CN106953054B - Long carbon chain polyamide porous membrane and preparation method and application thereof - Google Patents

Long carbon chain polyamide porous membrane and preparation method and application thereof Download PDF

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CN106953054B
CN106953054B CN201610007182.4A CN201610007182A CN106953054B CN 106953054 B CN106953054 B CN 106953054B CN 201610007182 A CN201610007182 A CN 201610007182A CN 106953054 B CN106953054 B CN 106953054B
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long carbon
chain polyamide
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CN106953054A (en
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董侠
王莉莉
王笃金
刘学新
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Institute of Chemistry CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
    • B01D67/0025—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching
    • B01D67/0027—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching by stretching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Hydrology & Water Resources (AREA)
  • Organic Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Cell Separators (AREA)

Abstract

The invention relates to a long carbon chain polyamide porous membrane and a preparation method and application thereof, wherein the porous membrane is a sheet-shaped structure with uniform thickness, the sheet-shaped structure is provided with a plurality of micropores which are basically independent from each other, the porous membrane is prepared from long carbon chain polyamide, the long carbon chain polyamide is aliphatic polyamide with the length of a carbon chain between two adjacent amide groups in a molecule being more than 10, the micropores are in an ellipse-like shape, and the long axes of at least two ellipse-like shapes are close to a straight line or are parallel; or the micropores are in an ellipse-like shape, a plurality of ellipse-like shapes form a plurality of micropore clusters on the sheet structure, and the major axes of a plurality of ellipse-like shapes are basically in one direction. The long carbon chain polyamide adopted by the invention has better affinity with polar electrolyte in a lithium battery, and meanwhile, the long carbon chain polyamide has higher melting point, thermal decomposition temperature and softening temperature, and the material has superiority in the aspect of preparing lithium ion battery diaphragms and water treatment membranes.

Description

Long carbon chain polyamide porous membrane and preparation method and application thereof
Technical Field
The invention relates to a porous membrane and a preparation method and application thereof, in particular to a long carbon chain polyamide porous membrane and a preparation method and application thereof
Background
The porous membrane is an advanced separation technology, and has been widely applied to various fields due to the characteristics of simple operation, high efficiency, energy conservation, small pollution and the like. Polyamide is an engineering plastic with excellent comprehensive performance, and polyamide filtering membranes are widely applied to filtering treatment in laboratories, industry and life. However, in the case of ordinary polyamide, the polyamide contains polar amide groups and the density of the amide groups is high, which results in strong water absorption, and the mechanical properties of the polyamide after water absorption are greatly reduced, which greatly limits the service life of the polyamide filtration membrane and the application in certain specific fields.
Another important application field of porous films is lithium ion battery separators, and with the continuous development of energy technology, lithium ion batteries have been widely used in various fields, from computers, mobile phones to electric vehicles, and have played a very important role. It has the excellent performances of high working voltage, large energy density, long cycle life, low pollution and the like. As an important part of a lithium ion battery, a separator is a microporous membrane material located between a positive electrode and a negative electrode, and is used for blocking physical contact between the positive electrode and the negative electrode, and simultaneously, ions in an electrolyte freely migrate and electrons in the battery cannot pass through, namely, current is blocked, the battery separator plays an important role, a polymer separator with a porous structure is melted at a high temperature, so that the porous structure is closed, impedance is rapidly increased, and current is blocked, wherein the temperature is called as a blocking (Shut-Down) temperature, and is also called as a self-closing temperature. In addition, if the battery temperature continues to increase beyond the heat-resistant temperature of the separator after the pores of the separator are closed, the separator is completely melted and broken, and the positive electrode and the negative electrode are in direct contact with each other to cause short-circuiting, which is called a break-out temperature. The diaphragm material obviously influences the energy, power density, cycle life and safety performance of the battery, and the structural optimization of the diaphragm material plays an important role in improving the comprehensive performance of the battery. Because polyolefin has the advantages of high mechanical strength, good chemical stability and the like, the polyolefin is widely applied to lithium ion battery diaphragm materials, at present, the commercial lithium battery diaphragm materials mainly adopt Polyethylene (PE), polypropylene (PP) microporous membranes and PP/PE multilayer composite membranes, and because the melting temperature is low (for example, the self-closing temperature of a PE diaphragm is 130-140 ℃, and the self-closing temperature of a PP diaphragm is about 170 ℃), under certain conditions, such as overhigh external temperature, overlarge discharge current or thermal inertia in the heating process of electrolyte, even if the current is blocked, the temperature of the battery can be continuously increased, the diaphragm can be completely damaged to cause short circuit of the battery, so that the battery explodes or catches fire, and the safety of the PE diaphragm and the PP diaphragm is low. In addition, the diaphragm material has the following defects that the polyolefin has small polarity and low surface energy, and the electrolyte belongs to an organic solvent with higher polarity, so that the polyolefin and the electrolyte have poor wettability, most of the electrolyte exists in gaps, and the electrolyte is easy to leak.
The patent application with the application number of 201510126639.9 discloses a preparation method of a hydrophilic polyolefin microporous membrane for a lithium ion battery, wherein a block copolymer prepared by 1, 1-disubstituted aromatic alkene monomers is coated on the polyolefin microporous membrane, one chain segment of the block copolymer contains a hydrophilic group, and the other chain segment has better affinity with the polyolefin membrane, so that the block copolymer has good affinity with the polyolefin microporous membrane and electrolyte in the lithium battery. However, the adhesion of the coating to the substrate and the complex process optimization thereof in the method are important problems faced by the technology.
Patent application No. 200680039461.3 discloses a polyolefin multilayer microporous membrane, a method for producing the same, and a battery separator, a polyolefin three-layer microporous membrane having microporous layers formed of polyethylene-based resin and forming both surface layers, and a microporous layer formed as an inner layer containing polypropylene and a heat-resistant resin having a melting point or glass transition temperature of 180 ℃ and 260 ℃, thereby improving the heat resistance of the microporous membrane.
Patent application No. 200810185300.6 discloses a method for preparing a microporous polyolefin multilayer film in which polyethylene, a diluent and a heat-resistant filler are mixed to form a film by stretching, thereby improving the thermal stability of polyolefin, but the weight and shedding of the filler seriously affect the use properties of such materials.
The long carbon chain polyamide has the advantages of good flexibility, low water absorption, good dimensional stability, excellent drug resistance, good abrasion resistance, corrosion resistance, low-temperature impact resistance, good electrical insulation property and the like, is widely applied to the fields of machinery, electronic and electric appliances, automobiles, information, textiles, aerospace and the like, is the development direction of the key research at home and abroad at present, and has no patent and report related to the preparation of the porous membrane by using the long carbon chain polyamide.
The present invention has been made in view of the above circumstances.
Disclosure of Invention
The first object of the present invention is to provide a long carbon chain polyamide porous film.
The second object of the present invention is to provide a method for producing the porous film.
The third object of the present invention is to provide the use of the porous film.
In order to realize the first purpose of the invention, the invention adopts the following technical scheme:
a long carbon chain polyamide porous membrane, characterized in that the porous membrane is a sheet structure with uniform thickness, the sheet structure is provided with a plurality of micropores which are basically independent of each other, the porous membrane is prepared by adopting long carbon chain polyamide, the long carbon chain polyamide is aliphatic polyamide with the carbon chain length between two adjacent amide groups in the molecule being more than 10, wherein, the long carbon chain polyamide porous membrane is characterized in that
The micropores are in an ellipse-like shape, and the long axes of at least two ellipse-like shapes are approximately in a straight line or in parallel;
or the micropores are in an ellipse-like shape, a plurality of ellipse-like shapes form a plurality of micropore clusters on the sheet structure, and the major axes of a plurality of ellipse-like shapes are basically in one direction.
The porous membrane with the structure has higher conductivity and higher mechanical strength in the battery diaphragm, and electrolyte is not easy to leak, thereby being beneficial to the migration of current carriers.
The long carbon chain polyamide has the advantages of good toughness, low melting point, low water absorption, good mechanical property, high bonding strength, low density, good impact property and the like, so that the long carbon chain polyamide is a material with good mechanical property and good dimensional stability.
In addition, amide bonds in long carbon chain polyamide molecular chains belong to polar bonds, the bonds have larger cohesive energy, and hydrogen bonds can be formed among the molecules, so that the molecular arrangement is more regular, and the polymer has higher crystallinity. Methylene is nonpolar, the molecular chain is softer due to the existence of the methylene, various properties of nylon depend on the relative proportion of methylene and amide groups in the molecular chain, the larger the ratio of amide groups to methylene is, the larger the polarity of polyamide is, and an organic solvent with high polarity is generally used in the electrolyte, so that the affinity of the diaphragm and the electrolyte is better, the battery is not easy to leak, and the material has superiority in the aspect of preparing the lithium ion battery diaphragm. And the distribution density of the amido and methylene in the long carbon chain polyamide is not uniform, so that the hydrogen bond density is influenced, and the melting point is higher.
Preferably, in a first direction, the major axes of a plurality of the ellipse-like shapes are arranged in a substantially straight line, and in a second direction perpendicular to the first direction, the major axes of the ellipse-like shapes are distributed substantially in parallel; preferably, in a second direction perpendicular to the first direction, the ellipse-like staggered distribution is realized;
or the major axes of the quasi-ellipses forming the micro-hole clusters are straight lines or are parallel, the quasi-ellipses are preferably distributed in a staggered mode to form the micro-hole clusters, and the central parts of the micro-hole clusters are preferably micro-holes with small apertures.
Preferably, the length of the major axis of the ellipse-like shape is much greater than the length of the minor axis.
Preferably, the long carbon chain polyamide is one or more of pure long carbon chain polyamide, additive-containing long carbon chain polyamide, polyamide alloy or polyamide nanocomposite, and has a melting point of 180-230 ℃ and a melt index of 0.5-20g/10min, preferably 1-10g/10 min.
The additive comprises a nucleating agent, an antioxidant and a chain extender, the polyamide alloy material comprises high polymer materials such as PP, PA and the like and reinforcing materials such as glass fiber, whisker and the like, and the nano composite material comprises carbon nano tube, montmorillonite, carbon black and the like.
The preferred long carbon chain polyamide is one or more of nylon 610, nylon 612, nylon 1010, nylon 1012 or nylon 1212, preferably nylon 1012 or/and nylon 1212. .
Preferably, the long carbon chain polyamide porous membrane is a single-layer membrane or a multi-layer composite membrane, and the pore diameter of the long carbon chain polyamide porous membrane is 0.01-5 μm.
The single-layer film is a single-direction tensile extension carbon chain polyamide single-layer film, and the mechanical strength of the single-layer film in the stretching direction is greater than that in the vertical stretching direction; the multi-layer composite film is a composite of single-layer films, which comprises single-layer films in various orientation directions and has excellent tensile strength, or a biaxially stretched long carbon chain polyamide porous film.
In order to achieve the second purpose, the invention adopts the following technical scheme:
a preparation method of a long carbon chain polyamide porous membrane comprises the following steps:
the preparation method comprises the following steps:
(1) preparing a long carbon chain polyamide flat sheet;
(2) the flat sheet is placed in a stretching device to be stretched in one step or two steps.
Preferably, the preparation method of the flat sheet in the step (1) is a melt extrusion method or a hot pressing method, and the extrusion or hot pressing temperature is 200-300 ℃, preferably 220-270 ℃.
Preferably, the one-step stretching in the step (2) is to place the flat sheet on a stretching device to perform isothermal treatment for 5-15min at the isothermal temperature of 10-170 ℃, and then perform unidirectional or bidirectional stretching at the temperature at the stretching rate of 5-500 μm/s to 10% -650% to obtain the porous membrane; the two-step stretching comprises placing the flat sheet on stretching equipment, keeping the temperature constant for 5-15min, wherein the isothermal temperature is T1At which temperature the film is stretched unidirectionally or bidirectionally to epsilon at a stretching rate of 5-500 mu m/s1The resulting stretched sample is brought to a temperature T2Constant temperature of 5-15min, then stretched unidirectionally or bidirectionally at a stretching rate of 5-500 μm/s to ε at this temperature2Obtaining the porous membrane with the temperature of T being more than or equal to 10 DEG C1≤T2≤170℃，10％≤ε1≤ε2650% or less, preferably a drawing rate of 10 μm/s to 100 μm/s.
Wherein, the uniaxial tension method comprises the following steps: on one hand, the preparation method can be realized by a one-step stretching method, wherein a long carbon chain polyamide extrusion film is firstly prepared, then the sample is placed on stretching equipment to be isothermal for 5-15min, and then unidirectional stretching is carried out at a certain speed, so that a sample strip with the stretching ratio of epsilon is obtained. On the other hand, the film can be prepared by a two-step stretching method, wherein a long carbon chain polyamide extrusion film sample is placed on a stretching device at a temperature T1Isothermal for 5-15min, then drawing unidirectionally at a certain rate to a draw ratio of ε 1, and then subjecting the drawn sample to temperature T2Keeping the temperature constant for 5-15min, and then performing unidirectional stretching at a certain speed until the stretching ratio is epsilon 2. The controllability of the pore diameter of the porous film can be realized by adjusting the isothermal temperature and the stretching ratio.
The biaxial stretching method is as follows: on one hand, the preparation method can be realized by a one-step stretching method, wherein a long carbon chain polyamide extrusion film is firstly prepared, then the sample is placed on stretching equipment to be isothermal for 5-15min, and then biaxial stretching is carried out at a certain speed, so that a sample strip with the stretching ratio of epsilon is obtained. On the other hand, the film can be prepared by a two-step stretching method, wherein a long carbon chain polyamide extrusion film sample is placed on a stretching device at a temperature T1Isothermal for 5-15min, and then bidirectionally stretching at a certain speed until the stretching ratio is epsilon1Then the stretched sample is at temperature T2Keeping the temperature constant for 5-15min, and then bidirectionally stretching at a certain speed until the stretching ratio is epsilon2. The controllability of the pore diameter of the porous film can be realized by adjusting the isothermal temperature and the stretching ratio.
The drawing method does not need any additive and solvent in the molding process, so the whole molding process has no pollution to the environment and the product has high purity.
In order to achieve the third object of the invention, the invention adopts the following technical scheme:
the invention discloses application of a long carbon chain polyamide porous membrane in the following fields:
(1) a lithium ion battery separator;
(2) a water filtration membrane.
Compared with the prior art, the invention has the following beneficial effects:
(1) the long-carbon-chain polyamide contains longer methylene chain, has lower water absorption rate and better dimensional stability compared with the common polyamide, and overcomes the defect that the mechanical property of the traditional polyamide filter membrane is greatly reduced due to water absorption.
(2) The long-carbon-chain polyamide contains polar amide groups, can be quickly infiltrated by organic electrolyte in the lithium ion battery, and has good infiltration.
(3) Compared with PP and PE, the long-carbon-chain polyamide has higher melting point and softening temperature (the melting point of PA1012 is 190 ℃ and the softening temperature is 156 ℃), has higher film breaking temperature and proper hole closing temperature, improves the film breaking temperature and the proper hole closing temperature by 20 percent, and provides more reliable safety performance in the application of lithium ion battery diaphragms.
(4) The long carbon chain polyamide has excellent mechanical properties similar to those of common polyamide, and can meet the use requirements of water filtration membranes and lithium battery isolation membranes on strength.
(5) The preparation method of the porous membrane is a flat sheet stretching method, and compared with methods such as thermally induced phase separation and the like, the preparation method does not need a solvent, and is simple and environment-friendly in preparation process.
Drawings
FIG. 1: scanning electron microscope images of the microstructure of example 2 of the invention.
FIG. 2: scanning electron microscope images of the microstructure of example 3 of the invention.
FIG. 3: scanning electron microscope images of the microstructure of example 4 of the invention.
FIG. 4: scanning electron micrographs of the microstructure of inventive example 7.
FIG. 5: scanning electron microscope images of the microstructure of inventive example 22.
FIG. 6: scanning electron microscope images of the microstructure of example 23 of the invention.
Detailed Description
The embodiments in the following examples can be further combined or replaced, and the examples are only for describing the preferred embodiments of the present invention, and do not limit the concept and scope of the present invention, and those skilled in the art can make various changes and modifications to the technical solution of the present invention without departing from the design concept of the present invention, and all fall within the protection scope of the present invention.
Example 1
(1) Firstly, preparing a PA1012 extrusion film, wherein the melting point of PA1012 is 190 ℃, the melt index is 20g/min, and the extrusion temperature is 210 ℃ by adopting a melt extrusion method;
(2) placing the extruded film on a stretching device, keeping the temperature constant for 5min at 10 ℃, and then stretching the extruded film in a single direction at the temperature and the stretching rate of 5 mu m/s, wherein the stretching elongation is 10 percent, so as to obtain the PA1012 porous film, the tensile breaking strength is 49.1MPa, and the pore diameter is 0.01 mu m.
Example 2
(1) Firstly, preparing a PA1012 extrusion film, wherein the melting point of PA1012 is 190 ℃, the melt index is 15g/min, and the extrusion temperature is 220 ℃ by adopting a melt extrusion method;
(2) placing the extruded film on a stretching device, keeping the temperature constant for 10min at 60 ℃, and then performing unidirectional stretching at the temperature at a stretching rate of 20 mu m/s, wherein the stretching elongation is 200%, so as to obtain the PA1012 porous film, the tensile breaking strength is 50.3MPa, the pore diameter is 1 mu m, a microstructure scanning electron microscope picture is shown in figure 1, the micropores are similar ellipses in figure 1, and the major axes of at least two similar ellipses are approximately a straight line or parallel.
Example 3
(1) Firstly, preparing a PA1012 extrusion film, wherein the melting point of PA1012 is 190 ℃, the melt index is 1g/min, and the extrusion temperature is 250 ℃ by adopting a melt extrusion method;
(2) placing the extruded film on a stretching device, keeping the temperature constant for 15min at 100 ℃, and then performing unidirectional stretching at the temperature at a stretching speed of 50 mu m/s with the stretching elongation of 200 percent to obtain the PA1012 porous film, wherein the tensile breaking strength is 49.5MPa, the pore diameter is 2 mu m, a microstructure scanning electron microscope picture is shown in figure 2, the micropores are similar ellipses in figure 2, and the long axes of at least two similar ellipses are approximately in a straight line or in parallel.
Example 4
(1) Firstly, preparing a PA1012 extrusion film, wherein the melting point of PA1012 is 190 ℃, the melt index is 0.5g/min, and the extrusion temperature is 260 ℃ by adopting a melt extrusion method;
(2) placing the extruded film on a stretching device, keeping the temperature constant for 8min at 100 ℃, and then performing unidirectional stretching at the temperature at a stretching speed of 10 mu m/s and a stretching elongation of 650 percent to obtain the PA1012 porous film, wherein the self-stretching breaking strength is 53.3MPa, the pore diameter is 5 mu m, and a microstructure scanning electron microscope picture is shown in figure 3.
It can be seen from fig. 3 that the major axes of a plurality of the ellipse-like shapes are arranged substantially in a straight line in a first direction, and the major axes of the ellipse-like shapes are arranged substantially in parallel in a second direction perpendicular to the first direction; in a second direction perpendicular to the first direction, the ellipse-like shapes are distributed in a staggered mode, and the length of the long axis of each ellipse-like shape is far larger than that of the short axis of each ellipse-like shape.
Example 5
(1) Firstly, preparing a PA1012 extrusion film, wherein the melting point of PA1012 is 190 ℃, the melt index is 10g/min, and the extrusion temperature is 230 ℃ by adopting a melt extrusion method;
(2) placing the extruded film on a stretching device, keeping the temperature constant for 10min at 170 ℃, and then stretching bidirectionally at the temperature at a stretching rate of 100 mu m/s and a tensile elongation of 400 percent to obtain the PA1012 porous film, wherein the tensile breaking strength is 52.3MPa, and the pore diameter is 4 mu m.
Example 6
(1) Firstly, preparing a PA1012 extrusion film, wherein the melting point of PA1012 is 190 ℃, the melt index is 20g/min, and the extrusion temperature is 210 ℃ by adopting a melt extrusion method;
(2) placing the extruded film on a stretching device, keeping the temperature constant for 10min at 30 ℃, and then performing unidirectional stretching at the temperature at a stretching speed of 400 mu m/s and a stretching elongation of 200 percent to obtain the PA1012 porous film, wherein the tensile breaking strength is 50.3MPa, and the pore diameter is 2 mu m.
Example 7
1) Firstly, preparing a PA612 extrusion film, wherein the melting point of the PA612 is 190 ℃, the melt index is 15g/min, and the extrusion temperature is 220 ℃ by adopting a melt extrusion method;
(2) placing the extruded film on a stretching device, keeping the temperature constant for 10min at 30 ℃, and then performing unidirectional stretching at the temperature at a stretching speed of 500 mu m/s and a stretching elongation of 200% to obtain the PA612 porous film, wherein the tensile breaking strength is 50.1MPa, the pore diameter is 2 mu m, and a microstructure scanning electron microscope image is shown in figure 4.
It can be seen from fig. 4 that the major axes of a plurality of the ellipse-like shapes are arranged substantially in a straight line in a first direction, and the major axes of the ellipse-like shapes are arranged substantially in parallel in a second direction perpendicular to the first direction; in a second direction perpendicular to the first direction, the ellipse-like shapes are distributed in a staggered mode, and the length of the long axis of each ellipse-like shape is far larger than that of the short axis of each ellipse-like shape.
Example 8
(1) Firstly, preparing a PA1012 hot-pressing film, wherein the melting point of the PA1012 is 190 ℃, the melt index is 5g/min, and the hot-pressing temperature is 250 ℃ by adopting a hot-pressing method;
(2) placing the extruded film on a stretching device, keeping the temperature constant for 10min at 150 ℃, and then stretching bidirectionally at the temperature at the stretching rate of 450 mu m/s and the stretching elongation of 500 percent to obtain the PA1012 porous film, wherein the tensile breaking strength is 51.3MPa, and the pore diameter is 4 mu m.
Example 9
(1) Firstly, preparing a PA1012 hot-pressing film, wherein the melting point of the PA1012 is 190 ℃, the melt index is 3g/min, and the hot-pressing temperature is 220 ℃ by adopting a hot-pressing method;
(2) placing the extruded film on a stretching device, keeping the temperature constant for 9min at 100 ℃, and then performing unidirectional stretching at the temperature at a stretching speed of 90 mu m/s and a stretching elongation of 300 percent to obtain the PA1012 porous film, wherein the self-stretching breaking strength is 50.5MPa, and the pore diameter is 3 mu m.
The following are examples 10-21, the procedure is as in example 1, and the specific process parameters and performance indices are shown in tables 1 and 2.
TABLE 1 processing and basic Performance parameters for examples 10-15
Figure BDA0000901429210000091
TABLE 2 processing and basic Performance parameters for examples 16-21
Example 22
(1) Firstly, preparing a PA1012 extrusion film, wherein the melting point of PA1012 is 190 ℃, the melt index is 20g/min, and the extrusion temperature is 220 ℃ by adopting a melt extrusion method;
(2) placing the obtained extruded film on stretching equipment, keeping the temperature constant for 10min, and keeping the temperature constant at T1At 30 ℃ and then uniaxially stretched at a stretching rate of 20 μm/s at this temperature, the elongation ∈1200% and then subjecting the previously obtained stretched sample to a temperature T2Isothermal at 100 deg.C for 10min, and uniaxially stretching at a stretching rate of 20 μm/s at the temperature with a tensile elongation of ε2The tensile breaking strength was 49.5MPa, the pore diameter was 0.9 μm, and the microstructure thereof was observed by scanning electron microscopy as shown in FIG. 5.
As can be seen from fig. 5, in a first direction, the major axes of a plurality of the ellipse-like shapes are arranged substantially in a straight line, and in a second direction perpendicular to the first direction, the major axes of the ellipse-like shapes are distributed substantially in parallel; in a second direction perpendicular to the first direction, the ellipse-like shapes are distributed in a staggered mode, and the length of the long axis of each ellipse-like shape is far larger than that of the short axis of each ellipse-like shape.
Example 23
(1) Firstly, preparing a PA1012 extrusion film, wherein the melting point of PA1012 is 190 ℃, the melt index is 15g/min, and the extrusion temperature is 220 ℃ by adopting a melt extrusion method;
(2) the obtained extruded film was placed on a stretching apparatus at an isothermal temperature of 30 ℃ for 8min, and then biaxially stretched at a stretching rate of 50 μm/s at a stretching rate of 200% at this temperature, and then the previously obtained stretched sample was allowed to stand at 100 ℃ for 10min, and then biaxially stretched at a stretching rate of 20 μm/s at this temperature at a stretching rate of 400% to obtain the porous film having a tensile break strength of 51.4MPa and a pore diameter of 4 μm, and a microstructure scanning electron microscope image thereof is shown in FIG. 6.
It can be seen from fig. 6 that the major axes of the ellipse-like shapes of the formed micro-pore clusters are straight lines or parallel to each other, the ellipse-like shapes are distributed in a staggered manner to form the micro-pore clusters, and the central parts of the micro-pore clusters are micro-pores with small pore diameters.
Example 24
(1) Firstly, preparing a PA1012 extrusion film, wherein the melting point of PA1012 is 190 ℃, the melt index is 0.5g/min, and the extrusion temperature is 260 ℃ by adopting a melt extrusion method;
(2) the obtained extruded film was placed on a stretching apparatus at an isothermal temperature of 40 ℃ for 15min, and then uniaxially stretched at a stretching rate of 100 μm/s at this temperature to give an elongation of 100%, and then the previously obtained stretched sample was allowed to stand at a temperature of 100 ℃ for 10min and then stretched at a stretching rate of 80 μm/s at this temperature to give a tensile elongation of 200%, to give the porous film having a tensile break strength of 50.8MPa and a pore diameter of 4 μm.
Example 25
(1) Firstly, preparing a PA1012 extrusion film, wherein the melting point of PA1012 is 190 ℃, the melt index is 1g/min, and the extrusion temperature is 250 ℃ by adopting a melt extrusion method;
(2) the obtained extruded film was placed on a stretching apparatus at an isothermal temperature of 40 ℃ for 14min, and then uniaxially stretched at a stretching rate of 90 μm/s at a stretching rate of 400% at that temperature, and then the previously obtained stretched sample was allowed to stand at a temperature of 100 ℃ for 10min, and then stretched at a stretching rate of 200 μm/s at that temperature at a stretching rate of 650% to obtain the porous film having a tensile break strength of 52.1MPa and a pore diameter of 5 μm.
The following are examples 26-31 and examples 32-37, the operating procedure is as in example 22, and the specific process parameters and performance criteria are shown in tables 3 and 4.
TABLE 3 processing and basic Performance parameters for examples 26-31
Figure BDA0000901429210000121
TABLE 4 processing and basic Performance parameters for examples 32-37
Figure BDA0000901429210000131
The water absorption properties of the long carbon chain polyamide (Table 5) and the mechanical properties of the long carbon chain polyamide and the long carbon chain polyamide after absorption of water (Table 6) are shown below.
TABLE 5 Water absorption parameter of long carbon chain polyamides after 5h immersion in boiling water
Figure BDA0000901429210000141
TABLE 6 mechanical Properties of Long carbon chain Polyamide before and after 5h Water absorption
Figure BDA0000901429210000142

Claims (11)

1. A long carbon chain polyamide porous membrane, characterized in that, the porous membrane is a sheet structure with uniform thickness, the sheet structure is provided with a plurality of micropores which are basically independent of each other, the porous membrane is prepared by adopting long carbon chain polyamide, the long carbon chain polyamide is aliphatic polyamide with the carbon chain length between two adjacent amide groups in the molecule being more than 10, wherein,
the micropores are in an ellipse-like shape, and the long axes of at least two ellipse-like shapes are approximately in a straight line or in parallel;
or the micropores are in an ellipse-like shape, a plurality of ellipse-like shapes form a plurality of micropore clusters on the sheet structure, and the major axes of a plurality of ellipse-like shapes are basically in one direction;
the major axes of a plurality of the ellipse-like shapes are arranged on a straight line in a first direction, and the major axes of the ellipse-like shapes are distributed in parallel in a second direction perpendicular to the first direction;
or the major axes of the quasi-elliptical shapes forming the micropore clusters are straight lines or are parallel to each other;
the melting point of the long carbon chain polyamide is 180-230 ℃, and the melt index is 0.5-20g/10 min;
the long carbon chain polyamide is nylon 1012 or/and nylon 1212;
the long carbon chain polyamide porous membrane is a single-layer membrane or a multilayer composite membrane, and the pore diameter of the long carbon chain polyamide porous membrane is 0.01-5 mu m.
2. The long carbon chain polyamide porous film according to claim 1, wherein the quasi-elliptical shape is arranged in a staggered manner in a second direction perpendicular to the first direction.
3. The long carbon chain polyamide porous membrane according to claim 1, wherein the quasi-elliptical dislocation distribution forms a micro-pore cluster.
4. The long carbon chain polyamide porous membrane according to claim 1, wherein the center portion of the pore cluster is a pore having a small pore size.
5. The porous film of long carbon chain polyamide according to claim 1, wherein the melt index of the long carbon chain polyamide is 1 to 10g/10 min.
6. A method for producing a long carbon chain polyamide porous film according to any one of claims 1 to 5, characterized by comprising the steps of:
(1) preparing a long carbon chain polyamide flat sheet;
(2) the flat sheet is placed in a stretching device to be stretched in one step or two steps.
7. The method according to claim 6, wherein the flat sheet is prepared by a melt extrusion method or a hot pressing method in the step (1), and the extrusion or hot pressing temperature is 200 ℃ to 300 ℃.
8. The method of claim 7, wherein the extrusion or hot pressing temperature is 220 ℃ to 270 ℃.
9. The production method according to claim 6, wherein the one-step stretching in the step (2) is to place the flat sheet on a stretching apparatus isothermally at 10 to 170 ℃ for 5 to 15min and then unidirectionally or bidirectionally stretch at a stretching rate of 5 to 500 μm/s to 10 to 650% at this temperature to obtain the porous film; the two-step stretching is to put the flat sheet on a stretching device to be isothermally stretched for 5-15min at an isothermal temperature of T1 at a stretching rate of 5-500 mu m/s to epsilon 1, to obtain a stretched sample, to be isothermally or bidirectionally stretched at a temperature of T2 at a stretching rate of 5-500 mu m/s for 5-15min, and to then be unidirectionally or bidirectionally stretched for epsilon 2 at a stretching rate of 5-500 mu m/s at a temperature of 10 ℃ to T1 to 170 ℃ and 10% to epsilon 1 to epsilon 2 to 650% to obtain the porous membrane, wherein T2 to epsilon 1 is more than or equal to 10% and epsilon 2 is more than or equal to 170.
10. The method of claim 9, wherein the stretching rate is 10 μm/s to 100 μm/s.
11. The application of the long carbon chain polyamide porous membrane of any one of claims 1 to 5 in the fields of lithium ion battery separators and water filtration membranes.
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