CN107814694A - Fluorenes class initiator, its preparation method, the Photocurable composition with it and its application in curing field - Google Patents
Fluorenes class initiator, its preparation method, the Photocurable composition with it and its application in curing field Download PDFInfo
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- CN107814694A CN107814694A CN201610821992.3A CN201610821992A CN107814694A CN 107814694 A CN107814694 A CN 107814694A CN 201610821992 A CN201610821992 A CN 201610821992A CN 107814694 A CN107814694 A CN 107814694A
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- fluorenes class
- class initiator
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- 239000003999 initiator Substances 0.000 title claims abstract description 50
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 150000002220 fluorenes Chemical class 0.000 title 1
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000003118 aryl group Chemical group 0.000 claims abstract description 15
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 13
- 150000002367 halogens Chemical class 0.000 claims abstract description 13
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 238000006467 substitution reaction Methods 0.000 claims abstract description 8
- 125000001424 substituent group Chemical group 0.000 claims abstract description 7
- -1 aminomethyl phenyl Chemical group 0.000 claims description 24
- 150000002148 esters Chemical group 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 21
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 claims description 6
- KJRRQXYWFQKJIP-UHFFFAOYSA-N 3-methylfuran Chemical compound CC=1C=COC=1 KJRRQXYWFQKJIP-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229920002120 photoresistant polymer Polymers 0.000 claims description 5
- 125000002541 furyl group Chemical group 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 claims description 3
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical class CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 claims description 3
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Chemical group 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 125000004799 bromophenyl group Chemical group 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 125000004802 cyanophenyl group Chemical group 0.000 claims description 3
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000007363 ring formation reaction Methods 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 3
- 125000006850 spacer group Chemical group 0.000 claims description 3
- 125000001544 thienyl group Chemical group 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- UJHSIDUUJPTLDY-UHFFFAOYSA-N (2-nitrophenyl)-phenylmethanone Chemical compound [O-][N+](=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 UJHSIDUUJPTLDY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims description 2
- 150000002240 furans Chemical class 0.000 claims description 2
- 239000000976 ink Substances 0.000 claims description 2
- ZJTLZYDQJHKRMQ-UHFFFAOYSA-N menadiol Chemical compound C1=CC=CC2=C(O)C(C)=CC(O)=C21 ZJTLZYDQJHKRMQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 230000005764 inhibitory process Effects 0.000 abstract description 5
- 125000004185 ester group Chemical group 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 66
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000000977 initiatory effect Effects 0.000 description 10
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 8
- 239000012965 benzophenone Substances 0.000 description 8
- 238000013508 migration Methods 0.000 description 7
- 230000005012 migration Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 235000011167 hydrochloric acid Nutrition 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000004383 yellowing Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- FAQJJMHZNSSFSM-UHFFFAOYSA-N phenylglyoxylic acid Chemical group OC(=O)C(=O)C1=CC=CC=C1 FAQJJMHZNSSFSM-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- PHDIJLFSKNMCMI-ITGJKDDRSA-N (3R,4S,5R,6R)-6-(hydroxymethyl)-4-(8-quinolin-6-yloxyoctoxy)oxane-2,3,5-triol Chemical compound OC[C@@H]1[C@H]([C@@H]([C@H](C(O1)O)O)OCCCCCCCCOC=1C=C2C=CC=NC2=CC=1)O PHDIJLFSKNMCMI-ITGJKDDRSA-N 0.000 description 1
- 0 *C1C=CC=CC1C1C=CC(C([Al])=O)=CC1* Chemical compound *C1C=CC=CC1C1C=CC(C([Al])=O)=CC1* 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- BYQYKYGNQQPJOH-UHFFFAOYSA-N CC(C(OC)=N)O Chemical compound CC(C(OC)=N)O BYQYKYGNQQPJOH-UHFFFAOYSA-N 0.000 description 1
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000006501 nitrophenyl group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
- C07C49/792—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic containing rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/22—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/738—Esters of keto-carboxylic acids or aldehydo-carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention provides a kind of fluorenes class initiator, its preparation method, Photocurable composition and its application in curing field.The fluorenes class initiator has the group as shown in formula (I)：Wherein, R1、R2Separately any one in hydrogen atom, halogen and chain base group；Ar is the substituent containing aromatic rings or miscellaneous aromatic rings；And the R being connected with the connecting key of the group shown in formula (I)3, R3For hydrogen atom, C (=O) R3' or C (=O) C (=O) O R3' group, wherein, R3' represent substitution or unsubstituted C1‑C40Straight or branched alkyl, C1‑C20Cycloalkyl, C1‑C40Alkenyl, the substituent containing aromatic rings or miscellaneous aromatic rings, or R3For the latter when, R3 ' groups are alcohol or polyalcohol by ester exchange reaction the group that connects.The initiator color inhibition, it is not easy to migrate, odor profiles it is low, dissolubility is good.
Description
Technical field
The present invention relates to organic photochemistry field, in particular to a kind of fluorenes class initiator, its preparation method, has
Its Photocurable composition and its application in curing field.
Background technology
Benzophenone and benzoyl formic acid ester lightlike initiating agent are common radical photoinitiators, due to structure
Simply, synthesis easily, price it is relatively low, the light trigger of right and wrong usually, but often exist in use migration,
The problems such as odor profiles, xanthochromia, dissolubility, largely limit its application.People try by being modified to its structure,
If Publication No. CN1789245A, CN103497263A, CN104987435A Chinese patent (or application) are to benzophenone
The macromolecular that photoinitiator is carried out, avoid to a certain extent small molecule migration and it is odor profiles the problem of, but its resistance to Huang
Denaturing problem is not still solved effectively.Such as the Chinese patent of Publication No. CN103709036A, CN102442909A
Application introduces polyalcohol to benzoyl formic acid ester lightlike initiating agent, solves its solubility problem to a certain extent, but absorb
Wavelength does not have the raising of high-lighting.On the other hand, these modifications in existing research, its efficiency of initiation need further to be improved,
And its photo absorption performance under long wavelength remains to be further improved.
On the other hand, growing to even greater heights with environmentally friendly cry, UV-LED light sources solidification substitution mercury lamp light source is photocuring row
The development trend of industry, the initiation effect of above-mentioned conventional benzophenone and benzoyl formic acid ester lightlike initiating agent under mercury lamp is still
Can, but the initiation effect under UV-LED light sources is had a greatly reduced quality, therefore the initiator that can be applied to UV-LED light sources needs
It is developed.
The content of the invention
It is a primary object of the present invention to provide a kind of fluorenes class initiator, its preparation method, have its photocurable composition
Thing and its application in curing field, to solve the problems, such as that light trigger has easy to migrate, easy xanthochromia in the prior art.
To achieve these goals, according to an aspect of the invention, there is provided a kind of fluorenes class initiator, the fluorenes class trigger
Agent has the group as shown in formula (I)：Wherein, R1、R2Separately it is selected from hydrogen
Any one in atom, halogen and chain base group, chain base group is C1-C20Straight chained alkyl, C1-C20Branched alkyl or
C1-C20Cycloalkyl, C4-C20Cycloalkyl-alkyl, C4-C20Alkyl-cycloalkyl and C2-C20Alkenyl, or R1And R2With
Any one in chain base group or two kinds of cyclization, the and-CH in chain base group2- optionally by-O- ,-C (=O) O-, halogen
Element, phenyl are substituted；Ar is the substituent containing aromatic rings or miscellaneous aromatic rings；And the connecting key with the group shown in formula (I)
Connected R3, R3For hydrogen atom ,-C (=O) R3' or-C (=O) C (=O) O-R3' group, wherein, R3' represent substitution or do not taken
The C in generation1-C40Straight chain, C1-C40Branched alkyl, C1-C20Cycloalkyl, C1-C40Alkenyl, contain aromatic rings or heteroaryl
The substituent of fragrant ring, or R3For-C (=O) C (=O) O-R3', group, R3 ' groups are that alcohol or polyalcohol pass through ester exchange reaction
And the group connected.
Further, above-mentioned chain base group is C1-C10Straight chained alkyl, C1-C10Branched alkyl or C4-C10Cycloalkyl
Alkyl.
Further, above-mentioned Ar is phenyl, aminomethyl phenyl, ethylphenyl, chlorphenyl, bromophenyl, methoxyphenyl, nitro
Phenyl, cyano-phenyl, diphenyl sulfide ether, pyridine radicals, thienyl, furyl, 2- methyl-thiophenes base, 3 methyl thiophene base, furans
Base, 2- methyl-furyls or 3- methylfuran bases.
Further, above-mentioned R3For-C (=O) C (=O) O-R3' group, fluorenes class initiator is with as shown in following formula (II)
Structure：Wherein, R4Externally connect with n
Key is connect, and is C1-C60Straight chained alkyl or branched alkyl, or C1-C60Straight chained alkyl or branched alkyl in arbitrary carbon or hydrogen
Substituted by oxygen, sulphur or phenyl；A represents there is-(Q-CHR5)mThe repeat unit of-structure, R5For hydrogen, methyl or ethyl, Q is represented
O or connector, wherein, connector expression-(CHR5)mIt is joined directly together with O, m is 1~6 integer；N represents 1~20 integer.
Further, above-mentioned R4Any one in following groups： *CH2-CH2*、*CH2-CH2CH2*、*CH2CH2CH2CH2*、
Further, above-mentioned A is selected from-[(Q-CHR5)m]y-, wherein R5For hydrogen or methyl, m is 1~3 integer, and y represents 1
~9 integer.
Further, above-mentioned n is 1~8 integer, preferably 1,2,3,4,5 or 6.
According to the another aspect of the application, there is provided the preparation method of a kind of any of the above-described kind of fluorenes class initiator, this is standby
Method includes：Step S1, the raw material a and raw material b with structural formula B with structural formula A occur Friedel-Crafts reaction, obtain having knot
Structure formula C intermediate c；With the raw material d with structural formula D Friedel-Crafts reaction occurs for optional step S2, intermediate c, is had
Structural formula E intermediate e；And with the alcohol with structural formula F or polyalcohol ester exchange occurs for optional step S3, intermediate e
Reaction, obtains fluorenes class initiator, wherein, structural formula A isStructural formula B isWherein X1For halogen,
Structural formula C isStructural formula D isWherein X2For halogen, structural formula E isStructural formula F is R4(AOH)n。
Further, above-mentioned steps S1 and step S2 Friedel-Crafts reaction enter in the presence of alchlor or zinc chloride and solvent
OK, the reaction temperature of preferred steps S1 and step S2 Friedel-Crafts reaction is each independently -10~40 DEG C.
Further, ester exchange reaction, preferred catalyst occur in the presence of catalyst and polymerization inhibitor for above-mentioned steps S3
For one or more titanium acid compounds, it is different to be selected from metatitanic acid -2- ethylhexyls, tetramethoxy titanate ester, metatitanic acid four for more preferably catalyst
One or more in the group that propyl ester, butyl titanate, tetrabutyl titanate, metatitanic acid four (2- ethyl hexyls) ester form, preferably hinder
Poly- agent is selected from MEHQ, N, N- diethyl hydroxylamines, hydroquinones, catechol, p-tert-Butylcatechol, methyl hydrogen
Quinone, p methoxy phenol, phenthazine and triphenylphosphine composition group in any one.
Further, in above-mentioned steps S3, intermediate e is n with the alcohol with structural formula F or the mol ratio of polyalcohol：1,
The weight of preferred catalyst is 3~the 10 ‰ of material gross weight, the weight of more preferably polymerization inhibitor be material gross weight 3~
10 ‰, the temperature of further preferred ester exchange reaction is 70~130 DEG C, the reaction time is 1~8h.
According to another aspect of the present invention, there is provided a kind of Photocurable composition, including light trigger, the light trigger are
Any of the above-described kind of fluorenes class initiator.
According to another aspect of the present invention, there is provided a kind of any of the above-described kind of fluorenes class initiator should curing field
With.
Further, above-mentioned application includes coating, ink, adhesive, chromatic photoresist, black matrix", light spacer, rib
Application in grid, dry film and/or semiconductor light photoresist.
Apply the technical scheme of the present invention, the structure based on fluorenes substitutes existing conventional benzophenone or benzoyl first
After the agent structure of acid esters so that the problems such as the efficiency of initiation of initiator and color inhibition, not easy to migrate, odor profiles low, dissolubility
It can preferably be improved and balanced, and by carrying out application study to its photosensitive composite, find to draw the fluorenes class
Hair agent is applied to the solidification that photocurable formulation conventional at present just can be good at being applied to UV-LED light sources.
Embodiment
It should be noted that in the case where not conflicting, the feature in embodiment and embodiment in the application can phase
Mutually combination.The present invention is described in detail below in conjunction with embodiment.
As background technology is analyzed, in the prior art there is the problem of easy to migrate, easy xanthochromia in light trigger, in order to solve
The problem, in the application one kind typically embodiments, provides a kind of fluorenes class initiator, the fluorenes class initiator is with such as formula
(I) group shown in：
(as is generally understood, structural formula
" --- " on middle right side phenyl ring represents to be connected with any position C of the phenyl ring, and * therein represents what can be connected with other groups
Connecting key),
Wherein, R1、R2Separately any one in hydrogen atom, halogen and chain base group, chain base group are
C1-C20Straight chained alkyl, C1-C20Branched alkyl or C1-C20Cycloalkyl, C4-C20Cycloalkyl-alkyl, C4-C20Alkyl
Cycloalkyl and C2-C20Alkenyl, or R1And R2With any one in chain base group or two kinds of cyclization, and in chain base group
- CH2- optionally substituted by-O- ,-C (=O) O-, halogen, phenyl；Ar is the substitution containing aromatic rings or miscellaneous aromatic rings
Base；And the R being connected with the connecting key of the group shown in formula (I)3, R3For hydrogen atom ,-C (=O) R3' or-C (=O) C (=O)
O-R3' group, wherein, R3' represent substitution or unsubstituted C1-C40Straight chain, C1-C40Branched alkyl, C1-C20Cycloalkanes
Base, C1-C40Alkenyl, (structure above can be expressed as the substituent containing aromatic rings or miscellaneous aromatic rings), or R3For-C (=O) C (=O) O-R3', group, R3 ' groups be alcohol or
Polyalcohol is by ester exchange reaction and the group that connects.
Present inventor passes through long-term experimental study, pleasantly surprised discovery：Structure substitution based on fluorenes is existing often
After the agent structure of benzophenone or benzoyl formiate so that the efficiency of initiation of initiator and color inhibition, it is not easy to migrate,
The problems such as odor profiles low, dissolubility, can preferably be improved and balanced, and by answering its photosensitive composite
With research, it is found that the fluorenes class initiator is applied into photocurable formulation conventional at present just can be good at being applied to UV-LED light
The solidification in source.
In order to which the fluorenes class initiator is more easily-synthesized, preferably above-mentioned chain base group is C1-C10Straight chained alkyl, C1-C10Branch
Alkyl group or C4-C10Cycloalkyl-alkyl.More preferably above-mentioned Ar be phenyl, aminomethyl phenyl, ethylphenyl, chlorphenyl, bromophenyl,
Methoxyphenyl, nitrobenzophenone, cyano-phenyl, diphenyl sulfide ether, pyridine radicals, thienyl, furyl, 2- methyl-thiophenes base, 3-
Methylthiophene base, furyl, 2- methyl-furyls or 3- methylfuran bases.
In a kind of preferred embodiment of the application, above-mentioned R3For-C (=O) C (=O) O-R3' group, fluorenes class initiator tool
Just like the structure shown in following formula (II)：
Wherein, R4With n external connection key, and it is C1-C60Straight chained alkyl or branched alkyl, or C1-C60Straight chain
Arbitrary carbon or hydrogen are substituted by oxygen, sulphur or phenyl in alkyl or branched alkyl；A represents there is-(Q-CHR5)mThe repetition of-structure
Unit, R5For hydrogen, methyl or ethyl, Q represents O or connector, wherein, connector expression-(CHR5)mIt is joined directly together with O, m 1
~6 integer；N represents 1~20 integer.
Fluorenes class initiator with said structure formula (II), it is bigger to be not only due to its molecular weight so that and its migration reduces,
And it also has the characteristics of solubility property is more excellent.
In addition, with the compound absorption bands shown in above-mentioned formula (I) and formula (II) between 330-400nm, almost without
Smell, there is good dissolubility in (methyl) acrylic resin and vinyl ethers compound, not easy to migrate after, resistance to Huang
Become.
In addition, as the R in structure formula (II)4During any one in following groups, its structure is more stable： *CH2-CH2*、*CH2-CH2-CH2*、*CH2CH2CH2CH2*、
Further, in order to reduce the cost of manufacture and manufacture difficulty of above-mentioned fluorenes class initiator, preferably above-mentioned A is selected from-
[(Q-CHR5)m]y-, wherein R5For hydrogen or methyl, m is 1~3 integer, and y represents 1~9 integer.More preferably above-mentioned n is 1~8
Integer, more preferably 1,2,3,4,5 or 6.
In another typical embodiment of the application, there is provided a kind of preparation side of any of the above-described kind of fluorenes class initiator
Method, the preparation method include：Friedel-Crafts reaction occurs for step S1, the raw material a and raw material b with structural formula B with structural formula A,
Obtain the intermediate c with structural formula C；Optional step S2, intermediate c and the raw material d generations Fu Ke with structural formula D are anti-
Should, obtain the intermediate e with structural formula E；And optional step S3, intermediate e and alcohol or polyalcohol with structural formula F
Generation ester exchange reaction, fluorenes class initiator is obtained, wherein, structural formula A isStructural formula B isWherein X1
For halogen, structural formula C isStructural formula D isWherein X2For halogen, structural formula E
ForStructural formula F is R4 (AOH) n.
Routinely understood according to those skilled in the art, the R in foregoing each structural formula1、R2、Ar、R3、R3' and R4And
Structure formula (I) is identical with group represented in structure formula (II).The chemical reaction process of above-mentioned preparation method is as follows：
The fluorenes class initiator of different the application is can obtain by said one step or two steps or three steps,
And the reaction that each step uses is ripe conventional reaction in the prior art, therefore, preparation process is easily achieved and controlled.Its
In, work as R4(AOH)nIn n when being integer more than 1, multiple intermediate Es and R4(AOH)nEster exchange reaction occurs simultaneously, and then
Obtain above-mentioned product.
Abovementioned steps S1 and step S2 Friedel-Crafts reaction condition may be referred to the conventional Friedel-Crafts reaction of prior art and implement, this
Application is directed to above-mentioned substrate, and preferably above-mentioned steps S1 and step S2 Friedel-Crafts reaction exists in alchlor or zinc chloride and solvent
The reaction temperature of lower progress, more preferably step S1 and step S2 Friedel-Crafts reaction is each independently -10~40 DEG C.Both of the aforesaid
Friedel-Crafts reaction condition in step can be the same or different, and solvent can be with identical or different, and wherein solvent can use
The conventional organic solvent of reaction, such as dichloromethane, dichloroethanes, toluene, benzene, dimethylbenzene are not involved in the prior art, when two
When individual step uses identical solvent, step S2 Friedel-Crafts reaction can be continued after the completion of step S1 without purification.
Weight after foregoing step S3 ester exchange reaction directly can be carried out or purified in the system that step S2 is completed
New be placed in solvent can be achieved, and there is no particular limitation for solvent of the application to step S3, as long as can dissolve each
Reaction reagent and reaction is had no adverse effects, such as toluene, benzene, dimethylbenzene.
In order to accelerate to react, and the generation that target product reduces accessory substance, preferably above-mentioned steps S3 are obtained as much as possible
Ester exchange reaction occurs in the presence of catalyst and polymerization inhibitor, preferred catalyst is one or more titanium acid compounds, more
Preferred catalyst is selected from metatitanic acid -2- ethylhexyls, tetramethoxy titanate ester, tetraisopropyl titanate, butyl titanate, the isobutyl of metatitanic acid four
One or more in the group that ester, metatitanic acid four (2- ethyl hexyls) ester form, preferably polymerization inhibitor are selected from MEHQ, N, N- bis-
Ethylhydroxyl amine, hydroquinones, catechol, p-tert-Butylcatechol, methylnaphthohydroquinone, p methoxy phenol, phenthazine and three
Phenylphosphine composition group in any one.
In addition, in order to save raw material on the basis of target product yield is ensured, in preferably above-mentioned steps S3, intermediate e
It is n with the alcohol with structural formula F or the mol ratio of polyalcohol：1, the weight of preferred catalyst is 3~the 10 ‰ of material gross weight,
The weight of more preferably polymerization inhibitor is 3~the 10 ‰ of material gross weight, and the temperature of further preferred ester exchange reaction is 70~130
DEG C, the reaction time be 1~8h.
In another typical embodiment of the application, there is provided a kind of Photocurable composition, including light trigger, should
Light trigger is any of the above-described kind of fluorenes class initiator.
Due to the application fluorenes class initiator efficiency of initiation with color inhibition, not easy to migrate, odor profiles low, dissolubility etc. asks
Topic can preferably be improved relative to the benzophenone or benzoyl formic acid esters initiator of prior art and equilibrium, because
This, it applies the structure properties that when in the composition composition can form more stable, and can make the photocuring group
Compound is i.e. curable under the irradiation of UV-LED light sources, therefore has saved the energy and more met environmental requirement.
In another typical embodiment of the application, there is provided a kind of any of the above-described kind of fluorenes class initiator is in photocuring
The application in field.
Because the fluorenes class initiator of the application makes with its Photocurable composition under the irradiation of UV-LED light sources
Solidification, therefore make to have saved the energy containing its application and more meet environmental requirement.It is preferred that above-mentioned application includes coating, ink, glued
Application in mixture, chromatic photoresist, black matrix", light spacer, rib grid, dry film and/or semiconductor light photoresist.
The present invention is described in further detail below with reference to specific embodiment, but should not be construed as to the present invention
The limitation of protection domain.
Prepare embodiment
(1) product 1a preparation：
Stirring after raw material 1a83g, dichloromethane 300mL, alchlor 67g is added into 1000mL four-hole boiling flasks and forms the
First mixed system is down to 0 DEG C by one mixed system, ice-water bath, and be added dropwise into first mixed system 77g raw materials 1b with
The mixed solution of the formation of 50mL dichloromethane, below 10 DEG C of temperature control, about 2h is dripped, and liquid phase tracking reaction is to no longer becoming
Change, obtain intermediate 1a reaction mixture, the reaction mixture is then poured slowly into 400g frozen water and 50mL concentrated hydrochloric acids (37%)
Stirring while adding in the watery hydrochloric acid being made into, reaction mixture is poured into separatory funnel after adding, and is separated down using separatory funnel
Layer dichloromethane layer, and continue to clean after water layer with 50mL dichloromethane and separate lower floor's dichloromethane layer again, merge and obtain twice
The dichloromethane layer arrived, the dichloromethane layer after being merged with 5% sodium bicarbonate aqueous solution (each 150mL, totally 3 times) cleaning,
Then dichloromethane layer is washed to pH in neutrality, with 50g anhydrous magnesium sulfate dry methylene chloride layers, and the dichloro after filtration drying
Methane layer, recrystallizing methanol is utilized after rotating the dichloromethane reaction mixture being filtrated to get, gained is crystallized in 80 DEG C of oven dryings
2h, obtain 135g product 1a, purity 98%, MS (m/z):285(M+1)+,1H-NMR(CDCl3, 500MHz)：2.3540 (3H, s),
3.8721 (2H, s), 7.1701-7.8411 (11H, m).
Further, different raw material a, b can be selected and carries out Friedel-Crafts reaction, so as to obtain the product a of different structure, but not
It is limited in this way, being shown in Table 1.
Table 1
(2) product 1b preparation：
It is stirred at room temperature after adding product 1a85g, dichloromethane 100mL into 500mL four-hole boiling flasks, continues to burn to this four mouthfuls
Bottle is added dropwise the mixed solution that raw material 1c38g and 50mL dichloromethane are formed, and below 30 DEG C of temperature control, about 1h is dripped, drip after
Continuous stirring 2h, liquid phase tracking reaction obtain the product system containing product 1b, are then poured slowly into the product system to complete
Stirring while adding in the watery hydrochloric acid that 400g frozen water and 50mL concentrated hydrochloric acids (37%) are made into, product system pours into point after being added completely into
In liquid funnel, lower floor's dichloromethane layer is separated using separatory funnel, and continue cleaning water layer with 50mL dichloromethane and separate again
Lower floor's dichloromethane layer, merge the dichloromethane layer that obtains twice, with 5% sodium bicarbonate aqueous solution (each 100mL, totally 3
It is secondary) dichloromethane layer after merging is cleaned, dichloromethane layer is then washed to pH in neutrality, with 50g anhydrous magnesium sulfates drying dichloro
Methane layer, and the dichloromethane layer after filtration drying, tied again using methanol after rotating the dichloromethane reaction mixture being filtrated to get
Crystalline substance, gained are crystallized in 80 DEG C of oven drying 2h, obtain 98g product 1b, purity 98%, MS (m/z):385(M+1)+,1H-NMR
(CDCl3, 500MHz)：1.2996-1.3025 (3H, m), 2.3535 (3H, s), 3.8757 (2H, s), 4.19543-4.2103
(2H, m) 7.1686-8.0943 (10H, m).
Further, different product a, raw material c can be selected and carries out Friedel-Crafts reaction, so as to obtain the product b of different structure,
But be not limited in this way, be shown in Table 2 (compound in table 2 is numbered in sequence, but the compound for not representing to obtain in table 2 be with
What compound in the table 1 of reference numeral was prepared for raw material, those skilled in the art can be according to preceding description and existing
Technology carries out Friedel-Crafts reaction from suitable product a and raw material c and obtains corresponding product b).
Table 2
(3) compound 1c preparation：
Added into 500mL four-hole boiling flask intermediate 1b 77g, raw material 1d100mL, tetraisopropyl titanate 0.1g, to hydroxyl
Base methyl phenyl ethers anisole 0.1g, heat four-hole boiling flask and control its temperature at 90~100 DEG C while stir what is added in the four-hole boiling flask
Material forms reaction solution, and then reaction solution is evaporated under reduced pressure, and steams ethanol caused by reaction, until being steamed without ethanol, takes advantage of
Heat filtering, obtain faint yellow solid 93g, as product 1c, MS (m/z):483(M+1)+,1H-NMR(CDCl3, 500MHz)：
0.9655-0.97231 (3H, t), 1.2897-1.3305 (12H, m), 1.5677-1.5708 (2H, m), 2.3546 (3H, s),
3.8777 (2H, s), 4.1607-4.1702 (2H, t) 7.1659-8.0902 (10H, m).
Further, different product b, raw material d can be selected and carries out ester exchange reaction, so as to obtain the product of different structure
C, but it is not limited to that (compound in table 3 is numbered in sequence, but the compound for not representing to obtain in table 3 is in this way, being shown in Table 3
It is prepared using the compound in the table 2 of reference numeral as raw material, those skilled in the art can be according to preceding description and existing
There is technology to carry out ester exchange reaction from suitable product b and raw material d and obtain corresponding product c).
Table 3
Performance evaluation
By preparing exemplary radiation-hardenable composition, to light trigger shown in formula (I) of the present invention and formula (II) and together
Application performance of the initiator of conventional benzophenone class and benzoyl formic acid esters in ink preparation is evaluated under sample formula.
From the monomer or oligomer needed for different free-radical curables, the sensitizing of proper proportion is added as needed on
Agent, colouring agent, dispersant, dispersion synergists, surfactant or polymerization inhibitor etc., prepare curable ink.
The preparation of radiation-hardenable composition：
Radiation-hardenable composition is prepared according to the formula of table 4, from conventional benzophenone and GA esters
Initiator and light trigger of the present invention contrasted, the gross weight of weight % (wt%) based on radiation-hardenable composition
Amount：
Table 4
Evaluation method：
<Sensitivity test>
Photocurable composition is stirred under yellow fluorescent lamp, feeding forms about 20 μm of thickness in roller coating film forming in PET templates
Film, exposed using crawler type, enclose mask plate, high-pressure sodium lamp (exposure machine model RW-UV70201, wavelength 200- is respectively adopted
500nm, light intensity 100mW/cm2) and LED (indigo plant spectrum in gram LP300w, wavelength 395nm, light intensity 100mW/cm2) radiated, with
Film, which is fully cured, is required through the number of crawler belt to evaluate, and test result is shown in Table 5.
<Yellowing resistance is evaluated>
Obtained cured film under above-mentioned high-pressure sodium lamp is subjected to senile experiment using RW-UV.2BP ultraviolet aging test chambers,
Light source is high-pressure sodium lamp (dominant wavelength 365nm, complete machine power：About 2.2KW), Continuous irradiation cured film 6h, observe the Huang of cured film
Change situation, evaluated according to following standard, be shown in Table 5.
◇：Water white transparency, surface is smooth, and expression has good anti-yellowing property；
□：Micro- yellow or surface has tacky, represents that anti-yellowing property is undesirable；
◆：Surface is turned to be yellow or viscosity increase, represents easy xanthochromia.
<The evaluation of odor profiles and migration>
Obtained cured film under the above-mentioned Photocurable composition high-pressure sodium lamp of same quality is weighed, by fanning news method to its smell
Property evaluated, be put into after then shredding in the methanol solution of same volume, Room-temperature seal immersion 24h, liquid phase (mobile phase first
Alcohol/water=80/20) detect whether have the presence of initiator in methanol solution, evaluated according to following standard：
It is 1. odor profiles：
◇ does not have smell；
◆ it is odorous.
2. migration：
◇：The presence of initiator is not detected by, is shown not easy to migrate；
◆：Detect with the presence of initiator, show that migration is to be improved.
Table 5
It is can be seen that from the evaluation result of table 5 in the case of other components identical, fluorenes class initiator of the invention is not only
There is higher sensitivity under high-pressure sodium lamp, under UV-LED light sources height it is also more satisfactory, and existing benzophenone and
Benzoyl formic acid ester lightlike initiating agent sensitivity under UV-LED light sources then shows clearly disadvantageous；And tested by color inhibition
And migration experiment is as can be seen that fluorenes photoinitiator of the present invention, has good anti-yellowing property, dissolubility and gas
The characteristics of taste is not low, easy to migrate.
In summary, compound shown in formula (I) and formula (II) of the present invention is being applied in curing field as light trigger,
Very excellent application performance can be shown, is had broad application prospects.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (14)
1. a kind of fluorenes class initiator, it is characterised in that the fluorenes class initiator has the group as shown in formula (I)：
Wherein, R1、R2Separately any one in hydrogen atom, halogen and chain base group, the chain base group are
C1-C20Straight chained alkyl, C1-C20Branched alkyl or C1-C20Cycloalkyl, C4-C20Cycloalkyl-alkyl, C4-C20Alkyl
Cycloalkyl and C2-C20Alkenyl, or the R1And R2With any one in the chain base group or two kinds of cyclization, and institute
State-the CH in chain base group2- optionally substituted by-O- ,-C (=O) O-, halogen, phenyl；
Ar is the substituent containing aromatic rings or miscellaneous aromatic rings；
And the R being connected with the connecting key of the group shown in the formula (I)3, the R3For hydrogen atom ,-C (=O) R3' or-C (=
O) C (=O) O-R3' group, wherein, R3' represent substitution or unsubstituted C1-C40Straight chain, C1-C40Branched alkyl, C1-
C20Cycloalkyl, C1-C40Alkenyl, the substituent containing aromatic rings or miscellaneous aromatic rings, or R3For-C (=O) C (=O) O-
R3', group, R3 ' groups are alcohol or polyalcohol by ester exchange reaction the group that connects.
2. fluorenes class initiator according to claim 1, it is characterised in that the chain base group is C1-C10Straight chained alkyl,
C1-C10Branched alkyl or C4-C10Cycloalkyl-alkyl.
3. fluorenes class initiator according to claim 1, it is characterised in that the Ar is phenyl, aminomethyl phenyl, ethylo benzene
Base, chlorphenyl, bromophenyl, methoxyphenyl, nitrobenzophenone, cyano-phenyl, diphenyl sulfide ether, pyridine radicals, thienyl, furans
Base, 2- methyl-thiophenes base, 3 methyl thiophene base, furyl, 2- methyl-furyls or 3- methylfuran bases.
4. fluorenes class initiator according to any one of claim 1 to 3, it is characterised in that the R3For-C (=O) C (=
O)O-R3' group, the fluorenes class initiator is with the structure as shown in following formula (II)：
Wherein, R4With n external connection key, and it is C1-C60Straight chained alkyl or branched alkyl, or the C1-C60Straight chain alkane
Arbitrary carbon or hydrogen are substituted by oxygen, sulphur or phenyl in base or branched alkyl；
A represents there is-(Q-CHR5)mThe repeat unit of-structure, R5For hydrogen, methyl or ethyl, Q represents O or connector, wherein,
The connector expression-(CHR5)mIt is joined directly together with O, m is 1~6 integer；
N represents 1~20 integer.
5. fluorenes class initiator according to claim 4, it is characterised in that the R4Any one in following groups：
6. fluorenes class initiator according to claim 4, it is characterised in that the A is selected from-[(Q-CHR5)m]y-, wherein R5For
Hydrogen or methyl, m are 1~3 integer, and y represents 1~9 integer.
7. fluorenes class initiator according to claim 4, it is characterised in that the n is 1~8 integer, preferably 1,2,3,
4th, 5 or 6.
A kind of 8. preparation method of the fluorenes class initiator any one of claim 1 to 7, it is characterised in that the preparation
Method includes：
Step S1, the raw material a and raw material b with structural formula B with structural formula A occur Friedel-Crafts reaction, obtained with structural formula C
Intermediate c；
With the raw material d with structural formula D Friedel-Crafts reaction occurs for optional step S2, the intermediate c, obtains with structural formula E
Intermediate e；And
With the alcohol with structural formula F or polyalcohol ester exchange reaction occurs for optional step S3, the intermediate e, obtains described
Fluorenes class initiator, wherein,
The structural formula A isThe structural formula B isWherein X1For halogen, the structural formula C isThe structural formula D isWherein X2For halogen, the structural formula E isThe structural formula F is R4(AOH)n。
9. preparation method according to claim 8, it is characterised in that the step S1 and the step S2 Friedel-Crafts reaction
Carried out in the presence of alchlor or zinc chloride and solvent, the reaction of preferably described step S1 and the step S2 Friedel-Crafts reaction
Temperature is each independently -10~40 DEG C.
10. preparation method according to claim 8, it is characterised in that the step S3 is in catalyst and the work of polymerization inhibitor
Occur the ester exchange reaction with lower, preferably described catalyst is one or more titanium acid compounds, more preferably described catalysis
Agent is selected from metatitanic acid -2- ethylhexyls, tetramethoxy titanate ester, tetraisopropyl titanate, butyl titanate, tetrabutyl titanate, metatitanic acid four
One or more in the group of (2- ethyl hexyls) ester composition, preferably described polymerization inhibitor are selected from MEHQ, N, N- diethyl
Azanol, hydroquinones, catechol, p-tert-Butylcatechol, methylnaphthohydroquinone, p methoxy phenol, phenthazine and triphenyl
Phosphine composition group in any one.
11. preparation method according to claim 10, it is characterised in that in the step S3, the intermediate e is with having
Structural formula F alcohol or the mol ratio of polyalcohol are n：1, the weight of preferred catalyst is 3~the 10 ‰ of material gross weight, more preferably
The weight of the polymerization inhibitor is 3~the 10 ‰ of the material gross weight, and the temperature of the further preferred ester exchange reaction is 70
~130 DEG C, the reaction time be 1~8h.
12. a kind of Photocurable composition, including light trigger, it is characterised in that the light trigger is in claim 1 to 7
Fluorenes class initiator described in any one.
13. a kind of fluorenes class initiator any one of claim 1 to 7 is in the application of curing field.
14. application according to claim 13, it is characterised in that the application includes coating, ink, adhesive, colour
Application in photoresistance, black matrix", light spacer, rib grid, dry film and/or semiconductor light photoresist.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610821992.3A CN107814694B (en) | 2016-09-13 | 2016-09-13 | Fluorene initiator, preparation method thereof, photocuring composition with fluorene initiator and application of composition in photocuring field |
| JP2019501481A JP6833171B2 (en) | 2016-09-13 | 2017-08-28 | Fluorene photoinitiators, methods for producing them, photocurable compositions having them, and use of fluorene photoinitiators in the field of photocuring. |
| PCT/CN2017/099294 WO2018049976A1 (en) | 2016-09-13 | 2017-08-28 | Fluorene photoinitiator, preparation method therefor, photocurable composition having same, and use of same in photocuring field |
| EP17850178.9A EP3514135B1 (en) | 2016-09-13 | 2017-08-28 | Fluorene photoinitiator, preparation method therefor, photocurable composition having same, and use of same in photocuring field |
| KR1020197004737A KR102197059B1 (en) | 2016-09-13 | 2017-08-28 | Fluorene photoinitiator, preparation method thereof, photocurable composition having same, and use thereof in the field of photocuring |
| US16/259,779 US10976660B2 (en) | 2016-09-13 | 2019-01-28 | Fluorene photoinitiator, preparation method therefor, photocurable composition having same, and use of same in photocuring field |
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| CN201610821992.3A CN107814694B (en) | 2016-09-13 | 2016-09-13 | Fluorene initiator, preparation method thereof, photocuring composition with fluorene initiator and application of composition in photocuring field |
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