for 24 hours, vibrating and uniformly mixing, and sieving to obtain powder for later use. Pouring the powder into a mould, pressing for 30 minutes under the pressure of 100 MPa, demoulding, and putting the formed material into a sintering furnace for sintering. The sintering temperature is raised to 220 ℃ from room temperature at 150 ℃/h, then the temperature is raised to 375 ℃ at 60 ℃/h, the temperature is kept for 2 hours, and after the sintering is finished, the temperature is lowered to 220 ℃ at 40 ℃/h, the temperature is kept for 2 hours, and then the composite material with the polytetrafluoroethylene network intercommunication porous structure is obtained by natural cooling.
Comparative example 2
96 Parts of polytetrafluoroethylene, 4 parts of polystyrene powder and 1 part of maltose are weighed, the components are dried at 80 ℃ for 24 hours, and then are uniformly mixed by shaking, and the powder is obtained after sieving for standby. Pouring the powder into a mould, pressing for 30 minutes under the pressure of 100 MPa, demoulding, and putting the formed material into a sintering furnace for sintering. The sintering temperature is raised to 220 ℃ from room temperature at 150 ℃/h, then the temperature is raised to 375 ℃ at 60 ℃/h, the temperature is kept for 2 hours, and after the sintering is finished, the temperature is lowered to 220 ℃ at 40 ℃/h, the temperature is kept for 2 hours, and then the composite material with the polytetrafluoroethylene network intercommunication porous structure is obtained by natural cooling.
Comparative example 3
91 Parts of polytetrafluoroethylene, 4 parts of polystyrene powder and 5 parts of flax fiber with the length-diameter ratio of 900 are weighed, the components are dried at 80 ℃ for 24 hours, and then are uniformly mixed by shaking, and the powder is obtained for standby after sieving. Pouring the powder into a mould, pressing for 30 minutes under the pressure of 100 MPa, demoulding, and putting the formed material into a sintering furnace for sintering. The sintering temperature is raised to 220 ℃ from room temperature at 150 ℃/h, then the temperature is raised to 375 ℃ at 60 ℃/h, the temperature is kept for 2 hours, and after the sintering is finished, the temperature is lowered to 220 ℃ at 40 ℃/h, the temperature is kept for 2 hours, and then the composite material with the polytetrafluoroethylene network intercommunication porous structure is obtained by natural cooling.
Comparative example 4
Weighing 90 parts of polytetrafluoroethylene, 4 parts of polystyrene powder, 1 part of maltose and 5 parts of flax fiber with the length-diameter ratio of 2500, drying the components at 80 ℃ for 24 hours, vibrating and uniformly mixing, and sieving to obtain powder for later use. Pouring the powder into a mould, pressing for 30 minutes under the pressure of 100 MPa, demoulding, and putting the formed material into a sintering furnace for sintering. The sintering temperature is raised to 220 ℃ from room temperature at 150 ℃/h, then the temperature is raised to 375 ℃ at 60 ℃/h, the temperature is kept for 2 hours, and after the sintering is finished, the temperature is lowered to 220 ℃ at 40 ℃/h, the temperature is kept for 2 hours, and then the composite material with the polytetrafluoroethylene network intercommunication porous structure is obtained by natural cooling.
Comparative example 5
74 Parts of polytetrafluoroethylene, 4 parts of polystyrene powder, 1 part of maltose and 21 parts of flax fiber with an aspect ratio of 800 are weighed, the components are dried at 80 ℃ for 24 hours, and then are uniformly mixed by shaking, and the powder is obtained for standby after sieving. Pouring the powder into a mould, pressing for 30 minutes under the pressure of 100 MPa, demoulding, and putting the formed material into a sintering furnace for sintering. The sintering temperature is raised to 220 ℃ from room temperature at 150 ℃/h, then the temperature is raised to 375 ℃ at 60 ℃/h, the temperature is kept for 2 hours, and after the sintering is finished, the temperature is lowered to 220 ℃ at 40 ℃/h, the temperature is kept for 2 hours, and then the composite material with the polytetrafluoroethylene network intercommunication porous structure is obtained by natural cooling.
The cake-shaped fluorine-based network interworking porous structure composite materials prepared in examples 1 to 4 and comparative examples 1 to 5 were subjected to test evaluation, and included: the specific surface area of the material system is tested, and the larger the specific surface area is, the higher the porosity is; carrying out vacuum oil absorption test on the material, wherein the test time is 24 hours; the compression strength is tested by a universal laboratory; the coefficient of friction characterizing the lubricating properties was determined using a reciprocating frictional wear tester. The test results are shown in Table 1.
TABLE 1
Comparative example 1 is a conventional pore-forming method, and as can be seen from table 1, the pore volume and oil absorption of comparative example 1 are both low; in comparative example 2, only the melt penetrant was added, and the porosity and oil absorption were slightly improved as compared with comparative example 1; in comparative example 3, only the intercalating agent was added, and the porosity and oil absorption were also improved to a small extent as compared with comparative example 1; however, unlike examples 1 to 4, it is assumed that the comparative example 3 has the intercalating agent bridged, but the pores left by the pore-forming agent cannot be expanded to the outer periphery due to the lack of the molten penetrating agent to form a radial structure, and a plurality of pores still cannot be contacted with the intercalating agent, so that the channels between part of the pores are relatively narrow, and the sufficient removal of the pore-forming agent is not facilitated. The network interconnected porous materials prepared in examples 1-4 have higher porosity and oil absorption, confirming that there is a synergistic effect of the melt penetrant and the intercalating agent. In comparative example 4, the addition of the excessively long intercalating agent material, although the porosity and oil absorption rate are improved, the compression strength is obviously reduced, and the application requirement cannot be met; in comparative example 5, too much intercalating agent was added, and the effect of coating the fluorine-based material was reduced by the more intercalating agent, resulting in a decrease in system strength and a decrease in friction lubrication performance, probably due to too severe entanglement of fibers, difficulty in uniform distribution, and concentration of material stress.
Therefore, the embodiment of the application fills the pore-forming agent, the melting penetrating agent and the intercalation agent into the fluorine-containing material, and the melting penetrating agent forms a radial three-dimensional pore structure taking the pore as the center while the pore-forming agent uniformly forms pores; the intercalating agent uses its larger aspect ratio to interpenetrate the radial pore structure into a network structure. The structure has larger specific surface area and porosity, can meet certain adsorption and liquid storage functions while endowing the material with better mechanical properties, greatly widens the application scene of the material, and is suitable for various micro-nano storage and adsorption working conditions.
In the description of the present specification, the descriptions of the terms "one embodiment," "certain embodiments," "an exemplary embodiment," "an example," "a particular example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that changes and modifications may be made without departing from the principles of the invention, such changes and modifications are also intended to be within the scope of the invention.

Claims (6)

1. The preparation method of the fluorine-based network intercommunicating porous structure composite material is characterized by comprising the following steps of: uniformly mixing raw materials comprising a pore-forming agent, a melt penetrating agent, an intercalation agent and fluorine-based resin; cold pressing the raw materials to obtain a preform; sintering the preform, and removing the pore-forming agent to obtain the fluorine-based network intercommunication porous structure composite material; the melt penetrating agent is sucrose or maltose; the intercalation agent is a fiber material, and the decomposition temperature of the intercalation agent is lower than the temperature required for sintering the preform;
the fluorine-based resin is selected from polytetrafluoroethylene, perfluoroethylene propylene or ethylene-tetrafluoroethylene copolymer;
The pore-forming agent is selected from citric acid, agarose, polystyrene powder, polyvinyl alcohol, polymethyl methacrylate, hydroxyethyl cellulose, urea, naphthalene or sodium chloride;
The intercalation agent is selected from ramie fiber, flax fiber, jute fiber, polyethylene fiber or polyvinyl chloride fiber; the length-diameter ratio of the intercalating agent is 500-2000;
The raw materials comprise 40-90% of fluorine-based resin, 4-30% of pore-forming agent, 1-10% of melt penetrating agent and 5-20% of intercalation agent by mass.
2. The method for preparing the fluorine-based network intercommunication porous structure composite material according to claim 1, wherein the fluorine-based resin is molding powder or dispersion powder, and the particle size is 90nm-3000 μm.
3. The method for preparing a fluorine-based network interworking porous structure composite material according to claim 1, wherein the pore-forming agent has a particle size ranging from 80nm to 2000 μm.
4. The method for preparing a fluorine-based network interworking porous structure composite material according to claim 1, wherein the particle size of the melt infiltration agent is in the range of 80nm to 1000 μm.
5. The method for producing a fluorine-based network interworking porous structure composite according to claim 1, wherein the intercalation agent is carbonized in a decomposition form at the decomposition temperature.
6. A fluorine-based network interworking porous structure composite material, characterized by being produced by the production method according to any one of claims 1 to 5.
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CN109535614A (en) * 2018-12-18 2019-03-29 上海三爱富新材料科技有限公司 The preparation method of fiber reinforcement porous fluoropolymer polymer

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CN104245827A (en) * 2012-04-20 2014-12-24 大金工业株式会社 Composition mainly composed of ptfe, mixed powder, molding material, filtering medium for filter, air filter unit, and porous membrane manufacturing method
CN109535614A (en) * 2018-12-18 2019-03-29 上海三爱富新材料科技有限公司 The preparation method of fiber reinforcement porous fluoropolymer polymer

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