CN105344258A - Trifluoromethyl group-containing polyimide/carboxyl multi-walled carbon nanotube mixed matrix membrane for gas separation, and preparation method thereof - Google Patents
Trifluoromethyl group-containing polyimide/carboxyl multi-walled carbon nanotube mixed matrix membrane for gas separation, and preparation method thereof Download PDFInfo
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- CN105344258A CN105344258A CN201510726253.1A CN201510726253A CN105344258A CN 105344258 A CN105344258 A CN 105344258A CN 201510726253 A CN201510726253 A CN 201510726253A CN 105344258 A CN105344258 A CN 105344258A
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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 trifluoromethyl group-containing polyimide/carboxyl multi-walled carbon nanotube mixed matrix membrane for gas separation, and a preparation method thereof, and belongs to the field of polymer nano-composite materials. A problem to be solved in the invention is unable consideration of present gas separation membranes to the permeability and the separation performance of gases. In the invention, trifluoromethyl group-containing polyimide is added to carboxyl multi-walled carbon nanotubes to form the mixed matrix membrane, interaction of polar groups in the trifluoromethyl group-containing polyimide and in the carboxyl multi-walled carbon nanotubes allows the carbon nanotubes to be uniformly dispersed in the mixed matrix membrane and a two-phase interface to have very good adhesion force, so the gas permeability and the selectivity of the mixed matrix membrane are improved. The mixed matrix membrane is used for preparing gas separation membranes and separating gases.
Description
Technical field
The invention belongs to the technical field of polymer nanocomposites, be specifically related to a kind of polymer carbon nano tube composite membrane and its production and use.
Background technology
In recent years, the demand of people to polymeric material of gas separation membrane for gas pair is increasing, requires also more and more higher, and it is more stable how to prepare separation process, and longer service life, the separation membrane that separative efficiency is higher is the emphasis that researcher pays close attention to.Because polyimides has excellent combination property and the designability of molecule, thus polyimides has important application in all trades and professions.Polyimides is owing to there being nitrogenous aromatic heterocycle structure, thus there is higher permeability and selective, also there is mechanical strength high, Heat stability is good simultaneously, solvent resistance is strong and can be made into the features such as high-throughout self-supported membrane, is the gas separation membrane material that a kind of combination property is very excellent.
In the polyimide polymer that kind is numerous, fluorinated polyimide has become the focus of polyimide material research with the character of its uniqueness, wherein excellent containing the 6FDA i.e. polyimides performance of 4,4'-(hexafluoro isopropyl) hexichol acid anhydride structure.Fluorine element in 6FDA polyimides all exists with C-F key form, and because fluorine atom has larger electronegativity, fluoro-containing group has very strong electron-withdrawing power, causes C-F key very strong, can improve the thermo oxidative stability of polymer to a certain extent.Due to the existence of fluoroform group in molecular structure, so polymer degree of crystallinity reduce, dielectric constant and refractive index also reduce, and due to electronic polarization degree low, fluorine material is made to have low cohesive energy and surface free energy, there is certain hydrophobicity, in addition, because trifluoromethyl belongs to the flexible side group of large volume, the bulk density of polymer can be reduced, increase the free volume of material, thus reach the permeance property increasing material, thus there is in gas separaion huge application potential.
Because the polymeric membrane of polyimide has plurality of advantages in gas separaion, as being easy to processing, designability, excellent separating property etc., has been widely used in industry.But polymeric membrane for separation also also exists some shortcomings, as not solvent resistant, non-refractory etc.And inoranic membrane to have unique physics, chemical property and have good permeability and selective relating in high temperature, Korrosionsmedium etc., but manufacturing cost is more much higher than polymeric membrane.Therefore people improve by inorganic particulate is incorporated into polymeric membrane, obtain mixed substrate membrane containing nano-grade molecular sieve (MMM film).This membrane material take organic polymer as continuous phase, and inorganic particulate is decentralized photo, is a kind of well trial.In mixed substrate membrane containing nano-grade molecular sieve, homodisperse inorganic particulate enhances mechanical performance and the gas selective penetrated property of polymer, also has the advantage of polymer film simultaneously, has become the new focus of gas separation membrane research field in recent years.
At present, along with the progress of science and technology, the development of gas separation membrane faces two stern challenges: the first improves the gas permeability of film and selective in larger degree, and it two is that gas separation membrane still can have good gas separaion ability under the environment that HTHP etc. is harsh.
Since utilizing transmission electron microscope to find CNT from Japanese professor Iijima in 1991, the application of CNT and modification have caused and have paid close attention to widely.CNT has excellent mechanics, electricity and chemical property, becomes rapidly the study hotspot of chemistry, physics and material science.CNT has one-dimentional structure and minimum caliber, have well selective to gas, and due to the pore passage structure that CNT inwall is smooth, the transfer rate of gas in CNT, much larger than the transfer rate in same apertures molecular screen membrane, is thus considered to there is potential application in gas separaion.The people such as Kim deliver result of study on J.MembraneSci.294 (2007) 147-158, he is first by carboxylation SWCN and octadecylamine (ODA) acid-base reaction, then be doped into polysulfones (PSF) matrix and made mixed substrate membrane containing nano-grade molecular sieve, gas permeability coefficient increases, but selective all have than PS membrane reduce in various degree.The people such as S.A.Hashemifard deliver result of study on J.ColloidInterf.Sci.359 (2011) 359-370, halloysite nanotubes (similar CNT) is doped into PEI (PEI) matrix makes mixed substrate membrane containing nano-grade molecular sieve through coupling agent N-β-(aminoethyl)-γ-propyl silane (AEAPTMS) process by researcher, gas permeability coefficient increases, although but carry out processing attempting the alternate interaction of increase by two to filler, no matter change processing method, the experiment conditions such as the consumption of coupling agent and amount of filler, selective all have than pure polyetherimde films reduce in various degree.So mixed substrate membrane containing nano-grade molecular sieve problems faced is the while of how improving diffusion barrier gas permeability, the selective of gas also can be improved.
Summary of the invention
Cause selective all than the problem that pure polyetherimde films reduces after use filler to solve prior art, the invention provides a kind of containing trifluoromethyl polyimides/carboxyl multi-walled carbon nano-tubes gas separaion mixed substrate membrane containing nano-grade molecular sieve, matrix is for containing trifluoromethyl polyimides, and carboxyl multi-walled carbon nano-tubes is filler; Wherein carboxyl multi-walled carbon nano-tubes content is 1 ~ 3wt%,
The described molecular formula containing trifluoromethyl polyimides is:
n＝90～150。
Preparation method containing trifluoromethyl polyimides/carboxyl multi-walled carbon nano-tubes gas separaion mixed substrate membrane containing nano-grade molecular sieve is as follows:
Get a certain amount of DMA (DMAc) and be divided into two parts, carboxyl multi-walled carbon nano-tubes is ultrasonic to dispersed after mixing in Part I DMA (DMAc); Evenly will be dissolved in Part II DMA (DMAc) containing trifluoromethyl polyimides; Wherein, carboxyl multi-walled carbon nano-tubes and the mass ratio containing trifluoromethyl polyimides are 1 ~ 3:97 ~ 99.When containing trifluoromethyl polyimides and N, the mass volume ratio of N-dimethylacetylamide (DMAc) total amount is more conducive to the carrying out of masking operation when being 15 ~ 15.5g/ml, when the ratio of two parts DMA is 1:1 ~ 1.15 masking better effects if.
Then finely dispersed carboxyl multi-walled carbon nano-tubes solution is joined mixed containing in trifluoromethyl polyimide solution, mixed solution is continued ultrasonic disperse until carboxyl multi-walled carbon nano-tubes is dispersed, being poured over by mixed solution immediately after ultrasonic end regulates on the glass plate of level in advance, keep 40 ~ 70 DEG C of oven dry at ambient pressure, treat most of N, after N-dimethylacetylamide is removed, slowly be warmed up to 80 ~ 150 DEG C, keep 80 ~ 150 DEG C of oven dry under vacuo, treat completely except desolventizing N, after N-dimethylacetylamide, namely obtain a kind of carboxyl multi-walled carbon nano-tubes content be 1 ~ 3wt% containing trifluoromethyl polyimides/carboxyl multi-walled carbon nano-tubes gas separaion mixed substrate membrane containing nano-grade molecular sieve.
Wherein, N, N-dimethylacetylamide uses as solvent, usually other solvents also can be used to replace, as: 1-METHYLPYRROLIDONE (NMP), DMF (DMF), methyl-sulfoxide (DMSO), metacresol, pyridine, oxolane, carrene, acetone, chloroform etc.
Containing the preparation method reference Jilin University high great thesis for the doctorate in 2008 of trifluoromethyl polyimides in the present invention, its synthetic route is as follows:
Wherein, trifluoromethyl diamine monomer (DPDA) is:
Its synthetic route is correlated with reference to Jilin University's high great thesis for the doctorate in 2008 synthetic method of polyimide monomers, as follows:
Advantage of the present invention:
Prepare mixed substrate membrane containing nano-grade molecular sieve by carboxyl many walls carbon Guan Yuhan trifluoromethyl polyimide solution is blended, utilize the interaction of polar group, filler requires no any coupling agent treatment and just can be uniformly dispersed in matrix, and two-phase interface can also be made to have better cohesive.CNT more uniformly disperses in the polymer, and two-phase interface has good bonding force, thus makes the mechanical property of mixed substrate membrane containing nano-grade molecular sieve, gas permeability and to be selectively all improved; The gas permeability that the inventive method can overcome prior art existence improves the contradiction causing selective decline.
The present invention is by designing the molecular structure of polyimides, trifluoromethyl and rigidity biphenyl structural is introduced respectively in emulsion stability, the former can make the free volume of polymer molecule increase, the latter makes the vitrification point of polymer, heat endurance increases, and the introducing of polar group can increase the interaction with carboxyl carbon pipe.
The trifluoromethyl that the present invention introduces simultaneously makes this polymer at 1-METHYLPYRROLIDONE (NMP), DMA (DMAc), N, dinethylformamide (DMF), methyl-sulfoxide (DMSO), metacresol, pyridine, oxolane, carrene, acetone, can dissolve in these solvents of chloroform soon.Therefore, the processing and manufacturing of diffusion barrier is very beneficial for.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum containing trifluoromethyl polyimides prepared in the embodiment of the present invention 1;
Fig. 2 is the fingerprint region enlarged drawing of Fig. 1;
Fig. 3 is the DSC spectrogram (in figure: what a was prepared by embodiment 1 is 3%CNTPI film prepared by embodiment 4 containing trifluoromethyl polyimides, b to be 1%CNTPI film, c prepared by embodiment 2 be 2%CNTPI film prepared by embodiment 3, d) of sample prepared in the embodiment of the present invention 1,2,3 and 4;
Fig. 4 is the TGA spectrogram 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.
Detailed description of the invention
Embodiment 1 (preparation and PI film preparation containing trifluoromethyl polyimides)
Dianhydride 2mmol4 is added in 100mL three-necked bottle, 4'-(hexafluoro isopropyl) two benzoic anhydride (6FDA), and be dissolved in 20mLDMAc solvent, attentive response system must keep dry, again 2mmol diamine monomer DPDA is joined in 20mLDMAc and dissolve completely, be slowly added drop-wise in reaction system, add in half an hour, under normal temperature mechanical agitation, continue reaction 24h, form polyamic acid.Add 2mL pyridine and 2.4mL acetic anhydride again, in oil bath, keep 60 DEG C, continue reaction 4h, discharging is in absolute ethyl alcohol, and question response thing staticly settles rear filtration, and washs 4 times with ethanol, dry in vacuum drying oven, obtain containing trifluoromethyl polyimides (6FDA/DPDA).
Take 1g and contain trifluoromethyl polyimides (6FDA/DPDA) polymer in 20mL beaker, and be dissolved in 15mLDMAc, put into stirrer, magnetic stirring apparatus stirs 24h, the polyimide solution be stirred is poured on the horizontal glass plate regulated in advance, keep 60 DEG C of normal pressures to be placed in vacuum drying oven and dry 48h, after most of solvent is removed, slowly be warmed up to 120 DEG C, at 120 DEG C, vacuum dries 8h, completely except desolventizing DMAc.The film obtained is 6FDA/DPDA polymer film, hereinafter referred to as PI film.
As depicted in figs. 1 and 2, at 1317cm
-1there is obvious characteristic peak at place, and this is the stretching vibration peak of C-N key, 1100 to 1200cm
-1between there are two strong and wide absworption peaks, this is the characteristic peak of trifluoromethyl.There is not amino characteristic absorption peak in figure, amino complete reaction is described.DSC result of study (as Fig. 3) shows, the polyimides glass transition temperature of preparation is 253.6 DEG C.
Embodiment 2 (1%CNTPI film)
Take 0.99g6FDA/DPDA in 20mL beaker, and be dissolved in 8mLDMAc, six agitators stir 24h, in 10mL beaker, take the Carboxylation multi-walled carbon nano-tubes of 0.01g (MWNT) is dissolved in 7mLDMAc, with the ultrasonic 6h of ultrasonic cell disrupte machine, then finely dispersed Carboxylation multi-walled carbon nano-tubes solution is joined in the polyimide solution having stirred 24h, mixed solution is continued ultrasonic 2h, being poured over by mixed solution immediately after ultrasonic end regulates on the glass plate of level in advance, keep 60 DEG C at ambient pressure and dry 48h, after most of solvent is removed, slowly be warmed up to 120 DEG C, keep 120 DEG C under vacuo and dry 8h, completely except desolventizing DMAc.The mixed substrate membrane containing nano-grade molecular sieve obtained, called after 1%CNTPI film.
DSC result of study (as Fig. 3) shows, the glass transition temperature of the composite polyimide material 1%CNTPI of preparation is 265.4 DEG C.
Embodiment 3 (2%CNTPI film)
Take 0.98g6FDA/DPDA in 20mL beaker, and be dissolved in 8mLDMAc, six agitators stir 24h, in 10mL beaker, take the Carboxylation MWNT of 0.02g is dissolved in 7mLDMAc, with the ultrasonic 6h of ultrasonic cell disrupte machine, then finely dispersed Carboxylation multi-walled carbon nano-tubes solution is joined in the polyimide solution having stirred 24h, mixed solution is continued ultrasonic 2h, being poured over by mixed solution immediately after ultrasonic end regulates on the glass plate of level in advance, keep 60 DEG C at ambient pressure and dry 48h, after most of solvent is removed, slowly be warmed up to 120 DEG C, keep 120 DEG C under vacuo and dry 8h, completely except desolventizing DMAc.The mixed substrate membrane containing nano-grade molecular sieve obtained, called after 2%CNTPI film.
DSC result of study (as Fig. 3) shows, the glass transition temperature of the composite polyimide material 2%CNTPI of preparation is 265.8 DEG C.
Embodiment 4 (3%CNTPI film)
Take 0.97g6FDA/DPDA in 20mL beaker, and be dissolved in 8mLDMAc, six agitators stir 24h, in 10mL beaker, take the Carboxylation MWNT of 0.03g is dissolved in 7mLDMAc, with the ultrasonic 6h of ultrasonic cell disrupte machine, then finely dispersed Carboxylation multi-walled carbon nano-tubes solution is joined in the polyimide solution having stirred 24h, mixed solution is continued ultrasonic 2h, being poured over by mixed solution immediately after ultrasonic end regulates on the glass plate of level in advance, keep 60 DEG C at ambient pressure and dry 48h, after most of solvent is removed, slowly be warmed up to 120 DEG C, keep 120 DEG C under vacuo and dry 8h, completely except desolventizing DMAc.The mixed substrate membrane containing nano-grade molecular sieve obtained, called after 3%CNTPI film.
DSC result of study (as Fig. 3) shows, the glass transition temperature of the composite polyimide material 3%CNTPI of preparation is 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 dispersed in the base as can see from Figure 5, does not observe agglomeration.
Effect detection:
Test 1 (measuring mechanical property)
Concrete method of testing is as follows: the AG-1 universal tensile machine adopting Shimadzu, Japan to produce carrys out the mechanical property of test polymer film.It is long that sample film is made into 50mm, and the batten that 5mm is wide, stretching-machine load is adjusted to 10kN, and draw speed is 20mm/min.Often kind of sample film prepares 10 ~ 12 battens, is taken to few five groups of panel data calculating mean values.Polymer tensile property test result is as shown in table 1, and compared with polymer film, the Young's modulus of composite membrane and hot strength, elongation at break are all improved, and add the increase of content along with CNT and increase.
Table 1
Test 2 (gas separaion tests)
According to document " the novel copolymerized acid imide film for gas separaion " (J.MembraneSci.2007,305, method 338-346) carries out gas separaion test to preparation-obtained gas separation membrane B, CB2 and B-CNT2, and its gas permeability coefficient and choosing coefficient are respectively as shown in table 2 and table 3.After can finding to add carbon pipe, gas permeability coefficient obviously increases, simultaneously to He/N
2, CO
2/ N
2, O
2/ N
2and He/O
2gas also increases to some extent to choosing coefficient.
Table 2
1Barrer＝1×10
-10cm
3(STP)cm/(cm
2·s·cmHg)
Table 3
In table 3, gas permeability coefficient P is by following formulae discovery:
Wherein, A is the surface area (cm of film
2), L is thickness (cm), p be upstream gas pressure (cmHg), V is per-meate side chamber volume (cm
3), R is gas constant (6236.56cm
3.cm.Hg/mol.K), the rate of change of pressure along with the time of T to be absolute temperature (K), dp/dt be gas in the air chamber of upstream.
And the separation of A gas to B gas is defined as:
N is adopted in the embodiment of the present invention, N-dimethylacetylamide is as solvent, its role is to 6FDA/DPDA be dissolved and carboxyl multi-walled carbon nano-tubes is disperseed, therefore its usage ratio is not limited to above-described embodiment, and the ratio of two parts DMA can obtain better masking effect when 1:1 ~ 1.15.
Claims (8)
1., containing trifluoromethyl polyimides/carboxyl multi-walled carbon nano-tubes gas separaion mixed substrate membrane containing nano-grade molecular sieve, it is characterized in that: matrix is trifluoromethyl polyimides, carboxyl multi-walled carbon nano-tubes is filler; Wherein carboxyl multi-walled carbon nano-tubes content is 1 ~ 3wt%,
The molecular formula of described trifluoromethyl polyimides is:
n＝90～150。
2. according to claim 1 containing trifluoromethyl polyimides/carboxyl multi-walled carbon nano-tubes gas separaion mixed substrate membrane containing nano-grade molecular sieve, it is characterized in that: carboxyl multi-walled carbon nano-tubes content is 1wt%.
3. according to claim 1 containing trifluoromethyl polyimides/carboxyl multi-walled carbon nano-tubes gas separaion mixed substrate membrane containing nano-grade molecular sieve, it is characterized in that: carboxyl multi-walled carbon nano-tubes content is 2wt%.
4. according to claim 1 containing trifluoromethyl polyimides/carboxyl multi-walled carbon nano-tubes gas separaion mixed substrate membrane containing nano-grade molecular sieve, it is characterized in that: carboxyl multi-walled carbon nano-tubes content is 3wt%.
5. the preparation method containing trifluoromethyl polyimides/carboxyl multi-walled carbon nano-tubes gas separaion mixed substrate membrane containing nano-grade molecular sieve according to claim 1 is as follows:
Get a certain amount of solvent and be divided into two parts, ultrasonic to dispersed after carboxyl multi-walled carbon nano-tubes is mixed in Part I solvent; Evenly will be dissolved in Part II solvent containing trifluoromethyl polyimides; Wherein, carboxyl multi-walled carbon nano-tubes and the mass ratio containing trifluoromethyl polyimides are 1 ~ 3:97 ~ 99;
Then finely dispersed carboxyl multi-walled carbon nano-tubes solution is joined mixed containing in trifluoromethyl polyimide solution, mixed solution is continued ultrasonic disperse until carboxyl multi-walled carbon nano-tubes is dispersed, immediately mixed solution is poured on the glass plate of level after ultrasonic end, keep 40 ~ 70 DEG C of oven dry at ambient pressure, after most of solvent is removed, slowly be warmed up to 80 ~ 150 DEG C, keep 80 ~ 150 DEG C of oven dry under vacuo, after completely except desolventizing, namely obtain described containing trifluoromethyl polyimides/carboxyl multi-walled carbon nano-tubes gas separaion mixed substrate membrane containing nano-grade molecular sieve.
6. the preparation method containing trifluoromethyl polyimides/carboxyl multi-walled carbon nano-tubes gas separaion mixed substrate membrane containing nano-grade molecular sieve according to claim 5, it is characterized in that, described solvent is DMA.
7. the preparation method containing trifluoromethyl polyimides/carboxyl multi-walled carbon nano-tubes gas separaion mixed substrate membrane containing nano-grade molecular sieve according to claim 5, it is characterized in that, the ratio of Part I solvent and Part II solvent is 1:1 ~ 1.15.
8. the preparation method containing trifluoromethyl polyimides/carboxyl multi-walled carbon nano-tubes gas separaion mixed substrate membrane containing nano-grade molecular sieve according to claim 6, it is characterized in that, mass volume ratio containing trifluoromethyl polyimides and DMA total amount is 15 ~ 15.5g/ml.
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| CN106008974B (en) * | 2016-06-02 | 2018-04-24 | 黑龙江科技大学 | A kind of preparation method of high hydrophobic fluorinated carbon nano-tube/polyimide composite material |
| CN107158972A (en) * | 2017-05-10 | 2017-09-15 | 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 |
| 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 |
| CN107162922A (en) * | 2017-05-24 | 2017-09-15 | 吉林大学 | A kind of diamine monomer of polyimides containing pi-allyl and its polyimide polymer and preparation method |
| 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 |
| CN108976135A (en) * | 2018-08-06 | 2018-12-11 | 吉林大学 | A kind of flexibility diamine monomer and preparation method thereof and preparing the application in polyimides |
| CN109053474A (en) * | 2018-08-06 | 2018-12-21 | 吉林大学 | A kind of flexibility diamine monomer and preparation method thereof and preparing the application in polyimides |
| CN109053470A (en) * | 2018-08-06 | 2018-12-21 | 吉林大学 | A kind of flexibility diamine monomer and preparation method thereof and preparing the application in polyimides |
| CN109053470B (en) * | 2018-08-06 | 2020-03-31 | 吉林大学 | Flexible diamine monomer, preparation method thereof and application thereof in preparation of polyimide |
| 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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