CN116655915A - Polyimide compound and preparation method and application thereof - Google Patents
Polyimide compound and preparation method and application thereof Download PDFInfo
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- CN116655915A CN116655915A CN202310921128.0A CN202310921128A CN116655915A CN 116655915 A CN116655915 A CN 116655915A CN 202310921128 A CN202310921128 A CN 202310921128A CN 116655915 A CN116655915 A CN 116655915A
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- polyimide
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- dianhydride
- microplastic
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 118
- 239000004642 Polyimide Substances 0.000 title claims abstract description 111
- 150000001875 compounds Chemical class 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920000426 Microplastic Polymers 0.000 claims abstract description 76
- 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 70
- 239000000178 monomer Substances 0.000 claims abstract description 62
- 230000015556 catabolic process Effects 0.000 claims abstract description 44
- 238000006731 degradation reaction Methods 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 37
- 150000004985 diamines Chemical class 0.000 claims abstract description 30
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 28
- 239000003960 organic solvent Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000004952 Polyamide Substances 0.000 claims abstract description 13
- 229920002647 polyamide Polymers 0.000 claims abstract description 13
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical compound [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- 239000004793 Polystyrene Substances 0.000 claims description 19
- 229920003023 plastic Polymers 0.000 claims description 19
- 239000004033 plastic Substances 0.000 claims description 19
- 229920002223 polystyrene Polymers 0.000 claims description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- -1 potassium 4-trifluoromethylbenzene sulfinate Chemical compound 0.000 claims description 13
- 238000001179 sorption measurement Methods 0.000 claims description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 238000005286 illumination Methods 0.000 claims description 7
- 229920005575 poly(amic acid) Polymers 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- KAVUKAXLXGRUCD-UHFFFAOYSA-M sodium trifluoromethanesulfinate Chemical compound [Na+].[O-]S(=O)C(F)(F)F KAVUKAXLXGRUCD-UHFFFAOYSA-M 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 5
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 5
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 claims description 4
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- YJPOHGDCIPEPET-UHFFFAOYSA-M potassium;trifluoromethanesulfinate Chemical compound [K+].[O-]S(=O)C(F)(F)F YJPOHGDCIPEPET-UHFFFAOYSA-M 0.000 claims description 4
- 230000000593 degrading effect Effects 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 239000005060 rubber Substances 0.000 claims description 2
- XEVKXYBGTZUIRF-UHFFFAOYSA-M potassium 2,3,4,5,6-pentafluorobenzenesulfinate Chemical compound FC1=C(C(=C(C(=C1S(=O)[O-])F)F)F)F.[K+] XEVKXYBGTZUIRF-UHFFFAOYSA-M 0.000 claims 1
- DDHQSTKTIIQGSV-UHFFFAOYSA-M sodium;2,3,4,5,6-pentafluorobenzenesulfinate Chemical compound [Na+].[O-]S(=O)C1=C(F)C(F)=C(F)C(F)=C1F DDHQSTKTIIQGSV-UHFFFAOYSA-M 0.000 claims 1
- IRJVONHUBTUTAL-UHFFFAOYSA-M sodium;4-(trifluoromethyl)benzenesulfinate Chemical compound [Na+].[O-]S(=O)C1=CC=C(C(F)(F)F)C=C1 IRJVONHUBTUTAL-UHFFFAOYSA-M 0.000 claims 1
- 238000010525 oxidative degradation reaction Methods 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 17
- 239000011521 glass Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 15
- 150000004292 cyclic ethers Chemical group 0.000 description 12
- 238000001035 drying Methods 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 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 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 239000005457 ice water Substances 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 230000000813 microbial effect Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000007857 degradation product Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 238000013032 photocatalytic reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 150000003983 crown ethers Chemical group 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920000379 polypropylene carbonate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to environmental pollutionThe technical field of dye treatment, in particular to a polyimide compound and a preparation method and application thereof. The polyimide compound has a structure shown in a formula (I), wherein n is an integer between 20 and 50; r is R 1 Selected from single bonds, O, SO 2 Fluorenyl group,、Any one of them;representative (CH) 2 ) m Or (CH) 2 ) 2 O(CH 2 ) 2 M has a value of 2 or 3. The preparation method comprises the following steps: s1, in an organic solvent, carrying out polymerization reaction on a diamine monomer and a dianhydride monomer to obtain polyamide acid; s2, performing heat treatment on the polyamide acid obtained in the step S1 to obtain the polyimide compound. The polyimide prepared by the invention is matched with the sulfinate accelerator, so that the oxidative degradation of the microplastic can be realized, the degradation efficiency is high, and the process is safe and environment-friendly.Formula (I).
Description
Technical Field
The invention relates to the technical field of environmental pollutant treatment, in particular to a polyimide compound and a preparation method and application thereof.
Background
Microplastic generally refers to plastic fragments, films or particles with the particle size smaller than 5 mm, and belongs to a novel synthetic pollutant. The sources of the microplastic mainly comprise primary microplastic and secondary microplastic, wherein the primary microplastic mainly refers to microplastic particles directly discharged into the environment in the production and life of people; the secondary micro-plastic refers to micro-plastic particles generated by decomposing plastic garbage after physical, chemical and microbial actions. Compared with common plastics, the micro-plastics have small particle size and strong hydrophobicity, are easy to attach heavy metal ions, organic pollutants, microorganisms and the like in the environment to form composite pollutants, cause pollution to soil, water bodies, atmospheric environment and food chains, finally cause a series of pollution problems and bring threat and hidden danger to the environment and human health.
Although researchers have developed degradable environment-friendly plastics or materials which are not easy to produce microplastic in recent years, the cost is still high, the mass production cannot be realized in large scale, and the traditional plastic products cannot be replaced. In addition, researchers also find microorganisms with the capability of degrading the plastics in insect intestinal tracts, soil, sea and activated sludge, and the degradation speed of single microorganisms is slow, so that the plastics are degraded by adopting the microbial composite microbial agent, but unfortunately, the plastics are difficult to enrich in water or soil, so that the microbial composite microbial agent has low degradation efficiency on the plastics, and is unfavorable for practical application. Therefore, efficient handling of microplastic has become a widely-regarded problem for society.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of poor adsorption effect and low degradation efficiency of the micro plastics in the prior art, thereby providing a polyimide compound, a preparation method and application thereof, and improving the degradation efficiency of the micro plastics.
According to an embodiment of the present invention, in one aspect, the present invention provides a polyimide-based compound having a structure represented by formula (I),
formula (I)
Wherein, the value of n is an integer between 20 and 50;
R 1 selected from single bonds, O, SO 2 Fluorenyl group,、/>Any one of them;
representative (CH) 2 ) m Or (CH) 2 ) 2 O(CH 2 ) 2 M has a value of 2 or 3.
In the embodiment of the invention, the polyimide compound has any one of the following structures,
、/>、、/>、、/>、、/>、、/>、、/>、、/>、、/>、、/>and。
according to an embodiment of the present invention, in another aspect, the present invention provides a method for preparing a polyimide-based compound, including the steps of:
s1, in an organic solvent, carrying out polymerization reaction on a diamine monomer shown in a formula (II) and a dianhydride monomer shown in a formula (III) to prepare polyamide acid;
in the formula (II) of the present invention,representative (CH) 2 ) m Or (CH) 2 ) 2 O(CH 2 ) 2 M has a value of 2 or 3;
in the formula (III), R 1 Selected from single bonds, O, SO 2 Fluorenyl group,、/>Any one of them;
s2, performing heat treatment on the polyamide acid obtained in the step S1 to obtain the polyimide compound.
In an embodiment of the present invention, the cyclic ether groups introduced into the diamine monomerSelected from crown ether groups containing at least three-OCH groups 2 CH 2 -a structural unit.
Alternatively, the diamine monomer containing a cyclic ether group is at least one of diaminodibenzo 12-crown-4-ether, diaminodibenzo 15-crown-5-ether, and diaminodibenzo 18-crown-6-ether.
Alternatively, the dianhydride monomer is selected from at least one of 3,3', 4' -biphenyl tetracarboxylic dianhydride, bisphenol AF dianhydride, 3, 4-diphenyl sulfone tetracarboxylic dianhydride, bis [ (3, 4-dianhydride) phenyl ] terephthalate, 4' -biphenyl ether dianhydride, 9-bis (3, 4-dicarboxylic acid phenyl) fluorene dianhydride.
In the embodiment of the invention, optionally, the molar ratio of the diamine monomer containing the cyclic ether group to the dianhydride monomer is 1:1-2.
In the embodiment of the invention, optionally, the diamine monomer is dissolved in the organic solvent, the dianhydride monomer is added at least 3 times at the temperature of-5 ℃ to 5 ℃, and the reaction is stirred at room temperature after the addition is completed.
In the embodiment of the present invention, optionally, the organic solvent is at least one of N, N-dimethylacetamide, dichloromethane, chloroform, acetonitrile, and dimethyl sulfoxide.
In an embodiment of the present invention, optionally, the polymerization time is 24 hours or more.
In the embodiment of the present invention, optionally, in step S2, the temperature of the heat treatment is 180 ℃ to 300 ℃ and the time is more than 2.5 hours.
In the embodiment of the present invention, the polyamic acid solution obtained in the step S1 is optionally coated on a support, dried, and then heat-treated to obtain a polyimide film.
In the embodiment of the invention, the carrier coated with the polyamic acid is optionally subjected to heat treatment at 150-180 ℃, 200-210 ℃, 230-240 ℃, 260-270 ℃ and 300 ℃ in sequence, and the heat treatment time under each temperature condition is more than 0.5 h.
According to the embodiment of the invention, on the other hand, the polyimide compound or the polyimide compound prepared by the preparation method provided by the invention is applied to degradation of microplastic or degradation of rubber particles.
According to the embodiment of the invention, the invention also provides a degradation method of the microplastic, which comprises the following steps:
mixing the micro-plastics, the accelerator, the adsorption material and the organic solvent to obtain a mixed solution, and irradiating the mixed solution with light with the wavelength of 400-405 nm in an aerobic environment; the adsorbent is polyimide compound provided by the invention or prepared by the preparation method, and the accelerator is sulfinate.
In the embodiment of the invention, optionally, the mass ratio of the adsorption material to the accelerator is 100:1-4.
In the embodiment of the present invention, optionally, the sulfinate is at least one of sodium trifluoromethylsulfinate, potassium trifluoromethylsulfinate, sodium 4-trifluoromethylsulfinate, potassium 4-trifluoromethylsulfinate, sodium pentafluorosulfinate and potassium pentafluorosulfinate.
In the embodiment of the invention, optionally, the illumination power is 3-6 w, and the illumination time is 1-14 d.
In the embodiment of the invention, optionally, the mass ratio of the micro plastic to the adsorption material is 1:50-100.
In an embodiment of the present invention, optionally, the micro plastic is at least one of polyethylene, polyvinyl chloride, polypropylene, polystyrene, and polycarbonate.
In the embodiment of the present invention, optionally, the organic solvent is at least one of dichloromethane, chloroform, and acetonitrile.
The technical scheme of the invention has the following advantages:
1. the polyimide compound with the structure shown in the formula (I) provided by the invention has the molecular structure containing the cyclic ether group, the benzene ring and the imide ring, on one hand, the polyimide compound provided by the invention can be well contacted with the microplastic dispersed in the organic solvent, so that the imide ring and the benzene ring can have pi-pi effect with the microplastic, and the alkyl in the cyclic ether group can also have hydrophobic effect with the microplastic, thereby realizing effective enrichment of the microplastic; on the other hand, the oxygen atoms in the cyclic ether groups and the proper cavity size can effectively complex metal ions in the sulfinate accelerator, so that the dispersibility of the accelerator is increased, the accelerator can be fully contacted with the microplastic, and meanwhile, the accelerator is collected on the surface of the polyimide compound to create a photocatalysis reaction site, promote the progress of the photocatalysis reaction and improve the degradation efficiency of the microplastic.
2. The preparation method of polyimide provided by the invention comprises the following steps of S1, carrying out polymerization reaction on diamine monomer and dianhydride monomer in an organic solvent to obtain polyamide acid; s2, performing heat treatment on the polyamide acid to obtain polyimide. The preparation method has the advantages of short synthetic line, simple and convenient operation, easily available raw materials and low preparation cost.
3. The degradation method of the microplastic comprises the steps of mixing the microplastic, the accelerator and the polyimide compound with an organic solvent to obtain a mixed solution, and irradiating the mixed solution with light with the wavelength of 400-405 nm in an aerobic environment. The invention utilizes the characteristics of polyimide compounds, such as enrichment adsorption of the microplastic and dispersion of the accelerator, so that the accelerator can fully contact with the microplastic, and degradation efficiency is improved. The degradation method provided by the invention is simple and convenient to operate, mild in reaction condition, high in degradation efficiency, simple and convenient to obtain, free from additional photosensitizer and potential in development value, and can be used for efficiently realizing the oxidative degradation of the microplastic at normal temperature and normal pressure by means of the photocatalytic oxidation reaction principle.
The degradation mixed solution has no waste, no use of strong acid and strong alkali, energy conservation and emission reduction, no pollution to the environment, and simultaneously, the polyimide compound can be uniformly dispersed in the organic solvent, after photocatalytic decomposition is completed, the solvent is concentrated, and the degradation products and salts can be washed by adopting the small-polarity ether solvent and water for washing, so that the polyimide compound material can be recovered and recycled.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared spectrum of a polyimide prepared in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance spectrum of the polyimide prepared in example 1 of the present invention.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Polyethylene, polyvinyl chloride, polypropylene, polystyrene, polycarbonate microplastic having a particle size of 1 μm used in the examples, comparative examples and application examples of the present invention were all purchased from Chemicals Inc.
In consideration of the fact that the microplastic generally has larger specific surface area and lipophilicity, in order to facilitate enrichment of the microplastic and improve the degradation rate of the microplastic, the invention provides a polyimide compound, the material can perform pi-pi action and hydrophobic action with the microplastic so as to absorb and enrich the microplastic on the surface of a polyimide material, and a cyclic ether cavity in the polyimide material can effectively complex metal ions (potassium or sodium) in a sulfinate accelerator, so that the dispersibility of the accelerator is improved, and meanwhile, the accelerator is collected on the surface of the polyimide material to create a photocatalytic reaction site, promote photocatalytic reaction and improve degradation efficiency, and the oxidative degradation of the microplastic can be realized under the condition of room temperature photocatalysis.
Taking diamino dibenzo-18-crown-6-ether as diamine monomer and taking 3,3', 4' -biphenyl tetracarboxylic dianhydride as dianhydride monomer as an example, the reaction formula for preparing the polyimide compound is as follows:
the polyimide compound adsorption/complexing metal principle is as follows:
m represents metal ions, and cavities with different cyclic ether structures can complex different kinds of metal ions.
The principle of photocatalytic degradation of the microplastic by adopting the polyimide compound and the accelerator is as follows:
on the one hand, the accelerator sulfinate generates high-valence sulfide under the condition of light reaction, and then is oxidized to generate a free radical intermediate; on the other hand, polystyrene microplastic enriched near the polyimide compound is used as a free radical acceptor to generate benzyl carbon free radical species, and the benzyl carbon free radical species and the free radical peroxy negative ions are continuously combined to react to obtain acetophenone and benzoic acid, so that the degradation of the microplastic polystyrene is realized.
The invention provides a preparation method of polyimide compounds, which comprises the following steps:
s1, in an organic solvent, carrying out polymerization reaction on a diamine monomer shown in a formula (II) and a dianhydride monomer shown in a formula (III) to prepare polyamide acid;
in the formula (II) of the present invention,representative (CH) 2 ) m Or (CH) 2 ) 2 O(CH 2 ) 2 M has a value of 2 or 3;
in the formula (III), R 1 Selected from single bonds, O, SO 2 Fluorenyl group,、/>Any one of them;
s2, performing heat treatment on the polyamide acid obtained in the step S1 to obtain the polyimide compound.
In the present invention, the cyclic ether group introduced into the diamine monomer is selected from crown ether groups containing at least three-OCH groups 2 CH 2 -structural units, preferably 3-6-OCH 2 CH 2 -a structural unit.
Preferably, the diamine monomer is selected from diaminodibenzo 12-crown-4-etherDiaminodibenzo 15-crown-5-ether +.>Diaminodibenzo-18-crown-6-ether->At least one of them.
The dianhydride monomer comprises but not limited to various commercially available dianhydrides selected from 3,3', 4' -biphenyl tetracarboxylic dianhydrideBisphenol AF dianhydride>3, 4-diphenyl sulfone tetracarboxylic acidAcid dianhydride->Bis [ (3, 4-dianhydride) phenyl ]]Terephthalic acid ester4,4' -Biphenyl ether dianhydride->9, 9-bis (3, 4-dicarboxylic acid phenyl) fluorene dianhydride +.>One of them.
In the present invention, the step of mixing the diamine monomer with the dianhydride monomer and the organic solvent includes: the diamine monomer with the cyclic ether group introduced is dissolved in an organic solvent to obtain a solution, and then the dianhydride monomer is added to the solution for a plurality of times (at least 3 times) to fully dissolve the dianhydride monomer. Preferably, the molar ratio of the dianhydride monomer to the cyclic ether group-incorporating diamine monomer is 1.0 to 2.0:1, preferably 1:1.
The organic solvent is at least one selected from N, N-dimethylacetamide, dichloromethane, chloroform, acetonitrile and dimethyl sulfoxide, preferably N, N-dimethylacetamide; the polymerization reaction temperature is-5 ℃ to 5 ℃, and is preferably an ice water bath environment with the temperature of 3 ℃ to 5 ℃; the polymerization time is 24 hours or more, preferably 24 hours.
In the invention, diamine monomer and dianhydride monomer are polymerized to obtain polyamide acid (PAA) solution, if the PAA solution is not directly used, the prepared PAA is transferred into a sealed bottle, stored at a low temperature for standby, taken out when the PAA solution is used, and placed until the PAA solution returns to normal temperature.
In the invention, the heat treatment can be gradient heating, the temperature range is 60-300 ℃, and the total treatment time is 4.5-11 h.
In the invention, the preparation method further comprises the step of preparing the polyimide compound into a film: and (2) coating the polyamic acid solution obtained in the step (S1) on a carrier, drying, and then performing heat treatment to obtain the polyimide film.
Preferably, firstly, a carrier (glass plate) after film formation is placed in a vacuum oven, solvent removal is carried out by respectively baking at 60-90 ℃, 100-140 ℃ and 150-170 ℃ for 0.5-2 hours, then the glass plate after solvent removal is placed in a muffle furnace, temperature programming is carried out sequentially at 150-180 ℃, 200-210 ℃, 230-240 ℃, 260-270 ℃ and 300 ℃, and each heat treatment is carried out for 0.5-1 hour, so that imidization operation is completed. Finally, the glass plate is taken out and placed in distilled water with the temperature of 70-90 ℃ for demoulding, and then the removed film is dried, and then the glass plate is placed in a vacuum oven with the temperature of 50-70 ℃ for drying treatment, so that the polyimide film is obtained. In the present invention, the thickness of the polyimide film is 25 μm to 100 μm.
The polyimide compound is applied to photocatalytic oxidative degradation of microplastic.
A method for degrading microplastic, comprising the steps of: the polyimide compound obtained by the method is used as an adsorption material, the micro plastic, the accelerator, the adsorption material and the organic solvent are mixed to obtain a mixed solution, and the mixed solution is irradiated by light with the wavelength of 400-405 nm in an aerobic environment.
In the invention, the accelerator is sulfinate, and the sulfinate is at least one of sodium trifluoromethylsulfinate, potassium trifluoromethylsulfinate, sodium 4-trifluoromethylsulfinate, potassium 4-trifluoromethylsulfinate, sodium pentafluorosulfinate and potassium pentafluorosulfinate.
The microplastic to be treated is at least one selected from polyethylene, polyvinyl chloride, polypropylene, polystyrene and polycarbonate.
The mass ratio of the adsorption material to the accelerator is 100:1-4.
In the invention, the solvent is selected from any one of dichloromethane, chloroform, acetonitrile, 1, 2-dichloromethane, dimethyl sulfoxide and N, N-dimethylformamide.
In the invention, the illumination wavelength of the photocatalytic oxidation reaction is 400-405 nm, the illumination power is 3-6W, and the illumination time is 1-14 d.
In the invention, the photocatalytic oxidation reaction can be performed in an aerobic environment, wherein the oxygen content in the air is 20-30%, preferably 21%, and the oxygen environment is pure oxygen.
In the invention, the step of dissolving the polyimide compound and the microplastic to be treated in an organic solvent to form a reaction mixed solution comprises the following steps: adding the microplastic into an organic solvent to obtain a microplastic solution, and dispersing the polyimide compound into the microplastic solution to form a reaction mixed solution.
Preferably, when preparing the micro plastic solution, weighing a certain mass of micro plastic powder, mixing with dichloromethane, preparing a micro plastic standard solution with the concentration of 10-20 mg/mL, and diluting into micro plastic solutions with different concentrations of 1-5 mg/mL for later use.
Because polyimide compounds are adopted, the polyimide compounds can generate pi-pi action and hydrophobic action with the microplastic, so that the microplastic is adsorbed and enriched on the surface of the polyimide compounds, after the accelerator is added, the cyclic ether pore cavity in the polyimide compounds can effectively complex metal ions in the accelerator, the dispersibility of the accelerator is increased, and the efficient photocatalytic oxidative degradation of the microplastic can be realized under the condition of photocatalysis at room temperature.
Example 1
The embodiment provides a preparation method of polyimide, which comprises the following steps:
(1) 0.39. 0.39 g (1.0 mmol) of diaminodibenzo-18-crown-6-ether was weighed out and had the structural formulaDissolving in a three-neck flask with a plug containing 15 mL of N, N-Dimethylacetamide (DMAC) under the dry nitrogen atmosphere, stirring for 1h under the ice-water bath environment at the temperature of 4 ℃, adding 3,3', 4' -biphenyl tetracarboxylic dianhydride (the molar ratio of the 3,3', 4' -biphenyl tetracarboxylic dianhydride to the diamine monomer is 1.02:1) into the three-neck flask for 3 times according to a half feeding method after the powdery diamine monomer is completely dissolved, adding 3 mL of DMAC solvent while adding the dianhydride monomer each time, and stirring for 1h under the ice-water bath environment at the temperature of about 4 ℃ to ensure that the dianhydride monomer is completely dissolved, and the total amount of the added DMAC solvent is 10mL; after all dianhydride monomers are added, stirring continuously for 24h under the room temperature environment to obtainThe polyamic acid (PAA) solution is obtained, and then the prepared PAA is transferred into a sealed bottle of 50 mL and is preserved at low temperature for standby;
(2) Taking out the PAA solution stored at the low temperature, placing the PAA solution in a normal temperature environment for recovery to normal temperature, coating the PAA solution on a glass plate, horizontally placing the glass plate in a vacuum oven after coating, respectively drying 1h in the vacuum oven at 80 ℃, 120 ℃ and 150 ℃, removing the solvent, placing the glass plate with the solvent removed in a muffle furnace, sequentially carrying out heat treatment at 180 ℃, 210 ℃, 240 ℃, 270 ℃ and 300 ℃ for 0.5h, completing imidization operation, cooling the muffle furnace to the room temperature, taking out the glass plate, demoulding in distilled water at 80 ℃, wiping the removed film, and then placing the dried film in the vacuum oven at 60 ℃ for drying treatment, thus finally obtaining the polyimide film with the thickness of 25 mu m.
The molecular weight of the polyimide was 2.9x10 as measured by gel chromatography (GPC) 4 It is found that the polymerization degree n is 38. Fig. 1 is an infrared spectrum of the polyimide prepared in this example, and fig. 2 is a nuclear magnetic hydrogen spectrum of the polyimide prepared in this example.
Example 2
The present example provides a method for preparing polyimide, which has the same specific steps and parameters as those of example 1, except that the diamine monomer is diaminodibenzo 12-crown-4-ether, and the polymerization degree n of the prepared polyimide is 44 according to the calculation.
Example 3
The present example provides a method for preparing polyimide, the specific steps and parameters are the same as those of example 1, except that diamine monomer is diaminodibenzo 15-crown-5-ether, and the polymerization degree n of the prepared polyimide is 39 according to calculation.
Example 4
The present example provides a method for preparing polyimide, which has the same specific steps and parameters as those of example 1, except that the dianhydride monomer is bisphenol AF dianhydride, and the polymerization degree n of the prepared polyimide is 42 according to the calculation.
Example 5
The embodiment provides a preparation method of polyimide, which comprises the following steps:
(1) 0.39. 0.39 g (1.0 mmol) of diaminodibenzo 12-crown-4-ether was weighed out and had the structural formulaDissolving in 15 mL of N, N-Dimethylacetamide (DMAC) in a three-neck flask with a plug under the atmosphere of dry nitrogen, stirring 1h in an ice-water bath environment at the temperature of 4 ℃, adding 9, 9-bis (3, 4-dicarboxylic acid phenyl) fluorene dianhydride (the molar ratio of the 9-bis (3, 4-dicarboxylic acid phenyl) to diamine is 2:1) into the three-neck flask for 4 times according to a half feeding method after the powdery diamine monomer is completely dissolved, adding 3 mL of DMAC solvent at the same time when adding dianhydride each time, stirring 1h at the temperature of about 4 ℃ in an ice-water bath environment each time, and ensuring that the dianhydride is completely dissolved, wherein the total amount of the DMAC solvent is 10mL; after all dianhydride is added into the reaction mixed solution, continuously stirring for 40 hours at room temperature to obtain polyamide acid (PAA) solution, and then transferring the prepared PAA into a 50 mL sealed bottle for low-temperature storage for later use;
(2) Taking out the PAA solution stored at the low temperature, placing the PAA solution in a normal temperature environment for recovery to normal temperature, coating the PAA solution on a glass plate, horizontally placing the glass plate in a vacuum oven after coating, respectively drying the glass plate in the vacuum oven at 80 ℃, 120 ℃ and 150 ℃ for removing the solvent, placing the glass plate with the solvent removed in a muffle furnace, sequentially heating the glass plate in a temperature condition of 150 ℃, 200 ℃, 230 ℃, 260 ℃ and 300 ℃ in sequence, wherein the heat treatment time under each temperature condition is 0.5h, completing imidization operation, taking out the glass plate after the muffle furnace is cooled to the room temperature, demoulding the glass plate in distilled water at 80 ℃, wiping the removed film, and then placing the glass plate in the vacuum oven at 60 ℃ for drying treatment to finally obtain the polyimide compound with the thickness of 100 mu m.
The molecular weight of the polyimide was 2.36x10 as measured by gel chromatography (GPC) 4 It was found that the polymerization degree n of the polyimide thus obtained was 31.
Example 6
The embodiment provides a preparation method of polyimide, which comprises the following steps:
(1) Weighing 0.39 g (1.0 mmol) of diaminodibenzo-18-crown-6-ether, dissolving in a three-neck flask with a plug containing 15 mL of N, N-Dimethylacetamide (DMAC) under a dry nitrogen atmosphere, stirring for 1h under an ice-water bath environment at 4 ℃, adding 3,3', 4' -biphenyltetracarboxylic dianhydride (the molar ratio of the 3,3', 4' -biphenyltetracarboxylic dianhydride to the diamine is 1:1) into the three-neck flask for 5 times according to a half feeding method after the powdery diamine monomer is completely dissolved, adding 3 mL of DMAC solvent each time when the dianhydride is added, stirring for 1h each time under an ice-water bath environment at about 4 ℃ to ensure that the dianhydride is completely dissolved, and the total amount of the DMAC solvent is 10mL; after all dianhydride is added into the reaction mixture, continuously stirring the mixture for 24h under the room temperature environment to obtain polyamide acid (PAA) solution, transferring the prepared PAA into a 50 mL sealed bottle, and preserving the PAA at a low temperature for later use;
(2) And (3) placing the PAA solution stored at the low temperature in a vacuum oven, respectively drying 1h in the vacuum oven at 80 ℃, 120 ℃ and 150 ℃, placing the solvent-removed solution in a muffle furnace, sequentially heating the solution at 180 ℃, 210 ℃, 240 ℃, 270 ℃ and 300 ℃ in a programmed manner, wherein the heat treatment time under each temperature condition is 0.5h, completing imidization operation, waiting for the muffle furnace to cool to room temperature, and then placing the solution in the vacuum oven at 60 ℃ for drying treatment, thus finally obtaining the polyimide material.
The molecular weight of the polyimide was 2.52x10 as measured by gel chromatography (GPC) 4 The polymerization degree n of the polyimide thus obtained was 33.
Example 7
The present example provides a method for preparing polyimide, the specific steps and parameters are the same as those of example 1, except that the dianhydride monomer is 3, 4-diphenyl sulfone tetracarboxylic dianhydride, and the polymerization degree n of the prepared polyimide is 42 according to the calculation.
Example 8
The present example provides a method for preparing polyimide, the specific steps and parameters are the same as those of example 1, except that the dianhydride monomer is bis [ (3, 4-dianhydride) phenyl ] terephthalate, and the polymerization degree n of the prepared polyimide is 50 according to the calculation.
Example 9
The present example provides a method for preparing polyimide, which has the same specific steps and parameters as those of example 1, except that the dianhydride monomer is 4,4' -biphenyl ether dianhydride, and the polymerization degree n of the prepared polyimide is 45 according to the calculation.
Example 10
The present example provides a method for preparing polyimide, the specific steps and parameters are the same as those of example 1, except that the dianhydride monomer is 9, 9-bis (3, 4-dicarboxylic acid phenyl) fluorene dianhydride, and the polymerization degree n of the prepared polyimide is 48 according to the calculation.
Example 11
The present example provides a method for preparing polyimide, which has the same specific steps and parameters as those of example 2, except that the dianhydride monomer is bisphenol AF dianhydride, and the polymerization degree n of the prepared polyimide is 33 according to the calculation.
Example 12
The present example provides a method for preparing polyimide, the specific steps and parameters are the same as those of example 2, except that the dianhydride monomer is 3, 4-diphenyl sulfone tetracarboxylic dianhydride, and the polymerization degree n of the prepared polyimide is 20 according to calculation.
Example 13
The present example provides a method for preparing polyimide, the specific steps and parameters are the same as those of example 2, except that the dianhydride monomer is bis [ (3, 4-dianhydride) phenyl ] terephthalate, and the polymerization degree n of the prepared polyimide is 40 according to the calculation.
Example 14
The present example provides a method for preparing polyimide, which has the same specific steps and parameters as those of example 2, except that the dianhydride monomer is 4,4' -biphenyl ether dianhydride, and the polymerization degree n of the prepared polyimide is 38 according to the calculation.
Example 15
The present example provides a method for preparing polyimide, which has the same specific steps and parameters as those of example 3, except that the dianhydride monomer is bisphenol AF dianhydride, and the polymerization degree n of the prepared polyimide is 46 according to the calculation.
Example 16
The present example provides a method for preparing polyimide, the specific steps and parameters are the same as those of example 3, except that the dianhydride monomer is 3, 4-diphenyl sulfone tetracarboxylic dianhydride, and the polymerization degree n of the prepared polyimide is 33 according to the calculation.
Example 17
The present example provides a method for preparing polyimide, the specific steps and parameters are the same as those of example 3, except that the dianhydride monomer is bis [ (3, 4-dianhydride) phenyl ] terephthalate, and the polymerization degree n of the prepared polyimide is 40 according to the calculation.
Example 18
The present example provides a method for preparing polyimide, which has the same specific steps and parameters as those of example 3, except that the dianhydride monomer is 4,4' -biphenyl ether dianhydride, and the polymerization degree n of the prepared polyimide is 28 according to the calculation.
Example 19
The present example provides a method for preparing polyimide, the specific steps and parameters are the same as those of example 3, except that the dianhydride monomer is 9, 9-bis (3, 4-dicarboxylic acid phenyl) fluorene dianhydride, and the polymerization degree n of the prepared polyimide is 32 according to the calculation.
Comparative example 1
This comparative example provides a method for producing polyimide, which is different from example 1 in that the diamine monomer is ethylenediamine.
Comparative example 2
This comparative example provides a method for producing polyimide, which is different from example 1 in that the diamine monomer is p-phenylenediamine.
Application example 1
The polyimide materials prepared in examples 1-4 and comparative examples 1-2 were used to create a method for photocatalytic oxidative degradation of microplastic, wherein the microplastic is polystyrene microplastic, comprising the steps of:
(1) Preparation of polystyrene microplastic solution
100mg of polystyrene micro-plastic powder (particle size: 1. Mu.M) was weighed and added to 10mL methylene chloride to prepare 10mg/mL of polystyrene plastic particle standard solution, which was then diluted to 1mg/mL.
(2) Reaction mixed solution for establishing photocatalytic oxidation degradation of polystyrene micro-plastics
Taking 2mL of 1mg/mL polystyrene micro-plastic solution, 100mg of polyimide material prepared in example 1 and 1mg of sodium triflate accelerator, namely sodium triflate, dispersing the polyimide material and the sodium triflate accelerator in 10mL methylene dichloride to form a reaction mixed solution, and then placing the reaction mixed solution into a 3W blue LED (with the wavelength of 400-405 nm) photoreaction device to react for 14d in an air atmosphere at room temperature.
Extracting the system after the reaction is finished with diethyl ether and water for 3 times, combining the extracted diethyl ether organic phases, adding anhydrous sodium sulfate for drying, then performing rotary evaporation, and purifying the concentrated crude product by column chromatography to obtain a degradation product, wherein the column chromatography silica gel is 200-300 meshes, the eluting agent is petroleum ether and ethyl acetate with the volume ratio of 10:1, and the degradation product is characterized and verified by nuclear magnetic spectrum, and the degradation product is proved to contain acetophenone and benzoic acid, acetophenone: 1 H NMR (400 MHz, CDCl 3 ) δ 7.96 (d, J = 8.0 Hz, 2H), 7.56 (t, J = 7.8 Hz, 1H), 7.46 (t, J = 7.2 Hz, 2H), 2.61 (s, 3H). 13 C NMR (101 MHz, CDCl 3 ) Delta 198.1, 137.1, 133.0, 128.5, 128.2, 26.6. Benzoic acid: 1 H NMR (400 MHz, DMSO-d 6 ) δ 7.95 (d, J = 7.6 Hz, 2H), 7.62 (t, J = 7.4 Hz, 1H), 7.49 (t, J = 7.6 Hz, 2H). 13 C NMR (101 MHz, DMSO-d 6 ) δ 167.5, 133.0, 130.8, 129.4, 128.7。
this shows that the oxidative degradation of polystyrene microplastic is achieved by this method, and the degradation rate of the microplastic is shown in table 1.
The reaction formula of the above reaction is expressed as:
the degradation effects of the microplastic in the presence of the polyimide materials prepared in examples 1 to 4 and comparative examples 1 to 2, respectively, were tested in the same manner as described above, and the results are shown in Table 1.
TABLE 1 degradation Rate of polystyrene microplastic in the Presence of different polyimides
As can be seen from table 1, after the diamine monomer is replaced by ethylenediamine and p-phenylenediamine in comparative examples 1-2, the prepared product cannot enrich the polystyrene, and the degradation efficiency is significantly reduced.
Application example 2
Degradation tests were carried out by the same method as in application example 1, and polystyrene microplastic was replaced with polyethylene, polyvinyl chloride, polypropylene, and polycarbonate microplastic of equal mass, and the products were tested and the degradation rate of the microplastic was calculated, wherein polyimide material was prepared in example 1, and the results are shown in table 2.
TABLE 2 degradation effects of different microplastic materials
Application example 3
Degradation test was performed by the same method as in application example 1, and the accelerator sodium trifluoromethylsulfinate was replaced with potassium trifluoromethylsulfinate, sodium 4-trifluoromethylsulfinate, potassium 4-trifluoromethylsulfinate, sodium pentafluorosulfinate, potassium pentafluorosulfinate, and the products were tested and the degradation rate of the microplastic was calculated, wherein a polyimide material was prepared in example 1, and the results are shown in Table 3.
TABLE 3 degradation effects of microplastic under the action of different accelerators
Application example 4
Degradation test was performed by the same method as in application example 1, the injection amount of accelerator sodium trifluoromethylsulfinate was adjusted to 2mg, 3mg, 4mg, 5mg, and the products were tested and the degradation rate of microplastic was calculated, wherein polyimide material was prepared in example 1, and the results are shown in Table 4.
TABLE 4 degradation effects of microplastic under the action of accelerators with different contents
/>
Application example 5
Degradation tests were conducted by the same method as in application example 1, except that the ambient atmosphere for the photocatalytic reaction was air (oxygen content 21%) and oxygen (oxygen content 100%), respectively, and the degradation rates of the photocatalytic oxidation on the polystyrene microplastic at different reaction times were measured, wherein a polyimide material was prepared in example 1, and the results are shown in table 5.
TABLE 5 degradation effects of microplastic in different aerobic environments
Application example 6
Degradation tests were conducted by the same method as in application example 1 except that polyimide film material was not added, and the degradation rate of the polystyrene micro-plastic by photocatalytic oxidation at different reaction times was measured, and the results are shown in Table 6.
TABLE 6 degradation of polystyrene microplastic by photocatalytic oxidation at different reaction times
Application example 7
A degradation test was conducted by the same method as in application example 1 except that the degradation material was styrene-butadiene rubber particles, and the styrene-butadiene rubber particle solution was prepared by weighing 100mg of styrene-butadiene rubber particle powder, adding 10mL methylene chloride for dissolution, preparing a styrene-butadiene rubber particle standard solution of 10mg/mL, and then diluting it to 1mg/mL. The degradation rate of the photocatalytic oxidation on the styrene-butadiene rubber at different reaction times is measured, and the results are shown in Table 7.
TABLE 7 degradation rates of styrene butadiene rubber by photocatalytic oxidation at different reaction times
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. A polyimide-based compound having a structure represented by formula (I):
formula (I)
Wherein, the value of n is an integer between 20 and 50;
R 1 is a single bond O, SO 2 Fluorenyl group,、/>Any one of them;
representative (CH) 2 ) m Or (CH) 2 ) 2 O(CH 2 ) 2 M has a value of 2 or 3.
2. The polyimide-based compound according to claim 1, which has any one of the following structures:
、/>、、/>、、/>、、/>、、/>、、/>、、/>、、/>、、/>and。
3. the preparation method of the polyimide compound is characterized by comprising the following steps:
s1, in an organic solvent, carrying out polymerization reaction on a diamine monomer shown in a formula (II) and a dianhydride monomer shown in a formula (III) to prepare polyamide acid;
in the formula (II) of the present invention,representative (CH) 2 ) m Or (CH) 2 ) 2 O(CH 2 ) 2 M has a value of 2 or 3;
in the formula (III), R 1 Is a single bond O, SO 2 Fluorenyl group,、/>Any one of them;
s2, performing heat treatment on the polyamide acid obtained in the step S1 to obtain the polyimide compound.
4. The method for producing a polyimide-based compound according to claim 3, wherein in the step S1, the diamine monomer is at least one of diaminodibenzo 12-crown-4-ether, diaminodibenzo 15-crown-5-ether, and diaminodibenzo 18-crown-6-ether; and/or the number of the groups of groups,
the dianhydride monomer is at least one of 3,3', 4' -biphenyl tetracarboxylic dianhydride, bisphenol AF dianhydride, 3, 4-diphenyl sulfone tetracarboxylic dianhydride, bis [ (3, 4-dianhydride) phenyl ] terephthalate, 4' -biphenyl ether dianhydride and 9, 9-bis (3, 4-dicarboxylic acid phenyl) fluorene dianhydride; and/or the number of the groups of groups,
the molar ratio of the diamine monomer to the dianhydride monomer is 1:1-2; and/or the number of the groups of groups,
and dissolving the diamine monomer in the organic solvent, adding the dianhydride monomer at least 3 times at the temperature of-5 ℃, and stirring for reaction at room temperature after the addition is completed.
5. The method for producing a polyimide-based compound according to claim 4, wherein the organic solvent is at least one of N, N-dimethylacetamide, methylene chloride, chloroform, acetonitrile, and dimethylsulfoxide; and/or the number of the groups of groups,
the polymerization reaction time is more than 24 hours; and/or the number of the groups of groups,
in the step S2, the temperature of the heat treatment is 180-300 ℃ and the time is more than 2.5 hours.
6. The method for producing a polyimide-based compound according to any one of claims 3 to 5, characterized in that the polyamic acid solution obtained in step S1 is coated on a support, dried, and then heat-treated to obtain a polyimide film; and/or the number of the groups of groups,
and (3) carrying out heat treatment on the carrier coated with the polyamic acid at 150-180 ℃, 200-210 ℃, 230-240 ℃, 260-270 ℃ and 300 ℃ in sequence, wherein the heat treatment time under each temperature condition is more than 0.5 h.
7. The use of the polyimide compound according to claim 1 or 2 or the polyimide compound produced by the production method according to any one of claims 3 to 6 for degrading microplastic and rubber particles.
8. The degradation method of the microplastic is characterized by comprising the following steps:
mixing the micro-plastics, the accelerator, the adsorption material and the organic solvent to obtain a mixed solution, and irradiating the mixed solution with light with the wavelength of 400-405 nm in an aerobic environment;
the adsorption material is the polyimide compound of claim 1 or 2 or the polyimide compound prepared by the preparation method of any one of claims 3-6;
the accelerator is sulfinate.
9. The degradation method of the microplastic according to claim 8, wherein the mass ratio of the adsorption material to the accelerator is 100:1-4; and/or the number of the groups of groups,
the sulfinate is at least one of sodium trifluoromethylsulfinate, potassium trifluoromethylsulfinate, sodium 4-trifluoromethylbenzene sulfinate, potassium 4-trifluoromethylbenzene sulfinate, sodium pentafluorobenzene sulfinate and potassium pentafluorobenzene sulfinate;
and/or the illumination power is 3W-6W, and the illumination time is 1 d-14 d.
10. The degradation method of the microplastic according to claim 8 or 9, wherein the mass ratio of the microplastic to the adsorption material is 1:50-100; and/or the number of the groups of groups,
the microplastic is at least one of polyethylene, polyvinyl chloride, polypropylene, polystyrene and polycarbonate; and/or the number of the groups of groups,
the organic solvent is at least one of dichloromethane, chloroform and acetonitrile.
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