CN110433672A - A kind of big steric hindrance polyimide gas separating film of non-co-planar and preparation method thereof - Google Patents
A kind of big steric hindrance polyimide gas separating film of non-co-planar and preparation method thereof Download PDFInfo
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- CN110433672A CN110433672A CN201810412254.2A CN201810412254A CN110433672A CN 110433672 A CN110433672 A CN 110433672A CN 201810412254 A CN201810412254 A CN 201810412254A CN 110433672 A CN110433672 A CN 110433672A
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 55
- 239000004642 Polyimide Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000007789 gas Substances 0.000 claims abstract description 47
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 150000004985 diamines Chemical class 0.000 claims abstract description 27
- 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 abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 238000004064 recycling Methods 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- 238000001764 infiltration Methods 0.000 claims description 50
- 125000003368 amide group Chemical group 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 229920005575 poly(amic acid) Polymers 0.000 claims description 26
- 239000003292 glue Substances 0.000 claims description 23
- 239000011521 glass Substances 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 18
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 14
- 235000010290 biphenyl Nutrition 0.000 claims description 13
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 12
- VLLNJDMHDJRNFK-UHFFFAOYSA-N adamantan-1-ol Chemical compound C1C(C2)CC3CC2CC1(O)C3 VLLNJDMHDJRNFK-UHFFFAOYSA-N 0.000 claims description 11
- 239000002798 polar solvent Substances 0.000 claims description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 10
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 10
- 239000012312 sodium hydride Substances 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 8
- 150000003949 imides Chemical class 0.000 claims description 8
- 230000008595 infiltration Effects 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 229960002317 succinimide Drugs 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 4
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 claims description 3
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 230000007246 mechanism Effects 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- SEXZHJJUKFXNDY-UHFFFAOYSA-N 1-(bromomethyl)-2-phenylbenzene Chemical group BrCC1=CC=CC=C1C1=CC=CC=C1 SEXZHJJUKFXNDY-UHFFFAOYSA-N 0.000 claims 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 2
- ALLIZEAXNXSFGD-UHFFFAOYSA-N 1-methyl-2-phenylbenzene Chemical group CC1=CC=CC=C1C1=CC=CC=C1 ALLIZEAXNXSFGD-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 125000002252 acyl group Chemical group 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 230000035699 permeability Effects 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000012528 membrane Substances 0.000 description 17
- 238000010792 warming Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000003755 preservative agent Substances 0.000 description 7
- 230000002335 preservative effect Effects 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000002362 mulch Substances 0.000 description 6
- 239000002985 plastic film Substances 0.000 description 6
- 229920006255 plastic film Polymers 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 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 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- -1 acyl Imines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000006160 pyromellitic dianhydride group Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses big steric hindrance polyimide gas separating film of a kind of non-co-planar and preparation method thereof, which uses, and there is the big steric hindrance structure diamine monomer of non-co-planar and aromatic dianhydride monomer polymerization to be made.The polyimide gas separating film has both high permeability and highly selective, while having good film forming.This kind of film separates and recovers hydrogen, CO in carbon containing, sulfurous gas in hydrogen-containing gas2、H2The separation and recycling of S, the fields such as oxygen enriching or rich nitrogen have important application.
Description
Technical field
The invention belongs to gas membrane Seperation Technology field, be related to a kind of high-performance polyimide film for gas separation,
Preparation method and application, in particular to the big steric hindrance polyimide gas separating film of a kind of non-co-planar, and preparation method thereof and answer
With.
Background technique
Membrane separation technique is a kind of new technique for efficiently separating, purifying and purifying to grow up in recent decades, and
Conventional separation techniques (such as rectifying, absorption and sorption, cryogenic separation) are compared, with low energy consumption, equipment is simple, flexibility is high, behaviour
Make safe ready, advantages of environment protection, research and application development are very fast.By the development of nearly half a century, scientific research
Personnel have developed a plurality of types of gas separation membranes according to the difference of separation system and purpose, oneself is successfully applied to air
Separation, hydrogen retrieval, removing, the recycling of organic steam of sour gas etc. in natural gas.Currently, the CO in China2Seperation film
Still there are certain gap in suitable with Foreign Advanced Lerel with organic steam film but oxygen-enriched and hydrogen membrane separating property and foreign countries.
Gas membrane Seperation Technology be using gas film two sides partial pressure difference as mass transfer force, it is saturating using gas with various molecule
The difference of membrane material infiltration rate is crossed to realize that component separates.Wherein membrane material is the core of membrane separation technique, is developed novel
High performance gas separation membrane material plays a significant role the fast development for promoting membrane technology, is current UF membrane research field
The most important thing.In the past 50 years, many novel polymer materials such as cellulose acetate, polysulfones, polyether sulfone, polyimides, polyethers acyl
Imines etc. has been applied to the preparation of gas separation membrane.Wherein nitrogenous aromatic heterocyclic polymer membrane material has both highly-breathable and Gao Xuan
Selecting property, it is especially best with the comprehensive performance of polyimides, it is the ideal material of gas separation.It is a kind of commercialization
Polyimides, in several commercialization gas separation membranes,It is obtained between gas permeability and selectivity good
Balance.Its gas separating property of different polyimide structures is different, and free volume and segment and side group local motion are shadows
Ring the principal element of copolyimide gas separating property.Currently, Monsanto company, the U.S., Du Pont, Ube company, Japan etc. are real
The industrialization of existing polyimide gas separating film, wherein the second generation Prism membrane separator of Monsanto company exploitation, represents
The highest level of commercialization polyimide gas separating film at present.
Although existing polyimide film has good selectivity, there are still poor permeability, dissolubility is poor, is difficult to simultaneously
The problems such as processing film forming.Therefore, it is sub- to prepare the polyamides that a kind of permeability and good film-forming property, preparation process are simple, are easy to industrialization
The technical issues of amine gas seperation film is current urgent need to resolve.To improve its permeability and dissolubility, can set on a molecular scale
Its structural unit is counted, by the control of screening monomer and synthesis new dianhydride and diamines and polymeric reaction condition, is prepared
Gas and selective all good membrane material.
Summary of the invention
To overcome the above-mentioned problems of the prior art, the purpose of the present invention is to provide a kind of separating property it is good and film forming
Property good polyimide gas separating film and preparation method.
The technical solution adopted by the invention is as follows:
A kind of big steric hindrance polyimide gas separating film of non-co-planar, the structure of non-co-planar polyimides are as follows:
Wherein, Ar is aromatic group, and n is positive number.
Particularly, Ar is selected from Deng n is taken as 30~200.
The big steric hindrance polyimide gas separating film of non-co-planar described above is with 4,4 '-two amidos -3,3 '-dimethyl connection
After benzene, N-bromosuccinimide, hydroxyadamantane have the big steric hindrance diamine monomer of non-co-planar for monomer preparation, then described in
Diamines polymerize with aromatic dianhydride is prepared polyamic acid glue, and polyamides then is prepared using hot-imide film forming mechanism
Imines gas separation membrane.
The preparation method of the polyimide gas separating film specifically includes following processing step:
(1) synthesis of diamine monomer: by 4,4 '-two amido -3,3 '-dimethyl diphenyls are dissolved in chlorobenzene, are then added appropriate
N-bromosuccinimide and azodiisobutyronitrile react 10~20h at 100~150 DEG C, pour into proper amount of methanol and precipitate, mistake
Filter is washed, dry, obtains 4,4 '-two amido -3,3 '-two bromomethylbiphenyls；1- hydroxyadamantane is dissolved in appropriate tetrahydro furan
It mutters, is added appropriate sodium hydride, react and be added appropriate 4 after 0.2~5h, 4 '-two amido -3,3 '-two bromomethylbiphenyls, 30~100
3~12h is reacted at DEG C, pours into methanol and precipitates, is filtered, and is washed, it is dry, it obtains with the big steric hindrance diamine monomer of non-co-planar；
(2) synthesis of polyamic acid: under nitrogen protection, the diamine monomer that step (1) is obtained is molten under stiring
Solution is in appropriate polar solvent, and after dissolution, appropriate aromatic dianhydride, every minor tick are added three times at 50~100 DEG C
5min continues 2~12h of stirring after charging, obtain polyamic acid glue, the obtained polyamic acid glue preservative film
It seals spare；
The polar solvent is DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, N-Methyl pyrrolidone, dimethyl
The one or more of sulfoxide, sulfolane；The aromatic dianhydride is pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, Biphenyl Ether tetracarboxylic acid
Acid dianhydride, biphenyl ketone tetracarboxylic dianhydride, hexafluorodianhydride (6FDA), dimethyl tetracarboxylic dianhydride one or more；
(3) preparation of polyimide film: knifing, adjusting on clean glass plate by polyamic acid described in step (2)
The thickness of film is put into baking oven between 50~150 μm and carries out hot imide reaction, hot-imide using gradient increased temperature
Temperature is 80~220 DEG C, and the time is 5~12h, naturally cools to after room temperature carries out demoulding and obtains polyimide film.
4,4 '-two amidos -3,3 '-dimethyl diphenyl described in step (1), N-bromosuccinimide, two isobutyl of azo
The molar ratio of nitrile is 1:(2~4): (1~2)；The 1- hydroxyadamantane, sodium hydride,-two bromomethyl of 4,4 '-two amido -3,3 '
The molar ratio of biphenyl is 1:1:(0.3~1).
The molar ratio of diamine monomer described in step (2) and aromatic dianhydride is 1:(0.5~2).
The H of the big steric hindrance polyimide film of the non-co-planar produced by the present invention2Infiltration coefficient is 20~150barrer, O2
Infiltration coefficient is 1~20barrer, N2Infiltration coefficient is 0.2~5barrer, CO2Infiltration coefficient is 5~60barrer.
The H of the polyimide gas separating film produced by the present invention2/N2Selectivity is 60~150, O2/N2Selectively it is
5~10, CO2/N2Selectivity is 10~50.
The big steric hindrance polyimide film of non-co-planar of the present invention is separated suitable for gas, especially suitable for hydrogen-containing gas
Middle separation and recovery hydrogen, CO in carbon containing, sulfurous gas2、H2Separation and the recycling (CO in such as natural gas of S2Removing etc.), air
Oxygen-enriched or rich nitrogen etc..
The big steric hindrance polyimide film material of non-co-planar of the present invention, the big steric hindrance Buddha's warrior attendant of two non-co-planar of side chain
Alkyl structure, so that polyimides of the invention has good dissolubility and high permeability, film forming is excellent, and machine-shaping is held
Easily, preparation process is simple, is easy to industrialization, easy to promote and utilize.
Detailed description of the invention
Fig. 1 is O2/N2Separation upper limit figure.
Straight line is upper bound line (2008), i.e. the Robeson upper limit (2008) in Fig. 1.Infiltration coefficient P and
Selective α is two major parameters for measuring air film separating property, but is existed between the gas permeability and separation property of seperation film
The raising of Trade-off relationship, i.e. infiltration coefficient often will lead to the reduction of selection coefficient, and vice versa, therefore improves separation property
It can be actually the equalization point that optimization is found between infiltration coefficient P and selectivity α.Robeson was, 2008 fraction of the year in 1991
Yan Jiu not summarize it is a large amount of oneself deliver gas separating property data in document, having obtained certain polymer materials at that time can reach
The empirical separating property upper limit arrived, and result is depicted as αij~PiDouble logarithmic chart, referred to as upper bound
Line, i.e. the Robeson upper limit.
Specific embodiment
Invention is further described in detail with reference to the accompanying drawings and detailed description.
Embodiment 1:
By 4,4 '-two amido -3 2.123g, 3 '-dimethyl diphenyls are dissolved in 50ml chlorobenzene, and 5.337g N- bromine is then added
For succinimide and 0.164g azodiisobutyronitrile, 130 DEG C of reaction 12h are poured into 500ml methanol and are precipitated, and are filtered, washing,
It is dry, obtain 4,4 '-two amido -3,3 '-two bromomethylbiphenyls.1.522g 1- hydroxyadamantane is dissolved in 50ml tetrahydrofuran,
0.24g sodium hydride is added, 4,4 '-two amido -3 1.85g, 3 '-two bromomethylbiphenyls, 40 DEG C of reactions are added after reacting 0.5h
10h is poured into methanol and is precipitated, and is filtered, and is washed, dry, is obtained with the big steric hindrance diamine monomer of non-co-planar.In nitrogen protection
Under, 1.709g diamine monomer is dissolved under stiring in 20ml polar solvent, after dissolution, is added three times at 70 DEG C
The pyromellitic dianhydride of equimolar amounts, every minor tick 5min continue to stir 3h after charging, obtain polyamic acid glue, obtain
The polyamic acid glue preservative film sealing arrived is spare.
Clean glass plate is spread in film-laying machine bottom, and mold is put to about 100 μ of thickness for adjusting film on a glass
M, then the polyamic acid glue obtained is poured into, rotating switch carries out plastic film mulch.The good glass plate of film is put into baking oven and is adopted
Hot imide reaction is carried out with gradient increased temperature, first 80 DEG C of preliminary dryings 2h, 120 DEG C of baking 1h are warming up to 160 DEG C of baking 1h, then heat up
To 180 DEG C of baking 1h, then it is warming up to 220 DEG C of baking 1h.It naturally cools to after room temperature carries out demoulding and obtains polyimide film.
The separating property of polyimide film made from the embodiment is as shown in table 1, to H2Infiltration coefficient it is reachable
55.36barrer O2Infiltration coefficient reaches 4.50barrer, N2Infiltration coefficient is 0.61barrer, CO2Infiltration coefficient reaches
17.81barrer H2/N2Selectivity is 90.1, O2/N2Selectivity is 7.3, CO2/N2Selectivity is 29.0.With comparative example, that is, quotient
Industry Matrimid film is compared, the O of the embodiment2/N2And CO2/N27%, 12%, while O has been respectively increased in selectivity2、N2With
CO2Infiltration coefficient be respectively increased 2.6,2.4,2.7 times.
Embodiment 2:
By 4,4 '-two amido -3 2.123g, 3 '-dimethyl diphenyls are dissolved in 50ml chlorobenzene, and 5.337g N- bromine is then added
For succinimide and 0.164g azodiisobutyronitrile, 130 DEG C of reaction 12h are poured into 500ml methanol and are precipitated, and are filtered, washing,
It is dry, obtain 4,4 '-two amido -3,3 '-two bromomethylbiphenyls.1.522g 1- hydroxyadamantane is dissolved in 50ml tetrahydrofuran,
0.24g sodium hydride is added, addition 4,4 '-two amido -3 1.85g after reaction 1h, 3 '-two bromomethylbiphenyls, 50 DEG C of reaction 8h,
Enter in methanol and precipitate, filter, washs, it is dry, it obtains with the big steric hindrance diamine monomer of non-co-planar.Under nitrogen protection, will
1.709g diamine monomer is dissolved under stiring in 20ml polar solvent, after dissolution, is added three times equimolar at 80 DEG C
The biphenyltetracarboxylic dianhydride of amount, every minor tick 5min continue to stir 5h after charging, obtain polyamic acid glue, obtain
Polyamic acid glue preservative film seals spare.
Clean glass plate is spread in film-laying machine bottom, and mold is put to about 100 μ of thickness for adjusting film on a glass
M, then the polyamic acid glue obtained is poured into, rotating switch carries out plastic film mulch.The good glass plate of film is put into baking oven and is adopted
Hot imide reaction is carried out with gradient increased temperature, first 80 DEG C of preliminary dryings 2h, 120 DEG C of baking 1h are warming up to 160 DEG C of baking 2h, then heat up
To 180 DEG C of baking 0.5h, then it is warming up to 220 DEG C of baking 2h.It naturally cools to after room temperature carries out demoulding and obtains polyimide film.
The separating property of polyimide film made from the embodiment is as shown in table 1, to H2Infiltration coefficient it is reachable
29.70barrer O2Infiltration coefficient reaches 2.03barrer, N2Infiltration coefficient is 0.25barrer, CO2Infiltration coefficient reaches
10.18barrer H2/N2Selectivity is 120.3, O2/N2Selectivity is 8.2, CO2/N2Selectivity is 41.2.With comparative example, that is, quotient
Industry Matrimid film is compared, the O of the embodiment2/N2And CO2/N221%, 58%, while O has been respectively increased in selectivity2And CO2
Infiltration coefficient be respectively increased 1.2,1.6 times.
Embodiment 3:
By 4,4 '-two amido -3 2.123g, 3 '-dimethyl diphenyls are dissolved in 50ml chlorobenzene, and 5.337g N- bromine is then added
For succinimide and 0.164g azodiisobutyronitrile, 130 DEG C of reaction 12h are poured into 500ml methanol and are precipitated, and are filtered, washing,
It is dry, obtain 4,4 '-two amido -3,3 '-two bromomethylbiphenyls.1.522g 1- hydroxyadamantane is dissolved in 50ml tetrahydrofuran,
0.24g sodium hydride is added, addition 4,4 '-two amido -3 1.85g after reaction 1h, 3 '-two bromomethylbiphenyls, 60 DEG C of reaction 6h,
Enter in methanol and precipitate, filter, washs, it is dry, it obtains with the big steric hindrance diamine monomer of non-co-planar.Under nitrogen protection, will
1.709g diamine monomer is dissolved under stiring in 20ml polar solvent, after dissolution, is added three times equimolar at 70 DEG C
The Biphenyl Ether tetracarboxylic dianhydride of amount, every minor tick 5min continue to stir 10h after charging, obtain polyamic acid glue, obtain
The polyamic acid glue with preservative film seal it is spare.
Clean glass plate is spread in film-laying machine bottom, and mold is put to about 100 μ of thickness for adjusting film on a glass
M, then the polyamic acid glue obtained is poured into, rotating switch carries out plastic film mulch.The good glass plate of film is put into baking oven and is adopted
Hot imide reaction is carried out with gradient increased temperature, first 80 DEG C of preliminary dryings 2h, 120 DEG C of baking 1h are warming up to 160 DEG C of baking 1h, then heat up
To 180 DEG C of baking 1.5h, then it is warming up to 220 DEG C of baking 1.5h.It naturally cools to after room temperature carries out demoulding and obtains polyimide film.
The separating property of polyimide film made from the embodiment is as shown in table 1, to H2Infiltration coefficient it is reachable
36.81barrer O2Infiltration coefficient reaches 2.44barrer, N2Infiltration coefficient is 0.32barrer, CO2Infiltration coefficient reaches
11.68barrer H2/N2Selectivity is 116.6, O2/N2Selectivity is 7.7, CO2/N2Selectivity is 37.0.With comparative example, that is, quotient
Industry Matrimid film is compared, the O of the embodiment2/N2And CO2/N213%, 42%, while O has been respectively increased in selectivity2、N2With
CO2Infiltration coefficient be respectively increased 1.4,1.3,1.8 times.
Embodiment 4:
By 4,4 '-two amido -3 2.123g, 3 '-dimethyl diphenyls are dissolved in 50ml chlorobenzene, and 5.337g N- bromine is then added
For succinimide and 0.164g azodiisobutyronitrile, 130 DEG C of reaction 12h are poured into 500ml methanol and are precipitated, and are filtered, washing,
It is dry, obtain 4,4 '-two amido -3,3 '-two bromomethylbiphenyls.1.522g 1- hydroxyadamantane is dissolved in 50ml tetrahydrofuran,
0.24g sodium hydride is added, addition 4,4 '-two amido -3 1.85g after reaction 3h, 3 '-two bromomethylbiphenyls, 60 DEG C of reaction 6h,
Enter in methanol and precipitate, filter, washs, it is dry, it obtains with the big steric hindrance diamine monomer of non-co-planar.Under nitrogen protection, will
1.709g diamine monomer is dissolved under stiring in 20ml polar solvent, after dissolution, is added three times equimolar at 70 DEG C
The biphenyl ketone tetracarboxylic dianhydride of amount, every minor tick 5min continue to stir 5h after charging, obtain polyamic acid glue, obtain
The polyamic acid glue with preservative film seal it is spare.
Clean glass plate is spread in film-laying machine bottom, and mold is put to about 100 μ of thickness for adjusting film on a glass
M, then the polyamic acid glue obtained is poured into, rotating switch carries out plastic film mulch.The good glass plate of film is put into baking oven and is adopted
Hot imide reaction is carried out with gradient increased temperature, first 80 DEG C of preliminary dryings 4h, 120 DEG C of baking 1h are warming up to 160 DEG C of baking 1h, then heat up
To 180 DEG C of baking 1h, then it is warming up to 220 DEG C of baking 1h.It naturally cools to after room temperature carries out demoulding and obtains polyimide film.
The separating property of polyimide film made from the embodiment is as shown in table 1, to H2Infiltration coefficient it is reachable
75.40barrer O2Infiltration coefficient reaches 6.27barrer, N2Infiltration coefficient is 0.87barrer, CO2Infiltration coefficient reaches
22.83barrer H2/N2Selectivity is 87.0, O2/N2Selectivity is 7.2, CO2/N2Selectivity is 26.3.With comparative example, that is, quotient
Industry Matrimid film is compared, although the O of the embodiment2/N2And CO2/N2Selectivity is basically unchanged, but O2、N2And CO2Infiltration
Coefficient raising is larger, has been respectively increased 3.7,3.5,3.5 times.
Embodiment 5:
By 4,4 '-two amido -3 2.123g, 3 '-dimethyl diphenyls are dissolved in 50ml chlorobenzene, and 5.337g N- bromine is then added
For succinimide and 0.164g azodiisobutyronitrile, 130 DEG C of reaction 12h are poured into 500ml methanol and are precipitated, and are filtered, washing,
It is dry, obtain 4,4 '-two amido -3,3 '-two bromomethylbiphenyls.1.522g 1- hydroxyadamantane is dissolved in 50ml tetrahydrofuran,
0.24g sodium hydride is added, addition 4,4 '-two amido -3 1.85g after reaction 1h, 3 '-two bromomethylbiphenyls, 70 DEG C of reaction 5h,
Enter in methanol and precipitate, filter, washs, it is dry, it obtains with the big steric hindrance diamine monomer of non-co-planar.Under nitrogen protection, will
1.709g diamine monomer is dissolved under stiring in 20ml polar solvent, after dissolution, is added three times equimolar at 70 DEG C
The hexafluorodianhydride (6FDA) of amount, every minor tick 5min continue to stir 3h after charging, obtain polyamic acid glue, and what is obtained is described poly-
Amic acid glue preservative film seals spare.
Clean glass plate is spread in film-laying machine bottom, and mold is put to about 100 μ of thickness for adjusting film on a glass
M, then the polyamic acid glue obtained is poured into, rotating switch carries out plastic film mulch.The good glass plate of film is put into baking oven and is adopted
Hot imide reaction is carried out with gradient increased temperature, first 80 DEG C of preliminary dryings 2h, 120 DEG C of baking 5h are warming up to 160 DEG C of baking 1h, then heat up
To 180 DEG C of baking 1h, then it is warming up to 220 DEG C of baking 1h.It naturally cools to after room temperature carries out demoulding and obtains polyimide film.
The separating property of polyimide film made from the embodiment is as shown in table 1, to H2Infiltration coefficient it is reachable
139.25barrer, O2Infiltration coefficient reaches 12.82barrer, N2Infiltration coefficient is 1.87barrer, CO2Infiltration coefficient reaches
43.98barrer H2/N2Selectivity is 74.3, O2/N2Selectivity is 6.8, CO2/N2Selectivity is 23.5.With comparative example, that is, quotient
Industry Matrimid film is compared, although the selectivity of the embodiment is declined, O2、N2And CO2Infiltration coefficient have and mention greatly very much
Height has been respectively increased 7.5,7.5,6.8 times.
Embodiment 6:
By 4,4 '-two amido -3 2.123g, 3 '-dimethyl diphenyls are dissolved in 50ml chlorobenzene, and 5.337g N- bromine is then added
For succinimide and 0.164g azodiisobutyronitrile, 130 DEG C of reaction 12h are poured into 500ml methanol and are precipitated, and are filtered, washing,
It is dry, obtain 4,4 '-two amido -3,3 '-two bromomethylbiphenyls.1.522g 1- hydroxyadamantane is dissolved in 50ml tetrahydrofuran,
0.24g sodium hydride is added, addition 4,4 '-two amido -3 1.85g after reaction 1h, 3 '-two bromomethylbiphenyls, 80 DEG C of reaction 4h,
Enter in methanol and precipitate, filter, washs, it is dry, it obtains with the big steric hindrance diamine monomer of non-co-planar.Under nitrogen protection, will
1.709g diamine monomer is dissolved under stiring in 20ml polar solvent, after dissolution, is added three times equimolar at 70 DEG C
The dimethyl tetracarboxylic dianhydride of amount, every minor tick 5min continue to stir 10h after charging, obtain polyamic acid glue, obtain
The polyamic acid glue with preservative film seal it is spare.
Clean glass plate is spread in film-laying machine bottom, and mold is put to about 100 μ of thickness for adjusting film on a glass
M, then the polyamic acid glue obtained is poured into, rotating switch carries out plastic film mulch.The good glass plate of film is put into baking oven and is adopted
Hot imide reaction is carried out with gradient increased temperature, first 80 DEG C of preliminary dryings 3h, 120 DEG C of baking 1h are warming up to 160 DEG C of baking 2h, then heat up
To 180 DEG C of baking 1h, then it is warming up to 220 DEG C of baking 1h.It naturally cools to after room temperature carries out demoulding and obtains polyimide film.
The separating property of polyimide film made from the embodiment is as shown in table 1, to H2Infiltration coefficient it is reachable
46.78barrer O2Infiltration coefficient reaches 3.22barrer, N2Infiltration coefficient is 0.43barrer, CO2Infiltration coefficient reaches
13.77barrer H2/N2Selectivity is 108.0, O2/N2Selectivity is 7.4, CO2/N2Selectivity is 31.8.With comparative example, that is, quotient
Industry Matrimid film is compared, the O of the embodiment2/N2And CO2/N29%, 22%, while O has been respectively increased in selectivity2、N2With
CO2Infiltration coefficient be respectively increased 1.9,1.7,2.1 times.
Comparative example:
Matrimid film reported in document (Journal membrane science, 2003,225,77-90) is chosen to do
Comparative example, by the big steric hindrance polyimide film of the non-co-planar of the embodiment of the present invention 1~6 compared with it, detailed performance such as 1 institute of table
Show.
The separating property of the big steric hindrance polyimide film of the non-co-planar of the present invention of table 1 and commercialization film compares
As it can be seen from table 1 the H of the big steric hindrance polyimide gas separating film of non-co-planar of the invention2Infiltration coefficient is
20~150barrer, O2Infiltration coefficient is 1~20barrer, N2Infiltration coefficient is 0.2~5barrer, CO2Infiltration coefficient is 5
~60barrer.The H of seperation film2/N2Selectivity is 60~150, O2/N2Selectivity is 5~10, CO2/N2Selectivity for 10~
50。
The big steric hindrance polyimide film of non-co-planar of the invention is keeping selectivity and commercialization Matrimid film similar
In the case where even higher, infiltration coefficient is greatly improved, O2Infiltration coefficient increase about 1.2~7.5 times, N2Infiltration system
Number increases about 1~7.5 times, CO2Infiltration coefficient increase about 1.6~6.8 times.
From the O of Fig. 1 Examples 1 to 6 and comparative example2/N2It separates and can be seen that the embodiment of the present invention 1~6 in upper limit figure
The big steric hindrance polyimide film ratio Matrimid film of non-co-planar has mentioning for conspicuousness closer to the Robeson upper limit, separating property
It rises.
Big steric hindrance polyimide gas separating film of a kind of non-co-planar of the invention and preparation method thereof is not limited to above-mentioned
Each embodiment, all technical solutions formed using equivalent replacement, all falls within protection scope of the present invention.
Claims (10)
1. a kind of big steric hindrance polyimide gas separating film of non-co-planar, it is characterised in that the structure of non-co-planar polyimides is logical
Formula are as follows:
Wherein Ar is aromatic group, and n is positive number.
2. the big steric hindrance polyimide gas separating film of non-co-planar according to claim 1, it is characterised in that: Ar is selected from
N is 30~200.
3. the big steric hindrance polyimide gas separating film of non-co-planar according to claim 1, it is characterised in that: seperation film
H2Infiltration coefficient is 20~150barrer, O2Infiltration coefficient is 1~20barrer, N2Infiltration coefficient is 0.2~5barrer, CO2
Infiltration coefficient is 5~60barrer.
4. the big steric hindrance polyimide gas separating film of non-co-planar according to claim 1, it is characterised in that: seperation film
H2/N2Selectivity is 60~150, O2/N2Selectivity is 5~10, CO2/N2Selectivity is 10~50.
5. the big steric hindrance polyimide gas separating film of non-co-planar according to claim 1, it is characterised in that: seperation film with
4,4 '-two amidos -3,3 '-dimethyl diphenyl, N-bromosuccinimide, hydroxyadamantane are that monomer preparation has non-co-planar
After big steric hindrance diamine monomer, then it is polymerize with the diamines with aromatic dianhydride and polyamic acid glue is prepared, then uses hot acyl
Polyimide gas separating film is prepared in imidization film forming mechanism.
6. the big steric hindrance polyimide gas separating film of non-co-planar according to claim 1, it is characterised in that: described non-total
The big steric hindrance polyimide gas separating film of plane separates and recovers hydrogen, CO in carbon containing, sulfurous gas suitable for hydrogen-containing gas2、
H2The separation and recycling of S, oxygen enriching, rich nitrogen.
7. the preparation method of the big steric hindrance polyimide gas separating film of non-co-planar according to any one of claims 1 to 6,
It is characterized in that this method comprises the following steps:
(1) synthesis of diamine monomer: by 4,4 '-two amido -3,3 '-dimethyl diphenyls are dissolved in chlorobenzene, and appropriate N- bromine is then added
For succinimide and azodiisobutyronitrile, 10~20h is reacted at 100~150 DEG C, pours into methanol and precipitates, is filtered, washing,
It is dry, obtain 4,4 '-two amido -3,3 '-two bromomethylbiphenyls；1- hydroxyadamantane is dissolved in tetrahydrofuran, appropriate hydrogen is added
Change sodium, is added appropriate 4 after reacting 0.2~5h, 4 '-two amido -3,3 '-two bromomethylbiphenyls, reaction 3 at 30~100 DEG C~
12h is poured into methanol and is precipitated, and is filtered, and is washed, dry, is obtained with the big steric hindrance diamine monomer of non-co-planar；
(2) synthesis of polyamic acid: under nitrogen protection, the diamine monomer that step (1) obtains is dissolved under stiring
In polar solvent, after dissolution, appropriate aromatic dianhydride is added three times at 50~100 DEG C, every minor tick 5min has fed
Continue 2~12h of stirring after finishing, obtains polyamic acid glue；
(3) preparation of polyimide film: by polyamic acid described in step (2) on clean glass plate knifing, be put into baking oven
Middle to carry out hot imide reaction using gradient increased temperature, hot-imide temperature is 80~220 DEG C, and the time is 5~12h, natural
It is cooled to after room temperature carries out demoulding and obtains polyimide film.
8. preparation method according to claim 7, it is characterised in that: polar solvent described in step (2) is N, N- diformazan
Yl acetamide, n,N-Dimethylformamide, one kind of N-Methyl pyrrolidone, dimethyl sulfoxide, sulfolane, the aromatic dianhydride
For pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, Biphenyl Ether tetracarboxylic dianhydride, biphenyl ketone tetracarboxylic dianhydride, hexafluorodianhydride (6FDA), diformazan
One kind of base tetracarboxylic dianhydride.
9. preparation method according to claim 7, it is characterised in that: 4,4 '-two amido -3 described in step (1), 3 '-two
Methyl biphenyl, N-bromosuccinimide, azodiisobutyronitrile molar ratio be 1:(2~4): (1~2), 1- hydroxyl gold
Rigid alkane, sodium hydride,-two bromomethylbiphenyl of 4,4 '-two amido -3,3 ' molar ratio be 1:1:(0.3~1)；Described in step (2)
The molar ratio of diamine monomer and aromatic dianhydride is 1:(0.5~2).
10. preparation method according to claim 7, it is characterised in that: described 4,4 '-two amido -3,3 '-dimethyl diphenyls
Amount be 1~20g, the amount of N-bromosuccinimide is 2~50g, the amount of azodiisobutyronitrile is 0.05~2g, 1- hydroxyl gold
The amount of rigid alkane is 1~15g, the amount of sodium hydride is 0.1~3g, the amount of-two bromomethylbiphenyl of 4,4 '-two amido -3,3 ' be 1~
20g, diamine monomer amount be 1~20g, the amount of aromatic dianhydride is 0.5~25g；The amount of the chlorobenzene is 20~500ml, methanol
Amount be 200~5000ml, the amount of tetrahydrofuran is 20~500ml, the amount of polar solvent is 10~200ml.
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