WO2017133375A1 - 一种芳香族聚酰胺多孔膜制备方法及芳香族聚酰胺多孔膜 - Google Patents

一种芳香族聚酰胺多孔膜制备方法及芳香族聚酰胺多孔膜 Download PDF

Info

Publication number
WO2017133375A1
WO2017133375A1 PCT/CN2017/070270 CN2017070270W WO2017133375A1 WO 2017133375 A1 WO2017133375 A1 WO 2017133375A1 CN 2017070270 W CN2017070270 W CN 2017070270W WO 2017133375 A1 WO2017133375 A1 WO 2017133375A1
Authority
WO
WIPO (PCT)
Prior art keywords
aromatic polyamide
porous film
solvent
producing
ionic liquid
Prior art date
Application number
PCT/CN2017/070270
Other languages
English (en)
French (fr)
Inventor
孙庆津
申大卫
沈祖亮
吴晖
李翔
Original Assignee
微宏动力系统（湖州）有限公司
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 微宏动力系统（湖州）有限公司 filed Critical 微宏动力系统（湖州）有限公司
Priority to US16/082,269 priority Critical patent/US11205821B2/en
Priority to EP17746695.0A priority patent/EP3441135A4/en
Publication of WO2017133375A1 publication Critical patent/WO2017133375A1/zh

Links

Images

Classifications

    • 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
    • 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
    • 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
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • 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
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0011—Casting solutions therefor
    • 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
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0011—Casting solutions therefor
    • B01D67/00111—Polymer pretreatment in the casting solutions
    • 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
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0016—Coagulation
    • B01D67/00165—Composition of the coagulation baths
    • 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
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0095—Drying
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • H01M50/406—Moulding; Embossing; Cutting
    • 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
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/219—Specific solvent system
    • B01D2323/226—Use of ionic liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/28—Pore treatments
    • 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

Definitions

  • the present invention relates to a method for producing an aromatic polyamide porous film and an aromatic polyamide porous film.
  • the prior art porous membranes are typically prepared by thermally induced phase separation (TIPS) or non-solvent phase inversion (NIPS).
  • TIPS thermally induced phase separation
  • NIPS non-solvent phase inversion
  • the thermally induced phase separation method utilizes crystallinity to form a homogeneous casting solution of a thermoplastic polymer with a high-boiling, low-molecular-weight diluent at a high temperature, and solid-liquid or liquid-liquid phase separation occurs when the temperature is lowered, followed by removal of the dilution.
  • the non-solvent phase inversion (NIPS) method is prepared by preparing a three-dimensional macromolecular network gel process in which a solvent solution is a continuous phase of a polymer solution converted into a continuous phase.
  • the disadvantages of both methods are: multi-component mixing of polymer, porogen and solvent, and requires a large amount of extraction solvent, the separation process is complicated, the additive is difficult to reuse, resulting in high production cost and pollution
  • the lithium battery separator is also a kind of porous membrane. With the vigorous development of the lithium battery industry, the demand for diaphragm production has increased dramatically.
  • the diaphragm is one of the key components of the battery. It is located between the positive and negative electrodes of the battery to isolate the positive and negative electrodes to avoid internal short circuit of the battery, and to ensure the smooth passage of lithium ions during charging and discharging.
  • the separator currently widely used in lithium ion secondary batteries is a polyolefin-based melt-stretched separator, and the ambient temperature of the polyolefin-based material itself is not too high due to limitations of the polyolefin-based material itself.
  • Aromatic polyamide polymers (PPTA, PMIA, PBA, PSA) have high heat resistance, glass transition temperature above 300 ° C, thermal decomposition temperature up to 560 ° C, in addition to high insulation and chemical resistance, As a good choice for lithium ion battery separators.
  • Aramids have been applied to lithium ion battery separators in domestic research institutes. For example, Chinese patents published as CN103242556A and Chinese patent publication No. CN202384420U apply aramid polymer fibers to the surface of polyolefin membranes. The method is greatly limited in applicability due to being limited by the polyolefin substrate.
  • the present invention provides a method for preparing an aromatic polyamide porous membrane, wherein an ionic liquid and an aromatic polyamide are formulated into a mixed solution by a solvent; the mixed solution forms a film in a gel bath; A porous film is formed by extracting a solvent and an ionic liquid by an extractant.
  • An ionic liquid is a liquid substance composed entirely of ions, which is a liquid at room temperature or low temperature, and is therefore also called a room temperature/low temperature molten salt, or a liquid organic salt.
  • ionic liquids can be classified into quaternary ammonium salts, quaternary phosphonium salts, nitrogen-containing heterocyclic sulfonium salts, etc., and nitrogen-containing heterocyclic ionic liquids include imidazolium salts. Pyridinium salts, piperidine salts, pyrrolidine salts, and the like.
  • the structures of the cations of several common ionic liquids are as follows:
  • anions constituting ionic liquids include F - , Cl - , Br - , I - , NO 3 - , CO 3 2- , PF 6 - , BF 4 - , C 2 O 4 2- , SO 4 2 - , PO 4 3- , Al 2 Cl 7 -, etc., organic anions including CH 3 COO - , CH 3 SO 3 - , CF 3 SO 3 - , C 4 H 9 SO 3 - , CF 3 COO - , N (FSO 2 ) 2 - , N(CF 3 SO 2 ) 2 - , N(C 2 F 5 SO 2 ) 2 - , N(C 4 F 9 SO 2 ) 2 - , N[(CF 3 SO 2 )(C 4 F 9 SO 2)] -, C (CF 3 SO 2) 3 - and the like.
  • the invention selects a porous membrane by the NIPS method, and the NIPS method does not require a higher temperature in the membrane forming process than the TIPS method, the production process parameters are more easily controlled, and a three-dimensional network pore structure can be obtained, which is widely used at present.
  • the field of porous membranes such as water treatment membranes and air separation membranes.
  • the present invention further prepares an aromatic polyamide-based polymer porous film by a NIPS method in combination with an ionic liquid as a pore former.
  • the invention selects an ionic liquid as a pore-forming agent, and selects an ionic liquid as the sole additive, and has the following advantages: (1) the ionic liquid is an ionic substance, which has both the property of a salt and the nature of an organic substance, so that the solvating ability is strong; (2) Ionic liquids have good thermal stability and chemical stability. The decomposition temperature of most ionic liquids is above 400 °C, which is quite different from the boiling point of common solvents, which is beneficial to the separation and reuse of other solvents; (3) ) No flash point, high ignition point, ensuring safety during use and recycling.
  • the ratio of the ionic liquid to the aromatic polyamide can be adjusted according to the required porosity.
  • the present invention has found through long-term research that the mass ratio of the ionic liquid to the aromatic polyamide When it is (1:1) to (8:1), a film having a relatively uniform pore distribution and a moderate porosity can be obtained. More preferably, the mass ratio of the ionic liquid to the aromatic polyamide is (1:1) to (6:1). More preferably, the mass ratio of the ionic liquid to the aromatic polyamide is (2:1) to (5:1).
  • the ionic liquid is at least one selected from the group consisting of a quaternary ammonium salt, a quaternary phosphonium salt, an imidazolium salt, a pyridinium salt, a piperidine salt, and a pyrrolidine salt.
  • a quaternary ammonium salt a quaternary phosphonium salt
  • imidazolium salt a pyridinium salt
  • a piperidine salt a pyrrolidine salt
  • the aromatic polyamide is selected from the group consisting of polyparaphenylene terephthalamide (aramid 1414, PPTA), poly(m-phenylene isophthalamide) (aramid 1313, PMIA), polyparaphenylene At least one of formamide (aramid I, PBA) and polyphenylsulfone terephthalamide.
  • the present invention does not limit how to configure a mixed solution of an ionic liquid and an aromatic polyacyl group.
  • the following three options are preferred:
  • the ionic liquid and the aromatic polyamide are mixed into a mixed solution by using a solvent, comprising: mixing the ionic liquid with the first solvent to form an ionic liquid solution; mixing the aromatic polyamide with the second solvent to form an aromatic polyamide solution; The above ionic liquid solution is mixed with an aromatic polyamide solution to form a mixed solution.
  • the aromatic polyamide may be an aramid fiber.
  • the specific form of the aramid fiber is not limited in the present invention, and may be short fibers, fibrids, and other commonly used aramid fibers for film preparation.
  • disposing the ionic liquid and the aromatic polyamide into a mixed solution by using a solvent comprises: mixing the ionic liquid with the first solvent to form an ionic liquid solution; forming an aromatic polyamide solution by polymerization, wherein the polymerization reaction is used. a solvent; the above ionic liquid solution is mixed with an aromatic polyamide solution to form a mixed solution.
  • the polymerization reactant solution can be obtained by twin-screw polymerization or polymerization in a reactor without particular limitation.
  • disposing the ionic liquid and the aromatic polyamide into a mixed solution by using a solvent comprises: mixing the ionic liquid, the aromatic polyamide, and the third solvent to form a mixed solution.
  • the aromatic polyamide may be an aramid fiber.
  • the specific form of the aramid fiber is not limited in the present invention, and may be short fibers, fibrids, and other commonly used aramid fibers for film preparation.
  • the first solvent of the present invention means a solvent capable of dissolving an ionic liquid; the second solvent means a solvent capable of dissolving an aromatic polyamide; and the third solvent means a solvent capable of simultaneously dissolving an ionic liquid and an aromatic polyamide.
  • the specific components of the first solvent, the second solvent, and the third solvent are not limited.
  • the first solvent of the present invention means a solvent capable of dissolving an ionic liquid, and preferably, the first solvent is selected from the group consisting of water, ethanol, propanol, isopropanol, glycerol, tetrahydrofuran, pyridine, dichloromethane, and chloroform. And at least one of ethyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and polyethylene glycol.
  • the second solvent of the present invention means a solvent capable of dissolving an aromatic polyamide, and preferably, the second solvent is selected from the group consisting of N-methylpyrrolidone (NMP), N,N-dimethylacetamide (DMAC), and N. At least one of N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and triethyl phosphate (TEP).
  • NMP N-methylpyrrolidone
  • DMAC N,N-dimethylacetamide
  • N N-dimethylacetamide
  • TEP triethyl phosphate
  • the mass ratio of the first solvent to the ionic liquid is (0.05:1) to (0.8:1). More preferably, the mass ratio of the first solvent to the ionic liquid is (0.1:1) to (0.5:1).
  • the mass ratio of the second solvent to the aromatic polyamide is (2:1) to (10:1). More preferably, the mass ratio of the second solvent to the aromatic polyamide is (3:1) to (8:1).
  • the third solvent of the present invention means a solvent capable of simultaneously dissolving an ionic liquid and an aromatic polyamide, and preferably, the third solvent is selected from the group consisting of N-methylpyrrolidone, N,N-dimethylacetamide, N,N- At least one of dimethylformamide and dimethyl sulfoxide.
  • the mass fraction of the third solvent in the mixed solution is 20 to 80%. Further preferably, the mass fraction of the third solvent in the mixed solution is 40 to 70%.
  • the gel bath comprises a first component; the first component is water or dichloromethane.
  • the gel bath of the present invention may contain only 100% by mass of water or dichloromethane, i.e., water or dichloromethane in a gel bath.
  • the gel bath further comprises a second component; the second component is selected from the group consisting of N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, At least one of dimethyl sulfoxide and triethyl phosphate.
  • the second component added here is mainly selected from the solvent capable of dissolving the aromatic polyamide; wherein the choice of the solvent varies depending on the preparation method: if the ionic liquid and the aromatic polyamide are separately dissolved and then mixed, Then, the second component can be selected from the second solvent of the present invention; if a solvent capable of simultaneously dissolving the ionic liquid and the aromatic polyamide is selected to form a mixed solution, the second component can be selected from the third solvent of the present invention.
  • the specific choice of the second component of the gel bath corresponds to the solvent used to configure the aromatic polyamide solution, such as preparing the aromatic polyamide solution by DMAC solvent, and the components of the gel bath may be water, water and DMAC, A combination of methyl chloride, dichloromethane and DMAC.
  • water or dichloromethane in the gel bath preferably has a mass fraction of from 5 to 99.9%. Further preferably, the mass fraction of water or dichloromethane in the gel bath is 20 to 60%. More preferably, the mass fraction of water or dichloromethane in the gel bath is 30 to 50%.
  • the temperature of the gel bath is controlled to be 0 to 80 °C. More preferably, the temperature of the gel bath is controlled to be 20 to 60 °C.
  • the gel bath of the present invention preferably optimizes the structure of the porous membrane at a temperature and a preferred component concentration; wherein the preferred concentration of water or methylene chloride of the present invention optimizes the diffusion rate of the solvent in the film, and an optimized concentration difference is formed. Excellent porous structure. Because the concentration of water or methylene chloride is too high, the porous film forms a dense skin layer, and the gas permeability time increases. Conversely, when the water or methylene chloride concentration is too low, the cast film slurry is difficult to solidify into a film. In addition, the preferred temperature range of the gel bath ensures that the solvent of the film diffuses faster into the gel bath, resulting in an excellent porous structure.
  • the gel bath temperature and composition play an important role in the formation of a high-quality porous film, and in particular, a combination of the two can give a preferred porous film.
  • the time during which the mixed solution forms a film in the gel bath is controlled to be 5 to 300 seconds. Further preferably, the time during which the mixed solution forms a film in the gel bath is controlled to be 10 to 200 seconds.
  • the extracting agent is at least one of water, dichloromethane, chloroform and ethanol.
  • the temperature of the extractant is controlled to be 20 to 100 °C. More preferably, the temperature of the extractant is controlled to be 30 to 80 °C.
  • the method for preparing an aromatic polyamide porous membrane of the present invention comprises: disposing an ionic liquid and an aromatic polyamide into a mixed solution by a solvent; the mixed solution flows out through a slit to form a film in a gel bath; A porous film is formed by extracting an ionic liquid and a solvent by an extractant in an extraction tank; and the porous film is dried to obtain an aromatic polyamide porous film.
  • the outflow of the slit in the present invention means that the mixed solution is formed into a film shape through the slit, so that any mold capable of forming a slit shape can be used, and it is generally preferred to form a slit by using a doctor blade to form a slit or an extrusion die. That is, the mixed solution is discharged through a slit formed by a doctor blade to form a film, or the mixed solution is discharged through a slit of an extrusion die to form a film.
  • the drying is infrared drying and/or blast drying.
  • the drying temperature is controlled to be 50 to 150 °C. More preferably, the drying temperature is controlled to be 80 to 120 °C.
  • a second object of the present invention is to provide an aromatic polyamide porous film which is prepared by the above-described method for producing an aromatic polyamide porous film.
  • a third object of the present invention is to provide a lithium ion secondary battery comprising the above-mentioned aromatic polyamide porous film.
  • Example 1 is an SEM image of the surface of an aromatic polyamide porous film prepared in Example 1 of the present invention.
  • Example 2 is an SEM image of a cross section of an aromatic polyamide porous film prepared in Example 1 of the present invention.
  • the solution was polymerized in a reaction vessel to obtain 2000 g of a poly(m-phenylene isophthalamide) solution having a solvent of DMAC and a polymer concentration percentage of 20%.
  • 800 g of 1-methyl-3-butylimidazolium hydrochloride and 240 g of absolute ethanol were mixed in a stirred tank to obtain an ionic liquid solution.
  • the pre-prepared ionic liquid solution and the poly-m-phenylene isophthalamide solution were separately injected into the twin-screw machine according to the mass ratio of 1:1.8, and dispersed and dispersed in the die through the melt pump to enter the gel.
  • a film was formed in the bath, and the gel bath was a mixed solvent of water and DMAC, wherein the mass of water was 50%, the gel bath temperature was 80 ° C, and the gel time was 20 seconds.
  • the film is drawn into the extraction tank, and the temperature of the extraction tank is At 30 ° C, the solvent was extracted with dichloromethane to form a film of a porous structure.
  • the above porous film was dried by hot air, and the drying temperature was 80 °C. Winding is completed after static electricity.
  • the measured air permeability was 80 sec/100 cc.
  • 2400 g of a poly-m-phenylene isophthalamide solution was obtained by two-stage screw polymerization, and the solvent was DMAC, and the polymer concentration percentage was 20%.
  • 1000 g of methyltriethylammonium acetate was mixed with 200 g of deionized water in a stirred tank, and the stirred kettle was heated to 50 °C.
  • the pre-prepared ionic liquid solution and poly-m-phenylene isophthalamide solution were metered into a twin-screw machine at a mass ratio of 1:1.5, mixed and dispersed, and extruded through a melt pump to form a condensation.
  • the gel bath forms a film.
  • the gel bath is a mixed solvent of water and DMAC.
  • the proportion of water in the gel bath is 20%, the gel bath temperature is 60 ° C, and the gel time is 5 seconds.
  • the film was drawn into an extraction tank, the temperature of the extraction tank was 80 ° C, and the solvent was extracted with water to form a film of a porous structure.
  • the above porous film was subjected to infrared drying at a drying temperature of 120 °C. Winding is completed after static electricity.
  • the measured air permeability was 105 sec/100 cc.
  • Example 2 In the same manner as in Example 2, the mass of deionized water added to methyltriethylammonium acetate was 50 g, and the gas permeability was measured to be 110 sec/100 cc.
  • the gel bath was water, the gel bath temperature was 80 ° C, the gel time was 20 seconds, the drying temperature was 150 ° C, and the air permeability was measured to be 820 sec / 100 cc.
  • 1600 g of p-benzamide and polyphenylsulfone terephthalamide solution were obtained by polymerization in a reaction vessel, and the solvent was NMP, and the polymer concentration percentage was 9%.
  • 800 g of 1-methyl-3-propylimidazolium acetate and 160 g of ethyl acetate were uniformly mixed in a stirred tank.
  • the pre-prepared ionic liquid solution and the para-benzamide and polyphenylsulfone terephthalamide solution were metered into the mixing kettle according to the mass ratio of 1:1.6, and uniformly stirred under the negative pressure condition, and passed through the melt pump in the mold. The head is extruded and enters the gel bath to form a film.
  • the gel bath is a mixed solvent of water and NMP.
  • the proportion of water in the gel bath is 20%, the gel bath temperature is 50 ° C, and the gel time is 80 seconds. .
  • the film is drawn into the extraction tank, The temperature of the extraction tank was 80 ° C, and the solvent was extracted with water to form a film of a porous structure.
  • the above porous film was subjected to infrared drying at a drying temperature of 120 °C. Winding is completed after static electricity.
  • the measured air permeability was 40 sec/100 cc.
  • Example 5 The same as in Example 5, except that the extraction bath temperature was 100 °C.
  • a solution of polyparaphenylene terephthalamide solution was obtained by polymerization in a reaction vessel, and the solvent was DMF, and the polymer concentration percentage was 18%.
  • 800 g of N-methyl-N-propylpyrroleium fluoroborate was mixed with 100 g of dichloromethane in a stirred tank, and the stirred kettle was heated to 50 °C.
  • the pre-prepared ionic liquid solution and the poly-p-phenylene terephthalamide solution were metered into a three-screw machine at a mass ratio of 1:1.3, mixed and dispersed, and extruded through a melt pump to form a condensation.
  • the film was formed by a glue bath.
  • the gel bath was a mixed solvent of dichloromethane and DMF.
  • the mass ratio of methylene chloride in the gel bath was 30%, the gel bath temperature was 20 ° C, and the gel time was 150 seconds.
  • the film was drawn into an extraction tank at a temperature of 30 ° C, and the solvent was extracted with dichloromethane to form a film having a porous structure.
  • the above porous film was air-dried at a drying temperature of 80 °C. Winding is completed after static electricity.
  • the measured air permeability was 180 seconds / 100 cc.
  • poly-m-phenylene isophthalamide short fiber 200 g was dissolved in 1200 g of DMAC solvent to prepare a polymer solution having a polymer concentration percentage of 16.7%.
  • 600 g of methyltributylammonium hydrochloride was mixed with 150 g of deionized water in a stirred tank, and the stirred kettle was heated to 50 °C.
  • the pre-prepared ionic liquid solution and poly-m-phenylene isophthalamide solution were metered into a three-screw machine at a mass ratio of 1:1.4, mixed and dispersed, and extruded through a melt pump to form a condensation.
  • the gel bath forms a film.
  • the gel bath is a mixed solvent of water and DMAC.
  • the proportion of water in the gel bath is 30%, the gel bath temperature is 50 ° C, and the gel time is 80 seconds.
  • the film was drawn into an extraction tank, the temperature of the extraction tank was 80 ° C, and the solvent was extracted with water to form a film of a porous structure.
  • the above porous film was subjected to infrared drying at a drying temperature of 120 °C. Winding is completed after static electricity.
  • the measured air permeability was 86 sec/100 cc.
  • the gel bath is a mixed solvent of DMAC and dichloromethane.
  • the mass ratio of methylene chloride in the gel bath is 30%, and the gel bath temperature is 0. °C, gel time is 250 seconds.
  • the film was drawn into an extraction tank at a temperature of 30 ° C, and the solvent was extracted with dichloromethane to form a film having a porous structure.
  • the above porous film was air-dried at a drying temperature of 50 °C. Winding is completed after static electricity.
  • the measured air permeability was 380 seconds / 100 cc.
  • Example 2 The same as in Example 1, except that the gel bath was dichloromethane, the extraction bath temperature was 30 ° C, and the gas permeability was measured to be 330 sec / 100 cc.
  • methyltributylammonium hydrochloride 300 g was uniformly mixed with 1200 g of DMAC, and then 200 g of parabenzamide and polyphenylsulfone terephthalamide short fiber were added to the above solution, and heated to 80 ° C, and uniformly stirred under a negative pressure.
  • the gel bath is a mixed solvent of DMAC and dichloromethane, and the proportion of methylene chloride in the gel bath is 20%, gel The bath temperature was 40 ° C and the gel time was 180 seconds.
  • the film was drawn into an extraction tank at a temperature of 30 ° C, and the solvent was extracted with dichloromethane to form a film having a porous structure. Finally, the above porous film was air-dried at a drying temperature of 60 °C. Winding is completed after static electricity. The air permeability was measured to be 120 sec / 100 cc.
  • the invention prepares a porous membrane by a non-solvent phase transformation method, and does not require a higher temperature in the membrane forming process than the thermally induced phase separation method, the production process parameters are more easily controlled, and a three-dimensional network pore structure can be obtained. It is widely used in the field of porous membranes such as water treatment membranes and air separation membranes.
  • the present invention further prepares an aromatic polyamide-based polymer porous film by a non-solvent phase inversion method in combination with an ionic liquid as a pore former, and is used as a separator for a lithium battery.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Cell Separators (AREA)

Abstract

一种芳香族聚酰胺多孔膜制备方法及芳香族聚酰胺多孔膜。其中制备方法是将离子液体与芳香族聚酰胺通过溶剂配制成混合溶液；将混合溶液在溶胶浴中制成膜，然后将膜通过萃取剂萃取出溶剂与离子液体，形成多孔膜。本方法使用了离子液体，减少了添加剂的使用，且稳定性高，易与其他溶剂分离并重复使用。

Description

一种芳香族聚酰胺多孔膜制备方法及芳香族聚酰胺多孔膜 技术领域
本发明涉及一种芳香族聚酰胺多孔膜制备方法及芳香族聚酰胺多孔膜。
背景技术
现有技术中多孔膜通常采用热致相分离法(TIPS)或非溶剂相转化法(NIPS)制备。热致相分离法是利用结晶性，使热塑性聚合物与高沸点、低分子量的稀释剂在高温时形成均相铸膜液，温度降低时发生固－液或液－液相分离，之后除去稀释剂，得到聚合物微孔膜。非溶剂相转化法(NIPS)是在溶剂体系为连续相的聚合物溶液转变为连续相的三维大分子网络凝胶过程中制备而形成的。两种方法均存在的缺点为：聚合物、致孔剂和溶剂等多元混合，且需要大量的萃取溶剂，分离过程复杂，添加剂难以重复利用，造成生产成本高，对环境产生污染。
锂电池隔膜同样属于多孔膜的一种，借助于锂电池产业的蓬勃发展，隔膜生产需求量剧增。隔膜是电池的关键组成部分之一，位于电池的正、负电极之间用来隔离正、负电极以避免电池内部短路，同时又保证锂离子在充放电时能够顺利通过。目前正广泛应用于锂离子二次电池中的隔膜为聚烯烃类融熔拉伸隔膜，而由于聚烯烃类材料本身的限制，其使用环境温度不宜太高。但在大电流充放电的工作环境中，电池内部温度可能迅速升高，容易使聚烯烃类隔膜闭孔甚至发生热收缩，进而使电池内阻显著增加，最终导致电池失效。芳香族聚酰胺类聚合物(PPTA、PMIA、PBA、PSA)具有高耐热性，玻璃化温度在300℃以上，热分解温度高达560℃，此外还有高绝缘性和耐化学腐蚀性，是作为锂离子电池隔膜的上佳选择。国内有研究机构已经将芳纶应用于锂离子电池隔膜，如公开号为CN103242556A的中国专利及公告号为CN202384420U的中国专利中将芳香族聚酰胺类聚合物纤维涂覆到聚烯烃隔膜表面，这些方法由于受限于聚烯烃基材，因此在应用性方面大打折扣。
发明内容
为解决上述问题，本发明提供一种芳香族聚酰胺多孔膜的制备方法，将离子液体与芳香族聚酰胺通过溶剂配制成混合溶液；所述混合溶液在凝胶浴中形成膜；所述膜通过萃取剂萃取出溶剂与离子液体后形成多孔膜。
离子液体是完全由离子组成的液态物质，在室温或低温下为液体，因此又称室温/低温熔融盐，或称液体有机盐。离子液体的种类很多，根据有机阳离子的不同，可以将离子液体分为季铵盐类、季鏻盐类、含氮杂环鎓盐类等，含氮杂环型离子液体包括咪唑鎓盐类、吡啶鎓盐类、哌啶盐类、吡咯烷盐类等。几种常见的离子液体的阳离子的结构如下所示：
Figure PCTCN2017070270-appb-000001
组成离子液体的阴离子种类繁多，无机阴离子包括F-、Cl-、Br-、I-、NO3 -、CO3 2-、PF6 -、BF4 -、C2O4 2-、SO4 2-、PO4 3-、Al2Cl7 -等，有机阴离子包括CH3COO-、CH3SO3 -、CF3SO3 -、C4H9SO3 -、CF3COO-、N(FSO2)2 -、N(CF3SO2)2 -、N(C2F5SO2)2 -、N(C4F9SO2)2 -、N[(CF3SO2)(C4F9SO2)]-、C(CF3SO2)3 -等。
本发明选择通过NIPS法制备多孔膜，NIPS法相对于TIPS法，在制膜工艺上并不要求较高的温度，生产过程参数更容易控制，而且可以制得三维网状孔结构，目前广泛应用于水处理膜、空气分离膜等多孔膜领域。
本发明进一步通过NIPS法与离子液体做造孔剂相结合制备芳香族聚酰胺类聚合物多孔膜。本发明选择离子液体作为造孔剂，且选择离子液体作为唯一的添加剂，具有以下优点：(1)离子液体是离子性物质，既有盐的性质，又有有机物的性质，所以溶解能力强；(2)离子液体具有较好的热稳定性和化学稳定性，大多数离子液体的分解温度在400℃以上，与一般溶剂沸点差别较大，有利于与其他溶剂的分离及重复利用；(3)无闪点，燃点高，保证了在使用过程及回收过程中的安全性。
在膜制备过程中，可以根据需要的孔隙率调整离子液体与芳香族聚酰胺的比例，本发明经过长期研究发现当所述离子液体与芳香族聚酰胺的质量比 为(1:1)～(8:1)时，可以获得孔分布较为均匀，孔隙率适中的薄膜。作为进一步优选，所述离子液体与芳香族聚酰胺的质量比为(1:1)～(6:1)。作为更进一步优选，所述离子液体与芳香族聚酰胺的质量比为(2:1)～(5:1)。
作为优选，所述离子液体选自季铵盐、季鏻盐、咪唑鎓盐、吡啶鎓盐、哌啶盐及吡咯烷盐中至少一种。此类离子液体更容易溶解于极性溶剂更方便配置成离子液体溶液。
作为优选，所述芳香族聚酰胺选自聚对苯二甲酰对苯二胺(芳纶1414，PPTA)、聚间苯二甲酰间苯二胺(芳纶1313，PMIA)、聚对苯甲酰胺(芳纶Ⅰ，PBA)及聚苯砜对苯二甲酰胺中至少一种。
本发明对如何配置成离子液体与芳香族聚酰的混合溶液不作限制。优选以下三种方案：
第一种，将离子液体与芳香族聚酰胺通过溶剂配置成混合溶液包括：将离子液体与第一溶剂混合形成离子液体溶液；将芳香族聚酰胺与第二溶剂混合形成芳香族聚酰胺溶液；再将上述离子液体溶液与芳香族聚酰胺溶液混合形成混合溶液。所述芳香族聚酰胺可以为芳香族聚酰胺纤维。本发明对芳香族聚酰胺纤维具体形式不作限制，可以是短纤维、沉析纤维及其它常用的膜制备用芳香族聚酰胺纤维。
第二种，将离子液体与芳香族聚酰胺通过溶剂配置成混合溶液包括：将离子液体与第一溶剂混合形成离子液体溶液；通过聚合反应形成芳香族聚酰胺溶液，所述聚合反应中使用第二溶剂；再将上述离子液体溶液与芳香族聚酰胺溶液混合形成混合溶液。所述聚合反应物溶液可以通过双螺杆机聚合或者反应釜内聚合获得，不作具体限制。
第三种，将离子液体与芳香族聚酰胺通过溶剂配置成混合溶液包括：将离子液体、芳香族聚酰胺及第三溶剂混合形成混合溶液。所述芳香族聚酰胺可以为芳香族聚酰胺纤维。本发明对芳香族聚酰胺纤维具体形式不作限制，可以是短纤维、沉析纤维及其它常用的膜制备用芳香族聚酰胺纤维。
本发明第一溶剂是指能溶解离子液体的溶剂；第二溶剂是指能溶解芳香族聚酰胺的溶剂；第三溶剂是指能同时溶解离子液体与芳香族聚酰胺的溶剂。至于第一溶剂、第二溶剂及第三溶剂的具体成分不作限制。
本发明第一溶剂是指能够溶解离子液体的溶剂，作为优选，所述第一溶剂选自水、乙醇、丙醇、异丙醇、丙三醇、四氢呋喃、吡啶、二氯甲烷、三氯甲烷、乙酸乙酯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮及聚乙二醇中至少一种。
本发明第二溶剂是指能够溶解芳香族聚酰胺的溶剂，作为优选，所述第二溶剂选自N－甲基吡咯烷酮(NMP)、N,N－二甲基乙酰胺(DMAC)、N,N－二甲基甲酰胺(DMF)、二甲亚砜(DMSO)及磷酸三乙酯(TEP)中至少一种。
作为优选，所述第一溶剂与离子液体的质量比为(0.05:1)～(0.8:1)。作为进一步优选，所述第一溶剂与离子液体的质量比为(0.1:1)～(0.5:1)。
作为优选，所述第二溶剂与芳香族聚酰胺的质量比为(2:1)～(10:1)。作为进一步优选，所述第二溶剂与芳香族聚酰胺的质量比为(3:1)～(8:1)。
本发明第三溶剂是指能够同时溶解离子液体和芳香族聚酰胺的溶剂，作为优选，所述第三溶剂选自N－甲基吡咯烷酮、N,N－二甲基乙酰胺、N,N－二甲基甲酰胺及二甲亚砜中至少一种。
作为优选，所述混合溶液中第三溶剂的质量分数为20～80％。作为进一步优选，所述混合溶液中第三溶剂的质量分数为40～70％。
作为优选，所述凝胶浴包括第一组分；所述第一组分为水或二氯甲烷。本发明的凝胶浴可以只含水或二氯甲烷，即水或二氯甲烷在凝胶浴中所占质量分数为100％。
作为进一步优选，所述凝胶浴还包括第二组分；所述第二组分选自N－甲基吡咯烷酮、N,N－二甲基乙酰胺、N,N－二甲基甲酰胺、二甲亚砜及磷酸三乙酯中至少一种。此处增加的第二组分主要选自能够溶解芳香族聚酰胺的溶剂；其中根据制备方法的不同，溶剂的选择会有所不同：如果选择分别溶解离子液体和芳香族聚酰胺后再混合，则第二组分可以从本发明第二溶剂中选择；如果选择能同时溶解离子液体和芳香族聚酰胺的溶剂配成混合溶液，则第二组分可以从本发明第三溶剂中选择。凝胶浴第二组分的具体选择对应于配置芳香族聚酰胺溶液所使用的溶剂，比如通过DMAC溶剂制备芳香族聚酰胺溶液，那么凝胶浴的组分可以为水、水和DMAC、二氯甲烷、二氯甲烷和DMAC等组合。
在含有其它溶剂的情况下，所述凝胶浴中水或二氯甲烷优选所占的质量分数为5～99.9％。作为进一步优选，所述凝胶浴中水或二氯甲烷所占的质量分数为20～60％。作为更进一步优选，所述凝胶浴中水或二氯甲烷所占的质量分数为30～50％。
作为优选，所述凝胶浴的温度控制为0～80℃。作为进一步优选，所述凝胶浴的温度控制为20～60℃。
本发明凝胶浴优选温度和优选组分浓度对多孔膜的结构起优化作用；其中，本发明优选的水或者二氯甲烷的浓度可以优化薄膜中的溶剂的扩散速度，优化的浓度差会形成优良的多孔结构。因为，水或者二氯甲烷浓度过高会导致多孔膜形成致密皮层，透气时间增加；反之，当水或者二氯甲烷浓度过低，铸膜浆料难以固化成膜。此外，凝胶浴的优选温度范围可以保证薄膜的溶剂较快地扩散至凝胶浴，形成优良的多孔结构。在本发明水或者二氯甲烷浓度优选前提下，如果凝胶浴温度过低会使薄膜内部溶剂扩散到凝胶浴中速度太慢，致使膜片孔隙率低，而且孔径小；反之，如果温度过高会导致膜片内部形成指状孔，而且孔隙率过高。因此，本发明优选凝胶浴温度和组分对优质多孔膜的形成起着重要作用，尤其是两者配合可以得到较佳的多孔膜。
作为优选，所述混合溶液在凝胶浴中形成膜的时间控制为5～300秒。作为进一步优选，所述混合溶液在凝胶浴中形成膜的时间控制为10～200秒。
作为优选，所述萃取剂为水、二氯甲烷、三氯甲烷及乙醇中至少一种。作为进一步优选，所述萃取剂的温度控制为20～100℃。作为更进一步优选，所述萃取剂的温度控制为30～80℃。
作为优选，本发明芳香族聚酰胺多孔膜的制备方法包括：将离子液体与芳香族聚酰胺通过溶剂配置成混合溶液；所述混合溶液通过狭缝流出在凝胶浴中形成膜；所述膜在萃取槽中通过萃取剂萃取出离子液体与溶剂后形成多孔薄膜；上述多孔薄膜经过干燥即得芳香族聚酰胺多孔膜。
本发明所述狭缝中流出，是指将混合溶液通过狭缝形成薄膜状，因此任何能形成狭缝形状的模具都可以采用，通常优选采用刮刀形成狭缝或挤出模头形成狭缝，即将所述混合溶液通过刮刀形成的狭缝流出后成薄膜，或将所述混合溶液通过挤出模头的狭缝流出后成薄膜。
作为优选，所述干燥为红外干燥和/或鼓风干燥。
作为优选，所述干燥温度控制为50～150℃。作为进一步优选，所述干燥温度控制为80～120℃。
本发明第二个目的是提供一种芳香族聚酰胺多孔膜，采用上述芳香族聚酰胺多孔膜的制备方法所制备而成。
本发明第三个目的是提供一种锂离子二次电池，包含如上述芳香族聚酰胺多孔膜。
上述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技术手段，而可依照说明书的内容予以实施，并且为了让本发明的上述和其它目的、特征和优点能够更明显易懂，以下特举实施例，并配合附图，详细说明如下。
附图概述
图1为本发明实施例1制备的芳香族聚酰胺多孔膜表面的SEM图；
图2为本发明实施例1制备的芳香族聚酰胺多孔膜截面的SEM图。
本发明的实施方式
以下的具体实施例对本发明进行了详细的描述，然而本发明并不限制于以下实施例。
实施例1
在反应釜中聚合获得聚间苯二甲酰间苯二胺溶液2000g，溶剂为DMAC，聚合物质量百分比浓度为20％。1-甲基-3-丁基咪唑鎓盐酸盐800g与无水乙醇240g在搅拌釜中进行混合，获得离子液体溶液。分别将前期制备好的离子液体溶液和聚间苯二甲酰间苯二胺溶液按照质量比1：1.8计量注入双螺杆机中混合分散，通过熔体泵，在模头挤出，进入凝胶浴中形成薄膜，凝胶浴为水和DMAC的混合溶剂，其中水的质量所占的比例为50％，凝胶浴温度为80℃，凝胶时间为20秒。接着，将上述薄膜牵引进入萃取槽中，萃取槽的温度 为30℃，用二氯甲烷萃取出溶剂，从而形成多孔结构的薄膜。最后，将上述多孔薄膜经过热风干燥，干燥温度为80℃。除静电后完成收卷。测得透气率为80秒/100CC。
实施例2
通过两级螺杆聚合获得聚间苯二甲酰间苯二胺溶液2400g，溶剂为DMAC，聚合物质量百分比浓度为20％。将1000g甲基三乙基铵乙酸盐与200g去离子水在搅拌釜中混合均匀，搅拌釜加热至50℃。分别将前期制备好的离子液体溶液和聚间苯二甲酰间苯二胺溶液按照质量比1：1.5，计量注入双螺杆机中混合分散，通过熔体泵，在模头挤出，进入凝胶浴形成薄膜，凝胶浴为水和DMAC的混合溶剂，凝胶浴中水的质量所占比例为20％，凝胶浴温度为60℃，凝胶时间为5秒。接着，将上述薄膜牵引进入萃取槽中，萃取槽的温度为80℃，用水萃取出溶剂，从而形成多孔结构的薄膜。最后，将上述多孔薄膜经过红外干燥，干燥温度为120℃。除静电后完成收卷。测得透气率为105秒/100CC。
实施例3
同实施例2，不同的是，加入到甲基三乙基铵乙酸盐中的去离子水质量为50g，测得透气率为110秒/100CC。
实施例4
同实施例2，不同的是，凝胶浴为水，凝胶浴温度为80℃，凝胶时间为20秒，干燥温度为150℃，测得透气率为820秒/100CC。
实施例5
通过反应釜内聚合获得对苯甲酰胺及聚苯砜对苯二甲酰胺溶液1600g，溶剂为NMP，聚合物质量百分比浓度为9％。将800g 1-甲基-3-丙基咪唑鎓乙酸盐与160g乙酸乙酯在搅拌釜中混合均匀。分别将前期制备好的离子液体溶液和对苯甲酰胺及聚苯砜对苯二甲酰胺溶液按照质量比1：1.6，计量注入混合釜，负压条件下搅拌均匀，通过熔体泵，在模头挤出，进入凝胶浴形成薄膜，凝胶浴为水和NMP的混合溶剂，凝胶浴中水的质量所占比例为20％，凝胶浴温度为50℃，凝胶时间为80秒。接着，将上述薄膜牵引进入萃取槽中， 萃取槽的温度为80℃，用水萃取出溶剂，从而形成多孔结构的薄膜。最后，将上述多孔薄膜经过红外干燥，干燥温度为120℃。除静电后完成收卷。测得透气率为40秒/100CC。
实施例6
同实施例5，不同的是萃取槽温度为100℃。
实施例7
通过反应釜内聚合获得聚对苯二甲酰对苯二胺溶液2000g，溶剂为DMF，聚合物质量百分比浓度为18％。将800g N-甲基-N-丙基吡咯鎓氟硼酸盐与100g二氯甲烷在搅拌釜中进行混合，搅拌釜加热至50℃。分别将前期制备好的离子液体溶液和聚对苯二甲酰对苯二胺溶液按照质量比1：1.3，计量注入三螺杆机中混合分散，通过熔体泵，在模头挤出，进入凝胶浴形成薄膜，凝胶浴为二氯甲烷和DMF的混合溶剂，凝胶浴中二氯甲烷的质量所占比例为30％，凝胶浴温度为20℃，凝胶时间为150秒。接着，将上述薄膜牵引进入萃取槽中，萃取槽的温度为30℃，用二氯甲烷萃取出溶剂，从而形成多孔结构的薄膜。最后，将上述多孔薄膜经过鼓风干燥，干燥温度为80℃。除静电后完成收卷。测得透气率为180秒/100CC。
实施例8
200g聚间苯二甲酰间苯二胺短纤维溶于1200g DMAC溶剂中，制得聚合物溶液，聚合物质量百分比浓度为16.7％。将600g甲基三丁基铵盐酸盐与150g去离子水在搅拌釜中进行混合，搅拌釜加热至50℃。分别将前期制备好的离子液体溶液和聚间苯二甲酰间苯二胺溶液按照质量比1：1.4，计量注入三螺杆机中混合分散，通过熔体泵，在模头挤出，进入凝胶浴形成薄膜，凝胶浴为水和DMAC的混合溶剂，凝胶浴中水的质量所占比例为30％，凝胶浴温度为50℃，凝胶时间为80秒。接着，将上述薄膜牵引进入萃取槽中，萃取槽的温度为80℃，用水萃取出溶剂，从而形成多孔结构的薄膜。最后，将上述多孔薄膜经过红外干燥，干燥温度为120℃。除静电后完成收卷。测得透气率为86秒/100CC。
实施例9
将180g对苯甲酰胺及聚苯砜对苯二甲酰胺短纤维溶于1000g DMAC溶剂中，制得聚合物溶液，聚合物质量百分比浓度为33.3％。将400g甲基三丁基鏻盐酸盐与320g二氯甲烷在搅拌釜中进行混合。分别将前期制备好的离子液体溶液和对苯甲酰胺及聚苯砜对苯二甲酰胺短纤维聚合物溶液按照质量比1：1.6，计量注入混合釜，负压条件下搅拌均匀，通过熔体泵，在模头挤出，进入凝胶浴形成薄膜，凝胶浴为DMAC和二氯甲烷的混合溶剂，凝胶浴中二氯甲烷的质量所占比例为30％，凝胶浴温度为0℃，凝胶时间为250秒。接着，将上述薄膜牵引进入萃取槽中，萃取槽的温度为30℃，用二氯甲烷萃取出溶剂，从而形成多孔结构的薄膜。最后，将上述多孔薄膜经过鼓风干燥，干燥温度为50℃。除静电后完成收卷。测得透气率为380秒/100CC。
实施例10
同实施例1，不同的是凝胶浴为二氯甲烷，萃取槽温度为30℃，测得透气率为330秒/100CC。
实施例11
将300g甲基三丁基铵盐酸盐与1200g DMAC混合均匀，然后向上述溶液加入200g对苯甲酰胺及聚苯砜对苯二甲酰胺短纤维，加热至80℃，负压条件下搅拌均匀，通过熔体泵，在模头挤出，进入凝胶浴形成薄膜，凝胶浴为DMAC和二氯甲烷的混合溶剂，凝胶浴中二氯甲烷的质量所占比例为20％，凝胶浴温度为40℃，凝胶时间为180秒。接着，将上述薄膜牵引进入萃取槽中，萃取槽的温度为30℃，用二氯甲烷萃取出溶剂，从而形成多孔结构的薄膜。最后，将上述多孔薄膜经过鼓风干燥，干燥温度为60℃。除静电后完成收卷。测得透气率为120秒/100CC。
实施例12
将250g 1-甲基-3-丁基咪唑鎓盐酸盐与1500g DMAC混合均匀，然后向上述溶液加入125g聚间苯二甲酰间苯二胺短纤维，加热至80℃，负压条件下搅拌均匀，通过熔体泵，在模头挤出，进入凝胶浴形成薄膜，凝胶浴为DMAC和水的混合溶剂，凝胶浴中水的质量所占比例为20％，凝胶浴温度为50℃，凝胶时间为30秒。接着，将上述薄膜牵引进入萃取槽中，萃取槽的温度为80℃，用水萃取出溶剂，从而形成多孔结构的薄膜。最后，将上述多孔薄膜 经过鼓风干燥，干燥温度为120℃。除静电后完成收卷。测得透气率为50秒/100CC。
以上所述，仅是本发明的实施例而已，并非对本发明作任何形式上的限制，虽然本发明已以实施例揭露如上，然而并非用以限定本发明，任何熟悉本专业的技术人员，在不脱离本发明技术方案范围内，当可利用上述揭示的技术内容作出些许更动或修饰为等同变化的等效实施例，但凡是未脱离本发明技术方案内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均仍属于本发明技术方案的范围内。
工业实用性
本发明通过非溶剂相转化法制备多孔膜，相对于热致相分离法，在制膜工艺上并不要求较高的温度，生产过程参数更容易控制，而且可以制得三维网状孔结构，目前广泛应用于水处理膜、空气分离膜等多孔膜领域。本发明进一步通过非溶剂相转化法与离子液体做造孔剂相结合制备芳香族聚酰胺类聚合物多孔膜，用作锂电池的隔膜。

Claims (38)

  1. 一种芳香族聚酰胺多孔膜的制备方法，包括：将离子液体与芳香族聚酰胺通过溶剂配制成混合溶液；所述混合溶液在凝胶浴中形成膜；所述膜通过萃取剂萃取出溶剂与离子液体后形成多孔膜。
  2. 如权利要求1所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述离子液体与芳香族聚酰胺的质量比为1:1～8:1。
  3. 如权利要求1所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述离子液体与芳香族聚酰胺的质量比为1:1～6:1。
  4. 如权利要求1所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述离子液体与芳香族聚酰胺的质量比为2:1～5:1。
  5. 如权利要求1所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述离子液体选自季铵盐、季鏻盐、咪唑鎓盐、吡啶鎓盐、哌啶盐及吡咯烷盐中至少一种。
  6. 如权利要求1所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述芳香族聚酰胺选自聚对苯二甲酰对苯二胺、聚间苯二甲酰间苯二胺、聚对苯甲酰胺及聚苯砜对苯二甲酰胺中至少一种。
  7. 如权利要求1所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：将离子液体与芳香族聚酰胺通过溶剂配置成混合溶液包括：将离子液体与第一溶剂混合形成离子液体溶液；将芳香族聚酰胺与第二溶剂混合形成芳香族聚酰胺溶液；再将上述离子液体溶液与芳香族聚酰胺溶液混合形成混合溶液。
  8. 如权利要求1所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：将离子液体与芳香族聚酰胺通过溶剂配置成混合溶液包括：将离子液体与第一溶剂混合形成离子液体溶液；通过聚合反应形成芳香族聚酰胺溶液，所述聚合反应中使用第二溶剂；再将上述离子液体溶液与芳香族聚酰胺溶液混合形成混合溶液。
  9. 如权利要求1所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：将离子液体与芳香族聚酰胺通过溶剂配置成混合溶液包括：将离子液体、芳香族聚酰胺及第三溶剂混合形成混合溶液。
  10. 如权利要求7或9所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述芳香族聚酰胺为芳香族聚酰胺纤维。
  11. 如权利要求7或8所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述第一溶剂选自水、乙醇、丙醇、异丙醇、丙三醇、四氢呋喃、吡啶、二氯甲烷、三氯甲烷、乙酸乙酯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮及聚乙二醇中至少一种。
  12. 如权利要求7或8所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述第二溶剂选自N－甲基吡咯烷酮、N,N－二甲基乙酰胺、N,N－二甲基甲酰胺、二甲亚砜及磷酸三乙酯中至少一种。
  13. 如权利要求7或8所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述第一溶剂与离子液体的质量比为0.05:1～0.8:1。
  14. 如权利要求13所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述第一溶剂与离子液体的质量比为0.1:1～0.5:1。
  15. 如权利要求7或8所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述第二溶剂与芳香族聚酰胺的质量比为2:1～10:1。
  16. 如权利要求15所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述第二溶剂与芳香族聚酰胺的质量比为3:1～8:1。
  17. 如权利要求9所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述第三溶剂选自N－甲基吡咯烷酮、N,N－二甲基乙酰胺、N,N－二甲基甲酰胺及二甲亚砜中至少一种。
  18. 如权利要求9所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述混合溶液中第三溶剂的质量分数为20-80％。
  19. 如权利要求18所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述混合溶液中第三溶剂的质量分数为40-70％。
  20. 如权利要求1所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述凝胶浴包括第一组分；所述第一组分为水或二氯甲烷。
  21. 如权利要求20所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述凝胶浴还包括第二组分；所述第二组分选自N－甲基吡咯烷酮、N,N －二甲基乙酰胺、N,N－二甲基甲酰胺、二甲亚砜及磷酸三乙酯中至少一种。
  22. 如权利要求21所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述凝胶浴中水或二氯甲烷所占的质量分数为5～99.9％。
  23. 如权利要求22所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述凝胶浴中水或二氯甲烷所占的质量分数为20～60％。
  24. 如权利要求23所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述凝胶浴中水或二氯甲烷所占的质量分数为30～50％。
  25. 如权利要求1所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述凝胶浴的温度控制为0～80℃。
  26. 如权利要求25所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述凝胶浴的温度控制为20～60℃。
  27. 如权利要求1所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述混合溶液在凝胶浴中形成膜的时间控制为5～300秒。
  28. 如权利要求27所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述混合溶液在凝胶浴中形成膜的时间控制为10～200秒。
  29. 如权利要求1所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述萃取剂为水、二氯甲烷、三氯甲烷及乙醇中至少一种。
  30. 如权利要求1所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述萃取剂的温度控制为20～100℃。
  31. 如权利要求30所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述萃取剂的温度控制为30～80℃。
  32. 如权利要求1所述一种芳香族聚酰胺多孔膜的制备方法，包括：将离子液体与芳香族聚酰胺通过溶剂配置成混合溶液；所述混合溶液通过狭缝流出在凝胶浴中形成膜；所述膜在萃取槽中通过萃取剂萃取出离子液体与溶剂后形成多孔薄膜；上述多孔薄膜经过干燥即得芳香族聚酰胺多孔膜。
  33. 如权利要求32所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述狭缝通过刮刀或挤出模头形成。
  34. 如权利要求32所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述干燥为红外干燥和/或鼓风干燥。
  35. 如权利要求32所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述干燥温度控制为50～150℃。
  36. 如权利要求35所述一种芳香族聚酰胺多孔膜的制备方法，其特征在于：所述干燥温度控制为80～120℃。
  37. 一种芳香族聚酰胺多孔膜，采用如权利要求1-9，14，16-36任一项所述芳香族聚酰胺多孔膜的制备方法所制备而成。
  38. 一种锂离子二次电池，包含如权利要求37所述芳香族聚酰胺多孔膜
PCT/CN2017/070270 2016-02-03 2017-01-05 一种芳香族聚酰胺多孔膜制备方法及芳香族聚酰胺多孔膜 WO2017133375A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US16/082,269 US11205821B2 (en) 2016-02-03 2017-01-05 Method for preparing aromatic polyamide porous membrane and aromatic polyamide porous membrane prepared thereby
EP17746695.0A EP3441135A4 (en) 2016-02-03 2017-01-05 PROCESS FOR PREPARING POROUS AROMATIC POLYAMIDE FILM AND POROUS AROMATIC POLYAMIDE FILM

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610075690.6A CN107029564B (zh) 2016-02-03 2016-02-03 一种芳香族聚酰胺多孔膜制备方法及芳香族聚酰胺多孔膜
CN201610075690.6 2016-02-03

Publications (1)

Publication Number Publication Date
WO2017133375A1 true WO2017133375A1 (zh) 2017-08-10

Family

ID=59499367

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/070270 WO2017133375A1 (zh) 2016-02-03 2017-01-05 一种芳香族聚酰胺多孔膜制备方法及芳香族聚酰胺多孔膜

Country Status (4)

Country Link
US (1) US11205821B2 (zh)
EP (1) EP3441135A4 (zh)
CN (1) CN107029564B (zh)
WO (1) WO2017133375A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3454394A1 (en) * 2017-09-07 2019-03-13 Microvast Power Systems Co., Ltd. Aromatic polyamide porous membrane, method for preparing and lithium secondary battery having the same
CN115463550A (zh) * 2022-08-28 2022-12-13 天津汉晴环保科技有限公司 一种具有对称结构的聚醚砜增湿膜及其制备方法

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109591417B (zh) * 2017-09-30 2021-03-16 翰诠特种纺织品（平湖）有限公司 一种透气均匀的地毯的生产工艺
CN109509856B (zh) * 2018-04-04 2021-06-22 深圳市合壹新能技术有限公司 一种芳香族聚酰胺微孔膜及其制备方法和用途
CN112751135B (zh) * 2019-10-29 2022-09-27 珠海恩捷新材料科技有限公司 一种芳纶隔膜
CN111170422B (zh) * 2020-01-07 2022-04-19 浙江工业大学 一种耐有机溶剂阴离子交换膜的制备方法
CN111249926A (zh) * 2020-02-24 2020-06-09 上海工程技术大学 间位芳纶/聚砜酰胺纳米复合空气过滤膜及其制备方法
CN112934005A (zh) * 2021-02-01 2021-06-11 华侨大学 基于绿色环保型离子液体制备聚酰胺类复合纳滤膜的方法
CN113750804B (zh) * 2021-09-15 2022-07-19 北京理工大学 改性聚间苯二甲酰间苯二胺超滤膜及其制备方法和应用
CN116531962A (zh) * 2023-07-06 2023-08-04 迈博瑞生物膜技术（南通）有限公司 一种聚酰胺微滤膜及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101935398A (zh) * 2010-06-24 2011-01-05 中国科学院宁波材料技术与工程研究所 一种高导电的芳香聚合物离子液体隔膜材料及其制备方法
CN102299376A (zh) * 2011-06-24 2011-12-28 中国科学院宁波材料技术与工程研究所 一种聚合物固体电解质膜及其制备方法
US20120302678A1 (en) * 2010-01-18 2012-11-29 Korea Institute Of Energy Research Ionic liquid-polymer gel membrane with improved gas permeability, and preparation method thereof
CN103665403A (zh) * 2013-11-08 2014-03-26 江南大学 聚醚嵌段酰胺/聚离子液体半互穿聚合物网络膜及其热固化制备方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3342823A1 (de) 1983-11-26 1985-06-05 Seitz-Filter-Werke Theo & Geo Seitz GmbH und Co, 6550 Bad Kreuznach Verfahren zum herstellen von filterelementen auf der basis von aromatischem polyamid
US5362582A (en) * 1993-04-01 1994-11-08 W.R. Grace & Co.-Conn. Battery separator
TWI287556B (en) * 1999-09-13 2007-10-01 Teijin Ltd Polymetaphenyleneisophthalamide-based polymer porous film, process for preparing same and separator for battery
EP1537906B1 (en) 2002-09-09 2008-10-08 NOK Corporation Process for production of poly(m-phenyleneisophthal- amide) porous hollow fiber membrane
WO2006087859A1 (ja) 2005-02-17 2006-08-24 Toray Industries, Inc. 芳香族ポリアミド多孔性フィルムおよび芳香族ポリアミド多孔性フィルムの製造方法、ならびに二次電池
WO2006123811A1 (ja) * 2005-05-17 2006-11-23 Teijin Limited リチウムイオン二次電池用セパレータ及びリチウムイオン二次電池
EP2242794B1 (de) * 2008-02-11 2014-04-30 Basf Se Verfahren zur herstellung poröser strukturen aus synthetischen polymeren
CN202384420U (zh) 2011-10-31 2012-08-15 珠海光宇电池有限公司 一种用于锂离子电池的隔膜及锂离子电池
CN103242556B (zh) 2013-04-17 2015-07-08 广东精进能源有限公司 一种芳香族聚酰胺复合隔膜的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120302678A1 (en) * 2010-01-18 2012-11-29 Korea Institute Of Energy Research Ionic liquid-polymer gel membrane with improved gas permeability, and preparation method thereof
CN101935398A (zh) * 2010-06-24 2011-01-05 中国科学院宁波材料技术与工程研究所 一种高导电的芳香聚合物离子液体隔膜材料及其制备方法
CN102299376A (zh) * 2011-06-24 2011-12-28 中国科学院宁波材料技术与工程研究所 一种聚合物固体电解质膜及其制备方法
CN103665403A (zh) * 2013-11-08 2014-03-26 江南大学 聚醚嵌段酰胺/聚离子液体半互穿聚合物网络膜及其热固化制备方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3454394A1 (en) * 2017-09-07 2019-03-13 Microvast Power Systems Co., Ltd. Aromatic polyamide porous membrane, method for preparing and lithium secondary battery having the same
US10879512B2 (en) 2017-09-07 2020-12-29 Microvast Power Systems Co., Ltd. Aromatic polyamide porous membrane, method for preparing and lithium secondary battery having the same
CN115463550A (zh) * 2022-08-28 2022-12-13 天津汉晴环保科技有限公司 一种具有对称结构的聚醚砜增湿膜及其制备方法

Also Published As

Publication number Publication date
CN107029564B (zh) 2020-11-06
CN107029564A (zh) 2017-08-11
US11205821B2 (en) 2021-12-21
US20190097196A1 (en) 2019-03-28
EP3441135A4 (en) 2019-05-29
EP3441135A1 (en) 2019-02-13

Similar Documents

Publication Publication Date Title
WO2017133375A1 (zh) 一种芳香族聚酰胺多孔膜制备方法及芳香族聚酰胺多孔膜
CN107240663B (zh) 一种聚合物涂层隔膜及其制备方法
CN107170942B (zh) 一种耐高温芳纶锂离子电池复合隔膜及其制备方法
EP3447822B1 (en) Composite separator containing aromatic polyamide and manufacturing method thereof, and secondary battery
Zhang et al. High thermal resistance polyimide separators prepared via soluble precusor and non-solvent induced phase separation process for lithium ion batteries
CN103531736B (zh) 一种高耐热锂离子电池隔膜及其制备方法
CN108346765B (zh) 一种复合锂离子电池隔膜及其制备方法
CN102122704B (zh) 用作锂离子电池隔膜的复合微孔膜及其制备方法与应用
TWI714744B (zh) 二次電池用隔板及二次電池
Yang et al. Design of block‐copolymer nanoporous membranes for robust and safer lithium‐ion battery separators
CN105633326B (zh) 芳香族聚酰胺复合隔膜
CN108341987B (zh) 一种芳香族聚酰胺多孔膜、其制备方法及锂离子二次电池
CN102015083A (zh) 具有高温热稳定性多孔层的微孔聚烯烃复合膜
CN103044917B (zh) 一种聚芳砜酰胺基多孔膜及其制备方法和应用
CN101665580A (zh) 一种聚酰亚胺多孔膜及包括该多孔膜的锂离子电池
CN101752540A (zh) 一种锂离子二次电池用聚酰亚胺隔膜以及锂离子电池
CN106229445A (zh) 一种锂离子电池隔膜及其制备方法和锂离子电池
CN108807818B (zh) 一种芳香族聚酰胺复合隔膜及其制备方法
CN101638490A (zh) 一种聚酰亚胺多孔膜及其制备方法以及锂离子电池
CN110752337A (zh) 一种复合隔膜、其制备方法及应用
CN110350131B (zh) 一种相转化法制备复合聚丙烯微孔膜的方法及其制品和用途
CN108598344A (zh) 一种复合隔膜及其制备方法和二次电池
CN106601970A (zh) 一种耐溶剂微孔膜、微孔复合膜及其制备方法、应用
CN105118950A (zh) 一种锂离子电池隔膜的制备方法
CN114709558A (zh) 一种高耐热聚酰胺酰亚胺复合隔膜及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17746695

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2017746695

Country of ref document: EP

Effective date: 20180831