CN114790171A - Bis-aziridine crosslinking agent, and preparation method and application thereof - Google Patents
Bis-aziridine crosslinking agent, and preparation method and application thereof Download PDFInfo
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- CN114790171A CN114790171A CN202110104340.9A CN202110104340A CN114790171A CN 114790171 A CN114790171 A CN 114790171A CN 202110104340 A CN202110104340 A CN 202110104340A CN 114790171 A CN114790171 A CN 114790171A
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- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 46
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 23
- 229920000547 conjugated polymer Polymers 0.000 claims abstract description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 125000005843 halogen group Chemical group 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 238000000059 patterning Methods 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 9
- 239000012634 fragment Substances 0.000 claims abstract description 8
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 68
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000003513 alkali Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- 239000003960 organic solvent Substances 0.000 claims description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 239000013067 intermediate product Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000011261 inert gas Substances 0.000 claims description 15
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 14
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 14
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052740 iodine Inorganic materials 0.000 claims description 14
- 239000011630 iodine Substances 0.000 claims description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000004065 semiconductor Substances 0.000 claims description 12
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 11
- 230000005669 field effect Effects 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 201000003241 brachydactyly type A1 Diseases 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- DQPBABKTKYNPMH-UHFFFAOYSA-N amino hydrogen sulfate Chemical compound NOS(O)(=O)=O DQPBABKTKYNPMH-UHFFFAOYSA-N 0.000 claims description 5
- 238000010898 silica gel chromatography Methods 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 125000002541 furyl group Chemical group 0.000 claims description 4
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000002883 imidazolyl group Chemical group 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000001725 pyrenyl group Chemical group 0.000 claims description 4
- 125000004076 pyridyl group Chemical group 0.000 claims description 4
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 4
- 125000000335 thiazolyl group Chemical group 0.000 claims description 4
- 125000001544 thienyl group Chemical group 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- 239000011698 potassium fluoride Substances 0.000 claims description 3
- 235000003270 potassium fluoride Nutrition 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 208000005573 brachydactyly type A3 Diseases 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims 1
- 230000005693 optoelectronics Effects 0.000 claims 1
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical group C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- -1 aromatic diaziridine compound Chemical class 0.000 description 6
- 150000001728 carbonyl compounds Chemical class 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000010382 chemical cross-linking Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- TZYWCYJVHRLUCT-VABKMULXSA-N N-benzyloxycarbonyl-L-leucyl-L-leucyl-L-leucinal Chemical compound CC(C)C[C@@H](C=O)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](CC(C)C)NC(=O)OCC1=CC=CC=C1 TZYWCYJVHRLUCT-VABKMULXSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- OSVHLUXLWQLPIY-KBAYOESNSA-N butyl 2-[(6aR,9R,10aR)-1-hydroxy-9-(hydroxymethyl)-6,6-dimethyl-6a,7,8,9,10,10a-hexahydrobenzo[c]chromen-3-yl]-2-methylpropanoate Chemical compound C(CCC)OC(C(C)(C)C1=CC(=C2[C@H]3[C@H](C(OC2=C1)(C)C)CC[C@H](C3)CO)O)=O OSVHLUXLWQLPIY-KBAYOESNSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 125000005493 quinolyl group Chemical group 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- RWWYLEGWBNMMLJ-YSOARWBDSA-N remdesivir Chemical compound NC1=NC=NN2C1=CC=C2[C@]1([C@@H]([C@@H]([C@H](O1)CO[P@](=O)(OC1=CC=CC=C1)N[C@H](C(=O)OCC(CC)CC)C)O)O)C#N RWWYLEGWBNMMLJ-YSOARWBDSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 1
- CZSOUHCUPOPPRC-UHFFFAOYSA-N 3-phenylphthalaldehyde Chemical compound O=CC1=CC=CC(C=2C=CC=CC=2)=C1C=O CZSOUHCUPOPPRC-UHFFFAOYSA-N 0.000 description 1
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical class [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- MWKJTNBSKNUMFN-UHFFFAOYSA-N trifluoromethyltrimethylsilane Chemical compound C[Si](C)(C)C(F)(F)F MWKJTNBSKNUMFN-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D229/00—Heterocyclic compounds containing rings of less than five members having two nitrogen atoms as the only ring hetero atoms
- C07D229/02—Heterocyclic compounds containing rings of less than five members having two nitrogen atoms as the only ring hetero atoms containing three-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/151—Copolymers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention discloses a crosslinking agent containing a diazirine substituent as well as a preparation method and application thereof. The structural formula is shown as formula I, R 1 Selected from hydrogen atoms, halogen atoms, C 1 ～C 20 Straight-chain or branched alkyl containing halogen atom or amide bond or ether bond or ester bond, C 1 ～C 20 Linear or branched perfluoroalkyl, substitutedAnd unsubstituted aryl or heteroaryl, or a combined fragment formed by connecting the units through one or more of single bond, double bond, triple bond, oxygen, sulfur, silicon or nitrogen; r 2 Is selected from C 1 ～C 20 Straight-chain or branched alkyl containing halogen atom or amide bond or ether bond or ester bond, C 1 ～C 20 One of linear chain or branched chain perfluoroalkyl, substituted and unsubstituted aryl or heteroaryl, or a combined fragment formed by connecting the units through one or more of single bond, double bond, triple bond, oxygen, sulfur, silicon or nitrogen. The compound has good chemical stability, and can efficiently and conveniently realize patterning of the conjugated polymer.
Description
Technical Field
The invention belongs to the field of chemistry, and particularly relates to a crosslinking agent containing a diazirine group, a preparation method thereof and application thereof in an organic photoelectric device.
Background
Many advances have been made in the fundamental research of organic semiconductor devices, but the unique properties of solution processible and flexible organic semiconductors are difficult to be applied in digital circuits. In the digital circuit, the patterning of the semiconductor can reduce electric leakage, avoid series connection between devices and facilitate high-efficiency interconnection and integration between the devices. There are many methods for patterning organic semiconductors, such as printing, nanoimprinting, electron beam exposure, etc., but these methods have difficulty in being compatible with the photolithography process of the conventional microelectronics industry. The photo-chemical crosslinking of organic semiconductors by molecular design is an effective solution, and a broad-spectrum efficient chemical crosslinking agent is not available at present.
Bizirine (diazirine) is an active group containing an unsaturated tricyclic substituent containing two nitrogen atoms, capable of rapidly generating carbene and nitrogen under ultraviolet irradiation or heating (Science 2019,366, 875-878). The generated carbene intermediate has high reactivity and can efficiently perform insertion reaction with C-H bonds of various adjacent chemical environments, thereby realizing chemical crosslinking. Meanwhile, the by-product of the reaction is only nitrogen, and the crosslinking agent is an ideal green crosslinking agent.
At present, a few studies on bisaziridine compounds as crosslinking agents in non-conjugated polymers and biomacromolecules have been reported (Angew. chem. int.Ed.2018,57,16688.; Angew. chem. int.Ed.2008,47,90.), but the crosslinking of conjugated polymers still lacks of universal and rational design principles and synthetic strategies, and the application of the bisaziridine compounds in the field of organic semiconductor patterning is still blank. Therefore, the design and synthesis of the diazirine cross-linking agent suitable for patterning of the organic semiconductor have important research significance and practical value, and the cross-linking agent has definite application advantages in the fields of organic field effect transistors, organic solar cells, organic thermoelectrics, organic light emitting diodes, organic lasers and the like.
Disclosure of Invention
The invention aims to provide a kind of bisaziridine compound with photo-thermal crosslinking activity and a preparation method thereof.
The invention provides a crosslinking agent containing bis-aziridine substituent, which has a structural formula shown as the following formula I:
in the formula I, R 1 Selected from hydrogen atoms, halogen atoms, C 1 ～C 20 A straight-chain or branched alkyl group or a branched alkyl group having a halogen atom, an amide bond, an ether bond or an ester bond, and C 1 ～C 20 One of linear chain or branched chain perfluoroalkyl, substituted and unsubstituted aryl or heteroaryl (phenyl, thienyl, thiazolyl, pyridyl, quinolyl, furyl, pyrrolyl, imidazolyl, naphthyl and pyrenyl), or a combined segment formed by connecting the units through one or more of single bond, double bond, triple bond, oxygen, sulfur, silicon or nitrogen;
for example R 1 Can be selected from hydrogen atom, halogen atom, CH 3 、CF 3 、C 2 F 5 、C 3 F 7 、C 4 F 9 Or an aryl group;
R 2 is selected from C 1 ～C 20 A straight-chain or branched alkyl group or a branched alkyl group having a halogen atom, an amide bond, an ether bond or an ester bond, and C 1 ～C 20 Linear or branched perfluoroalkyl, substituted and unsubstituted aryl or heteroaryl (phenyl, thienyl, thiazolyl, pyridyl, quinolinyl, furanyl)Pyranyl, pyrrolyl, imidazolyl, naphthyl and pyrenyl) or a combined segment formed by connecting the units through one or more of single bond, double bond, triple bond, oxygen, sulfur, silicon or nitrogen.
For example R 2 Can be selected from the following fragments:
in the present invention, R is 2 In the group illustrated
Represents the attachment position of the bisaziridine group in formula I.
n is an integer of 2-10, specifically: 2.3, 4, 6,8 and 10.
In the above-mentioned C-BDA1, R 1 Can be H or CF 3 ；
In the above-mentioned C-QDA2, R 1 Can be H or CF 3 ；
In the above-mentioned C-BDA3, R 1 Can be CH 3 Or CF 3 And n is 0 or 2.
The invention also provides a preparation method of the crosslinking agent containing the diazirine substituent shown in the formula I.
The preparation method comprises a first preparation method and a second preparation method, wherein the first preparation method is suitable for synthesizing the aromatic diaziridine compound R2, and the second preparation method is suitable for synthesizing the aliphatic diaziridine compound R2.
The first preparation method comprises the following steps:
(1.1) in an organic solvent, adding R 1 Mixing a substituted carbonyl compound (a compound shown in a formula II), alkali and hydroxylamine hydrochloride, and heating to react to obtain an intermediate product 1 (a compound shown in a formula III);
wherein in the formula II, R 1 N is defined as formula I; in the formula II, R 2 Is one of substituted and unsubstituted aryl or heteroaryl (phenyl, thienyl, thiazolyl, pyridyl, quinolyl, furyl, pyrrolyl, imidazolyl, naphthyl and pyrenyl) or a combined fragment formed by connecting the units through one or more of single bond, double bond, triple bond, oxygen, sulfur, silicon or nitrogen;
in the formula III, R 1 、R 2 And n is defined as formula II;
(1.2) mixing the intermediate product 1 obtained in the step 1.1, alkali and p-toluenesulfonyl chloride in an organic solvent for reaction to obtain an intermediate product 2 (a compound shown in a formula IV);
in the formula IV, R 1 、R 2 N is defined as formula III;
(1.3) mixing the intermediate product 2 obtained in the step 1.2 with liquid ammonia or ammonia water in an organic solvent at a low temperature, and heating to room temperature for reaction to obtain an intermediate product 3 (a compound shown in a formula V);
in the formula V, R 1 、R 2 N is defined as formula IV;
(1.4) in an organic solvent, mixing the intermediate product 3 obtained in the step 1.3, alkali and iodine or silver salt, and reacting at room temperature to obtain the bis-aziridine compound shown in the formula I.
The second preparation method comprises the following steps:
(2.1) in an organic solvent, adding R 1 Substituted carbonyl compound (compound shown in formula II), hydroxylamine-O-sulfonic acid (hydroxyimine-O-sulfonic acid)acid) and liquid ammonia are mixed at low temperature, and slowly heated to room temperature for reaction to obtain an intermediate product 4 (a compound shown in a formula VI);
wherein in the formula II, R 1 N is defined as formula I; in the formula II, R 2 Is selected from C 1 ～C 20 A straight-chain or branched alkyl group containing a halogen atom, an amide bond, an ether bond or an ester bond, C 1 ～C 20 The linear chain or the branched chain perfluoroalkyl group of (a), or a combined segment formed by connecting the units through one or more of single bond, double bond, triple bond, oxygen, sulfur, silicon or nitrogen;
in the formula VI, R 1 、R 2 N is defined as formula II;
(2.2) in an organic solvent, mixing the intermediate product 4 obtained in the step 2.1, alkali and iodine or silver salt, and reacting at room temperature to obtain the diaziridine compound shown in the formula I.
In the above method, the organic solvent is selected from one or more of Tetrahydrofuran (THF), toluene (toluene), ethanol, methanol, dichloromethane, chloroform, acetone, N-methylpyrrolidone (NMP), Dimethylformamide (DMF), Dimethylacetamide (DMAC), Dimethylsulfoxide (DMSO), Hexamethylphosphoramide (HMP), sulfolane, acetonitrile and benzonitrile.
In the above method, the base is selected from one or more of triethylamine, pyridine, N-diisopropylethylamine, potassium carbonate, sodium bicarbonate, sodium hydroxide, potassium fluoride and cesium fluoride.
In the above first method, in step 1.1, the R 1 The molar ratio of the substituted carbonyl compound to the alkali and the hydroxylamine hydrochloride can be 1: 3-20, and the equivalent weight of the alkali and the hydroxylamine hydrochloride is equal; in step 1.2, the molar ratio of the intermediate product 1 to the alkali and the p-toluenesulfonyl chloride can be 1: 3-20, and the equivalent weight of the alkali and the p-toluenesulfonyl chloride is equal; in step 1.3, the molar ratio of the intermediate product 2 to ammonia gas or ammonia water may beIs 1: 1-200; in the step 1.4, the molar ratio of the intermediate product 3 to alkali to iodine or silver salt can be 1: 3-20, and the equivalent weight of the alkali to the iodine or silver salt is equal;
in the second method, step 2.1, the R 1 The molar ratio of the substituted carbonyl compound to hydroxylamine-O-sulfonic acid may be 1:3 to 20; in step 2.2, the molar ratio of the intermediate product 4 to the alkali to the iodine or silver salt can be 1: 3-20, and the equivalents of the alkali to the iodine or silver salt are equal.
In the above method, in step 1.1, the volume of the organic solvent and the R 1 The mass ratio of the substituted carbonyl compound is 10-400 mL:1 g; in the step 1.2, the mass ratio of the volume of the organic solvent to the intermediate product 1 is 10-400 mL:1 g; in the step 1.3, the volume ratio of the organic solvent to the liquid ammonia or the ammonia water is 1:1, 1:2 or 1: 10-100. In the step 1.4, the mass ratio of the volume of the organic solvent to the intermediate product 3 is 10-400 mL:1 g; in step 2.1, R 1 The molar ratio of the substituted carbonyl compound to the liquid ammonia may be 1:2 or 1:10 to 100. In the step 2.2, the mass ratio of the volume of the organic solvent to the intermediate product 4 is 10-400 mL:1 g.
In the above method, in step 1.1, the heating reaction conditions are as follows: under the protection of inert gas, heating to 30-150 ℃, and reacting for 1-24 hours; in step 1.2, the reaction conditions are as follows: under the protection of inert gas, heating to 30-110 ℃, and reacting for 1-24 hours; in step 1.3, the reaction conditions are as follows: under the protection of inert gas, the charging temperature is-70 to 0 ℃, the reaction temperature is room temperature, and the reaction lasts for 1 to 24 hours; in step 1.4, the reaction conditions are as follows: under the protection of inert gas, the reaction temperature is 20-30 ℃, and the reaction lasts for 1-24 hours at 20-30 ℃; in step 2.1, the reaction conditions are as follows: under the protection of inert gas, the charging temperature is-70-25 ℃, the reaction temperature is room temperature, and the reaction lasts for 1-24 hours; in step 2.2, the heating reaction conditions are as follows: under the protection of inert gas, the reaction temperature is 20-30 ℃, and the reaction lasts for 1-24 hours at 20-30 ℃.
The inert gas is specifically nitrogen or argon.
In the invention, the room temperature is common knowledge in the field and refers to 10-30 ℃.
All the steps of the method comprise the step of carrying out post-treatment on a reaction system after the reaction is finished;
the post-treatment process comprises the following steps: the reaction system is cooled and then the solvent is removed by rotary evaporation, the residue is extracted with dichloromethane or ethyl acetate or diethyl ether, washed with 1N HCl, saturated sodium bicarbonate solution and saturated sodium chloride solution respectively, dried with anhydrous sodium sulfate or anhydrous magnesium sulfate and concentrated under reduced pressure. In steps 1.4 and 2.2, after the post-treatment, the crude product is subjected to silica gel column chromatography to obtain the diazirine compound.
The invention also protects the application of the bis-aziridine compound.
The invention provides the application of the bis-aziridine compound in at least one of the following 1) to 3): 1) as a polymer cross-linking agent; 2) patterning an organic semiconductor; 3) application in the preparation of organic photoelectric devices.
The polymer comprises a non-conjugated polymer and a conjugated polymer (such as a copolymer DPP4T, the structural formula of which is shown in figure 7; or an N-type polymer N2200, the structural formula of which is shown in figure 9 b).
In the above application, the organic photoelectric device includes at least one of an organic field effect transistor, an organic digital circuit, an organic solar cell, an organic thermoelectric, an organic laser, and an organic light emitting diode.
The invention has the following advantages:
1. the synthesis steps are simple and short, the conditions are mild, and the operation is simple and convenient.
2. The raw materials used in the synthesis are convenient and easy to obtain, and the industrial production is easy to realize.
3. The compound has good chemical stability.
4. The nitrogen as a byproduct generated after the compound is subjected to crosslinking reaction is environment-friendly.
5. The crosslinking reaction of the bisaziridine compound and the conjugated polymer is efficient and does not influence the performance of a semiconductor.
Drawings
FIG. 1 is a diagram of a diarylbisaziridine molecule C-BDA1b of example 1 of the present invention 1 H-NMR chart.
FIG. 2 is a diagram of a diarylbisaziridine molecule C-BDA1b of example 1 of the present invention 13 C-NMR chart.
FIG. 3 is a diagram of example 2 of the tetraarylbisaziridine molecule C-QDA2b 1 H-NMR chart.
FIG. 4 is a schematic representation of the tetraarylbisaziridine molecule C-QDA2b of example 2 of the present invention 13 C-NMR chart.
FIG. 5 is a diagram showing the structure of the diethanediylbis aziridine molecule C-BDA3b of example 3 of the present invention 1 H-NMR chart.
FIG. 6 is a diagram showing the structure of the diethanediylbis aziridine molecule C-BDA3b of example 3 of the present invention 13 C-NMR chart.
FIG. 7 is a schematic representation of the DPP4T polymer structure and the conjugated polymer patterning achieved by the tetraarylbisaziridine molecule C-QDA2 of example 2 of the present invention.
FIG. 8 is a structural diagram of a diarylbisaziridine molecule C-BDA1 cross-linked field effect transistor device in accordance with example 2 of the present invention.
FIG. 9 is an output curve and transfer curve of a diarylbisaziridine molecule C-BDA1 cross-linked field effect transistor based on example 2 of the present invention.
FIG. 10 is a circuit diagram and output voltage curve of an inverter prepared based on the diarylbisaziridine molecule C-BDA1 crosslinker of example 2 of the present invention.
FIG. 11 is a structural diagram of a diarylbisaziridine molecule C-BDA1 crosslinked organic solar cell donor-acceptor structure and device structure according to example 1 of the present invention.
FIG. 12 is an I-V curve for an organic solar cell crosslinked device and a comparative device based on the diarylbisaziridine molecule C-BDA1 of example 1 of the present invention.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Example 1:
the scheme for the synthesis of the diarylbisaziridine molecule (designated as C-BDA1) of this example is as follows:
the specific synthesis steps are as follows:
(1) 200mL of tetrahydrofuran and 15mL of trifluoromethyltrimethylsilane were added to a reaction flask containing 10g of biphenyl dialdehyde 1a under nitrogen. The reaction was allowed to warm to 0 deg.C and tetrabutylammonium fluoride (1M, 1.9mL) was slowly added dropwise. After completion of the dropwise addition, the reaction was carried out at room temperature for 24 hours, followed by addition of 3M HCl (500mL), vigorous stirring for 24 hours, extraction with methylene chloride (500mL), washing with water and saturated brine, spin-drying of the organic layer, and purification by silica gel column chromatography to give Compound 2.
(2) Methylene chloride (200mL) was added to a reaction flask containing the compound 2 obtained in the above step, and 12g of activated manganese dioxide was added under nitrogen protection, followed by reflux reaction for 24 hours. After the reaction is finished, filtering, washing with saturated sodium bicarbonate solution, water and saturated saline solution, and spin-drying and drying the product to obtain the compound 1 b.
(3) To a reaction flask containing 4.5g of diaryl ketone 1b was added 5.38g of hydroxylamine hydrochloride. Under the protection of nitrogen, 400mL of ethanol and 50mL of triethylamine are injected, and stirring is carried out at 80 ℃; after 12 hours of reaction, the product was cooled and spun dry, extracted with 200mL dichloromethane, 1N HCl, saturated sodium bicarbonate, saturated brine, and the organic layer was spun dry to give compound 3b (intermediate 1).
(4) To a reaction flask containing the compound 3b obtained in the above step, 9.8g of p-toluenesulfonyl chloride and 400mL of tetrahydrofuran were added. Under the protection of nitrogen, 10mL of triethylamine was injected, the mixture was heated under reflux and stirred for 24 hours, and then the reaction mixture was dried by spinning and purified by silica gel column chromatography to obtain compound 4b (intermediate 2).
(5) Adding 100mL of methanol into a reaction bottle containing the compound 4b obtained in the step, cooling to 0 ℃, adding 100mL of ammonia water, slowly raising the temperature to room temperature, reacting for 12 hours, and spin-drying and drying the product to obtain a compound 5b (an intermediate product 3).
(6) 100mL of methanol and 10mL of triethylamine are added into a reaction bottle containing the compound 5b obtained in the step, 1.4g of iodine is added under the protection of nitrogen, after reaction is carried out for 24 hours at 30 ℃, the reaction liquid is dried by spinning, and pure C-BDA1b 450mg is obtained after silica gel column chromatographic separation and recrystallization separation, wherein the total reaction yield is 16%.
The structure of C-BDA1b prepared above is confirmed as follows:
1 H NMR(400MHz,298K,CDCl 3 ,ppm)δ＝7.83(d,J＝8.5Hz,4H),7.38(d,J＝8.1Hz,4H). 13 C NMR(100MHz,298K,CDCl 3 ,ppm)δ＝140.83,128.21,127.84,127.52,122.34(q,J＝273Hz),28.49(q,J＝39.8Hz).Elemental anal.calcd.for C 16 H 8 F 6 N 4 :C51.90,H 2.18,N 15.13；found:C 52.08,H 2.31,N 14.84.
of C-BDA1b 1 The H-NMR spectrum is shown in figure 1, 13 the C-NMR spectrum is shown in FIG. 2.
The synthesis procedure for CBDA1a was similar to that of C-BDA1b, the only difference being that intermediate 1a was the starting material.
Example 2:
the synthetic route for the tetraarylbisaziridine molecule (denoted as C-QDA2) of this example is as follows:
the specific synthesis procedure is similar to that of example 1 of the present invention, the only difference being the tetraarylketone (aldehyde) 6 as the starting material, the structure confirmation result of C-QDA2 b: 1 the H-NMR spectrum is shown in figure 3, 13 the C-NMR spectrum is shown in FIG. 4.
Example 3:
the synthetic route for the dialiphatic bis-aziridine molecule (denoted as C-BDA3b) of this example is as follows:
the specific synthetic steps are as follows:
(1) adding 100mL of methanol into a reaction bottle containing 2g of the di-aliphatic ketone 10, cooling to-70 ℃, adding 200mL of liquid ammonia, slowly heating to-30 ℃ for reaction for 5 hours, then cooling to-70 ℃, slowly dropwise adding 2.8g of methanol solution (100mL) of hydroxylamine-O-sulfonic acid, slowly heating the reaction solution to room temperature, continuing the reaction for 12 hours, filtering, washing a filter cake with methanol, and spin-drying the filtrate to obtain the compound 11 (intermediate product 4).
(2) 100mL of methanol and 3mL of triethylamine are added into a reaction bottle containing the compound 11 obtained in the previous step, 3.1g of iodine is added under the protection of nitrogen, the reaction solution is dried by spinning after 24 hours of reaction at 30 ℃, pure C-BDA3b 250mg is obtained after silica gel column chromatography separation, and the total yield of the two steps is 11%.
Of C-BDA3b 1 The H-NMR spectrum is shown in FIG. 5, 13 the C-NMR spectrum is shown in FIG. 6.
Example 4:
the specific steps for realizing the patterning of the conjugated polymer based on the tetraarylbisaziridine molecule C-QDA2 of example 2 of the present invention are:
the copolymer DPP4T (structural formula is shown in figure 7) of pyrrolopyrroledione and bithiophene and C-QDA2 are dissolved in a chloroform solution at room temperature according to the mass ratio of 100:2, wherein the concentration of DPP4T is 3 mg per ml. And then the blended solution is subjected to film spinning on a silicon wafer through a spin coater at a rotating speed of 2000 rpm, and the film thickness is about 20 nanometers. The mask was then covered on the film and irradiated with a 365 nm UV LED lamp at 70 milliwatts per square centimeter for 40 seconds. And then soaking the irradiated film in chloroform for 30 seconds, taking out the film, then leaching the film twice by using 5ml of chloroform, and drying the silicon wafer by using nitrogen to realize patterning, wherein a patterned graph is shown in figure 7.
Example 5:
the application of the patterned P-type conjugated polymer film based on the tetraarylbisaziridine molecule C-QDA2 of example 2 of the present invention in a field effect transistor comprises the following specific steps:
firstly, DPP4T patterns are fabricated in an electrode channel on a prefabricated bottom electrode silicon wafer by the method in embodiment 4, and a field effect transistor device structure is a bottom gate-top contact, and a specific structure is as shown in fig. 8: the source electrode and the drain electrode are made of gold with the thickness of 25 nanometers, the gate electrode is made of silicon with the thickness of 400 micrometers, the insulating layer is made of silicon dioxide modified by OTS (ottacyclinichlorosilane) and with the thickness of 300 nanometers, and the organic semiconductor part is patterned DPP4T with the thickness of 40-60 nanometers.
The test results show that the average hole mobility for 20 devices after annealing the patterned material at 160 degrees celsius for 10 minutes was 2.3cm 2 V -1 s -1 Average hole mobility of 20 unpatterned contrast devices was 2.6cm 2 V -1 s -1 And a representative transfer curve and an output curve are shown in fig. 9a, which proves that the cross-linking agent does not damage the transmission performance of the P-type conjugated polymer after the cross-linking reaction, and has potential application value in the aspect of organic field effect transistors.
Example 6:
the application of the patterned N-type conjugated polymer film based on the tetraarylbisaziridine molecule C-QDA2 of example 2 of the present invention in a field effect transistor comprises the following specific steps:
following the specific procedure of example 5, a thin film field effect transistor device was fabricated from N-type polymer N2200 (structural formula shown in fig. 9 b), and the results of the test showed that the average hole mobility of 20 devices after annealing the patterned material at 160 degrees celsius for 10 minutes was 0.15cm 2 V -1 s -1 Average hole mobility of 20 unpatterned contrast devices was 0.25cm 2 V - 1 s -1 And a representative transfer curve and an output curve are shown in fig. 9b, which proves that the transmission performance of the N-type conjugated polymer is not damaged after the crosslinking reaction of the crosslinking agent, and the crosslinking agent has potential application value in the aspect of organic field effect transistors.
Example 7:
the application of the patterned conjugated polymer film based on the tetraarylbisaziridine molecule C-QDA2 of example 2 of the present invention in an inverter was performed with the following specific steps:
the procedure described in example 4 was used to prepare DPP4T and N2200The material was patterned according to the circuit diagram in fig. 10a to construct a simple logic gate circuit: an inverter. The specific test condition is V dd 60V, the input voltage and the output voltage range are both 0-60V, and the test result shows that the highest gain value is 112 (figure 10b), which proves that the cross-linking agent has potential application value in the aspect of organic digital circuits.
Example 8:
the diaryl bis-aziridine molecule C-BDA1 crosslinking agent prepared in example 1 of the invention is applied to organic solar cell devices:
the specific device structure of the organic solar cell is shown in the accompanying figure 11: PSS (indium tin oxide/PEDOT) is used as an electrode on a glass substrate, an organic semiconductor active layer is spin-coated on the electrode, and PDINN/silver is used as an electrode on the electrode. Wherein the thickness of the PEDOT/PSS layer is about 40 nm, the thickness of the active layer is about 100 nm, the thickness of the PDINN is about 10 nm, and the thickness of the silver is about 100 nm. Preparation of a polycarbonate based on PM6: PC by the method of the invention example 4 71 BM: N3 (structural formula shown in figure 11) ternary blended active layer battery device, wherein PM6: PC 71 BM: Y6 mass ratio of 0.8:0.2:1.2, diarylbisaziridine molecule C-BDA1 crosslinker to PM6: PC 71 BM 2% of the total mass of N3. Thermal stability of cell performance was tested in comparison with the crosslinked film and the comparative device without the addition of the crosslinking agent, respectively, and the IV curve of the specific device is shown in fig. 12. Test results show that the photoelectric conversion efficiency of the device after the cross-linking device is annealed for two hours at 80 ℃ is 96.5% of that before annealing, and the photoelectric conversion efficiency of a comparative device without the cross-linking agent is 90.8% of that before annealing after the cross-linking device is annealed for two hours at 80 ℃, so that the material has potential application value in the aspect of improving the thermal stability of the organic solar cell.
Claims (10)
1. A compound of formula I:
in the formula I, R 1 Selected from hydrogen atoms, halogen atoms, C 1 ～C 20 Containing halogen atoms or amides ofStraight-chain or branched alkyl radicals having a bond or ether or ester bond, C 1 ～C 20 The linear chain or the branched chain perfluoroalkyl group, the substituted and unsubstituted aryl or heteroaryl group, or the combined fragments formed by connecting the units through one or more of single bond, double bond, triple bond, oxygen, sulfur, silicon or nitrogen;
R 2 is selected from C 1 ～C 20 A straight-chain or branched alkyl group containing a halogen atom, an amide bond, an ether bond or an ester bond, C 1 ～C 20 The linear chain or the branched chain perfluoroalkyl group, the substituted and unsubstituted aryl or heteroaryl, or the combined fragments connected by one or more of single bond, double bond, triple bond, oxygen, sulfur, silicon or nitrogen;
n is an integer of 2 to 10.
2. The compound of claim 1, wherein: the aryl or heteroaryl is selected from any one of the following: phenyl, thienyl, thiazolyl, pyridyl, quinolinyl, furanyl, pyrrolyl, imidazolyl, naphthyl, and pyrenyl;
or, said R 1 Selected from hydrogen atom, halogen atom, CH 3 、C 2 F 5 、C 3 F 7 、C 4 F 9 Or an aryl group;
or, said R 2 Selected from the following fragments:
said R is 2 In the above groups
Represents the attachment position of the bisaziridine group in formula I.
3. The compound of claim 1 or 2, wherein: the compound is any one of the following compounds:
in the above-mentioned C-BDA1, R 1 Is H or CF 3 ；
In the above-mentioned C-QDA2, R 1 Is H or CF 3 ；
In the above-mentioned C-BDA3, R 1 Is CH 3 Or CF 3 And n is 0 or 2.
4. A process for the preparation of a compound of formula i as claimed in claim 1, comprising the steps of:
(1.1) mixing a compound shown in a formula II, alkali and hydroxylamine hydrochloride in an organic solvent, and carrying out heating reaction to obtain a compound shown in a formula III;
wherein in the formula II, R 1 N is defined as formula I; in the formula II, R 2 Is one of substituted and unsubstituted aryl or heteroaryl, or a combined fragment formed by connecting the units through one or more of single bond, double bond, triple bond, oxygen, sulfur, silicon or nitrogen;
in the formula III, R 1 、R 2 N is defined as formula II;
(1.2) in an organic solvent, mixing the compound shown in the formula III obtained in the step 1.1, alkali and p-toluenesulfonyl chloride for reaction to obtain a compound shown in a formula IV;
in the formula IV, R 1 、R 2 N is defined as formula III;
(1.3) mixing the compound shown in the formula IV obtained in the step 1.2 with liquid ammonia or ammonia water in an organic solvent at a low temperature, and heating to room temperature for reaction to obtain a compound shown in a formula V;
in the formula V, R 1 、R 2 N is defined as formula IV;
(1.4) in an organic solvent, mixing the compound shown in the formula V obtained in the step 1.3, alkali and iodine or silver salt, and reacting at room temperature to obtain the compound shown in the formula I.
5. The method of claim 4, wherein: the organic solvent is selected from one or more of tetrahydrofuran, toluene, ethanol, methanol, dichloromethane, chloroform, acetone, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, sulfolane, acetonitrile and benzonitrile;
the alkali is selected from one or more of triethylamine, pyridine, N-diisopropylethylamine, potassium carbonate, sodium bicarbonate, sodium hydroxide, potassium fluoride and cesium fluoride.
In the step 1.1, the molar ratio of the compound shown in the formula II to the alkali and the hydroxylamine hydrochloride is 1: 3-20, and the equivalent weight of the alkali and the hydroxylamine hydrochloride is equal; in the step 1.2, the molar ratio of the compound shown in the formula III to the alkali and the p-toluenesulfonyl chloride is 1: 3-20, and the equivalent weight of the alkali and the p-toluenesulfonyl chloride is equal; in the step 1.3, the molar ratio of the compound shown in the formula IV to ammonia gas or ammonia water is 1: 1-200; in the step 1.4, the molar ratio of the compound shown in the formula V to alkali to iodine or silver salt is 1: 3-20, and the equivalents of the alkali to the iodine or silver salt are equal;
in the step 1.1, the ratio of the volume of the organic solvent to the compound shown in the formula II is 10-400 mL to 1 g; in the step 1.2, the ratio of the volume of the organic solvent to the compound shown in the formula III is 10-400 mL:1 g; in the step 1.3, the volume ratio of the organic solvent to the liquid ammonia or ammonia water is 1:1, 1:2 or 1: 10-100; in the step 1.4, the mass ratio of the volume of the organic solvent to the compound shown in the formula V is 10-400 mL:1 g;
in the step 1.1, the heating reaction conditions are as follows: under the protection of inert gas, heating to 30-150 ℃, and reacting for 1-24 hours; in the step 1.2, the reaction conditions are as follows: under the protection of inert gas, heating to 30-110 ℃, and reacting for 1-24 hours; in the step 1.3, the reaction conditions are as follows: under the protection of inert gas, the charging temperature is-70-0 ℃, the reaction temperature is room temperature, and the reaction lasts for 1-24 hours; in step 1.4, the reaction conditions are as follows: under the protection of inert gas, the reaction temperature is 20-30 ℃, and the reaction lasts for 1-24 hours at 20-30 ℃;
the inert gas is specifically nitrogen or argon.
6. A process for the preparation of a compound of formula i as claimed in claim 1, comprising the steps of:
(2.1) mixing a compound shown in a formula II, hydroxylamine-O-sulfonic acid and liquid ammonia in an organic solvent at a low temperature, slowly heating to room temperature for reaction to obtain a compound shown in a formula VI;
wherein in the formula II, R 1 N is defined as formula I; in the formula II, R 2 Is selected from C 1 ～C 20 A straight-chain or branched alkyl group containing a halogen atom, an amide bond, an ether bond or an ester bond, C 1 ～C 20 The linear chain or the branched chain perfluoroalkyl group of (a), or a combined segment formed by connecting the units through one or more of single bond, double bond, triple bond, oxygen, sulfur, silicon or nitrogen;
in the formula VI, R 1 、R 2 N is defined as formula II;
(2.2) in an organic solvent, mixing the intermediate product 4 obtained in the step 2.1, alkali and iodine or silver salt, and reacting at room temperature to obtain the bis-aziridine compound shown in the formula I.
7. The method of claim 6, wherein: in the method, the organic solvents are selected from one or more of tetrahydrofuran, toluene, ethanol, methanol, dichloromethane, chloroform, acetone, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, sulfolane, acetonitrile and benzonitrile;
the alkali is selected from one or more of triethylamine, pyridine, N-diisopropylethylamine, potassium carbonate, sodium bicarbonate, sodium hydroxide, potassium fluoride and cesium fluoride;
in the step 2.1, the molar ratio of the compound shown in the formula II to hydroxylamine-O-sulfonic acid is 1: 3-20; in step 2.2, the molar ratio of the compound shown in the formula VI to alkali to iodine or silver salt is 1: 3-20, and the equivalent of the alkali to the iodine or silver salt is equal;
in the step 2.1, the molar ratio of the compound shown in the formula II to liquid ammonia is 1: 10-100; in the step 2.2, the ratio of the volume of the organic solvent to the compound shown in the formula VI is 10-400 mL:1 g;
in the step 2.1, the reaction conditions are as follows: under the protection of inert gas, the charging temperature is-70 to 25 ℃, the reaction temperature is room temperature, and the reaction lasts for 1 to 24 hours; in the step 2.2, the heating reaction conditions are as follows: under the protection of inert gas, the reaction temperature is 20-30 ℃, and the reaction lasts for 1-24 hours at 20-30 ℃;
the inert gas is specifically nitrogen or argon.
8. The method according to any one of claims 4-7, wherein: all the steps of the method comprise the step of carrying out post-treatment on a reaction system after the reaction is finished;
the post-treatment process comprises the following steps: cooling the reaction system, performing rotary evaporation to remove the solvent, extracting the residue with dichloromethane or ethyl acetate or diethyl ether, washing with 1N HCl, saturated sodium bicarbonate solution and saturated sodium chloride solution respectively, drying with anhydrous sodium sulfate or anhydrous magnesium sulfate, and concentrating under reduced pressure;
in the steps 1.4 and 2.2, after the post-treatment, the crude product is subjected to silica gel column chromatography separation to obtain the compound shown in the formula I.
9. Use of a compound of the formula I according to claim 1 in at least one of the following 1) to 3):
1) as a polymer cross-linking agent;
2) patterning an organic semiconductor;
3) application in the preparation of organic photoelectric devices.
10. Use according to claim 9, characterized in that:
the polymer comprises a non-conjugated polymer and a conjugated polymer;
the organic optoelectronic device comprises at least one of an organic field effect transistor, an organic digital circuit, an organic solar cell, an organic thermoelectric, an organic laser, and an organic light emitting diode.
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