CN117603109A - Photo-crosslinking agent and preparation method thereof - Google Patents
Photo-crosslinking agent and preparation method thereof Download PDFInfo
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- CN117603109A CN117603109A CN202311338564.1A CN202311338564A CN117603109A CN 117603109 A CN117603109 A CN 117603109A CN 202311338564 A CN202311338564 A CN 202311338564A CN 117603109 A CN117603109 A CN 117603109A
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- photocrosslinker
- reaction
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- crosslinking agent
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- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 19
- 229940125904 compound 1 Drugs 0.000 claims description 18
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000013067 intermediate product Substances 0.000 claims description 12
- 150000008282 halocarbons Chemical class 0.000 claims description 11
- 150000001266 acyl halides Chemical class 0.000 claims description 8
- UOQACRNTVQWTFF-UHFFFAOYSA-N decane-1,10-dithiol Chemical group SCCCCCCCCCCS UOQACRNTVQWTFF-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- DWFDQVMFSLLMPE-UHFFFAOYSA-N (2-fluorophenyl)-phenylmethanone Chemical compound FC1=CC=CC=C1C(=O)C1=CC=CC=C1 DWFDQVMFSLLMPE-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000004440 column chromatography Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- PGTWZHXOSWQKCY-UHFFFAOYSA-N 1,8-Octanedithiol Chemical compound SCCCCCCCCS PGTWZHXOSWQKCY-UHFFFAOYSA-N 0.000 claims description 5
- 239000002841 Lewis acid Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000011549 crystallization solution Substances 0.000 claims description 5
- 150000007517 lewis acids Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000003444 phase transfer catalyst Substances 0.000 claims description 5
- CZKLEJHVLCMVQR-UHFFFAOYSA-N 4-fluorobenzoyl chloride Chemical compound FC1=CC=C(C(Cl)=O)C=C1 CZKLEJHVLCMVQR-UHFFFAOYSA-N 0.000 claims description 4
- WHIHIKVIWVIIER-UHFFFAOYSA-N 3-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC(Cl)=C1 WHIHIKVIWVIIER-UHFFFAOYSA-N 0.000 claims description 3
- SYVNVEGIRVXRQH-UHFFFAOYSA-N 3-fluorobenzoyl chloride Chemical compound FC1=CC=CC(C(Cl)=O)=C1 SYVNVEGIRVXRQH-UHFFFAOYSA-N 0.000 claims description 3
- RKIDDEGICSMIJA-UHFFFAOYSA-N 4-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=C(Cl)C=C1 RKIDDEGICSMIJA-UHFFFAOYSA-N 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- 239000002096 quantum dot Substances 0.000 abstract description 30
- 239000003446 ligand Substances 0.000 abstract description 21
- 150000001335 aliphatic alkanes Chemical group 0.000 abstract description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 abstract description 8
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 abstract description 8
- 238000001259 photo etching Methods 0.000 abstract description 7
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 4
- 239000012965 benzophenone Substances 0.000 abstract description 3
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 230000001988 toxicity Effects 0.000 abstract description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 abstract description 3
- 239000012454 non-polar solvent Substances 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 9
- 238000000206 photolithography Methods 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000000059 patterning Methods 0.000 description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 description 8
- 150000003335 secondary amines Chemical class 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 5
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- -1 fluorohydrocarbons Chemical class 0.000 description 4
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 4
- GVWISOJSERXQBM-UHFFFAOYSA-N n-methylpropan-1-amine Chemical compound CCCNC GVWISOJSERXQBM-UHFFFAOYSA-N 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- LKFIWRPOVFNPKR-UHFFFAOYSA-N (2-fluorophenyl)-(4-fluorophenyl)methanone Chemical group C1=CC(F)=CC=C1C(=O)C1=CC=CC=C1F LKFIWRPOVFNPKR-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000001540 azides Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- 150000005826 halohydrocarbons Chemical class 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 2
- 210000003097 mucus Anatomy 0.000 description 2
- HNPPKZRZKDKXDO-UHFFFAOYSA-N n,n-dimethylformamide;propan-2-one Chemical compound CC(C)=O.CN(C)C=O HNPPKZRZKDKXDO-UHFFFAOYSA-N 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 238000010023 transfer printing Methods 0.000 description 2
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical compound CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of preparation of organic compounds, and discloses a photocrosslinker and a preparation method thereof, wherein the photocrosslinker contains two S and N substituted diphenyl ketone groups and can be directly crosslinked with hydrocarbon ligands of quantum dots under UV irradiation without being connected with the quantum dots through ligand exchange; in addition, the QLED device is mostly prepared by using quantum dots dissolved in heptane or octane, and the long alkane chain is modified on the benzophenone, so that the photo-crosslinking agent can be dissolved in hydrocarbon solvents, the alkane solvents are nonpolar solvents, the toxicity is extremely low, the photo-crosslinking agent can be used in a friendly environment, and the photo-crosslinking agent can be directly used for photoetching in a mixed mode in the preparation of the QLED without worrying about incompatibility of solvents.
Description
Technical Field
The invention belongs to the technical field of preparation of organic compounds, and particularly relates to a photocrosslinking agent and a preparation method thereof.
Background
Current quantum dot patterning methods include transfer printing, inkjet printing, and photolithography. Transfer printing typically covers small area patterns and standard instrumentation has not been developed. Inkjet printing is an effective method in this respect, but results in limited resolution (less than 500 ppi) due to the characteristic size of the ejected droplets (maximum diameter 25-30 μm). On the other hand, photolithography is already a relatively well-established manufacturing process that can create patterns on the micrometer to submicron scale over a large area of the desired substrate.
Conventional photolithography, in which patterning is performed using photoresist, direct photolithography, which is a method in which light exposure directly induces a change in the solubility of the QD layer, is considered as an effective solution to alleviate the above-mentioned problems. Currently, some direct patterning schemes have been proposed, such as using photosensitive ligands that decompose under UV irradiation, causing a change in the quantum dot solubility; the azide-containing ligand or photocrosslinking additive may form stable chemical bonds with the aliphatic ligands of adjacent quantum dots; the use of benzophenone ligands can also form covalent bonds with hydrocarbyl ligands on quantum dots to crosslink. However, the use of photolytic ligands typically produces corrosive byproducts, such as acids, which can lead to reduced QD layer quantum dot light emission efficiency; the synthesis of azide cross-linked molecules is relatively complex, and the use of highly toxic and explosive sodium azide is unavoidable, limiting the possibility of large-scale use; furthermore, in many cases the cross-linking molecules need to be attached to the quantum dots by ligand exchange for use, and the operation is relatively complex. Furthermore, most of the existing photocrosslinkers are insoluble in alkane solvents, so that the use occasions of photocrosslinkers are limited.
In view of this, it is necessary to design a photocrosslinker that is lossless to quantum dots so as to directly pattern the quantum dots in a lossless manner by photolithography, thereby being suitable for multiple use occasions.
Disclosure of Invention
In view of the above, the present invention aims to provide a photocrosslinker and a preparation method thereof, so as to perform lossless direct patterning on quantum dots through photolithography, and adapt to multiple use occasions.
According to a first aspect of the present application, there is provided a photocrosslinker having the chemical structural formula shown below:
in the method, in the process of the invention,R 1 、R 2 is (CH) 2 ) m CH 3 Wherein n is independently selected from natural numbers greater than or equal to 1, and m is more than or equal to 2 and less than or equal to 15.
As a preferable scheme of the photo-crosslinking agent, n is more than or equal to 2 and less than or equal to 20.
As a preferable embodiment of the photocrosslinker, n is 10.
Preferably, the chemical structural formula of the photocrosslinker of the present invention is specifically:
the structural formula contains long alkane chains, so that the photocrosslinker can be dissolved in alkane solvents such as ethane, heptane, octane and the like.
According to a second aspect of the present application, there is provided a method for preparing the photocrosslinker described above, comprising the steps of:
s1, mixing aniline, halohydrocarbon, an organic solvent, an acid binding agent and a phase transfer catalyst for reaction, washing after the reaction is finished, and drying and purifying an organic phase to obtain a compound 1; halogenated hydrocarbons such as fluorohydrocarbons, chlorohydrocarbons, bromohydrocarbons, iodohydrocarbons, and the like, with halohexadecanes being preferred in the present invention; organic solvents such as toluene, methyl chloride, methanol, etc.; acid binding agents such as sodium hydroxide, sodium acetate, potassium carbonate, triethylamine, etc.; phase transfer catalysts such as benzyltriethylammonium chloride (TEBA), tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride, tetrabutylammonium bisulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, and the like;
s2, taking compound 1, acyl halide, lewis acid and polar halogenated hydrocarbon solvent for mixed reaction, and drying and purifying an organic phase after the reaction is finished to obtain an intermediate product; the Lewis acid can be aluminum chloride, zinc chloride, ferric chloride or boron trifluoride, and the polar halogenated hydrocarbon solvent can be dichloromethane, chloroform, dichloroethane, etc.;
s3, taking an intermediate product, dimercaptoalkane, an alkaline agent and a dipolar solvent, carrying out mixed reaction, washing after the reaction is finished, and drying and purifying an organic phase to obtain the photocrosslinker. Alkaline agents such as potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, or the like; dipolar solvents such as N, N-dimethylformamide acetone, N-dimethylacrylamide, N-dimethylformamide, N- [ (3- (dimethylamino) propyl ] methacrylamide, and the like;
the chemical structural formula of the photo-crosslinking agent is specifically as follows:
as a preferable mode of the preparation method of the photocrosslinker, in the step S1, the molar ratio of the aniline to the halogenated hydrocarbon is 1:2;
preferably, in the step S2, the molar ratio of the compound 1 to the acyl halide is 1:1.1-1.3;
preferably, the acyl halide is selected from at least one of p-fluorobenzoyl chloride, 4-chlorobenzoyl chloride, 3-fluorobenzoyl chloride and 3-chlorobenzoyl chloride;
in the step S3, the molar ratio of the intermediate product to the dimercaptoalkane is 2:1.
As a preferable scheme of the preparation method of the photocrosslinker, in the step S1, the reaction temperature is 80-120 ℃; the reaction temperature in the step S2 is 40-80 ℃; the reaction temperature in the step S3 is 80-120 ℃.
As a preferable mode of the above-mentioned method for producing a photocrosslinker, the dimercaptoalkane is 1, 10-dimercaptodecane or 1, 8-dimercaptooctane.
As a preferred embodiment of the method for preparing a photocrosslinker, the steps S1, S2, S3 are purified by column chromatography.
According to a third aspect of the present application, there is provided a method for preparing another photocrosslinker, comprising the steps of:
s11, dissolving fluorobenzophenone and secondary amine in a dipolar solvent, heating for reaction, and recrystallizing a reaction product in a crystallization solution to obtain a pure compound 1;
s22, dissolving the compound 1, dimercaptoalkane and an alkaline agent in a dipolar solvent, heating for reaction, and precipitating a reaction product to obtain the photocrosslinker;
preferably, the molar ratio of the fluorobenzophenone to the secondary amine is 1:1;
preferably, in the step S22, the molar ratio of the compound 1, dimercaptoalkane and alkaline agent is 2:1:4.
As a preferred embodiment of the above-mentioned method for producing a photocrosslinker soluble in an alkane solvent, the fluorobenzophenone is 2,4 '-difluorobenzophenone or 4,4' -difluorobenzophenone;
preferably, the secondary amine is a compound having a structure represented by formula 1,
wherein R is 4 、R 5 Each is alkyl or aryl, R 3 、R 4 May be different; specifically, the secondary amine is selected from one of dimethylamine, diethylamine, dipropylamine, dibutylamine, N-ethylmethylamine and N-methyl N-propylamine;
preferably, the crystallization solution is a mixed solution of ethyl acetate and ethanol;
preferably, the dimercaptoalkane is 1, 10-dimercaptodecane or 1, 8-dimercaptooctane;
preferably, the alkaline agent is one of potassium carbonate, potassium hydroxide, sodium carbonate or sodium hydroxide.
The chemical structural formula of the prepared photocrosslinker is specifically as follows:
namely, in the chemical structural formula (CH 2 ) m CH 3 M is 2.
The photocrosslinker with the chemical structural formula can be dissolved in solvents such as chloroform, methylene dichloride, ethyl acetate and the like.
The chemical structural formula of the photocrosslinker prepared by the two preparation methods can be shown as followsIt can be seen that when (CH 2 ) m CH 3 When m is less than 3, the second method is used for synthesis, and when m is more than 3, the first method is used for synthesis. The inventors found that after m is greater than 7, the prepared photocrosslinkers are soluble in alkanes.
Compared with the prior art, the invention has at least the following advantages:
1. the photocrosslinker prepared by the invention contains two S and N substituted diphenyl ketone groups, and can be directly crosslinked with the hydrocarbon-based ligand of the quantum dot under UV irradiation without being connected with the quantum dot through ligand exchange;
2. the main body of the photo-crosslinking agent is a benzophenone unit with 365nmUV absorption, and is matched with the UV wavelength commonly used in the photoetching process, so that the technical cost of later photoetching is reduced;
3. in general, QLED devices are mostly prepared by using quantum dots dissolved in heptane or octane, and the long alkane chain is modified on the benzophenone, so that the photo-crosslinking agent can be dissolved in hydrocarbon solvents, the alkane solvents are nonpolar solvents, the toxicity is extremely low, the photo-crosslinking agent can be used in friendly environment, and the photo-crosslinking agent can be directly used for photoetching in a mixed mode during QLED preparation, and the problem of incompatibility of solvents is not worry;
4. the photocrosslinker has simple molecular structure and synthesis path, and the preparation raw materials are cheap and easy to obtain, thereby being beneficial to large-scale use.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a nuclear magnetic resonance chart of a photo-crosslinking agent prepared in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance chart of the photo-crosslinking agent prepared in example 2 of the present invention;
FIG. 3 is a photograph showing a mixture of a photo-crosslinking agent prepared in example 1 of the present invention and a quantum dot solution after photolithography;
FIG. 4 is a photograph showing a mixture of a photo-crosslinking agent prepared in example 2 of the present invention and a quantum dot solution after photolithography.
Detailed Description
The technical solutions in the examples will be described in detail below in connection with the implementation of the present application. It should be noted that this embodiment is only a partial way, not an entire way.
At least one of the "when preceding or following a list of elements" as for example "is described herein modifies the entire list of elements without modifying individual elements of the list. Unless otherwise defined, all terms (including technical and scientific terms) in the specification can be defined as commonly understood by one of ordinary skill in the art. Terms defined in commonly used dictionaries should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein. Furthermore, unless expressly stated to the contrary, the words "comprise" and the words "comprising" when used in this specification mean the presence of stated features, regions, integers, steps, operations, elements, and/or components, but does not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof. Accordingly, the above phraseology is to be understood as meaning to include the stated elements, but not to exclude any other elements.
As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. The term "or" means "and/or".
It will be understood that, although the terms first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms.
As used herein, "about" or "approximately" includes the stated values and is meant to be within an acceptable range of deviation from the particular values as determined by one of ordinary skill in the art in view of the measurements in question and the errors associated with the measurement of the particular quantities (i.e., limitations of the measurement system). For example, "about" may mean that the deviation from the stated value is within one or more standard deviations, or within + -10%, + -5%.
The invention aims to design a photocrosslinker, and the chemical structural formula of the photocrosslinker is shown as follows:
wherein R is 1 、R 2 Is (CH) 2 ) m CH 3 Wherein n is independently selected from natural numbers greater than or equal to 1, and m is more than or equal to 2 and less than or equal to 15. When m is smaller, the polarity is increased; when m is larger, the synthesis difficulty and cost are greatly increased.
As a preferable scheme of the photo-crosslinking agent, n is more than or equal to 2 and less than or equal to 20.
As a preferable embodiment of the photocrosslinker, n is 10.n > 10, the acquisition cost of dimercaptoalkane (one of the raw materials for preparation) can be very high, which can greatly increase the cost of the photocrosslinker; n < 10, two benzophenone groups in the molecule are close together and can be crosslinked with the ligand of only one quantum dot, so that the patterning performance can be reduced.
Preferably, the chemical structural formula of the photocrosslinker of the present invention is specifically:
therefore, the structural formula contains long alkane chains, so that the photocrosslinker can be dissolved in alkane solvents such as ethane, heptane, octane and the like.
The invention also provides a preparation method of the photo-crosslinking agent, which comprises the following steps:
s1, mixing aniline, halohydrocarbon, an organic solvent, an acid binding agent and a phase transfer catalyst for reaction, washing after the reaction is finished, and drying and purifying an organic phase to obtain a compound 1; halogenated hydrocarbons such as fluorohydrocarbons, chlorohydrocarbons, bromohydrocarbons, iodohydrocarbons, and the like, with halohexadecanes being preferred in the present invention; organic solvents such as toluene, methyl chloride, methanol, etc.; acid binding agents such as sodium hydroxide, sodium acetate, potassium carbonate, triethylamine, etc.; phase transfer catalysts such as benzyltriethylammonium chloride (TEBA), tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride, tetrabutylammonium bisulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, and the like;
s2, taking compound 1, acyl halide, lewis acid and polar halogenated hydrocarbon solvent for mixed reaction, and drying and purifying an organic phase after the reaction is finished to obtain an intermediate product; the Lewis acid can be aluminum chloride, zinc chloride, ferric chloride or boron trifluoride, and the polar halogenated hydrocarbon solvent can be dichloromethane, chloroform, dichloroethane, etc.;
s3, taking an intermediate product, dimercaptoalkane, an alkaline agent and a dipolar solvent, carrying out mixed reaction, washing after the reaction is finished, and drying and purifying an organic phase to obtain the photocrosslinker. Alkaline agents such as potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, or the like; dipolar solvents such as N, N-dimethylformamide acetone, N-dimethylacrylamide, N-dimethylformamide, N- [ (3- (dimethylamino) propyl ] methacrylamide, and the like;
the chemical structural formula of the photo-crosslinking agent is specifically as follows:
as a preferable mode of the preparation method of the photocrosslinker, in the step S1, the molar ratio of the aniline to the halogenated hydrocarbon is 1:2;
preferably, in the step S2, the molar ratio of the compound 1 to the acyl halide is 1:1.1-1.3;
preferably, the acyl halide is selected from at least one of p-fluorobenzoyl chloride, 4-chlorobenzoyl chloride, 3-fluorobenzoyl chloride and 3-chlorobenzoyl chloride.
In the step S3, the molar ratio of the intermediate product to the dimercaptoalkane is 2:1.
As a preferable scheme of the preparation method of the photocrosslinker, in the step S1, the reaction temperature is 80-120 ℃; the reaction temperature in the step S2 is 40-80 ℃; the reaction temperature in the step S3 is 80-120 ℃.
As a preferable mode of the above-mentioned method for producing a photocrosslinker, the dimercaptoalkane is 1, 10-dimercaptodecane or 1, 8-dimercaptooctane.
As a preferred embodiment of the method for preparing a photocrosslinker, the steps S1, S2, S3 are purified by column chromatography.
The invention also provides a preparation method of the photo-crosslinking agent, which comprises the following steps:
s11, dissolving fluorobenzophenone and secondary amine in a dipolar solvent, heating for reaction, and recrystallizing a reaction product in a crystallization solution to obtain a pure compound 1;
s22, dissolving the compound 1, dimercaptoalkane and an alkaline agent in a dipolar solvent, heating for reaction, and precipitating a reaction product to obtain the photocrosslinker;
preferably, the molar ratio of the fluorobenzophenone to the secondary amine is 1:1;
preferably, in the step S22, the molar ratio of the compound 1, dimercaptoalkane and alkaline agent is 2:1:4.
As a preferable mode of the above-mentioned method for producing a photocrosslinker, the fluorobenzophenone is 2,4 '-difluorobenzophenone or 4,4' -difluorobenzophenone;
preferably, the secondary amine is a compound having a structure represented by formula 1,
wherein R is 4 、R 5 Each is alkyl or aryl, R 3 、R 4 May be different; specifically, the secondary amine is selected from one of dimethylamine, diethylamine, dipropylamine, dibutylamine, N-ethylmethylamine and N-methyl N-propylamine;
preferably, the crystallization solution is a mixed solution of ethyl acetate and ethanol;
preferably, the dimercaptoalkane is 1, 10-dimercaptodecane or 1, 8-dimercaptooctane;
preferably, the alkaline agent is one of potassium carbonate, potassium hydroxide, sodium carbonate or sodium hydroxide.
The chemical structural formula of the photo-crosslinking agent is specifically as follows:
namely, in the chemical structural formula (CH 2 ) m CH 3 M is 2.
The photocrosslinker with the chemical structural formula can be dissolved in solvents such as chloroform, methylene dichloride, ethyl acetate and the like.
From the two preparation methods and the chemical structural formulas of the prepared photocrosslinkers, it can be seen that when (CH 2 ) m CH 3 When m is less than 3, the second method is used for synthesis, and when m is more than 3, the first method is used for synthesis. The inventors found that after m is greater than 7, the prepared photocrosslinkers are soluble in alkanes.
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples, and the implementation conditions adopted in the examples may be further adjusted according to different requirements of specific use, and the conditions not specified are conventional conditions in the industry.
Example 1
Firstly, taking 1 part of aniline, 2 parts of bromohexadecane, 50-100 parts of toluene, 50-100 parts of water, 10-30 parts of sodium hydroxide and 0.05-0.2 part of tetrabutylammonium bromide according to the mass. The reaction is carried out for 24 hours at the temperature of 80-120 ℃. After the reaction, the mixture was washed with water, and the organic phase was dried and the solvent was removed by rotary evaporation. Purifying the crude product by column chromatography with n-hexane as mobile phase to obtain white solid with the molecular formula: phN (C) 16 H 33 ) 2 。
Then, 1 part of the white solid, 1.1 to 1.3 parts of p-fluorobenzoyl chloride, 1.1 to 1.5 parts of anhydrous aluminum trichloride and 50 to 100 parts of dichloromethane are taken for reaction for 12 hours at 50 ℃. After the reaction, the mixture was washed with water, and the organic phase was dried and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography using dichloromethane and n-hexane as mobile phases to give the intermediate as yellow mucus.
Finally, 2 parts of the intermediate product, 1 part of 1, 10-dimercaptodecane, 5-10 parts of potassium carbonate and 50-100 parts of N, N' -dimethylformamide are taken and reacted for 24 hours at 80-120 ℃. After the reaction, the mixture was washed with water and ethyl acetate, and the organic phase was dried and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography using methylene chloride and n-hexane as mobile phases to give the photocrosslinker (code: NS-2 BP-C16) as a yellow mucus.
The reaction route is as follows:
the photocrosslinker of example 1 was mixed with a quantum dot solution (the solvent was ethane), spin-coated on a substrate to form a film, and then the substrate was subjected to selective exposure by using 365nm UV, and then washed with the original solvent (ethane), so that a pattern of exposed areas could be left on the substrate, as shown in fig. 3.
Example 2
Taking 1 part of 4,4' -difluorobenzophenone, 1 part of diethylamine and 50-100 parts of DMSO according to the weight parts of substances, mixing, reacting for 20 hours at 60 ℃, and then recrystallizing the reaction product in a mixed solution of ethyl acetate and ethanol to obtain a pure compound 1; 2 parts of compound 1,1 part of 1, 10-dimercaptodecane, 4 parts of potassium carbonate and 50-100 parts of DMF are taken and mixed, the mixture is reacted for 20 hours at 80 ℃, the product after the reaction is precipitated in water, the precipitate is taken to be added into a mixed solvent of ethanol and ethyl acetate for recrystallization, and a pure photo-crosslinking agent (code: NS-2 BP-C2) can be obtained.
The reaction route is as follows:
the photocrosslinkers prepared in this example were soluble in chloroform, methylene chloride, ethyl acetate and the like.
The photocrosslinker of example 2 was mixed with a quantum dot solution (chloroform as the solvent) and spin-coated on a substrate to form a film, and then the substrate was selectively exposed by using 365nm UV and then washed with a raw solvent (chloroform), so that a pattern of exposed areas could be left on the substrate, as shown in fig. 4.
Comparative example 1
4,4' -difluorobenzophenone (20.00 g), 2-pyrrolidone (6.52 g) and 200ml of anhydrous dimethyl sulfoxide were charged into an RB flask, and the mixture was heated to 60℃under an argon atmosphere to react for 8 hours. The mixture was cooled to room temperature and quenched with deionized water. The resulting precipitate was collected by filtration and recrystallized from a mixture of acetone and ethanol to give the intermediate product. Then 15g of intermediate product were added to the mixture containing 1, 10-decanedithiol (19.2 g), K 2 CO 3 (15.4 g) and 70ml anhydrous DMF. The flask was heated to 60 ℃ and kept overnight. After precipitation, the precipitate was collected with deionized water. The solid was dissolved in ethyl acetate and filtered to remove impurities. The filtrate was concentrated under reduced pressure and the residue was purified by recrystallization to give the photocrosslinked ligand as an off-white solid.
The patterning method comprises the following steps:
the photo-crosslinking ligand of comparative example 1 was dissolved in chloroform and added dropwise to a quantum dot dispersion containing oleic acid ligand, and after one hour of ligand exchange reaction, the double ligand quantum dot was obtained by repeated purification by a precipitation (ethanol)/redispersion (toluene) method. And finally, re-dispersing the double-ligand quantum dots in a required nonpolar organic solvent to obtain double-ligand quantum dot dispersion liquid.
Photolithography was performed using a mask aligner (MA 6 Karl Suss). The 20mg/ml dual ligand quantum dot dispersion was spin coated on the substrate at 4000rpm for 30 seconds. With Sup>A UV-A source (20 mW/cm) 2 ) The mask irradiates the quantum dot film, and the quantum dot film is patterned. After irradiation, the uncrosslinked layer of the film is removed with the above-mentioned nonpolar organic solvent to develop the film.
Therefore, when in photoetching patterning, the photo-crosslinking agent can be directly mixed with quantum dots for use without ligand exchange, and the photo-crosslinking agent containing the benzophenone unit does not generate corrosive byproducts and does not influence the luminous efficiency of the quantum dots; compared with a photoresist system, the photo-crosslinking agent can be used for directly patterning, so that the quantum dot layer can be prevented from being damaged in post-treatment, and the photoetching process is optimized. In addition, nonpolar alkane solvents can be used, the toxicity is extremely low, the photocrosslinker can be used in a friendly environment, and the photocrosslinker can be directly used for photoetching in a mixed mode in the preparation of QLEDs, so that the problem of incompatibility of solvents is not worry.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A photo-crosslinking agent is characterized by having the following chemical structural formula:
wherein R is 1 、R 2 Is (CH) 2 ) m CH 3 Wherein n is independently selected from natural numbers greater than or equal to 1, and m is more than or equal to 2 and less than or equal to 15.
2. The photocrosslinker according to claim 1, wherein n.ltoreq.n.ltoreq.20.
3. The photocrosslinker according to claim 2, characterized in that n is 10.
4. A method for preparing a photocrosslinker, comprising the steps of:
s1, mixing aniline, halogenated hydrocarbon, an organic solvent, an acid binding agent and a phase transfer catalyst for reaction to obtain a compound 1;
s2, taking compound 1, acyl halide, lewis acid and polar halogenated hydrocarbon solvent for mixed reaction to obtain an intermediate product;
s3, taking an intermediate product, dimercaptoalkane, an alkaline agent and a dipolar solvent, and carrying out a mixing reaction to obtain the photocrosslinker;
the chemical structural formula of the photo-crosslinking agent is specifically as follows:
5. the method for producing a photocrosslinker according to claim 4, characterized in that in step S1, the molar ratio of aniline to halogenated hydrocarbon is 1:2.
6. The method for producing a photocrosslinker according to claim 4, wherein in said step S2, the molar ratio of said compound 1 to said acid halide is 1:1.1 to 1.3;
preferably, the acyl halide is selected from at least one of p-fluorobenzoyl chloride, 4-chlorobenzoyl chloride, 3-fluorobenzoyl chloride and 3-chlorobenzoyl chloride;
in the step S3, the molar ratio of the intermediate product to the dimercaptoalkane is 2:1.
7. The method for preparing a photocrosslinker according to claim 4, wherein in step S1, the temperature of the reaction is 80 to 120 ℃; the reaction temperature in the step S2 is 40-80 ℃; the reaction temperature in the step S3 is 80-120 ℃.
8. The method for producing a photocrosslinker according to claim 4, wherein the dimercaptoalkane is 1, 10-dimercaptodecane or 1, 8-dimercaptooctane.
9. The method for preparing a photocrosslinker according to claim 4, wherein the steps S1, S2 and S3 are purified by column chromatography.
10. A method for preparing a photocrosslinker, comprising the steps of:
s11, dissolving fluorobenzophenone and secondary amine in a dipolar solvent, heating for reaction, and recrystallizing a reaction product in a crystallization solution to obtain a pure compound 1;
s22, dissolving the compound 1, dimercaptoalkane and an alkaline agent in a dipolar solvent, heating for reaction, and precipitating a reaction product to obtain the photocrosslinker;
the chemical structural formula of the photocrosslinker is specifically as follows:
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