CN114853714B - Photo-crosslinkable photosensitive material and application thereof - Google Patents
Photo-crosslinkable photosensitive material and application thereof Download PDFInfo
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- CN114853714B CN114853714B CN202210520614.7A CN202210520614A CN114853714B CN 114853714 B CN114853714 B CN 114853714B CN 202210520614 A CN202210520614 A CN 202210520614A CN 114853714 B CN114853714 B CN 114853714B
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- 239000000463 material Substances 0.000 title claims abstract description 31
- 239000004642 Polyimide Substances 0.000 claims abstract description 32
- 229920001721 polyimide Polymers 0.000 claims abstract description 32
- 238000002360 preparation method Methods 0.000 claims description 5
- 150000001925 cycloalkenes Chemical class 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 abstract description 25
- 150000008065 acid anhydrides Chemical class 0.000 abstract description 9
- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 abstract description 9
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 abstract description 8
- 238000010146 3D printing Methods 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 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
- 125000003277 amino group Chemical group 0.000 abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 4
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 4
- 229920000620 organic polymer Polymers 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 112
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 81
- 238000006243 chemical reaction Methods 0.000 description 64
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 48
- 239000000203 mixture Substances 0.000 description 42
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 39
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- 238000010189 synthetic method Methods 0.000 description 37
- 239000000243 solution Substances 0.000 description 35
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- 230000015572 biosynthetic process Effects 0.000 description 27
- 238000003786 synthesis reaction Methods 0.000 description 27
- 238000012544 monitoring process Methods 0.000 description 24
- 239000000178 monomer Substances 0.000 description 24
- 239000012299 nitrogen atmosphere Substances 0.000 description 24
- 238000004440 column chromatography Methods 0.000 description 23
- 239000012043 crude product Substances 0.000 description 23
- 238000003756 stirring Methods 0.000 description 22
- 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 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
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 17
- 238000001035 drying Methods 0.000 description 16
- 239000000843 powder Substances 0.000 description 16
- 235000019441 ethanol Nutrition 0.000 description 15
- 239000011541 reaction mixture Substances 0.000 description 13
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 239000003208 petroleum Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000010992 reflux Methods 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
- 239000004952 Polyamide Substances 0.000 description 9
- 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
- 229920002647 polyamide Polymers 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000005406 washing Methods 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
- 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
- 239000012298 atmosphere Substances 0.000 description 7
- 239000011261 inert gas Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 125000005462 imide group Chemical group 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 5
- 101150033824 PAA1 gene Proteins 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000012295 chemical reaction liquid 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
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 125000000623 heterocyclic group Chemical group 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
- 238000000034 method Methods 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 230000036211 photosensitivity Effects 0.000 description 4
- 230000001376 precipitating effect 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
- 238000001308 synthesis method Methods 0.000 description 4
- 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
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 3
- -1 spiro aromatic compound Chemical class 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 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
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 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
- 125000003003 spiro group Chemical group 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 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
- 229940126062 Compound A Drugs 0.000 description 1
- 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 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 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
- 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
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 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
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 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
- 239000011521 glass Substances 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
- 239000003999 initiator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 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
- 238000002156 mixing 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 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
- 230000000379 polymerizing effect 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
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
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
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- 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 groups and phenolic hydroxyl groups on a xanthene ring as derivative sites to connect with crosslinkable photosensitive groups, and obtains different photosensitive polyimides through polymerization of fluorene ring 2, 7-diamino groups and different dibasic acid anhydrides, thus being applicable to photo-crosslinking and photo-curing materials, and being 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 used as a special functional polymer material, and is an aromatic heterocyclic polymer compound containing imide groups in the main chain of the molecule. The polymer molecular chain contains aromatic rings and imine rings, and the imide rings are in planar symmetrical annular structures, so that the polyimide molecules have classical Van der Waals force, dominant interlayer stacking of charge transfer complexes, mixed layer stacking and the like, and the structures jointly determine the excellent performances of high rigidity, high melting point, good heat resistance, chemical corrosion resistance, high mechanical strength, radiation resistance, good electrical insulation property, low dielectric constant, flame retardance and the like of the polyimide. Therefore, the polymer is 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
Polyimide molecular main chains generally contain benzene rings and imide ring structures, and polyimide has stronger intermolecular action due to electron polarization and crystallinity, so that polyimide molecular chains are closely stacked, and the traditional polyimide is not melted or dissolved and is difficult to process. When the method 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 the photosensitive polyimide (PSPI) material which can not only keep the excellent performances of heat resistance, good electrical insulation and the like of the traditional polyimide, but also improve the solubility and increase the photosensitivity.
The spiro aromatic compound has the advantages of large conjugated system, unique spiro conjugated effect, rigid coplanar structure, high glass transition temperature, good heat stability and the like, and becomes an important structural unit of an organic polymer material. In the spiro aromatic hydrocarbon material, spiro [ fluorene-9, 9' -xanthene ] connects two parts of fluorene ring and xanthene ring through 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 xanthene ring and the fluorene ring rich in electrons can effectively construct a non-planar three-dimensional molecular conformation in the molecular field. The steric hindrance effect can effectively inhibit pi-pi interaction between molecules, so that the solubility and stability of the material are improved. Therefore, it is very promising to research the application of the material to polyimide to improve the solubility and the like.
Disclosure of Invention
The invention researches photosensitive diamine monomer and application thereof, develops a photo-crosslinkable photosensitive diamine monomer, and the photo-crosslinkable photosensitive diamine monomer can be polymerized with different types of dibasic acid anhydride to obtain different photo-crosslinkable photosensitive polyimide, and is used as photo-crosslinking and photo-curing material, 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 a structure shown in a general formula Z, PAA, PSPI:
Wherein X is each independently selected from n is a number greater than 1;
specifically, n is a number from 1 to 1000;
Specifically, n is a number from 2 to 500.
R 1,R2 is independently selected from m which is an integer of 0-10, and R 3 is C3-C8 cycloolefin containing substituent or not containing substituent.
The substituent is selected from C1-C20 alkane and halogen.
Specifically, R 3 may be selected from
Y is each independently selected from the group consisting of commercial aliphatic tetracarboxylic dianhydride, cycloaliphatic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, heterocyclic tetracarboxylic dianhydride.
Specifically, Y is each independently selected from the group consisting of commercial C4-C30 aliphatic tetracarboxylic dianhydride, C4-C30 cycloaliphatic tetracarboxylic dianhydride, C4-C30 aromatic tetracarboxylic dianhydride, C4-C30 heterocyclic tetracarboxylic dianhydride, and parent structures.
The parent structure is a structure other than anhydride bond on tetracarboxylic dianhydride.
Specifically, Y is each independently selected from
Specifically, the novel photo-crosslinkable photosensitive material can be selected from the following structures:
Wherein, the definition of X and Y is the same as the definition in the structural general formula.
The photocrosslinkable photosensitive diamine monomer shown in the general formula W takes spiro [ fluorene-9, 9' -xanthene ] as a core, and two perpendicular unconjugated units of the fluorene ring and the xanthene ring enable the photocrosslinkable photosensitive diamine monomer to have a three-dimensional large-volume steric hindrance rigid structure, and a series of derivatives synthesized by the photocrosslinkable photosensitive diamine monomer have higher melting point and glass transition temperature, can inhibit crystallization of molecules, have good film forming property, and improve thermodynamic stability of the molecules. The amino and phenolic hydroxyl groups on the xanthene ring are connected with photo-crosslinkable groups, so that the monomer has photosensitivity, and the 2, 7-positions of the fluorene ring have good reactivity, thereby providing convenience for the extension of the structure of the xanthene ring to a three-dimensional space. The crosslinkable photosensitive diamine monomer is polymerized with different binary acid anhydrides to obtain a series of photosensitive polyimide (shown as general formulas PAA and PSPI), can be used as photocrosslinking and photocuring materials, and is 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 steps of constructing spiro [ fluorene-9, 9' -xanthene ] by taking fluorenone and different substituted phenols as raw materials, connecting the amino group and the phenolic hydroxyl group on the xanthene ring as derivative sites, and polymerizing the 2, 7-diamino group of the fluorene ring with different binary acid anhydrides to obtain different photosensitive polyimides, wherein the preparation method comprises the following steps:
Compound B obtained by one-step nitration of compound a:
Compound B forms a ring with a different substituted phenol (compound U) in the acid catalyzed next step to build compound C:
The compound C and the compound V are subjected to esterification reaction of acyl chloride and hydroxyl or amidation reaction of acyl chloride and amino to obtain a compound D:
wherein X is defined as in the structural general formula, and the compound V is selected from the following structures:
Wherein m=an integer of 0 to 10, and R 3 is a cyclic olefin having 3 to 8 carbons and a derivative thereof;
the compound D and Zn powder react under acidic condition to reduce nitro to obtain a compound W:
wherein, the definition of X is the same as the definition in the structural general formula.
The compound W is polymerized with different dibasic acid anhydrides (compound K) to obtain different polyamide acid PAA or photosensitive polyimide PSPI:
Wherein X, Y is defined as the above structural formula. Selected from the group consisting of commercial aliphatic tetracarboxylic dianhydride, cycloaliphatic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, heterocyclic tetracarboxylic dianhydride, wherein Y is the parent structure of the aliphatic tetracarboxylic dianhydride, cycloaliphatic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, heterocyclic tetracarboxylic dianhydride, and the ring in/() is not used to limit that Y must be a cyclic structure.
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 ℃, dropwise adding a mixed solution of concentrated HNO 3/concentrated H 2SO4 into the solution, heating and refluxing for 1H, dropwise adding a mixed solution of concentrated HNO 3/concentrated H 2SO4 again, continuing heating and refluxing reaction, gradually thickening and turning yellow, cooling after the reaction is finished, pouring the reaction solution into water, precipitating yellow precipitate, filtering, washing and drying, and recrystallizing the dried crude product in ethanol to obtain the pure compound B.
2) Uniformly mixing a compound B and a compound U in 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, filtering, drying to obtain a brown solid, and purifying the dried crude product through column chromatography to obtain a compound C;
The feeding mole ratio of the compound B to the different substituted phenols (compound U) is 1:2-10.
3) Under the atmosphere of inert gas, dissolving the compound C in dry acetone, dropwise adding triethylamine into the solution, stirring for 10min, dispersing the compound V into the dry acetone, dropwise adding the dry acetone into the reaction mixed solution in an ice bath, stirring at room temperature, adding ethyl acetate into the reaction solution after the reaction is finished, washing with water, drying, and performing column chromatography to obtain the compound D.
4) Dissolving the compound D in a mixed system of water/ethanol (volume ratio=1/3) in inert gas atmosphere, adding reduced Zn powder, ammonium chloride and glacial acetic acid, stirring for 4-6h at 50 ℃, carrying out suction filtration, extracting, 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) Under the atmosphere of inert gas, dissolving a compound W in dry and deoxidized nitrogen methyl pyrrolidone, adding different dibasic acid anhydrides (compound K) into the solution after the compound W is completely dissolved, reacting for more than 0.5h at 25 ℃, precipitating the reaction solution in a proper organic solvent, washing and drying to obtain different photosensitive polyamide acid PAA; adding triethylamine, pyridine and toluene into a solution of polyamide acid PAA in nitrogen methyl pyrrolidone, dehydrating and cyclizing for 5 hours at 180 ℃, cooling, precipitating, washing and drying the reaction solution in a proper organic solvent to obtain different photosensitive polyimide PSPI;
the feeding mole ratio of the compound Y to the different dibasic acid anhydrides (compound K) is 1:0.95-1.10.
The ratio of the two batches of concentrated HNO 3/concentrated H 2SO4 in step 1 is 1:1.
The molar ratio of compound B to the differently substituted phenol (compound U) described in step 2 is preferably 1:2.5.
The feeding mole ratio of the compound D to the reduced Zn powder in the step 4 is preferably 1:12.
The molar ratio of compound W to dibasic acid anhydride (compound M) in step 5 is preferably 1:1.05.
The organic solvent in the step5 is selected from dichloromethane, ethyl acetate and ethanol.
The photo-crosslinkable photosensitive diamine monomer has good application effect in improving the property of polyimide.
The photosensitive polyimide prepared from the photo-crosslinkable photosensitive diamine monomer has good application prospect in photo-crosslinking and photo-curing materials.
The invention has the beneficial effects that: a novel photo-crosslinkable photosensitive material and application thereof are disclosed, wherein the photo-crosslinkable photosensitive diamine material takes spiro [ fluorene-9, 9' -xanthene ] as a core, two vertical non-conjugated units of fluorene ring and xanthene ring are provided with a three-dimensional large-volume steric hindrance rigid structure, and amino groups on the xanthene ring are connected with phenolic hydroxyl groups to enable the photo-crosslinkable diamine material to have photosensitivity. The two amino groups at the 2, 7-positions of the fluorene ring can be polymerized with different binary acid anhydrides to obtain the photo-crosslinkable photosensitive polyimide with good solubility, film forming property and thermodynamic stability, and the photo-crosslinkable photosensitive polyimide is used as a photo-crosslinking and photo-curing 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 chart showing nuclear magnetic resonance hydrogen spectrum of a photo-crosslinkable diamine monomer W-1.
FIG. 3 is a chart showing nuclear magnetic resonance spectroscopy of the photo-crosslinkable diamine monomer W-1.
FIG. 4 is a chart showing the Fourier infrared spectra of PAA-1 and PSPI-1.
FIG. 5 is a chart showing the characterization of Fourier infrared spectra before and after PSPI-1 UV irradiation.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way. It is intended that all those skilled in the art can make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof within the technical scope of the present invention disclosed in the present invention.
In the examples described below, the reagents used, unless otherwise specified, were prepared by conventional methods or purchased commercially.
Example 1
Synthetic route of photo-crosslinkable diamine monomer (W-1):
(1) Synthesis of intermediate B
A (2.00 g,11.10 mmol) was dispersed in 5ml deionized water under nitrogen atmosphere, the mixture was heated to 80℃and a mixture of concentrated HNO 3 (65%, 6.92ml,99.89 mmol)/concentrated H 2SO4 (98%, 6.64ml,112.08 mmol) was added dropwise, and after refluxing for 1H, a mixture of concentrated HNO 3 (65%, 6.92ml,99.89 mmol)/concentrated H 2SO4 (98%, 6.64ml,112.08 mmol) was added dropwise again, and the refluxing reaction was continued. After the TLC monitoring reaction is finished, the reaction liquid is cooled and poured into ice water to generate yellow precipitate, the yellow precipitate is filtered by suction, a filter cake is washed for 3 times and then is dried in vacuum, and the crude product obtained by drying is recrystallized in ethanol and is filtered by suction to obtain the compound B.
(2) Synthesis of intermediate C1
Under nitrogen atmosphere, compound B (2.00 g,7.40 mmol) and resorcinol (2.04 g,18.50 mmol) were mixed uniformly, p-toluenesulfonic acid (2.55 g,14.80 mmol) was added to the mixture, dry powder was reacted at 140 ℃, after TLC monitoring the reaction was completed, 15ml deionized water was added to the reaction flask, stirred for 0.5h, the crude product was precipitated from the reaction mixture, filtered off with suction, washed and dried to a brown solid, and the dried crude product was isolated and purified by column chromatography (methanol/dichloromethane system=1/50) to obtain compound C1 as a yellow solid;
(3) Synthesis of intermediate D1
Under nitrogen atmosphere, compound C1 (1.00 g,2.20 mmol) was dissolved in 8ml of dry acetone, triethylamine (672.99 ml,4.84 mmol) was added dropwise to the solution, after stirring for 10min, methacryloyl chloride (468.62 ml,4.84 mmol) was dispersed in 2ml of dry acetone, dropwise added to the above reaction mixture under ice bath, a catalytic amount of DMAP was added to catalyze the reaction, stirring at room temperature, after TLC monitoring the end of the reaction, ethyl acetate was added to the reaction solution, washed with water, dried, and isolated and purified by column chromatography (ethyl acetate/petroleum ether system=1/1) to give compound D1.
(4) Synthesis of diamine monomer W-1
Compound D1 (1.00 g,1.70 mmol) was dissolved in a mixture of 4ml of water/ethanol (volume ratio=1/3) under a nitrogen atmosphere, reduced Zn powder (1.33 g,20.39 mmol), ammonium chloride (363.51 mg,6.80 mmol) and glacial acetic acid (97.17 mml,1.70 mmol) were added to the mixture, stirred at 50℃and after the completion of the TLC monitoring reaction, the mixture was filtered off while hot, extracted and dried, and the crude product was isolated and purified by column chromatography (ethyl acetate/petroleum ether system=2/1) to give compound W-1.
Mass spectrum and nuclear magnetic data of the compound W-1 are shown in fig. 1-3.
Example 2
Synthetic method referring to example 1, compound W-2 was synthesized with instead of/> .
Example 3
Synthetic method referring to example 1, compound W-3 was synthesized with instead of/> .
Example 4
The synthesis method of the compound B and the compound C1 is described in example 1.
(1) Synthesis of intermediate D4
Under nitrogen atmosphere, compound C1 (1.00 g,2.20 mmol) was dissolved in 8ml of dry acetone, triethylamine (672.99 ml,4.84 mmol) was added dropwise to the solution, after stirring for 10min, acryloyl chloride (405.74 ml,4.84 mmol) was dispersed in 2ml of dry acetone, dropwise added dropwise to the above reaction mixture under ice bath, a catalytic amount of DMAP was added to catalyze the reaction, stirring at room temperature, after TLC monitoring the end of the reaction, ethyl acetate was added to the reaction solution, washed with water, dried, and isolated and purified by column chromatography (ethyl acetate/petroleum ether system=1/1) to give compound D4.
(2) Synthesis of diamine monomer W-4
Compound D4 (1.00 g,1.78 mmol) was dissolved in a mixture of 4ml of water/ethanol (volume ratio=1/3) under a nitrogen atmosphere, reduced Zn powder (1.39 g,21.33 mmol), ammonium chloride (380.37 mg,7.11 mmol) and glacial acetic acid (101.68 mml,1.78 mmol) were added to the mixture, stirred at 50℃and after the completion of the TLC monitoring reaction, the mixture was filtered while hot, extracted and dried, and the crude product was isolated 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, compound W-5 was synthesized with instead of/> .
Example 6
Synthetic method referring to example 4, compound W-6 was synthesized with instead of/> .
Example 7
Synthetic method referring to example 4, compound W-7 was synthesized with instead of/> .
Example 8
Synthetic method referring to example 4, compound W-8 was synthesized with instead of/> .
Example 9
Synthetic method referring to example 4, compound W-9 was synthesized with instead of/> .
Example 10
(1) Synthesis of intermediate B
A (2.00 g,11.10 mmol) was dispersed in 5ml deionized water under nitrogen atmosphere, the mixture was heated to 80℃and a mixture of concentrated HNO 3 (65%, 6.92ml,99.89 mmol)/concentrated H 2SO4 (98%, 6.64ml,112.08 mmol) was added dropwise, and after refluxing for 1H, a mixture of concentrated HNO 3 (65%, 6.92ml,99.89 mmol)/concentrated H 2SO4 (98%, 6.64ml,112.08 mmol) was added dropwise again, and the refluxing reaction was continued. After the TLC monitoring reaction is finished, the reaction liquid is cooled and poured into ice water to generate yellow precipitate, the yellow precipitate is filtered by suction, a filter cake is washed for 3 times and then is dried in vacuum, and the crude product obtained by drying is recrystallized in ethanol and is filtered by suction to obtain the compound B.
(2) Synthesis of intermediate C2
In nitrogen atmosphere, compound B (2.00 g,7.40 mmol) and hydroquinone (2.04 g,18.50 mmol) were mixed uniformly, p-toluenesulfonic acid (2.55 g,14.80 mmol) was added to the mixture, dry powder was reacted at 140 ℃, after TLC monitoring the reaction was completed, 15ml deionized water was added to the reaction flask, stirred for 0.5h, crude product was precipitated from the reaction mixture, was filtered off with suction, washed and dried to brown solid, and the dried crude product was isolated and purified by column chromatography (methanol/dichloromethane system=1/50) to obtain compound C2 as yellow solid;
(3) Synthesis of intermediate D10
Under nitrogen atmosphere, compound C2 (1.00 g,2.20 mmol) was dissolved in 8ml of dry acetone, triethylamine (672.99 ml,4.84 mmol) was added dropwise to the solution, after stirring for 10min, methacryloyl chloride (468.62 ml,4.84 mmol) was dispersed in 2ml of dry acetone, dropwise added to the above reaction mixture under ice bath, a catalytic amount of DMAP was added to catalyze the reaction, stirring at room temperature, after TLC monitoring the end of the reaction, ethyl acetate was added to the reaction solution, washed with water, dried, and isolated and purified by column chromatography (ethyl acetate/petroleum ether system=1/1) to give compound D10.
(4) Synthesis of diamine monomer W-10
Compound D10 (1.00 g,1.70 mmol) was dissolved in a mixture of 4ml of water/ethanol (volume ratio=1/3) under a nitrogen atmosphere, reduced Zn powder (1.33 g,20.39 mmol), ammonium chloride (363.51 mg,6.80 mmol) and glacial acetic acid (97.17 mml,1.70 mmol) were added to the mixture, stirred at 50℃and after the completion of the TLC monitoring reaction, the mixture was filtered while hot, extracted and dried, and the crude product was isolated and purified by column chromatography (ethyl acetate/petroleum ether system=2/1) to give compound W-10. The product structure was identified by HRMS.
Example 11
Synthetic method referring to example 10, compound W-11 was synthesized with instead of/> .
Example 12
Synthetic method referring to example 10, compound W-12 was synthesized with instead of/> .
Example 13
The synthesis method of the compound B and the compound C2 is described in example 10.
(1) Synthesis of intermediate D13
Under nitrogen atmosphere, compound C2 (1.00 g,2.20 mmol) was dissolved in 8ml of dry acetone, triethylamine (672.99 ml,4.84 mmol) was added dropwise to the solution, after stirring for 10min, acryloyl chloride (405.74 ml,4.84 mmol) was dispersed in 2ml of dry acetone, dropwise added dropwise to the above reaction mixture under ice bath, a catalytic amount of DMAP was added to catalyze the reaction, stirring at room temperature, after TLC monitoring the end of the reaction, ethyl acetate was added to the reaction solution, washed with water, dried, and isolated and purified by column chromatography (ethyl acetate/petroleum ether system=1/1) to give compound D13.
(2) Synthesis of diamine monomer W-13
Compound D13 (1.00 g,1.78 mmol) was dissolved in a mixture of 4ml of water/ethanol (volume ratio=1/3) under a nitrogen atmosphere, reduced Zn powder (1.39 g,21.33 mmol), ammonium chloride (380.37 mg,7.11 mmol) and glacial acetic acid (101.68 mml,1.78 mmol) were added to the mixture, stirred at 50℃and after the completion of the TLC monitoring reaction, the mixture was filtered while hot, extracted and dried, and the crude product was isolated 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, compound W-14 was synthesized using instead of/> .
Example 15
Synthetic method referring to example 13, compound W-15 was synthesized using instead of/> .
Example 16
Synthetic method referring to example 13, compound W-16 was synthesized using instead of/> .
Example 17
Synthetic method referring to example 13, compound W-17 was synthesized using instead of/> .
Example 18
Synthetic method referring to example 13, compound W-18 was synthesized using instead of/> .
Example 19
(1) Synthesis of intermediate B
A (2.00 g,11.10 mmol) was dispersed in 5ml deionized water under nitrogen atmosphere, the mixture was heated to 80℃and a mixture of concentrated HNO 3 (65%, 6.92ml,99.89 mmol)/concentrated H 2SO4 (98%, 6.64ml,112.08 mmol) was added dropwise, and after refluxing for 1H, a mixture of concentrated HNO 3 (65%, 6.92ml,99.89 mmol)/concentrated H 2SO4 (98%, 6.64ml,112.08 mmol) was added dropwise again, and the refluxing reaction was continued. After the TLC monitoring reaction is finished, the reaction liquid is cooled and poured into ice water to generate yellow precipitate, the yellow precipitate is filtered by suction, a filter cake is washed for 3 times and then is dried in vacuum, and the crude product obtained by drying is recrystallized in ethanol and is filtered by suction to obtain the compound B.
(2) Synthesis of intermediate C3
Under nitrogen atmosphere, compound B (2.00 g,7.40 mmol) and catechol (2.04 g,18.50 mmol) were mixed uniformly, p-toluenesulfonic acid (2.55 g,14.80 mmol) was added to the mixture, dry powder was reacted at 140 ℃, after TLC monitoring the reaction was completed, cooled, 15ml deionized water was added to the reaction flask, stirred for 0.5h, the crude product was precipitated from the reaction mixture, filtered off with suction, washed, dried to brown solid, and the dried crude product was separated and purified by column chromatography (methanol/dichloromethane system=1/50) to obtain compound C3 as yellow solid;
(3) Synthesis of intermediate D19
Under nitrogen atmosphere, compound C3 (1.00 g,2.20 mmol) was dissolved in 8ml of dry acetone, triethylamine (672.99 ml,4.84 mmol) was added dropwise to the solution, after stirring for 10min, methacryloyl chloride (468.62 ml,4.84 mmol) was dispersed in 2ml of dry acetone, dropwise added to the above reaction mixture under ice bath, a catalytic amount of DMAP was added to catalyze the reaction, stirring at room temperature, after TLC monitoring the end of the reaction, ethyl acetate was added to the reaction solution, washed with water, dried, and isolated and purified by column chromatography (ethyl acetate/petroleum ether system=1/1) to give compound D19.
(4) Synthesis of diamine monomer W-19
Compound D19 (1.00 g,1.70 mmol) was dissolved in a mixture of 4ml of water/ethanol (volume ratio=1/3) under a nitrogen atmosphere, reduced Zn powder (1.33 g,20.39 mmol), ammonium chloride (363.51 mg,6.80 mmol) and glacial acetic acid (97.17 mml,1.70 mmol) were added to the mixture, stirred at 50℃and after the completion of the TLC monitoring reaction, the mixture was filtered off while hot, extracted and dried, and the crude product was isolated and purified by column chromatography (ethyl acetate/petroleum ether system=2/1) to give compound W-19. The product structure was identified by HRMS.
Example 20
Synthetic method referring to example 19, compound W-20 was synthesized with instead of/> .
Example 21
Synthetic method referring to example 19, compound W-21 was synthesized with instead of/> .
Example 22
The synthesis method of the compound B and the compound C3 is described in example 19.
(1) Synthesis of intermediate D22
Under nitrogen atmosphere, compound C3 (1.00 g,2.20 mmol) was dissolved in 8ml of dry acetone, triethylamine (672.99 ml,4.84 mmol) was added dropwise to the solution, after stirring for 10min, acryloyl chloride (405.74 ml,4.84 mmol) was dispersed in 2ml of dry acetone, dropwise added dropwise to the above reaction mixture under ice bath, a catalytic amount of DMAP was added to catalyze the reaction, stirring at room temperature, after TLC monitoring the end of the reaction, ethyl acetate was added to the reaction solution, washed with water, dried, and isolated and purified by column chromatography (ethyl acetate/petroleum ether system=1/1) to give compound D22.
(2) Synthesis of diamine monomer W-22
Compound D22 (1.00 g,1.78 mmol) was dissolved in a mixture of 4ml of water/ethanol (volume ratio=1/3) under a nitrogen atmosphere, reduced Zn powder (1.39 g,21.33 mmol), ammonium chloride (380.37 mg,7.11 mmol) and glacial acetic acid (101.68 mml,1.78 mmol) were added to the mixture, stirred at 50℃and after the completion of the TLC monitoring reaction, the mixture was filtered while hot, extracted and dried, and the crude product was isolated 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 referring to example 23, compound W-23 was synthesized with instead of/> .
Example 24
Synthetic method referring to example 23, compound W-24 was synthesized with instead of/> .
Example 25
Synthetic method referring to example 23, compound W-25 was synthesized with instead of/> .
Example 26
Synthetic method referring to example 23, compound W-26 was synthesized with instead of/> .
Example 27
Synthetic method referring to example 23, compound W-27 was synthesized using instead of/> .
Example 28
Synthetic route of crosslinkable photosensitive diamine monomer (W-28):
(1) Synthesis of intermediate B
A (2.00 g,11.10 mmol) was dispersed in 5ml deionized water under nitrogen atmosphere, the mixture was heated to 80℃and a mixture of concentrated HNO 3 (65%, 6.92ml,99.89 mmol)/concentrated H 2SO4 (98%, 6.64ml,112.08 mmol) was added dropwise, and after refluxing for 1H, a mixture of concentrated HNO 3 (65%, 6.92ml,99.89 mmol)/concentrated H 2SO4 (98%, 6.64ml,112.08 mmol) was added dropwise again, and the refluxing reaction was continued. After the TLC monitoring reaction is finished, the reaction liquid is cooled and poured into ice water to generate yellow precipitate, the yellow precipitate is filtered by suction, a filter cake is washed for 3 times and then is dried in vacuum, and the crude product obtained by drying is recrystallized in ethanol and is filtered by suction to obtain the compound B.
(2) Synthesis of intermediate C4
Under nitrogen atmosphere, compound B (2.00 g,7.40 mmol) and meta-aminophenol (2.02 g,18.50 mmol) were mixed uniformly, p-toluene sulfonic acid (2.55 g,14.80 mmol) was added to the mixture, dry powder was reacted at 140 ℃, after TLC monitoring the reaction was completed, cooled, 15ml deionized water was added to the reaction flask, stirred for 0.5h, the crude product was precipitated from the reaction mixture, filtered off with suction, washed, dried to a brown solid, and the dried crude product was separated and purified by column chromatography (methanol/dichloromethane system=1/50) to obtain compound C4 as a brown solid;
(3) Synthesis of intermediate D28
Under nitrogen atmosphere, compound C4 (1.00 g,2.21 mmol) was dissolved in 8ml of dry acetone, triethylamine (675.92 mml,4.86 mmol) was added dropwise to the solution, after stirring for 10min, methacryloyl chloride (470.66 mml,4.86 mmol) was dispersed in 2ml of dry acetone, dropwise added to the above reaction mixture under ice bath, a catalytic amount of DMAP was added to catalyze the reaction, stirring at room temperature, after TLC monitoring the end of the reaction, ethyl acetate was added to the reaction solution, washed with water, dried, and isolated and purified by column chromatography (ethyl acetate/dichloromethane system=1/100) to give compound D28.
(4) Synthesis of diamine monomer W-31
Compound D28 (1.00 g,1.70 mmol) was dissolved in a mixture of 4ml of water/ethanol (volume ratio=1/3) under a nitrogen atmosphere, reduced Zn powder (1.33 g,20.39 mmol), ammonium chloride (363.51 mg,6.80 mmol) and glacial acetic acid (97.17 mml,1.70 mmol) were added to the mixture, stirred at 50℃and after the completion of the TLC monitoring reaction, the mixture was filtered off while hot, extracted and dried, and the crude product was isolated and purified by column chromatography (methanol/dichloromethane system=1/60) to give compound W-28. The product structure was identified by HRMS.
Example 29
Synthetic method referring to example 28, compound W-29 was synthesized with instead of/> .
Example 30
Synthetic method referring to example 28, compound W-30 was synthesized with instead of/> .
Example 31
The synthesis method of the compound B and the compound C4 is described in example 28.
(1) Synthesis of intermediate D31
Under nitrogen atmosphere, compound C4 (1.00 g,2.21 mmol) was dissolved in 8ml of dry acetone, triethylamine (675.92 ml,4.86 mmol) was added dropwise to the solution, after stirring for 10min, acryloyl chloride (407.50 ml,4.86 mmol) was dispersed in 2ml of dry acetone, dropwise added dropwise to the above reaction mixture under ice bath, a catalytic amount of DMAP was added to catalyze the reaction, stirring at room temperature, after TLC monitoring the end of the reaction, ethyl acetate was added to the reaction solution, washed with water, dried, and isolated and purified by column chromatography (ethyl acetate/dichloromethane system=1/100) to give compound D31.
(4) Synthesis of diamine monomer W-31
Compound D31 (1.00 g,1.78 mmol) was dissolved in a mixture of 4ml of water/ethanol (volume ratio=1/3) under a nitrogen atmosphere, reduced Zn powder (1.40 g,21.41 mmol), ammonium chloride (381.71 mg,7.14 mmol) and glacial acetic acid (102.03 mml,1.78 mmol) were added to the mixture, stirred at 50℃and after the completion of the TLC monitoring reaction, the mixture was filtered while hot, extracted and dried, and the crude product was isolated and purified by column chromatography (methanol/dichloromethane system=1/60) to obtain compound W-31. The product structure was identified by HRMS.
Example 32
Synthetic method referring to example 31, compound W-32 was synthesized with instead of/> .
Example 33
Synthetic method referring to example 31, compound W-33 was synthesized with instead of/> .
Example 34
Synthetic method referring to example 31, compound W-34 was synthesized with instead of/> .
Example 35
Synthetic method referring to example 31, compound W-35 was synthesized with instead of/> .
Example 36
Synthetic method referring to example 31, compound W-36 was synthesized with instead of/> .
Example 37
The synthesis of compound W-1 is described in example 1.
Synthetic route of photo-crosslinkable photosensitive polyimide (PSPI-1)
Under inert gas atmosphere, compound W-1 (100.00 mg,188.47 mu mol) is dissolved in 2ml of dry and deoxidized nitrogen methyl pyrrolidone, after complete dissolution, 3', 4' -benzophenone tetracarboxylic dianhydride (63.77 mg,197.90 mu mol) is added into the solution, stirred and reacted for 8 hours at 25 ℃, the reaction liquid is added into ethyl acetate in a dropwise manner, yellow matters are precipitated, washed and dried, and polyamide acid PAA-1 is obtained; adding 0.5ml of triethylamine, 0.5ml of pyridine and 2ml of toluene into a solution of polyamide acid PAA-1 in azomethine pyrrolidone, dehydrating and cyclizing for 5 hours at 180 ℃, cooling, dripping the reaction solution into absolute ethyl alcohol to precipitate, washing and drying to obtain photo-crosslinkable photosensitive polyimide PSPI-1.
Fourier infrared spectral data for PAA-1 and PSPI-1 are shown in FIG. 4. Comparing the curves of PAA-1 and PSPI-1, it can be seen that the 1363cm -1 is the telescopic vibration absorption peak of C-N bond on the imide ring, the 1783cm -1 and the 1731cm -1 are the symmetrical and asymmetrical telescopic vibration absorption peaks of 2 C=O on the imide ring, and the existence of the imide ring structure can be determined; the monomer W-1 has a methacrylate group, and a characteristic absorption peak of C=C in the methacrylate structure is clearly observed in a PSPI-1 map at 1608cm -1, so that the PSPI-1 can be determined to be prepared.
Example 38
Synthetic method referring to example 37, polymers PAA-2, PSPI-2 were synthesized.
Example 39
Synthetic method referring to example 37, polymers PAA-3, PSPI-3 were synthesized.
Example 40
Synthetic method referring to example 37, polymers PAA-4, PSPI-4 were synthesized.
Example 41
/>
The synthesis of compound W-7 is described in example 7.
Synthetic route of photo-crosslinkable photosensitive polyimide (PSPI-5)
Under inert gas atmosphere, compound W-7 (100.00 mg,152.74 mu mol) is dissolved in 2ml of dry and deoxidized nitrogen methyl pyrrolidone, after complete dissolution, 2-bis (3, 4-dicarboxyphenyl) methane dianhydride (49.43 mg,160.37 mu mol) is added into the solution, stirring is carried out at 25 ℃ for 8 hours, the reaction solution is added into ethyl acetate in a dropwise manner, yellow matters are precipitated out, washing and drying are carried out, and polyamide acid PAA-5 is obtained; adding 0.5ml of triethylamine, 0.5ml of pyridine and 2ml of toluene into a solution of polyamide acid PAA-5 in azomethyl pyrrolidone, dehydrating and cyclizing for 5 hours at 180 ℃, cooling, dripping the reaction solution into absolute ethyl alcohol to precipitate, washing and drying to obtain photo-crosslinkable photosensitive polyimide PSPI-5.
Example 42
Synthetic method referring to example 41, polymers PAA-6, PSPI-6 were synthesized.
Example 43
Synthetic method referring to example 41, polymers PAA-7, PSPI-7 were synthesized.
Example 44
The synthesis of compound W-31 is described in example 31.
Synthetic route of photo-crosslinkable photosensitive polyimide (PSPI-8)
Under inert gas atmosphere, compound W-31 (100.00 mg,199.78 mu mol) is dissolved in 2ml of dry and deoxidized nitrogen methyl pyrrolidone, after complete dissolution, dibenzo dioxane dianhydride (68.01 mg,209.77 mu mol) is added into the solution, stirring reaction is carried out for 8 hours at 25 ℃, the reaction solution is added into ethyl acetate in a dropwise manner, yellow matters are precipitated, washing and drying are carried out, and polyamide acid PAA-8 is obtained; adding 0.5ml of triethylamine, 0.5ml of pyridine and 2ml of toluene into a solution of polyamide acid PAA-8 in azomethine pyrrolidone, dehydrating and cyclizing for 5 hours at 180 ℃, cooling, dripping the reaction solution into absolute ethyl alcohol to precipitate, washing and drying to obtain photo-crosslinkable photosensitive polyimide PSPI-8.
Example 45
Synthetic method referring to example 44, polymers PAA-9, PSPI-9 were synthesized.
Example 46
Synthetic method referring to example 44, polymers PAA-10, PSPI-10 were synthesized.
Example 47
Synthetic method referring to example 44, polymers PAA-11, PSPI-11 were synthesized.
Example 48
/>
Synthetic method referring to example 44, polymers PAA-12, PSPI-12 were synthesized.
Example 49
30Mg of PSPI-1 was dissolved iN 0.2mL of dry DMAc, 5% of diphenyl- (2, 4, 6-trimethylbenzoyl) oxyphosphorus (photo-initiator TPO) was added, stirred at room temperature for 2h, a film was formed on a clean glass plate, the solvent was removed by drying, and a sample was taken for infrared spectroscopy (Nicolet iN10 micro-infrared spectrometer) after irradiation with 390nm ultraviolet light. Fig. 5 is an infrared spectrogram of the photo-crosslinkable polyimide PSPI-1 before and after ultraviolet irradiation, and compared with the photo-crosslinkable polyimide PSPI-1 before ultraviolet irradiation, the infrared characteristic absorption peak intensity of the c=c double bond of the photo-crosslinked Cl-PSPI-1 at the position 1606cm -1 is obviously weakened, which proves that the photo-crosslinking reaction occurs under ultraviolet irradiation.
Namely, it is shown that polyimide PSPI-1 can undergo photocrosslinking under ultraviolet irradiation.
Claims (5)
1. A class of photo-crosslinkable photosensitive materials, characterized in that the materials have the structure of formula I, formula II or formula III:
Wherein X is each independently selected from n is a number greater than 1;
R 1,R2 is independently selected from m, each independently is an integer of 0-10, and R 3 is C3-C8 cycloolefin;
y is each independently selected from
2. The photo-crosslinkable photosensitive material of claim 1, wherein X is each independently selected from the group consisting of
3. The photo-crosslinkable photosensitive material of claim 1, wherein R 1,R2 is independently selected from the group consisting of
4. Use of a photo-crosslinkable photosensitive material of formula I according to claim 1 for the preparation of a photo-crosslinkable polyimide.
5. Use of a photo-crosslinkable photosensitive material of formula I as claimed in claim 1 for the preparation of a photo-curable polyimide.
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| JP2006089492A (en) * | 2005-10-11 | 2006-04-06 | Kaneka Corp | New diamine and new polyimide composition using the same |
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