CN116442625B - PTFE composite film and preparation method thereof - Google Patents

PTFE composite film and preparation method thereof Download PDF

Info

Publication number
CN116442625B
CN116442625B CN202310723246.0A CN202310723246A CN116442625B CN 116442625 B CN116442625 B CN 116442625B CN 202310723246 A CN202310723246 A CN 202310723246A CN 116442625 B CN116442625 B CN 116442625B
Authority
CN
China
Prior art keywords
film
ptfe
stretching
membrane
graphene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202310723246.0A
Other languages
Chinese (zh)
Other versions
CN116442625A (en
Inventor
胥平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong Senrong New Materials Co ltd
Original Assignee
Shandong Senrong New Materials Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shandong Senrong New Materials Co ltd filed Critical Shandong Senrong New Materials Co ltd
Priority to CN202310723246.0A priority Critical patent/CN116442625B/en
Publication of CN116442625A publication Critical patent/CN116442625A/en
Application granted granted Critical
Publication of CN116442625B publication Critical patent/CN116442625B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32—Component parts, details or accessories; Auxiliary operations
    • B29C43/58—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
    • B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely thereto
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/02—Thermal after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

The invention belongs to the technical field of membrane materials, and particularly relates to a PTFE composite membrane and a preparation method thereof. The PTFE composite membrane provided by the invention is formed by compounding a base membrane and a reinforcing membrane, wherein the base membrane is arranged between two layers of reinforcing membranes; the base membrane is a dopamine modified PTFE membrane, and the reinforcing membrane is an Al-doped graphene modified PTFE membrane; the thickness of the basic film is 20-30 mu m; the thickness of the reinforcing film is 5-8 mu m. Through the cooperation of the base film and the reinforcing film, the prepared PTFE composite film not only has excellent tensile strength, but also has remarkably excellent wear resistance, greatly widens the application field of PTFE film materials, can be widely applied to high-frequency friction environments, and has longer service life.

Description

PTFE composite film and preparation method thereof
Technical Field
The invention belongs to the technical field of membrane materials, and particularly relates to a PTFE composite membrane and a preparation method thereof.
Background
Polytetrafluoroethylene (hereinafter abbreviated as PTFE) has excellent chemical stability and thermal stability, so that the polytetrafluoroethylene has good service performance and long service life under severe environments such as strong acid, strong alkali and the like and high-temperature working conditions, and is widely applied to the fields of air filtration, water filtration and clothing. At present, the preparation process of the mature PTFE membrane comprises the working procedures of mixing, preforming, calendaring, degreasing, longitudinal drawing, transverse drawing and the like, and the finished membrane has the characteristics of high porosity, large pore diameter and rough surface, so that the PTFE membrane has low tensile strength, and in an antifriction experiment, the surface of the membrane is extremely easy to generate heat, a fiber layer is induced to break, and the membrane surface is perforated and has poor abrasive resistance.
In the prior art, graphene is hybridized into a PTFE film, and the mutual interweaving of a graphene layer and PTFE resin can be realized by utilizing a multi-layer sheet structure of the graphene, so that the mechanical property of the PTFE film can be enhanced to a certain extent. However, the inventor finds that the wear resistance of the PTFE membrane material is still to be improved only by adopting a graphene hybridization mode, and the application of the PTFE membrane material in a high-frequency friction environment is often limited.
Disclosure of Invention
Aiming at the problem of low wear resistance of PTFE membrane materials in the prior art, the invention provides a PTFE composite membrane and a preparation method thereof. According to the invention, the dopamine-modified PTFE membrane is used as a base membrane, the Al-doped graphene-modified PTFE membrane is used as a reinforcing membrane, and the base membrane is arranged between two layers of reinforcing membranes, so that the prepared PTFE composite membrane has excellent tensile strength and also has remarkably excellent wear resistance, the application field of PTFE membrane materials is greatly widened, and the PTFE composite membrane can be widely applied to high-frequency friction environments and has longer service life.
The first aspect of the present invention provides a PTFE composite membrane, which is formed by compositing a base membrane and a reinforcing membrane, the base membrane being disposed between two reinforcing membranes; the base membrane is a dopamine modified PTFE membrane, and the reinforcing membrane is an Al-doped graphene modified PTFE membrane;
the thickness of the base film is 20-30 mu m, and the thickness of the reinforcing film is 5-8 mu m;
the preparation method of the Al-doped graphene comprises the following steps: adding graphene into deionized water, and performing ultrasonic treatment to obtain graphene dispersion; and adding the Al powder and the graphene dispersion liquid into absolute ethyl alcohol, and stirring, wherein the mass ratio of the Al powder to the graphene is 2:3, so as to obtain the Al-doped graphene material.
The PTFE composite film provided by the invention is a structure which is fully arranged in consideration of improving mechanical strength, particularly abrasion resistance. According to the invention, the PTFE membrane modified by dopamine is used as a basic membrane, dopamine can be oxidized and polymerized under the condition of a mild Tris-HCl buffer solution to form polydopamine which is adhered to the surface of the PTFE membrane, and the polydopamine has rich amino and hydroxyl, so that the surface of the PTFE membrane is modified, the PTFE membrane is easier to contact and fuse with the interface of the reinforcing membrane, substances in the reinforcing layer are more favorable to fill in gaps of the basic membrane, the compactness of the composite membrane is improved, and the tensile strength and the wear resistance of the composite membrane are further improved.
According to the invention, the Al-doped graphene-modified PTFE film is used as the reinforcing layer, and when graphene is mixed with PTFE dispersion resin, the multi-layer sheet structure of the graphene can promote the mutual interweaving of the graphene layer and the PTFE resin layer, so that the mechanical property of the composite film is improved. In order to further optimize the wear resistance, the invention introduces Al metal into the graphene as a reinforcing phase, so that the wear resistance of the PTFE film can be remarkably improved. It is particularly emphasized that the method selects to dope Al into graphene firstly and then modify PTFE together, and the main reason is that the graphene is helpful to help Al to be better dispersed, so that Al can be doped on the layered structure of the graphene with high dispersibility, and then the Al can be better crosslinked with the PTFE film layer to play the reinforcing effect when the mixture is blended and rolled with PTFE resin later.
Further, in the preparation method of the Al-doped graphene, after adding the Al powder and the graphene dispersion liquid into absolute ethyl alcohol, stirring and mixing for 12-24 hours at 50-80 ℃, and then washing, filtering and drying to obtain the Al-doped graphene material.
The second aspect of the invention provides a method for preparing a PTFE composite membrane, which comprises the following specific steps: cutting a base film and a reinforcing film into widths of 1-1.5m, arranging the base film and the reinforcing film in sequence, then pressing by adopting a roller, adjusting the pressure to 1-1.2MPa, enabling the pressed film to be transparent, standing for 3-4 hours in an environment of 300-350 ℃ for shaping after rolling, finally quickly immersing the shaped film in low-temperature water for 1-2min, taking out, standing and airing to obtain the PTFE composite film.
Based on the special structure of the PTFE composite film, the invention carries out reasonable design on the preparation process: firstly, cutting the basic film and the reinforcing film into required widths, after arranging the basic film and the reinforcing film in sequence, pressing the basic film and the reinforcing film by using a roller, and pressing the bulked composite film into a transparent blank film with less gaps, so that the basic film and the reinforcing film can be tightly combined together. Because the fiber structures inside the blank film are connected only by tiny Van der Waals force and are unstable, a one-step heat setting process is additionally arranged, the blank film is sintered at high temperature, the fiber structures inside the blank film are fused, the molecular structures are more compact after heat setting, the density is high, the surface smoothness is high, and the friction resistance performance is better. Since a large amount of stress still exists in the film and is not eliminated, the final step rapidly anneals the shaped film, and then the PTFE composite film with high tensile strength and high wear resistance is obtained.
The preparation method of the reinforced film comprises the following steps:
s1: ball-milling and mixing PTFE dispersion resin and Al-doped graphene, adding an extrusion aid and a coupling agent, fully mixing by a mixer, and aging in an oven;
s2: preforming and rolling the aged mixture to obtain an Al-doped graphene-modified PTFE film rolled tape;
s3: carrying out heat treatment on the Al-doped graphene-modified PTFE film rolled tape in a degreasing machine, removing extrusion aids, and fully puffing;
s4: and stretching the degreased film material, including longitudinal stretching and transverse stretching.
Further, the mass ratio of the PTFE dispersion resin to the Al-doped graphene to the extrusion aid to the coupling agent is 12:5:2:1.
Further, in the preparation method of the reinforced film: the coupling agent is a silane coupling agent; the extrusion aid is petroleum ether; the aging temperature is 40-60 ℃ and the aging time is 12-24 hours; in the rolling process, the rolling pressure is 0.5-0.8 MPa, and the compression ratio is 100-200; the temperature of the heat treatment in a degreasing machine is 250-300 ℃; the stretching treatment adopts the sequence of longitudinal stretching and transverse stretching, the stretching temperature is 300-350 ℃, the longitudinal stretching multiplying power is 10-20, and the transverse stretching multiplying power is 15-25.
The preparation method of the base film comprises the following steps:
A. dissolving dopamine hydrochloride in Tris-HCl buffer solution to obtain dopamine solution, soaking PTFE dispersion resin in the dopamine solution, and modifying under the condition that the pH value is 8.3-8.7;
B. fully mixing the dopamine modified PTFE dispersion resin and an extrusion aid through a mixer, and then aging in an oven;
C. preforming and rolling the aged mixture to obtain a dopamine modified PTFE membrane rolled tape;
D. carrying out heat treatment on the dopamine modified PTFE membrane rolled tape in a degreasing machine, removing extrusion assisting agent, and fully puffing;
E. and stretching the degreased film material, including longitudinal stretching and transverse stretching.
Further, the concentration of the dopamine solution is 5g/L-10g/L.
Further, the PTFE dispersion resin is soaked in the dopamine solution for modification for 10-12 hours.
Further, the mass ratio of the dopamine modified PTFE dispersion resin to the extrusion aid is 10:1.
Further, in the preparation method of the base film: the extrusion aid is petroleum ether; the aging temperature is 40-60 ℃ and the aging time is 12-24 hours; in the rolling process, the rolling pressure is 0.5-0.8 MPa, and the compression ratio is 100-200; the temperature of the heat treatment in a degreasing machine is 250-300 ℃; the stretching treatment adopts the sequence of longitudinal stretching and transverse stretching, the stretching temperature is 300-350 ℃, the longitudinal stretching multiplying power is 10-20, and the transverse stretching multiplying power is 15-25.
The beneficial effects obtained by one or more of the technical schemes of the invention are as follows:
according to the PTFE composite membrane provided by the invention, the dopamine modified PTFE membrane is used as a base membrane, the Al-doped graphene modified PTFE membrane is used as a reinforcing membrane, and the two membranes act together, so that the mechanical property of the composite membrane can be effectively improved. The PTFE composite film has the warp tensile strength and weft tensile strength of more than 60MPa, and also has excellent wear resistance, and friction is carried out under the conditions of 750g weights and 280-mesh grinding wheels, and the friction times can be more than 3 ten thousand times.
Detailed Description
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail below with reference to specific examples and comparative examples.
Example 1, this example provides a PTFE composite membrane, specifically prepared as follows:
(1) Preparation of the reinforcing film:
s1: adding graphene into deionized water, and performing ultrasonic treatment to obtain graphene dispersion; adding Al powder and graphene dispersion liquid into absolute ethyl alcohol (the mass ratio of the Al powder to the graphene is 2:3), stirring and mixing for 24 hours at 50 ℃, and then washing, filtering and drying to obtain an Al-doped graphene material;
s2: ball-milling and mixing PTFE dispersion resin and Al-doped graphene, adding petroleum ether and a silane coupling agent KH550 (the mass ratio of the PTFE dispersion resin to the Al-doped graphene to the petroleum ether to the silane coupling agent KH550 is 12:5:2:1), fully mixing by a mixer, and aging for 12 hours at 60 ℃ in an oven;
s3: preforming and rolling the aged mixture, wherein the rolling pressure is 0.6MPa, and the compression ratio is 100, so that the Al-doped graphene modified PTFE film rolled tape is obtained;
s4: carrying out heat treatment on the Al-doped graphene-modified PTFE film rolled tape in a degreasing machine at 300 ℃, removing extrusion aids, and fully puffing;
s5: and (3) stretching the degreased film material, wherein the stretching treatment adopts the sequence of longitudinal stretching and transverse stretching, the stretching temperature is 350 ℃, the longitudinal stretching multiplying power is 10, and the transverse stretching multiplying power is 15.
(2) Preparation of a base film:
A. 1g of dopamine hydrochloride is dissolved in 100ml of Tris-HCl buffer solution to obtain a dopamine solution, and PTFE dispersion resin is soaked in the dopamine solution for 10 hours for modification under the condition of pH=8.5;
B. fully mixing the dopamine modified PTFE dispersion resin and petroleum ether by a mixer, and aging for 24 hours at 40 ℃ in an oven (the mass ratio of the dopamine modified PTFE dispersion resin to the petroleum ether is 10:1);
C. preforming and rolling the aged mixture, wherein the rolling pressure is 0.5MPa, and the compression ratio is 200, so that the dopamine modified PTFE membrane rolled tape is obtained;
D. carrying out heat treatment on the dopamine modified PTFE membrane rolled tape in a degreasing machine at the temperature of 250 ℃, removing extrusion aids, and fully puffing;
E. and (3) stretching the degreased film material, wherein the stretching treatment adopts the sequence of longitudinal stretching and transverse stretching, the stretching temperature is 300 ℃, the longitudinal stretching multiplying power is 10, and the transverse stretching multiplying power is 15.
(3) Preparation of PTFE composite film:
cutting a base film and a reinforcing film into widths of 1m, arranging the base film and the reinforcing film in sequence, then adopting a roller to press, regulating the pressure to 1MPa, enabling the pressed film to be transparent, standing for 4 hours at 300 ℃ for shaping after rolling, finally quickly putting the shaped film into water for soaking for 1min, taking out, standing and airing to obtain a PTFE composite film with the film thickness of 30 mu m (the thickness of the base film is 20 mu m, and the thickness of the reinforcing film is 5 mu m).
Example 2 this example provides a PTFE composite membrane, specifically prepared as follows:
(1) Preparation of the reinforcing film:
s1: adding graphene into deionized water, and performing ultrasonic treatment to obtain graphene dispersion; adding Al powder and graphene dispersion liquid into absolute ethyl alcohol (the mass ratio of the Al powder to the graphene is 2:3), stirring and mixing for 12 hours at 80 ℃, and then washing, filtering and drying to obtain an Al-doped graphene material;
s2: ball-milling and mixing PTFE dispersion resin and Al-doped graphene, adding petroleum ether and a silane coupling agent KH550 (the mass ratio of the PTFE dispersion resin to the Al-doped graphene to the petroleum ether to the silane coupling agent KH550 is 12:5:2:1), fully mixing by a mixer, and aging for 24 hours at 40 ℃ in an oven;
s3: preforming and rolling the aged mixture, wherein the rolling pressure is 0.5MPa, and the compression ratio is 150, so that the Al-doped graphene modified PTFE film rolled tape is obtained;
s4: carrying out heat treatment on the Al-doped graphene-modified PTFE film rolled tape in a degreasing machine at 250 ℃, removing extrusion aids, and fully puffing;
s5: and (3) stretching the degreased film material, wherein the stretching treatment adopts the sequence of longitudinal stretching and transverse stretching, the stretching temperature is 300 ℃, the longitudinal stretching multiplying power is 20, and the transverse stretching multiplying power is 25.
(2) Preparation of a base film:
A. 1g of dopamine hydrochloride is dissolved in 100ml of Tris-HCl buffer solution to obtain a dopamine solution, and PTFE dispersion resin is soaked in the dopamine solution for 12 hours for modification under the condition of pH=8.5;
B. fully mixing the dopamine modified PTFE dispersion resin and petroleum ether by a mixer, and aging for 20 hours at 40 ℃ in an oven (the mass ratio of the dopamine modified PTFE dispersion resin to the petroleum ether is 10:1);
C. preforming and rolling the aged mixture, wherein the rolling pressure is 0.8MPa, and the compression ratio is 100, so that the dopamine modified PTFE membrane rolled tape is obtained;
D. carrying out heat treatment on the dopamine modified PTFE membrane rolled tape in a degreasing machine at 280 ℃, removing extrusion aids, and fully puffing;
E. and (3) stretching the degreased film material, wherein the stretching treatment adopts the sequence of longitudinal stretching and transverse stretching, the stretching temperature is 300 ℃, the longitudinal stretching multiplying power is 20, and the transverse stretching multiplying power is 25.
(3) Preparation of PTFE composite film:
cutting a base film and a reinforcing film into widths of 1m, arranging the base film and the reinforcing film in sequence, then adopting a roller to press, regulating the pressure to 1MPa, enabling the pressed film to be transparent, standing for 4 hours at the temperature of 350 ℃ for shaping after rolling, finally quickly putting the shaped film into water for soaking for 1min, taking out, standing and airing to obtain a PTFE composite film with the film thickness of 40 mu m (the thickness of the base film is 30 mu m, and the thickness of the reinforcing film is 5 mu m).
Example 3 this example provides a PTFE composite membrane, specifically prepared as follows:
(1) Preparation of the reinforcing film:
s1: adding graphene into deionized water, and performing ultrasonic treatment to obtain graphene dispersion; adding Al powder and graphene dispersion liquid into absolute ethyl alcohol (the mass ratio of the Al powder to the graphene is 2:3), stirring and mixing for 18 hours at 60 ℃, and then washing, filtering and drying to obtain an Al-doped graphene material;
s2: ball-milling and mixing PTFE dispersion resin and Al-doped graphene, adding petroleum ether and a silane coupling agent KH550 (the mass ratio of the PTFE dispersion resin to the Al-doped graphene to the petroleum ether to the silane coupling agent KH550 is 12:5:2:1), fully mixing by a mixer, and aging for 18 hours at 50 ℃ in an oven;
s3: preforming and rolling the aged mixture, wherein the rolling pressure is 0.5MPa, and the compression ratio is 200, so that the Al-doped graphene modified PTFE film rolled tape is obtained;
s4: carrying out heat treatment on the Al-doped graphene-modified PTFE film rolled tape in a degreasing machine at 250 ℃, removing extrusion aids, and fully puffing;
s5: and (3) stretching the degreased film material, wherein the stretching treatment adopts the sequence of longitudinal stretching and transverse stretching, the stretching temperature is 330 ℃, the longitudinal stretching multiplying power is 15, and the transverse stretching multiplying power is 20.
(2) Preparation of a base film:
A. 1g of dopamine hydrochloride is dissolved in 100ml of Tris-HCl buffer solution to obtain a dopamine solution, and PTFE dispersion resin is soaked in the dopamine solution for 12 hours for modification under the condition of pH=8.7;
B. fully mixing the dopamine modified PTFE dispersion resin and petroleum ether by a mixer, and aging for 12 hours at 60 ℃ in an oven (the mass ratio of the dopamine modified PTFE dispersion resin to the petroleum ether is 10:1);
C. preforming and rolling the aged mixture, wherein the rolling pressure is 0.8MPa, and the compression ratio is 100, so that the dopamine modified PTFE membrane rolled tape is obtained;
D. carrying out heat treatment on the dopamine modified PTFE membrane rolled tape in a degreasing machine at the temperature of 250 ℃, removing extrusion aids, and fully puffing;
E. and (3) stretching the degreased film material, wherein the stretching treatment adopts the sequence of longitudinal stretching and transverse stretching, the stretching temperature is 350 ℃, the longitudinal stretching multiplying power is 18, and the transverse stretching multiplying power is 20.
(3) Preparation of PTFE composite film:
cutting a base film and a reinforcing film into widths of 1.5m, arranging the base film and the reinforcing film in sequence, then adopting a roller to press, adjusting the pressure to 1.2MPa, enabling the pressed film to be transparent, standing for 3 hours for shaping in an environment of 300 ℃ after rolling, finally quickly putting the shaped film into water for soaking for 2min, taking out, standing and airing to obtain a PTFE composite film with the film thickness of 36 mu m (the thickness of the base film is 20 mu m, and the thickness of the reinforcing film is 8 mu m).
Example 4, this example provides a PTFE composite membrane, specifically prepared as follows:
(1) Preparation of the reinforcing film:
s1: adding graphene into deionized water, and performing ultrasonic treatment to obtain graphene dispersion; adding Al powder and graphene dispersion liquid into absolute ethyl alcohol (the mass ratio of the Al powder to the graphene is 2:3), stirring and mixing for 15 hours at 70 ℃, and then washing, filtering and drying to obtain an Al-doped graphene material;
s2: ball-milling and mixing PTFE dispersion resin and Al-doped graphene, adding petroleum ether and a silane coupling agent KH550 (the mass ratio of the PTFE dispersion resin to the Al-doped graphene to the petroleum ether to the silane coupling agent KH550 is 12:5:2:1), fully mixing by a mixer, and aging for 20 hours at 40 ℃ in an oven;
s3: preforming and rolling the aged mixture, wherein the rolling pressure is 0.8MPa, and the compression ratio is 200, so that the Al-doped graphene modified PTFE film rolled tape is obtained;
s4: carrying out heat treatment on the Al-doped graphene-modified PTFE film rolled tape in a degreasing machine at 280 ℃, removing extrusion assisting agent, and fully puffing;
s5: and (3) stretching the degreased film material, wherein the stretching treatment adopts the sequence of longitudinal stretching and transverse stretching, the stretching temperature is 300 ℃, the longitudinal stretching multiplying power is 10, and the transverse stretching multiplying power is 25.
(2) Preparation of a base film:
A. 1g of dopamine hydrochloride is dissolved in 100ml of Tris-HCl buffer solution to obtain a dopamine solution, and PTFE dispersion resin is soaked in the dopamine solution for 10 modification under the condition of pH=8.3;
B. fully mixing the dopamine modified PTFE dispersion resin and petroleum ether by a mixer, and aging for 16 hours at 50 ℃ in an oven (the mass ratio of the dopamine modified PTFE dispersion resin to the petroleum ether is 10:1);
C. preforming and rolling the aged mixture, wherein the rolling pressure is 0.5MPa, and the compression ratio is 150, so that the dopamine modified PTFE membrane rolled tape is obtained;
D. carrying out heat treatment on the dopamine modified PTFE membrane rolled tape in a degreasing machine at 300 ℃, removing extrusion aids, and fully puffing;
E. and (3) stretching the degreased film material, wherein the stretching treatment adopts the sequence of longitudinal stretching and transverse stretching, the stretching temperature is 350 ℃, the longitudinal stretching multiplying power is 15, and the transverse stretching multiplying power is 15.
(3) Preparation of PTFE composite film:
cutting a base film and a reinforcing film into widths of 1.3m, arranging the base film and the reinforcing film in sequence, then adopting a roller to press, adjusting the pressure to 1.2MPa, enabling the pressed film to be transparent, standing for 3 hours for shaping after rolling in an environment of 350 ℃, finally quickly putting the shaped film into water for soaking for 1min, taking out, standing and airing to obtain a PTFE composite film with the film thickness of 35 mu m (the thickness of the base film is 25 mu m, and the thickness of the reinforcing film is 5 mu m).
Comparative example 1
This comparative example provides a PTFE composite film having a film thickness of 30 μm (the base film has a thickness of 20 μm and the reinforcing film has a thickness of 5 μm), differing from example 1 in the method of producing the reinforcing film, specifically as follows:
preparation of the reinforcing film:
s1: directly ball-milling and mixing PTFE dispersion resin and graphene, then adding petroleum ether and a silane coupling agent KH550 (the mass ratio of the PTFE dispersion resin to the graphene to the petroleum ether to the silane coupling agent KH550 is 12:5:2:1), fully mixing by a mixer, and aging for 18 hours at 50 ℃ in an oven;
s2: preforming and rolling the aged mixture, wherein the rolling pressure is 0.6MPa, and the compression ratio is 100, so that the graphene modified PTFE film rolled tape is obtained;
s3: carrying out heat treatment on the graphene modified PTFE film rolled tape in a degreasing machine at 300 ℃, removing extrusion aids, and fully puffing;
s4: and (3) stretching the degreased film material, wherein the stretching treatment adopts the sequence of longitudinal stretching and transverse stretching, the stretching temperature is 350 ℃, the longitudinal stretching multiplying power is 10, and the transverse stretching multiplying power is 15.
Comparative example 2
This comparative example provides a PTFE composite film having a film thickness of 30 μm (the base film has a thickness of 20 μm and the reinforcing film has a thickness of 5 μm), differing from example 1 in the method of producing the reinforcing film, specifically as follows:
preparation of the reinforcing film:
s1: directly ball-milling and mixing PTFE dispersion resin with graphene and Al powder, adding petroleum ether and a silane coupling agent KH550 (the mass ratio of the PTFE dispersion resin to the graphene to the Al powder is 12:3:2:2:1), fully mixing by a mixer, and aging for 18 hours at 50 ℃ in an oven;
s2: preforming and rolling the aged mixture, wherein the rolling pressure is 0.6MPa, and the compression ratio is 100, so that the PTFE film rolled tape modified by Al and graphene is obtained;
s3: carrying out heat treatment on the PTFE film rolled tape modified by Al and graphene in a degreasing machine at 300 ℃, removing extrusion assisting agent, and fully puffing;
s4: and (3) stretching the degreased film material, wherein the stretching treatment adopts the sequence of longitudinal stretching and transverse stretching, the stretching temperature is 350 ℃, the longitudinal stretching multiplying power is 10, and the transverse stretching multiplying power is 15.
Comparative example 3
This comparative example provides a PTFE composite film having a film thickness of 30 μm (the base film has a thickness of 20 μm and the reinforcing film has a thickness of 5 μm), which differs from example 1 in the method of producing the base film, specifically as follows:
preparation of a base film:
A. and fully mixing the PTFE dispersion resin and the petroleum ether by a mixer, and then aging for 12 hours at 60 ℃ in an oven (the mass ratio of the PTFE dispersion resin to the petroleum ether is 10:1).
B. Preforming and rolling the aged mixture, wherein the rolling pressure is 0.5MPa, and the compression ratio is 200, so that a PTFE film rolled tape is obtained;
C. carrying out heat treatment on the PTFE film rolled tape in a degreasing machine at 250 ℃, removing extrusion assisting agent, and fully puffing;
D. and (3) stretching the degreased film material, wherein the stretching treatment adopts the sequence of longitudinal stretching and transverse stretching, the stretching temperature is 300 ℃, the longitudinal stretching multiplying power is 10, and the transverse stretching multiplying power is 15.
Comparative example 4
The comparative example provides a PTFE film with a film thickness of 30 μm, which is prepared by the following steps:
A. fully mixing PTFE dispersion resin and petroleum ether by a mixer, and aging for 16 hours at 50 ℃ in an oven (the mass ratio of the PTFE dispersion resin to the petroleum ether is 10:1);
B. preforming and rolling the aged mixture, wherein the rolling pressure is 0.5MPa, and the compression ratio is 150, so that a PTFE film rolled tape is obtained;
C. carrying out heat treatment on the PTFE film rolled tape in a degreasing machine at 300 ℃, removing extrusion assisting agent, and fully puffing;
D. and (3) stretching the degreased film material, wherein the stretching treatment adopts the sequence of longitudinal stretching and transverse stretching, the stretching temperature is 350 ℃, the longitudinal stretching multiplying power is 15, and the transverse stretching multiplying power is 15.
E. Cutting the stretched film material into a width of 1m, pressing by adopting a roller, regulating the pressure to 1MPa, enabling the pressed film to be transparent, standing for 4 hours at 300 ℃ for shaping after rolling, and finally quickly putting the shaped film into warm water for soaking for 1min, taking out, standing and airing to obtain the PTFE film.
Performance tests were performed on the film materials prepared in examples 1 to 4 and comparative examples 1 to 4:
(1) Determination of tensile Strength
Tensile strength of the film material was measured using a YG026D electronic power machine: samples 50mm wide and 250mm long were taken in the warp and weft directions of the film material, the tensile speed of the electronic power machine was set to 100mm/min, the clamping length was set to 200mm, the samples were fixed on a jig and screwed, and the test was started, and the results are shown in table 1.
TABLE 1
(2) Abrasion resistance test
At normal temperature, the friction coefficients of the film materials are respectively tested by adopting a ZP-G028-191 type friction coefficient instrument, a load of 200G, a test distance of 50mm and a test speed of 1000mm/min according to a test method for obtaining an average value by five tests, and the results are shown in Table 2:
to further verify the abrasion resistance of the PTFE composite films of examples 1-4, abrasion resistance test was performed on the samples using a 750g weight, 280 mesh grinding wheel to grind the samples to bare leakage, and the number of times of abrasion was measured to be 3 ten thousand times or more.
TABLE 2
According to the test results, the film materials provided by the embodiments 1-4 have good tensile strength, the warp tensile strength and the weft tensile strength can both reach more than 60MPa, and meanwhile, the film materials also have remarkably excellent wear resistance, and the friction times can reach more than 3 ten thousand times under the conditions of a 750g weight and a 280-mesh grinding wheel. As can be seen by comparing the performances of the membrane materials in comparative examples 1-4, the tensile strength and the wear resistance of the PTFE composite membrane are improved by taking the Al-doped graphene modified PTFE membrane as a reinforcing layer and the dopamine modified PTFE membrane as a base layer which are matched with each other. The PTFE composite film provided by the invention can be widely applied to high-frequency friction environments, greatly widens the application field of PTFE film materials, and has important significance for the field of PTFE films.

Claims (9)

1. A PTFE composite membrane, characterized in that: the base film is formed by compounding a base film and a reinforcing film, and the base film is arranged between two layers of reinforcing films; the base membrane is a dopamine modified PTFE membrane, and the reinforcing membrane is an Al-doped graphene modified PTFE membrane;
the thickness of the basic film is 20-30 mu m; the thickness of the reinforcing film is 5-8 mu m;
the preparation method of the Al-doped graphene comprises the following steps: adding graphene into deionized water, and performing ultrasonic treatment to obtain graphene dispersion; and adding the Al powder and the graphene dispersion liquid into absolute ethyl alcohol, and stirring, wherein the mass ratio of the Al powder to the graphene is 2:3, so as to obtain the Al-doped graphene material.
2. The PTFE composite membrane of claim 1, wherein: adding Al powder and graphene dispersion liquid into absolute ethyl alcohol, stirring and mixing for 12-24 hours at 50-80 ℃, and then washing, filtering and drying to obtain the Al-doped graphene material.
3. The method for producing a PTFE composite membrane according to claim 1 or 2, characterized in that: cutting a base film and a reinforcing film into widths of 1-1.5m, arranging the base film, the reinforcing film and the reinforcing film in sequence, then pressing by adopting a roller, adjusting the pressure to 1-1.2MPa, enabling the pressed film to be transparent, standing for 3-4 hours in an environment of 300-350 ℃ for shaping after rolling, finally quickly immersing the shaped film in low-temperature water for 1-2 minutes, taking out, standing and airing to obtain the PTFE composite film.
4. A method of producing a PTFE composite membrane according to claim 3, wherein: the preparation method of the reinforced film comprises the following steps:
s1: ball-milling and mixing PTFE dispersion resin and Al-doped graphene, adding an extrusion aid and a coupling agent, fully mixing by a mixer, and aging in an oven;
s2: preforming and rolling the aged mixture to obtain an Al-doped graphene-modified PTFE film rolled tape;
s3: carrying out heat treatment on the Al-doped graphene-modified PTFE film rolled tape in a degreasing machine, removing extrusion aids, and fully puffing;
s4: and stretching the degreased film material, including longitudinal stretching and transverse stretching.
5. The method for producing a PTFE composite membrane according to claim 4, wherein: the mass ratio of the PTFE dispersion resin to the Al-doped graphene to the extrusion aid to the coupling agent is 12:5:2:1.
6. The method for producing a PTFE composite membrane according to claim 4, wherein:
the coupling agent is a silane coupling agent;
the extrusion aid is petroleum ether;
the aging temperature is 40-60 ℃ and the aging time is 12-24 hours;
in the rolling process, the rolling pressure is 0.5-0.8 MPa, and the compression ratio is 100-200;
the temperature of the heat treatment in a degreasing machine is 250-300 ℃;
the stretching treatment adopts the sequence of longitudinal stretching and transverse stretching, the stretching temperature is 300-350 ℃, the longitudinal stretching multiplying power is 10-20, and the transverse stretching multiplying power is 15-25.
7. A method of producing a PTFE composite membrane according to claim 3, wherein: the preparation method of the base film comprises the following steps:
A. dissolving dopamine hydrochloride in Tris-HCl buffer solution to obtain dopamine solution, soaking PTFE dispersion resin in the dopamine solution, and modifying under the condition that the pH value is 8.3-8.7;
B. fully mixing the dopamine modified PTFE dispersion resin and an extrusion aid through a mixer, and then aging in an oven;
C. preforming and rolling the aged mixture to obtain a dopamine modified PTFE membrane rolled tape;
D. carrying out heat treatment on the dopamine modified PTFE membrane rolled tape in a degreasing machine, removing extrusion assisting agent, and fully puffing;
E. and stretching the degreased film material, including longitudinal stretching and transverse stretching.
8. The method of producing a PTFE composite membrane according to claim 7, wherein: the concentration of the dopamine solution is 5g/L-10g/L;
the PTFE dispersion resin is soaked in the dopamine solution for modification for 10-12 hours;
the mass ratio of the dopamine modified PTFE dispersion resin to the extrusion aid is 10:1.
9. The method of producing a PTFE composite membrane according to claim 7, wherein:
the extrusion aid is petroleum ether;
the aging temperature is 40-60 ℃ and the aging time is 12-24 hours;
in the rolling process, the rolling pressure is 0.5-0.8 MPa, and the compression ratio is 100-200;
the temperature of the heat treatment in a degreasing machine is 250-300 ℃;
the stretching treatment adopts the sequence of longitudinal stretching and transverse stretching, the stretching temperature is 300-350 ℃, the longitudinal stretching multiplying power is 10-20, and the transverse stretching multiplying power is 15-25.
CN202310723246.0A 2023-06-19 2023-06-19 PTFE composite film and preparation method thereof Active CN116442625B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310723246.0A CN116442625B (en) 2023-06-19 2023-06-19 PTFE composite film and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310723246.0A CN116442625B (en) 2023-06-19 2023-06-19 PTFE composite film and preparation method thereof

Publications (2)

Publication Number Publication Date
CN116442625A CN116442625A (en) 2023-07-18
CN116442625B true CN116442625B (en) 2023-08-15

Family

ID=87122393

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310723246.0A Active CN116442625B (en) 2023-06-19 2023-06-19 PTFE composite film and preparation method thereof

Country Status (1)

Country Link
CN (1) CN116442625B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117107369B (en) * 2023-10-18 2023-12-22 山东森荣新材料股份有限公司 Short fiber production device and process

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008092328A1 (en) * 2007-01-26 2008-08-07 Guangdong Decro Package Films Co., Ltd. A biaxially orientated polypropylene film for combining paper and plastic without adhesive and a preparation method thereof
CN105014982A (en) * 2015-07-30 2015-11-04 湖州森诺膜技术工程有限公司 Preparation method of graphene and polytetrafluoroethylene osmotic distillation film
CN106221155A (en) * 2016-08-04 2016-12-14 苏州锐特捷化工制品有限公司 A kind of function external wall board material of magnetic plastotype Graphene and preparation method thereof
CN108638611A (en) * 2018-05-18 2018-10-12 浙江鹏远新材料股份有限公司 A kind of automatically cleaning heat insulating reflecting material and preparation method thereof
CN109263080A (en) * 2018-08-30 2019-01-25 杨仲辉 With the artificial composite synthetic paper and preparation method for improving printing performance
CN112625384A (en) * 2020-12-18 2021-04-09 任国峰 Graphene polytetrafluoroethylene composite material and preparation method thereof
CN112662077A (en) * 2020-12-14 2021-04-16 东莞市三至新材料技术有限公司 Antistatic graphene-coated aluminum microsphere modified PP composite material and preparation method thereof
CN115738752A (en) * 2022-10-20 2023-03-07 安徽元琛环保科技股份有限公司 Preparation method of graphene hybrid PTFE composite membrane and prepared composite membrane

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008092328A1 (en) * 2007-01-26 2008-08-07 Guangdong Decro Package Films Co., Ltd. A biaxially orientated polypropylene film for combining paper and plastic without adhesive and a preparation method thereof
CN105014982A (en) * 2015-07-30 2015-11-04 湖州森诺膜技术工程有限公司 Preparation method of graphene and polytetrafluoroethylene osmotic distillation film
CN106221155A (en) * 2016-08-04 2016-12-14 苏州锐特捷化工制品有限公司 A kind of function external wall board material of magnetic plastotype Graphene and preparation method thereof
CN108638611A (en) * 2018-05-18 2018-10-12 浙江鹏远新材料股份有限公司 A kind of automatically cleaning heat insulating reflecting material and preparation method thereof
CN109263080A (en) * 2018-08-30 2019-01-25 杨仲辉 With the artificial composite synthetic paper and preparation method for improving printing performance
WO2020043121A1 (en) * 2018-08-30 2020-03-05 杨仲辉 Artificial composite synthetic paper for improving printing performance, and preparation method therefor
CN112662077A (en) * 2020-12-14 2021-04-16 东莞市三至新材料技术有限公司 Antistatic graphene-coated aluminum microsphere modified PP composite material and preparation method thereof
CN112625384A (en) * 2020-12-18 2021-04-09 任国峰 Graphene polytetrafluoroethylene composite material and preparation method thereof
CN115738752A (en) * 2022-10-20 2023-03-07 安徽元琛环保科技股份有限公司 Preparation method of graphene hybrid PTFE composite membrane and prepared composite membrane

Also Published As

Publication number Publication date
CN116442625A (en) 2023-07-18

Similar Documents

Publication Publication Date Title
CN116442625B (en) PTFE composite film and preparation method thereof
CN110592937A (en) Preparation method of carbon fiber/polyethyleneimine/carbon nanotube multi-scale reinforcement
CN111647196B (en) Preparation method of wood-based carbon nanotube composite conductive film
JP2018506492A (en) Graphite sheet and method for producing the same
CN114197205A (en) Modified carbon fiber and preparation method and application thereof
CN113480328A (en) Large-scale graphene heat-conducting roll film and preparation method thereof
CN111979766A (en) Method for enhancing interfacial bonding performance of aramid fiber and epoxy resin
CN109923091B (en) Method for preparing graphite flake
CN112044278A (en) Preparation method of PTFE microporous membrane with multilayer structure
CN114409424A (en) Method for preparing low-density, high-strength and large-size carbon aerogel composite material by water-phase normal-pressure drying
CN104151827B (en) The preparation method of carbon fiber/carbon nanotube/organic siliconresin multi-dimensional hybrid composite
CN111394991A (en) Method for grafting carbon nano tube on surface of carbon fiber based on plasma technology
CN114921052B (en) Aerospace material and preparation method thereof
CN115959841A (en) Graphene/basalt fiber multi-scale material and preparation method and application thereof
KR102113382B1 (en) Method for preparing carbon nanotube fiber assemblies having improved strength
CN115738752A (en) Preparation method of graphene hybrid PTFE composite membrane and prepared composite membrane
JP2010047865A (en) Carbon fiber for composite material and composite material produced by using the same
CN110951016B (en) Preparation method of high-strength carbon nanotube/TiAl composite material
KR20190001045A (en) Method of manufacturing carbon paper using cabon nano tube containing polyacrylonitrile short fiber
CN113773043A (en) Preparation method of low-density carbon fiber reinforced carbon aerogel composite material
CN114023978B (en) Preparation method of gas diffusion layer substrate
CN111808398A (en) Preparation method of ZIF-67 lossless modified carbon fiber reinforced composite material
CN115012216B (en) Modified PEEK-based sizing agent, preparation thereof and application thereof in preparation of carbon fiber/epoxy resin composite material
CN117691301B (en) Modified polyvinylidene fluoride lithium ion battery diaphragm and preparation method thereof
CN115873249B (en) Plasma-treated fiber-reinforced polyimide material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant