CN106279685A - Polyimide material, its preparation method and application of based on Teller lattice alkali structure - Google Patents
Polyimide material, its preparation method and application of based on Teller lattice alkali structure Download PDFInfo
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Abstract
The invention discloses a kind of polyimide material based on Teller lattice alkali structure and preparation method thereof.In one embodiment, described preparation method may include that and Teller lattice alkali diamine monomer and aromatic acid dianhydride monomer is dissolved in high boiling point intensive polar solvent and mix homogeneously, make both form target product in the pyroreaction with the presence of catalyst again, and by the way of toluene azeotropic anhydrates, promote that reaction is carried out in course of reaction.The polyimide material that the present invention provides has the features such as high gas permeation rate, high gas-selectively, solvent processability and filming performance be outstanding, and the membrane material being such as made up of such polyimide material is for H2/N2、H2/CH4、CO2/CH4Deng gas pair separating property already close to or surmount 2008 update the Robeson upper limit; at industrial gases separation field; such as have wide application prospects in the industries such as High Purity Hydrogen manufacture, synthetic ammonia tailgas recovery, purification of natural gas; and its preparation technology is the most controlled; reproducible, be suitable to large-scale industrial and produce.
Description
Technical field
The present invention relates to a kind of polyimide macromolecular material and preparation method thereof, particularly to a class based on Teller lattice alkali structure
Polyimide material, its preparation method and application, such as the application of gas separation material.
Background technology
Gas separation is at the purification (H of such as hydrogen2/N2,H2/CH4), the separation (O of air2/N2), catching of carbon dioxide
Obtain and separate (CO2/CH4,CO2/N2) etc. field have important and be widely applied.Polymeric film gas separation is due to it
Efficiently mental retardation and be prone to the features such as processing, becomes the focus of gas separation field research in recent years.Traditional polymer gas divides
From material mainly by cellulose acetate, polyether sulfone, polyimides etc., but all there are some defects in it, with tradition polyimide
As a example by material, though its high selectivity, due to its relatively low transmission, increasingly commercial production can not be met growing
Demand.
Summary of the invention
For the deficiencies in the prior art, present invention is primarily targeted at a kind of polyimides material based on Teller lattice alkali structure of offer
Material, its preparation method and application.
For realizing aforementioned invention purpose, a case study on implementation of the present invention provides a kind of polyimides based on Teller lattice alkali structure
Material, it has a structure shown in formula I:
Wherein, n=100-500, M (i.e. Teller lattice base groups) at least any one in group as follows:
R is at least selected from-CH3, OH and Br, Ar derive from compound shown in lower formula II:
At least any one in following compound of compound shown in this formula II:
The most following common dianhydride monomer:
Or, following kink rigidity dianhydride monomer (SBI):
Further, M derives from NH2-M-NH2(diamine monomer), this diamine monomer at least has in structure as shown below
Any one:
R is at least selected from-CH3, OH and Br.
One case study on implementation of the present invention provides a kind of method preparing described polyimide material based on Teller lattice alkali structure,
Comprising: Teller lattice alkali diamine monomer is reacted, by one with aromatic acid dianhydride monomer initial ring aminimide under the conditions of selected
Step is reacted and is formed described polyimide material.
As more one of preferred embodiment, described preparation method may include that Teller lattice alkali diamine monomer and aromatic acid
Dianhydride monomer is dissolved in high boiling point intensive polar solvent and mix homogeneously, and makes these two kinds of reactants with the presence of catalyst and temperature be
React under conditions of 160～230 DEG C, form described polyimide material.
As more one of preferred embodiment, described preparation method may include that at room temperature by Teller lattice alkali diamidogen
Monomer is dissolved in high boiling point intensive polar solvent, then is dividedly in some parts aromatic acid dianhydride monomer, mix homogeneously formed total solid content be 0.4～
The reaction system of 0.8mol/L, is then heated to 160～230 DEG C and is incubated 5～10h, it is thus achieved that described polyimide material.
Further, described preparation method may also include that in course of reaction, reaction is produced by the way of toluene azeotropic anhydrates
Raw moisture removal, thus promote that reaction is carried out.
Wherein, described Teller lattice alkali diamine monomer can be about 1:1 with the mol ratio of aromatic acid dianhydride monomer.
Further, described preparation method may also include that
A, after completion of the reaction, is dissolved in reaction product mixture selected solvent, adds alcohol medium precipitation afterwards；
B, the operation of repetition step a, it is thus achieved that the product after purification.
Further, described selected solvent the most certainly but is not limited to chloroform.
Further, described alcohol medium is selected from but is not limited to methanol, ethanol etc..
Further, described catalyst the most certainly but is not limited to quinoline.
Further, described high boiling point intensive polar solvent the most certainly but is not limited to N-Methyl pyrrolidone, metacresol etc..
One embodiment of the invention additionally provides described polyimide material answering in the Selective Separation of mixed gas system
With, described mixed gas system include by oxygen, nitrogen, carbon dioxide, methane, hydrogen arbitrarily both or both more than
Any one in the mixed gas system formed, preferably is selected from hydrogen/methane, hydrogen/nitrogen, carbon dioxide/methane gas pair.
Additionally providing a kind of gas separation material in one embodiment of the invention, it comprises described based on Teller lattice alkali structure poly-
Acid imide material.
Additionally providing a kind of gas separation membrane in one embodiment of the invention, it is mainly made up of described polyimide material.
One embodiment of the invention additionally provides a kind of method preparing described gas separation membrane, comprising:
Take described polyimide material to be dissolved in selected organic solvent, formed uniform and bubble-free, concentration be 2wt%～
The film forming solution of 10wt%；
Film forming solution is carried out film forming process, forms thin film,
And, described thin film is soaked in alcohol medium 10h～24h, is vacuum dried more than 24h in 70 DEG C～120 DEG C afterwards.
Further, described selected organic solvent includes chloroform, but is not limited to this.
Further, described alcohol medium is at least selected from methanol and ethanol, but is not limited to this.
Additionally providing a kind of gas separation membrane in one embodiment of the invention, it comprises described gas separation membrane or described polyamides is sub-
Amine material.
Compared with prior art, the invention have the advantages that
(1) such polyimide material based on Teller lattice alkali structure provided have high gas permeation rate, high gas-selectively,
The features such as solvent processability and filming performance are outstanding, particularly have the most excellent gas separating property, such as, by this
The polymeric film material that quasi-polyimide material is made is for gases pair such as hydrogen/nitrogen, hydrogen/methane, carbon dioxide/methane
Separating property already close to or surmounted 2008 update the Robeson upper limit, at industrial gases separation field, such as at height
The industries such as pure hydrogen manufacture, synthetic ammonia tailgas recovery, purification of natural gas have wide application prospects；
(2) such polyimide material preparation technology provided is the most controlled, reproducible, is suitable to large-scale industrial and produces.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart of a kind of polyimide material among the present invention one typical embodiments；
Fig. 2 is the structural representation of a kind of gas separation membrane based on polyimide material in one embodiment of the invention；
Fig. 3 be the classical macromolecular material of obtained typical sample and document report in embodiment of the present invention 1-10 (Adv.Mater.2008,
20,2766.；Macromolecules 2009,42,7881.；Polym.Chem.2013,4,3813.；Macromol.Rapid
Commun.2011,32,579.；Macromolecules 2012,45,3841.；Macromolecules,2013,46,9618.；J.
Membr.Sci.2005,251,263.) gas separation membrane gas permeability-Selective Separation combination property comparison 1991,2008
Robeson upper limit figure.
Detailed description of the invention
One aspect of the present invention provides class polyimide material based on Teller lattice alkali stereoeffect and (is also regarded as
One class intrinsic microporous polyamide imines material), this analog copolymer is mainly by the diamine monomer containing Teller lattice base groups and aromatic acid dianhydride
Obtained by cyclic imidesization reaction.
Further, the general structure of such polyimide material is as follows:
The wherein span of n, the structure of M, Ar can as indicated earlier, and here is omitted.
As it has been described above, tradition polyimide-type materials has high gas-selectively, but flux ratio is relatively low.The present invention is by cyclisation
The kink rigid structure of Teller lattice alkali is introduced polyimides chain by imide reaction, it is thus achieved that the rigid polymer backbone structure of kink,
So that obtained polymer has the highest gas flux and excellent gas-selectively.
Some typical case's polyimide materials of the present invention can have a structure shown below (n=100-500):
Another aspect of the present invention provides the method synthesizing described polyimide material, comprising: by Teller lattice alkali diamidogen list
Body and aromatic acid dianhydride monomer are dissolved in high boiling point intensive polar solvent, are reacted by high temperature initial ring aminimide, by a step
Reaction obtains target product.
Particularly, in course of reaction, with quinoline as catalyst, by the way of toluene azeotropic anhydrates, promote that reaction is carried out.
The synthesis route figure of a kind of polyimide material in the present invention one typical embodiments is illustrated refering to Fig. 1.
Among one more specifically embodiment, the synthetic method of a quasi-polyimide material may include that
At room temperature Teller lattice alkali diamine monomer is dissolved in metacresol solvent, is added thereto to aromatic acid dianhydride monomer the most in batches,
Be uniformly mixed, form a total solid content in the reaction system of 0.4～0.8mol/L, be heated to 160～230 DEG C, insulation 5～
10h, during reaction, uses the mode that toluene azeotropic anhydrates, the moisture removal constantly reaction produced, can pass through molten afterwards
The mode purified product of agent dissolving-methanol reprecipitation.
An additional aspect of the present invention provides the purposes of described polyimide material, such as high performance gas separation material
Purposes.
Among a preferred embodiment, described polyimide material can be used as polymeric film material, this kind of polymeric film material tool
There are the gas flux of superelevation, outstanding gas-selectively, and there is excellent solvent processability and filming performance, at hydrogen
In the separation of the gases pair such as gas/nitrogen, hydrogen/methane, carbon dioxide/methane, (principle please be joined to be demonstrated by the most excellent performance
Read Fig. 3), such as at 35 DEG C, under the conditions of 0.1MPa, to gases pair such as hydrogen/nitrogen, hydrogen/methane, carbon dioxide/methane
The combination property separated has been sufficiently close to or has surmounted 2008 update the Robeson upper limit (for the index of evaluated for film performance),
Thus have huge potentiality in high-purity hydrogen manufacture, ammonia synthesizing industry tail gas recycle, purification of natural gas etc. commercial Application.
Another aspect of the invention provides the preparation technology of a kind of gas separation membrane, and it comprises the steps that
Take described polyimide material to be dissolved in selected organic solvent, formed uniform and bubble-free, concentration be 2wt%～
The film forming solution of 10wt%；
Film forming solution is carried out film forming process, forms thin film, more described thin film is soaked in alcohol medium 10h～24h, afterwards in
70 DEG C～120 DEG C vacuum drying more than 24h.
Wherein, the film-forming process of employing can be conventional spin coating, spray, print, casting etc..
In a typical case, the preparation technology of a kind of Flat Membrane is as follows:
A, the configuration of casting solution: described polyimide material is dissolved in chloroform, stir 2h-5h, obtain the solution of 2-10wt%,
Filtration, de-soak.
B, the solution obtained is placed in the surface plate of glass or politef, adds a cover, slow solvent flashing, 3-4 days.
C, the thin film obtained is placed in 70 DEG C of vacuum drying ovens 10-24 hour, thoroughly removes the solvent in residual film.
D, the membrane material obtained is inserted alcohol medium soak 10-24 hour, be placed again into 70-120 DEG C of vacuum drying oven 24 hours.
Preferably, step A filter process filters the undissolved impurity of removal by the teflon membrane filter of 0.45 μm.
Preferably, the vacuum drying oven used by step C be fine vacuum without oil environment, to film formed pollute.
Preferably, the alcohol medium used by step D is generally methanol, ethanol etc..
Below in conjunction with some embodiments and accompanying drawing, technical scheme more specifically explained explanation.
The synthesis of embodiment 1TBDA1-6FDA-PI
To 2,8-bis-amido-4,10-dimethyl-6H, 12H-5,11-methylene dibenzo [b, f] [1,5] containing 0.51g (1.83mmol)
In the m-cresol solution of the 10ml of diazocine, the 4 of addition 0.81g, 4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids, stir one hour
To forming homogeneous solution, in mixture, then add the quinoline of 0.1ml and the dry toluene of 2ml.System is gradually heated up
To 200 DEG C, it is incubated 6 hours.Cooling, is poured into reaction mixture in methanol, is stirred continuously.The purification of product is by inciting somebody to action
To the mode of polymeric articles chloroform dissolving-methanol extraction remove the unreacted little molecule in polymer and solvent realizes.
Being vacuum dried 12 hours at the product 120 DEG C that will obtain, the yield of product is 1.15g, productivity 92%, characterizes data as follows:1H NMR(400MHz,CDCl3) δ: 8.00 (d, J=8.0Hz, 2H), 7.90 (s, 2H), 7.84 (d, J=8.4Hz, 2H), 7.09
(s, 2H), 6.84 (s, 2H), 4.67 (d, J=16.7Hz, 2H), 4.33 (s, 2H), 4.08 (d, J=16.2Hz, 2H), 2.45 (s, 6H).13C NMR(CDCl3,100MHz)δ:166.20,146.36,139.05,135.83,134.65,132.64,132.35,128.97,
127.14,126.60,125.04,124.07,122.59,121.93,67.09,65.18,54.64,17.26.ATR-FTIR(film,ν,
cm-1): 2960 (str, aromatic C-H), 2920,2850 (C-H), 1781 (C=O), 1720 (C=O), 1376 (C-N), 750
(C-N-C). molecular weight: (GPC, eluant-THF, polystyrene standard comparison, Mn=30000, Mw=78000g mol-1,
PDI=2.6. specific surface area=80m2/g。
The synthesis of embodiment 2TBDA1-PMDA-PI
To 2,8-bis-amido-4,10-dimethyl-6H, 12H-5,11-methylene dibenzo [b, f] [1,5] containing 0.51g (1.83mmol)
In the m-cresol solution of the 10ml of diazocine, it is dividedly in some parts the pyromellitic acid anhydride of 0.40g, stirs one hour to being formed
Homogeneous solution, then adds the quinoline of 0.1ml and the dry toluene of 2ml in mixture.System is gradually heating to 200 DEG C,
It is incubated 6 hours.Then reaction mixture is poured in 500ml methanol, is stirred continuously.The purification of product is by poly-by obtain
The mode of composition powder chloroform dissolving-methanol extraction removes the unreacted little molecule in polymer and solvent realizes.To obtain
Product 120 DEG C at be vacuum dried 12 hours, the yield of product is 0.82g, productivity 90%, is partially soluble in chloroform, tetrahydrochysene furan
In muttering, dissolve in the highly polar aprotic solvent such as NMP, DMF.It is as follows that it characterizes data: ATR-FTIR (film, ν, cm-1):
2960 (str, aromatic C-H), 2920,2850 (C-H), 1785 (C=O), 1719 (C=O), 1375 (C-N), 749
(C-N-C)。
The synthesis of embodiment 3TBDA1-BTDA-PI
To 2,8-bis-amido-4,10-dimethyl-6H, 12H-5,11-methylene dibenzo [b, f] [1,5] containing 0.51g (1.83mmol)
In the m-cresol solution of the 10ml of diazocine, it is dividedly in some parts the 3 of 0.589g, 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, stirs one
Hour to forming homogeneous solution, in mixture, then add the quinoline of 0.1ml and the dry toluene of 2ml.By system gradually
It is warming up to 200 DEG C, is incubated 6 hours.Then reaction mixture is poured in 500ml methanol, is stirred continuously.The purification of product is
The unreacted little molecule in polymer and solvent is removed by the way of by the polymeric articles obtained chloroform dissolving-methanol extraction
Realize.Being vacuum dried 12 hours at the product 120 DEG C that will obtain, Product yields is 0.97g, and productivity 88%, part is molten
In chloroform, oxolane, dissolve in the highly polar aprotic solvent such as NMP, DMF.It is as follows that it characterizes data: ATR-FTIR
(film,ν,cm-1): 2960 (str, aromatic C-H), 2920,2850 (C-H), 1781 (C=O), 1720 (C=O), 1376
(C-N),750(C-N-C)。
The synthesis of embodiment 4TBDA1-ODPA-PI
To 2,8-bis-amido-4,10-dimethyl-6H, 12H-5,11-methylene dibenzo [b, f] [1,5] containing 0.51g (1.83mmol)
In the m-cresol solution of the 10ml of diazocine, be dividedly in some parts the 4 of 0.567g, the double phthalic anhydride of 4'-oxygen, stir one little
Up to forming homogeneous solution, in mixture, then add the quinoline of 0.1ml and the dry toluene of 2ml.System is gradually risen
Temperature, to 200 DEG C, is incubated 6 hours.Then reaction mixture is poured in 500ml methanol, is stirred continuously.The purification of product is logical
Cross the unreacted little molecule removing in polymer by the mode of the polymeric articles chloroform dissolving-methanol extraction obtained and solvent comes
Realize.Being vacuum dried 12 hours at the product 120 DEG C that will obtain, Product yields is 1.00g, productivity 93%, characterizes data
As follows:1H NMR(400MHz,CDCl3) δ: 7.95 (d, J=8.1Hz, 2H), 7.51 (s, 2H), 7.42 (d, J=8.2Hz, 2H),
(7.09 s, 2H), 6.85 (s, 2H), 4.66 (d, J=16.2Hz, 2H), 4.33 (s, 2H), 4.08 (d, J=19.8Hz, 2H), 2.45 (s,
6H).13C NMR(100MHz,CDCl3)δ:166.38,161.09,146.11,134.59,134.48,128.87,127.26,127.12,
126.86,126.14,124.67,122.55,113.97,67.14,54.68,17.25.ATR-FTIR(film,ν,cm-1):2960
(C-H), 2920,2850 (C-H), 1778 (C=O), 1712 (C=O), 1373 (C-N), 742 (C-N-C). molecular weight: (GPC,
Eluant-THF, polystyrene standards contrasts) Mn=26000, Mw=71000g mol-1, PDI=2.7.BET specific surface area=
24m2/g。
The synthesis of embodiment 5TBDA2-6FDA-PI
To 3,9-bis-amido-4,10-dimethyl-6H, 12H-5,11-methylene dibenzo [b, f] [1,5] containing 0.51g (1.83mmol)
In the m-cresol solution of the 10ml of diazocine, it is dividedly in some parts the 4 of 0.81g, 4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids, stir one
Hour to forming homogeneous solution, in mixture, then add the quinoline of 0.1ml and the dry toluene of 2ml.By system gradually
It is warming up to 200 DEG C, is incubated 6 hours.Period, the moisture by the way of toluene azeotropic anhydrates, system produced with water knockout drum,
Constantly extract.During cooling, in reactant liquor, it is gradually added 20ml chloroform, to reduce the viscosity of system.Then product is molten
Liquid is poured in 500ml methanol, is stirred continuously.The purification of product is the polymeric articles chloroform dissolving-methanol extraction by obtaining
Mode remove the unreacted little molecule in polymer and solvent realizes.12 it are vacuum dried at the product 120 DEG C that will obtain
Hour, Product yields is 1.19g, productivity 91%, characterizes data as follows:1H NMR(400MHz,CDCl3)δ:8.05(dd,2H),
7.93 (s, 4H), 6.96 (dd, J=8.1Hz, 4H), 4.68 (d, J=16.1Hz, 2H), 4.35 (s, 2H), 4.08 (d, J=12.1Hz,
2H),2.28(s,6H).13C NMR(100MHz CDCl3)δ:166.08,147.30,139.08,135.82,132.80,132.57,
132.20,129.71,129.42,125.46,125.08,124.18,123.95,121.92,66.88,65.22,55.20,12.44.
ATR-FTIR(film,ν,cm-1): 2960 (C-H), 2920,2850 (C-H), 1785 (C=O), 1722 (C=O), 1370 (C-N),
746 (C-N-C). (GPC, eluant-THF, polystyrene standards) Mn=23000, Mw=52000g mol-1, PDI=2.3.
BET specific surface area=325m2/g。
The synthesis of embodiment 6TBDA2-PMDA-PI
To 3,9-bis-amido-4,10-dimethyl-6H, 12H-5,11-methylene dibenzo [b, f] [1,5] containing 0.51g (1.83mmol)
In the m-cresol solution of the 10ml of diazocine, it is dividedly in some parts the pyromellitic acid anhydride of 0.40g, stirs one hour to being formed
Homogeneous solution, then adds the quinoline of 0.1ml and the dry toluene of 2ml in mixture.System is gradually heating to 200 DEG C,
It is incubated 6 hours.Period, the moisture by the way of toluene azeotropic anhydrates, system produced with water knockout drum, constantly extract.
During cooling, in reactant liquor, it is gradually added 20ml chloroform, to reduce the viscosity of system.Then reaction mixture is poured into 500ml
In methanol, it is stirred continuously.The purification of product be remove by the way of by the polymeric articles obtained chloroform dissolving-methanol extraction poly-
Unreacted little molecule in compound and solvent realize.It is vacuum dried 12 hours at the product 120 DEG C that will obtain.Product produces
Amount is 0.85g, and productivity 93%, it is partially soluble in chloroform, oxolane, dissolves in NMP, DMF etc. highly polar non-proton
In solvent.Sign data are as follows: ATR-FTIR (film, ν, cm-1): 2960 (C-H), 2920,2850 (C-H), 1785 (C=O),
1722 (C=O), 1370 (C-N), 746 (C-N-C).
The synthesis of embodiment 7TBDA2-BTDA-PI
To 3,9-bis-amido-4,10-dimethyl-6H, 12H-5,11-methylene dibenzo [b, f] [1,5] containing 0.51g (1.83mmol)
In the m-cresol solution of the 10ml of diazocine, be dividedly in some parts the 3,3' of 0.589g, 4,4'-benzophenone tetracarboxylic dianhydrides, stir one little
Up to forming homogeneous solution, in mixture, then add the quinoline of 0.1ml and the dry toluene of 2ml.System is gradually risen
Temperature, to 200 DEG C, is incubated 6 hours.Period, the moisture by the way of toluene azeotropic anhydrates, system produced with water knockout drum, no
Break and extract.During cooling, in reactant liquor, it is gradually added 20ml chloroform, to reduce the viscosity of system.Then by reaction mixture
It is poured in 500ml methanol, is stirred continuously.The purification of product is the polymeric articles chloroform dissolving-methanol extraction by obtaining
Mode removes the unreacted little molecule in polymer and solvent realizes.12 it are vacuum dried little at the product 120 DEG C that will obtain
Time.Product yields is 1.01g, productivity 92%, and it is partially soluble in chloroform, oxolane, dissolves in NMP, DMF etc. strong
In polar non-solute.It is as follows that it characterizes data: ATR-FTIR (film, ν, cm-1):2960(C-H),2920,2850(C-H),
1780 (C=O), 1718 (C=O), 1370 (C-N), 746 (C-N-C).
The synthesis of embodiment 8TBDA2-ODPA-PI
To 3,9-bis-amido-4,10-dimethyl-6H, 12H-5,11-methylene dibenzo [b, f] [1,5] containing 0.51g (1.83mmol)
In the m-cresol solution of the 10ml of diazocine, be dividedly in some parts the 4 of 0.567g, the double phthalic anhydride of 4'-oxygen, stir one little
Up to forming homogeneous solution, in mixture, then add the quinoline of 0.1ml and the dry toluene of 2ml.System is gradually risen
Temperature, to 200 DEG C, is incubated 6 hours.Period, the moisture by the way of toluene azeotropic anhydrates, system produced with water knockout drum, no
Break and extract.During cooling, in reactant liquor, it is gradually added 20ml chloroform, to reduce the viscosity of system.Then by reaction mixture
It is poured in 500ml methanol, is stirred continuously.The purification of product is the polymeric articles chloroform dissolving-methanol extraction by obtaining
Mode removes the unreacted little molecule in polymer and solvent realizes.12 it are vacuum dried little at the product 120 DEG C that will obtain
Time.Product yields is 0.98g, productivity 92%, and it is as follows that it characterizes data:1H NMR(400MHz,CDCl3) δ: 8.01 (t, J=
7.6Hz, 2H), 7.56 (d, J=8.0Hz, 2H), 7.50 (d, J=7.8Hz, 2H), 7.00 6.87 (m, 4H), 4.67 (d, J=15.8
Hz, 2H), 4.34 (s, 2H), 4.07 (d, J=16.1Hz, 2H), 2.27 (s, 6H).13C NMR(100MHz,CDCl3)δ:
166.40,161.20,147.27,134.79,132.20,129.65,127.54,126.30,125.29,124.86,124.04,114.08,
66.93,55.21,12.41.ATR-FTIR(film,ν,cm-1): 2960 (C-H), 2920,2850 (C-H), 1778 (C=O), 1712
(C=O), 1369 (C-N), 744 (C-N-C). (GPC, eluent-THF, polystyrene standards) Mn=27000, Mw=73000g
mol-1, PDI=2.7.BET specific surface area=38m2/g。
The synthesis of embodiment 9TBDA1-SBI-PI
To 2,8-bis-amido-4,10-dimethyl-6H, 12H-5,11-methylene dibenzo [b, f] [1,5] containing 0.51g (1.83mmol)
In the m-cresol solution of the 10ml of diazocine, be dividedly in some parts the SBI of 1.15g, stir one hour to forming homogeneous solution,
Then in mixture, add the quinoline of 0.1ml and the dry toluene of 2ml.System is gradually heating to 200 DEG C, is incubated 6 hours.
Period, the moisture by the way of toluene azeotropic anhydrates, system produced with water knockout drum, constantly extract.During cooling, to instead
Answer and liquid is gradually added 20ml chloroform, to reduce the viscosity of system.Then reaction mixture is poured in 500ml methanol, constantly stirs
Mix.The purification of product is the unreacted removing in polymer by the way of by the polymeric articles obtained chloroform dissolving-methanol extraction
Little molecule and solvent realize.It is vacuum dried 12 hours at the product 120 DEG C that will obtain.Product yields is 1.48g, produces
Rate 93%.Sign data are as follows:1H NMR(400MHz,CDCl3)δ:7.32(s,1H),7.23(s,1H),7.06(s,1H),6.81
(s, 1H), 6.70 (s, 1H), 6.36 (s, 1H), 4.63 (d, J=16.0Hz, 2H), 4.30 (s, 2H), 4.05 (d, J=20.0Hz 2H),
2.43 (s, 6H), 2.33 (d, J=12.0Hz, 2H), 2.18 (d, J=12.0Hz, 2H), 1.34 (d, J=24.0Hz, 12H).
ATR-FTIR(film,ν,cm-1): 2955 (C-H), 2920,2850 (C-H), 1778 (C=O), 1716 (C=O), 1353 (C-N),
743 (C-N-C) .Molecular mass:(GPC, eluant-CHCl3, polystyrene standards) and Mn=23000, Mw=41000
g mol-1, PDI=1.8.BET specific surface area=560m2/g。
The synthesis of embodiment 10TBDA2-SBI-PI
To 3,9-bis-amido-4,10-dimethyl-6H, 12H-5,11-methylene dibenzo [b, f] [1,5] containing 0.51g (1.83mmol)
In the m-cresol solution of the 10ml of diazocine, be dividedly in some parts the SBI of 1.15g, stir one hour to forming homogeneous solution,
Then in mixture, add the quinoline of 0.1ml and the dry toluene of 2ml.System is gradually heating to 200 DEG C, is incubated 6 hours.
Period, the moisture by the way of toluene azeotropic anhydrates, system produced with water knockout drum, constantly extract.During cooling, to instead
Answer and liquid is gradually added 20ml chloroform, to reduce the viscosity of system.Then reaction mixture is poured in 500ml methanol, constantly stirs
Mix.The purification of product is the unreacted removing in polymer by the way of by the polymeric articles obtained chloroform dissolving-methanol extraction
Little molecule and solvent realize.It is vacuum dried 12 hours at the product 120 DEG C that will obtain.Product yields is 1.49g, produces
Rate 90%, characterizes data as follows:1H NMR(400MHz,CDCl3) δ: 7.36 (d, J=12.0Hz 1H), 7.28 (s, 1H), 6.91
(s, 1H), 6.73 (s, 1H), 6.39 (s, 1H), 4.64 (d, J=16.0Hz, 2H), 4.32 (s, 2H), 4.05 (d, J=20.0Hz, 2H),
2.34 (s, J=16.0Hz, 2H), 2.30-2.17 (br.m, 8H), 1.36 (d, J=24.0Hz, 12H) .ATR-FTIR (film, ν,
cm-1): 2955 (C-H), 2920,2850 (C-H), 1778 (C=O), 1716 (C=O), 1353 (C-N), 743 (C-N-C). molecule
Amount: (GPC, eluant-CHCl3, polystyrene standards) and Mn=54000, Mw=69000g mol-1, PDI=1.3.BET
Specific surface area=615m2/g。
In order to obtain can be used for the membrane material of gas separation test, the obtained target product of Example 1-10 is dissolved in chloroform, shape respectively
Becoming concentration is the solution of 2wt%-3wt%, is filtered by the teflon membrane filter of aperture 0.45 μm respectively by these solution, super
Sound, standing de-soak, then the solution obtained is respectively placed in the surface plate of politef, add a cover.Slowly solvent flashing, greatly
About 3-4 days, afterwards the thin film obtained is placed in 70 DEG C of vacuum drying ovens 24 hours, thoroughly removes the solvent in residual film, then will
The membrane material obtained is inserted methanol and is soaked 24 hours, is then placed again into 70 DEG C of vacuum drying ovens 24 hours, and resulting in one is
Row thickness is the membrane material of 80-90 μm, utilizes pressure differential method to test every kind of membrane material respectively at 0.1Mpa, at 35 DEG C afterwards, right
H2, He, N2, O2, CH4, CO2Gas permeability Deng six kinds of gases.
By the gas permeability obtained is compared, obtain film and the ideal chose performance between gas with various, its gas have been oozed
Rate and ideal selectivity are listed in the table below 1-table 2, additionally by the same Robeson of relation of the gas permeability of film Yu ideal selectivity thoroughly
The upper limit compares, and is listed in lower Fig. 3.
Should be appreciated that and the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for the skill of this area
For art personnel, all within the spirit and principles in the present invention, any amendment of being made, improvement etc., the present invention all should be included in
Protection domain within.
1 four kinds of polyimide film gas permeabilities of table and ideal selectivity (1barrer=10-10[cm3(STP)cm]/(cm2s cmHg))
2 two kinds of ultra micro permeability polyimide film gas permeabilities of table and ideal selectivity (1barrer=10-10[cm3(STP)cm]/(cm2s
cmHg))
Claims (12)
1. a polyimide material based on Teller lattice alkali structure, it is characterised in that it has a structure shown in formula I:
Wherein, n=100-500, M at least any one in group as follows:
R is at least selected from-CH3, OH and Br, Ar derive from compound shown in lower formula II:
At least any one in following compound of compound shown in this formula II:
Polyimide material based on Teller lattice alkali structure the most according to claim 1, it is characterised in that M derives from diamidogen
Monomer NH2-M-NH2, this diamine monomer is at least selected from following compound:
R is at least selected from-CH3, OH and Br.
3. the preparation method of the polyimide material based on Teller lattice alkali structure according to any one of claim 1-2, its feature
It is to include: reacted with aromatic acid dianhydride monomer initial ring aminimide under the conditions of selected by Teller lattice alkali diamine monomer, pass through
Single step reaction and form described polyimide material.
The preparation method of polyimide material the most according to claim 3, it is characterised in that including: by Teller lattice alkali diamidogen
Monomer and aromatic acid dianhydride monomer are dissolved in high boiling point intensive polar solvent and mix homogeneously, and make these two kinds of reactants have catalyst
Existence and temperature are reacted under conditions of being 160～230 DEG C, form described polyimide material.
The preparation method of polyimide material the most according to claim 4, it is characterised in that including: at room temperature by Teller
Lattice alkali diamine monomer is dissolved in high boiling point intensive polar solvent, then is dividedly in some parts aromatic acid dianhydride monomer, and mix homogeneously forms total solid content
It is the reaction system of 0.4～0.8mol/L, is then heated to 160～230 DEG C and is incubated 5～10h, it is thus achieved that described polyimides material
Material.
6. according to the preparation method of the polyimide material described in claim 4 or 5, it is characterised in that also include: reacting
Cheng Zhong, the moisture removal by the way of toluene azeotropic anhydrates, reaction produced, thus promote that reaction is carried out.
7. according to the preparation method of the polyimide material described in claim 4 or 5, it is characterised in that also include:
A, after completion of the reaction, is dissolved in reaction product mixture selected solvent, adds alcohol medium precipitation afterwards；
B, the operation of repetition step a, it is thus achieved that the product after purification；
Wherein, described selected solvent includes that chloroform, described alcohol medium include methanol or ethanol.
8. according to the preparation method of the polyimide material described in claim 4 or 5, it is characterised in that
Described catalyst includes quinoline；
And/or, described high boiling point intensive polar solvent includes N-Methyl pyrrolidone or metacresol.
9. the application in the Selective Separation of mixed gas system of the polyimide material described in claim 1, described gaseous mixture
Body system includes by arbitrarily both or both mixed gas formed above in oxygen, nitrogen, carbon dioxide, methane, hydrogen
Any one in system, preferably is selected from hydrogen/methane, hydrogen/nitrogen, carbon dioxide/methane gas pair.
10. a gas separation material, it is characterised in that comprise the polyimides based on Teller lattice alkali structure described in claim 1
Material.
11. 1 kinds of gas separation membranes, it is characterised in that it is mainly made up of the polyimide material described in claim 1.
The preparation method of gas separation membrane described in 12. claim 11, it is characterised in that including:
Taking the polyimide material described in claim 1 to be dissolved in selected organic solvent, forming uniform and bubble-free, concentration is 2
The film forming solution of wt%～10wt%, described selected organic solvent includes chloroform；
Film forming solution is carried out film forming process, forms thin film,
And, described thin film is soaked in alcohol medium 10h～24h, is vacuum dried more than 24h in 70 DEG C～120 DEG C afterwards,
Described alcohol medium is at least selected from methanol and ethanol.
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