CN114853714A - Novel photo-crosslinkable photosensitive material and application thereof - Google Patents
Novel photo-crosslinkable photosensitive material and application thereof Download PDFInfo
- Publication number
- CN114853714A CN114853714A CN202210520614.7A CN202210520614A CN114853714A CN 114853714 A CN114853714 A CN 114853714A CN 202210520614 A CN202210520614 A CN 202210520614A CN 114853714 A CN114853714 A CN 114853714A
- Authority
- CN
- China
- Prior art keywords
- compound
- photo
- reaction
- crosslinkable
- synthesized
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 34
- 239000004642 Polyimide Substances 0.000 claims abstract description 33
- 229920001721 polyimide Polymers 0.000 claims abstract description 33
- 238000010146 3D printing Methods 0.000 claims abstract description 7
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 5
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 11
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 5
- -1 cyclic olefin Chemical class 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 abstract description 21
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 abstract description 8
- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 abstract description 8
- 238000004132 cross linking Methods 0.000 abstract description 5
- 238000000016 photochemical curing Methods 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 5
- QQNLHOMPVNTETJ-UHFFFAOYSA-N spiro[fluorene-9,9'-xanthene] Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11C2=CC=CC=C2C2=CC=CC=C21 QQNLHOMPVNTETJ-UHFFFAOYSA-N 0.000 abstract description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 4
- 150000008064 anhydrides Chemical class 0.000 abstract description 3
- 229920000620 organic polymer Polymers 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 description 83
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 81
- 238000006243 chemical reaction Methods 0.000 description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 48
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 36
- 238000001035 drying Methods 0.000 description 31
- 239000000243 solution Substances 0.000 description 31
- 230000015572 biosynthetic process Effects 0.000 description 29
- 238000003786 synthesis reaction Methods 0.000 description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- 238000003756 stirring Methods 0.000 description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- 238000012544 monitoring process Methods 0.000 description 24
- 238000001308 synthesis method Methods 0.000 description 24
- 238000004440 column chromatography Methods 0.000 description 23
- 239000012043 crude product Substances 0.000 description 23
- 239000000178 monomer Substances 0.000 description 22
- 238000000967 suction filtration Methods 0.000 description 22
- 239000011259 mixed solution Substances 0.000 description 21
- 239000011541 reaction mixture Substances 0.000 description 21
- 239000012299 nitrogen atmosphere Substances 0.000 description 20
- 239000000203 mixture Substances 0.000 description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000005406 washing Methods 0.000 description 18
- 239000000843 powder Substances 0.000 description 16
- 235000019441 ethanol Nutrition 0.000 description 15
- 238000010189 synthetic method Methods 0.000 description 13
- 239000003208 petroleum Substances 0.000 description 12
- 230000001376 precipitating effect Effects 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 10
- 229960000583 acetic acid Drugs 0.000 description 9
- 235000019270 ammonium chloride Nutrition 0.000 description 9
- 239000012362 glacial acetic acid Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- JVVRCYWZTJLJSG-UHFFFAOYSA-N 4-dimethylaminophenol Chemical compound CN(C)C1=CC=C(O)C=C1 JVVRCYWZTJLJSG-UHFFFAOYSA-N 0.000 description 8
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 8
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-dimethylaminopyridine Substances CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 8
- 238000000605 extraction Methods 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000011261 inert gas Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000004952 Polyamide Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 125000005462 imide group Chemical group 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920002647 polyamide Polymers 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- 101150033824 PAA1 gene Proteins 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- NSGDYZCDUPSTQT-UHFFFAOYSA-N N-[5-bromo-1-[(4-fluorophenyl)methyl]-4-methyl-2-oxopyridin-3-yl]cycloheptanecarboxamide Chemical compound Cc1c(Br)cn(Cc2ccc(F)cc2)c(=O)c1NC(=O)C1CCCCCC1 NSGDYZCDUPSTQT-UHFFFAOYSA-N 0.000 description 4
- 206010034972 Photosensitivity reaction Diseases 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 230000036211 photosensitivity Effects 0.000 description 4
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- FVIZARNDLVOMSU-UHFFFAOYSA-N ginsenoside K Natural products C1CC(C2(CCC3C(C)(C)C(O)CCC3(C)C2CC2O)C)(C)C2C1C(C)(CCC=C(C)C)OC1OC(CO)C(O)C(O)C1O FVIZARNDLVOMSU-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920005575 poly(amic acid) Polymers 0.000 description 3
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 2
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000003003 spiro group Chemical group 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 229940018563 3-aminophenol Drugs 0.000 description 1
- CWJJAFQCTXFSTA-UHFFFAOYSA-N 4-methylphthalic acid Chemical compound CC1=CC=C(C(O)=O)C(C(O)=O)=C1 CWJJAFQCTXFSTA-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101100273988 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) paa-3 gene Proteins 0.000 description 1
- 101100167427 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) paa-7 gene Proteins 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- NWWQVENFTIRUMF-UHFFFAOYSA-N diphenylphosphanyl 2,4,6-trimethylbenzoate Chemical compound CC1=CC(C)=CC(C)=C1C(=O)OP(C=1C=CC=CC=1)C1=CC=CC=C1 NWWQVENFTIRUMF-UHFFFAOYSA-N 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 125000000879 imine group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/96—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings spiro-condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/128—Unsaturated polyimide precursors the unsaturated precursors containing heterocyclic moieties in the main chain
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
A novel photo-crosslinkable material and application thereof belong to the field of functional organic polymer materials. The photo-crosslinkable diamine material takes spiro [ fluorene-9, 9' -xanthene ] as a core, takes amino and phenolic hydroxyl on a xanthene ring as derivative sites to be connected with a crosslinkable photosensitive group, obtains different photosensitive polyimides by polymerizing 2, 7-diamino on the fluorene ring and different dicarboxylic anhydrides, can be used as photo-crosslinking and photo-curing materials, and is expected to be applied to the fields of photoresist, three-dimensional printing and the like.
Description
Technical Field
The invention belongs to the field of functional organic polymer materials, and particularly relates to a novel photo-crosslinkable photosensitive material and application thereof.
Background
Polyimide (PI) is a kind of aromatic heterocyclic high molecular compound containing imide group in the main molecular chain as a special functional high molecular material. The polymer molecular chain contains aromatic ring and imine ring, because the imide ring is a plane-symmetrical annular structure, the bond angle and bond length are in stable state, so the polyimide molecule has classical van der Waals force, and also has the advantages of interlayer stacking of charge transfer complex, mixed layer stacking and the like, and the structures jointly determine that the polyimide has the excellent performances of high rigidity, high melting point, good heat resistance, chemical corrosion resistance, high mechanical strength, radiation resistance, good electrical insulation, low dielectric constant, flame retardance and the like. Therefore, the polymer material has been widely applied to the fields of semiconductors, three-dimensional printing, optical waveguide materials, liquid crystal materials, nonlinear optical materials and the like, and becomes a functional polymer material with wide application prospect
The main chain of the polyimide molecule generally contains a benzene ring and an imide ring structure, and the polyimide has stronger intermolecular action due to electronic polarization and crystallinity, so that the molecular chains of the polyimide are closely packed, and the traditional polyimide is not melted and dissolved and is difficult to process. When the photosensitive material is applied to the fields of semiconductors and three-dimensional printing materials, the process flow is complicated due to lack of photosensitivity, the manufacturing cost is increased, and certain limitations exist. Therefore, the method has very important significance for researching photosensitive polyimide (PSPI) materials which can not only keep excellent performances such as heat resistance, good electrical insulation and the like of the traditional polyimide, but also improve the solubility and increase the photosensitivity.
The spiro aromatic hydrocarbon compound is an important structural unit of an organic polymer material because of the advantages of a large conjugated system, a unique spiro conjugated effect, a rigid coplanar structure, a high glass transition temperature, good thermal stability and the like. In the spiro aromatic hydrocarbon material, spiro [ fluorene-9, 9' -xanthene ] connects two parts of fluorene ring and xanthene ring through a central sp3 hybridized C atom, and different organic groups can be used for modification at different sites, so that the spiro combined structure of the electron-rich xanthene ring and the fluorene ring can effectively construct a non-planar three-dimensional molecular conformation in the molecular field. The steric hindrance effect can effectively inhibit the pi-pi interaction between molecules, thereby improving the solubility and the stability of the material. Therefore, it is promising to research the application of the material in polyimide to improve solubility and the like.
Disclosure of Invention
The invention researches a photosensitive diamine monomer and application thereof, develops a photo-crosslinkable photosensitive diamine monomer, can be polymerized with different types of dicarboxylic anhydrides to obtain different photo-crosslinkable photosensitive polyimides, can be used as photo-crosslinking and photo-curing materials, and is expected to be applied to the fields of photoresist, three-dimensional printing and the like.
The invention firstly provides a novel photo-crosslinkable photosensitive material, which has the following structures of general formulas Z, PAA and PSPI:
wherein each X is independently selected from
n is a number greater than 1;
specifically, n is a number of 1 to 1000;
specifically, n is a number of 2 to 500.
R 1 ，R 2 Each independently is selected from
m is an integer of 0 to 10, R 3 Is C3-C8 cyclic olefin containing substituent or not containing substituent.
The substituent is selected from C1-C20 alkane and halogen.
In particular, R 3 Can be selected from
Each Y is independently selected from the group consisting of the parent structures of commercially available aliphatic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides, aromatic tetracarboxylic acid dianhydrides, and heterocyclic tetracarboxylic acid dianhydrides.
Specifically, each Y is independently selected from the parent structures of commercial C4-C30 aliphatic tetracarboxylic acid dianhydride, C4-C30 alicyclic tetracarboxylic acid dianhydride, C4-C30 aromatic tetracarboxylic acid dianhydride, and C4-C30 heterocyclic tetracarboxylic acid dianhydride.
The parent structure is a structure other than the acid anhydride bond of the tetracarboxylic dianhydride.
Specifically, each Y is independently selected from
Specifically, the novel photo-crosslinkable photosensitive material can be selected from the following structures:
wherein, the definitions of X and Y are the same as those in the structural general formula.
The photo-crosslinkable photosensitive diamine monomer represented by the general formula W takes spiro [ fluorene-9, 9' -xanthene ] as a core, and two vertical non-conjugated units of a fluorene ring and a xanthene ring enable the monomer to have a rigid structure with three-dimensional large-volume steric hindrance. The amino and phenolic hydroxyl groups on the xanthene ring are connected with photocrosslinkable groups, so that the monomer has photosensitivity, and the 2 and 7-positions of the fluorene ring have good reactivity, thereby facilitating the extension of the structure to a three-dimensional space. The cross-linkable photosensitive diamine monomer is polymerized with different dibasic acid anhydrides to obtain a series of photosensitive polyimides (shown as general formulas PAA and PSPI), which can be used as photo-crosslinking and photo-curing materials and are expected to be applied to the fields of photoresist, three-dimensional printing and the like.
The preparation method of the photo-crosslinkable photosensitive material comprises the following steps of constructing spiro [ fluorene-9, 9' -xanthene ] by using fluorenone and different substituted phenols as raw materials, connecting a crosslinkable photosensitive group by using amino and phenolic hydroxyl on a xanthene ring as derivative sites, and polymerizing diamino at 2, 7-positions of the fluorene ring and different dicarboxylic anhydrides to obtain different photosensitive polyimides:
and (3) obtaining a compound B after the compound A is subjected to one-step nitration reaction:
and (3) cyclizing the compound B and different substituted phenols (compound U) under acid catalysis to construct a compound C:
and (3) carrying out esterification reaction of acyl chloride and hydroxyl or amidation reaction of acyl chloride and amino on the compound C and the compound V to obtain a compound D:
wherein X is as defined in the general structural formula and compound V is selected from the following structures:
wherein m is an integer of 0 to 10, R 3 Is cycloolefine containing 3-8 carbon and its derivative;
and (3) reacting the compound D with Zn powder under an acidic condition to reduce nitro to obtain a compound W:
wherein X is as defined in the above general structural formula.
Polymerizing the compound W with different dibasic acid anhydrides (compound K) to obtain different polyamic acids PAA or photosensitive polyimide PSPI:
wherein X, Y is as defined in the above general structural formula.
Selected from the group consisting of the commercially available aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, heterocyclic tetracarboxylic dianhydrides, wherein Y is the parent structure of said aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, heterocyclic tetracarboxylic dianhydrides,
the ring in (1) is not limited to the ring structure of Y.
Specifically, the preparation method of the photo-crosslinkable photosensitive material can adopt the following steps:
1) adding the compound A into a small amount of deionized water, heating the mixture to 80 ℃, and dropwise adding concentrated HNO into the solution dropwise 3 Concentrated H 2 SO 4 Heating and refluxing the mixed solution for 1h, and dropwise adding concentrated HNO again 3 Concentrated H 2 SO 4 And (3) continuously heating and refluxing the mixed solution for reaction, wherein the mixed solution is gradually viscous and yellow, cooling after the reaction is finished, pouring the reaction solution into water, separating out yellow precipitate, performing suction filtration, washing and drying, and recrystallizing the dried crude product in ethanol to obtain the pure compound B.
2) Uniformly mixing the compound B and the compound U under the inert gas atmosphere, adding p-toluenesulfonic acid into the mixture, reacting at 140 ℃, cooling, adding deionized water into a reaction bottle, stirring for 0.5h, precipitating a crude product from the reaction mixture, performing suction filtration and drying to obtain a brown solid, and purifying the dried crude product by column chromatography to obtain a compound C;
the feeding molar ratio of the compound B to the different substituted phenols (compound U) is 1: 2-10.
3) Dissolving the compound C in dry acetone under the atmosphere of inert gas, dropwise adding triethylamine into the solution, stirring for 10min, dispersing the compound V into the dry acetone, dropwise adding the mixture into the reaction mixed solution under ice bath, stirring at room temperature, adding ethyl acetate into the reaction solution after the reaction is finished, washing with water, drying, and carrying out column chromatography to obtain a compound D.
4) Dissolving the compound D in a mixed system of water/ethanol (volume ratio is 1/3) under the atmosphere of inert gas, adding reduced Zn powder, ammonium chloride and glacial acetic acid, stirring for 4-6h at 50 ℃, performing suction filtration, extraction, drying and column chromatography to obtain a compound W,
the feeding molar ratio of the compound D to the reduced Zn powder is 1: 6-15.
5) Dissolving a compound W in dry and oxygen-removed nitrogen methyl pyrrolidone in an inert gas atmosphere, adding different binary acid anhydrides (compound K) into the solution after the compound W is completely dissolved, reacting for more than 0.5h at 25 ℃, precipitating, washing and drying the reaction solution in a proper organic solvent to obtain different photosensitive polyamic acids PAA; adding triethylamine, pyridine and toluene into a solution of polyamide acid PAA in N-methyl pyrrolidone, dehydrating and cyclizing for 5h at 180 ℃, cooling, precipitating a reaction solution in a proper organic solvent, washing and drying to obtain different photosensitive polyimide PSPI;
the feeding molar ratio of the compound Y to different dibasic acid anhydrides (compound K) is 1: 0.95-1.10.
The feeding molar ratio of the compound B to the differently substituted phenol (compound U) in step 2 is preferably 1: 2.5.
The feeding molar ratio of the compound D and the reduced Zn powder in the step 4 is preferably 1: 12.
The feeding molar ratio of the compound W to the dibasic acid anhydride (compound M) in the step 5 is preferably 1: 1.05.
The organic solvent in the step 5 is selected from dichloromethane, ethyl acetate and ethanol.
The photo-crosslinkable photosensitive diamine monomer has a good application effect in the aspect of improving the property of polyimide.
The photosensitive polyimide prepared from the photo-crosslinkable photosensitive diamine monomer has good application prospects in photo-crosslinking and photo-curing materials.
The invention has the beneficial effects that: the photo-crosslinkable photosensitive diamine material takes spiro [ fluorene-9, 9' -xanthene ] as a core, two vertical non-conjugated units of a fluorene ring and a xanthene ring enable the material to have a rigid structure with three-dimensional large-volume steric hindrance, and amino groups and phenolic hydroxyl groups on the xanthene ring are connected with photo-crosslinkable groups to enable the material to have photosensitivity. The two amino groups at the 2, 7-positions of the fluorene ring can be polymerized with different dibasic acid anhydrides to obtain the photocrosslinkable photosensitive polyimide with good solubility, film forming property and thermodynamic stability, and the photocrosslinkable photosensitive polyimide is taken as a photocrosslinking and photocuring material and is expected to be applied to the fields of photoresist, three-dimensional printing and the like.
Drawings
FIG. 1 is a high-resolution mass spectrum of a photo-crosslinkable diamine monomer W-1.
FIG. 2 is a characteristic diagram of nuclear magnetic resonance hydrogen spectrum of a photo-crosslinkable diamine monomer W-1.
FIG. 3 is a nuclear magnetic resonance carbon spectrum characterization diagram of a photo-crosslinkable diamine monomer W-1.
FIG. 4 is a Fourier transform infrared spectrum of PAA-1 and PSPI-1.
FIG. 5 is a Fourier infrared spectrum characterization chart before and after irradiation of PSPI-1 ultraviolet light.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way. Any person skilled in the art can substitute or change the technical solution of the present invention and its inventive concept within the technical scope of the present invention.
In the following examples, all reagents used were prepared by conventional methods or purchased from commercial sources, unless otherwise specified.
Example 1
Synthesis route of photo-crosslinkable diamine monomer (W-1):
(1) synthesis of intermediate B
A (2.00g, 11.10mmol) was dispersed in 5ml of deionized water under nitrogen, the mixture was heated to 80 ℃ and concentrated HNO was added dropwise 3 (65%, 6.92ml, 99.89 mmol)/concentrated H 2 SO 4 (98%, 6.64ml, 112.08mmol) of the mixture, heating and refluxing for 1h, and dropwise adding concentrated HNO again 3 (65%, 6.92ml, 99.89 mmol)/concentrated H 2 SO 4 (98%, 6.64ml, 112.08mmol) was added to the mixture, and the reaction was further refluxed. And after TLC monitoring reaction, cooling the reaction solution, pouring the reaction solution into ice water to generate yellow precipitate, performing suction filtration, washing a filter cake for 3 times, performing vacuum drying, recrystallizing a crude product obtained by drying in ethanol, and performing suction filtration to obtain a compound B.
(2) Synthesis of intermediate C1
Uniformly mixing a compound B (2.00g, 7.40mmol) and resorcinol (2.04g, 18.50mmol) in a nitrogen atmosphere, adding p-toluenesulfonic acid (2.55g, 14.80mmol) into the mixture, drying at 140 ℃ for a powder reaction, reducing the temperature after TLC monitoring reaction is finished, adding 15ml of deionized water into a reaction bottle, stirring for 0.5h, precipitating a crude product from the reaction mixture, performing suction filtration, washing and drying to obtain a brown solid, and separating and purifying the dried crude product by column chromatography (a methanol/dichloromethane system is 1/50) to obtain a yellow solid compound C1;
(3) synthesis of intermediate D1
Under a nitrogen atmosphere, compound C1(1.00g, 2.20mmol) was dissolved in 8ml of dry acetone, triethylamine (672.99mml, 4.84mmol) was added dropwise to the solution, and after stirring for 10min, methacryloyl chloride (468.62mml, 4.84mmol) was dispersed in 2ml of dry acetone, and dropwise added to the above reaction mixture in ice bath, and a catalytic amount of DMAP was added for catalytic reaction, and after TLC monitoring reaction was completed, ethyl acetate was added to the reaction mixture, washed with water, dried, and separated and purified by column chromatography (ethyl acetate/petroleum ether system ═ 1/1) to give compound D1.
(4) Synthesis of diamine monomer W-1
Under a nitrogen atmosphere, compound D1(1.00g, 1.70mmol) was dissolved in a 4ml mixed solution of water/ethanol (volume ratio ═ 1/3), reduced Zn powder (1.33g, 20.39mmol), ammonium chloride (363.51mg, 6.80mmol) and glacial acetic acid (97.17mml, 1.70mmol) were added to the mixed solution, stirring was performed at 50 ℃, after TLC monitoring reaction was completed, suction filtration was performed while hot, extraction and drying were performed, and the obtained crude product was separated and purified by column chromatography (ethyl acetate/petroleum ether system ═ 2/1) to obtain compound W-1.
Mass spectrum and nuclear magnetic data of compound W-1 are shown in FIGS. 1-3.
Example 2
Synthetic method referring to example 1, using
Instead of the former
Compound W-2 was synthesized.
Example 3
Synthetic method referring to example 1, using
Substitute for
Compound W-3 was synthesized.
Example 4
The synthesis of compound B and compound C1 was performed according to example 1.
(1) Synthesis of intermediate D4
Under a nitrogen atmosphere, compound C1(1.00g, 2.20mmol) was dissolved in 8ml of dry acetone, triethylamine (672.99mml, 4.84mmol) was added dropwise to the solution, and after stirring for 10min, acryloyl chloride (405.74mml, 4.84mmol) was dispersed in 2ml of dry acetone, and dropwise added to the reaction mixture in ice bath, a catalytic amount of DMAP was added for catalytic reaction, and after TLC monitoring reaction was completed, ethyl acetate was added to the reaction mixture, washed with water, dried, and separated and purified by column chromatography (ethyl acetate/petroleum ether system ═ 1/1) to give compound D4.
(2) Synthesis of diamine monomer W-4
Under a nitrogen atmosphere, compound D4(1.00g, 1.78mmol) was dissolved in a 4ml mixed solution of water/ethanol (volume ratio ═ 1/3), reduced Zn powder (1.39g, 21.33mmol), ammonium chloride (380.37mg, 7.11mmol) and glacial acetic acid (101.68mml, 1.78mmol) were added to the mixed solution, stirring was performed at 50 ℃, after TLC monitoring reaction was completed, suction filtration was performed while hot, extraction and drying were performed, and the obtained crude product was separated and purified by column chromatography (ethyl acetate/petroleum ether system ═ 2/1) to obtain compound W-4. The product structure was identified by HRMS.
Example 5
Synthetic method referring to example 4, using
Instead of the former
Compound W-5 was synthesized.
Example 6
Synthetic method referring to example 4, using
Substitute for
Compound W-6 was synthesized.
Example 7
Synthetic method referring to example 4, using
Instead of the former
Compound W-7 was synthesized.
Example 8
Synthetic method referring to example 4, using
Instead of the former
Compound W-8 was synthesized.
Example 9
Synthetic method referring to example 4, using
Instead of the former
Compound W-9 was synthesized.
Example 10
(1) Synthesis of intermediate B
A (2.00g, 11.10mmol) was dispersed in 5ml of deionized water under nitrogen, the mixture was heated to 80 ℃ and concentrated HNO was added dropwise 3 (65%, 6.92ml, 99.89 mmol)/concentrated H 2 SO 4 (98%, 6.64ml, 112.08mmol) of the mixture, heating and refluxing for 1h, and dropwise adding concentrated HNO again 3 (65%, 6.92ml, 99.89 mmol)/concentrated H 2 SO 4 (98%, 6.64ml, 112.08mmol) was added to the mixture, and the reaction was further refluxed. And after TLC monitoring reaction, cooling the reaction solution, pouring the reaction solution into ice water to generate yellow precipitate, performing suction filtration, washing a filter cake for 3 times, performing vacuum drying, recrystallizing a crude product obtained by drying in ethanol, and performing suction filtration to obtain a compound B.
(2) Synthesis of intermediate C2
Uniformly mixing a compound B (2.00g, 7.40mmol) and hydroquinone (2.04g, 18.50mmol) in a nitrogen atmosphere, adding p-toluenesulfonic acid (2.55g, 14.80mmol) into the mixture, drying at 140 ℃ for a powder reaction, reducing the temperature after the TLC monitoring reaction is finished, adding 15ml of deionized water into a reaction bottle, stirring for 0.5h, precipitating a crude product from the reaction mixture, performing suction filtration, washing and drying to obtain a brown solid, and separating and purifying the dried crude product by column chromatography (a methanol/dichloromethane system is 1/50) to obtain a yellow solid compound C2;
(3) synthesis of intermediate D10
Under a nitrogen atmosphere, compound C2(1.00g, 2.20mmol) was dissolved in 8ml of dry acetone, triethylamine (672.99mml, 4.84mmol) was added dropwise to the solution, and after stirring for 10min, methacryloyl chloride (468.62mml, 4.84mmol) was dispersed in 2ml of dry acetone, and dropwise added to the above reaction mixture in ice bath, and a catalytic amount of DMAP was added for catalytic reaction, and after TLC monitoring reaction was completed, ethyl acetate was added to the reaction mixture, washed with water, dried, and separated and purified by column chromatography (ethyl acetate/petroleum ether system ═ 1/1) to give compound D10.
(4) Synthesis of diamine monomer W-10
Under a nitrogen atmosphere, compound D10(1.00g, 1.70mmol) was dissolved in a 4ml mixed solution of water/ethanol (volume ratio ═ 1/3), reduced Zn powder (1.33g, 20.39mmol), ammonium chloride (363.51mg, 6.80mmol) and glacial acetic acid (97.17mml, 1.70mmol) were added to the mixed solution, stirring was performed at 50 ℃, after TLC monitoring reaction was completed, suction filtration was performed while hot, extraction and drying were performed, and the obtained crude product was separated and purified by column chromatography (ethyl acetate/petroleum ether system ═ 2/1) to obtain compound W-10. The product structure was identified by HRMS.
Example 11
Synthesis method with reference to example 10
Instead of the former
Compound W-11 was synthesized.
Example 12
Synthesis method with reference to example 10
Instead of the former
Compound W-12 was synthesized.
Example 13
Compound B and compound C2 were synthesized according to the method described in example 10.
(1) Synthesis of intermediate D13
Under a nitrogen atmosphere, compound C2(1.00g, 2.20mmol) was dissolved in 8ml of dry acetone, triethylamine (672.99mml, 4.84mmol) was added dropwise to the solution, and after stirring for 10min, acryloyl chloride (405.74mml, 4.84mmol) was dispersed in 2ml of dry acetone, and dropwise added to the reaction mixture in ice bath, a catalytic amount of DMAP was added for catalytic reaction, and after TLC monitoring reaction was completed, ethyl acetate was added to the reaction mixture, washed with water, dried, and separated and purified by column chromatography (ethyl acetate/petroleum ether system ═ 1/1) to give compound D13.
(2) Synthesis of diamine monomer W-13
Under a nitrogen atmosphere, compound D13(1.00g, 1.78mmol) was dissolved in a 4ml mixed solution of water/ethanol (volume ratio ═ 1/3), reduced Zn powder (1.39g, 21.33mmol), ammonium chloride (380.37mg, 7.11mmol) and glacial acetic acid (101.68mml, 1.78mmol) were added to the mixed solution, stirring was performed at 50 ℃, after TLC monitoring reaction was completed, suction filtration was performed while hot, extraction and drying were performed, and the obtained crude product was separated and purified by column chromatography (ethyl acetate/petroleum ether system ═ 2/1) to obtain compound W-13. The product structure was identified by HRMS.
Example 14
Synthetic method referring to example 13, using
Instead of the former
Compound W-14 was synthesized.
Example 15
Synthetic method referring to example 13, using
Instead of the former
Compound W-15 was synthesized.
Example 16
Synthetic method referring to example 13, using
Substitute for
Compound W-16 was synthesized.
Example 17
Synthetic method referring to example 13, using
Instead of the former
Compound W-17 was synthesized.
Example 18
Synthetic method referring to example 13, using
Instead of the former
Compound W-18 was synthesized.
Example 19
(1) Synthesis of intermediate B
A (2.00g, 11.10mmol) was dispersed in 5ml of deionized water under nitrogen, the mixture was heated to 80 ℃ and concentrated HNO was added dropwise 3 (65%, 6.92ml, 99.89 mmol)/concentrated H 2 SO 4 (98%, 6.64ml, 112.08mmol) of the mixture, heating and refluxing for 1h, and dropwise adding concentrated HNO again 3 (65%, 6.92ml, 99.89 mmol)/concentrated H 2 SO 4 (98%, 6.64ml, 112.08mmol) was added to the mixture, and the reaction was further refluxed. And after TLC monitoring reaction, cooling the reaction solution, pouring the reaction solution into ice water to generate yellow precipitate, performing suction filtration, washing a filter cake for 3 times, performing vacuum drying, recrystallizing a crude product obtained by drying in ethanol, and performing suction filtration to obtain a compound B.
(2) Synthesis of intermediate C3
Uniformly mixing a compound B (2.00g, 7.40mmol) and catechol (2.04g, 18.50mmol) in a nitrogen atmosphere, adding p-toluenesulfonic acid (2.55g, 14.80mmol) into the mixture, drying at 140 ℃ for a powder reaction, reducing the temperature after TLC monitoring reaction is finished, adding 15ml of deionized water into a reaction bottle, stirring for 0.5h, precipitating a crude product from the reaction mixture, performing suction filtration, washing and drying to obtain a brown solid, and separating and purifying the dried crude product by column chromatography (a methanol/dichloromethane system is 1/50) to obtain a yellow solid compound C3;
(3) synthesis of intermediate D19
Under a nitrogen atmosphere, compound C3(1.00g, 2.20mmol) was dissolved in 8ml of dry acetone, triethylamine (672.99mml, 4.84mmol) was added dropwise to the solution, and after stirring for 10min, methacryloyl chloride (468.62mml, 4.84mmol) was dispersed in 2ml of dry acetone, and dropwise added to the above reaction mixture in ice bath, and a catalytic amount of DMAP was added for catalytic reaction, and after TLC monitoring reaction was completed, ethyl acetate was added to the reaction mixture, washed with water, dried, and separated and purified by column chromatography (ethyl acetate/petroleum ether system ═ 1/1) to give compound D19.
(4) Synthesis of diamine monomer W-19
Under a nitrogen atmosphere, compound D19(1.00g, 1.70mmol) was dissolved in a 4ml mixed solution of water/ethanol (volume ratio ═ 1/3), reduced Zn powder (1.33g, 20.39mmol), ammonium chloride (363.51mg, 6.80mmol) and glacial acetic acid (97.17mml, 1.70mmol) were added to the mixed solution, stirring was performed at 50 ℃, after TLC monitoring reaction was completed, suction filtration was performed while hot, extraction and drying were performed, and the obtained crude product was separated and purified by column chromatography (ethyl acetate/petroleum ether system ═ 2/1) to obtain compound W-19. The product structure was identified by HRMS.
Example 20
Synthesis method with reference to example 19
Instead of the former
Compound W-20 was synthesized.
Example 21
Synthesis method with reference to example 19
Instead of the former
Compound W-21 was synthesized.
Example 22
Compound B, compound C3 were synthesized according to the method described in example 19.
(1) Synthesis of intermediate D22
Under a nitrogen atmosphere, compound C3(1.00g, 2.20mmol) was dissolved in 8ml of dry acetone, triethylamine (672.99mml, 4.84mmol) was added dropwise to the solution, and after stirring for 10min, acryloyl chloride (405.74mml, 4.84mmol) was dispersed in 2ml of dry acetone, and dropwise added to the reaction mixture in ice bath, a catalytic amount of DMAP was added for catalytic reaction, and after TLC monitoring reaction was completed, ethyl acetate was added to the reaction mixture, washed with water, dried, and separated and purified by column chromatography (ethyl acetate/petroleum ether system ═ 1/1) to give compound D22.
(2) Synthesis of diamine monomer W-22
Under a nitrogen atmosphere, compound D22(1.00g, 1.78mmol) was dissolved in a 4ml mixed solution of water/ethanol (volume ratio ═ 1/3), reduced Zn powder (1.39g, 21.33mmol), ammonium chloride (380.37mg, 7.11mmol) and glacial acetic acid (101.68mml, 1.78mmol) were added to the mixed solution, stirring was performed at 50 ℃, after TLC monitoring reaction was completed, suction filtration was performed while hot, extraction and drying were performed, and the obtained crude product was separated and purified by column chromatography (ethyl acetate/petroleum ether system ═ 2/1) to obtain compound W-22. The product structure was identified by HRMS.
Example 23
Synthetic method reference example 23 was made to
Instead of the former
Compound W-23 was synthesized.
Example 24
Synthesis method with reference to example 23
Instead of the former
Compound W-24 was synthesized.
Example 25
Synthesis method with reference to example 23
Substitute for
Compound W-25 was synthesized.
Example 26
Synthesis method with reference to example 23
Instead of the former
Compound W-26 was synthesized.
Example 27
Synthesis method with reference to example 23
Instead of the former
Compound W-27 was synthesized.
Example 28
Synthetic route of crosslinkable photosensitive diamine monomer (W-28):
(1) synthesis of intermediate B
A (2.00g, 11.10mmol) was dispersed in 5ml of deionized water under nitrogen, the mixture was heated to 80 ℃ and concentrated HNO was added dropwise 3 (65%, 6.92ml, 99.89 mmol)/concentrated H 2 SO 4 (98%, 6.64ml, 112.08mmol) of the mixture, heating and refluxing for 1h, and dropwise adding concentrated HNO again 3 (65%, 6.92ml, 99.89 mmol)/concentrated H 2 SO 4 (98%, 6.64ml, 112.08mmol) was added to the mixture, and the reaction was further refluxed. And after TLC monitoring reaction, cooling the reaction solution, pouring the reaction solution into ice water to generate yellow precipitate, performing suction filtration, washing a filter cake for 3 times, performing vacuum drying, recrystallizing a crude product obtained by drying in ethanol, and performing suction filtration to obtain a compound B.
(2) Synthesis of intermediate C4
Uniformly mixing a compound B (2.00g, 7.40mmol) and m-aminophenol (2.02g, 18.50mmol) in a nitrogen atmosphere, adding p-toluenesulfonic acid (2.55g, 14.80mmol) into the mixture, carrying out dry powder reaction at 140 ℃, cooling after TLC monitoring reaction is finished, adding 15ml of deionized water into a reaction bottle, stirring for 0.5h, precipitating a crude product from the reaction mixture, carrying out suction filtration, washing and drying to obtain a brown solid, and separating and purifying the dried crude product by column chromatography (a methanol/dichloromethane system is 1/50) to obtain a brown solid compound C4;
(3) synthesis of intermediate D28
Under a nitrogen atmosphere, compound C4(1.00g, 2.21mmol) was dissolved in 8ml of dry acetone, triethylamine (675.92mml, 4.86mmol) was added dropwise to the solution, and after stirring for 10min, methacryloyl chloride (470.66mml, 4.86mmol) was dispersed in 2ml of dry acetone, and dropwise added to the reaction mixture in ice bath, and a catalytic amount of DMAP was added for catalytic reaction, and after TLC monitoring reaction was completed, ethyl acetate was added to the reaction mixture, washed with water, dried, and separated and purified by column chromatography (ethyl acetate/dichloromethane system ═ 1/100) to give compound D28.
(4) Synthesis of diamine monomer W-31
Under a nitrogen atmosphere, compound D28(1.00g, 1.70mmol) was dissolved in 4ml of a mixed solution of water/ethanol (volume ratio ═ 1/3), reduced Zn powder (1.33g, 20.39mmol), ammonium chloride (363.51mg, 6.80mmol) and glacial acetic acid (97.17mml, 1.70mmol) were added to the mixed solution, stirring was performed at 50 ℃, after TLC monitoring reaction was completed, suction filtration was performed while hot, extraction and drying were performed, and the obtained crude product was separated and purified by column chromatography (methanol/dichloromethane system ═ 1/60) to obtain compound W-28. The product structure was identified by HRMS.
Example 29
Synthesis method with reference to example 28
Instead of the former
Compound W-29 was synthesized.
Example 30
Synthesis method with reference to example 28
Instead of the former
Compound W-30 was synthesized.
Example 31
Compound B, compound C4 were synthesized according to the method described in example 28.
(1) Synthesis of intermediate D31
Under a nitrogen atmosphere, compound C4(1.00g, 2.21mmol) was dissolved in 8ml of dry acetone, triethylamine (675.92mml, 4.86mmol) was added dropwise to the solution, and after stirring for 10min, acryloyl chloride (407.50mml, 4.86mmol) was dispersed in 2ml of dry acetone, and dropwise added to the reaction mixture in ice bath, a catalytic amount of DMAP was added for catalytic reaction, and after TLC monitoring reaction was completed, ethyl acetate was added to the reaction mixture, washed with water, dried, and separated and purified by column chromatography (ethyl acetate/dichloromethane system ═ 1/100) to give compound D31.
(4) Synthesis of diamine monomer W-31
Compound D31(1.00g, 1.78mmol) was dissolved in 4ml of a mixed solution of water/ethanol (volume ratio: 1/3) under a nitrogen atmosphere, reduced Zn powder (1.40g, 21.41mmol), ammonium chloride (381.71mg, 7.14mmol) and glacial acetic acid (102.03 mmol, 1.78mmol) were added to the mixed solution, stirred at 50 ℃, after completion of TLC monitoring reaction, suction filtered, extracted and dried while hot, and the resulting crude product was separated and purified by column chromatography (methanol/dichloromethane system: 1/60) to obtain compound W-31. The product structure was identified by HRMS.
Example 32
Synthesis method with reference to example 31
Instead of the former
Compound W-32 was synthesized.
Example 33
Synthesis method with reference to example 31
Instead of the former
Compound W-33 was synthesized.
Example 34
Synthesis method with reference to example 31
Instead of the former
Compound W-34 was synthesized.
Example 35
Synthesis method with reference to example 31
Instead of the former
Compound W-35 was synthesized.
Example 36
Synthesis method with reference to example 31
Instead of the former
Compound W-36 was synthesized.
Example 37
Synthesis of Compound W-1 reference is made to example 1.
Synthetic route of photocrosslinkable photosensitive polyimide (PSPI-1)
Dissolving a compound W-1(100.00mg, 188.47 mu mol) in 2ml of dry and oxygen-removed azomethylpyrrolidone under an inert gas atmosphere, adding 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride (63.77mg, 197.90 mu mol) into the solution after complete dissolution, stirring and reacting for 8 hours at 25 ℃, dropwise adding the reaction liquid into ethyl acetate, precipitating yellow substances, washing and drying to obtain polyamide acid PAA-1; adding 0.5ml of triethylamine, 0.5ml of pyridine and 2ml of methylbenzene into solution of polyamide acid PAA-1 in N-methyl pyrrolidone, dehydrating and cyclizing for 5 hours at 180 ℃, cooling, dripping the reaction liquid into absolute ethyl alcohol to precipitate, washing and drying to obtain the photo-crosslinkable photosensitive polyimide PSPI-1.
Fourier infrared spectrum data of PAA-1 and PSPI-1 are shown in FIG. 4. Comparison of the PAA-1 curve with the PSPI-1 curve shows that 1363cm -1 Is the absorption peak of the stretching vibration of the C-N bond on the imide ring, 1783cm -1 And 1731cm -1 Symmetric and asymmetric stretching vibration absorption peaks of 2C ═ O on the imide ring respectively can determine the existence of the imide ring structure; the monomer W-1 has a methacrylate group in the structure, and can be clearly observed in a PSPI-1 map, 1608cm -1 The peak is a characteristic absorption peak of C ═ C in the methacrylate structure, and thus PSPI-1 can be determined.
Example 38
Synthesis method with reference to example 37, polymers PAA-2, PSPI-2 were synthesized.
Example 39
Synthesis method with reference to example 37, polymers PAA-3, PSPI-3 were synthesized.
Example 40
Synthesis method with reference to example 37, polymers PAA-4, PSPI-4 were synthesized.
EXAMPLE 41
Synthesis of Compound W-7 reference is made to example 7.
Synthetic route of photocrosslinkable photosensitive polyimide (PSPI-5)
Dissolving a compound W-7(100.00mg, 152.74 mu mol) in dried and deoxygenated 2ml of azomethylpyrrolidone under an inert gas atmosphere, adding 2, 2-bis (3, 4-dicarboxyphenyl) methane dianhydride (49.43mg, 160.37 mu mol) into the solution after complete dissolution, stirring and reacting for 8 hours at 25 ℃, dropwise adding the reaction liquid into ethyl acetate, precipitating yellow substances, washing and drying to obtain polyamide acid PAA-5; adding 0.5ml triethylamine, 0.5ml pyridine and 2ml toluene into polyamide acid PAA-5 in the solution of nitrogen methyl pyrrolidone, dehydrating and cyclizing for 5h at 180 ℃, cooling, dripping the reaction liquid into absolute ethyl alcohol, precipitating, washing and drying to obtain the photo-crosslinkable photosensitive polyimide PSPI-5.
Example 42
Synthesis method with reference to example 41, polymers PAA-6, PSPI-6 were synthesized.
Example 43
Synthesis method with reference to example 41, polymers PAA-7, PSPI-7 were synthesized.
Example 44
Synthesis of compound W-31 reference is made to example 31.
Synthetic route of photocrosslinkable photosensitive polyimide (PSPI-8)
Dissolving a compound W-31(100.00mg, 199.78 mu mol) in dried and deoxygenated 2ml of azomethylpyrrolidone under an inert gas atmosphere, adding dibenzo dioxane dianhydride (68.01mg, 209.77 mu mol) into the solution after complete dissolution, stirring and reacting for 8 hours at 25 ℃, dropwise adding the reaction liquid into ethyl acetate, precipitating yellow substances, washing and drying to obtain polyamide acid PAA-8; adding 0.5ml triethylamine, 0.5ml pyridine and 2ml toluene into polyamic acid PAA-8 solution in N-methyl pyrrolidone, dehydrating and cyclizing for 5h at 180 ℃, cooling, dripping the reaction liquid into absolute ethyl alcohol, precipitating, washing and drying to obtain the photo-crosslinkable photosensitive polyimide PSPI-8.
Example 45
Synthesis method with reference to example 44, polymers PAA-9, PSPI-9 were synthesized.
Example 46
Synthesis method with reference to example 44, polymers PAA-10, PSPI-10 were synthesized.
Example 47
Synthesis method with reference to example 44, polymers PAA-11, PSPI-11 were synthesized.
Example 48
Synthesis methods with reference to example 44, polymers PAA-12, PSPI-12 were synthesized.
Example 49
Dissolving 30mg PSPI-1 in 0.2mL dry DMAc, adding 5% diphenyl- (2,4, 6-trimethylbenzoyl) oxyphosphorus (photoinitiator TPO), stirring at room temperature for 2h, coating on a clean glass sheet, drying to remove solvent, irradiating with 390nm ultraviolet light, and taking a sample as an infrared sampleSpectroscopic testing (Nicolet iN10 micro infrared spectrometer). FIG. 5 is an infrared spectrum of a photo-crosslinkable polyimide PSPI-1 before and after UV irradiation, from which it can be seen that Cl-PSPI-1 after photo-crosslinking was 1606cm in length compared to PSPI-1 before UV irradiation -1 The infrared characteristic absorption peak intensity of C ═ C double bonds at the position is obviously weakened, and the photocrosslinking reaction is proved to occur under the irradiation of ultraviolet light.
I.e., indicating that the polyimide PSPI-1 can undergo photocrosslinking under ultraviolet irradiation.
Claims (8)
1. A novel class of photo-crosslinkable photosensitive materials having the structure of formula I, formula II or formula III:
wherein each X is independently selected from
、
N is a number greater than 1;
R 1 ，R 2 each independently selected from
、
、
、
、
M each ofIndependently is an integer of 0 to 10, R 3 Is C3-C8 cyclic olefin containing substituent or not containing substituent;
y is independently selected from the parent structure of aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride and heterocyclic tetracarboxylic dianhydride.
2. The novel class of photo-crosslinkable photosensitive materials of claim 1 wherein each X is independently selected from
。
3. The novel class of photocrosslinkable photosensitive materials of claim 1 wherein R is 1 ，R 2 Each independently selected from
、
。
4. The novel class of photocrosslinkable photosensitive materials of claim 1 wherein each Y is independently selected from
、
、
、
、
、
、
、
、
、
、
、
、
、
、
、
。
5. The use of a novel class of photo-crosslinkable photosensitive materials of claim 1 in the preparation of photo-crosslinkable polyimides.
6. Use of a novel class of photo-crosslinkable photosensitive materials according to claim 1 in the preparation of a photocurable polyimide.
7. Photosensitive polyimides prepared with the new class of photo-crosslinkable photosensitive materials according to claim 1.
8. Use of the photosensitive polyimide according to claim 6 in photoresists, three-dimensional printing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210520614.7A CN114853714B (en) | 2022-05-13 | 2022-05-13 | Photo-crosslinkable photosensitive material and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210520614.7A CN114853714B (en) | 2022-05-13 | 2022-05-13 | Photo-crosslinkable photosensitive material and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114853714A true CN114853714A (en) | 2022-08-05 |
| CN114853714B CN114853714B (en) | 2024-04-16 |
Family
ID=82636987
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210520614.7A Active CN114853714B (en) | 2022-05-13 | 2022-05-13 | Photo-crosslinkable photosensitive material and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114853714B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006089492A (en) * | 2005-10-11 | 2006-04-06 | Kaneka Corp | New diamine and new polyimide composition using the same |
| CN102516541A (en) * | 2011-11-22 | 2012-06-27 | 中国航空工业集团公司北京航空材料研究院 | Polyimide containing phenolic hydroxy |
| EP3604390A1 (en) * | 2018-08-01 | 2020-02-05 | Shin-Etsu Chemical Co., Ltd. | Polymer having a structure of polyamide, polyamide-imide, or polyimide, photosensitive resin composition, patterning process, photosensitive dry film, and protective film for electric and electronic parts |
| CN111303417A (en) * | 2019-11-14 | 2020-06-19 | 上海极紫科技有限公司 | Photocrosslinkable polyimide resin |
| CN111303419A (en) * | 2019-11-14 | 2020-06-19 | 上海极紫科技有限公司 | Photo-crosslinkable polyimide resin structure |
| CN112979949A (en) * | 2021-03-03 | 2021-06-18 | 广东工业大学 | Transparent photosensitive polyimide resin, polyimide film and preparation method thereof |
-
2022
- 2022-05-13 CN CN202210520614.7A patent/CN114853714B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006089492A (en) * | 2005-10-11 | 2006-04-06 | Kaneka Corp | New diamine and new polyimide composition using the same |
| CN102516541A (en) * | 2011-11-22 | 2012-06-27 | 中国航空工业集团公司北京航空材料研究院 | Polyimide containing phenolic hydroxy |
| EP3604390A1 (en) * | 2018-08-01 | 2020-02-05 | Shin-Etsu Chemical Co., Ltd. | Polymer having a structure of polyamide, polyamide-imide, or polyimide, photosensitive resin composition, patterning process, photosensitive dry film, and protective film for electric and electronic parts |
| CN111303417A (en) * | 2019-11-14 | 2020-06-19 | 上海极紫科技有限公司 | Photocrosslinkable polyimide resin |
| CN111303419A (en) * | 2019-11-14 | 2020-06-19 | 上海极紫科技有限公司 | Photo-crosslinkable polyimide resin structure |
| CN112979949A (en) * | 2021-03-03 | 2021-06-18 | 广东工业大学 | Transparent photosensitive polyimide resin, polyimide film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张文豪: "可溶性光敏聚酰亚胺的合成与性能研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》, no. 02, pages 016 - 1683 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114853714B (en) | 2024-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2014034760A1 (en) | Polyimide, and alicyclic tetracarboxylic acid dianhydride for use in production of same | |
| CN105085281A (en) | Diamine monomer containing diphenylamine-fluorene, preparation method and application of same in polyimide preparation | |
| KR101548877B1 (en) | Preparation method for polyimide from salt of monomer and the polyimide thereby | |
| CN105492965A (en) | Liquid-crystal alignment agent, liquid-crystal alignment film, and liquid-crystal display element | |
| CN107533260A (en) | Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal represent element | |
| CN111303426B (en) | Polyimide film and method for preparing polyimide film by click chemistry | |
| JPS6072925A (en) | Organic solvent-soluble photosensitive polyimide | |
| CN114133565B (en) | Hyperbranched polyimide resin and preparation method and application thereof | |
| CN114106326B (en) | Photosensitive resin, photoresist, preparation method and application thereof | |
| CN114853714A (en) | Novel photo-crosslinkable photosensitive material and application thereof | |
| CN112500307B (en) | Ester group-containing aromatic diamine monomer and preparation method thereof | |
| CN108864014B (en) | Alicyclic dianhydride compound containing perhydronaphthalene structure and preparation method and application thereof | |
| WO2024113697A1 (en) | Benzocyclobutene resin containing olefinic bond, and preparation method therefor | |
| CN111217839A (en) | 2, 6-disubstituted pyrimidine aromatic anhydride and synthesis method and application thereof | |
| CN109369613B (en) | Diamine compound for preparing liquid crystal aligning agent and application thereof | |
| JPH10310640A (en) | Spiroacid dianhydiride, polyamic acid, spiropolyimide, and their production | |
| CN103265395A (en) | 2, 3, 6, 7-tetramethyl-9,10-o-naphthylanthracene and synthetic method thereof | |
| Kudo et al. | Synthesis of optically active alicyclic polyimides from a chiral, nonracemic dianhydride | |
| CN108139634B (en) | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element | |
| CN114805333A (en) | Bismaleimide with main chain containing oxazine and Cardo structures and preparation method thereof | |
| WO2007034716A1 (en) | Soluble transparent polybenzoxazole precursor, polybenzoxazole and methods for producing those | |
| CN115260056A (en) | Cross-linking agent and preparation method thereof, polyimide 3D printing ink and preparation method of recyclable thermosetting polyimide product | |
| Bender et al. | Introduction of a [5] helicene unit in polyimides by chemical and thermal transformations of precursor polymers | |
| CN1680375A (en) | Bisphenols monomer with imide structure and its synthesis | |
| CN108997579B (en) | Aromatic hyperbranched polyimide containing anthracene structure and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |