CN105344258B - A kind of polyimides containing trifluoromethyl/carboxyl multi-walled carbon nanotube gas separation mixed substrate membrane containing nano-grade molecular sieve and preparation method thereof - Google Patents
A kind of polyimides containing trifluoromethyl/carboxyl multi-walled carbon nanotube gas separation mixed substrate membrane containing nano-grade molecular sieve and preparation method thereof Download PDFInfo
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- CN105344258B CN105344258B CN201510726253.1A CN201510726253A CN105344258B CN 105344258 B CN105344258 B CN 105344258B CN 201510726253 A CN201510726253 A CN 201510726253A CN 105344258 B CN105344258 B CN 105344258B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/34—Use of radiation
Abstract
The invention discloses a kind of polyimides containing trifluoromethyl/carboxyl multi-walled carbon nanotube gas separation mixed substrate membrane containing nano-grade molecular sieve and preparation method thereof, the invention belongs to polymer nanocomposites field, problem solved by the invention is gas permeability existing for existing gas separation membrane and the problem of separating property can not be taken into account, the present invention by the polyimides containing trifluoromethyl by adding carboxyl multi-walled carbon nanotube to form mixed substrate membrane containing nano-grade molecular sieve, CNT is set to be uniformly dispersed in mixed substrate membrane containing nano-grade molecular sieve using the interaction of the two polar groups, make two-phase interface that there is good bonding force simultaneously, so that the gas permeability of mixed substrate membrane containing nano-grade molecular sieve and selectivity are improved.The present invention is used to prepare gas separation membrane and gas separation.
Description
Technical field
The invention belongs to the technical field of polymer nanocomposites, and in particular to a kind of polymer carbon nano tube is compound
Film and its production and use.
Background technology
In recent years, people are increasing to the demand of polymeric material of gas separation membrane for gas pair, it is desirable to also more and more higher, how
It is more stable to prepare separation process, service life is longer, the higher separation membrane of separative efficiency, is that researcher pays close attention to
Emphasis.Because polyimides has an excellent combination property and the designability of molecule, thus polyimides in all trades and professions all
There is important application.Polyimides has higher permeability and selectivity due to there is nitrogenous aromatic heterocycle structure, together
When also there is high mechanical strength, heat endurance is good, and solvent resistance is a kind of by force and the features such as can be made into high-throughout self-supported membrane
The very excellent gas separation membrane material of combination property.
Fluorinated polyimide has become polyamides Asia with its unique property in the numerous polyimide polymer of kind
The focus of amine investigation of materials, wherein containing 6FDA be the polyimides performance of 4,4'- (hexafluoro isopropyl) hexichol acid anhydride structure the most
It is excellent.Fluorine element in 6FDA polyimides all exists with C-F key-shapeds formula, fluorine-containing because fluorine atom has larger electronegativity
Group has very strong electron-withdrawing power, causes C-F keys very strong, and the thermal oxide that can improve polymer to a certain extent is stable
Property.Due to the presence of fluoroform group in molecular structure, so the crystallinity of polymer reduces, dielectric constant and refractive index also drop
It is low, and because electronic polarization degree is low so that fluorine material has low cohesive energy and surface free energy, has necessarily hydrophobic
Property, further, since trifluoromethyl belongs to the flexible side group of large volume, the bulk density of polymer can be reduced, increases material oneself
By volume, so as to reach the permeance property of increase material, thus there is huge application potential in terms of gas separation.
Because the polymeric membrane of polyimide has many advantages, such as in terms of gas separation, such as easy to process, designability,
Excellent separating property etc., has been widely used in industry.But polymeric membrane for separation is there is also some shortcomings, if not
Solvent resistant, non-refractory etc..And inoranic membrane be related to high temperature, Korrosionsmedium etc. have uniqueness physics, chemical property and
There are good permeability and selectivity, but manufacturing cost is more much higher than polymeric membrane.Therefore people are by the way that inorganic particulate is drawn
Enter to polymeric membrane and improved, obtained mixed substrate membrane containing nano-grade molecular sieve (MMM films).This membrane material is continuous using organic polymer
Phase, inorganic particulate are dispersed phase, are a kind of trials well.Dispersed inorganic particulate enhances polymerization in mixed substrate membrane containing nano-grade molecular sieve
The mechanical performance and gas selective penetrated property of thing, while also there is the advantages of polymer film, have become gas separation in recent years
The new focus of film research field.
At present, as the progress of science and technology, the development of gas separation membrane face two stern challenges：One is more
The gas permeability and selectivity of film are improved in big degree, the second is the gas separation membrane under the harsh environments such as HTHP
Still there can be good gas separating capacity.
Since finding CNT using transmission electron microscope from Japanese professor Iijima in 1991, the application of CNT and change
Property has caused extensive concern.CNT has excellent mechanics, electricity and chemical property, rapidly become chemistry,
The study hotspot of physics and materials science field.CNT has one-dimentional structure and minimum caliber, has to gas very well
Selectivity, and because CNT inwall is smooth pore passage structure, transmission rate of the gas in CNT is long-range
Transmission rate in same apertures molecular screen membrane, thus it is considered as having potential application in terms of gas separation.Kim et al.
Result of study is delivered on J.Membrane Sci.294 (2007) 147-158, he is first by carboxylation single-walled carbon nanotube and 18
Alkylamine (ODA) acid-base reaction, then it is doped into polysulfones (PSF) matrix and mixed substrate membrane containing nano-grade molecular sieve is made, gas permeability coefficient has
Improved, but selectivity has different degrees of reduction than PS membrane.S.A.Hashemifard et al. is in J.Colloid
Result of study is delivered on Interf.Sci.359 (2011) 359-370, (structure is similar to carbon nanometer by halloysite nanotubes by researcher
Manage) it is doped into PEI by coupling agent N- β-(aminoethyl)-γ-propyl silane (AEAPTMS) processing
(PEI) mixed substrate membrane containing nano-grade molecular sieve is made in matrix, and gas permeability coefficient increases, and attempts to increase but while having carried out filler processing
Two alternate interactions, no matter change the experiment conditions such as processing method, the dosage of coupling agent and amount of filler, selectivity is
There is different degrees of reduction than pure polyetherimde films.So mixed substrate membrane containing nano-grade molecular sieve problems faced is how to improve seperation film gas
While permeance property, the selectivity of gas can be also improved.
The content of the invention
Selectivity is caused to be reduced than pure polyetherimde films in order to solve the problems, such as prior art after using filler, this
Invention provides a kind of polyimides containing trifluoromethyl/carboxyl multi-walled carbon nanotube gas separation mixed substrate membrane containing nano-grade molecular sieve, matrix for containing
Trifluoromethyl polyimides, carboxyl multi-walled carbon nanotube are filler；Wherein carboxyl multi-walled carbon nanotube content is 1~3wt%,
The molecular formula of the described polyimides containing trifluoromethyl is：
N=90~150.
The preparation method of polyimides containing trifluoromethyl/carboxyl multi-walled carbon nanotube gas separation mixed substrate membrane containing nano-grade molecular sieve is as follows：
Take a certain amount of DMA (DMAc) and be classified as two parts, by carboxyl multi-walled carbon nanotube
Ultrasound is to dispersed after mixing in a part of DMAC N,N' dimethyl acetamide (DMAc)；It is uniformly molten that trifluoromethyl polyimides will be contained
In Part II DMAC N,N' dimethyl acetamide (DMAc)；Wherein, carboxyl multi-walled carbon nanotube and polyimides containing trifluoromethyl
Mass ratio be 1~3:97~99.When polyimides containing trifluoromethyl and the quality of DMAC N,N' dimethyl acetamide (DMAc) total amount
The progress of film operation is more conducive to when volume ratio is 15~15.5g/ml, when the ratio of two parts DMA is 1:
1~1.15 film effect is more preferable.
Then finely dispersed carboxyl multi-walled carbon nanotube solution is added to gathering containing trifluoromethyl by evenly mixing
In imide solution, mixed solution is continued into ultrasonic disperse until carboxyl multi-walled carbon nanotube is dispersed, ultrasound is stood after terminating
Mixed solution is poured over and has been pre-adjusted on horizontal glass plate, 40~70 DEG C of drying is kept at ambient pressure, treats major part
After DMA is removed, 80~150 DEG C are slowly warming up to, 80~150 DEG C of drying is kept under vacuo, treats completely
After removing solvent DMA, that is, obtain a kind of carboxyl multi-walled carbon nanotube content and contain fluoroform for 1~3wt%
Base polyimides/carboxyl multi-walled carbon nanotube gas separation mixed substrate membrane containing nano-grade molecular sieve.
Wherein, DMA uses as solvent, generally can also be used other solvents to replace, such as：N- methyl
Pyrrolidones (NMP), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), metacresol, pyridine, tetrahydrofuran, dichloro
Methane, acetone, chloroform etc..
The 2008 high great thesis for the doctorate of preparation method reference Jilin University of the polyimides containing trifluoromethyl in the present invention, its
Synthetic route is as follows：
Wherein, trifluoromethyl diamine monomer (DPDA) is：
Its synthetic route refers to the synthetic method of the 2008 high great thesis for the doctorate correlation polyimide monomers of Jilin University, such as
Under：
Advantage of the present invention：
Mixed substrate membrane containing nano-grade molecular sieve is prepared by the more wall carbon Guan Yuhan trifluoromethyls polyimide solution blendings of carboxyl, utilizes polar group
The interaction of group, filler require no any coupling agent treatment and just can be uniformly dispersed in matrix, moreover it is possible to have two-phase interface
There is preferable cohesive.CNT spreads more evenly across in the polymer, and two-phase interface has good bonding force, so that mixed
Mechanical property, gas permeability and the selectivity for closing matrix membrane are improved；The inventive method can overcome prior art
Existing gas permeability improves the contradiction for causing selectively to decline.
The present invention introduces trifluoromethyl respectively by being designed to the molecular structure of polyimides in emulsion stability
And rigid biphenyl structural, the former can increase the free volume of polymer molecule, and the latter makes the glass transition temperature of polymer, heat
Stability increase, and the introducing of polar group can increase the interaction with carboxyl carbon pipe.
The trifluoromethyl that the present invention introduces simultaneously makes the polymer in 1-METHYLPYRROLIDONE (NMP), N, N- dimethyl second
Acid amides (DMAc), DMF (DMF), dimethyl sulfoxide (DMSO), metacresol, pyridine, tetrahydrofuran, dichloromethane
Alkane, acetone, can soon it dissolve in these solvents of chloroform.Accordingly, it is appreciated that in the processing and manufacturing of seperation film.
Brief description of the drawings
Fig. 1 is the infrared spectrum of the polyimides containing trifluoromethyl prepared in the embodiment of the present invention 1；
Fig. 2 is Fig. 1 fingerprint region enlarged drawing；
Fig. 3 is the DSC spectrograms of sample prepared in the embodiment of the present invention 1,2,3 and 4 (in figure：A is prepared by embodiment 1
Polyimides containing trifluoromethyl, b be embodiment 2 prepare 1%CNTPI films, c be embodiment 3 prepare 2%CNTPI films, d
The 3%CNTPI films prepared for embodiment 4)；
Fig. 4 is the TGA spectrograms of sample prepared in the embodiment of the present invention 1,2,3 and 4；
Fig. 5 is the stereoscan photograph of mixed substrate membrane containing nano-grade molecular sieve prepared in the embodiment of the present invention 4.
Embodiment
Embodiment 1 (preparation and PI film preparations of the polyimides containing trifluoromethyl)
Dianhydride 2mmol 4, the benzoic anhydrides (6FDA) of 4'- (hexafluoro isopropyl) two are added in 100mL three-necked bottles, and is dissolved in
In 20mL DMAc solvents, attentive response system must keep drying, then 2mmol diamine monomers DPDA is added into 20mL
It is completely dissolved, is slowly dropped in reaction system in DMAc, added in half an hour, continues to react 24h under normal temperature mechanical agitation,
Form polyamic acid.2mL pyridines and 2.4mL acetic anhydrides are added, 60 DEG C are kept in oil bath, continues to react 4h, discharges in nothing
In water-ethanol, question response thing filters after staticly settling, and is washed 4 times with ethanol, is dried in vacuum drying oven, obtains containing fluoroform
Base polyimides (6FDA/DPDA).
1g polyimides containing trifluoromethyl (6FDA/DPDA) polymer is weighed in 20mL beakers, and is dissolved in
In 15mLDMAc, stirrer is put into, 24h is stirred on magnetic stirring apparatus, the polyimide solution being stirred is poured in advance
In the horizontal glass plate regulated, keep 60 DEG C of normal pressures to be placed in vacuum drying oven and dry 48h, after most of solvent is removed, delay
Slowly 120 DEG C are warming up to, vacuum dries 8h at 120 DEG C, removes solvent DMAc completely.Obtained film is 6FDA/DPDA polymer films,
Hereinafter referred to as PI films.
As depicted in figs. 1 and 2, in 1317cm-1There is obvious characteristic peak at place, and this is the stretching vibration peak of C-N keys, 1100
To 1200cm-1Between two strong and wide absworption peaks be present, this is the characteristic peak of trifluoromethyl.Do not occur the spy of amino in figure
Absworption peak is levied, illustrates that amino has completely reacted.DSC results of study (such as Fig. 3) show, the polyimides glass transition of preparation
Temperature is 253.6 DEG C.
Embodiment 2 (1%CNTPI films)
0.99g 6FDA/DPDA are weighed in 20mL beakers, and are dissolved in 8mL DMAc, are stirred on six agitators
24h is mixed, the Carboxylation multi-walled carbon nanotubes of 0.01g (MWNT) are weighed in 10mL beakers and are dissolved in 7mL DMAc, it is thin with ultrasound
Born of the same parents pulverizer ultrasound 6h, then by finely dispersed carboxylic acid multi-walled carbon nano-tube solution be added to 24h agitated it is poly-
In imide solution, mixed solution is continued into ultrasonic 2h, mixed solution is poured over and has been pre-adjusted water by ultrasound immediately after terminating
On flat glass plate, 60 DEG C of drying 48h are kept at ambient pressure, after most of solvent is removed, are slowly warming up to 120 DEG C,
120 DEG C of baking 8h are kept under vacuum, remove solvent DMAc completely.Obtained mixed substrate membrane containing nano-grade molecular sieve, it is named as 1%CNTPI films.
DSC results of study (such as Fig. 3) show, the composite polyimide material 1%CNTPI of preparation glass transition temperature
For 265.4 DEG C.
Embodiment 3 (2%CNTPI films)
0.98g 6FDA/DPDA are weighed in 20mL beakers, and are dissolved in 8mL DMAc, are stirred on six agitators
24h is mixed, the Carboxylation MWNT of 0.02g are weighed in 10mL beakers and are dissolved in 7mL DMAc, with ultrasonic cell disrupte machine ultrasound 6h,
Then, will in the polyimide solution for being added to 24h agitated by finely dispersed carboxylic acid multi-walled carbon nano-tube solution
Mixed solution continues ultrasonic 2h, and mixed solution is poured over and has been pre-adjusted on horizontal glass plate by ultrasound immediately after terminating,
60 DEG C of drying 48h are kept under normal pressure, after most of solvent is removed, 120 DEG C is slowly warming up to, keeps 120 DEG C under vacuo
8h is dried, removes solvent DMAc completely.Obtained mixed substrate membrane containing nano-grade molecular sieve, it is named as 2%CNTPI films.
DSC results of study (such as Fig. 3) show, the composite polyimide material 2%CNTPI of preparation glass transition temperature
For 265.8 DEG C.
Embodiment 4 (3%CNTPI films)
0.97g 6FDA/DPDA are weighed in 20mL beakers, and are dissolved in 8mL DMAc, are stirred on six agitators
24h is mixed, the Carboxylation MWNT of 0.03g are weighed in 10mL beakers and are dissolved in 7mL DMAc, with ultrasonic cell disrupte machine ultrasound 6h,
Then, will in the polyimide solution for being added to 24h agitated by finely dispersed carboxylic acid multi-walled carbon nano-tube solution
Mixed solution continues ultrasonic 2h, and mixed solution is poured over and has been pre-adjusted on horizontal glass plate by ultrasound immediately after terminating,
60 DEG C of drying 48h are kept under normal pressure, after most of solvent is removed, 120 DEG C is slowly warming up to, keeps 120 DEG C under vacuo
8h is dried, removes solvent DMAc completely.Obtained mixed substrate membrane containing nano-grade molecular sieve, it is named as 3%CNTPI films.
DSC results of study (such as Fig. 3) show, the composite polyimide material 3%CNTPI of preparation glass transition temperature
For 266.1 DEG C.As shown in figure 4, the heat endurance of mixed substrate membrane containing nano-grade molecular sieve slightly improves.CNT is in base as can see from Figure 5
It is dispersed in body, agglomeration is not observed.
Effect detection：
Test 1 (measuring mechanical property)
Specific method of testing is as follows：Using the AG-1 universal tensile machines of Shimadzu, Japan's production come test polymer
The mechanical property of film.Sample film is made into 50mm length, batten wide 5mm, and stretching-machine load is adjusted to 10kN, and draw speed is
20mm/min.Every kind of 10~12 battens of sample film preparation, at least five groups of panel datas are taken to calculate average value.Polymer draftability
Energy test result is as shown in table 1, and compared with polymer film, the Young's modulus and tensile strength of composite membrane, elongation at break obtain
Increase to raising, and as CNT adds the increase of content.
Table 1
Test 2 (gas separation test)
According to document《Novel copolymerized acid imide film for gas separation》(J.Membrane Sci.2007,305,338-
346) method described in carries out gas separation test to preparation-obtained gas separation membrane B, CB2 and B-CNT2, and its gas oozes
Saturating coefficient and selection coefficient are respectively as shown in table 2 and table 3.It can be found that after adding carbon pipe, gas permeability coefficient substantially increases, together
When to He/N2、CO2/N2、O2/N2And He/O2Gas also increases selection coefficient to some extent.
Table 2
1Barrer=1 × 10-10cm3(STP)cm/(cm2·s·cmHg)
Table 3
Gas permeability coefficient P is calculated by below equation in table 3：
Wherein, A is the surface area (cm of film2), L is thickness (cm), and p is upstream gas pressure (cmHg), and V is per-meate side gas
Building volume (cm3), R is gas constant (6236.56cm3.cm.Hg/mol.K), T is absolute temperature (K), and dp/dt is upstream plenum
The rate of change of the pressure of middle gas over time.
And A gases are defined as to the separation of B gases：
Using DMA as solvent in the embodiment of the present invention, its role is to dissolve 6FDA/DPDA
Disperse with by carboxyl multi-walled carbon nanotube, therefore its use ratio is not limited to above-described embodiment, and two parts N, N- dimethyl
The ratio of acetamide is 1:Preferably film effect can be obtained when 1~1.15.
Claims (8)
- A kind of 1. polyimides containing trifluoromethyl/carboxyl multi-walled carbon nanotube gas separation mixed substrate membrane containing nano-grade molecular sieve, it is characterised in that：Base Matter is trifluoromethyl polyimides, and carboxyl multi-walled carbon nanotube is filler；Wherein carboxyl multi-walled carbon nanotube content be 1~ 3wt%,The molecular formula of described trifluoromethyl polyimides is：N=90~150.
- 2. polyimides containing trifluoromethyl according to claim 1/carboxyl multi-walled carbon nanotube gas separation mixed-matrix Film, it is characterised in that：Carboxyl multi-walled carbon nanotube content is 1wt%.
- 3. polyimides containing trifluoromethyl according to claim 1/carboxyl multi-walled carbon nanotube gas separation mixed-matrix Film, it is characterised in that：Carboxyl multi-walled carbon nanotube content is 2wt%.
- 4. polyimides containing trifluoromethyl according to claim 1/carboxyl multi-walled carbon nanotube gas separation mixed-matrix Film, it is characterised in that：Carboxyl multi-walled carbon nanotube content is 3wt%.
- A kind of 5. polyimides containing trifluoromethyl/carboxyl multi-walled carbon nanotube gas separation mixed-matrix described in claim 1 The preparation method of film is as follows：Take a certain amount of solvent and be classified as two parts, it is ultrasonic after carboxyl multi-walled carbon nanotube is mixed in Part I solvent It is extremely dispersed；Trifluoromethyl polyimides will be contained uniformly to be dissolved in Part II solvent；Wherein, carboxyl multi-walled carbon nanotube and The mass ratio of the polyimides containing trifluoromethyl is 1~3:97~99；Then it is sub- finely dispersed carboxyl multi-walled carbon nanotube solution to be added to polyamides containing trifluoromethyl by evenly mixing In amine aqueous solution, mixed solution is continued into ultrasonic disperse until carboxyl multi-walled carbon nanotube is dispersed, ultrasound immediately will after terminating Mixed solution is poured on horizontal glass plate, keeps 40~70 DEG C of drying, after most of solvent is removed, delay at ambient pressure Slowly 80~150 DEG C are warming up to, keep 80~150 DEG C of drying under vacuo, after solvent is removed completely, that is, obtain described containing trifluoro Methyl polyimides/carboxyl multi-walled carbon nanotube gas separation mixed substrate membrane containing nano-grade molecular sieve.
- 6. polyimides containing trifluoromethyl according to claim 5/carboxyl multi-walled carbon nanotube gas separation mixed-matrix The preparation method of film, it is characterised in that the solvent is DMA.
- 7. polyimides containing trifluoromethyl according to claim 5/carboxyl multi-walled carbon nanotube gas separation mixed-matrix The preparation method of film, it is characterised in that the ratio of Part I solvent and Part II solvent is 1:1~1.15.
- 8. polyimides containing trifluoromethyl according to claim 6/carboxyl multi-walled carbon nanotube gas separation mixed-matrix The preparation method of film, it is characterised in that polyimides containing trifluoromethyl and the mass volume ratio of DMA total amount For 15~15.5g/ml.
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| CN107158972B (en) * | 2017-05-10 | 2019-07-23 | 浙江工商大学 | A kind of Nano carbon balls-polyimides binary gas separation mixed substrate membrane containing nano-grade molecular sieve and preparation method thereof |
| CN107162922B (en) * | 2017-05-24 | 2020-04-21 | 吉林大学 | Allyl-containing polyimide diamine monomer, polyimide polymer thereof and preparation method |
| CN108993176A (en) * | 2018-07-31 | 2018-12-14 | 天津工业大学 | Block polyetheramides-amination graphene oxide hydridization film preparation and its application |
| CN109053474B (en) * | 2018-08-06 | 2020-03-31 | 吉林大学 | Flexible diamine monomer, preparation method thereof and application thereof in preparation of polyimide |
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