CN105348551B - A kind of polyimide porous membrane and preparation method thereof - Google Patents
A kind of polyimide porous membrane and preparation method thereof Download PDFInfo
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- CN105348551B CN105348551B CN201510918127.6A CN201510918127A CN105348551B CN 105348551 B CN105348551 B CN 105348551B CN 201510918127 A CN201510918127 A CN 201510918127A CN 105348551 B CN105348551 B CN 105348551B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
The invention discloses a kind of polyimide porous membranes and preparation method thereof.The pore-size distribution of the polyimide porous membrane is between 30~550nm, porosity of=30%, tensile strength >=75MPa.The preparation method of the polyimide porous membrane is：Imidizing agent is added into polyamic acid solution to be reacted, stop reaction before reactant forms gel, reaction acquired solution obtains part imidization Polyamic Acid Film through deaeration, plastic film mulch, imidization Polyamic Acid Film drawn in gained part, which is placed in solidification liquid, to be impregnated, it takes out, polyimide porous membrane is obtained through hot-imide after cleaning；The imidizing agent is made of dehydrating agent and catalyst.The moderate and mechanical performance higher by polyimide porous membrane pore size distribution range made from method of the present invention.
Description
Technical field
The present invention relates to Kaptons, and in particular to a kind of polyimide porous membrane and preparation method thereof.
Background technology
Polyimides (PI) is most important product in aromatic heterocyclic copolymer, has high temperature resistant, high mechanical strength, chemistry
The excellent comprehensive performance such as stabilization, good stability of the dimension is widely used in industries such as aerospace, electrical, microelectronics.
Hole is introduced in PI films, PI perforated membranes are made, can be used as dielectric materials, battery diaphragm, gas separation membrane, high temperature filtration
Material, sound-absorbing insulation material use.
Preparing PI perforated membranes mainly has following three kinds of approach：First method is addition pore former, and polyamic acid is made
(PAA)/pore former composite membrane, then pore former volatilization or thermal decomposition leave hole during heating up imidizate, obtain PI
Perforated membrane, or after obtaining PI/ pore former composite membranes, pore former is removed using the method for chemical reaction or extraction, it is more to obtain PI
Pore membrane；Second method is to introduce the segment of thermally labile in PAA molecular backbones or side chain using the method for copolymerization or grafting,
It heats up in imidization, thermally labile segment resolves into small molecule effusion film, obtains PI perforated membranes；The third method is phase
Reversal process after obtaining PAA films, is dried or low temperature drying, is then impregnated in coagulating bath, it is more to obtain PI for hot imidization after cleaning
Pore membrane.
Above-mentioned first method is reunited there are pore former and finely dispersed technical barrier, it is difficult to obtain hole size and divide
The uniform PI perforated membranes of cloth.Second method introduces the segment of thermally labile in PAA molecular backbones or side chain, and there are synthesis technologies
Complexity, and thermally decompose after obtain film bad mechanical property the problems such as.Relative to two methods of front, the third method need not draw
Enter pore former, also need not be by complicated synthesis technology, PI perforated membranes obtained are very pure, have higher chemical stabilization
Property.Technology at present in this way is also very much, such as：
The patent of invention of Publication No. CN101665580A discloses a kind of PI perforated membranes, is made by following methods：First
PAA, pore-forming substance will be contained (selected from benzoic acid polyol ester, dialkyl, polynary acid alkyl ester, alkyl sulfonic acid
One or more of phenyl ester, chlorinated paraffin and epoxidized soybean oil) and solvent mixture formed PAA/ pore shaping object plasma membranes, then
The film is subjected to imidizate under the decomposition temperature higher than pore-forming substance.Obtained PI perforated membrane average pore sizes be 99~
246nm, porosity are 36%~67%, intensity is 30~60MPa.
The patent of invention of Publication No. CN101659753A discloses a kind of preparation method of the PI perforated membranes of stretching, tool
Body is：The mixture that PAA, pore-forming substance and solvent (dissolving PAA but slightly soluble or insoluble pore-forming substance) will be contained forms PAA/
Then the composite membrane is contacted with solidification liquid (liquid of dissolving pore-forming substance but slightly soluble or insoluble PAA), is obtained by pore shaping object plasma membrane
To PAA perforated membranes, PAA perforated membranes stretched, and carry out imidization, you can obtain PI perforated membranes, average pore size is 50~
290nm, porosity 24%-71%, elongation 3.2%-10.4%, intensity >=51MPa.
But the moisture in solidification liquid and cleaning solution can cause PAA to degrade, it is difficult to obtain the PI perforated membranes of high-mechanical property.
The patent of invention of Publication No. CN101412817A, discloses a kind of preparation method of PI perforated membranes, including by PAA
Solution forms polyamide acid film, is then cured PAA film immersions in coagulating bath, pore-forming, then with ethyl alcohol, acetone or two
The mixture of person cleans, and is kept for 0.5~4 hour at being finally 70~200 DEG C in temperature, at more than 200 DEG C to 400 DEG C
Being kept for 0.5~3 hour to get PI perforated membranes, average pore size is 10nm~50 μm, and porosity is 60% or more, intensity >=
60MPa.Although PI perforated membranes obtained by the patent of invention have higher mechanical performance, using PI made from the technical solution
The floating of perforated membrane average pore size is larger, and pore-size distribution is very wide, and aperture is down to 10nm, and macropore is then up to 50 μm, and practicability is not
By force.
Invention content
The higher polyamides of moderate and mechanical performance the technical problem to be solved in the present invention is to provide a kind of pore size distribution range
Imines perforated membrane and preparation method thereof.
Polyimide porous membrane of the present invention, pore-size distribution (can also further provide between 30~550nm
Aperture is that the pore volume in the hole of 50~300nm accounts for 80% of total pore volume or more, and bore dia is less than 50nm and bore dia is more than
The total pore volume in the hole of 300nm accounts for 20% or less total pore volume), porosity of=30%, tensile strength >=75MPa.
Polyimide porous membrane of the present invention is in faint yellow opaque shape, and thickness is usually 15~150 μm, preferably 20
~50 μm.
The invention also includes the preparation methods of above-mentioned polyimide porous membrane, are synthesized by two-step process using polycondensation reaction,
Include mainly：Imidizing agent is added into polyamic acid solution to be reacted, stops before reactant forms gel anti-
It answers, reaction acquired solution obtains part imidization Polyamic Acid Film through deaeration, plastic film mulch, and imidization polyamic acid in gained part is thin
Film drawn, which is placed in solidification liquid, to be impregnated, and takes out, polyimide porous membrane is obtained through hot-imide after cleaning；The acyl
Imidizing agent is made of dehydrating agent and catalyst, wherein：
The dehydrating agent is selected from acetic anhydride, propionic andydride, n butanoic anhydride, positive valeric anhydride, trifluoroacetic anhydride and benzoic acid
The combination of one or more of acid anhydride, the dosage of the dehydrating agent are 0.1~4 times of the amount of polyamic acid substance；
The catalyst is selected from pyridine, 3- picolines, isoquinolin, picoline, lutidines, trimethyl pyrrole
The combination of one or more of pyridine, quinoline, triethylamine and triethanolamine, the catalyst amount are polyamic acid substance
0.5~8 times of amount.
In above-mentioned preparation method, the solid content of the polyamic acid solution is 10~50%, more preferably 15~35%.Institute
The polyamic acid solution stated can be obtained by existing conventional techniques, specifically can be by aromatic diamines and dianhydride monomer in the non-matter of polarity
It is obtained by polycondensation reaction in sub- solvent.Wherein, the selection of aromatic diamines, dianhydride monomer and polar non-solute and dosage
It is the same as those in the prior art, the temperature and time of polycondensation reaction is also same as the prior art.Preferably, the aromatic diamine
To be selected from p-phenylenediamine, 4,4 '-diamino-diphenyl ethers, 3,4 '-diamino-diphenyl ethers and 4,4 '-diamino diphenyl sulfones etc.
One or more of combination.When the combination for being selected as above two or more of aromatic diamine, between them
Proportioning can be arbitrary proportioning.The dianhydride monomer is selected from pyromellitic acid anhydride, 3,3 ', 4,4 '-diphenyl ether tetraformics
Dianhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA)s and hexafluoroisopropyli,ene hexichol tetramethyl
The combination of one or more of acid dianhydride etc..When the combination for being selected as above two or more of dianhydride monomer, they
Between proportioning can be arbitrary proportioning.The polar non-solute is selected from N-Methyl pyrrolidone, N, N- dimethyl
The combination of one or more of formamide and DMAC N,N' dimethyl acetamide etc..When being selected as polar non-solute
When stating two or more combinations, the proportioning between them can be arbitrary proportioning.
In above-mentioned preparation method, the dosage of the dehydrating agent is preferably 0.6~2 times of the amount of polyamic acid substance, described
The dosage of catalysis aqua is preferably 1~3 times of the amount of polyamic acid substance.The dehydrating agent and catalyst is preferably by them
It is then added in polyamic acid solution after being made into solution with solvent dissolving, is more advantageous to polyamic acid solution and acid imide in this way
Change the reaction of reagent.It is described to be used for dissolving dehydrating agent and the solvent of catalyst is identical as the selection of above-mentioned polar non-solute,
Its dosage is that can dissolve dehydrating agent and catalyst.
In above-mentioned preparation method, reacting for being carried out between the polyamic acid solution and imidizing agent is not complete
(upon completion of the reaction, gained reactant be in gel state), but make polyamic acid part chemical imidization, therefore, polyamides
The needs that react between amino acid solution and imidizing agent stop reaction before reactant forms gel, and after stopping reaction
Gained reactant is in the solution of clear.By addition imidizing agent, make polyamic acid part chemical imidization, to
The adverse effect of moisture in subsequent cure, pore-forming and cleaning process to polyamic acid molecular weight is effectively reduced, to improve final institute
Obtaining the mechanical strength offer of polyimide porous membrane energetically influences.
In above-mentioned preparation method, the polyamic acid solution is reacted with imidizing agent in the item being heated or not heated
It is carried out under part.When polyamic acid solution and imidizing agent react carried out under the conditions of 15~35 DEG C when, reaction time control
It is made as 5min~5h, can ensure that the reactant that polyamic acid solution reacts gained with imidizing agent is in clear in this way
Solution.When being performed under heating conditions, reaction can carry out faster, can the reduction reaction time appropriate.
In above-mentioned preparation method, the defoaming, plastic film mulch and stretched operation are the same as those in the prior art.
In above-mentioned preparation method, the selection of solidification liquid and dosage are same as the prior art, it is preferable that solidification liquid is anhydrous second
Alcohol and/or water, when solidification liquid is when being selected as absolute ethyl alcohol and water combination, the proportioning between them can be arbitrary proportioning.It is solidifying
The dosage of solid-liquid is usually 20~100 times of part imidization Polyamic Acid Film weight.
In above-mentioned preparation method, the time impregnated in solidification liquid can be same as the prior art, and preferably control impregnates
Time is 10s~30min, and dipping can carry out under the conditions of 0~60 DEG C.
In above-mentioned preparation method, the cleaning solution for cleaning the part imidization Polyamic Acid Film taken out from solidification liquid
Selection and cleaning mode it is same as the prior art, the usually alcohol and/or ketone of 1~4 carbon atom, preferably absolute ethyl alcohol
Or the mixture of acetone or absolute ethyl alcohol and acetone arbitrary proportion.
In above-mentioned preparation method, imidizate operation is same as the prior art, and preferred parameter is as follows：According to 70
~90 DEG C/1h, 130~150 DEG C/20min, 210~230 DEG C/20min, 290~310 DEG C/20min, 370~390 DEG C/2min,
The program phase formula elevated cure of 420 DEG C/1min, is then down to room temperature.Specific temperature program can be according to polyimide molecule
Depending on structure, highest solidification temperature is preferably lower than the glass transition temperature of polyimide porous membrane.
Compared with prior art, the method have the characteristics that：
1, by be added imidizing agent, make polyamic acid part chemical imidization, effectively reduce subsequent cure, at
Moisture is to the adverse effect of polyamic acid molecular weight in hole and cleaning process, to improve the machine of final gained polyimide porous membrane
The offer of tool intensity energetically influences；On the other hand, after the chemical imidization of polyamic acid part, gained part imidization polyamic acid
The mechanical strength of film is opposite to be improved, and can be stretched, is further increased with higher draw ratio in follow-up stretched
The mechanical performance of gained polyimide porous membrane.
2, it is smaller to press polyimide porous membrane pore size distribution range made from the method for the invention, heat resistance and mechanicalness
It can higher.
Specific implementation mode
With reference to specific embodiment, the present invention is described in further detail, to more fully understand present disclosure, but
The present invention is not limited to following embodiments.
Polyimide porous membrane provided by the invention has the structure as shown in following formula (I)：
Wherein,
N is the integer more than or equal to 1；
AI be binary anhydride monomer residue, be following structures in any one,
R is any one in following structures,
Embodiment 1：
In the present embodiment, polyimide porous membrane material has the following structure formula：
Specifically preparation method is：
1) 10.0g (0.05mol) 4,4 '-diamino-diphenyl ether (ODA) is added in three-necked flask and is dissolved in 90g N-
In methyl pyrrolidone, 3,3 ', 4,4 '-diphenyl ether tetraformic dianhydride (ODPA) (molar ratios of ODA and ODPA are then added
It is 1：1) 5h, is stirred at 25 DEG C, obtains polyamic acid solution, the solid content for adjusting solution is 20%；
2) 10gN- methyl pyrrolidones are weighed in beaker, are separately added into the acetic anhydride of 0.5 times of amide acid unit mole
Pyridine with 0.5 times, is stirring evenly and then adding into polyamic acid solution, reacts 1.5h, obtains solution A；
3) solution A vacuum outgas is steeped, the plastic film mulch on clean glass plate, 80 DEG C of baking 40min, after being cooled to room temperature,
Film is taken off, obtains part imidization Polyamic Acid Film, 10% then is stretched to it with static stretch machine；
4) film after stretching then is fixed with metal frame, is immersed in the mixed liquor (volume ratio 1 of absolute ethyl alcohol and water:
5) pore-forming in, dipping temperature are 25 DEG C, dip time 30s；With the mixed liquor (volume ratio 2 of absolute ethyl alcohol and acetone:3) right
Perforated membrane is cleaned, and is eluted 3 times；It impregnates pore-forming and elutes alternately 3 times；
5) perforated membrane that step 4) obtains is fixed with metal frame, according to 80 DEG C/1h, 140 DEG C/20min, 220 DEG C/
20min, 300 DEG C/20min, the heating of the program phase formula of 320 DEG C/2min, keep imidization complete, are then down to room temperature, be made poly-
The thickness of acid imide perforated membrane, the film is 30 μm.
Comparative example：
In this comparative example, polyimide porous membrane material has the following structure formula：
Specifically preparation method is：
1) 10.0g (0.05mol) 4,4 '-diamino-diphenyl ether (ODA) is added in three-necked flask and is dissolved in 90g N-
In methyl pyrrolidone, 3,3 ', 4,4 '-diphenyl ether tetraformic dianhydride (ODPA) (molar ratios of ODA and ODPA are then added
It is 1：1) 5h, is stirred at 25 DEG C and obtains polyamic acid solution to all dissolvings, and the solid content for adjusting solution is 20%.
2) polyamic acid solution vacuum outgas is steeped, the plastic film mulch on clean glass plate, 80 DEG C of baking 40min；
3) after being cooled to room temperature, by the thin film dipped mixed liquor (volume ratio in absolute ethyl alcohol and water with glass plate
It is 1:5) pore-forming in, dipping temperature are 25 DEG C, dip time 30s；With the mixed liquor (volume ratio 2 of absolute ethyl alcohol and acetone:
3) perforated membrane is cleaned, is eluted 3 times；It impregnates pore-forming and elutes alternately 3 times；
4) perforated membrane that step 3) obtains is fixed with metal frame, be placed in baking oven according to 80 DEG C/1h, 140 DEG C/20min,
220 DEG C/20min, 300 DEG C/20min, the heating of the program phase formula of 320 DEG C/2min, keep imidization complete, are then down to room temperature,
Polyimide porous membrane is made, the thickness of the film is 33 μm.
Embodiment 2：
In the present embodiment, polyimide porous membrane material has the following structure formula：
Specifically preparation method is：
1) 10.0g (0.05mol) 4,4 '-diamino-diphenyl ether (ODA) is added in three-necked flask and is dissolved in 95g N-
In methyl pyrrolidone, 3,3 ', 4,4 '-diphenyl ether tetraformic dianhydrides (ODPA) and pyromellitic acid anhydride (PMDA) is then added
(molar ratio of ODA and dianhydride is 1：The molar ratio of 1, ODPA and PMDA is 2:1) 5h, is stirred at 30 DEG C, obtains polyamides
Amino acid solution, the solid content for adjusting solution are 20%.
2) 10gN- methyl pyrrolidones are weighed in beaker, be separately added into 1 times of amide acid unit mole acetic anhydride and
0.5 times of triethylamine, is stirred evenly with glass bar, is added in polyamic acid solution, is reacted 50min, is obtained solution A；
3) solution A vacuum outgas is steeped, the plastic film mulch on clean glass plate, 80 DEG C of baking 40min, after being cooled to room temperature,
Film is taken off, obtains part imidization Polyamic Acid Film, 10% then is stretched to it with static stretch machine；
4) film after stretching then is fixed with metal frame, is immersed in the mixed liquor (volume ratio 1 of absolute ethyl alcohol and water:
6) pore-forming in, dipping temperature are 30 DEG C, dip time 15s；With the mixed liquor (volume ratio 2 of absolute ethyl alcohol and acetone:3) right
Perforated membrane is cleaned, and is eluted 4 times；It impregnates pore-forming and elutes alternately 2 times；
5) perforated membrane that step 4) obtains is fixed with metal frame, according to 80 DEG C/1h, 140 DEG C/20min, 220 DEG C/
20min, 300 DEG C/20min, the heating of the program phase formula of 320 DEG C/2min, keep imidization complete, are then down to room temperature, be made poly-
The thickness of acid imide perforated membrane, the film is 35 μm.
Embodiment 3：
In the present embodiment, polyimide porous membrane material has the following structure formula：
Specifically preparation method is：
1) 12.4g (0.05mol) 4,4 '-diamino diphenyl sulfone (DDS) is added in three-necked flask and is dissolved in 100g N-
In methyl pyrrolidone, 3,3 ', 4,4 '-diphenyl ether tetraformic dianhydride (ODPA) (molar ratios of DDS and ODPA are then added
It is 1：1) 5h, is stirred at 20 DEG C, obtains polyamic acid solution, the solid content for adjusting solution is 18%；
2) 10gN- methyl pyrrolidones are weighed in beaker, are separately added into the dehydrating agent of 1.2 times of amide acid unit mole
(propionic andydride and acetic anhydride, molar ratio 2：1) pyridine with 0.6 times, is stirred evenly with glass bar, is added to polyamic acid solution
In, 40min is reacted, solution A is obtained；
3) solution A vacuum outgas is steeped, the plastic film mulch on clean glass plate, 80 DEG C of baking 40min, after being cooled to room temperature,
Film is taken off, obtains part imidization Polyamic Acid Film, 10% then is stretched to it with static stretch machine；
4) film after stretching then is fixed with metal frame, is immersed in the mixed liquor (volume ratio 1 of absolute ethyl alcohol and water:
5) pore-forming in, dipping temperature are 35 DEG C, dip time 10s；With the mixed liquor (volume ratio 2 of absolute ethyl alcohol and acetone:3) right
Perforated membrane is cleaned, and 4h is impregnated；
5) step 4) perforated membrane is fixed with metal frame, according to 80 DEG C/1h, 140 DEG C/20min, 220 DEG C/20min, 300
DEG C/20min, 320 DEG C/2min program phase formula heating, keep imidization complete, be then down to room temperature, be made polyimides it is more
The thickness of pore membrane, the film is 35 μm.
Embodiment 4：
In the present embodiment, polyimide porous membrane material has the following structure formula：
Specifically preparation method is：
1) 5.4g (0.05mol) p-phenylenediamine (PDA) is added in three-necked flask and is dissolved in 45g N, N- dimethyl formyls
In amine and 30g N-Methyl pyrrolidones, be then added 3,3 ', 4,4 '-diphenyl ether tetraformic dianhydrides (ODPA) (PDA and ODPA's
Molar ratio is 1.05：1) 4h, is stirred at 35 DEG C, obtains polyamic acid solution polyamic acid solution, adjusts consolidating for solution
Body content is 30%.
2) 10gN is weighed in beaker, dinethylformamide is separately added into the positive fourth of 0.9 times of amide acid unit mole
Acid anhydrides and 0.6 times of pyridine, are stirred evenly with glass bar, are added in polyamic acid solution, are reacted 1h, are obtained solution A；
3) solution A vacuum outgas is steeped, the plastic film mulch on clean glass plate, 80 DEG C of baking 40min, after being cooled to room temperature,
Film is taken off, obtains part imidization Polyamic Acid Film, 10% then is stretched to it with static stretch machine；
4) film after stretching then is fixed with metal frame, is immersed in the mixed liquor (volume ratio 1 of absolute ethyl alcohol and water:
5) pore-forming in, dipping temperature are 45 DEG C, dip time 10s；With the mixed liquor (volume ratio 2 of absolute ethyl alcohol and acetone:3) right
Perforated membrane is cleaned, and is eluted 3 times；It impregnates pore-forming and elutes alternately 3 times；
5) step 4) perforated membrane is fixed with metal frame, according to 80 DEG C/1h, 140 DEG C/20min, 220 DEG C/20min, 300
DEG C/20min, 320 DEG C/2min program phase formula heating, keep imidization complete, be then down to room temperature, be made polyimides it is more
The thickness of pore membrane, the film is 30 μm.
Embodiment 5：
In the present embodiment, polyimide porous membrane material has the following structure formula：
Specifically preparation method is：
1) 5.0g (0.025mol) 3,4 '-diamino-diphenyl ethers (3,4 '-ODA) and 5.0g are added in three-necked flask
(0.025mol) 4,4 '-diamino-diphenyl ether (ODA) is dissolved in 140g n,N-dimethylacetamide, and equal benzene is then added
(molar ratio of diamines and PMDA are 0.95 to tetracarboxylic acid dianhydride (PMDA)：1), at 20 DEG C stir 8h to all dissolving obtain
Polyamic acid solution polyamic acid solution, the solid content for adjusting solution are 10%.
2) 10gN is weighed in beaker, N- dimethylacetylamides are separately added into the positive valeric acid of 2 times of amide acid unit mole
Acid anhydride and 1 times of 3- picolines, are stirred evenly with glass bar, are added in polyamic acid solution, are reacted 20min, are obtained solution
A；
3) solution A vacuum outgas is steeped, the plastic film mulch on clean glass plate, 80 DEG C of baking 40min, after being cooled to room temperature,
Film is taken off, obtains part imidization Polyamic Acid Film, 10% then is stretched to it with static stretch machine；
4) film after stretching then is fixed with metal frame, is immersed in the mixed liquor (volume ratio 1 of absolute ethyl alcohol and water:
5) pore-forming in, dipping temperature are 15 DEG C, dip time 3min；With the mixed liquor (volume ratio 2 of absolute ethyl alcohol and acetone:3)
Perforated membrane is cleaned, is eluted 5 times；It impregnates pore-forming and elutes alternately 2 times；
5) step 4) perforated membrane is fixed with metal frame, according to 80 DEG C/1h, 140 DEG C/20min, 220 DEG C/20min, 300
DEG C/20min, 380 DEG C/2min, the heating of the program phase formula of 420 DEG C/1min, keep imidization complete, be then down to room temperature, is made
The thickness of polyimide porous membrane, the film is 20 μm.
Embodiment 6：
In the present embodiment, polyimide porous membrane material has the following structure formula：
Specifically preparation method is：
1) 12.4g (0.05mol) 4,4 '-diamino diphenyl sulfone (DDS) is added in three-necked flask and is dissolved in 70g N,
In N- dimethylacetylamides, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (BPDA) (molar ratios of DDS and BPDA are then added
It is 1：1) 4h, is stirred at 50 DEG C, obtains polyamic acid solution, the solid content for adjusting solution is 25%.
2) 10gN is weighed in beaker, N- dimethylacetylamides are separately added into the benzene first of 1.6 times of amide acid unit mole
Acid anhydrides and 2 times of catalyst (isoquinolin and pyridine, molar ratio 1:2) it, is stirred evenly with glass bar, it is molten to be added to polyamic acid
In liquid, 30min is reacted, solution A is obtained；
3) solution A vacuum outgas is steeped, the plastic film mulch on clean glass plate, 80 DEG C of baking 40min, after being cooled to room temperature,
Film is taken off, obtains part imidization Polyamic Acid Film, 10% then is stretched to it with static stretch machine；
4) film after stretching then is fixed with metal frame, is immersed in the mixed liquor (volume ratio 1 of absolute ethyl alcohol and water:
5) pore-forming in, dipping temperature are 20 DEG C, dip time 1min；With the mixed liquor (volume ratio 2 of absolute ethyl alcohol and acetone:3)
Perforated membrane is cleaned, is eluted 3 times；It impregnates pore-forming and elutes alternately 4 times；
5) step 4) perforated membrane is fixed with metal frame, according to 80 DEG C/1h, 140 DEG C/20min, 220 DEG C/20min, 300
DEG C/20min, 360 DEG C/2min program phase formula heating, keep imidization complete, be then down to room temperature, be made polyimides it is more
The thickness of pore membrane, the film is 29 μm.
Embodiment 7：
In the present embodiment, polyimide porous membrane material has the following structure formula：
Specifically preparation method is：
1) 12.4g (0.05mol) 4,4 '-diamino diphenyl sulfone (DDS) is added in three-necked flask and is dissolved in 40g N,
In N- dimethylacetylamides, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA)s (BTDA) are then added, and (DDS and BTDA's feeds intake mole
Than being 1.1：1) 4h, is stirred at 50 DEG C, obtains polyamic acid solution, the solid content for adjusting solution is 40%.
2) 10gN is weighed in beaker, N- dimethylacetylamides are separately added into the propionic acid of 2.5 times of amide acid unit mole
Acid anhydride and 1.6 times of triethylamine, are stirred evenly with glass bar, are added in polyamic acid solution, are reacted 5min, are obtained solution A；
3) solution A vacuum outgas is steeped, the plastic film mulch on clean glass plate, 80 DEG C of baking 40min, after being cooled to room temperature,
Film is taken off, obtains part imidization Polyamic Acid Film, 10% then is stretched to it with static stretch machine；
4) film after stretching then is fixed with metal frame, is immersed in the mixed liquor (volume ratio 1 of absolute ethyl alcohol and water:
5) pore-forming in, dipping temperature are 30 DEG C, dip time 20s；With the mixed liquor (volume ratio 2 of absolute ethyl alcohol and acetone:3) right
Perforated membrane is cleaned, and by the way of dipping, impregnates 3h；
5) step 4) perforated membrane is fixed with metal frame, according to 80 DEG C/1h, 140 DEG C/20min, 220 DEG C/20min, 300
DEG C/20min, 330 DEG C/2min program phase formula heating, keep imidization complete, be then down to room temperature, be made polyimides it is more
The thickness of pore membrane, the film is 24 μm.
Embodiment 8：
In the present embodiment, polyimide porous membrane material has the following structure formula：
Specifically preparation method is：
1) 5.4g (0.05mol) p-phenylenediamine (PDA) is added in three-necked flask and is dissolved in 120g N-Methyl pyrrolidones
In, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA)s (BTDA) are then added, and (molar ratio of PDA and BTDA are 0.95：1), exist
10h is stirred at 26 DEG C, obtains polyamic acid solution, the solid content for adjusting solution is 15%.
2) 10gN- methyl pyrrolidones are weighed in beaker, be separately added into 1 times of amide acid unit mole acetic anhydride and
8 times of three absolute ethyl alcohol amine, are stirred evenly with glass bar, are added in polyamic acid solution, are reacted 20min, are obtained solution A；
3) solution A vacuum outgas is steeped, the plastic film mulch on clean glass plate, 80 DEG C of baking 40min, after being cooled to room temperature,
Film is taken off, obtains part imidization Polyamic Acid Film, 10% then is stretched to it with static stretch machine；
4) film after stretching then is fixed with metal frame, is immersed in the mixed liquor (volume ratio 1 of absolute ethyl alcohol and water:
1) pore-forming in, dipping temperature are 25 DEG C, dip time 30s；With the mixed liquor (volume ratio 1 of absolute ethyl alcohol and acetone:1) right
Perforated membrane is cleaned, and by the way of dipping, impregnates 3.5h；
5) step 4) perforated membrane is fixed with metal frame, according to 80 DEG C/1h, 140 DEG C/20min, 220 DEG C/20min, 300
DEG C/20min, 380 DEG C/2min program phase formula heating, keep imidization complete, be then down to room temperature, be made polyimides it is more
The thickness of pore membrane, the film is 26 μm.
Embodiment 9：
In the present embodiment, polyimide porous membrane material has the following structure formula：
Specifically preparation method is：
1) 10.0g (0.05mol) 4,4 '-diamino-diphenyl ether (ODA) is added in three-necked flask and is dissolved in 30g N-
In methyl pyrrolidone, two pyromellitic dianhydride of hexafluoroisopropyli,ene (6FDA) is then added, and (molar ratio of ODA and 6FDA is
0.9：1) 10h, is stirred at 35 DEG C, obtains polyamic acid solution, the solid content for adjusting solution is 50%；
2) 10g solvents are weighed in beaker, are separately added into 4 times of positive valeric anhydride of amide acid unit mole and the three of 4 times
Absolute ethyl alcohol amine, is stirred evenly with glass bar, is added in polyamic acid solution, is reacted 6min, is obtained solution A；
3) solution A vacuum outgas is steeped, the plastic film mulch on clean glass plate, 80 DEG C of baking 40min, after being cooled to room temperature,
Film is taken off, obtains part imidization Polyamic Acid Film, 10% then is stretched to it with static stretch machine；
4) film after stretching then is fixed with metal frame, pore-forming, dipping temperature are 10 DEG C to dipping in water, dip time
For 5min；Perforated membrane is cleaned with absolute ethyl alcohol, is eluted 2 times；It impregnates pore-forming and elutes alternately 3 times；
5) step 4) perforated membrane is fixed with metal frame, according to 80 DEG C/1h, 140 DEG C/20min, 220 DEG C/20min, 300
DEG C/20min, 340 DEG C/2min program phase formula heating, keep imidization complete, be then down to room temperature, be made polyimides it is more
The thickness of pore membrane, the film is 32 μm.
Embodiment 10：
In the present embodiment, polyimide porous membrane material has the following structure formula：
Specifically preparation method is：
1) 10.0g (0.05mol) 3,4 '-diamino-diphenyl ether (3,4 '-ODA) is added in three-necked flask to be dissolved in
In 100g n,N-Dimethylformamide, two pyromellitic dianhydride of hexafluoroisopropyli,ene (6FDA) (3,4 '-ODA and 6FDA is then added
Molar ratio be 1.05：1) 8h, is stirred at 40 DEG C, obtains polyamic acid solution, the solid content for adjusting solution is
20%.
2) 10g solvents are weighed in beaker, are separately added into 3 times of acetic anhydride of amide acid unit mole and 6 times of isoquinoline
Quinoline is stirred evenly with glass bar, is added in polyamic acid solution, is reacted 5min, is obtained solution B；
3) solution B vacuum outgas is steeped, the plastic film mulch on clean glass plate, 80 DEG C of baking 40min, after being cooled to room temperature,
Film is taken off, obtains part imidization Polyamic Acid Film, 10% then is stretched to it with static stretch machine；
4) film after stretching then is fixed with metal frame, is immersed in pore-forming in absolute ethyl alcohol, dipping temperature is 28 DEG C, leaching
The stain time is 25s；Perforated membrane is cleaned with acetone, by the way of dipping, impregnates 6h；
5) step 4) perforated membrane is fixed with metal frame, according to 80 DEG C/1h, 140 DEG C/20min, 220 DEG C/20min, 300
DEG C/20min, 340 DEG C/2min program phase formula heating, keep imidization complete, be then down to room temperature, be made polyimides it is more
The thickness of pore membrane, the film is 30 μm.
The performance of polyimide porous membrane made from the embodiment of the present invention 1~10 and comparative example is measured, it is as follows
It states shown in table 2.
Table 2：
By the table it is found that polyimide porous membrane made from the method for the present invention and the polyimide porous membrane phase in comparative example
Than tensile strength and elongation at break have raising by a relatively large margin, porosity to increase, and pore-size distribution is more concentrated.It can
See, mechanicalness can be made using polyamic acid solution drawn and the phase inversion technique again of part chemical imidization in the present invention
It can preferable polyimide porous membrane.
Claims (7)
1. a kind of polyimide porous membrane, it is characterised in that：The pore-size distribution of the polyimide porous membrane between 30 ~ 550 nm it
Between, porosity of=30%, tensile strength >=75MPa；
The preparation method of the polyimide porous membrane is：Imidizing agent is added into polyamic acid solution to be reacted,
Reactant stops reacting before forming gel, and reaction acquired solution obtains part imidization Polyamic Acid Film through deaeration, plastic film mulch,
Imidization Polyamic Acid Film drawn in gained part, which is placed in solidification liquid, to be impregnated, and is taken out, is obtained through hot-imide after cleaning
To polyimide porous membrane；The imidizing agent is made of dehydrating agent and catalyst, wherein：
The dehydrating agent is in acetic anhydride, propionic andydride, n butanoic anhydride, positive valeric anhydride, trifluoroacetic anhydride and benzoyl oxide
A combination of one or more, the dosage of the dehydrating agent is 0.1 ~ 4 times of the amount of polyamic acid substance；
The catalyst is selected from pyridine, isoquinolin, picoline, lutidines, trimethylpyridine, quinoline, triethylamine
With the combination of one or more of triethanolamine, the catalyst amount is 0.5 ~ 8 times of the amount of polyamic acid substance.
2. polyimide porous membrane according to claim 1, it is characterised in that：The thickness of the polyimide porous membrane is 15
~150 μm。
3. the preparation method of polyimide porous membrane described in claim 1, it is characterised in that：Acyl is added into polyamic acid solution
Imidizing agent is reacted, and stops reaction before reactant forms gel, and reaction acquired solution obtains portion through deaeration, plastic film mulch
Dividing imidization Polyamic Acid Film, imidization Polyamic Acid Film drawn in gained part, which is placed in solidification liquid, to be impregnated, and is taken out,
After cleaning polyimide porous membrane is obtained through hot-imide；The imidizing agent is made of dehydrating agent and catalyst,
Wherein：
The dehydrating agent is in acetic anhydride, propionic andydride, n butanoic anhydride, positive valeric anhydride, trifluoroacetic anhydride and benzoyl oxide
A combination of one or more, the dosage of the dehydrating agent is 0.1 ~ 4 times of the amount of polyamic acid substance；
The catalyst is selected from pyridine, isoquinolin, picoline, lutidines, trimethylpyridine, quinoline, triethylamine
With the combination of one or more of triethanolamine, the catalyst amount is 0.5 ~ 8 times of the amount of polyamic acid substance.
4. preparation method according to claim 3, it is characterised in that：The polyamic acid solution and imidizing agent
Reaction carries out under conditions of being heated or not heated.
5. preparation method according to claim 3 or 4, it is characterised in that：When polyamic acid solution and imidizing agent
Reaction when being carried out under the conditions of 15 ~ 35 DEG C, the time of reaction is 5min ~ 5h.
6. preparation method according to claim 3 or 4, it is characterised in that：The solidification liquid be absolute ethyl alcohol and/or
Water.
7. preparation method according to claim 3 or 4, it is characterised in that：The time of the dipping is 10s ~ 30min, leaching
Stain carries out under the conditions of 0 ~ 60 DEG C.
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| CN105566907B (en) * | 2016-03-22 | 2018-11-06 | 天津工业大学 | A kind of polyimide filtering membranes and its method based on collaboration imidization preparation |
| CN107099048B (en) * | 2017-03-13 | 2020-05-08 | 桂林电器科学研究院有限公司 | Preparation method of solvent-resistant porous polyimide film |
| CN108794782B (en) * | 2018-06-26 | 2021-05-11 | 无锡高拓新材料股份有限公司 | Preparation method of polyimide film |
| CN108752931A (en) * | 2018-06-27 | 2018-11-06 | 桂林电器科学研究院有限公司 | Micro-nano inorganic particle hybrid modified black matt polyimide film and preparation method thereof |
| CN109280190B (en) * | 2018-08-01 | 2021-06-04 | 乳源东阳光氟树脂有限公司 | Polyimide porous film and preparation method thereof |
| CN114940759B (en) * | 2022-06-30 | 2024-01-26 | 天津众泰材料科技有限公司 | Fluorine-containing polyimide film, preparation method thereof and supercapacitor |
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| CN101580596A (en) * | 2009-06-24 | 2009-11-18 | 宜兴市高拓高分子材料有限公司 | Polyimide film and preparation method thereof |
| CN103509186A (en) * | 2012-06-27 | 2014-01-15 | 比亚迪股份有限公司 | Polyamide acid solution and preparation method thereof, polyimide solution, polyimide porous membrane and lithium ion battery |
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| CN101580596A (en) * | 2009-06-24 | 2009-11-18 | 宜兴市高拓高分子材料有限公司 | Polyimide film and preparation method thereof |
| CN103509186A (en) * | 2012-06-27 | 2014-01-15 | 比亚迪股份有限公司 | Polyamide acid solution and preparation method thereof, polyimide solution, polyimide porous membrane and lithium ion battery |
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