CN117069931B - Hyperbranched fluorenyl photosensitive polyaryletherketone precursor, composition, film and preparation method thereof - Google Patents
Hyperbranched fluorenyl photosensitive polyaryletherketone precursor, composition, film and preparation method thereof Download PDFInfo
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- CN117069931B CN117069931B CN202311045763.3A CN202311045763A CN117069931B CN 117069931 B CN117069931 B CN 117069931B CN 202311045763 A CN202311045763 A CN 202311045763A CN 117069931 B CN117069931 B CN 117069931B
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- Prior art keywords
- polyaryletherketone
- hyperbranched
- photosensitive
- fluorenyl
- precursor
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- 229920006260 polyaryletherketone Polymers 0.000 title claims abstract description 130
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 title claims abstract description 120
- 239000002243 precursor Substances 0.000 title claims abstract description 99
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003085 diluting agent Substances 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 26
- -1 mercaptan compound Chemical class 0.000 claims abstract description 17
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 15
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 13
- RIXRZNFBNRCDAJ-UHFFFAOYSA-N (2,6-difluorophenyl)-(4-fluorophenyl)methanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=C(F)C=CC=C1F RIXRZNFBNRCDAJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- XWWMKJADTYYKPY-UHFFFAOYSA-N (3,5-difluorophenyl)-(4-fluorophenyl)methanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC(F)=CC(F)=C1 XWWMKJADTYYKPY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000016 photochemical curing Methods 0.000 claims abstract description 8
- 125000005396 acrylic acid ester group Chemical group 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 38
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 238000001723 curing Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- HCZMHWVFVZAHCR-UHFFFAOYSA-N 2-[2-(2-sulfanylethoxy)ethoxy]ethanethiol Chemical compound SCCOCCOCCS HCZMHWVFVZAHCR-UHFFFAOYSA-N 0.000 claims description 4
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 238000007790 scraping Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 3
- HAQZWTGSNCDKTK-UHFFFAOYSA-N 2-(3-sulfanylpropanoyloxy)ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOC(=O)CCS HAQZWTGSNCDKTK-UHFFFAOYSA-N 0.000 claims description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 claims description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 2
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 2
- RHNJVKIVSXGYBD-UHFFFAOYSA-N 10-prop-2-enoyloxydecyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCCOC(=O)C=C RHNJVKIVSXGYBD-UHFFFAOYSA-N 0.000 claims description 2
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 claims description 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 2
- HFEHLDPGIKPNKL-UHFFFAOYSA-N allyl iodide Chemical compound ICC=C HFEHLDPGIKPNKL-UHFFFAOYSA-N 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- MDNDTNWWCWIJST-UHFFFAOYSA-N decanedioic acid prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)CCCCCCCCC(O)=O MDNDTNWWCWIJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 claims description 2
- 239000003495 polar organic solvent Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 15
- 229920005989 resin Polymers 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000011229 interlayer Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract 1
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 12
- 239000011521 glass Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 229920000090 poly(aryl ether) Polymers 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000007156 chain growth polymerization reaction Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000007155 step growth polymerization reaction Methods 0.000 description 4
- 150000003573 thiols Chemical group 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- PHBAKVPDAOWHDH-QUFRNCFNSA-N tricyclo[5.2.1.02,6]decanedimethanol diacrylate Chemical compound C12CCCC2[C@H]2C(COC(=O)C=C)C(COC(=O)C=C)[C@@H]1C2 PHBAKVPDAOWHDH-QUFRNCFNSA-N 0.000 description 2
- ONUFSRWQCKNVSL-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(2,3,4,5,6-pentafluorophenyl)benzene Chemical group FC1=C(F)C(F)=C(F)C(F)=C1C1=C(F)C(F)=C(F)C(F)=C1F ONUFSRWQCKNVSL-UHFFFAOYSA-N 0.000 description 1
- LVJZCPNIJXVIAT-UHFFFAOYSA-N 1-ethenyl-2,3,4,5,6-pentafluorobenzene Chemical compound FC1=C(F)C(F)=C(C=C)C(F)=C1F LVJZCPNIJXVIAT-UHFFFAOYSA-N 0.000 description 1
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 239000012957 2-hydroxy-2-methyl-1-phenylpropanone Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 1
- 229920006391 phthalonitrile polymer Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
Abstract
The invention relates to a hyperbranched fluorenyl photosensitive polyaryletherketone precursor, a composition, a film and a preparation method thereof. First using BB with unequal activity 2 ' monomer 2,4', 6-trifluoro-benzophenone or 3,4', 5-trifluoro-benzophenone with high volume A 2 Synthesizing a hydroxyl-terminated hyperbranched fluorenyl polyaryletherketone by taking bisphenol fluorene as a reactant, and then introducing allyl into the end of a molecular chain to synthesize a hyperbranched fluorenyl photosensitive polyaryletherketone precursor; and preparing a ternary photo-curing system from the hyperbranched fluorenyl photosensitive polyaryletherketone precursor, the acrylic acid ester reactive diluent, the mercaptan compound, the photoinitiator and the solvent, and preparing the polyaryletherketone resin film. The polyaryletherketone resin film prepared by the invention has excellent dielectric property, heat resistance and mechanical property, and can promote the development and application of interlayer insulating dielectric manufacturing technology.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a hyperbranched fluorenyl photosensitive polyaryletherketone precursor, a composition, a film and a preparation method thereof.
Background
Polyarylether (pae) is a typical high-performance resin, and has advantages of high strength, high toughness, acid and alkali resistance, excellent thermal properties, low thermal expansion coefficient, low water absorption, excellent dielectric properties, and the like, so that it has been widely used as a dielectric material in the fields of communication industry and microelectronics. The property of a polymer to store and consume electrical energy under the action of an external electric field is called dielectric property, and is generally represented by dielectric constant and dielectric loss due to polarization of polymer molecules under the action of an electric field.
Researchers at home and abroad conduct various exploratory researches on dielectric modification of polyarylether. For example, chinese patent 200410011421.0 provides a photosensitive fluorine-containing polyarylether, in which the polarity of the system is reduced by introducing hexafluorobisphenol a and decafluorobiphenyl and blocking with pentafluorostyrene, and then the polymer film obtained by thermal crosslinking or ultraviolet crosslinking has a low dielectric constant and low dielectric loss. However, the decrease in rigidity of the molecular chain causes a decrease in glass transition temperature. Polyhedral oligomeric silsesquioxanes (POSS) with hollow nanostructures are incorporated in polyarylether structures by copolymerization (Zhang WH, xu JD, li XS, et al journal of Polymer Science Part A: polymer Chemistry,2014,52 (6): 780-788.), cross-linking (Geng Z, huo MX, mu JX, et al journal ofMaterials Chemistry C,2014,2 (6): 1094-1103.), or doping (Shalma B, verma R, baur C, et al journal ofMaterials Chemistry C,2013,1 (43): 7222-7227.) and the like, the dielectric constant of some polymers has reached 2.0, but the mechanical properties of the material tend to decrease dramatically with increasing porosity. Chinese patent 201910898254.2 provides a cross-linked polyarylether, wherein phthalonitrile is introduced at the tail end of a molecular main chain to obtain cross-linked polyarylether nitrile, and a film obtained by cross-linking has excellent thermal performance, mechanical performance and dielectric performance, but the preparation of the cross-linked polyarylether requires long-time heat treatment at high temperature, which makes the preparation process excessively complicated.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a hyperbranched fluorenyl photosensitive polyaryletherketone precursor, a composition, a film and a preparation method thereof, so that the polyaryletherketone resin film has excellent insulating property, thermodynamic property and mechanical property.
The first aspect of the invention provides a hyperbranched fluorenyl photosensitive polyaryletherketone precursor. Firstly, from the design of a molecular structure, the invention introduces the full aromatic ring bisphenol fluorene with ultra-large volume, ultra-high rigidity and lower polarity into the main chain of the hyperbranched polyaryletherketone molecule, on one hand, the invention can endow the main chain of the polymer with stronger rigidity and promote the heat resistance and mechanical property thereof; on the other hand, the free volume inside the polymer can be greatly increased, and the dielectric constant is reduced. Secondly, the polyaryletherketone with the hyperbranched structure has a larger cavity structure, so that the dielectric constant of the resin can be reduced, and the thermal performance can be improved. Finally, a three-dimensional network structure can be quickly constructed by means of the photosensitive groups, on one hand, molecular movement is limited, dielectric loss and linear thermal expansion coefficient of the resin are reduced, heat resistance, mechanical property and the like of the resin are improved, and on the other hand, the ultraviolet curing technology can shorten the curing time to a few minutes or even a few seconds, so that the production efficiency is greatly increased, and the production cost is reduced.
In order to achieve the above object, the present invention adopts the following technical scheme.
A hyperbranched fluorenyl photosensitive polyaryletherketone precursor, which has a structure shown in a formula (I) and/or a formula (II):
further, the number average molecular weight of the hyperbranched fluorenyl photosensitive polyaryletherketone precursor is 2000 to 20000g/mol (e.g., 3000g/mol, 5000g/mol, 8000g/mol, 10000g/mol, 12000g/mol, 15000g/mol, 17000g/mol, or 19000 g/mol).
Further, the hyperbranched fluorenyl photosensitive polyaryletherketone precursor is a product obtained by polymerizing a 2,4', 6-trifluoro-benzophenone monomer and a bisphenol fluorene monomer and capping with allyl, or a product obtained by polymerizing a 3,4', 5-trifluoro-benzophenone monomer and a bisphenol fluorene monomer and capping with allyl.
In the polymerization process, a nucleophilic substitution reaction occurs between a halogen atom on the 2,4', 6-trifluoro-benzophenone monomer or the 3,4', 5-trifluoro-benzophenone monomer and a phenolic hydroxyl group on the bisphenol fluorene monomer, thereby forming the hyperbranched fluorenyl photosensitive polyaryletherketone precursor.
The invention also provides a preparation method of the hyperbranched fluorenyl photosensitive polyaryletherketone precursor, which comprises the following steps:
BB is carried out 2 ' monomer, A 2 Adding a monomer, a salifying agent, a first organic solvent and a water-carrying agent into a reaction vessel protected by inert gas atmosphere, heating and refluxing at a temperature of 120-130 ℃ (for example, 122 ℃, 124 ℃, 125 ℃, 127 ℃ or 129 ℃) for 1-4 hours (for example, 1.5 hours, 2 hours, 2.5 hours, 3 hours or 3.5 hours), and then continuously heating and distilling off water and toluene generated by the reaction at a temperature of 130-140 ℃ (for example, 132 ℃, 134 ℃, 135 ℃, 137 ℃ or 139 ℃); then, the temperature of the reaction system is increased to 180-200 ℃ (for example, 182 ℃, 185 ℃, 190 ℃, 195 ℃ or 198 ℃) for 8-12 hours (for example, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours or 11.5 hours), and the polymerization reaction is finished; and then cooling the reaction system to room temperature, adding a blocking agent for blocking reaction, and finally obtaining the allyl blocked hyperbranched fluorenyl photosensitive polyaryletherketone precursor through aftertreatment.
Further, the BB 2 The ' monomer comprises one of 2,4', 6-trifluoro-benzophenone and 3,4', 5-trifluoro-benzophenone, the A 2 The type monomer comprises bisphenol fluorene. Further, A 2 Monomers and BB 2 The' monomer feed ratio is fed at a molar ratio of functional groups OH to F (OH: F) of 1.33 to 2.1:1 (e.g., 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, or 2.0:1).
Further, the salt forming agent is one or more than two of potassium carbonate, cesium carbonate, potassium hydroxide, sodium hydroxide, potassium hydride and sodium hydride.
Further, the molar amount of the metal cation in the salifying agent is A 2 The molar amount of OH functions in the monomer is 1 to 1.2 times (e.g., 1.05 times, 1.1 times, or 1.15 times).
Further, the first organic solvent is a polar organic solvent, preferably, the first organic solvent includes one or more of N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide, and dimethylsulfoxide.
Further, the water-carrying agent is one or more of benzene, toluene (abbreviated as PhMe), dimethylbenzene and chlorobenzene. Further, the water-carrying agent is used in an amount of 0.4 to 1 times (e.g., 0.5 times, 0.6 times, 0.7 times, 0.8 times, or 0.9 times) the volume of the first organic solvent.
Further, the end-capping reaction is performed in a gradual temperature rise manner, and further, the gradual temperature rise manner is as follows: reacting at 48-52 ℃ for 2-4 hours (e.g., 2.5 hours, 3 hours, or 3.5 hours), 58-62 ℃ for 2-4 hours (e.g., 2.5 hours, 3 hours, or 3.5 hours), 68-72 ℃ for 2-4 hours (e.g., 2.5 hours, 3 hours, or 3.5 hours), 88-92 ℃ for 4-8 hours (e.g., 4.5 hours, 5 hours, 6 hours, 7 hours, or 7.5 hours).
Further, the gradual temperature rise mode is as follows: reacting for 2-4 hours at 50 ℃, reacting for 2-4 hours at 60 ℃, reacting for 2-4 hours at 70 ℃, and reacting for 4-8 hours at 90 ℃.
Further, the end-capping agent is 3-halo-1-propene, preferably comprising at least one of 3-bromo-1-propene, 3-chloro-1-propene and 3-iodo-1-propene, further, the end-capping agent is mixed with A 2 The molar ratio of OH functions in the monomer is 1 to 1.2:1 (e.g., 1.05 times, 1.1 times, or 1.15 times).
Further, the post-processing includes the steps of:
and (3) settling the reaction product obtained after the end-capping reaction in deionized water, sequentially washing, boiling the sediment with water, dissolving with chloroform, settling with ethanol, carrying out suction filtration, and drying the obtained product (for example, putting the product into a vacuum oven for drying at 120 ℃) to obtain the allyl end-capped hyperbranched fluorenyl photosensitive polyaryletherketone precursor.
In the invention, a specific reaction route for preparing the hyperbranched fluorenyl photosensitive polyaryletherketone precursor by taking 3,4', 5-trifluoro-benzophenone and bisphenol fluorene as raw materials is shown in the following formula (III).
In the invention, a specific reaction route for preparing the hyperbranched fluorenyl photosensitive polyaryletherketone precursor by taking 2,4', 6-trifluoro-benzophenone and bisphenol fluorene as raw materials is shown in the following formula (IV).
The second aspect of the invention provides a composition containing hyperbranched fluorenyl photosensitive polyaryletherketone precursor, which adopts the following technical scheme.
A composition containing hyperbranched fluorenyl photosensitive polyaryletherketone precursor comprises the hyperbranched fluorenyl photosensitive polyaryletherketone precursor, a reactive diluent, a mercaptan compound, a photoinitiator and a second organic solvent; wherein,
the mass ratio of the hyperbranched fluorenyl photosensitive polyaryletherketone precursor to the reactive diluent is 50:50-90:10 (for example, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20 or 85:15), and the sum of the mass percentages of the hyperbranched fluorenyl photosensitive polyaryletherketone precursor and the reactive diluent is 100%.
Further, the molar ratio of thiol functional groups in the thiol compound to the sum of allyl groups in the hyperbranched fluorenyl photosensitive polyaryletherketone precursor and acrylate groups in the reactive diluent is from 0.2:1 to 1:1 (i.e., thiol: double bond = 0.2:1 to 1:1, e.g., 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, or 0.9:1);
further, the photoinitiator is present in an amount of 1% to 5% (e.g., 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, or 4.5%) of the total mass of the composition excluding the solvent.
In the invention, the mass ratio of the hyperbranched fluorenyl photosensitive polyaryletherketone precursor to the reactive diluent is calculated based on the sum of the total mass of the hyperbranched fluorenyl photosensitive polyaryletherketone precursor and the reactive diluent to be 100.
Further, in the hyperbranched fluorenyl photosensitive polyaryletherketone precursor composition, the concentration of the hyperbranched fluorenyl photosensitive polyaryletherketone precursor is 0.3 to 1.5g/ml (e.g., 0.5g/ml, 0.8g/ml, 1.0g/ml, 1.2g/ml, or 1.4 g/ml).
Further, the reactive diluent is an acrylic reactive diluent, typically, but not limited to, one or more of tripropylene glycol diacrylate, polyethylene glycol (200) diacrylate, 1, 6-hexanediol diacrylate, tricyclo [5.2.1.02,6] sebacic acid diacrylate, 1, 10-bis (acryloyloxy) decane, trimethylolpropane triacrylate and pentaerythritol tetraacrylate.
Further, the thiol compound is one or more than two of 3, 6-dioxa-1, 8-octanedithiol, ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate) and pentaerythritol tetrasulfoacetate.
Further, the photoinitiator is one or more than two of 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthiophenyl) -2-morpholinyl-1-propanone ], 2-hydroxy-2-methyl-1-phenyl propanone, 2-phenylbenzyl-2-dimethyl amine-1- (4-morpholinyl) butanone, 2-dimethoxy-2-phenylacetophenone, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, benzophenone, 2,4, 6-trimethylbenzophenone, 4-methylbenzophenone and the like.
Further, the second organic solvent is one or more of acetone, cyclohexanone, butanone, propylene glycol methyl ether acetate, N-methylpyrrolidone, chloroform and tetrahydrofuran.
In the composition containing the hyperbranched fluorenyl photosensitive polyaryletherketone precursor, the hyperbranched fluorenyl photosensitive polyaryletherketone precursor contains an allyl structure, the active diluent contains an acrylate structure, and the thiol compound contains a thiol structure, so that the composition can be used for preparing a cured film by adopting a 'thiol-ene-acrylate' ternary photocuring system, and a mixed growth mechanism of free radical step-growth polymerization and free radical chain-growth polymerization is realized to quickly polymerize to form a three-dimensional network structure; the step-growth polymerization of the 'mercaptan-alkene' free radical can obviously reduce volume shrinkage and stress and overcome oxygen inhibition; the "acrylate" free radical chain growth polymerization can significantly increase the crosslink density of the system, thereby improving the mechanical and thermal properties of the cured film.
The invention also provides a preparation method of the composition containing the hyperbranched fluorenyl photosensitive polyaryletherketone precursor, which comprises the following steps:
dissolving a hyperbranched fluorenyl photosensitive polyaryletherketone precursor, a reactive diluent, a mercaptan compound and a photoinitiator in a second organic solvent, and fully and uniformly stirring the mixture at room temperature in a dark place to obtain a composition containing the photosensitive hyperbranched polyaryletherketone precursor; wherein the concentration of the hyperbranched fluorenyl photosensitive polyaryletherketone precursor in the composition is from 0.3 to 1.5g/ml (e.g., 0.4g/ml, 0.5g/ml, 0.6g/ml, 0.8g/ml, 1.0g/ml, 1.2g/ml, or 1.4 g/ml).
The third aspect of the invention also provides a hyperbranched fluorenyl photosensitive polyaryletherketone film, which is prepared from the composition containing the hyperbranched fluorenyl photosensitive polyaryletherketone precursor.
Further, the hyperbranched fluorenyl photosensitive polyaryletherketone resin film has a dielectric constant of less than 3.0 at 1GHz, a dielectric loss of less than 0.015 and excellent insulating performance; thermal decomposition temperature T 5％ Above 300 ℃, T g Above 150 ℃, exhibits excellent thermodynamic properties; the tensile strength is more than 35MPa, the elongation at break is more than 5%, and the mechanical properties are excellent.
The fourth aspect of the invention also provides a preparation method of the hyperbranched fluorenyl photosensitive polyaryletherketone film, which sequentially comprises the following steps:
scraping a film: pouring the composition containing the hyperbranched fluorenyl photosensitive polyaryletherketone precursor onto a clean carrier, and coating by using a coating film scraper;
curing: placing the coated carrier into an ultraviolet curing box, and performing photo-curing at room temperature so as to form a film on the carrier;
removing the solvent: subjecting the film attached to the support to vacuum heating to remove the solvent from the film (i.e., the second organic solvent in the composition);
removing the film: immersing the carrier with the film after vacuum heating in water to enable the film to fall off, wherein the film after falling off is the hyperbranched fluorenyl photosensitive polyaryletherketone film.
Further, the curing time is 20 to 100s (e.g., 30s, 40s, 50s, 60s, 70s, 80s or 90 s), and the ultraviolet energy density is 20mw/cm 2 ～100mw/cm 2 (e.g., 30 mw/cm) 2 、40mw/cm 2 、50mw/cm 2 、60mw/cm 2 、70mw/cm 2 、80mw/cm 2 Or 90mw/cm 2 )。
Further, the vacuum heating removes the solvent by gradually increasing the temperature to the boiling point of the solvent.
Further, the film attached to the support is immersed in water to peel off the film.
Further, coating is performed with a paint film scraper at a speed of 50 to 150mm/s (e.g., 60mm/s, 80mm/s, 100mm/s, 120mm/s, or 140 mm/s); the film thickness obtained by the coating film is 30 to 300 μm (e.g., 40 μm, 45 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 150 μm, 200 μm, 300 μm or 400 μm).
Further, the specification of the paint film scraper is 100 to 500 μm (e.g., 150 μm, 200 μm, 300 μm or 400 μm).
Further, the film thickness of the hyperbranched fluorenyl photosensitive polyaryletherketone film is 40 to 100 μm (e.g., 40 μm, 45 μm, 50 μm, 60 μm, 70 μm, 80 μm, or 90 μm).
Further, the carrier may be a glass plate.
The invention firstly utilizes BB with unequal activity 2 ' monomer (2, 4', 6-trifluoro-benzophenone or 3,4', 5-trifluoro-benzophenone) with bulky A 2 Synthesizing hydroxyl end capped hyperbranched fluorene by using monomer (bisphenol fluorene) as reactantAnd then introducing allyl into the molecular chain end to synthesize the hyperbranched fluorenyl photosensitive polyaryletherketone resin precursor. And secondly, preparing a composition containing hyperbranched fluorenyl photosensitive polyaryletherketone resin precursor, namely the precursor, an acrylic acid ester reactive diluent, a mercaptan compound, a photoinitiator and a solvent into a ternary photocuring system, and preparing the polyaryletherketone resin film from the curing system. The polyaryletherketone resin film prepared by adopting the technical scheme of the invention has excellent dielectric property, heat resistance and mechanical property, and can promote the development and application of interlayer insulating dielectric manufacturing technology.
In the invention, the technical characteristics can be freely combined to form a new technical scheme under the condition of no conflict.
Compared with the prior art, the invention has the following beneficial effects:
(1) The full aromatic ring bisphenol fluorene with ultra-large volume, ultra-high rigidity and lower polarity can not only endow the main chain of the polymer with stronger rigidity, but also improve the heat resistance and mechanical property of the polymer; but also greatly increases the free volume inside the polymer and reduces the dielectric constant;
(2) The polyaryletherketone with the hyperbranched structure has a larger cavity structure, so that the dielectric constant of the resin can be reduced, and the thermal performance can be improved;
(3) Preparing a cured film by adopting a 'mercaptan-alkene-acrylate' ternary photocuring system, and realizing a mixed growth mechanism of free radical step-growth polymerization and free radical chain-growth polymerization, so as to quickly polymerize to form a three-dimensional network structure; the step-growth polymerization of the 'mercaptan-alkene' free radical can obviously reduce volume shrinkage and stress and overcome oxygen inhibition; the acrylate free radical chain growth polymerization can obviously improve the crosslinking density of the system, so that the mechanical property and the thermal property of the cured film are improved.
(4) The ultraviolet curing technology can shorten the curing time to a few minutes or even a few seconds, greatly increases the production efficiency and is beneficial to reducing the production cost.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of a hyperbranched fluorenyl photosensitive polyaryletherketone precursor 1 prepared in preparation example 1 of the invention;
FIG. 2 is a quantitative nuclear magnetic resonance spectrum of hyperbranched fluorenyl photosensitive polyaryletherketone precursor 1-3 prepared in preparation example 1-3;
FIG. 3 is an infrared spectrum of the hyperbranched fluorenyl photosensitive polyaryletherketone film prepared in examples 6-9 of the present invention;
FIG. 4 is a drawing showing the stretching-displacement of the hyperbranched fluorenyl photosensitive polyaryletherketone film prepared in example 7 of the present invention;
FIG. 5 is a graph of dynamic thermo-mechanical analysis of the hyperbranched fluorenyl photosensitive polyaryletherketone film prepared in example 10 of the present invention;
FIG. 6 is a graph showing the thermal decomposition performance of the hyperbranched fluorenyl photosensitive polyaryletherketone film prepared in examples 6, 10 and 11 of the present invention;
FIG. 7 is a graph showing the dielectric properties of the hyperbranched fluorenyl photosensitive polyaryletherketone films prepared in examples 6, 10 and 11 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The process parameters for the specific conditions not noted in the examples below are generally as usual.
The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be obtained in combination with each other between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point values, and are to be considered as specifically disclosed in the present invention.
Quantitative nuclear magnetic test method: the double bond value of the hyperbranched fluorenyl photosensitive polyaryletherketone precursor (the amount of the double bond contained in 100g of resin is the double bond value) is accurately tested by taking dimethyl terephthalate as an internal standard substance on a BrookVaian DLG400 spectrometer.
Dynamic mechanical thermal analysis (DMA) test conditions: the temperature rise rate was 5℃per minute at a frequency of 1Hz in a TA Q800 instrument.
Tensile property test conditions: the test piece was carried out on an AnInstron-5869 machine with a load of 500N, a strain rate of 2mm/min, an effective tensile length of 20mm and a width of 6mm.
Thermal weight loss (TGA) test conditions: the reaction was performed in a Metreler TGA apparatus with a nitrogen flow rate of 50mL/min and a heating rate of 20 ℃/min.
Dielectric property test conditions: the test is performed in an Aglient E4980A impedance analyzer, the test temperature is room temperature, and the test frequency is 1 MHz-1 GHz.
The method for preparing the hyperbranched fluorenyl photosensitive polyaryletherketone precursor according to the present invention will be explained.
Preparation example 1
2,4', 6-trifluoro-benzophenone (1.18 g,5 mmol), bisphenol fluorene (3.68 g,10.5 mmol), potassium carbonate (1.74 g,12.6 mmol), N-methylpyrrolidone (32 mL), toluene (20 mL) were added to N 2 In the atmosphere-protected three-neck flask, the temperature of the system is raised to 120 ℃ and the reaction is carried out by heating and refluxing for 4 hours, then the temperature is raised to 135 ℃, toluene and water generated by the reaction are distilled off, and then the temperature is raised to 180 ℃ for reaction for 8 hours. Subsequently, the temperature of the reaction system was lowered to room temperature, 3-bromo-1-propene (2.54 g,21 mmol) was added thereto and the capping reaction was carried out by gradually increasing the temperature, the specific operation of gradually increasing the temperature being as follows: the temperature of the reaction system is raised to 50 ℃ to react for 2 hours, then raised to 60 ℃ to react for 2 hours, then raised to 70 ℃ to react for 2 hours, and then raised to 90 ℃ to react for 4 hours.
Settling the end-capped reaction product in deionized water, washing, boiling with water, filtering, dissolving with chloroform, settling with ethanol, suction filtering, and drying the obtained product in a vacuum oven at 120deg.C to obtain hyperbranched fluorenyl photosensitive polyaryletherketone precursor 1 with number average molecular weight (Ma) and purity (P) a ) Double bond value (DB va)lue) is listed in table 1.
Fig. 1 shows a nuclear magnetic hydrogen spectrum of the hyperbranched fluorenyl photosensitive polyaryletherketone precursor 1 prepared in the present embodiment. The proton signal at 7.7ppm was attributed to the proton H8 of 2,4', 6-trifluorobenzophenone. Meanwhile, the multiple peaks with chemical shifts of 6.4-8.0ppm are hydrogen belonging to benzene ring. More importantly, proton signals for typical photoactive group allylic structures occur near 6.0ppm (H13), 5.4 and 5.2ppm (H12), 4.4ppm (H11). All hydrogen can be effectively attributed, indicating that the product structure is consistent with the design.
FIG. 2 shows a quantitative nuclear magnetic resonance spectrum of the precursor obtained in preparation example 1. The underlying principle of quantitative nuclear magnetic analysis is achieved by comparing the intensities of the different absorption peaks, the integral of which is proportional to the molar concentration of a determined proton when the quantitative analysis is performed. P is as described in formula (I) a The purity of the hyperbranched fluorenyl photosensitive polyaryletherketone precursor 1 is 0.99; i a An integrated value at 6.0ppm (H13) of 1; n (N) a Representing the number of protons of the signal to be calculated; m is M a Represents the molar mass (number average molecular weight) of the hyperbranched fluorenyl photosensitive polyaryletherketone precursor 1, which is 8400g/mol; w (W) a The weight of the hyperbranched fluorenyl photosensitive polyaryletherketone precursor 1 is 15.5mg. P (P) s The purity of the dimethyl terephthalate standard is 0.999; i s Represents an integral value of 24.4, N of dimethyl terephthalate at 8.1ppm s The number of protons at 8.1ppm of dimethyl terephthalate is 4; m is M s Represents a molar mass of dimethyl terephthalate of 194.18g/mol, W s The weight of dimethyl terephthalate was 15.7mg. The double bond value of the hyperbranched fluorenyl photosensitive polyaryletherketone precursor 1 can be 100 x N a /M a Calculated.
TABLE 1 preparation examples 1-3 number average molecular weight and double bond values of hyperbranched fluorenyl photosensitive polyaryletherketone precursor
Preparation example 2
2,4', 6-trifluorobenzophenone (1.18 g,5 mmol), bisphenol fluorene (3.49 g,10 mmol), potassium carbonate (1.65 g,11.9 mmol), N-methylpyrrolidone (31 mL), toluene (20 mL) were added to N 2 In the atmosphere-protected three-neck flask, the temperature of the system is raised to 120 ℃ and the reaction is carried out by heating and refluxing for 4 hours, then the temperature is raised to 135 ℃, toluene and water generated by the reaction are distilled off, and then the temperature is raised to 180 ℃ for reaction for 8 hours. Subsequently cooled to room temperature, 3-bromo-1-propene (2.54 g,21 mmol) was added thereto and the capping reaction was carried out by gradually increasing the temperature, as follows: the temperature of the reaction system is raised to 50 ℃ to react for 2 hours, then raised to 60 ℃ to react for 2 hours, then raised to 70 ℃ to react for 2 hours, and then raised to 90 ℃ to react for 4 hours.
Settling the end-capped reaction product in deionized water, washing, boiling in water, filtering, dissolving in chloroform, filtering with ethanol, and vacuum oven drying at 120deg.C to obtain hyperbranched fluorenyl photosensitive polyaryletherketone precursor 2 with number average molecular weight (Ma) and purity (P) a ) And double bond values (DB value) are listed in Table 1. FIG. 2 shows a quantitative nuclear magnetic hydrogen spectrum of the precursor obtained in preparation example 2.
Preparation example 3
3,4', 5-trifluoro-benzophenone (1.18 g,5 mmol), bisphenol fluorene (5.26 g,15 mmol), potassium carbonate (2.48 g,17.9 mmol), N-methylpyrrolidone (43 mL), toluene (20 mL) were added to N 2 In the three-neck flask in atmosphere, the temperature of the system is raised to 120 ℃ and the reflux reaction is heated for 4 hours, then the temperature is raised to 135 ℃, toluene and water generated by the reaction are distilled off, the temperature is raised to 180 ℃, and the reaction is carried out for 8 hours. Then cooling to room temperature, adding 3-bromo-1-propylene (3.75 g,31 mmol), and gradually raising the temperature of the reaction system to perform end-capping reaction, wherein the specific operation is as follows: the temperature of the reaction system was raised to 50℃for 2 hours, followed by raising to 60℃for 2 hours, then raising to 70℃for 2 hours, and then raising to 90℃for 4 hours.
The end-capped reaction product is settled to removeWashing in ionized water, decocting in water, filtering, dissolving in chloroform, precipitating with ethanol, suction filtering, and vacuum oven drying at 120deg.C to obtain hyperbranched fluorenyl photosensitive polyaryletherketone precursor 3 with number average molecular weight (Ma) and purity (P a ) And double bond values (DB value) are listed in Table 1. FIG. 2 shows a quantitative nuclear magnetic resonance spectrum of the precursor obtained in preparation example 3.
The following examples 1 to 13 illustrate the composition containing the hyperbranched fluorenyl photosensitive polyaryletherketone precursor and the hyperbranched fluorenyl photosensitive polyaryletherketone film according to the present invention, using the hyperbranched fluorenyl photosensitive polyaryletherketone precursor prepared in the above preparation example as a reaction raw material.
TABLE 2 raw materials in examples 1-13
Example 1
A hyperbranched fluorenyl photosensitive polyaryletherketone film is prepared by the following steps.
(1) Dissolving hyperbranched fluorenyl photosensitive polyaryletherketone precursor 1 (prepared in example 1), trimethylolpropane triacrylate (reactive diluent), ethylene glycol bis (3-mercaptopropionate) (thiol compound) and Irgacure 184 (photoinitiator: 1-hydroxycyclohexyl phenyl ketone) in cyclohexanone solvent, and stirring at room temperature in a dark place until the dissolution is complete to obtain hyperbranched fluorenyl photosensitive polyaryletherketone precursor composition; wherein the mass ratio of the hyperbranched fluorenyl photosensitive polyaryletherketone precursor 1 to the trimethylolpropane triacrylate is 50:50, the ethylene glycol bis (3-mercaptopropionate) mercapto group and double bond (i.e. the sum of allyl groups in the hyperbranched fluorenyl photosensitive polyaryletherketone precursor and acrylate groups in the reactive diluent) are added according to the molar ratio of 1:1, irgacure 184 is 4% of the total mass of the composition except the solvent, the concentration of the hyperbranched fluorenyl photosensitive polyaryletherketone precursor in the composition is 0.8g/mL, and the specific addition amounts are listed in Table 2.
(2) Slowly and continuously pouring the hyperbranched fluorenyl photosensitive polyaryletherketone precursor composition obtained in the step (1) into glassScraping film on the glass plate with a 250 μm film scraper at a speed of 60mm/s, and then placing into an ultraviolet curing box for curing at room temperature for 60s with an ultraviolet energy density of 35mw/cm 2 。
The cured film was placed in a vacuum oven and the temperature was gradually increased to 155 ℃ to remove cyclohexanone.
Immersing the glass plate with the film in water, and removing the film from the glass plate to obtain the transparent hyperbranched fluorenyl photosensitive polyaryletherketone film with the thickness of 40-45 microns.
Examples 2 to 5
Examples 2-5 differ from example 1 in that the mass ratio of hyperbranched fluorenyl photosensitive polyaryletherketone precursor 1 to trimethylolpropane triacrylate is 60:40, 70:30, 80:20, 90:10. The remainder was the same as in example 1, and the specific amounts of the feeds are shown in Table 2.
The film thickness prepared in example 2 is 45-50 microns; the film thickness prepared in example 3 is 50-60 microns; the film thickness prepared in example 4 was 60 to 70 microns; the film thickness prepared in example 5 was 65 to 75 microns.
Examples 6 to 9
Examples 6-9 differ from example 3 in that the molar ratio of thiol functional groups in the thiol compound to the sum of allyl groups in the hyperbranched fluorenyl photosensitive polyaryletherketone precursor and acrylate groups in the reactive diluent is 0.8:1, 0.6:1, 0.4:1, 0.2:1, respectively. The remainder was the same as in example 3, and the specific amounts of the feeds are shown in Table 2.
The film thickness prepared in example 6 is 60-65 microns; the film thickness prepared in example 7 was 63-68 microns; the film thickness prepared in example 8 is 70-75 microns; the film thickness prepared in example 9 was 80 to 90 microns.
Example 10
Example 10 differs from example 6 in that the hyperbranched fluorenyl photosensitive polyaryletherketone precursor prepared in preparation example 2 was used, the remainder being the same as in example 6, and the specific amounts of the feeds are listed in table 2.
The film thickness prepared in example 10 was 70-80 microns.
Example 11
Example 11 differs from example 6 in that the hyperbranched fluorenyl photosensitive polyaryletherketone precursor prepared in preparation example 3 was used, the remainder being the same as in example 6, and the specific amounts of the feeds are listed in table 2.
The film thickness prepared in example 11 was 50 to 60 microns.
Example 12
A hyperbranched fluorenyl photosensitive polyaryletherketone film is prepared by the following steps.
(1) Dissolving hyperbranched fluorenyl photosensitive polyaryletherketone precursor 2 (prepared by preparation 2), tricyclo [5.2.1.02,6] decane dimethanol diacrylate (active diluent), 3, 6-dioxa-1, 8-octanedithiol (thiol compound) and Irgacure 1173 (photoinitiator: 2-hydroxy-2-methyl-1-phenylpropionyl) in chloroform, and stirring at room temperature in a dark place until the components are dissolved to obtain hyperbranched fluorenyl photosensitive polyaryletherketone precursor composition 2; wherein the mass ratio of the hyperbranched fluorenyl photosensitive polyaryletherketone precursor 2 to the tricyclo [5.2.1.02,6] decanedimethanol diacrylate is 70:30, the mercapto group and the double bond (the sum of the allyl groups in the hyperbranched fluorenyl photosensitive polyaryletherketone precursor and the acrylate groups in the reactive diluent) of the 3, 6-dioxa-1, 8-octanedithiol are added according to the molar ratio of 0.6:1, irgacure 1173 is 4% of the total mass except the solvent in the composition, the concentration of the hyperbranched fluorenyl photosensitive polyaryletherketone precursor in the composition is 1g/mL, and the specific feeding amount is listed in table 2.
(2) Slowly and continuously pouring the hyperbranched fluorenyl photosensitive polyaryletherketone precursor composition obtained in the step (1) on a glass plate, scraping a film at a speed of 60mm/s by using a 250 mu m film scraper, and then placing the film in an ultraviolet curing box for curing for 40s with an ultraviolet energy density of 35mw/cm 2 。
The cured film was placed in a vacuum oven and gradually warmed to 61 ℃ to remove chloroform.
Immersing the glass plate with the film in water, and enabling the film to fall off from the glass plate, thus obtaining the transparent hyperbranched fluorenyl photosensitive polyaryletherketone film with the thickness of 55-65 microns.
Example 13
A hyperbranched fluorenyl photosensitive polyaryletherketone film is prepared by the following steps.
(1) Dissolving hyperbranched fluorenyl photosensitive polyaryletherketone precursor 3 (prepared in example 3), 1, 6-hexanediol diacrylate, pentaerythritol tetrasulfuryl acetate and benzophenone (photoinitiator) in cyclohexanone, and stirring for 6 hours at room temperature in a dark place to obtain hyperbranched fluorenyl photosensitive polyaryletherketone precursor composition 3; wherein the mass ratio of the hyperbranched fluorenyl photosensitive polyaryletherketone precursor 3 to the 1, 6-hexanediol diacrylate is 60:40, the mercapto group and the double bond (the sum of the allyl group in the hyperbranched fluorenyl photosensitive polyaryletherketone precursor and the acrylate group in the reactive diluent) of pentaerythritol tetramercapto acetate are added according to the molar ratio of 0.8:1, the benzophenone accounts for 1% of the total mass of the composition except the solvent, the concentration of the hyperbranched fluorenyl photosensitive polyaryletherketone precursor in the composition is 1.2g/mL, and the specific feeding amount is listed in table 2.
(2) Slowly and continuously pouring the hyperbranched fluorenyl photosensitive polyaryletherketone precursor composition obtained in the step (1) on a glass plate, scraping a film at a speed of 60mm/s by using a 250 mu m film scraper, and then placing the film in an ultraviolet curing box for curing for 60s with an ultraviolet energy density of 35mw/cm 2 。
The cured film was placed in a vacuum oven and the temperature was gradually increased to 155 ℃ to remove cyclohexanone.
Immersing the glass plate with the film in water, and enabling the film to fall off from the glass plate to obtain the transparent hyperbranched fluorenyl photosensitive polyaryletherketone film, wherein the thickness of the film is 50-60 microns.
Performance of hyperbranched fluorenyl photosensitive polyaryletherketone film
The performance test of the hyperbranched fluorenyl photosensitive polyaryletherketone films prepared in examples 1 to 13 is shown in table 3.
TABLE 3 Properties of hyperbranched fluorenyl photosensitive polyaryletherketone films prepared in examples 1-13
FIG. 3 is an infrared spectrum of the hyperbranched fluorenyl photosensitive polyaryletherketone film prepared in examples 6 to 9 of the present invention. It can be seen that C=C in the cured photosensitive resin is 1632cm -1 、1408cm -1 And 810cm -1 The bending vibration peak of (C) disappeared while SH was at 2570cm -1 The characteristic peak of (2) also disappears. This illustrates the gradual polymerization of thiol-ene by the combination of uv light and photoinitiator of the thiol compound and precursor in the system. At the same time, reactive diluent c=c also participates in the photocuring reaction and connects to form a crosslinked network.
FIG. 4 is a drawing showing the stretching-displacement of the hyperbranched fluorenyl photosensitive polyaryletherketone film prepared in example 7 of the present invention. As can be seen from the figure, the tensile test procedure is good.
FIG. 5 is a graph of dynamic thermo-mechanical analysis of the hyperbranched fluorenyl photosensitive polyaryletherketone film prepared in example 10 of the present invention. It can be seen from the figure that the glass transition temperature of the film can reach 248 ℃ and the film has excellent heat resistance.
Claims (12)
1. The hyperbranched fluorenyl photosensitive polyaryletherketone precursor is characterized by having a structure shown in a formula I and/or a formula II:
2. a method for preparing the hyperbranched fluorenyl photosensitive polyaryletherketone precursor according to claim 1, wherein the preparation method comprises the following steps:
BB is carried out 2 ' monomer, A 2 Adding a monomer, a salifying agent, a first organic solvent and a water-carrying agent into a reaction container protected by inert gas atmosphere, heating and refluxing at 120-130 ℃ for reaction for 1-4 h, and then continuously heating and distilling out water and toluene generated by the reaction at 130-140 ℃; then the temperature of the reaction system is increased to 180-200 ℃ for reaction for 8-12 h, and the polymerization reaction is finished; subsequentlyCooling the reaction system to room temperature, adding a capping reagent for capping reaction, and finally obtaining an allyl capped hyperbranched fluorenyl photosensitive polyaryletherketone precursor through aftertreatment, wherein the BB 2 The ' monomer comprises one of 2,4', 6-trifluoro-benzophenone and 3,4', 5-trifluoro-benzophenone, the A 2 The type monomer comprises bisphenol fluorene.
3. The method for preparing hyperbranched fluorenyl photosensitive polyaryletherketone precursor according to claim 2, wherein a is 2 Monomers and BB 2 The monomer is fed according to the mole ratio of the functional group OH to F (OH: F) of 1.33-2.1:1;
and/or the salt forming agent is one or more than two of potassium carbonate, cesium carbonate, potassium hydroxide, sodium hydroxide, potassium hydride and sodium hydride; the molar dosage of the metal cations in the salifying agent is A 2 1 to 1.2 times of the molar amount of OH functional groups in the monomers;
and/or, the first organic solvent is a polar organic solvent;
and/or the water carrying agent is one or more than two of benzene, toluene, dimethylbenzene and chlorobenzene;
and/or the volume dosage of the water-carrying agent is 0.4-1 times of the volume of the first organic solvent;
and/or the end-capping agent is 3-halogeno-1-propylene, and the end-capping agent is a 2 The molar ratio of OH functional groups in the monomer is 1-1.2:1.
4. The method for preparing a hyperbranched fluorenyl photosensitive polyaryletherketone precursor according to claim 3, wherein the first organic solvent comprises one or more of N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide, and dimethylsulfoxide;
and/or the end-capping agent comprises at least one of 3-bromo-1-propene, 3-chloro-1-propene and 3-iodo-1-propene.
5. The method for preparing hyperbranched fluorenyl photosensitive polyaryletherketone precursor according to any one of claims 2 to 4, wherein the end-capping reaction is performed in a gradual temperature rise manner, and the gradual temperature rise manner is as follows: reacting for 2-4 hours at 48-52 ℃, 2-4 hours at 58-62 ℃, 2-4 hours at 68-72 ℃, and 4-8 hours at 88-92 ℃;
and/or, the post-processing comprises the following steps:
and (3) settling the reaction product obtained after the end-capping reaction in deionized water, washing and boiling the sediment in water, dissolving in chloroform, settling in ethanol, carrying out suction filtration, and drying the obtained product to obtain the allyl end-capped hyperbranched fluorenyl photosensitive polyaryletherketone precursor.
6. A composition comprising a hyperbranched fluorenyl photosensitive polyaryletherketone precursor, characterized in that the composition comprises the hyperbranched fluorenyl photosensitive polyaryletherketone precursor according to claim 1, a reactive diluent, a thiol compound, a photoinitiator, and a second organic solvent; wherein,
the mass ratio of the hyperbranched fluorenyl photosensitive polyaryletherketone precursor to the reactive diluent is 50:50-90:10, and the sum of the mass percentages of the hyperbranched fluorenyl photosensitive polyaryletherketone precursor and the reactive diluent is 100%.
7. The composition comprising a hyperbranched fluorenyl photosensitive polyaryletherketone precursor according to claim 6, wherein the concentration of the hyperbranched fluorenyl photosensitive polyaryletherketone precursor in the composition is 0.3 to 1.5g/ml;
and/or, the reactive diluent is an acrylic acid ester reactive diluent;
and/or the thiol compound is one or more than two of 3, 6-dioxa-1, 8-octanedithiol, ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate) and pentaerythritol tetramercaptoacetate;
and/or the photoinitiator is one or more than two of 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthiophenyl) -2-morpholinyl-1-acetone ], 2-hydroxy-2-methyl-1-phenyl acetone, 2-phenylbenzyl-2-dimethyl amine-1- (4-morpholinyl) butanone, 2-dimethoxy-2-phenylacetophenone, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, benzophenone, 2,4, 6-trimethylbenzophenone, 4-methylbenzophenone and the like;
and/or the second organic solvent is one or more than two of acetone, cyclohexanone, butanone, propylene glycol methyl ether acetate, N-methylpyrrolidone, chloroform and tetrahydrofuran;
and/or the molar ratio of the mercapto functional group in the thiol compound to the sum of the allyl group in the hyperbranched fluorenyl photosensitive polyaryletherketone precursor and the acrylate group in the reactive diluent is 0.2:1-1:1;
and/or the photoinitiator is used in an amount of 1 to 5% by weight of the total mass of the composition excluding the second organic solvent.
8. The composition of claim 6, wherein the reactive diluent comprises one or more of tripropylene glycol diacrylate, polyethylene glycol (200) diacrylate, 1, 6-hexanediol diacrylate, tricyclo [5.2.1.02,6] sebacic acid diacrylate, 1, 10-bis (acryloyloxy) decane, trimethylolpropane triacrylate and pentaerythritol tetraacrylate.
9. A method of preparing a composition comprising a hyperbranched fluorenyl photosensitive polyaryletherketone precursor according to claim 6 or 7, wherein the preparation method employs the following steps:
dissolving a hyperbranched fluorenyl photosensitive polyaryletherketone precursor, a reactive diluent, a mercaptan compound and a photoinitiator in a second organic solvent, and fully and uniformly stirring the mixture at room temperature in a dark place to obtain a photosensitive hyperbranched polyaryletherketone precursor composition; wherein the concentration of the hyperbranched fluorenyl photosensitive polyaryletherketone precursor in the composition is 0.3-1.5 g/ml.
10. A hyperbranched fluorenyl photosensitive polyaryletherketone film, characterized in that the film is prepared from the composition comprising the hyperbranched fluorenyl photosensitive polyaryletherketone precursor according to claim 6 or 7.
11. A method for preparing the hyperbranched fluorenyl photosensitive polyaryletherketone film according to claim 10, wherein the preparation method sequentially comprises the following steps:
scraping a film: pouring a composition comprising a hyperbranched fluorenyl photosensitive polyaryletherketone precursor according to claim 6 or 7 onto a clean support, and coating with a coating wiper;
curing: placing the coated carrier into an ultraviolet curing box, and performing photo-curing at room temperature so as to form a film on the carrier;
removing the solvent: vacuum heating the film attached to the carrier to remove the second organic solvent in the film;
removing the film: immersing the carrier with the film after vacuum heating in water to enable the film to fall off, wherein the film after falling off is the hyperbranched fluorenyl photosensitive polyaryletherketone film.
12. The method for preparing the hyperbranched fluorenyl photosensitive polyaryletherketone film according to claim 11, wherein the photo-curing time is 20-100 s, and the ultraviolet energy density is 20mw/cm 2 ～100mw/cm 2 ；
And/or, said vacuum heating removes said second organic solvent by gradually increasing the temperature to the boiling point of the solvent;
and/or coating film with a coating film scraper at a speed of 50 to 150mm/s, the obtained film thickness being 30 to 300 μm.
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