CN112574184A - Epoxide substituted pyrazoline derivative, light-cured composition and preparation method - Google Patents
Epoxide substituted pyrazoline derivative, light-cured composition and preparation method Download PDFInfo
- Publication number
- CN112574184A CN112574184A CN202011567423.3A CN202011567423A CN112574184A CN 112574184 A CN112574184 A CN 112574184A CN 202011567423 A CN202011567423 A CN 202011567423A CN 112574184 A CN112574184 A CN 112574184A
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- China
- Prior art keywords
- substituted
- unsubstituted
- epoxide
- formula
- alkyl
- Prior art date
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- 150000003219 pyrazolines Chemical class 0.000 title claims abstract description 44
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 125000003700 epoxy group Chemical group 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title description 10
- 238000000034 method Methods 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 26
- -1 aryl formaldehyde Chemical compound 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 15
- 125000000623 heterocyclic group Chemical group 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 150000002118 epoxides Chemical class 0.000 claims description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 150000003254 radicals Chemical class 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical class CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- ZFHUHPNDGVGXMS-UHFFFAOYSA-N 4-(hydroxymethyl)benzaldehyde Chemical class OCC1=CC=C(C=O)C=C1 ZFHUHPNDGVGXMS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- 150000002429 hydrazines Chemical class 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 2
- 125000006272 (C3-C7) cycloalkyl group Chemical group 0.000 claims description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229930194542 Keto Natural products 0.000 claims description 2
- 125000002837 carbocyclic group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000000468 ketone group Chemical group 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims 1
- 238000000016 photochemical curing Methods 0.000 abstract description 21
- 230000015572 biosynthetic process Effects 0.000 abstract description 16
- 238000003786 synthesis reaction Methods 0.000 abstract description 16
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 51
- 239000003504 photosensitizing agent Substances 0.000 description 25
- 239000011248 coating agent Substances 0.000 description 19
- 238000000576 coating method Methods 0.000 description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000001723 curing Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000004593 Epoxy Substances 0.000 description 10
- 238000009472 formulation Methods 0.000 description 10
- 238000006748 scratching Methods 0.000 description 10
- 230000002393 scratching effect Effects 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000003822 epoxy resin Substances 0.000 description 9
- 229920000647 polyepoxide Polymers 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000013508 migration Methods 0.000 description 8
- 230000005012 migration Effects 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229940067157 phenylhydrazine Drugs 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 125000005409 triarylsulfonium group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 description 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- IWYVYUZADLIDEY-UHFFFAOYSA-N 4-methoxybenzenesulfonic acid Chemical compound COC1=CC=C(S(O)(=O)=O)C=C1 IWYVYUZADLIDEY-UHFFFAOYSA-N 0.000 description 2
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- BNWNNTAGTHIQER-UHFFFAOYSA-N CCOC(C=C1)=CC=C1C1=CC(C(C=C2)=CC=C2O)N(C2=CC=CC=C2)N1 Chemical compound CCOC(C=C1)=CC=C1C1=CC(C(C=C2)=CC=C2O)N(C2=CC=CC=C2)N1 BNWNNTAGTHIQER-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ZRQPNDLGUQIFBO-UHFFFAOYSA-N OCC1=CC=C(C2N(C3=CC=CC=C3)NC(C3=CC=CC=C3)=C2)C=C1 Chemical compound OCC1=CC=C(C2N(C3=CC=CC=C3)NC(C3=CC=CC=C3)=C2)C=C1 ZRQPNDLGUQIFBO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 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
- 239000012046 mixed solvent Substances 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 2
- PVRSIFAEUCUJPK-UHFFFAOYSA-N (4-methoxyphenyl)hydrazine Chemical compound COC1=CC=C(NN)C=C1 PVRSIFAEUCUJPK-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- YJFNFQHMQJCPRG-UHFFFAOYSA-N 1-(4-ethoxyphenyl)ethanone Chemical compound CCOC1=CC=C(C(C)=O)C=C1 YJFNFQHMQJCPRG-UHFFFAOYSA-N 0.000 description 1
- HHAISVSEJFEWBZ-UHFFFAOYSA-N 1-[4-(trifluoromethyl)phenyl]ethanone Chemical compound CC(=O)C1=CC=C(C(F)(F)F)C=C1 HHAISVSEJFEWBZ-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- XKQQFGSSJLXNRD-UHFFFAOYSA-N 1-methyl-4-[3-[3-(6-methyl-7-oxabicyclo[4.1.0]heptan-3-yl)prop-2-enoxy]prop-1-enyl]-7-oxabicyclo[4.1.0]heptane Chemical compound CC12C(CC(CC1)C=CCOCC=CC1CC3C(CC1)(O3)C)O2 XKQQFGSSJLXNRD-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- UKRQMDIFLKHCRO-UHFFFAOYSA-N 2,4,6-trimethylbenzoyl chloride Chemical compound CC1=CC(C)=C(C(Cl)=O)C(C)=C1 UKRQMDIFLKHCRO-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 1
- SNGZGCFWZHOVOS-UHFFFAOYSA-N 2-(2-methyloctoxymethyl)oxirane Chemical compound CCCCCCC(C)COCC1CO1 SNGZGCFWZHOVOS-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- WAPRZVXVTPSWEB-UHFFFAOYSA-N 2-[(2-butan-2-ylphenoxy)methyl]oxirane Chemical compound CCC(C)C1=CC=CC=C1OCC1OC1 WAPRZVXVTPSWEB-UHFFFAOYSA-N 0.000 description 1
- HHRACYLRBOUBKM-UHFFFAOYSA-N 2-[(4-tert-butylphenoxy)methyl]oxirane Chemical compound C1=CC(C(C)(C)C)=CC=C1OCC1OC1 HHRACYLRBOUBKM-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- DOQQIEJZBMOSKR-UHFFFAOYSA-N 2-[2,3,4,5-tetramethyl-6-(oxiran-2-ylmethoxy)phenyl]phenol Chemical compound CC=1C(C)=C(C)C(C)=C(C=2C(=CC=CC=2)O)C=1OCC1CO1 DOQQIEJZBMOSKR-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-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
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- ORTNTAAZJSNACP-UHFFFAOYSA-N 6-(oxiran-2-ylmethoxy)hexan-1-ol Chemical compound OCCCCCCOCC1CO1 ORTNTAAZJSNACP-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical class CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- OGFDPHNOHNFRDB-UHFFFAOYSA-N C(=O)OC1(CC2C(CC1)O2)CCC2CC1C(CC2)O1 Chemical compound C(=O)OC1(CC2C(CC1)O2)CCC2CC1C(CC2)O1 OGFDPHNOHNFRDB-UHFFFAOYSA-N 0.000 description 1
- WYRFRZSEKRTPDV-UHFFFAOYSA-N CC(C=C1)=CC=C1N1NC(C2=CC=C(C(F)(F)F)C=C2)=CC1C1=CC=C(CBr)C=C1 Chemical compound CC(C=C1)=CC=C1N1NC(C2=CC=C(C(F)(F)F)C=C2)=CC1C1=CC=C(CBr)C=C1 WYRFRZSEKRTPDV-UHFFFAOYSA-N 0.000 description 1
- KSSMSFRECMUMLB-UHFFFAOYSA-N CC(C=C1)=CC=C1N1NC(C2=CC=C(C(F)(F)F)C=C2)=CC1C1=CC=C(CO)C=C1 Chemical compound CC(C=C1)=CC=C1N1NC(C2=CC=C(C(F)(F)F)C=C2)=CC1C1=CC=C(CO)C=C1 KSSMSFRECMUMLB-UHFFFAOYSA-N 0.000 description 1
- WPYCRFCQABTEKC-UHFFFAOYSA-N Diglycidyl resorcinol ether Chemical compound C1OC1COC(C=1)=CC=CC=1OCC1CO1 WPYCRFCQABTEKC-UHFFFAOYSA-N 0.000 description 1
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- ZXUJYIQZKNWLQN-UHFFFAOYSA-N [3-(7-oxabicyclo[4.1.0]heptan-3-ylmethyl)-7-oxabicyclo[4.1.0]heptan-3-yl] formate Chemical compound C(=O)OC1(CC2C(CC1)O2)CC1CC2C(CC1)O2 ZXUJYIQZKNWLQN-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000012952 cationic photoinitiator Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 125000006431 methyl cyclopropyl group Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 150000004031 phenylhydrazines Chemical class 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 125000002755 pyrazolinyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
-
- 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
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/223—Di-epoxy compounds together with monoepoxy compounds
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/687—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing sulfur
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
Abstract
The present application relates to epoxide-substituted pyrazoline derivatives represented by the following formulae (I) and (II), photocurable compositions, and processes for producing the epoxide-substituted pyrazoline derivatives represented by the formulae (I) and (II). The invention has the formula (I)The epoxide-substituted pyrazoline derivative shown in the formula (II) has good absorption at the wavelength of more than 350nm and can be used as a sensitizer for photocuring polymerization; the synthesis steps of the molecules are simple, and the method is suitable for industrial production and application; meanwhile, the molecule can form chemical bond bonding with the photocured product, and the mobility of the molecule is reduced.
Description
Technical Field
The invention belongs to the field of new material organic chemistry, and particularly relates to preparation of an epoxide substituted pyrazoline derivative, which is used as a sensitizer in a photocuring system.
Background
Ultraviolet-visible light (UV-Vis) curing is a curing mode using ultraviolet light or visible light to cure a coating, has the advantages of rapid curing, energy conservation, environmental protection, no VOC (volatile organic solvent) generation, wide applicability and the like, and is widely applied to the fields of printing ink, electronic packaging, rapid photo-curing forming, photoresist, adhesives and the like. Photocuring can be classified into radical curing and cationic curing depending on the radical generated by the photoinitiator.
Compared with free radical curing, the cationic curing system (non-acrylate) has the advantages of difficult influence of oxygen inhibition, small curing shrinkage rate and the like, and expands the research and development range of the photocuring material. Under the action of ultraviolet-visible light, when the light energy is greater than the bond-breaking energy of the photoinitiator, the cationic photoinitiator generates protonic acid or Lewis acid to form a positive ion active center to initiate polymerization. This process requires that the absorption spectrum of the photoinitiator match the wavelength range of the light source.
The traditional cationic initiator is mainly composed of bisaryliodonium salt and triarylsulfonium salt, and the main absorption light domain of the conventional cationic initiator is 200-330 nm. This absorption domain is matched to the wavelength of a conventional mercury lamp light source. The mercury lamp has great harm to the environment, the energy is too high, and the side reactions in the curing process are more, so that the novel low-energy LED light source gradually becomes a substitute. However, the wavelength of the new LED light source is in the near uv-visible region, i.e. above 360nm, which does not match the main absorption range of conventional cationic initiators. This results in that conventional photoinitiators do not have good photoinitiating capability under LED light sources.
Photosensitizers are a class of substances that can absorb photon energy and transfer it to reactive components, and are used primarily in the field of solar cells. The addition of the LED sensitive dye in the light curing component can effectively improve the polymerization rate of the formula under an LED light source. The photosensitizer has small molecular weight and is not easy to generate chemical reaction, so that a large amount of small molecules in the formula can be remained although the formula is free from redundant side reaction in the illumination process, and the photosensitizer is easy to migrate after a product is cured, so that the product performance is reduced.
Therefore, how to obtain a photosensitizer with a larger wavelength absorption peak, good electron transfer or energy transfer capability and low migration capability in a photocuring product by a simple synthesis method is a problem to be solved.
Disclosure of Invention
As a result of intensive studies to overcome the disadvantages of the prior art, the inventors have found that the lowest unoccupied orbital (LUMO) energy of pyrazoline molecules is generally higher (about-2.20 eV relative to vacuum) than that of commercially available bisaryliodonium salts and triarylsulfonium salts. Therefore, pyrazoline molecules have good sensitization effect on the onium salt initiator; meanwhile, pyrazoline has intramolecular charge transfer, so that the pyrazoline has good absorption property in a light domain of more than 350nm, and the absorption range of the pyrazoline is greatly overlapped with that of a commercial LED light source. Therefore, when a cationically polymerizable functional group is introduced into a pyrazoline molecule, requirements of red shift of an absorption peak, strong electron transfer capability, and low mobility can be satisfied at the same time. Meanwhile, the preparation method of the epoxide substituted pyrazoline derivative shown in the formula (I) and the formula (II) is simple and convenient, high in yield, low in cost and suitable for industrial production and application.
[ epoxide-substituted pyrazoline derivative ]
The epoxide-substituted pyrazoline derivative is shown in the following formula (I) and formula (II),
R1is selected from C1-12Unsubstituted or substituted by 1 to 5R4Substituted phenyl, unsubstituted or substituted by 1 to 9R4Substituted condensed ring aryl, unsubstituted or substituted by 1 to 4R4Substituted aromatic heterocyclic radical, or unsubstituted or substituted by 1-8R4Substituted benzoaromatic heterocyclic groups;
R2is selected from C1-6Alkyl radical, C3-6Cycloalkyl, unsubstituted or substituted by 1-5R4Substituted phenyl, unsubstituted or substituted by 1 to 9R4Substituted condensed ring aryl, unsubstituted or substituted by 1 to 4R4Substituted aromatic heterocyclic radical, unsubstituted or substituted by 1-8R4Substituted benzoaromatic heterocyclic groups;
R3selected from H, C unsubstituted or substituted by 1-3O, S, N atoms1-6Alkyl, unsubstituted or substituted by 1 to 3O, S, N atoms3-6Unsubstituted or substituted by 1 to 5R4Substituted benzyl, unsubstituted or substituted by 1 to 5R4Substituted phenyl;
R4selected from unsubstituted or substituted by 1-5RaSubstituted C1-6Alkyl, -F, -Cl, -Br, -I, -CN, -CF2CF3、-CF3、-NO2、-NRbRb、-ORb、-SRb、-C(＝O)Rb、-CO2Rb、-OC(＝O)Rb、-NRbC(＝O)Rb、-S(＝O)Rb、-S(＝O)2RbUnsubstituted or substituted by 1 to 5RcSubstituted carbocyclic ring, unsubstituted or substituted by 1 to 5RdA substituted heterocycle;
Raeach independently selected from C1-6Alkyl group, (CH)2)rC3-6Cycloalkyl or- (CH)2)rA phenyl group;
Rbeach independently selected from H, unsubstituted or substituted by 1-5ReSubstituted C1-6Alkyl, unsubstituted or substituted by 1-5ReSubstituted- (CH)2)rPh；
RcEach independently selected from unsubstituted or substituted by 1-5ReSubstituted C1-6Alkyl, unsubstituted or substituted by 1-5ReSubstituted (CH)2)rPh；
RdEach independently selected from unsubstituted or substituted by 1-5ReSubstituted C1-6Alkyl, unsubstituted or substituted by 1-5ReSubstituted (CH)2)rPh；
ReEach independently selected from-F, -Cl, -Br, -I, -OH, -NO2、-CN，-CF3、-CF2CF3、C1-4Alkyl radical, C1-4Alkoxy radical, C3-7Cycloalkyl, phenyl, benzyl, phenethyl, naphthyl, heterocyclic aryl, or, keto;
each r is independently 0, 1, 2, 3, or 4;
w, z are each independently selected from 0 or 1.
The foregoing term "C1-12The "alkyl group" of (1) is an alkyl group having 1 to 12 carbon atoms, and may be a linear or branched alkyl group, and is not particularly limited. As "C1-12Examples of the "alkyl group" include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like.
The foregoing term "C1-6The "alkyl group" of (a) is an alkyl group having 1 to 6 carbon atoms, and may be a linear or branched alkyl group, and is not particularly limited. As "C1-6Examples of the "alkyl group" include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl and hexyl groups.
The aforementioned term "condensed ring aryl group" means a polycyclic aryl group in which two or more benzene rings are constituted by sharing a ring edge, and examples of the condensed ring aryl group include, for example, naphthyl, anthryl, phenanthryl, pyrenyl, and the like;
the term "aromatic heterocyclic group" refers to a heterocyclic group having aromatic characteristics, and examples of the aromatic heterocyclic group include furyl group, imidazolyl group, pyridyl group and the like.
The term "benzoaromatic heterocyclic group" as used herein means an aromatic heterocyclic group in which a benzene ring is fused with a heterocyclic ring, and examples of the "benzoaromatic heterocyclic group" include quinolyl, indolyl, purinyl and the like.
The foregoing terms“C3-6The "cycloalkyl group" is a cycloalkyl group having 3 to 6 carbon atoms, and the term "C" is3-6Examples of cycloalkyl "are, for example, cyclopropyl, methylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclobutyl, dimethylcyclobutyl, cyclohexyl and the like.
The foregoing term "C1-4The "alkyl group" is an alkyl group having 1 to 4 carbon atoms, and is "C1-4Examples of the "alkyl group" include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.
The foregoing "Ph" represents a phenyl group.
The epoxide-substituted pyrazoline derivative of the formula (I) according to the invention, preferably R1、R2Each independently an aromatic heterocyclic group selected from the following (A) and (B):
(A) a 6-membered aromatic heterocyclic group containing 1 to 3 heteroatoms selected from the group consisting of O, N and S on the heterocyclic ring;
(B) a 5-membered aromatic heterocyclic group containing a hetero atom of any one of the following groups in the heterocyclic ring,
1) 1O, 1N, or, 1S;
2) 1S and 1N, 1O and 1N, or, 2N; or
3) 1O and 2N, or, 1S and 2N.
In addition, by introducing hybridization into the molecular structure, a new electronic structure can be further formed by the pyrazoline group and the lone pair of electrons of the heteroatom, and the absorption of the molecule is further influenced.
In the epoxide-substituted pyrazoline derivative of the formula (I) according to the invention, R is preferably1、R2Each independently selected from the group consisting of the following structural formulae:
wherein R is4The definitions of (a) are the same as those described above.
In the epoxide-substituted pyrazoline derivative represented by the formula (I) of the present invention, it is preferably selected from the group consisting of compounds represented by the following structural formulae,
[ Photocurable composition ]
The photocurable composition of the present invention contains the aforementioned epoxide-substituted pyrazoline derivative of the present invention and a polymerizable component containing a photoinitiator, a monomer having an epoxy group, or an ethylenic bond or a polymer.
In the photocurable composition of the present invention, the epoxide-substituted pyrazoline derivative represented by the formula (I) or (II) is preferably contained in an amount of 0.5 to 10 parts by weight, based on 100 parts by weight of the total amount of the polymerizable components. More preferably, the content of the epoxide-substituted pyrazoline derivative represented by the formula (I) or the formula (II) is 1 to 10 parts by weight.
Examples of the photoinitiator include (2,4, 6-trimethylbenzoyl chloride) diphenylphosphine oxide (TPO) and its derivatives, 1-hydroxycyclohexylphenylketone (184), 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173), 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-propanone (907), thioxanthone (ITX) and its derivatives, bisaryliodonium salt (Iod), triarylsulfonium salt (6976), and the like.
Examples of the monomer having an epoxy group include monofunctional glycidyl ethers, polyfunctional aliphatic glycidyl ethers, polyfunctional aromatic glycidyl ethers, glycidyl esters, and aliphatic epoxy compounds.
Examples of the monofunctional glycidyl ether include allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, sec-butylphenyl glycidyl ether, tert-butylphenyl glycidyl ether, and 2-methyloctyl glycidyl ether.
Examples of the polyfunctional aliphatic glycidyl ether include 1, 6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, glycerol triglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether.
Examples of the polyfunctional aromatic glycidyl ethers include bisphenol a glycidyl ether, bisphenol F glycidyl ether, brominated bisphenol a glycidyl ether, biphenol glycidyl ether, tetramethylbiphenol glycidyl ether, and resorcinol glycidyl ether.
Examples of the glycidyl esters include glycidyl acrylate, glycidyl methacrylate, diglycidyl phthalate, and diglycidyl hexahydrophthalate.
Examples of the aliphatic epoxy compound include 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl formate, 3, 4-epoxycyclohexylethyl-3, 4-epoxycyclohexyl formate, ethylene cyclohexenyl dioxide, propylene cyclohexenyl dioxide, and 3, 4-epoxy-4-methylcyclohexyl-2-propenyl oxide.
Examples of the monomer having an ethylenic bond include (meth) acrylates, acrolein, olefins, conjugated dienes, styrene, maleic anhydride, fumaric anhydride, vinyl acetate, vinylpyrrolidone, vinylimidazole, (meth) acrylic acid, and (meth) acrylic acid derivatives such as (meth) acrylamide, vinyl halides, vinylidene halides, and the like.
In the photocurable composition of the present invention, the polymerizable component may be in the form of a polymer such as an oligomer or a prepolymer, or a copolymer formed from at least one of a monomer, an oligomer, and a prepolymer. In addition, it may be in the form of an aqueous dispersion.
As the aforementioned epoxy group-containing polymer, for example, an epoxy group-containing polymer or resin such as bisphenol a epoxy resin, dicyclopentadiene type epoxy resin, diaminodiphenylmethane type epoxy resin, aminophenol type epoxy resin, naphthalene type epoxy resin, novolak type epoxy resin, biphenyl type epoxy resin, hydrogenated biphenyl type epoxy resin, aliphatic type epoxy resin, and the like can be cited.
Examples of such an ethylenic bond-containing polymer include (meth) acrylic copolymers having a (meth) acryloyl functional group, urethane (meth) acrylates, polyester (meth) acrylates, unsaturated polyesters, polyether (meth) acrylates, silicone (meth) acrylates, epoxy resin (meth) acrylates, and the like which are water-soluble or water-dispersible.
[ Process for producing epoxide-substituted pyrazoline derivative ]
The preparation method of the epoxide-substituted pyrazoline derivative comprises the following steps (c):
in the aforementioned step (c), the compound represented by the formula (I) -b or the formula (II) -b is reacted with R3Reacting substituted halogenated epoxide in the presence of tetrabutylammonium bromide and alkali to respectively obtain epoxide-substituted pyrazoline derivatives shown in formula (I) or formula (II), wherein the reaction temperature is 0-80 ℃;
the R is1、R2、R3Y, w and z are as defined in the epoxide-substituted pyrazoline derivative of the formula (I).
As an example of the aforementioned step (c), for example, a method of reacting a compound represented by the formula (I) -b with R4Reacting substituted halogenated propylene oxide in sodium hydroxide, tetrabutylammonium bromide and toluene, removing solvent, and repeatingCrystallizing to obtain the epoxide-substituted pyrazoline derivative shown in the formula (I), namely the target product.
As the foregoing step (c), optionally, the base may be selected from sodium hydroxide, potassium carbonate, potassium tert-butoxide, sodium hydride and the like; the solvent can be selected from toluene, carbon tetrachloride, tetrahydrofuran, acetonitrile, N, N' -dimethylformamide and the like.
When z is 1, the method for preparing the epoxide-substituted pyrazoline derivative of the present invention further comprises the following step (c'):
in the step (c'), the compound represented by the formula (I) -b or the formula (II) -b is reacted with R3Reacting substituted halogenated epoxide under the catalysis of p-toluenesulfonic acid to respectively obtain epoxide substituted pyrazoline derivatives shown in formula (I) or formula (II), wherein the reaction temperature is room temperature to 60 ℃;
the R is1、R2、R3Y, w is as defined in claim 1.
As an example of the aforementioned step (c'), there may be mentioned, for example, a step of reacting a compound represented by the formula (II) -b with R4The substituted halogenated oxetane compound reacts in p-toluenesulfonic acid, and after the solvent is removed, the epoxide substituted pyrazoline derivative shown in the formula (I) is prepared by recrystallization, namely the target product.
As an embodiment of the method for producing the epoxide-substituted pyrazoline derivative, the method for producing the compound represented by the formula (I) -b and the formula (II) -b when z is 0 comprises the following step (a)1) Step (b)1)：
Said step (a)1) In, R1Substituted ethanones with 4-hydroxybenzaldehydes or 5-hydroxy-2-heterocyclic arylsReacting formaldehyde in absolute ethyl alcohol by using alkali as a catalyst at the temperature of room temperature to 60 ℃, and then acidifying by using acid to respectively obtain a product (I) -a1Or (II) -a1(ii) a The aforementioned step (a)1) The reaction time of (a) may be 0.5 to 6 hours, preferably 1 to 4 hours;
said step (b)1) In the step (a), the step (a)1) The (I) -a obtained in (1)1Or (II) -a1The compounds shown are reacted with R in acetic acid2Carrying out reflux reaction on substituted hydrazine to respectively obtain compounds shown as formulas (I) -b and (II) -b; the aforementioned step (b)1) The reaction time of (a) may be 1 to 10 hours, preferably 2 to 6 hours;
the aforementioned step (a)1) The base in (1) is not particularly limited, but is preferably sodium hydroxide, potassium hydroxide or potassium carbonate.
The aforementioned step (a)1) The acid in (1) is not particularly limited, but is preferably hydrochloric acid, sulfuric acid or acetic acid.
As an embodiment of the method for producing the epoxide-substituted pyrazoline derivative, the method for producing the compound represented by the formula (I) -b and the formula (II) -b when z is 1 comprises the following step (a)2) Step (b)2)：
Said step (a)2) In, R1Substituted ethyl ketone and 4-hydroxymethyl benzaldehyde or 5-hydroxymethyl-2-heterocyclic aryl formaldehyde react in absolute ethyl alcohol by taking alkali as a catalyst to respectively obtain a product (I) -a2Or (II) -a2The reaction temperature is between room temperature and 60 ℃; the aforementioned step (a)2) The reaction time of (a) may be 1 to 10 hours, preferably 2 to 6 hours;
said step (b)2) In the step (a), the step (a)2) The (I) -a obtained in (1)2Or (II) -a2The compound shown and R2Reacting substituted hydrazine in absolute ethyl alcohol by using alkali as a catalyst to respectively obtain compounds shown as formulas (I) -b and (II) -b at the reaction temperature of80 ℃; the aforementioned step (b)2) The reaction time of (a) may be 1 to 8 hours, preferably 1 to 5 hours;
the aforementioned step (a)2) The base in (1) is not particularly limited, but is preferably sodium hydroxide, potassium hydroxide or potassium carbonate.
The aforementioned step (b)2) The base in (1) is not particularly limited, but is preferably sodium hydroxide, potassium hydroxide or potassium carbonate.
The beneficial effects and the application are as follows:
the epoxide-substituted pyrazoline derivatives shown in the formula (I) and the formula (II) have good absorption at the wavelength of more than 350 nm. The epoxide-substituted pyrazoline derivative shown in the formula (I) and the formula (II) has good application prospect as a polymerizable photosensitizer, can be used as the photosensitizer to be applied to a photocuring composition, and can also be polymerized in a photocuring system as a polymerizable monomer to reduce the mobility of the polymerizable monomer.
The photocurable composition of the present invention contains the epoxide-substituted pyrazoline derivatives represented by the formulae (I) and (II) of the present invention, and thus has good absorption at a wavelength of 350nm or more.
The epoxide-substituted pyrazoline derivatives shown in the formula (I) and the formula (II) have the advantages of simple synthetic steps and low raw material cost, and are suitable for industrial production and application.
Detailed Description
Examples
In order to more clearly illustrate the disclosure, the disclosure is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the present disclosure.
The first embodiment is as follows: synthesis of target molecule (I) -1 according to the following scheme
(a) Sodium hydroxide and absolute ethyl alcohol are used at normal temperature for 1 hour;
(b) sodium hydroxide, anhydrous ethanol, 80 deg.C, 2 hr
(c) Potassium hydroxide, tetrabutylammonium bromide, toluene, 110 ℃ and 4 hours;
1. synthesis of 3- (4-hydroxymethylphenyl) -1-phenyl-2-en-1-one
Acetophenone (12.00g, 0.10mol), 4-hydroxymethylbenzaldehyde (13.62g, 0.10mol) and absolute ethanol (30mL) as a solvent were added to a 100mL three-necked flask containing a magnetic rotor, and stirred at room temperature. An aqueous solution of sodium hydroxide (12.00g, 0.30mol, 12mL) was then prepared and added dropwise to the reaction via a constant pressure dropping funnel. The reaction process is monitored by a silica gel chromatography plate, after the reaction is finished, the reaction is filtered, and the filtrate is filtered after being concentrated. And washing the solid obtained by filtering twice with water, washing twice with absolute ethyl alcohol, drying, and recrystallizing with absolute ethyl alcohol to obtain yellow crystals with the yield of 89.6%. HRMS for C16H12O3: 238.1031 (calculated), 238.1023 (actual).
2. Synthesis of 1, 3-diphenyl-5- (4-hydroxymethylphenyl) pyrazoline
Sodium hydroxide (5.60g, 0.14mol) and absolute ethanol (100mL) as a solvent were added to a 250mL three-necked flask containing a magnetic rotor, and the mixture was dissolved by refluxing at 80 ℃ with stirring; phenylhydrazine (7.57g, 0.08mol) was then added, and after 15 minutes 3- (4-hydroxymethylphenyl) -1-phenyl-2-en-1-one (16.68g, 0.07mol) was added, the reaction was incubated and the progress of the reaction was monitored by a silica gel chromatography plate. After the reaction, the reaction mixture was cooled to room temperature, filtered, and the obtained solid was washed twice with 95% ethanol and recrystallized from a mixed solvent of anhydrous ethanol/ethyl acetate (10/1, v/v) to obtain a yellow crystalline product with a yield of 84.2%. HRMS for C22H20N2O: 328.1604 (calculated), 328.1620 (actual).
3. Synthesis of target molecule (I)
1, 3-diphenyl-5- (4-hydroxymethylphenyl) pyrazoline (12.42g, 0.05mol), potassium hydroxide (4.49g, 0.08mol), tetrabutylammonium bromide (1.0g) and toluene (150mL) are added into a 250mL three-neck flask containing a magnetic rotor, the temperature is increased to reflux the toluene, and the temperature is kept for 1 h; then adding epichlorohydrin (5.55g, 0.06mol), continuing the heat preservation reaction, and passing through silica gel in the reaction processAnd (5) monitoring a chromatographic plate. After the reaction was completed, toluene and excess epichlorohydrin were removed by distillation under reduced pressure, followed by dissolution in dichloromethane (100mL), washing twice with saturated brine (2 × 200mL), washing once with deionized water (150mL), collection of the organic phase, drying with anhydrous sodium sulfate, followed by removal of all organic solvents by suspension evaporation under reduced pressure, and purification of the obtained product by a silica gel chromatography column (petroleum ether/ethyl acetate: 4/1, v/v) gave the objective molecule (I) -1 in 82.1% yield. HRMS for C25H24N2O2: 384.1834 (calculated), 384.1842 (actual).
Example two: synthesis of target molecules (I) -2 to (I) -8
The preparation method of the pyrazoline photosensitizer is the same as that of the embodiment I, and arylethanone and R are changed4And then the implementation can be realized. Specific yields and mass spectral characterization results are as follows.
Example three: synthesis of target molecules (I) -9 to (I) -14
The preparation method of the pyrazoline photosensitizer is the same as that of the embodiment I, and the substituted phenylhydrazine and the R are changed4And then the implementation can be realized. Specific yields and mass spectral characterization results are as follows.
Example four: synthesis of target molecule (I) -15 according to the following scheme
(a) Sodium hydroxide and absolute ethyl alcohol are used at normal temperature for 2 hours;
(b) sodium hydroxide, anhydrous ethanol, 80 deg.C, 2 hr
(c) P-methoxybenzenesulfonic acid, acetone, 40 ℃ and 10 hours;
1. synthesis of 1- (4-trifluoromethylphenyl) -3- (4-hydroxymethylphenyl) -2-en-1-one
The 4-trifluoromethyl acetophenone and 4-hydroxymethyl benzaldehyde were reacted in sodium hydroxide and anhydrous ethanol in 88.6% yield. HRMS for C17H13F3O2: 306.0911 (calculated), 306.0923 (actual).
2. Synthesis of 1- (4-methylphenyl) -3- (4-trifluoromethylphenyl) -5- (4-hydroxymethylphenyl) -pyrazoline
The 1- (4-trifluoromethylphenyl) -3- (4-hydroxymethylphenyl) -2-en-1-one and 4-methoxyphenylhydrazine are reacted in sodium hydroxide and absolute ethyl alcohol, and the yield is 88.6%. HRMS for C24H21F3N2O2: 426.1604 (calculated), 426.1620 (actual).
3. Synthesis of target molecule (I) -15
In a 250mL three-necked flask, 1- (4-methylphenyl) -3- (4-trifluoromethylphenyl) -5- (4-bromomethylphenyl) -pyrazoline (12.23g, 25.0mmol), glycidol (16.50g, 0.25mol) and p-methoxybenzenesulfonic acid (0.42g, 2.5mmol) and acetone (80mL) as a solvent were charged, followed by stirring at room temperature. The progress of the reaction was checked by means of a silica gel chromatographic plate. After completion of the reaction, the mixture was extracted with 200mL of a 20% aqueous solution of sodium hydroxide and 400mL of methylene chloride. The aqueous phase was washed 3 times with dichloromethane, the organic phases were combined, the organic phase was washed 3 times with saturated brine, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the product was recrystallized from ethanol to obtain a yield of 82.6%. HRMS for C26H23F3N2O3: 468.1741 (calculated), 468.1733 (actual).
Example five: target molecules (I) -16 to (I) -22 were synthesized.
The preparation method of the pyrazoline derivative is basically the same as that of the fourth embodiment, and the preparation can be realized by changing methyl-substituted aryl formaldehyde and hydroxyl-containing epoxide. Specific yields and mass spectral characterization results are as follows.
Example six: synthesis of target molecule (I) -23 according to the following scheme
(a) Sodium hydroxide and absolute ethyl alcohol are used at normal temperature for 1 hour; hydrochloric acid, pH 7; (ii) a
(b) Acetic acid, 135 ℃, 2 h;
(c) potassium hydroxide, acetone, 60 ℃,6 h.
1. Synthesis of 3- (4-ethoxyphenyl) -1- (4-hydroxyphenyl) -2-en-1-one
In a 100mL three-necked flask containing a magnetic rotor, 4-ethoxyacetophenone (16.42g, 0.10mol), 4-hydroxybenzaldehyde (12.21g, 0.10mol) and anhydrous ethanol (25mL) as a solvent were placed and stirred at room temperature. An aqueous solution of sodium hydroxide (12.00g, 0.30mol, 12mL) was then prepared and added dropwise to the reaction via a constant pressure dropping funnel. After the addition was completed, the reaction was carried out for 2 hours, and the reaction process was monitored by a silica gel chromatography plate. After the reaction, brine was added to adjust the pH of the system to 7, and the mixture was filtered, and the filtrate was concentrated and then filtered. And washing the solid obtained by filtering twice with water, washing twice with absolute ethyl alcohol, drying, and recrystallizing with absolute ethyl alcohol to obtain yellow crystals with the yield of 89.1%. HRMS for C17H16O3: 268.1141 (calculated), 268.1138 (actual).
2. Synthesis of 1-phenyl-3- (4-ethoxyphenyl) -5- (4-hydroxyphenyl) -pyrazoline
A250 mL three-necked flask containing a magnetic rotor was charged with acetic acid solvent (40mL), followed by 3- (4-ethoxyphenyl) -1- (4-hydroxyphenyl) -2-en-1-one (14.09g, 0.06mmol), warmed to dissolve the solids, followed by phenylhydrazine (7.57g, 0.08mol), warmed to 135 deg.C, allowed to reflux the acetic acid, and the reaction was incubated, with the progress of the reaction monitored by silica gel chromatography. Cooling to room temperature after the reaction is finished, filtering, and obtaining solidThe product was obtained as yellow crystals in 79.4% yield by recrystallization from a mixed solvent of anhydrous ethanol/ethyl acetate (10/1, v/v) after washing twice with 95% ethanol. HRMS for C23H22N2O2: 358.1701 (calculated), 358.1720 (actual).
3. Synthesis of target molecule (I) -23
The method is the same as the first example and the yield is 92.6 percent by using the reaction of 1-phenyl-3- (4-ethoxyphenyl) -5- (4-hydroxyphenyl) -pyrazoline and epichlorohydrin in sodium hydroxide and acetone. HRMS for C26H26N2O3: 414.1941 (calculated), 414.1933 (actual).
Example seven: synthesis of target molecules (I) -24 to (I) -30
The preparation method of the pyrazoline derivative is basically the same as that of the sixth embodiment, and can be realized by changing substituted arylethanone and halogen-containing epoxide. Specific yields and mass spectral characterization results are as follows.
Example eight: (I) -1 LED photocuring experiments and sensitizer migration Property testing
Sample systems containing epoxide-substituted pyrazoline photosensitizers were prepared according to the following formulation (in weight percent)
Dual-functional epoxy monomer (EPOX): 97 percent
Photoinitiator (Iod): 1.5 percent
Photosensitizer ((I) -1): 1.5 percent
The mixture of the above formulation examples was applied to cardboard to form a coating of about 25-30 microns at a unit power of 1000mW/cm, produced by Guangzhou and Guangshi technologies Inc2The LED light source (3 cm wide and 80 cm long LED surface light source) with the emission wavelength of 365 nm is an excitation light sourceAnd is placed on a variable speed conveyor belt. The criterion for completing photopolymerization curing is that repeated nail scratching and scratching can not generate marks.
The results show that the compounds containing this example all cure efficiently at a rate of greater than 25 m/min.
And (3) carrying out a micromolecule migration test on the coating obtained by photocuring in an organic solvent soaking mode, and measuring that the mass of the photosensitizer which is migrated out accounts for 0.2% of the mass of the original photosensitizer in the coating.
Example nine: (I) LED photocuring experiments and sensitizer migration Property testing of-8
Sample systems containing epoxide-substituted pyrazoline photosensitizers were prepared according to the following formulation (in weight percent)
Monofunctional epoxy monomer (CHO): 68.5 percent of
Difunctional epoxy monomer (EPOX): 30.0 percent
Photoinitiator (Iod): 0.5 percent
Photosensitizer ((I) -8): 1.0 percent
The above formulation example mixture was applied to cardboard to form a coating of about 30-35 microns at a unit power of 1000mW/cm, produced by Guangzhou and Guangsheng technology Ltd2The LED light source (an LED surface light source with the width of 3 cm and the length of 80 cm) with the emission wavelength of 385 nanometers is used as an excitation light source and is placed on a variable-speed conveyor belt. The criterion for completing photopolymerization curing is that repeated nail scratching and scratching can not generate marks.
The results show that the compounds containing this example all cured efficiently at a rate of greater than 30 m/min.
And (3) carrying out a micromolecule migration test on the coating obtained by photocuring in an organic solvent soaking mode, and measuring that the mass of the photosensitizer which is migrated out accounts for 0.2% of the mass of the original photosensitizer in the coating.
Example ten: (I) LED photocuring experiments and paint Property testing of-16
The epoxy-containing sample system was prepared according to the following formulation (in weight percent)
Dual-functional epoxy monomer (EPOX): 97.0 percent
Photoinitiator (6976): 1.0 percent
Photosensitizer ((I) -16): 2.0 percent
The mixture of the above formulation examples was applied to cardboard to form a coating of about 25-30 microns at a unit power of 1000mW/cm, produced by Guangzhou and Guangshi technologies Inc2The LED light source (3 cm wide and 80 cm long LED surface light source) with the emission wavelength of 395 nm is an excitation light source and is placed on a variable-speed conveyor belt. The criterion for completing photopolymerization curing is that repeated nail scratching and scratching can not generate marks.
The results show that the compounds containing this example all cure efficiently at a rate of greater than 35 m/min.
The coating obtained by photocuring was subjected to hardness test by a hand-operated pencil hardness tester, and the hardness was measured to be 4H.
And (3) carrying out a micromolecule migration test on the coating obtained by photocuring in an organic solvent soaking mode, and measuring that the mass of the photosensitizer which is migrated out accounts for 0.2% of the mass of the original photosensitizer in the coating.
Example eleven: (I) LED photocuring experiments and paint Property testing of-25
Epoxy group-containing sample systems were prepared according to the following formulation (in weight percent)
Monofunctional epoxy monomer (CHO): 18.5 percent
Bisphenol a epoxy resin: 35.0 percent
Difunctional epoxy monomer (EPOX): 45.0 percent
Photoinitiator (6976): 0.5 percent
Photosensitizers ((I) -25): 1.0%
The above formulation example mixture was applied to cardboard to form a coating of about 30-35 microns at a unit power of 1500mW/cm, produced by Guangzhou and Guangsheng technology Ltd2The LED light source (3 cm wide and 80 cm long LED surface light source) with the emission wavelength of 395 nm is an excitation light source and is placed on a variable-speed conveyor belt. The criterion for completing photopolymerization curing is that repeated nail scratching and scratching can not generate marks.
The results show that the compounds containing this example all cure efficiently at a rate of greater than 20 m/min.
The coating obtained by photocuring was subjected to hardness test by a hand-operated pencil hardness tester, and the hardness was measured to be 4H.
And (3) carrying out a micromolecule migration test on the coating obtained by photocuring in an organic solvent soaking mode, and measuring that the mass of the photosensitizer which is migrated out accounts for 0.2% of the mass of the original photosensitizer in the coating.
Example twelve: (I) LED photocuring experiments and paint Property testing of-30
The sample systems containing acrylate and epoxy groups were prepared according to the following formulation (in weight percent):
trifunctional acrylate monomer (TMPTA): 20.0 percent
Urethane acrylate resin: 25.0 percent
Bisphenol a epoxy resin: 29.0 percent
Difunctional epoxy monomer (EPOX): 20.0 percent
Photosensitizer ((I) -31): 3.0 percent
Photoinitiator (907): 1.0 percent
Photoinitiator (Iod): 2.0 percent
The mixture of the above formulation examples was applied to cardboard to form a coating of about 25-30 microns at a unit power of 2000mW/cm, manufactured by Guangzhou and Guangshi technologies Inc2The LED light source (3 cm wide and 80 cm long LED surface light source) with the emission wavelength of 405 nm is an excitation light source and is placed on a variable-speed conveyor belt. The criterion for completing photopolymerization curing is that repeated nail scratching and scratching can not generate marks.
The results show that the compounds containing this example all cure efficiently at a rate of greater than 25 m/min.
The coating obtained by photocuring was subjected to a hardness test by a hand-operated pencil hardness tester, and the hardness was measured to be 5H.
And (3) carrying out a micromolecule migration test on the coating obtained by photocuring in an organic solvent soaking mode, and measuring that the mass of the photosensitizer which is migrated out accounts for 0.3% of the mass of the original photosensitizer in the coating.
It should be understood that the above-mentioned examples are for illustrative purposes only and are not intended to limit the embodiments of the present disclosure, and that various other modifications and changes in light thereof will be suggested to persons skilled in the art and are not intended to be exhaustive or to limit the present disclosure to the precise embodiments disclosed herein.
Claims (8)
1. Epoxide-substituted pyrazoline derivatives represented by the following formulae (I) and (II),
wherein:
R1is selected from C1-12Unsubstituted or substituted by 1 to 5R4Substituted phenyl, unsubstituted or substituted by 1 to 9R4Substituted condensed ring aryl, unsubstituted or substituted by 1 to 4R4Substituted aromatic heterocyclic radical, or unsubstituted or substituted by 1-8R4Substituted benzoaromatic heterocyclic groups;
R2is selected from C1-6Alkyl radical, C3-6Cycloalkyl, unsubstituted or substituted by 1-5R4Substituted phenyl, unsubstituted or substituted by 1 to 9R4Substituted condensed ring aryl, unsubstituted or substituted by 1 to 4R4Substituted aromatic heterocyclic radical, unsubstituted or substituted by 1-8R4Substituted benzoaromatic heterocyclic groups;
R3selected from H, C unsubstituted or substituted by 1-3O, S, N atoms1-6Alkyl, unsubstituted or substituted by 1 to 3O, S, N atoms3-6Unsubstituted or substituted by 1 to 5R4Substituted benzyl, unsubstituted or substituted by 1 to 5R4Substituted phenyl;
y is selected from O, S and NH;
w, z are each independently selected from 0 or 1;
R4selected from unsubstituted or substitutedIs covered by 1-5RaSubstituted C1-6Alkyl, -F, -Cl, -Br, -I, -CN, -CF2CF3、-CF3、-NO2、-NRbRb、-ORb、-SRb、-C(＝O)Rb、-CO2Rb、-OC(＝O)Rb、-NRbC(＝O)Rb、-S(＝O)Rb、-S(＝O)2RbUnsubstituted or substituted by 1 to 5RcSubstituted carbocyclic ring, unsubstituted or substituted by 1 to 5RdA substituted heterocycle;
Raeach independently selected from C1-6Alkyl group, (CH)2)rC3-6Cycloalkyl or- (CH)2)rA phenyl group;
Rbeach independently selected from H, unsubstituted or substituted by 1-5ReSubstituted C1-6Alkyl, unsubstituted or substituted by 1-5ReSubstituted- (CH)2)rPh；
RcEach independently selected from unsubstituted or substituted by 1-5ReSubstituted C1-6Alkyl, unsubstituted or substituted by 1-5ReSubstituted (CH)2)rPh；
RdEach independently selected from unsubstituted or substituted by 1-5ReSubstituted C1-6Alkyl, unsubstituted or substituted by 1-5ReSubstituted (CH)2)rPh；
ReEach independently selected from-F, -Cl, -Br, -I, -OH, -NO2、-CN，-CF3、-CF2CF3、C1-4Alkyl radical, C1-4Alkoxy radical, C3-7Cycloalkyl, phenyl, benzyl, phenethyl, naphthyl, heterocyclic aryl, or, keto;
each r is independently 0, 1, 2, 3, or 4.
2. The epoxide-substituted pyrazoline derivative according to claim 1, in which R1、R2The aromatic heterocyclic group in (A) and (B) are each independently an aromatic heterocyclic group selected from the following groups (A) and (B):
(A) a 6-membered aromatic heterocyclic group containing 1 to 3 heteroatoms selected from the group consisting of O, N and S on the heterocyclic ring;
(B) a 5-membered aromatic heterocyclic group containing a hetero atom of any one of the following groups in the heterocyclic ring,
1) 1O, 1N, or, 1S;
2) 1S and 1N, 1O and 1N, or, 2N; or
3) 1O and 2N, or, 1S and 2N.
3. The epoxide-substituted pyrazoline derivative according to claim 1, in which R1、R2Each independently selected from the group consisting of the following structural formulae:
wherein R is4Is as defined in claim 1.
4. A photocurable composition comprising the epoxide-substituted pyrazoline derivative according to any one of claims 1 to 4 and a polymerizable component comprising a photoinitiator, a monomer having an epoxy group, or an ethylenic bond or a polymer. The content of the epoxide-substituted pyrazoline derivative represented by the formula (I) or the formula (II) is 0.5 to 10 parts by weight relative to 100 parts by weight of the total amount of the polymerizable components.
5. The process for preparing epoxide-substituted pyrazoline derivatives according to claims 1 to 4, which comprises the following step (c):
in the step (c), the compound shown as the formula (I) -b or the formula (II) -b and R3Reacting substituted halogenated epoxide in the presence of tetrabutylammonium bromide and alkali to respectively obtain epoxide-substituted pyrazoline derivatives shown in formula (I) or formula (II), wherein the reaction temperature is 0-80 ℃;
the R is1、R2、R3Y, w, z are as defined in claim 1.
6. The process for preparing epoxide-substituted pyrazoline derivatives according to claim 5, which further comprises the following step (c') when z is 1:
in the step (c'), the compound represented by the formula (I) -b or the formula (II) -b is reacted with R3Reacting substituted halogenated epoxide under the catalysis of p-toluenesulfonic acid to respectively obtain epoxide substituted pyrazoline derivatives shown in formula (I) or formula (II), wherein the reaction temperature is room temperature to 60 ℃;
the R is1、R2、R3Y, w is as defined in claim 1.
7. The process for producing an epoxide-substituted pyrazoline derivative according to claim 5, in which when z is 0, the process for producing the compounds represented by formulae (I) -b and (II) -b comprises the following step (a)1) Step (b)1)：
Said step (a)1) In, R1Substituted ethyl ketone reacts with 4-hydroxy benzaldehyde or 5-hydroxy-2-heterocyclic aryl formaldehyde in absolute ethyl alcohol by taking alkali as a catalyst,the reaction temperature is between room temperature and 60 ℃, and then the product (I) -a is obtained by acidification with acid1Or (II) -a1；
Said step (b)1) In the step (a), the step (a)1) The (I) -a obtained in (1)1Or (II) -a1The compounds shown are reacted with R in acetic acid2And (3) refluxing the substituted hydrazine for reaction to respectively obtain the compounds shown as the formulas (I) -b and (II) -b.
8. The process for producing epoxide-substituted pyrazoline derivative according to claims 5 to 6, in which when z is 1, the process for producing the compounds represented by formulae (I) to (b) and (II) to (b) comprises the following step (a)2) Step (b)2)：
Said step (a)2) In, R1Substituted ethyl ketone and 4-hydroxymethyl benzaldehyde or 5-hydroxymethyl-2-heterocyclic aryl formaldehyde react in absolute ethyl alcohol by taking alkali as a catalyst to respectively obtain a product (I) -a2Or (II) -a2The reaction temperature is between room temperature and 60 ℃;
said step (b)2) In the step (a), the step (a)2) The (I) -a obtained in (1)2Or (II) -a2The compound shown and R2The substituted hydrazine reacts in absolute ethyl alcohol by taking alkali as a catalyst to respectively obtain compounds shown as formulas (I) -b and (II) -b, and the reaction temperature is 80 ℃.
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