CN105498557A - Triptycene-based VOCs (volatile organic chemicals) retained type polymer separating membrane and preparation method thereof - Google Patents
Triptycene-based VOCs (volatile organic chemicals) retained type polymer separating membrane and preparation method thereof Download PDFInfo
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- CN105498557A CN105498557A CN201510883253.2A CN201510883253A CN105498557A CN 105498557 A CN105498557 A CN 105498557A CN 201510883253 A CN201510883253 A CN 201510883253A CN 105498557 A CN105498557 A CN 105498557A
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- Prior art keywords
- triptycene
- chloride
- dish
- dianhydride
- type polymer
- Prior art date
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- NGDCLPXRKSWRPY-UHFFFAOYSA-N Triptycene Chemical compound C12=CC=CC=C2C2C3=CC=CC=C3C1C1=CC=CC=C12 NGDCLPXRKSWRPY-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229920000642 polymer Polymers 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000012528 membrane Substances 0.000 title abstract description 34
- 230000000717 retained effect Effects 0.000 title abstract 4
- 239000000126 substance Substances 0.000 title abstract 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 47
- 238000000926 separation method Methods 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 20
- 239000011230 binding agent Substances 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 230000000694 effects Effects 0.000 claims abstract description 6
- 239000012855 volatile organic compound Substances 0.000 claims description 41
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 39
- -1 anhydrides compound Chemical class 0.000 claims description 38
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 28
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 28
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 239000000460 chlorine Substances 0.000 claims description 17
- 229910052801 chlorine Inorganic materials 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 14
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 14
- WMPOZLHMGVKUEJ-UHFFFAOYSA-N decanedioyl dichloride Chemical compound ClC(=O)CCCCCCCCC(Cl)=O WMPOZLHMGVKUEJ-UHFFFAOYSA-N 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 10
- MGCLCEIUDPDURN-UHFFFAOYSA-N 4-phenylcyclohexa-3,5-diene-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)C(C(=O)O)(C(O)=O)C=CC(C=2C=CC=CC=2)=C1 MGCLCEIUDPDURN-UHFFFAOYSA-N 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 150000007529 inorganic bases Chemical class 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 150000007530 organic bases Chemical group 0.000 claims description 8
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- 150000001263 acyl chlorides Chemical class 0.000 claims description 7
- 230000004888 barrier function Effects 0.000 claims description 7
- 238000009792 diffusion process Methods 0.000 claims description 7
- JDTUPLBMGDDPJS-UHFFFAOYSA-N 2-methoxy-2-phenylethanol Chemical compound COC(CO)C1=CC=CC=C1 JDTUPLBMGDDPJS-UHFFFAOYSA-N 0.000 claims description 5
- MQAHXEQUBNDFGI-UHFFFAOYSA-N 5-[4-[2-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenyl]propan-2-yl]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)C(C)(C=2C=CC(OC=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)C)=C1 MQAHXEQUBNDFGI-UHFFFAOYSA-N 0.000 claims description 5
- OLQWMCSSZKNOLQ-ZXZARUISSA-N (3s)-3-[(3r)-2,5-dioxooxolan-3-yl]oxolane-2,5-dione Chemical compound O=C1OC(=O)C[C@H]1[C@@H]1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-ZXZARUISSA-N 0.000 claims description 4
- ZLYYJUJDFKGVKB-OWOJBTEDSA-N (e)-but-2-enedioyl dichloride Chemical compound ClC(=O)\C=C\C(Cl)=O ZLYYJUJDFKGVKB-OWOJBTEDSA-N 0.000 claims description 4
- IEEHKTFVUIVORU-UHFFFAOYSA-N 2-methylpropanedioyl dichloride Chemical compound ClC(=O)C(C)C(Cl)=O IEEHKTFVUIVORU-UHFFFAOYSA-N 0.000 claims description 4
- POLIXZIAIMAECK-UHFFFAOYSA-N 4-[2-(2,6-dioxomorpholin-4-yl)ethyl]morpholine-2,6-dione Chemical compound C1C(=O)OC(=O)CN1CCN1CC(=O)OC(=O)C1 POLIXZIAIMAECK-UHFFFAOYSA-N 0.000 claims description 4
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 claims description 4
- AMPZBWRBSNODSO-UHFFFAOYSA-N C(C(CCCCC(C(CCCC)C(=O)O)C(=O)O)C(=O)O)C(=O)O Chemical compound C(C(CCCCC(C(CCCC)C(=O)O)C(=O)O)C(=O)O)C(=O)O AMPZBWRBSNODSO-UHFFFAOYSA-N 0.000 claims description 4
- ZPAKUZKMGJJMAA-UHFFFAOYSA-N Cyclohexane-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)CC1C(O)=O ZPAKUZKMGJJMAA-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- XJMMNTGIMDZPMU-UHFFFAOYSA-N beta-methylglutaric acid Natural products OC(=O)CC(C)CC(O)=O XJMMNTGIMDZPMU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 4
- HGEVGSTXQGZPCL-UHFFFAOYSA-N nonanedioyl dichloride Chemical compound ClC(=O)CCCCCCCC(Cl)=O HGEVGSTXQGZPCL-UHFFFAOYSA-N 0.000 claims description 4
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 claims description 4
- 229940072033 potash Drugs 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 235000015320 potassium carbonate Nutrition 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 4
- 210000004379 membrane Anatomy 0.000 abstract 8
- 210000002469 basement membrane Anatomy 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 239000002131 composite material Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 11
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000012466 permeate Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 230000003760 hair shine Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- 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
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
Abstract
The invention discloses a triptycene-based VOCs (volatile organic chemicals) retained type polymer separating membrane and a preparation method thereof and relates to a gas separating membrane and a preparation method thereof. According to the preparation method of the separating membrane, a compound shown in a formula I and a compound containing active groups are taken as monomers and have a polymerization reaction for 0.5-60 h under the action of an acid-binding agent, and a membrane solution is obtained after the reaction ends; a solvent resistance basement membrane is coated with the obtained membrane solution, vacuum crosslinking drying is performed, and the triptycene-based VOCs retained type polymer separating membrane is obtained. The preparation method of the triptycene-based VOCs retained type polymer separating membrane is simple, and the prepared separating membrane can be independently used, has a good separation effect and has solvent resistance and higher separating stability.
Description
Technical field
The invention belongs to polymeric film art, be specifically related to a kind of gas separation membrane and preparation method thereof, more specifically relate to a kind of three dish thiazolinyl VOCs and retain type polymer separation film and preparation method thereof.
Background technology
Volatile organic matter is the material that a class volatility is higher.It in use inevitably there will be the phenomenon of leakage, thus a large amount of discharge containing volatile organic exhaust gas can be made to enter in air, affects the physical and mental health of people, contaminated environment.Country has promulgated that multiple laws and regulations are to control the concentration of emission of volatile organic matter, such as " discharge standard of air pollutants " for this reason.In order to satisfied national emission request, software engineering researchers invent multiple technologies such as adopt absorption, absorption, condensation, UF membrane etc. to process recovery organic exhaust gas, adopt the technology such as catalytic combustion, plasma oxidation to eliminate Organic Waste Gas Pollution etc.Wherein have economic worth for some, the waste gas that consumption is larger, recycling technology has good economy and environment benefit.And wherein membrane separation technique due to have efficient, low energy consumption, facility compact, environmentally friendly, do not produce the reasons such as secondary pollution, and be considered to process the effective isolation technics of organic pollution at present.
Key in membrane separation technology is the performance of diffusion barrier.What current use was more is preferential organic matter film thoroughly, this film mainly based on the polydimethylsiloxanepolymer polymer of rubbery state, to adsorb the different osmosis concentration organic matters of selective penetrated property, entrapped air, thus the separation both realizing.But preferential organic matter film thoroughly in use, can not be used alone, must use together with other equipment such as vavuum pump, cause apparatus and process complicated, energy consumption is higher.The swollen rubber of volatile organic matter meeting simultaneously state polymer film, thus affect the further raising of its separating property, limit it to a certain extent and widely use.
Summary of the invention
The preferential nitrogen thoroughly that can be used for volatile organic compounds process that the object of the invention is the technical problem development of new existed for prior art retains organic diffusion barrier, widens the application of diffusion barrier in volatile organic compounds process field.
Object of the present invention can be achieved through the following technical solutions:
A kind of three dish thiazolinyl VOCs retain type polymer separation film, this diffusion barrier prepares by the following method: the method with the compound shown in formula I and containing the compound of active group for monomer, under the effect of acid binding agent, polymerisation 0.5h-60h, obtains film liquid after reaction terminates; Be coated on solvent resistant counterdie by the film liquid obtained, vacuum is crosslinked dry, obtains three dish thiazolinyl VOCs and retains type polymer separation film;
The described compound containing active group is selected from least one in acyl chloride compound, anhydrides compound or Pyromellitic Acid;
Preferred acyl chloride compound be selected from benzene diacid chloride, ethanedioly chloride, glutaryl chlorine, succinyl chloride, sebacoyl chloride, azelaoyl chloride, suberoyl chlorine, phenylphosphonyl dichloride, fumaryl chloride, methyl malonyl chloride, ethyl ethanedioly chloride ester and 1,7-pimeloyl chloride any one;
Preferred anhydrides compounds is selected from hexafluorodianhydride (6FDA), 3-methylglutaric acid acid anhydride, ethylenediamine tetra-acetic acid dianhydride, cyclobutanetetracarboxylic dianhydride, 1, 2, 3, 4-ring penta tetracarboxylic dianhydride, 3, 4, 9, 10-perylene tetracarboxylic acid dianhydride, 1, 2, 4, 5-cyclohexanetetracarboxylic acid dianhydride, 3, 3, 4, 4-bibenzene tetracarboxylic dianhydride, 3, 3, 4, 4-bibenzene tetracarboxylic dianhydride, 3, 34, 4-benzophenone tetracarboxylic dianhydride, meso-butane-1, 2, 3, 4-tetracarboxylic dianhydride, pungent-7-the alkene-2 of dicyclo [2.2.2], 3, 5, 6-tetracarboxylic dianhydride, 1, 2, 3, 4-tetramethyl-1, 2, 3, 4-cyclobutane tetracarboxylic dianhydride, three rings [6.4.0.0 (2, 7)] dodecane-1, 2, 7, 8-tetracarboxylic acid dianhydride, bisphenol A dianhydride.
The described structural formula of compound shown in formula I is as follows:
Wherein, R
1, R
2and R
3be separately H, Cl, Br, I, OH, NH
2, any one in COOH, n1=1 ~ 4, n2=1 ~ 4, n3=1 ~ 4; R
4and R
5be separately H or the alkyl containing 1 ~ 3 carbon atom;
And: the compound shown in formula I: the mol ratio of the compound containing active group is 2:1 ~ 1:5; Acid binding agent: the mol ratio of the compound shown in formula I is 6:1 ~ 1:1.
As preferably: the compound shown in formula I: the mol ratio of the compound containing active group is 1:2 ~ 1:3.
In the preparation method of diffusion barrier of the present invention: described acid binding agent is organic base or inorganic base, and described organic base is selected from triethylamine or pyridine, and described inorganic base is selected from sodium carbonate, sodium acid carbonate, potash, NaOH or potassium hydroxide; The temperature of polymerisation is-10 ~ 150 DEG C, and the temperature of preferred polymeric reaction is 0 ~ 10 DEG C.; Polymerisation solvent used is selected from methyl pyrrolidone, dimethyl formamide, dimethylacetylamide, carrene, ether, carbon tetrachloride or toluene.
As preferably: R
4and R
5when being separately H, R
1, R
2and R
3pass be: R
2≠ H, R
1=R
3and R
1=R
3=H; Or R
1for H, R
2=R
3and R
2=R
3≠ H; Or R
1=R
2=R
3≠ H;
Or R
4and R
5be separately CH
2cH
3time, R
1, R
2and R
3pass be: R
1=R
2=R
3≠ H.
As more preferably: the compound shown in formula I be selected from following compound any one:
2,3-diaminourea triptycene; Or 2,3-dihydroxy triptycene;
Or 2,6-diaminourea triptycene; Or 2,6-dihydroxy triptycene; Or 2,6-dichloro triptycene; Or 2,6-diiodo-triptycene; Or 2,6-dibromo triptycene;
Or 2,7-diaminourea triptycene; Or 2,7-dihydroxy triptycene; Or 2,7-diiodo-triptycene; Or 2,7-dibromo triptycene; Or 2,7-dichloro triptycene;
Or 2,6,14-tri-iodo triptycene; Or 2,6,14-tribromo triptycene; Or 2,6,14-trihydroxy triptycene; Or 2,6,14-triamido triptycene;
Or 2,7,14-tri-iodo triptycene; Or 2,7,14-tribromo triptycene; Or 2,7,14-triamido triptycene; Or 2,7,14-trihydroxy triptycene;
Or 2,3,6,7-tetrahydroxy three dish alkene; Or 2,3,6,7-tetramino three dish alkene; Or 2,3,6,7-tetracarboxylic acid triptycene;
Or the amino triptycene of 2,3,6,7,14,15-six; Or 2,3,6,7,14,15-hexahydroxy triptycene; Or 2,3,6,7,14,15-hexabromo base triptycene; Or 2,3,6,7,14,15-hexaiodo base triptycene; Or 2,3,6,7,14,15-chlordene base triptycene;
Or 9,10-diethyl-2,3,6,7,12,13-hexahydroxy triptycene.
A kind of three dish thiazolinyl VOCs according to claim 1 retain the preparation method of type polymer separation film, the method be with the compound shown in formula I and containing the compound of active group for monomer, under the effect of acid binding agent, polymerisation 0.5h-60h, obtains film liquid after reaction terminates; Be coated on solvent resistant counterdie by the film liquid obtained, vacuum is crosslinked dry, obtains three dish thiazolinyl VOCs and retains type polymer separation film;
The described compound containing active group is selected from least one in acyl chloride compound, anhydrides compound or Pyromellitic Acid;
Preferred acyl chloride compound be selected from benzene diacid chloride, ethanedioly chloride, glutaryl chlorine, succinyl chloride, sebacoyl chloride, azelaoyl chloride, suberoyl chlorine, phenylphosphonyl dichloride, fumaryl chloride, methyl malonyl chloride, ethyl ethanedioly chloride ester and 1,7-pimeloyl chloride any one;
Preferred anhydrides compounds is selected from hexafluorodianhydride (6FDA), 3-methylglutaric acid acid anhydride, ethylenediamine tetra-acetic acid dianhydride, cyclobutanetetracarboxylic dianhydride, 1, 2, 3, 4-ring penta tetracarboxylic dianhydride, 3, 4, 9, 10-perylene tetracarboxylic acid dianhydride, 1, 2, 4, 5-cyclohexanetetracarboxylic acid dianhydride, 3, 3, 4, 4-bibenzene tetracarboxylic dianhydride, 3, 3, 4, 4-bibenzene tetracarboxylic dianhydride, 3, 34, 4-benzophenone tetracarboxylic dianhydride, meso-butane-1, 2, 3, 4-tetracarboxylic dianhydride, pungent-7-the alkene-2 of dicyclo [2.2.2], 3, 5, 6-tetracarboxylic dianhydride, 1, 2, 3, 4-tetramethyl-1, 2, 3, 4-cyclobutane tetracarboxylic dianhydride, three rings [6.4.0.0 (2, 7)] dodecane-1, 2, 7, 8-tetracarboxylic acid dianhydride, bisphenol A dianhydride.
The described structural formula of compound shown in formula I is as follows:
Wherein, R
1, R
2and R
3be separately H, Cl, Br, I, OH, NH
2, any one in COOH, n1=1 ~ 4, n2=1 ~ 4, n3=1 ~ 4; R
4and R
5be separately H or the alkyl containing 1 ~ 3 carbon atom.
And: the compound shown in formula I: the mol ratio of the compound containing active group is 2:1 ~ 1:5; Acid binding agent: the mol ratio of the compound shown in formula I is 6:1 ~ 1:1.
As preferably: the compound shown in formula I: the mol ratio of the compound containing active group is 1:2 ~ 1:3.
In described preparation method: acid binding agent is organic base or inorganic base, and described organic base is selected from triethylamine or pyridine, and described inorganic base is selected from sodium carbonate, sodium acid carbonate, potash, NaOH or potassium hydroxide; The temperature of polymerisation is-10 ~ 150 DEG C, and the temperature of preferred polymeric reaction is 0 ~ 10 DEG C; Polymerisation solvent used is selected from methyl pyrrolidone, dimethyl formamide, dimethylacetylamide, carrene, ether, carbon tetrachloride or toluene.
As preferably: R
4and R
5when being separately H, R
1, R
2and R
3pass be: R
2≠ H, R
1=R
3and R
1=R
3=H; Or R
1for H, R
2=R
3and R
2=R
3≠ H; Or R
1=R
2=R
3≠ H;
Or R
4and R
5be separately CH
2cH
3time, R
1, R
2and R
3pass be: R
1=R
2=R
3≠ H.
As more preferably: the compound shown in formula I be selected from following compound any one:
2,3-diaminourea triptycene; Or 2,3-dihydroxy triptycene;
Or 2,6-diaminourea triptycene; Or 2,6-dihydroxy triptycene; Or 2,6-dichloro triptycene; Or 2,6-diiodo-triptycene; Or 2,6-dibromo triptycene;
Or 2,7-diaminourea triptycene; Or 2,7-dihydroxy triptycene; Or 2,7-diiodo-triptycene; Or 2,7-dibromo triptycene; Or 2,7-dichloro triptycene;
Or 2,6,14-tri-iodo triptycene; Or 2,6,14-tribromo triptycene; Or 2,6,14-trihydroxy triptycene; Or 2,6,14-triamido triptycene;
Or 2,7,14-tri-iodo triptycene; Or 2,7,14-tribromo triptycene; Or 2,7,14-triamido triptycene; Or 2,7,14-trihydroxy triptycene;
Or 2,3,6,7-tetrahydroxy three dish alkene; Or 2,3,6,7-tetramino three dish alkene; Or 2,3,6,7-tetracarboxylic acid triptycene;
Or the amino triptycene of 2,3,6,7,14,15-six; Or 2,3,6,7,14,15-hexahydroxy triptycene; Or 2,3,6,7,14,15-hexabromo base triptycene; Or 2,3,6,7,14,15-hexaiodo base triptycene; Or 2,3,6,7,14,15-chlordene base triptycene;
Or 9,10-diethyl-2,3,6,7,12,13-hexahydroxy triptycene.
The name of above-mentioned particular compound is being numbered in the following order:
Beneficial effect of the present invention:
It is simple that three dish thiazolinyl VOCs of the present invention retain type polymer separation film preparation method, and the diffusion barrier prepared can be used alone, good separating effect, and film has solvent resistance, has higher segregational stability.
Accompanying drawing explanation
Fig. 1 is that the number of counterdie shines.
Fig. 2 is the number photograph that three dish thiazolinyl VOCs retain type polymer separation film.
Fig. 3 is the SEM figure that three dish thiazolinyl VOCs retain type surface of separating film of polymer.
Fig. 4 is the SEM figure that three dish thiazolinyl VOCs retain type polymer separation film section.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described, but protection scope of the present invention is not limited thereto:
Embodiment 1
The specific embodiment of the invention adopts 2, 3-diaminourea triptycene, sebacoyl chloride is as the principal monomer of synthesis, triethylamine is as acid binding agent, dimethyl formamide carries out synthetic reaction as solvent, its concrete steps are as follows: by 2 of 1mol, 3-diaminourea triptycene, the triethylamine of 3.5mol, the sebacoyl chloride of 2.5mol joins stirring and dissolving in dimethyl formamide solution, under temperature is 2 DEG C of (nitrogen protection) conditions, reaction 3h, the homopolycondensation mixed liquor of reaction is coated on polytetrafluoroethylene (PTFE) counterdie and is prepared into composite membrane, the composite membrane of coating is put into vacuum drying oven 70 DEG C oven dry, namely obtain three dish thiazolinyl VOCs and retain type polymer separation film.
The number of polytetrafluoroethylene (PTFE) counterdie shines as shown in Figure 1, the number that three dish thiazolinyl VOCs retain type polymer separation film shines as shown in Figure 2, three dish thiazolinyl VOCs retain the SEM figure on the surface of type polymer separation film as shown in Figure 3, and three dish thiazolinyl VOCs retain the SEM figure of type polymer separation film section as shown in Figure 4.
The average pore size that the three dish thiazolinyl VOCs prepared through BET testing example 1 retain type polymer separation film is 5nm.
Test condition is: under 25 DEG C of conditions, and with nitrogen/cyclohexane for separate raw materials gas, concentration is 20000ppm, and under pressure 10kpa, seepage velocity is at 10L/m
2during min, after UF membrane, per-meate side concentration is reduced to 7530ppm, and rejection is 62.35%.
Embodiment 2
The specific embodiment of the invention adopts 2, 6-dihydroxy triptycene, sebacoyl chloride is as the principal monomer of synthesis, triethylamine is as acid binding agent, carrene carries out synthetic reaction as solvent, its concrete steps are as follows: by 2 of 1mol, 3-diaminourea triptycene, the triethylamine of 4mol, the sebacoyl chloride of 2.5mol joins stirring and dissolving in dimethyl formamide solution, under temperature is 2 DEG C of (nitrogen protection) conditions, reaction 3.5h, the homopolycondensation mixed liquor of reaction is coated on polytetrafluoroethylene (PTFE) counterdie and is prepared into composite membrane, the composite membrane of coating is put into vacuum drying oven 70 DEG C oven dry, namely obtain three dish thiazolinyl VOCs and retain type polymer separation film.It is 3.4nm that the three dish thiazolinyl VOCs prepared through BET testing example 2 retain type polymer separation film average pore size.
Test condition is: under 25 DEG C of conditions, and with nitrogen/cyclohexane for separate raw materials gas, concentration is 20000ppm, and under pressure 10kpa, seepage velocity is at 5L/m
2during min, after UF membrane, per-meate side concentration is reduced to 5510ppm, and rejection is 72.45%.
Embodiment 3
The specific embodiment of the invention adopts 2, 6, 14-triamido triptycene, sebacoyl chloride is as the principal monomer of synthesis, pyridine is as acid binding agent, methyl pyrrolidone carries out synthetic reaction as solvent, its concrete steps are as follows: by 2 of 1mol, 6, 14-triamido triptycene, the pyridine of 3mol, the sebacoyl chloride of 2mol joins stirring and dissolving in methylpyrrolidone solution, under temperature is 2 DEG C of (nitrogen protection) conditions, reaction 3.5h, the homopolycondensation mixed liquor of reaction is coated on polytetrafluoroethylene (PTFE) counterdie and is prepared into composite membrane, the composite membrane of coating is put into vacuum drying oven 70 DEG C oven dry, namely obtain three dish thiazolinyl VOCs and retain type polymer separation film.The average pore size that the three dish thiazolinyl VOCs prepared through BET testing example 3 retain type polymer separation film is 2.8nm.
Test condition is: under 25 DEG C of conditions, and with nitrogen/cyclohexane for separate raw materials gas, concentration is 20000ppm, and under pressure 10kpa, seepage velocity is at 0.30L/m
2during min, after UF membrane, per-meate side concentration is reduced to 1750ppm, and rejection is more than 91.25%.
Embodiment 4
The specific embodiment of the invention adopts 2, 7, 14-triamido triptycene, sebacoyl chloride is as the principal monomer of synthesis, pyridine is as acid binding agent, methyl pyrrolidone carries out synthetic reaction as solvent, its concrete steps are as follows: by 2 of 1mol, 7, 14-triamido triptycene, the pyridine of 5mol, the sebacoyl chloride of 3mol joins stirring and dissolving in methylpyrrolidone solution, under temperature is 2 DEG C of (nitrogen protection) conditions, reaction 3.5h, the homopolycondensation mixed liquor of reaction is coated on polytetrafluoroethylene (PTFE) counterdie and is prepared into composite membrane, the composite membrane of coating is put into vacuum drying oven 70 DEG C oven dry, namely obtain three dish thiazolinyl VOCs and retain type polymer separation film.The average pore size that the three dish thiazolinyl VOCs prepared through BET testing example 4 retain type polymer separation film is 2.2nm.
Test condition is: under 25 DEG C of conditions, and with nitrogen/cyclohexane for separate raw materials gas, concentration is 20000ppm, and under pressure 10kpa, seepage velocity is at 0.27L/m
2during min, after UF membrane, per-meate side concentration is reduced to 1240ppm, and rejection is more than 93.8%.
Embodiment 5
The specific embodiment of the invention adopts 2, 3, 6, 7-tetrahydroxy three dish alkene, 1, 7-pimeloyl chloride is as the principal monomer of synthesis, pyridine is as acid binding agent, methyl pyrrolidone carries out synthetic reaction as solvent, its concrete steps are as follows: by 2 of 1.5mol, 3, 6, 7-tetrahydroxy three dish alkene, the pyridine of 3mol, 1 of 4.5mol, 7-pimeloyl chloride joins stirring and dissolving in methylpyrrolidone solution, under temperature is 2 DEG C of (nitrogen protection) conditions, reaction 3.5h, the homopolycondensation mixed liquor of reaction is coated on polytetrafluoroethylene (PTFE) counterdie and is prepared into composite membrane, the composite membrane of coating is put into vacuum drying oven 70 DEG C oven dry, namely obtain three dish thiazolinyl VOCs and retain type polymer separation film.The average pore size that the three dish thiazolinyl VOCs prepared through BET testing example 5 retain type polymer separation film is 2.0nm.
Test condition is: under 25 DEG C of conditions, and with nitrogen/cyclohexane for separate raw materials gas, concentration is 20000ppm, and under pressure 10kpa, seepage velocity is at 0.26L/m
2during min, after UF membrane, per-meate side concentration is reduced to 1530ppm, and rejection is more than 92.35%.
Embodiment 6
The specific embodiment of the invention adopts 2, 3, 6, 7, 14, the amino triptycene of 15-six, suberoyl chlorine is as the principal monomer of synthesis, pyridine is as acid binding agent, methyl pyrrolidone carries out synthetic reaction as solvent, its concrete steps are as follows: by 2 of 1mol, 3, 6, 7, 14, the amino triptycene of 15-six, the pyridine of 3.5mol, the suberoyl chlorine of 3mol joins stirring and dissolving in methylpyrrolidone solution, under temperature is 2 DEG C of (nitrogen protection) conditions, reaction 3.5h, the homopolycondensation mixed liquor of reaction is coated on polytetrafluoroethylene (PTFE) counterdie and is prepared into composite membrane, the composite membrane of coating is put into vacuum drying oven 70 DEG C oven dry, namely obtain three dish thiazolinyl VOCs and retain type polymer separation film.The average pore size that the three dish thiazolinyl VOCs prepared through BET testing example 6 retain type polymer separation film is 1.6nm.
Test condition is: under 25 DEG C of conditions, and with nitrogen/cyclohexane for separate raw materials gas, concentration is 20000ppm, and under pressure 10kpa, seepage velocity is at 0.15L/m
2during min, after UF membrane, per-meate side concentration is reduced to 710ppm, and rejection is more than 96.45%.
Embodiment 7
The specific embodiment of the invention adopts 9, 10-diethyl-2, 3, 6, 7, 12, 13-hexahydroxy triptycene, suberoyl chlorine is as the principal monomer of synthesis, pyridine is as acid binding agent, methyl pyrrolidone carries out synthetic reaction as solvent, its concrete steps are as follows: by 9 of 1mol, 10-diethyl-2, 3, 6, 7, 12, 13-hexahydroxy triptycene, the pyridine of 3.5mol, the suberoyl chlorine of 3mol joins stirring and dissolving in methylpyrrolidone solution, under temperature is 2 DEG C of (nitrogen protection) conditions, reaction 3.5h, the homopolycondensation mixed liquor of reaction is coated on polytetrafluoroethylene (PTFE) counterdie and is prepared into composite membrane, the composite membrane of coating is put into vacuum drying oven 70 DEG C oven dry, namely obtain three dish thiazolinyl VOCs and retain type polymer separation film.It is 1.3nm that the three dish thiazolinyl VOCs prepared through BET testing example 7 retain type polymer separation film average pore size.
Test condition is: under 25 DEG C of conditions, and with nitrogen/cyclohexane for separate raw materials gas, concentration is 20000ppm, and under pressure 10kpa, seepage velocity is at 0.10L/m
2during min, after UF membrane, per-meate side concentration is reduced to 630ppm, and rejection is more than 96.85%.
Claims (10)
1. a dish thiazolinyl VOCs retains type polymer separation film, it is characterized in that: this diffusion barrier prepares by the following method: the method with the compound shown in formula I and containing the compound of active group for monomer, under the effect of acid binding agent, polymerisation 0.5 ~ 60h under the condition of-10 ~ 150 DEG C, obtains film liquid after reaction terminates; Be coated on solvent resistant counterdie by the film liquid obtained, vacuum is crosslinked dry, obtains three dish thiazolinyl VOCs and retains type polymer separation film;
The described compound containing active group is selected from least one in acyl chloride compound, anhydrides compound or Pyromellitic Acid;
The described structural formula of compound shown in formula I is as follows:
Wherein, R
1, R
2and R
3be separately H, Cl, Br, I, OH, NH
2, any one in COOH, n1=1 ~ 4, n2=1 ~ 4, n3=1 ~ 4; R
4and R
5be separately H or the alkyl containing 1 ~ 3 carbon atom;
And: the compound shown in formula I: the mol ratio of the compound containing active group is 2:1 ~ 1:5, the compound shown in preferred formula I: the mol ratio of the compound containing active group is 1:2 ~ 1:3; Acid binding agent: the mol ratio of the compound shown in formula I is 6:1 ~ 1:1.
2. three dish thiazolinyl VOCs according to claim 1 retain type polymer separation film, it is characterized in that: described acid binding agent is organic base or inorganic base, described organic base is selected from triethylamine or pyridine, and described inorganic base is selected from sodium carbonate, sodium acid carbonate, potash, NaOH or potassium hydroxide;
Preferred acyl chloride compound be selected from benzene diacid chloride, ethanedioly chloride, glutaryl chlorine, succinyl chloride, sebacoyl chloride, azelaoyl chloride, suberoyl chlorine, phenylphosphonyl dichloride, fumaryl chloride, methyl malonyl chloride, ethyl ethanedioly chloride ester and 1,7-pimeloyl chloride any one;
Preferred anhydrides compounds is selected from hexafluorodianhydride (6FDA), 3-methylglutaric acid acid anhydride, ethylenediamine tetra-acetic acid dianhydride, cyclobutanetetracarboxylic dianhydride, 1, 2, 3, 4-ring penta tetracarboxylic dianhydride, 3, 4, 9, 10-perylene tetracarboxylic acid dianhydride, 1, 2, 4, 5-cyclohexanetetracarboxylic acid dianhydride, 3, 3, 4, 4-bibenzene tetracarboxylic dianhydride, 3, 3, 4, 4-bibenzene tetracarboxylic dianhydride, 3, 34, 4-benzophenone tetracarboxylic dianhydride, meso-butane-1, 2, 3, 4-tetracarboxylic dianhydride, pungent-7-the alkene-2 of dicyclo [2.2.2], 3, 5, 6-tetracarboxylic dianhydride, 1, 2, 3, 4-tetramethyl-1, 2, 3, 4-cyclobutane tetracarboxylic dianhydride, three rings [6.4.0.0 (2, 7)] dodecane-1, 2, 7, 8-tetracarboxylic acid dianhydride, bisphenol A dianhydride.
3. three dish thiazolinyl VOCs according to claim 1 retain type polymer separation film, it is characterized in that: the temperature of polymerisation is-10 ~ 150 DEG C.
4. three dish thiazolinyl VOCs according to claim 1 retain type polymer separation film, it is characterized in that: polymerisation solvent used is selected from methyl pyrrolidone, dimethyl formamide, dimethylacetylamide, carrene, ether, carbon tetrachloride or toluene.
5. three dish thiazolinyl VOCs according to claim 1 retain type polymer separation film, it is characterized in that:
R
4and R
5when being separately H, R
1, R
2and R
3pass be: R
2≠ H, R
1=R
3and R
1=R
3=H; Or R
1for H, R
2=R
3and R
2=R
3≠ H; Or R
1=R
2=R
3≠ H;
Or R
4and R
5be separately CH
2cH
3time, R
1, R
2and R
3pass be: R
1=R
2=R
3≠ H.
6. three dish thiazolinyl VOCs according to claim 5 retain type polymer separation film, it is characterized in that: the compound shown in formula I be selected from following compound any one:
2,3-diaminourea triptycene; Or 2,3-dihydroxy triptycene;
Or 2,6-diaminourea triptycene; Or 2,6-dihydroxy triptycene; Or 2,6-dichloro triptycene; Or 2,6-diiodo-triptycene; Or 2,6-dibromo triptycene;
Or 2,7-diaminourea triptycene; Or 2,7-dihydroxy triptycene; Or 2,7-diiodo-triptycene; Or 2,7-dibromo triptycene; Or 2,7-dichloro triptycene;
Or 2,6,14-tri-iodo triptycene; Or 2,6,14-tribromo triptycene; Or 2,6,14-trihydroxy triptycene; Or 2,6,14-triamido triptycene;
Or 2,7,14-tri-iodo triptycene; Or 2,7,14-tribromo triptycene; Or 2,7,14-triamido triptycene; Or 2,7,14-trihydroxy triptycene;
Or 2,3,6,7-tetrahydroxy three dish alkene; Or 2,3,6,7-tetramino three dish alkene; Or 2,3,6,7-tetracarboxylic acid triptycene;
Or the amino triptycene of 2,3,6,7,14,15-six; Or 2,3,6,7,14,15-hexahydroxy triptycene; Or 2,3,6,7,14,15-hexabromo base triptycene; Or 2,3,6,7,14,15-hexaiodo base triptycene; Or 2,3,6,7,14,15-chlordene base triptycene;
Or 9,10-diethyl-2,3,6,7,12,13-hexahydroxy triptycene.
7. three dish thiazolinyl VOCs according to claim 1 retain the preparation method of type polymer separation film, it is characterized in that: the method be with the compound shown in formula I and containing the compound of active group for monomer, under the effect of acid binding agent, polymerisation 0.5 ~ 60h under the condition of-10 ~ 150 DEG C, obtains film liquid after reaction terminates; Be coated on solvent resistant counterdie by the film liquid obtained, vacuum is crosslinked dry, obtains three dish thiazolinyl VOCs and retains type polymer separation film;
The described compound containing active group is selected from least one in benzene diacid chloride, ethanedioly chloride, glutaryl chlorine, succinyl chloride, sebacoyl chloride, hexafluorodianhydride (6FDA), bisphenol A dianhydride and Pyromellitic Acid; The described structural formula of compound shown in formula I is as follows:
Wherein, R
1, R
2and R
3be separately H, Cl, Br, I, OH, NH
2, any one in COOH, n1=1 ~ 4, n2=1 ~ 4, n3=1 ~ 4; R
4and R
5be separately H or the alkyl containing 1 ~ 3 carbon atom.
And: the compound shown in formula I: the mol ratio of the compound containing active group is 2:1 ~ 1:5; Acid binding agent: the mol ratio of the compound shown in formula I is 6:1 ~ 1:1; Compound shown in preferred formula I: the mol ratio of the compound containing active group is 1:2 ~ 1:3.
8. three dish thiazolinyl VOCs according to claim 7 retain the preparation method of type polymer separation film, it is characterized in that: described acid binding agent is organic base or inorganic base; Described organic base is selected from triethylamine or pyridine, and described inorganic base is selected from sodium carbonate, sodium acid carbonate, potash, NaOH or potassium hydroxide; Preferred: the temperature of polymerisation is-10 ~ 150 DEG C; Preferred: polymerisation solvent used is selected from methyl pyrrolidone, dimethyl formamide, dimethylacetylamide, carrene, ether, carbon tetrachloride or toluene;
Preferred acyl chloride compound be selected from benzene diacid chloride, ethanedioly chloride, glutaryl chlorine, succinyl chloride, sebacoyl chloride, azelaoyl chloride, suberoyl chlorine, phenylphosphonyl dichloride, fumaryl chloride, methyl malonyl chloride, ethyl ethanedioly chloride ester and 1,7-pimeloyl chloride any one;
Preferred anhydrides compounds is selected from hexafluorodianhydride (6FDA), 3-methylglutaric acid acid anhydride, ethylenediamine tetra-acetic acid dianhydride, cyclobutanetetracarboxylic dianhydride, 1, 2, 3, 4-ring penta tetracarboxylic dianhydride, 3, 4, 9, 10-perylene tetracarboxylic acid dianhydride, 1, 2, 4, 5-cyclohexanetetracarboxylic acid dianhydride, 3, 3, 4, 4-bibenzene tetracarboxylic dianhydride, 3, 3, 4, 4-bibenzene tetracarboxylic dianhydride, 3, 34, 4-benzophenone tetracarboxylic dianhydride, meso-butane-1, 2, 3, 4-tetracarboxylic dianhydride, pungent-7-the alkene-2 of dicyclo [2.2.2], 3, 5, 6-tetracarboxylic dianhydride, 1, 2, 3, 4-tetramethyl-1, 2, 3, 4-cyclobutane tetracarboxylic dianhydride, three rings [6.4.0.0 (2, 7)] dodecane-1, 2, 7, 8-tetracarboxylic acid dianhydride, bisphenol A dianhydride.
9. three dish thiazolinyl VOCs according to claim 1 retain type polymer separation film, it is characterized in that: R
4and R
5when being separately H, R
1, R
2and R
3pass be: R
2≠ H, R
1=R
3and R
1=R
3=H; Or R
1for H, R
2=R
3and R
2=R
3≠ H; Or R
1=R
2=R
3≠ H;
Or R
4and R
5be separately CH
2cH
3time, R
1, R
2and R
3pass be: R
1=R
2=R
3≠ H.
10. three dish thiazolinyl VOCs according to claim 9 retain type polymer separation film, it is characterized in that: the compound shown in formula I be selected from following compound any one:
2,3-diaminourea triptycene; Or 2,3-dihydroxy triptycene;
Or 2,6-diaminourea triptycene; Or 2,6-dihydroxy triptycene; Or 2,6-dichloro triptycene; Or 2,6-diiodo-triptycene; Or 2,6-dibromo triptycene;
Or 2,7-diaminourea triptycene; Or 2,7-dihydroxy triptycene; Or 2,7-diiodo-triptycene; Or 2,7-dibromo triptycene; Or 2,7-dichloro triptycene;
Or 2,6,14-tri-iodo triptycene; Or 2,6,14-tribromo triptycene; Or 2,6,14-trihydroxy triptycene; Or 2,6,14-triamido triptycene;
Or 2,7,14-tri-iodo triptycene; Or 2,7,14-tribromo triptycene; Or 2,7,14-triamido triptycene; Or 2,7,14-trihydroxy triptycene;
Or 2,3,6,7-tetrahydroxy three dish alkene; Or 2,3,6,7-tetramino three dish alkene; Or 2,3,6,7-tetracarboxylic acid triptycene;
Or the amino triptycene of 2,3,6,7,14,15-six; Or 2,3,6,7,14,15-hexahydroxy triptycene; Or 2,3,6,7,14,15-hexabromo base triptycene; Or 2,3,6,7,14,15-hexaiodo base triptycene; Or 2,3,6,7,14,15-chlordene base triptycene;
Or 9,10-diethyl-2,3,6,7,12,13-hexahydroxy triptycene.
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