CN105566907B - A kind of polyimide filtering membranes and its method based on collaboration imidization preparation - Google Patents
A kind of polyimide filtering membranes and its method based on collaboration imidization preparation Download PDFInfo
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 112
- 239000004642 Polyimide Substances 0.000 title claims abstract description 94
- 239000012528 membrane Substances 0.000 title claims abstract description 69
- 238000001914 filtration Methods 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title description 18
- 239000000126 substance Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract 2
- 238000003786 synthesis reaction Methods 0.000 claims abstract 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 24
- 229920005575 poly(amic acid) Polymers 0.000 claims description 23
- 238000013019 agitation Methods 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 19
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 18
- 238000005266 casting Methods 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 9
- 230000001112 coagulating effect Effects 0.000 claims description 8
- 238000005191 phase separation Methods 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000013557 residual solvent Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 230000001360 synchronised effect Effects 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000002344 surface layer Substances 0.000 claims description 7
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- -1 4,4 '-diaminodiphenyl ethers Chemical class 0.000 claims description 2
- 238000005576 amination reaction Methods 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims 2
- 241001614291 Anoplistes Species 0.000 claims 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims 1
- 229940113088 dimethylacetamide Drugs 0.000 claims 1
- 238000003359 percent control normalization Methods 0.000 claims 1
- 238000001728 nano-filtration Methods 0.000 abstract description 10
- 238000000926 separation method Methods 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 240000008254 Rosa chinensis Species 0.000 description 6
- 235000000664 Rosa chinensis Nutrition 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- AZJPTIGZZTZIDR-UHFFFAOYSA-L rose bengal Chemical compound [K+].[K+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 AZJPTIGZZTZIDR-UHFFFAOYSA-L 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions 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 C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a kind of polyimide filtering membranes prepared based on collaboration imidization and its methods, first pass through the polyimides synthesis that chemical imidization realizes part, then form a film, then further reset pore structure by hot imidization；NF membrane is obtained by the collaboration of two imidizations.Method provided by the present invention is simple and practicable, it is not related to the complex reactions such as grafting, obtained polyimide filtering membranes have higher intensity and solvent resistance, show higher nanofiltration separation ability, unsymmetric structure is presented in fenestra, fenestra road is flourishing, and the problem of high-performance NF membrane can not be prepared by overcoming single imidization method, and prepared polyimide filtering membranes may be reused.
Description
Technical field
The present invention relates to the preparation methods of polyimide filtering membranes, more particularly to one kind passing through collaboration imidization and preparing
Polyimide filtering membranes and its method.
Background technology
Polyimides (abbreviation PI), is a kind of functional heat-resistant polymer, and polyimides has heat resistance outstanding
With superior mechanical performance, also there is excellent thermal stability, radiation resistance, dielectric properties, oxidation stability and chemically-resistant
Medicament.It is widely used in heat proof material, aerospace equipment, remaining aspect further includes the electronic packaging material of electronic information
Expect industry, new high-tech industry, viscose, engineering plastics and photoresist etc..However, to have its excellent for polyimide material
Performance while, also have it is clearly disadvantageous, be mainly shown as it is non-fusible under common heating, it is insoluble in ordinary organic solvents
Solution, largely constrains the development and application of polyimides, oneself limits the bottleneck of polyimides development through becoming.
With the development of the times, insoluble polyimides cannot meet the needs of people, especially by polyimides
It when for membrane material, generally requires that first polyimides is dissolved in solvent, then is prepared with duct by the methods of phase separation
The seperation film of structure, therefore it is extremely important in the application in film field and popularization for it to prepare soluble polyimide.
Polyimides is generally made by two-step method through polycondensation by aromatic diamine monomers and aromatic dianhydride monomer, i.e. diamines list
Body and dianhydride monomer reaction obtain polyamic acid, and then by adding thermally or chemically, it is sub- that intramolecular dehydration closed loop generates polyamides
Amine.Wherein, hot imidization method is that the polyamic acid that will have been synthesized is heated for a period of hours at high temperature, and polyamic acid is made to be converted into polyamides
Imines, this method need higher temperature, and the reaction time is short, and degree is high, but easy tos produce bubble.And chemical imidization is to use
Tertiary amine, pyridine etc. are catalyst, and acid anhydrides is dehydrating agent, are acted on polyamic acid under room temperature or slightly heat condition, this method
Required condition is milder, and the imidization time is longer, but can be to avoid negative effects such as embrittlement, the ruptures that pyrolytic conversion is brought.
Two kinds of insoluble polyimides and soluble polyimide can be prepared by above-mentioned imidization method, polyamides is sub-
The performance of amine especially solubility property, it is closely related with the molecular structure of monomer, conventional aromatic diamine monomers (such as ODA, PMDA,
PDA) generally there is symmetrical structure, unsubstituted side group, it is often insoluble to cause it to correspond to polyimides obtained, gives its processing
Molding brings prodigious difficulty, is especially difficult to that the seperation film of high comprehensive performance is prepared.In order to improve polyimides
Processing performance, introduce flexible structure unit, side group or side chain etc. in monomer often through in MOLECULE DESIGN, destroy strand
Repetition regularity and symmetry, improve its solubility property, although there is more report to be related to the preparation of soluble polyimide,
Its invention effect, which is only the material prepared, has resolvability, is not directed to the preparation of NF membrane, and by the polyamides of resolvability Asia
Amine polymer is prepared as NF membrane and often relates to complicated technology or creative work.
The method for preparing polyimide filtering membranes includes the common scheme of two classes, when by means of polyamic acid performed polymer and
Hot imidization, but had the following disadvantages using polyimide filtering membranes prepared by the program：(1) single hot imidization process relates to
And pyroreaction, the negative effects such as film embrittlement, rupture can be led to, this is clearly unfavorable to the mechanical performance of film, influences film
The repeat performance of practical performance, film is also limited；(2) single chemical imidization method for this scheme and is not suitable for, because
During chemical imidization, to need that imidizing agent is added into uniform polyamic acid solution and being uniformly mixed, it is clear that
In the program, since polyamic acid performed polymer has formed a film, do not have uniformly mixed condition.
Second is that using soluble polyimide as membrane material, polyimide filtering membranes are prepared by means of the methods of being grafted, being crosslinked,
But the program is related to the reactions such as grafting, crosslinking, the problems such as modifying agent is more, and there are complex technical process, and with involved by the present invention
And the strategy that NF membrane is prepared based on imidization it is different.
In addition, by single chemical imidization, although the polyimides polymerization of high comprehensive performance can be prepared
Object, but this single method is difficult to that polyimide filtering membranes are prepared, because polyimide filtering membranes are in addition in molecule knot
It requires to be also to have higher requirement to pore structure outside imidization structure on structure.
Invention content
The technical solution that the present invention solves the technical problem is that a kind of polyimides based on collaboration imidization of design is received
The preparation method of filter membrane.
Technical scheme is as follows：
A method of polyimide filtering membranes are prepared based on collaboration imidization, chemical imidization is first passed through and realizes part
Polyimides synthesizes, and then forms a film, and then further resets pore structure by hot imidization；Pass through the collaboration of two imidizations
Obtain NF membrane.
The imidization degree of the method, chemical imidization step is 50~80%.
The method, specifically includes following steps：
(1) by diamines and dianhydride monomer in molar ratio 1：0.95~1:1.05 are dissolved in organic solvent, at room temperature machine
Tool stirs 2~6 hours, after it is completely dissolved, obtains polyamic acid solution, and it is sub- that chemistry is then added dropwise into polyamic acid solution
Amination reagent, mechanical agitation 24~48 hours occur chemical imidization reaction, obtain polyimide solution, and solid content is 10~
15%, imidization degree is 50~80%；
(2) additive is added into polyimide solution, mechanical agitation scratches casting solution in cleaning at uniform casting solution
It on glass plate, after control 5~90 seconds time of volatilization, immerses in water coagulating bath, phase separation film-forming occurs, impregnates 24 hours and takes
Go out up to hygrometric state polyimide film；
(3) hygrometric state polyimide film is placed in heating plate, by being heated twice up to polyimide filtering membranes, specific mistake
Cheng Shi：Hygrometric state film is heated 2~5 hours at 100 DEG C, the moisture in film is volatilized, and residual solvent moves to film table in film
Layer；Film is heated 10~60 minutes at 250 DEG C, the complete imidization of film, and synchronous realization membrane structure are realized by hot imidization
It resets, obtains polyimide filtering membranes.
The method, the dianhydride monomer be in 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides or hexafluorodianhydride (6FDA) at least
It is a kind of；The diamine monomer be in 3,3 '-dimethyl -4,4 '-diaminodiphenylmethane or 4,4 '-diaminodiphenyl ethers extremely
Few one kind.
The method, the organic solvent are N-Methyl pyrrolidone, n,N-dimethylacetamide or N, N- diformazans
At least one of base formamide.
The method, the chemical imidization reagent are the mixed solvent of acetic anhydride and pyridine.
The method, the additive are at least one of acetone, polyvinylpyrrolidone or tetrahydrofuran, are added
It is the 2%~10% of polyimide solution quality to add the dosage of agent.
The method, specific practice are：(1) by 3,3 '-dimethyl -4,4 '-diaminodiphenylmethane and 3,3 ', 4,
4 '-benzophenone tetracarboxylic dianhydride monomers in molar ratio 1:1 is dissolved in N-Methyl pyrrolidone, and mechanical agitation 4 is small at room temperature
When, after it is completely dissolved, polyamic acid solution is obtained, acetic anhydride and pyridine, machinery are then added dropwise into polyamic acid solution
Chemical imidization reaction occurs for stirring 36 hours, obtains polyimide solution, solid content 12%, and control imidization degree is
70%；(2) it is respectively polyimide solution matter acetone and polyvinylpyrrolidone, dosage to be added into polyimide solution
The 2% and 5% of amount, mechanical agitation is at uniform casting solution, by casting solution blade coating on cleaned glass plate, control 30 seconds time of volatilization
Afterwards, it immerses in water coagulating bath, phase separation film-forming occurs, impregnates and takes out within 24 hours up to hygrometric state polyimide film；It (3) will be wet
State polyimide film is placed in heating plate, and by being heated twice up to polyimide filtering membranes, detailed process is：Hygrometric state film is existed
It is heated 3 hours at 100 DEG C, the moisture in film is volatilized, and residual solvent moves to film surface layer in film；Film is heated at 250 DEG C
30 minutes, the complete imidization of film is realized by hot imidization, and synchronous realization membrane structure is reset, and polyimide filtering is obtained
Film.
The method, specific practice be, (1) is by 3,3 '-dimethyl -4,4 '-diaminodiphenylmethane and hexafluorodianhydride (6FDA)
Monomer in molar ratio 1:1 is dissolved in N-Methyl pyrrolidone, and mechanical agitation 3 hours obtain after it is completely dissolved at room temperature
To polyamic acid solution, acetic anhydride and pyridine are then added dropwise into polyamic acid solution, chemistry occurs for mechanical agitation 48 hours sub-
Aminating reaction, obtains polyimide solution, solid content 13%, and control imidization degree is 80%；(2) to polyimide solution
Middle addition tetrahydrofuran and polyvinylpyrrolidone, mass percent are respectively 3% and 5%, and mechanical agitation is at uniform casting
Film liquid after the control 45 seconds time of volatilization, is immersed in water coagulating bath, is separated by casting solution blade coating on cleaned glass plate
Film-forming is impregnated and is taken out within 24 hours up to hygrometric state polyimide film；(3) hygrometric state polyimide film is placed in heating plate, is passed through
After being heated twice up to polyimide filtering membranes, detailed process is：Hygrometric state film is heated 4 hours at 100 DEG C, the moisture in film
It is volatilized, residual solvent moves to film surface layer in film；Film is heated 45 minutes at 250 DEG C, film is realized by hot imidization
Complete imidization, and synchronous realization membrane structure is reset, and polyimide filtering membranes are obtained.
Polyimide filtering membranes produced by the present invention have the advantages that：
The present invention be directed to above-mentioned problem, propose using collaboration imidization strategy and scheme prepare may be reused,
The polyimide filtering membranes of high comprehensive performance are reacted by diamines and dianhydride monomer first, obtain polyamic acid solution, add
Enter chemical imidization reagent, realizes its molecular structure from polyamic acid to the mistake of polyimide molecule structure by chemical imidization
It crosses, is then prepared and formed a film by phase conversion method, ensure that flexibility, mechanical strength of film etc. are in higher level, then into one
Step realizes that its pore structure is reset, obtains the polyimide filtering membranes with nanofiltration separation effect by hot imidization.It is final to prepare
Polyimide filtering membranes not only high mechanical strength, flexibility is high, and has good nanofiltration separation effect, comprehensive performance compared with
Height, and film may be reused, and avoid the discarded and secondary pollution of membrane material.
Method provided by the present invention is simple and practicable, is not related to the complex reactions such as grafting, obtained polyimide filtering
Film has higher intensity and solvent resistance, shows higher nanofiltration separation ability, and unsymmetric structure, fenestra is presented in fenestra
Road is flourishing, and the problem of high-performance NF membrane can not be prepared by overcoming single imidization method, and prepared polyimides is received
Filter membrane can be applied to the separation of more occasion organic matters.
Description of the drawings
Fig. 1 is the appearance photo of the polyimide filtering membranes prepared in embodiment one；Wherein, a indicates tiling effects, b tables
Show folding effect.
Fig. 2 is the cross-sectional scans electron microscope of the polyimide filtering membranes prepared in embodiment three, amplification factor 2000.
Specific implementation mode
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1：
The present embodiment it is a kind of based on collaboration imidization polyimide filtering membranes preparation method, according to the following steps into
Row：
(1) by 3,3 '-dimethyl -4,4 '-diaminodiphenylmethane and 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride monomers
In molar ratio 1:1 is dissolved in N-Methyl pyrrolidone, and mechanical agitation 4 hours are gathered after it is completely dissolved at room temperature
Amide acid solution, is then added dropwise acetic anhydride and pyridine into polyamic acid solution, and chemical imidization occurs for mechanical agitation 36 hours
Reaction, obtains polyimide solution, solid content 12%, and control imidization degree is 70%；
(2) it is respectively that polyimides is molten acetone and polyvinylpyrrolidone, dosage to be added into polyimide solution
The 2% of liquid quality and 5%, mechanical agitation is at uniform casting solution, by casting solution blade coating on cleaned glass plate, control volatilization time
It after 30 seconds, immerses in water coagulating bath, phase separation film-forming occurs, impregnates and takes out within 24 hours up to hygrometric state polyimide film；
(3) hygrometric state polyimide film is placed in heating plate, by being heated twice up to polyimide filtering membranes, specific mistake
Cheng Shi：Hygrometric state film is heated 3 hours at 100 DEG C, the moisture in film is volatilized, and residual solvent moves to film surface layer in film；
Film is heated 30 minutes at 250 DEG C, the complete imidization of film is realized by hot imidization, and synchronous realization membrane structure is reset, and is obtained
To polyimide filtering membranes.
Implementation result：The appearance photo of the polyimide filtering membranes of preparation is shown in Fig. 1, as seen from Figure 1, the polyimides of preparation
It is NF membrane surface-brightening, smooth, good flexibility is presented, the mechanical property and mechanical strength of film are expressed using tensile strength, film
Tensile strength reach 98Mpa；The solvent-resistant polyimide nanofiltration membrane of preparation is subjected to the logical of ethylene glycol/Bengal rose red system
Amount and rejection test, the results showed that, the rejection of Bengal rose red reaches 99.1%, and flux reaches 42L/ (m2.h), explanation
Prepared NF membrane has higher nanofiltration separation performance；Film is in Conventional solvents such as ethyl alcohol, butanone, dichloromethane, ethyl acetate
In all have good stability；It is molten that the polyimide filtering membranes of preparation can fully be re-dissolved in N-Methyl pyrrolidone
In agent, uniform casting solution can be made again, show that film has good repeat performance.
Embodiment 2：
The present embodiment it is a kind of based on collaboration imidization polyimide filtering membranes preparation method, according to the following steps into
Row：
(1) this step is identical as embodiment 1 step (1).
(2) this step is identical as embodiment 1 step (2).
(3) hygrometric state polyimide film is placed in heating plate, by being heated twice up to polyimide filtering membranes, specific mistake
Cheng Shi：Hygrometric state film is heated 3 hours at 100 DEG C, the moisture in film is volatilized, and polyimide separation membrane is obtained.In order to test
Influence of the card collaboration imidization to film properties, carries out comparative analysis, the present embodiment does not carry out subsequent hot imines with embodiment 1
Change step.
Implementation result：The tensile strength of film is 75Mpa；By the solvent-resistant polyimide nanofiltration membrane of preparation carry out ethylene glycol/
The flux and rejection of Bengal rose red system are tested, the results showed that, the rejection of Bengal rose red is 15.8%, flux
Up to 63L/ (m2.h), illustrate that prepared polyimide film has lower nanofiltration separation performance, it can by being compared with embodiment 1
Know, high-performance polyimide NF membrane can not be obtained using single chemical imidization, this also illustrates associations of the present invention
With imidization strategy for the importance of nanofiltration film preparation.
Embodiment 3：
The present embodiment it is a kind of based on collaboration imidization polyimide filtering membranes preparation method, according to the following steps into
Row：
(1) by 3,3 '-dimethyl -4,4 '-diaminodiphenylmethane and hexafluorodianhydride (6FDA) monomer in molar ratio 1:1 is dissolved in N-
In methyl pyrrolidone, mechanical agitation 3 hours obtain polyamic acid solution after it is completely dissolved at room temperature, then to poly-
Acetic anhydride and pyridine are added dropwise in amide acid solution, mechanical agitation 48 hours occurs chemical imidization reaction, it is molten to obtain polyimides
Liquid, solid content 13%, control imidization degree are 80%；
(2) tetrahydrofuran is added into polyimide solution and polyvinylpyrrolidone, mass percent is respectively
3% and 5%, mechanical agitation is at uniform casting solution, by casting solution blade coating on cleaned glass plate, after the control 45 seconds time of volatilization,
It immerses in water coagulating bath, phase separation film-forming occurs, impregnates and takes out within 24 hours up to hygrometric state polyimide film；
(3) hygrometric state polyimide film is placed in heating plate, by being heated twice up to polyimide filtering membranes, specific mistake
Cheng Shi：Hygrometric state film is heated 4 hours at 100 DEG C, the moisture in film is volatilized, and residual solvent moves to film surface layer in film；
Film is heated 45 minutes at 250 DEG C, the complete imidization of film is realized by hot imidization, and synchronous realization membrane structure is reset, and is obtained
To polyimide filtering membranes.
Implementation result：The microstructure of the polyimide filtering membranes of preparation is shown in Fig. 2, by the cross-sectional scans Electronic Speculum in Fig. 2
Figure is as it can be seen that the pore passage structure of film is flourishing, in unsymmetric structure；The tensile strength of film reaches 95Mpa；The solvent resistant polyamides of preparation is sub-
Amine NF membrane carries out flux and the rejection test of ethylene glycol/Bengal rose red system, the results showed that, Bengal rose red
Rejection reaches 98%, and flux reaches 45L/ (m2.h), illustrate that prepared NF membrane has higher nanofiltration separation performance；Film is in second
Good stability is all had in the Conventional solvents such as alcohol, butanone, dichloromethane, ethyl acetate；The polyimide filtering membranes of preparation
It can fully be re-dissolved in N-Methyl pyrrolidone and n,N-dimethylacetamide isopolarity solvent, can be made again
Uniform casting solution shows that film has good repeat performance.
It should be understood that for those of ordinary skills, it can be modified or changed according to the above description,
And all these modifications and variations should all belong to the protection domain of appended claims of the present invention.
Claims (3)
1. a kind of method preparing polyimide filtering membranes based on collaboration imidization, which is characterized in that first pass through chemical imidization
The polyimides synthesis for realizing part, then forms a film, and then further resets pore structure by hot imidization；Pass through two Asias
The collaboration of amination obtains NF membrane；Specifically include following steps：
(1) by diamines and dianhydride monomer in molar ratio 1：0.95~1:1.05 are dissolved in organic solvent, and machinery stirs at room temperature
It mixes 2~6 hours, after it is completely dissolved, obtains polyamic acid solution, chemical imidization is then added dropwise into polyamic acid solution
Chemical imidization reaction occurs for reagent, mechanical agitation 24~48 hours, obtains polyimide solution, and solid content is 10~15%,
Imidization degree is 50~80%；The dianhydride monomer be in 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides or hexafluorodianhydride (6FDA) extremely
Few one kind；The diamine monomer is in 3,3 '-dimethyl -4,4 '-diaminodiphenylmethane or 4,4 '-diaminodiphenyl ethers
It is at least one；The organic solvent is in N-Methyl pyrrolidone, DMAC N,N' dimethyl acetamide or N,N-dimethylformamide
It is at least one；The chemical imidization reagent is the mixed solvent of acetic anhydride and pyridine；
(2) additive is added into polyimide solution, mechanical agitation scratches casting solution in cleaned glass at uniform casting solution
On plate, control was volatilized after 5~90 seconds time, was immersed in water coagulating bath, and phase separation film-forming occurs, and is impregnated taking-up in 24 hours and is
Obtain hygrometric state polyimide film；The additive is at least one of acetone, polyvinylpyrrolidone or tetrahydrofuran, addition
The dosage of agent is the 2%~10% of polyimide solution quality；
(3) hygrometric state polyimide film is placed in heating plate, by being heated twice up to polyimide filtering membranes, detailed process
It is：Hygrometric state film is heated 2~5 hours at 100 DEG C, the moisture in film is volatilized, and residual solvent moves to film surface layer in film；
Film is heated 10~60 minutes at 250 DEG C, the complete imidization of film, and synchronous realization membrane structure weight are realized by hot imidization
Row, obtains polyimide filtering membranes.
2. according to the method described in claim 1, it is characterized in that, specific practice is：(1) by 3,3 '-dimethyl -4,4 '-two
Diaminodiphenylmethane and 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride monomers in molar ratio 1:1 is dissolved in N-Methyl pyrrolidone
In, mechanical agitation 4 hours obtain polyamic acid solution, then into polyamic acid solution after it is completely dissolved at room temperature
Acetic anhydride and pyridine is added dropwise, mechanical agitation 36 hours occurs chemical imidization reaction, obtains polyimide solution, solid content is
12%, control imidization degree is 70%；(2) acetone and polyvinylpyrrolidone are added into polyimide solution, uses
Amount is respectively the 2% and 5% of polyimide solution quality, and mechanical agitation scratches casting solution in clean glass at uniform casting solution
In glass plate, control was volatilized after 30 seconds time, was immersed in water coagulating bath, and phase separation film-forming occurs, and is impregnated taking-up in 24 hours and is
Obtain hygrometric state polyimide film；(3) hygrometric state polyimide film is placed in heating plate, by being heated twice up to polyimide filtering
Film, detailed process are：Hygrometric state film is heated 3 hours at 100 DEG C, the moisture in film is volatilized, and residual solvent moves in film
To film surface layer；Film is heated 30 minutes at 250 DEG C, the complete imidization of film, and synchronous realization film knot are realized by hot imidization
Structure is reset, and polyimide filtering membranes are obtained.
3. according to the method described in claim 1, it is characterized in that, specific practice is, (1) by 3,3 '-dimethyl -4,4 '-two
Diaminodiphenylmethane and hexafluorodianhydride (6FDA) monomer in molar ratio 1:1 is dissolved in N-Methyl pyrrolidone, at room temperature mechanical agitation 3
Hour, after it is completely dissolved, polyamic acid solution is obtained, acetic anhydride and pyridine, machine are then added dropwise into polyamic acid solution
Tool stirs 48 hours, and chemical imidization reaction occurs, and obtains polyimide solution, and solid content 13% controls imidization degree
It is 80%；(2) tetrahydrofuran is added into polyimide solution and polyvinylpyrrolidone, mass percent is respectively
3% and 5%, mechanical agitation is at uniform casting solution, by casting solution blade coating on cleaned glass plate, after the control 45 seconds time of volatilization,
It immerses in water coagulating bath, phase separation film-forming occurs, impregnates and takes out within 24 hours up to hygrometric state polyimide film；(3) by hygrometric state
Polyimide film is placed in heating plate, and by being heated twice up to polyimide filtering membranes, detailed process is：Hygrometric state film is existed
It is heated 4 hours at 100 DEG C, the moisture in film is volatilized, and residual solvent moves to film surface layer in film；Film is heated at 250 DEG C
45 minutes, the complete imidization of film is realized by hot imidization, and synchronous realization membrane structure is reset, and polyimide filtering is obtained
Film.
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| CN1911494A (en) * | 2005-08-11 | 2007-02-14 | 中国石油天然气股份有限公司 | Preparation method of polyimide nanofiltration membrane |
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| CN1314478C (en) * | 2005-01-20 | 2007-05-09 | 石油大学(华东) | Preparation of sodium polyimide filtering membranes for concentrated extracted liquid of antibionic solvent |
| CN101338217B (en) * | 2007-07-04 | 2012-03-07 | 中国石油天然气股份有限公司 | Method for manufacturing composite membrane for gasoline desulfurization |
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| CN1911494A (en) * | 2005-08-11 | 2007-02-14 | 中国石油天然气股份有限公司 | Preparation method of polyimide nanofiltration membrane |
| CN101837254A (en) * | 2009-03-20 | 2010-09-22 | 北京化工大学 | Method for preparing solvent-resistant polyimide nanofiltration membrane |
| CN101785977A (en) * | 2010-03-22 | 2010-07-28 | 北京化工大学 | Preparation method of solvent resistant polyimide nanofiltration film |
| CN103172891A (en) * | 2013-04-17 | 2013-06-26 | 华威聚酰亚胺有限责任公司 | Method for preparing polyimide film by adopting chemical imidization in combined mode |
| CN104262661A (en) * | 2014-09-17 | 2015-01-07 | 天津工业大学 | Method for controlling performance of polyimide film through imidization degree |
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