CN102875835B - Polyimide porous film and preparation method thereof - Google Patents
Polyimide porous film and preparation method thereof Download PDFInfo
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- CN102875835B CN102875835B CN201110194248.2A CN201110194248A CN102875835B CN 102875835 B CN102875835 B CN 102875835B CN 201110194248 A CN201110194248 A CN 201110194248A CN 102875835 B CN102875835 B CN 102875835B
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Abstract
The invention discloses a polyimide porous film and a preparation method thereof. The method comprises the steps of mixing polyimide performed polymer and polyaldehyde in a solvent; adding polyamine to the mixture for reaction; forming a film after the reaction is finished; and immersing and washing the film in an acid to obtain the polyimide porous film. The obtained polyimide porous film has controllable aperture distributions from nanometer level to micrometer level. The preparation method provided by the invention is simple, has high preparation efficiency and is environmental protection; and the raw materials can be used repeatedly, so that the method is helpful for large-scale production and has good universality.
Description
Technical field
The invention belongs to material technology field, particularly a kind of polyimide porous membrane and preparation method thereof.
Background technology
Lithium ion battery becomes the focus of novel power supply technical study in recent years, enjoys great popularity at high-energy and superpower field.Because lithium ion battery has superior performance.Voltage is high, and the operating voltage of cell, up to 3.6-3.9V, is Ni-Cd, Ni-H battery 3 times; Energy density is high, and the actual energy density that can arrive is at present 100-250Wh/kg and 240-300Wh/L (2 times to Ni-Cd, 1.5 times to Ni-H); Have extended cycle life, general equal reaching more than 500 times, even more than 1000 times; Safety performance is good, nuisanceless, memory-less effect; Self-discharge is little, and under room temperature, being full of the self-discharge rate of electric Li-ion storage after 1 month is 10% left and right, is significantly less than the 25-30% of Ni-Cd, the 30-35% of Ni-H; Operating temperature range is high, and working temperature is-25-45 ℃.
In lithium ion battery structure, battery diaphragm is one of critical material in lithium ion battery, and battery diaphragm can be isolated battery plus-negative plate, to prevent short circuit, allows the ion in ionogen to pass through simultaneously, forms charging and discharging circuit.Battery diaphragm itself does not participate in any cell reaction, but its structure and character affect the performance of battery energy force density, cycle life, security and various aspects.First diaphragm material will have good chemical stability, does not react with ionogen and electrode materials.To there is certain intensity simultaneously, not fragile in series of cells process of assembling.Further, diaphragm material will will have certain wettability to electrolyte solution, and the ion in ionogen is more easily passed through.Diaphragm material also will have the dimensions stability and thermostability, prevents that barrier film from melting contraction in the time of high temperature, destroys, and causes short circuit.
At present, lithium ion battery separator is mainly porous polyolefin, single-layer polypropylene porous-film (PP), monolayer polyethylene porous-film (PE), polyethylene, polypropylene multi-layer porous-film.But the temperature of fusion of polyolefins barrier film not high (180 ℃ of < conventionally), and the thermal contraction performance of high temperature lower diaphragm plate is bad, often occurs causing internal short-circuit because barrier film shrinks.Therefore, the resistance to elevated temperatures of raising battery diaphragm is to improve the key of high-temperature lithium ion battery safety performance.
Because polyimide (PI) has high temperature resistant, corrosion-resistant, high-dimensional stability, the performance that high electric insulation etc. are good, therefore, the polyimide porous membrane being made by polyimide is one of ideal material of lithium ion battery separator.
Summary of the invention
The object of this invention is to provide a kind of polyimide porous membrane and preparation method thereof.
The method of preparing polyimide porous membrane provided by the invention, comprise the steps: polyimide prepolymer and polyaldehyde to mix in solvent, then add polyamine to carry out nucleophilic addition, after completion of the reaction film forming, washing by soaking in acid again, obtains described polyimide porous membrane.
In the method, described polyimide prepolymer is selected from the polyimide prepolymer that number-average molecular weight is 1000-5000;
Described polyamine is selected from polymine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, Ursol D, O-Phenylene Diamine, mphenylenediamine, 4,4 '-diaminodiphenylsulfone(DDS), 3, at least one in 4 '-diaminodiphenyl oxide and trimeric cyanamide, at least one in preferably polyethylene imines, triethylene tetramine, tetraethylene pentamine, Ursol D, O-Phenylene Diamine, mphenylenediamine, 4,4′ diaminodiphenyl sulfone and trimeric cyanamide; The weight-average molecular weight of described polymine is 1000-10000;
Described polyaldehyde be selected from oxalic dialdehyde, at least one in glutaraldehyde, terephthalaldehyde, m-terephthal aldehyde and 2,4-dimethyl-2-methoxymethyl glutaraldehyde, preferably at least one in glutaraldehyde, terephthalaldehyde and m-terephthal aldehyde; Due to glutaraldehyde highly volatile, therefore in actually operating, can select the glutaraldehyde water solution that the mass percentage concentration that is purchased is 50%;
Described solvent is selected from N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, N, at least one in 2-methyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), m-cresol, tetrahydrofuran (THF), ethanol, methyl alcohol, methylene dichloride and trichloromethane, preferably N, at least one in N-N,N-DIMETHYLACETAMIDE, DMF and methylene dichloride;
Described acid is selected from least one in hydrochloric acid, acetic acid, nitric acid and sulfuric acid, preferably at least one in hydrochloric acid, acetic acid and nitric acid.
In aforesaid method, the mass ratio of described polyimide prepolymer, described polyaldehyde and described polyamine is 0.5-4: 0.5-2: 0.5-2, preferably 2: 1: 1;
The volumetric molar concentration of described acid is 0.001-4mol/L, preferably 2mol/L.
In described nucleophilic addition step, temperature is 5-80 ℃, and preferably 25 ℃, the time is 0.5-4 hour, preferably 0.5 hour;
In described film forming step, temperature is 50-100 ℃, specifically can be 60 ℃-90 ℃, 60-80 ℃, 80-90 ℃, preferably 80 ℃, time is 0.5-4 hour, specifically can be 1-4 hour, 3-4 hour, 0.5-3 hour, 0.5-2 hour, 2-4 hour or 2-3 hour, preferably 2 hours;
In described soaking step, the time is 0.5-8 hour, preferably 1 hour;
In described washing step, number of times is 1-5 time, preferably 3 times, cleaning solvent is selected from the hydrochloric acid that concentration is 0.001-4mol/L, concentration is the acetic acid of 0.001-4mol/L, concentration is the nitric acid of 0.001-4mol/L, concentration is at least one in the sulfuric acid of 0.001-4mol/L and phosphoric acid that concentration is 0.001-4mol/L, preferred concentration is the hydrochloric acid of 0.5-4mol/L, concentration is the sulfuric acid of 0.5-4mol/L, concentration is at least one in the nitric acid of 0.5-4mol/L and acetic acid that concentration is 0.5-4mol/L, more preferably at least one in the acetic acid that the hydrochloric acid that concentration is 2mol/L and concentration are 2mol/L.
Various conventional films are all applicable to the method, as spin coating, flow coat, dip-coating or blade coating etc.
In order to make the further curing cross-linked of film, improve the thermostability of film, the described method of preparing polyimide porous membrane, also comprises the steps: after washing by soaking step, gained polyimide porous membrane to be cured in be set forth in acid;
In described curing schedule, temperature is 80-300 ℃, and preferably 300 ℃, the time is 0.5-6 hour, preferably 2 hours.This solidification value and time can adopt the mode of ladder-elevating temperature to be cured, as carried out in the following manner: successively at 80 ℃ of insulation 1h, 120 ℃ of insulation 1h, 160 ℃ of insulation 1h, 200 ℃ of insulation 1h, 250 ℃ of insulation 1h, 300 ℃ of insulation 1h.
In aforesaid method, polyimide prepolymer used is according to the method preparation comprising the steps and obtain: dibasic acid anhydride and diamine are mixed and carry out polycondensation, react the complete described polyimide prepolymer that obtains.
Wherein, described dibasic acid anhydride is selected from 1, 2, 4, the equal benzene tertacarbonic acid's dianhydride of 5-(PMDA), 3, 3 ', 4, 4 '-BPDA (BPDA), 3, 3 ', 4, 4 '-phenyl ether tetracarboxylic dianhydride (ODPA), 3, 3 ', 4, 4 '-Benzophenone carboxylic acid dianhydride (BTDA), 3, 3 ', 4, 4 '-bis-methyl-phenoxide tetracarboxylic dianhydrides (OPDA), 4, 4 '-(hexafluoro sec.-propyl) two O-phthalic acid dianhydrides (6FDA), 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride (CBDA), 1, 2, 4, 5-pentamethylene tetracarboxylic dianhydride (CPDA), 1, 2, 4, any one in 5-hexanaphthene tetracarboxylic dianhydride (CHDA) and dihydroxyphenyl propane two ether dianhydrides (BPADA),
Described diamine is selected from Ursol D (p-PDA), mphenylenediamine (m-PDA), 4, 4 '-diaminodiphenylsulfone(DDS) (DDS), 3, 4 '-diaminodiphenyl oxide (ODA), 1, two (4-amino-benzene oxygen) benzene (APB) of 3-, 1, 4-two (4 '-amino-2 '-4-trifluoromethylphenopendant) benzene (BTPB), 1, 4-two (4 '-amino-2 '-4-trifluoromethylphenopendant) benzene (6FAPB), 4, 4 '-bis-(4-amino-2-4-trifluoromethylphenopendant) biphenyl (6FBAB), 3, 3 '-diethyl-4, any one in 4 '-diaminodiphenylmethane (DEDADPM),
The molar ratio of described dibasic acid anhydride and diamine is 0.8-1.2: 0.8-1.2, specifically can be 0.8-1: 1,0.8-1.2: 1,1-1.2: 1,1: 0.8-1.2,1: 0.8-1 or 1: 1-1.2, preferably 1: 1;
In described polycondensation steps, temperature is 50-80 ℃, specifically can be 50-75 ℃, 50-70 ℃, 50-60 ℃, 60-80 ℃, 60-75 ℃, 70-80 ℃, 70-75 ℃ or 75-80 ℃, preferably 75 ℃, time is 3-15 hour, specifically can be 3-10 hour, 3-7 hour, 3-5 hour, 5-15 hour, 5-10 hour, 7-15 hour, 7-10 hour or 10-15 hour, preferably 5 hours.
The polyimide porous membrane preparing according to the method described above, also belongs to protection scope of the present invention.The aperture of described polyimide porous membrane is 9 nanometers to 20 micron, and BET specific surface area is 179-190m
2/ g, pore volume is 0.59-0.63cm
3/ g.
In the preparation method of polyimide porous membrane provided by the invention, polyaldehyde react with polyamine and pore-creating agent compound there is Schiff's base (Schiff base) structure, Schiff's base is that nitrogen-atoms and the two keys of carbon atom link the compounds forming, and is formed by aldehyde and amine condensation.Its reaction mechanism is: carry out nucleophilic addition by aldehyde compound and primary amine compounds containing carbonyl, nucleophilic reagent is aminated compounds, in its compound structure with the carbon atom with positive charge on the nitrogen-atoms attack carbonyl group of lone electron pair, complete nucleophilic addition, form intermediate Alpha-hydroxy aminated compounds, then further dehydration forms Schiff's base.Polyaldehyde and polyamine are under alkaline condition, and easily reaction generates Schiff's base, forms gel network structure; Because Schiff's base is not rock steady structure, under acidic conditions, can again be decomposed into amine and aldehyde.Therefore the present invention is applied in this characteristic of Schiff's base in body material, first the co-continuous gel network structure that two-phase runs through under alkaline condition, then under acidic conditions, be decomposed into micromolecular amine and aldehyde, easily unreacted polyaldehyde or polyamine removed from body material.The method technique is simple, environmental protection, and preparation efficiency is high, and raw material can reclaim Reusability, is conducive to scale operation, and universality is good.The aperture of gained polyimide porous membrane can be 9 nanometers to 20 micron, and BET specific surface area can be 179-216m
2/ g, pore volume can be 0.59-0.65cm
3/ g, has important using value.
Accompanying drawing explanation
Fig. 1 is the electron scanning micrograph of polyimide prepolymer of the present invention and Schiff's base pore-creating agent composite membrane.
Fig. 2 is the electron scanning micrograph of the embodiment of the present invention 1 polyimide porous membrane.
Fig. 3 is nitrogen adsorption-desorption curve of the embodiment of the present invention 1 polyimide porous membrane.
Fig. 4 is the pore size distribution curve of the embodiment of the present invention 1 polyimide porous membrane.
Fig. 5 is the electron scanning micrograph of the embodiment of the present invention 2 polyimide porous membranes.
Fig. 6 is the electron scanning micrograph of the embodiment of the present invention 2 polyimide porous membranes.
Fig. 7 is nitrogen adsorption-desorption curve of the embodiment of the present invention 2 polyimide porous membranes.
Fig. 8 is the electron scanning micrograph of the embodiment of the present invention 3 polyimide porous membranes.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described material all can obtain from open commercial sources if no special instructions.Described concentration if no special instructions, is mass percentage concentration.
In following embodiment nitrogen adsorption-desorption curve of gained porous-film, aperture respectively curve all measure as follows and obtain: porous-film vacuumize degassing at 100 ℃ is processed after 10h, with BET specific surface area, pore volume and the pore size distribution of ASAP 2020M specific surface area and micropore/mesoporous analysis-e/or determining sample.
(this polyimide prepolymer is by dibasic acid anhydride 1 to the polyimide prepolymer that is 1000 by 0.1g number-average molecular weight, 2, 4, the equal benzene tertacarbonic acid's dianhydride of 5-(PMDA) and diamine 3, after 4 '-diaminodiphenyl oxide (ODA) mixes take mol ratio as 1: 1, at 75 ℃, polycondensation obtains for 5 hours) be dissolved in 5g solvent N, in N-N,N-DIMETHYLACETAMIDE (DMAc), ultrasonic being uniformly dispersed, add 0.048g terephthalaldehyde, dissolving is uniformly dispersed, add again 0.052g triethylene tetramine in 25 ℃ of nucleophilic additions after 0.5 hour, in 80 ℃ of dry 2 hours volatilization film forming, in 2M hydrochloric acid soln, soak 1 hour again, under acidic conditions, Schiff's base resolves into terephthalaldehyde and triethylene tetramine again, with 2M hydrochloric acid soln washing 3 times, remove Schiff's base, obtain polyimide prepolymer porous-film.
In order to improve the thermostability of this polyimide prepolymer porous-film, this performed polymer porous-film is cured in accordance with the following steps: successively at 80 ℃ of insulation 1h, 120 ℃ of insulation 1h, 160 ℃ of insulation 1h, 200 ℃ of insulation 1h, 250 ℃ of insulation 1h, 300 ℃ of insulation 1h, obtain polyimide porous membrane provided by the invention.
The stereoscan photograph of this porous-film as shown in Figure 2.As shown in Figure 2, film is vesicular structure, and aperture is 10nm to 5 μ m.As shown in Figure 3, as seen from the figure, BET specific surface area is 179m to nitrogen adsorption-desorption curve
2/ g.As shown in Figure 4, as seen from the figure, the aperture of this porous-film is 10.6nm to pore size distribution curve, and pore volume is 0.59cm
3/ g.
Embodiment 2
(this polyimide prepolymer is by dibasic acid anhydride 1 to the polyimide prepolymer that is 2000 by 0.1g number-average molecular weight, 2, 4, the equal benzene tertacarbonic acid's dianhydride of 5-(PMDA) and diamine 3, after 4 '-diaminodiphenyl oxide (ODA) mixes take mol ratio as 1: 1, at 75 ℃, polycondensation obtains for 5 hours) be dissolved in 5g solvent N, in N-N,N-DIMETHYLACETAMIDE (DMAc), ultrasonic being uniformly dispersed, add 0.041g terephthalaldehyde, dissolving is uniformly dispersed, add again 0.059g tetraethylene pentamine in 25 ℃ of nucleophilic additions after 0.5 hour, in 80 ℃ of dry 2 hours volatilization film forming, in 2M hydrochloric acid soln, soak 1 hour again, under acidic conditions, Schiff's base resolves into terephthalaldehyde and tetraethylene pentamine again, with 2M hydrochloric acid soln washing 3 times, remove Schiff's base, obtain polyimide prepolymer porous-film.
In order to improve the thermostability of this polyimide prepolymer porous-film, this performed polymer porous-film is cured in accordance with the following steps: successively at 80 ℃ of insulation 1h, 120 ℃ of insulation 1h, 160 ℃ of insulation 1h, 200 ℃ of insulation 1h, 250 ℃ of insulation 1h, 300 ℃ of insulation 1h, obtain polyimide porous membrane provided by the invention.The stereoscan photograph of this porous-film as shown in Figure 5.As shown in Figure 5, film is vesicular structure, and aperture is 10nm to 200nm.As shown in Figure 6, as seen from the figure, BET specific surface area is 179m to nitrogen adsorption-desorption curve
2/ g.As shown in Figure 7, as seen from the figure, the aperture of this porous-film is 10.6nm to pore size distribution curve, and pore volume is 0.65cm
3/ g.
Embodiment 3
(this polyimide prepolymer is by dibasic acid anhydride 1 to the polyimide prepolymer that is 3000 by 0.1g number-average molecular weight, 2, 4, the equal benzene tertacarbonic acid's dianhydride of 5-(PMDA) and diamine 3, after 4 '-diaminodiphenyl oxide (ODA) mixes take mol ratio as 1: 1, at 75 ℃, polycondensation obtains for 5 hours) be dissolved in 5g solvent N, in N-N,N-DIMETHYLACETAMIDE (DMAc), ultrasonic being uniformly dispersed, add 0.055g terephthalaldehyde, dissolving is uniformly dispersed, add again 0.045g Ursol D in 25 ℃ of nucleophilic additions after 0.5 hour, in 80 ℃ of dry 2 hours volatilization film forming, in 2M hydrochloric acid soln, soak 1 hour again, under acidic conditions, Schiff's base resolves into terephthalaldehyde and Ursol D again, with 2M hydrochloric acid soln washing 3 times, remove Schiff's base, obtain polyimide prepolymer porous-film.
In order to improve the thermostability of this polyimide prepolymer porous-film, this performed polymer porous-film is cured in accordance with the following steps: successively at 80 ℃ of insulation 1h, 120 ℃ of insulation 1h, 160 ℃ of insulation 1h, 200 ℃ of insulation 1h, 250 ℃ of insulation 1h, 300 ℃ of insulation 1h, obtain polyimide porous membrane provided by the invention.The stereoscan photograph of this porous-film as shown in Figure 8.As shown in Figure 8, film is vesicular structure, and aperture is 10nm to 50nm.
Embodiment 4
(this polyimide prepolymer is by dibasic acid anhydride 1 to the polyimide prepolymer that is 4000 by 0.1g number-average molecular weight, 2, 4, the equal benzene tertacarbonic acid's dianhydride of 5-(PMDA) and diamine 3, after 4 '-diaminodiphenyl oxide (ODA) mixes take mol ratio as 1: 1, at 50 ℃, polycondensation obtains for 15 hours) be dissolved in 5g solvent N, in N-N,N-DIMETHYLACETAMIDE (DMAc), ultrasonic being uniformly dispersed, add 0.055g terephthalaldehyde, dissolving is uniformly dispersed, add again 0.045g O-Phenylene Diamine in 25 ℃ of nucleophilic additions after 0.5 hour, in 80 ℃ of dry 2 hours volatilization film forming, in 2M hydrochloric acid soln, soak 1 hour again, under acidic conditions, Schiff's base resolves into terephthalaldehyde and O-Phenylene Diamine again, with 2M hydrochloric acid soln washing 3 times, remove Schiff's base, obtain polyimide prepolymer porous-film.
In order to improve the thermostability of this polyimide prepolymer porous-film, this performed polymer porous-film is cured in accordance with the following steps: successively at 80 ℃ of insulation 1h, 120 ℃ of insulation 1h, 160 ℃ of insulation 1h, 200 ℃ of insulation 1h, 250 ℃ of insulation 1h, 300 ℃ of insulation 1h, obtain polyimide porous membrane provided by the invention.The aperture of this film is 10nm to 100nm.
Embodiment 5
(this polyimide prepolymer is by dibasic acid anhydride 3 to the polyimide prepolymer that is 5000 by 0.1g number-average molecular weight, 3 ', 4, after 4 '-BPDA (BPDA) and diamine Ursol D (p-PDA) mix take mol ratio as 0.8: 1, at 60 ℃, polycondensation obtains for 10 hours) be dissolved in 5g solvent N, in N-N,N-DIMETHYLACETAMIDE (DMAc), ultrasonic being uniformly dispersed, add 0.035g terephthalaldehyde, dissolving is uniformly dispersed, add again 0.065g4, 4 '-diaminodiphenylsulfone(DDS) is in 25 ℃ of nucleophilic additions after 0.5 hour, in 80 ℃ of dry 2 hours volatilization film forming, in 2M hydrochloric acid soln, soak 1 hour again, under acidic conditions, Schiff's base resolves into terephthalaldehyde and 4 again, 4 '-diaminodiphenylsulfone(DDS), with 2M hydrochloric acid soln washing 3 times, remove Schiff's base, obtain polyimide prepolymer porous-film.
In order to improve the thermostability of this polyimide prepolymer porous-film, this performed polymer porous-film is cured in accordance with the following steps: successively at 80 ℃ of insulation 1h, 120 ℃ of insulation 1h, 160 ℃ of insulation 1h, 200 ℃ of insulation 1h, 250 ℃ of insulation 1h, 300 ℃ of insulation 1h, obtain polyimide porous membrane provided by the invention.The aperture of this film is 10nm to 200nm.
Embodiment 6
(this polyimide prepolymer is by dibasic acid anhydride 3 to the polyimide prepolymer that is 1000 by 0.1g number-average molecular weight, 3 ', 4, after 4 '-BPDA (BPDA) and diamine Ursol D (p-PDA) mix take mol ratio as 1: 1.2, at 70 ℃, polycondensation obtains for 7 hours) be dissolved in 5g solvent N, in N-N,N-DIMETHYLACETAMIDE (DMAc), ultrasonic being uniformly dispersed, add 0.05g terephthalaldehyde, dissolving is uniformly dispersed, adding 0.05g weight-average molecular weight is that 1000 polymine (PEI) is in 50 ℃ of nucleophilic additions after 1 hour again, in 80 ℃ of dry 2 hours volatilization film forming, in 2M hydrochloric acid soln, soak 1 hour again, under acidic conditions, Schiff's base resolves into terephthalaldehyde and polymine again, with 2M hydrochloric acid soln washing 3 times, remove Schiff's base, obtain polyimide prepolymer porous-film.
In order to improve the thermostability of this polyimide prepolymer porous-film, this performed polymer porous-film is cured in accordance with the following steps: successively at 80 ℃ of insulation 1h, 120 ℃ of insulation 1h, 160 ℃ of insulation 1h, 200 ℃ of insulation 1h, 250 ℃ of insulation 1h, 300 ℃ of insulation 1h, obtain polyimide porous membrane provided by the invention.The aperture of this film is 5 μ m to 20 μ m.
Embodiment 7
(this polyimide prepolymer is by dibasic acid anhydride 3 to the polyimide prepolymer that is 1000 by 0.1g number-average molecular weight, 3 ', 4, after 4 '-BPDA (BPDA) and diamine Ursol D (p-PDA) mix take mol ratio as 1: 1, at 80 ℃, polycondensation obtains for 3 hours) be dissolved in 5g solvent N, in N-N,N-DIMETHYLACETAMIDE (DMAc), ultrasonic being uniformly dispersed, adding 0.1g concentration is 50wt% glutaraldehyde water solution, dissolving is uniformly dispersed, adding 0.05g weight-average molecular weight is that 10000 polymine (PEI) is in 80 ℃ of nucleophilic additions after 0.5 hour again, in 80 ℃ of dry 2 hours volatilization film forming, in 2M hydrochloric acid soln, soak 1 hour again, under acidic conditions, Schiff's base resolves into glutaraldehyde and polymine again, with 2M hydrochloric acid soln washing 3 times, remove Schiff's base, obtain polyimide prepolymer porous-film.
In order to improve the thermostability of this polyimide prepolymer porous-film, this performed polymer porous-film is cured in accordance with the following steps: successively at 80 ℃ of insulation 1h, 120 ℃ of insulation 1h, 160 ℃ of insulation 1h, 200 ℃ of insulation 1h, 250 ℃ of insulation 1h, 300 ℃ of insulation 1h, obtain polyimide porous membrane provided by the invention.The aperture of this film is 1 μ m to 10 μ m.
Embodiment 8
(this polyimide prepolymer is by dibasic acid anhydride 3 to the polyimide prepolymer that is 2000 by 0.1g number-average molecular weight, 3 ', 4, after 4 '-BPDA (BPDA) and diamine Ursol D (p-PDA) mix take mol ratio as 1: 1, at 75 ℃, polycondensation obtains for 5 hours) be dissolved in 5g solvent N, in N-N,N-DIMETHYLACETAMIDE (DMAc), ultrasonic being uniformly dispersed, adding 0.081g concentration is 50wt% glutaraldehyde water solution, dissolving is uniformly dispersed, add again 0.059g triethylene tetramine in 5 ℃ of nucleophilic additions after 4 hours, in 80 ℃ of dry 2 hours volatilization film forming, in 2M hydrochloric acid soln, soak 1 hour again, under acidic conditions, Schiff's base resolves into glutaraldehyde and triethylene tetramine again, with 2M hydrochloric acid soln washing 3 times, remove Schiff's base, obtain polyimide prepolymer porous-film.
In order to improve the thermostability of this polyimide prepolymer porous-film, this performed polymer porous-film is cured in accordance with the following steps: successively at 80 ℃ of insulation 1h, 120 ℃ of insulation 1h, 160 ℃ of insulation 1h, 200 ℃ of insulation 1h, 250 ℃ of insulation 1h, 300 ℃ of insulation 1h, obtain polyimide porous membrane provided by the invention.The aperture of this film is 10nm to 2 μ m.
Embodiment 9
(this polyimide prepolymer is by dibasic acid anhydride 3 to the polyimide prepolymer that is 3000 by 0.1g number-average molecular weight, 3 ', 4, 4 '-phenyl ether tetracarboxylic dianhydride (ODPA) and diamine 4, after 4 '-diaminodiphenylsulfone(DDS) (DDS) mixes take mol ratio as 1: 1, at 75 ℃, polycondensation obtains for 5 hours) be dissolved in 5g solvent N, in N-N,N-DIMETHYLACETAMIDE (DMAc), ultrasonic being uniformly dispersed, adding 0.069g concentration is 50wt% glutaraldehyde water solution, dissolving is uniformly dispersed, add again 0.066 tetraethylene pentamine in 25 ℃ of nucleophilic additions after 0.5 hour, in 90 ℃ of dry 1 hour volatilization film forming, in 2M sulphuric acid soln, soak 1 hour again, under acidic conditions, Schiff's base resolves into glutaraldehyde and tetraethylene pentamine again, with 2M sulphuric acid soln washing 3 times, remove Schiff's base, obtain polyimide prepolymer porous-film.
In order to improve the thermostability of this polyimide prepolymer porous-film, this performed polymer porous-film is cured in accordance with the following steps: successively at 80 ℃ of insulation 1h, 120 ℃ of insulation 1h, 160 ℃ of insulation 1h, 200 ℃ of insulation 1h, 250 ℃ of insulation 1h, 300 ℃ of insulation 1h, obtain polyimide porous membrane provided by the invention.The aperture of this film is 10nm to 500nm.
Embodiment 10
(this polyimide prepolymer is by dibasic acid anhydride 3 to the polyimide prepolymer that is 4000 by 0.1g number-average molecular weight, 3 ', 4, 4 '-phenyl ether tetracarboxylic dianhydride (ODPA) and diamine 4, after 4 '-diaminodiphenylsulfone(DDS) (DDS) mixes take mol ratio as 1: 1, at 75 ℃, polycondensation obtains for 5 hours) be dissolved in 5g solvent N, in N-N,N-DIMETHYLACETAMIDE (DMAc), ultrasonic being uniformly dispersed, adding 0.096g concentration is 50wt% glutaraldehyde water solution, dissolving is uniformly dispersed, add again 0.052 Ursol D in 25 ℃ of nucleophilic additions after 0.5 hour, in 100 ℃ of dry 0.5 hour volatilization film forming, in 2M salpeter solution, soak 1 hour again, under acidic conditions, Schiff's base resolves into glutaraldehyde and Ursol D again, with 2M salpeter solution washing 3 times, remove Schiff's base, obtain polyimide prepolymer porous-film.
In order to improve the thermostability of this polyimide prepolymer porous-film, this performed polymer porous-film is cured in accordance with the following steps: successively at 80 ℃ of insulation 1h, 120 ℃ of insulation 1h, 160 ℃ of insulation 1h, 200 ℃ of insulation 1h, 250 ℃ of insulation 1h, 300 ℃ of insulation 1h, obtain polyimide porous membrane provided by the invention.The aperture of this film is 10nm to 100nm.
Embodiment 11
(this polyimide prepolymer is by dibasic acid anhydride 3 to the polyimide prepolymer that is 5000 by 0.1g number-average molecular weight, 3 ', 4, 4 '-phenyl ether tetracarboxylic dianhydride (ODPA) and diamine 4, after 4 '-diaminodiphenylsulfone(DDS) (DDS) mixes take mol ratio as 1.2: 1, at 75 ℃, polycondensation obtains for 5 hours) be dissolved in 5g solvent N, in N-N,N-DIMETHYLACETAMIDE (DMAc), ultrasonic being uniformly dispersed, adding 0.096g concentration is 50wt% glutaraldehyde water solution, dissolving is uniformly dispersed, add again 0.052 O-Phenylene Diamine in 25 ℃ of nucleophilic additions after 0.5 hour, in 50 ℃ of dry 4 hours volatilization film forming, in 0.5M acetum, soak 0.5 hour again, under acidic conditions, Schiff's base resolves into glutaraldehyde and O-Phenylene Diamine again, with 0.5M hydrochloric acid soln washing 5 times, remove Schiff's base, obtain polyimide prepolymer porous-film.
In order to improve the thermostability of this polyimide prepolymer porous-film, this performed polymer porous-film is cured in accordance with the following steps: successively at 80 ℃ of insulation 1h, 120 ℃ of insulation 1h, 160 ℃ of insulation 1h, 200 ℃ of insulation 1h, 250 ℃ of insulation 1h, 300 ℃ of insulation 1h, obtain polyimide porous membrane provided by the invention.The aperture of this film is 10nm to 100nm.
Embodiment 12
(this polyimide prepolymer is by dibasic acid anhydride 3 to the polyimide prepolymer that is 1000 by 0.1g number-average molecular weight, 3 ', 4, 4 '-phenyl ether tetracarboxylic dianhydride (ODPA) and diamine 4, after 4 '-diaminodiphenylsulfone(DDS) (DDS) mixes take mol ratio as 1: 0.8, at 75 ℃, polycondensation obtains for 5 hours) be dissolved in 5g solvent N, in N-N,N-DIMETHYLACETAMIDE (DMAc), ultrasonic being uniformly dispersed, adding 0.057g concentration is 50wt% glutaraldehyde water solution, dissolving is uniformly dispersed, add again 0.072g4, 4 '-diaminodiphenylsulfone(DDS) is in 25 ℃ of nucleophilic additions after 0.5 hour, in 60 ℃ of dry 3 hours volatilization film forming, in 4M hydrochloric acid soln, soak 8 hours again, under acidic conditions, Schiff's base resolves into glutaraldehyde and 4 again, 4 '-diaminodiphenylsulfone(DDS), with 2M hydrochloric acid soln washing 1 time, remove Schiff's base, obtain polyimide prepolymer porous-film.
In order to improve the thermostability of this polyimide prepolymer porous-film, this performed polymer porous-film is cured in accordance with the following steps: successively at 80 ℃ of insulation 1h, 120 ℃ of insulation 1h, 160 ℃ of insulation 1h, 200 ℃ of insulation 1h, 250 ℃ of insulation 1h, 300 ℃ of insulation 1h, obtain polyimide porous membrane provided by the invention.The aperture of this film is 10nm to 2 μ m.
Claims (9)
1. prepare the method for polyimide porous membrane for one kind, comprise the steps: polyimide prepolymer and polyaldehyde to mix in solvent, then add polyamine to carry out nucleophilic addition, after completion of the reaction film forming, washing by soaking in acid again, obtains described polyimide porous membrane;
The number-average molecular weight of described polyimide prepolymer is 1000-5000;
Described polyamine is selected from polymine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, Ursol D, O-Phenylene Diamine, mphenylenediamine, 4,4'-diaminodiphenylsulfone(DDS), 3, at least one in 4'-diaminodiphenyl oxide and trimeric cyanamide; The weight-average molecular weight of described polymine is 1000-10000;
Described polyaldehyde be selected from oxalic dialdehyde, at least one in glutaraldehyde, terephthalaldehyde, m-terephthal aldehyde and 2,4-dimethyl-2-methoxymethyl glutaraldehyde;
Described solvent is selected from least one in N,N-dimethylacetamide, DMF, METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), m-cresol, tetrahydrofuran (THF), ethanol, methyl alcohol, methylene dichloride and trichloromethane;
Described acid is selected from least one in hydrochloric acid, acetic acid, nitric acid and sulfuric acid;
The mass ratio of described polyimide prepolymer, described polyaldehyde and described polyamine is 0.5-4:0.5-2:0.5-2;
The volumetric molar concentration of described acid is 0.001-4mol/L;
Described polyimide prepolymer is according to the method preparation comprising the steps and obtain: dibasic acid anhydride and diamine are mixed and carry out polycondensation, react the complete described polyimide prepolymer that obtains;
Described dibasic acid anhydride is selected from the equal benzene tertacarbonic acid's dianhydride of 1,2,4,5-, 3,3', 4,4'-BPDA, 3,3', 4,4'-phenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-Benzophenone carboxylic acid dianhydride, 3,3', 4,4'-, bis-methyl-phenoxide tetracarboxylic dianhydrides, 4,4 '-(hexafluoro sec.-propyl) two O-phthalic acid dianhydrides, 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,4,5-pentamethylene tetracarboxylic dianhydride, 1,2,4, any one in 5-hexanaphthene tetracarboxylic dianhydride and dihydroxyphenyl propane two ether dianhydrides;
Described diamine is selected from Ursol D, mphenylenediamine, 4,4'-diaminodiphenylsulfone(DDS), 3,4'-diaminodiphenyl oxide, 1, two (4-amino-benzene oxygen) benzene, 1 of 3-, two (4'-amino-2'-4-trifluoromethylphenopendant) benzene of 4-, Isosorbide-5-Nitrae-bis-(4'-amino-2'-4-trifluoromethylphenopendant) benzene, 4, two (4-amino-2-4-trifluoromethylphenopendant) biphenyl, 3 of 4'-, 3'-diethyl-4, any one in 4'-diaminodiphenylmethane;
The molar ratio of described dibasic acid anhydride and diamine is 0.8-1.2:0.8-1.2;
In described polycondensation steps, temperature is 50-80 ℃, and the time is 3-15 hour.
2. method according to claim 1, is characterized in that:
Described polyamine is selected from polymine, triethylene tetramine, tetraethylene pentamine, Ursol D, O-Phenylene Diamine, mphenylenediamine, 4, at least one in 4'-diaminodiphenylsulfone(DDS) and trimeric cyanamide;
Described polyaldehyde is selected from least one in glutaraldehyde, terephthalaldehyde and m-terephthal aldehyde;
Described solvent is selected from least one in N,N-dimethylacetamide, DMF and methylene dichloride;
Described acid is selected from least one in hydrochloric acid, acetic acid and nitric acid.
3. method according to claim 1, is characterized in that: the mass ratio of described polyimide prepolymer, described polyaldehyde and described polyamine is 2:1:1;
The volumetric molar concentration of described acid is 2mol/L.
4. method according to claim 1, is characterized in that: in described nucleophilic addition step, temperature is 5-80 ℃, and the time is 0.5-4 hour;
In described film forming step, temperature is 50-100 ℃, and the time is 0.5-4 hour;
In described soaking step, the time is 0.5-8 hour;
In described washing step, number of times is 1-5 time, and cleaning solvent is selected from least one in the sulfuric acid that hydrochloric acid that concentration is 0.001-4mol/L, acetic acid that concentration is 0.001-4mol/L, nitric acid that concentration is 0.001-4mol/L and concentration are 0.001-4mol/L.
5. method according to claim 4, is characterized in that: in described nucleophilic addition step, temperature is 25 ℃, and the time is 0.5 hour;
In described film forming step, temperature is 80 ℃, and the time is 2 hours;
In described soaking step, the time is 1 hour;
In described washing step, number of times is 3 times, and cleaning solvent is selected from least one in the acetic acid that hydrochloric acid that concentration is 0.5-4mol/L, sulfuric acid that concentration is 0.5-4mol/L, nitric acid that concentration is 0.5-4mol/L and concentration are 0.5-4mol/L.
6. according to the method described in any one in claim 1-5, it is characterized in that: the described method of preparing polyimide porous membrane, also comprises the steps: after washing by soaking step, gained polyimide porous membrane to be cured in be set forth in acid;
In described curing schedule, temperature is 80-300 ℃, and the time is 0.5-6 hour.
7. method according to claim 6, is characterized in that: in described curing schedule, temperature is 300 ℃, and the time is 2 hours.
The arbitrary described method preparation of claim 1-7 and polyimide porous membrane.
9. polyimide porous membrane according to claim 8, is characterized in that: the aperture of described polyimide porous membrane is 9 nanometers to 20 micron, and BET specific surface area is 179-190m
2/ g, pore volume is 0.59-0.63cm
3/ g.
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| CN104211980B (en) * | 2014-09-19 | 2017-07-14 | 桂林电器科学研究院有限公司 | A kind of low dielectric coefficient polyimide film and preparation method thereof |
| CN104309232B (en) * | 2014-10-27 | 2017-04-19 | 江西先材纳米纤维科技有限公司 | Acid-resisting and alkali-resisting porous film enhanced by polyimide nanofiber and preparation method and application of porous film |
| CN104785121B (en) * | 2015-03-30 | 2017-03-08 | 天津大学 | Sodium alginate/poly-dopamine polyethyleneimine/polyacrylonitrile sandwich diaphragm and preparation and application |
| JP6622287B2 (en) * | 2015-03-31 | 2019-12-18 | 旭化成株式会社 | Polyimide film, polyimide varnish, product using polyimide film, and laminate |
| CN105670029A (en) * | 2016-04-18 | 2016-06-15 | 成都正威新材料研发有限公司 | Method for preparing polyimide aerogel through direct vacuum drying |
| CN106087095B (en) * | 2016-08-02 | 2018-11-06 | 中鸿纳米纤维技术丹阳有限公司 | A kind of nanofiber preparation method of sea water desalination |
| CN106280447A (en) * | 2016-08-15 | 2017-01-04 | 瑞安市智造科技有限公司 | A kind of high resiliency antidetonation Polyimide foams and preparation method thereof |
| CN106967205B (en) * | 2017-03-17 | 2019-03-22 | 暨南大学 | Preparation method and applications with excellent photocatalysis hydrogen production performance conjugation Schiff base polymer |
| US10889678B2 (en) | 2019-01-28 | 2021-01-12 | King Fahd University Of Petroleum And Minerals | Amine-based porous polymer for selective carbon dioxide capture |
| CN109942815B (en) * | 2019-03-20 | 2021-06-01 | 浙江福斯特新材料研究院有限公司 | Polyimide composite resin with low dielectric constant, preparation method and application |
| CN109942816B (en) * | 2019-04-09 | 2020-03-10 | 中国科学院兰州化学物理研究所 | Preparation method of thermosetting polyimide |
| CN111129529B (en) * | 2019-12-24 | 2022-06-21 | 江苏大学 | Covalent organic framework material used for fuel cell self-humidifying membrane electrode and preparation method thereof |
| CN112250863A (en) * | 2020-10-12 | 2021-01-22 | 江南大学 | Recoverable and recyclable thermosetting polyimide material, preparation method and application |
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