CN110105256B - Alpha-aminoketone-stilbene sulfonium salt compound and preparation method and application thereof - Google Patents
Alpha-aminoketone-stilbene sulfonium salt compound and preparation method and application thereof Download PDFInfo
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- CN110105256B CN110105256B CN201910360630.2A CN201910360630A CN110105256B CN 110105256 B CN110105256 B CN 110105256B CN 201910360630 A CN201910360630 A CN 201910360630A CN 110105256 B CN110105256 B CN 110105256B
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- China
- Prior art keywords
- stilbene
- gas
- sulfonium salt
- aminoketone
- alpha
- Prior art date
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Links
- 238000002360 preparation method Methods 0.000 title abstract description 13
- -1 phenyl Chemical group 0.000 claims abstract description 29
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 150000001450 anions Chemical class 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000003847 radiation curing Methods 0.000 claims description 10
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims description 10
- 235000021286 stilbenes Nutrition 0.000 claims description 10
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical group [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 8
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 claims description 8
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 7
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 7
- 238000010526 radical polymerization reaction Methods 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 150000004768 bromobenzenes Chemical class 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- QARVLSVVCXYDNA-UHFFFAOYSA-N phenyl bromide Natural products BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 150000003440 styrenes Chemical class 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 229910001414 potassium ion Inorganic materials 0.000 claims description 3
- 229910001415 sodium ion Chemical group 0.000 claims description 3
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 16
- 238000001914 filtration Methods 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical group [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 229910052708 sodium Chemical group 0.000 claims 1
- 239000011734 sodium Chemical group 0.000 claims 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims 1
- 238000001723 curing Methods 0.000 abstract description 13
- 239000003999 initiator Substances 0.000 abstract description 12
- 150000005839 radical cations Chemical class 0.000 abstract description 6
- 230000005284 excitation Effects 0.000 abstract description 4
- 239000012949 free radical photoinitiator Substances 0.000 abstract description 3
- 238000000016 photochemical curing Methods 0.000 abstract description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 abstract description 2
- JFLKFZNIIQFQBS-FNCQTZNRSA-N trans,trans-1,4-Diphenyl-1,3-butadiene Chemical group C=1C=CC=CC=1\C=C\C=C\C1=CC=CC=C1 JFLKFZNIIQFQBS-FNCQTZNRSA-N 0.000 abstract description 2
- 238000004896 high resolution mass spectrometry Methods 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- 125000002091 cationic group Chemical group 0.000 description 7
- 238000010538 cationic polymerization reaction Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 150000003839 salts Chemical group 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005349 anion exchange Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012952 cationic photoinitiator Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- OIRDBPQYVWXNSJ-UHFFFAOYSA-N methyl trifluoromethansulfonate Chemical compound COS(=O)(=O)C(F)(F)F OIRDBPQYVWXNSJ-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- HQFXXLULXWUTIM-UHFFFAOYSA-N 1-benzylsulfanyl-4-ethenylbenzene Chemical compound C=Cc1ccc(SCc2ccccc2)cc1 HQFXXLULXWUTIM-UHFFFAOYSA-N 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 102100025403 Epoxide hydrolase 1 Human genes 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101100451963 Homo sapiens EPHX1 gene Proteins 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 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
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
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- 238000001704 evaporation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000012682 free radical photopolymerization Methods 0.000 description 1
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- 230000001939 inductive effect Effects 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
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- 238000001819 mass spectrum Methods 0.000 description 1
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- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical class N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/12—Sulfonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
- C07D295/104—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
- C07D295/104—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/108—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
-
- 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)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides an alpha-amidoketone-stilbene sulfonium salt compound, a preparation method and application thereof, wherein R in the sulfonium salt compound1Selected from halogen atoms, CF3、NO2CN, R OR OR, R2And R3Are respectively selected from hydrogen and C1‑C6Alkyl, linear or branched C substituted by phenyl1‑C6Alkyl, linear C2‑C3Alkenyl, branched C2‑C3Alkene, R4And R5Are respectively selected from hydrogen and C1‑C12Alkyl, linear or branched C substituted by 1-4 OH groups1‑C12Alkyl, unsubstituted C2‑C6The invention introduces distyryl sulfonium salt group into alpha-aminoketone free radical photoinitiator, which realizes the function of free radical-cation hybrid photopolymerization initiator, especially free radical-cation hybrid photocuring under the excitation of LED, thereby having wide application prospect in the field of ultraviolet-visible light curing.
Description
Technical Field
The invention belongs to the technical field of new materials, organic chemicals, and particularly relates to a novel free radical-cation hybrid photopolymerization initiator, and more particularly relates to an alpha-aminoketone-stilbene sulfonium salt compound and a preparation method and application thereof.
Background
Photopolymerization initiator compounds are an important class of fine organic chemical materials, which can be decomposed to generate active species under the excitation of light so as to initiate the polymerization of corresponding monomers. Generally, the compounds can be divided into radical type initiators and cationic type initiators, and the compounds generate radical or cationic active species under the irradiation condition of ultraviolet light or visible light, are key species for inducing unsaturated systems containing alkene or epoxy to carry out high-efficiency photopolymerization, and are one of important radiation curing formula components.
Among the numerous photoinitiator products that have been commercially used, α -aminoketone photoinitiators occupy a prominent position, and representative products thereof, such as 907, 369, 379 and the like (molecular structures are shown below), these molecules have good light absorption properties in the near ultraviolet region and a fast photodecomposition speed, and are a class of radical photoinitiators widely used in the fields of coatings, inks and the like. The cationic photoinitiator with obvious absorption in the near ultraviolet-visible light region has a large class of sulfonium salt, and can generate strong protonic acid under illumination by cooperating with non-electrophilic anions thereof, so that the cationic photoinitiator can efficiently initiate cationic polymerization of epoxy and vinyl ether compounds. For example, Chemistry of Materials,2012,24, 237-. Meanwhile, anions of the sulfonium salt can be used for preparing different series, such as hexafluoroantimonate and the like, through simple salt exchange reaction, and higher initiation activity is embodied.
On the other hand, the Light-curing Light source usually uses mercury lamp, mercury vapor is not in line with the new strategic trend of the development of the world energy-saving and environment-friendly industry, so that in recent years, the LED (Light-Emitting Diode) Light source obtains increasingly wide attention and rapid development, and the application of the LED Light-curing technology greatly reduces the energy consumption and ozone generation, and the industry continues to grow strongly. For curing of the LED system, a photoinitiator with sensitive absorption for the long-wave emission wavelength of the LED (365-. Therefore, designing, developing, and industrialization of novel photoinitiator compounds is a critical technical challenge facing the current field.
However, in radical polymerization, especially in the state of thin film, oxygen in the air is easy to react with free radicals generated by light excitation, and peroxy radicals with low initiation activity are generated, so that oxygen resistance is a very important technical problem in radical polymerization; in cationic polymerization, the monomer generally has a relatively slow initiation rate, and heating is generally required to effectively increase the rate of cationic photoinitiated polymerization. If the free radical polymerization and the cationic polymerization occur together, hybrid polymerization can be realized to form an interpenetrating polymer network of the free radical polymerization and the cationic polymerization, a large amount of heat generated by the free radical polymerization can improve the speed of the cationic polymerization, and the cationic polymerization can also play a role in resisting oxygen.
In view of the above technical challenges, it is necessary to invent a class of hybrid photoinitiators that are sensitive to LED light sources and that have dual free radical/cation initiation capability. In addition, the synthesis steps of the initiator have the advantages of simplicity, low cost, environment-friendly synthesis process, less three wastes and the like. The hybrid photoinitiator can be effectively compatible with free radical and cation curing resin and compounded to form photocuring ink or paint with stable storage, and has profound influence on the fields of woodware green coating, environment-friendly printing, ink-jet printing, 3D printing, energy-saving materials and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention mainly aims to provide an alpha-aminoketone-stilbene sulfonium salt compound.
The second purpose of the invention is to provide a preparation method of the alpha-aminoketone-stilbene sulfonium salt compound.
The third purpose of the invention is to provide the application of the alpha-aminoketone-stilbene sulfonium salt compound.
In order to achieve the above purpose, the solution of the invention is as follows:
an alpha-aminoketone-stilbene sulfonium salt compound has the following general formula:
wherein R is1Selected from halogen atoms, CF3、NO2CN, R and OR.
R is selected from C1-C24Straight chain alkyl, C1-C24Branched alkyl and-C6-C12More than one aryl group.
Specifically, the structure of R may contain 1-6 discontinuous S, O, N elements, that is, the structure of R not only contains carbon chain, but also can introduce hetero atom into the carbon chain, thereby forming C-C-O-C-C, C-C-S-C-C, etc., that is, only pure carbon chain can be used as substituent no longer, and carbon chain containing hetero atom can be used as substituent.
When two R exist simultaneously, a 3-6 membered ring system structure can be formed, such as cyclobutyl amino, cyclopentyl amino, cyclohexyl amino and the like.
R2And R3Are respectively selected from hydrogen and unsubstituted C1-C6Alkyl, linear C substituted by phenyl1-C6Alkyl, branched C substituted by phenyl1-C6Alkyl, linear C2-C3Alkenyl, branched C2-C3One or more of alkenyl groups, or R2And R3Together with the carbon atom to which they are bonded form a cyclopentyl or cyclohexyl group.
R4And R5Are respectively selected from hydrogen and unsubstituted C1-C12Alkyl, linear C substituted by 1-4 OH groups1-C12Alkyl, branched C substituted by 1-4 OH groups1-C12Alkyl, unsubstituted C2-C6Alkenyl, C interrupted by one or more O1-C6Alkyl and C interrupted by one or more O5-C8One or more cycloalkyl groups; or R4And R5Together with the nitrogen atom to which they are bonded, form a pyrrolidine, piperidine or morpholine group or a hexamethyleneimine.
n is an integer of 0 to 5, X-Selected from the anions of organic acids or the anions of inorganic acids.
Further, X-Selected from hexafluorophosphate, hexafluoroantimonate, trifluoromethanesulfonate and tetrafluoroborateMore than one.
The preparation method of the alpha-aminoketone-stilbene sulfonium salt compound comprises the following steps:
(1) containing R1Reacting benzylthio substituted styrene of a substituent group with alpha-amino ketone substituted bromobenzene in a solvent under the action of a catalyst, and purifying by column chromatography or recrystallization to obtain a stilbene conjugate (I) -a:
(2) dissolving the stilbene conjugate (I) -a and water with equivalent weight in acetonitrile solution, adding excessive dimethyl sulfate for reaction, cooling to room temperature, adding proper amount of toluene to precipitate the dispersion, decanting supernatant liquid, and drying residual oily matter to obtain precipitate (I) -b, wherein the intermediate containing two cations can be directly subjected to the next reaction without purification:
(3) adding three equivalents of MX into the aqueous solution of the precipitate (I) -b, adjusting the pH value of the obtained solution to 9.0-9.2 by adding 2mol/L of sodium hydroxide solution and sodium carbonate solid, reacting, and separating out a precipitate to obtain the alpha-aminoketone-stilbene sulfonium salt compound:
further, in the step (1), R is contained1The molar ratio of the substituted benzylthio substituted styrene to the alpha-amino ketone substituted bromobenzene to the catalyst is 1: (0.05-0.1).
Further, in the step (1), the catalyst is selected from more than one of palladium acetate/tri (o-methylphenyl) phosphine or tetra (triphenylphosphine) palladium dichloride, and potassium carbonate is used as an acid-binding agent.
Wherein palladium acetate/tris (o-methylphenyl) phosphine represents palladium acetate and tris (o-methylphenyl) phosphine.
Further, in the step (1), the reaction temperature is 60-90 ℃, and the reaction time is 6-24 h.
Further, in the step (1), the solvent is one or more selected from acetonitrile, tetrahydrofuran and N, N-dimethylformamide.
Further, in the step (2), the reaction temperature is 40-80 ℃, and the reaction time is 5-24 h.
In step (2), dimethyl sulfate can be replaced by methyl trifluoromethanesulfonate, but the sulfonium salt with the anion has low solubility in water, and the subsequent salt exchange reaction needs to be carried out by adding an organic solvent, and the MX saline solution and the organic sulfonium salt solution with trifluoromethanesulfonate are mixed and stirred. The solvent in the anion exchange reaction may be one or more selected from acetone, acetonitrile, tetrahydrofuran, Dimethylformamide (DMF) and Dimethylsulfoxide (DMSO), and a mixed solvent of these solvents and water, but is not limited thereto.
Further, in the step (3), the reaction temperature is 25-30 ℃, and the reaction time is 30-40 min.
Further, in the step (3), M is selected from one or more of potassium ions and sodium ions.
Further, in the step (3), X-Is selected from more than one of hexafluorophosphate or hexafluoroantimonate.
The preparation method of the alpha-aminoketone-stilbene sulfonium salt compound comprises the following steps:
(1) containing R1Reacting substituted benzylthio substituted styrene with alpha-amino ketone substituted bromobenzene in a solvent under the action of a catalyst, and purifying by column chromatography or recrystallization to obtain a stilbene conjugate (I) -a:
(2) dissolving the stilbene conjugate (I) -a and water with equivalent weight in acetonitrile solution, adding excessive dimethyl sulfate for reaction, cooling to room temperature, adding proper amount of toluene to precipitate the dispersion, decanting supernatant liquid, and drying residual oily matter to obtain precipitate (I) -b, wherein the intermediate containing two cations can be directly subjected to the next reaction without purification:
(3) dissolving one equivalent of precipitate (I) -b in an aqueous solution containing one equivalent of 2mol/L sodium hydroxide, adjusting the resulting solution to pH 9.0 by adding sodium carbonate (in small amounts) in portions, reacting, extracting with dichloromethane and drying, evaporating the organic solvent to obtain a sulfonium salt intermediate (I) -c, which has only one cation of a sulfonium salt, and can be directly subjected to the next reaction without purification:
(4) adding MX into the aqueous solution of the sulfonium salt intermediate (I) -c, and separating out a precipitate to obtain an alpha-aminoketone-stilbene sulfonium salt compound:
further, in the step (1), R is contained1The molar ratio of the substituted benzylthio substituted styrene to the alpha-amino ketone substituted bromobenzene to the catalyst is 1: (0.05-0.1).
Further, in the step (1), the catalyst is selected from more than one of palladium acetate/tri (o-methylphenyl) phosphine or tetra (triphenylphosphine) palladium dichloride, and potassium carbonate is used as an acid-binding agent.
Wherein palladium acetate/tris (o-methylphenyl) phosphine represents palladium acetate and tris (o-methylphenyl) phosphine.
Further, in the step (1), the reaction temperature is 60-90 ℃, and the reaction time is 6-24 h.
Further, in the step (1), the solvent is one or more selected from acetonitrile, tetrahydrofuran and N, N-dimethylformamide.
Further, in the step (2), the reaction temperature is 40-80 ℃, and the reaction time is 5-24 h.
In step (2), dimethyl sulfate can be replaced by methyl trifluoromethanesulfonate, but the sulfonium salt with the anion has low solubility in water, and the subsequent salt exchange reaction needs to be carried out by adding an organic solvent, and the MX saline solution and the organic sulfonium salt solution with trifluoromethanesulfonate are mixed and stirred. The solvent in the anion exchange reaction may be one or more selected from acetone, acetonitrile, tetrahydrofuran, Dimethylformamide (DMF) and Dimethylsulfoxide (DMSO), and a mixed solvent of these solvents and water, but is not limited thereto.
Further, in the step (3), the reaction temperature is 25-30 ℃, and the reaction time is 30-40 min.
Further, in the step (4), M is selected from one or more of potassium ions and sodium ions.
Further, in the step (4), X-Is selected from more than one of trifluoromethanesulfonate or tetrafluoroborate.
The application of the alpha-aminoketone-stilbene sulfonium salt compound as a radiation curing photoinitiator. In particular to the application of the cationic hybrid polymerization system initiator containing epoxy and vinyl ether and free radical photopolymerization containing unsaturated double bonds.
Further, the light source of the radiation curing photoinitiator is selected from one or more of ultraviolet light and visible light.
Further, the light source of the radiation curing photoinitiator is selected from more than one of mercury lamp, LED light source and LDI light source which can emit ultraviolet light and visible light.
Further, the radiation curing photoinitiator includes 0.01 to 30 parts by weight of an α -aminoketone-stilbene sulfonium salt-based compound and 100 parts by weight of an ethylenically (C ═ C) unsaturated compound.
Further, the radiation curing photoinitiator includes 0.5 to 10 parts by weight of an α -aminoketone-stilbene sulfonium salt-based compound and 100 parts by weight of an ethylenically (C ═ C) unsaturated compound.
Further, the ethylenically unsaturated compound means a compound or a mixture in which the ethylenic bond is crosslinked by radical polymerization.
Further, the ethylenically unsaturated compound is selected from the group consisting of monomers, oligomers, or prepolymers, or mixtures or copolymers of the three, or aqueous dispersions of the three.
Exemplary compounds conforming to the structure of formula (I) are listed below:
wherein, X-Selected from CF3SO3 -、BF4 -、PF6 -、B(F5-Ph)4 -And the like.
Due to the adoption of the scheme, the invention has the beneficial effects that:
compared with the existing method of physically mixing the free radical initiator and the cationic initiator, the alpha-aminoketone-stilbene sulfonium salt compound combines the free radical initiator and the cationic initiator together in a chemical linking mode, has good comprehensive performance, has high initiation efficiency of the alpha-aminoketone free radical photoinitiator, and can accelerate the initiation of cationic polymerization reaction by heating a polymerization system through reaction heat and light source heat in the polymerization process, thereby realizing dual hybrid polymerization; in addition, the molecular structure synthesis methods are simple, the steps are few, the three wastes are low, and the purification is convenient; the absorption spectrum of the UV curing light source has better overlapping with the emission spectrum of cheap light sources such as LEDs, and is consistent with the development direction of the UV curing technology.
Secondly, the invention introduces distyryl sulfonium salt group into alpha-aminoketone free radical photoinitiator, which realizes the function of free radical-cation hybrid photopolymerization initiator, especially free radical-cation hybrid photocuring under the excitation of LED, thereby having wide application prospect in the field of ultraviolet-visible light curing.
Drawings
FIG. 1 is a general structural formula of the alpha-aminoketone-stilbene sulfonium salt compound of the invention.
Detailed Description
As shown in figure 1, the invention provides an alpha-aminoketone-stilbene sulfonium salt compound, and a preparation method and application thereof.
The present invention will be further described with reference to the following examples.
Example 1: preparation process of stilbene conjugate (1) -a:
4-benzylthiostyrene (10mmol), 1- (4-bromophenyl) -2-methyl-2-morpholinopropan-1-one (1- (4-bromophenyl) -2-methyl-2-morpholinopropan-1-one) (10mmol), tetrakis (triphenylphosphine) palladium dichloride (0.1mmol) and potassium carbonate (10mmol) are added into 30mL of DMF solution, placed in an oil bath at 100 ℃ under the protection of nitrogen, stirred for reaction for 10h, the solvent is recovered by concentration under reduced pressure, 100mL of deionized water is added, the precipitate separated by suction filtration is dissolved in 50mL of dichloromethane, the catalyst is recovered by a short silica gel column, and the filtrate is recrystallized by absolute ethyl alcohol after being evaporated to dryness to prepare the product as white powder.
(1) A, yield 92%. HR-MS (C)29H31NO2S): 457.2075 for m/e; the experimental results are as follows: 458.2166(M + H)+)。
Example 2: preparation process of intermediate precipitate (1) -b:
the stilbene conjugate (1) -a (0.01mol) was dissolved in 50mL of acetonitrile at 25 deg.C, an equivalent amount of water was added, dimethyl sulfate (0.1mol) was slowly added dropwise to the above solution with stirring, and after the addition, the temperature of the system was raised to 60 deg.C and stirred for 12 hours. After cooling to room temperature, the dispersion was added to 40mL of toluene to allow the dispersion to settle. The supernatant was decanted and the remaining oil was dried to give the title compound as a yellow oil.
(1) B, yield 87%. HR-MS (C)30H35NO2S2+): 473.2389 for m/e; the experimental results are as follows: 236.6196150 (M)2 +)。
Example 3: process for neutralizing protons of amine groups in precipitate (1) -b:
the precipitate (1) -b (10mmol) was dissolved in 2mol/L aqueous sodium hydroxide solution (10mmol), solid sodium carbonate (about 1g) was added in portions, the pH of the solution was adjusted to 9.0, and after stirring at room temperature for 30min, the solution was extracted with dichloromethane, dried and evaporated to dryness to obtain the target compound in yellow.
(1) -c, yield 93%. HR-MS (C)30H34NO2S+): 472.2310 for m/e; the experimental results are as follows: 472.2311.
example 4: the α -aminoketone-stilbene sulfonium salt compound (photoinitiator) (1) -PF of this example6 -The preparation process comprises the following steps:
the precipitate (1) -b or the sulfonium salt intermediate (1) -c was dissolved in an appropriate amount of water, an aqueous solution (2 equivalents) of sodium hexafluorophosphate or potassium hexafluorophosphate was added dropwise, the pH of the solution was adjusted to 9.0 with an aqueous solution of sodium hydroxide or sodium carbonate, and the precipitated yellow precipitate was suction-filtered, washed with water and dried to give the target compound (1) in yellow color. The yield was 90%. HR-MS (C)30H34NO2S+): 472.2310 for m/e; the experimental results are as follows: 472.2310.
example 5: the preparation process of the rest alpha-aminoketone-stilbene sulfonium salt compounds (photoinitiator) comprises the following steps:
the preparation of the rest of the photoinitiators with different anions is essentially the same as in the above example, and it is possible to vary the starting materials with different MXs.
Since the mass spectrum cannot show the molecular weight of the corresponding anion, the molecular ion peak of the sulfonium salt is not changed by the anion. Specific characterization results such as hexafluorophosphate molecular weight criteria are as follows. The remaining salts showed similar results and are not described in detail.
2-PF6 -And the total yield of the four steps is as follows: 62%, HR-MS: 430.2205 for m/e; the experimental results are as follows: 430.2204(M + H)+)。
3-PF6 -And the total yield of the four steps is as follows: 61%, HR-MS: 458.2518 for m/e; the experimental results are as follows: 458.2518(M + H)+)。
4-PF6 -And the total yield of the four steps is as follows: 65%, HR-MS: 470.2518 for m/e; the experimental results are as follows: 470.2516(M + H)+)。
5-PF6 -And the total yield of the four steps is as follows: 61%, HR-MS: 512.2623 for m/e; the experimental results are as follows: 512.2620(M + H)+)。
6-PF6 -And the total yield of the four steps is as follows: 55%, HR-MS: 510.2831 for m/e; the experimental results are as follows: 510.2830(M + H)+)。
7-PF6 -And the total yield of the four steps is as follows: 60%, HR-MS: 497.2263 for m/e; the experimental results are as follows: 497.2259(M + H)+)。
8-PF6 -And the total yield of the four steps is as follows: 68%, HR-MS: 455.2157 for m/e; the experimental results are as follows: 455.2156(M + H)+)。
9-PF6 -And the total yield of the four steps is as follows: 60%, HR-MS: 483.2470 for m/e; the experimental results are as follows: 483.2470(M + H)+)。
10-PF6 -And the total yield of the four steps is as follows: 55%, HR-MS: 495.2470 for m/e; the experimental results are as follows: 495.2466(M + H)+)。
11-PF6 -And the total yield of the four steps is as follows: 60%, HR-MS: 537.2576 for m/e; the experimental results are as follows: 537.2560(M + H)+)。
12-PF6 -And the total yield of the four steps is as follows: 59%, HR-MS: 535.2783 for m/e; the experimental results are as follows: 535.2779(M + H)+)。
13-PF6 -And the total yield of the four steps is as follows: 57%, HR-MS: 520.2674 for m/e; the experimental results are as follows: 520.2672(M + H)+)。
14-PF6 -And the total yield of the four steps is as follows: 55%, HR-MS: 534.2831 for m/e; fruit of Chinese wolfberryAnd (4) testing results: 534.2831(M + H)+)。
15-PF6 -And the total yield of the four steps is as follows: 53%, HR-MS: 545.2627 for m/e; the experimental results are as follows: 545.2626(M + H)+)。
< experiment >
The following experiments were carried out with the products of the above examples, respectively.
< experiment 1>
Film polymerization reaction:
free radical-cationic hybrid cure test samples were formulated according to the following weight percentages: epoxy acrylate: 14 parts of (1); polyester acrylate: 16 parts of a mixture; hexanediol diacrylate: 3 parts of a mixture; pentaerythritol triacrylate: 12 parts of (1); diol or branched polyol having a molecular weight of about 400: 12 parts of (1); difunctional epoxycyclohexane EPOX: 23 parts; titanium dioxide dye: 16 parts of a mixture; substituted sulfonium salts in selected examples: 4 parts.
A part of the mixture was sufficiently and uniformly ground and then coated on a white ABS substrate, and an image layer of about 20 μm was formed under air. Irradiation was carried out at a distance of 2cm from the sample using 365nm, 385nm and 405nm LED curing testers (light, Guangzhou), the conveyor speed being 20 m/min. And judging the complete curing condition of the coating by finger-pressing and scraping. The compounds of the above examples all initiate complete curing of the film layer, showing good photoinitiating properties. And the heat of reaction effectively promotes cationic curing.
< experiment 2>
Thick film polymerization:
the formulation was the same as in experiment 1.
A part of the above mixture was sufficiently ground and coated on a white ABS substrate, and a pattern layer of about 200 μm was formed under air. Irradiation was carried out at a distance of 2cm from the sample using 365nm, 385nm and 405nm LED curing testers (light, Guangzhou), the belt speed being 10 m/min. And judging the complete curing condition of the coating by pressing and scraping. The compounds of the above examples all initiate complete curing of the film layer, showing good radical-cation dual photoinitiating properties.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments and the generic principles defined herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments. Those skilled in the art should appreciate that many modifications and variations are possible in light of the above teaching without departing from the scope of the invention.
Claims (12)
1. An alpha-aminoketone-stilbene sulfonium salt compound is characterized in that: the general formula is as follows:
wherein R is1Selected from halogen atoms, CF3、NO2One of CN, R and OR;
r is selected from C1-C24Straight chain alkyl, C1-C24Branched alkyl and C6-C12One of aryl groups;
R2and R3Are respectively selected from hydrogen and C1-C6Alkyl, linear C substituted by phenyl1-C6Alkyl, branched C substituted by phenyl1-C6Alkyl, linear C2-C3Alkenyl and branched C2-C3One of alkenyl groups;
R4and R5Are respectively selected from hydrogen and unsubstituted C1-C12Alkyl, linear C substituted by 1-4 OH groups1-C12Alkyl, branched C substituted by 1-4 OH groups1-C12Alkyl, unsubstituted C2-C6Alkenyl, C interrupted by one or more O1-C6Alkyl, C interrupted by one or more O5-C8One of cycloalkyl groups;
n is an integer of 0 to 5, X-Selected from the anions of organic acids or the anions of inorganic acids.
2. The α -aminoketone-stilbene sulfonium salt compound of claim 1, wherein: x-Selected from one of hexafluorophosphate, hexafluoroantimonate, trifluoromethanesulfonate and tetrafluoroborate.
3. A method for preparing α -aminoketone-stilbene sulfonium salt compound according to claim 1, which comprises the following steps: which comprises the following steps:
(1) containing R1Reacting substituted benzylthio substituted styrene with alpha-amino ketone substituted bromobenzene in a solvent under the action of a catalyst to obtain a stilbene conjugate (I) -a:
(2) and dissolving the stilbene conjugate (I) -a and water with equivalent weight in acetonitrile solution, adding dimethyl sulfate for reaction, and filtering to obtain a precipitate (I) -b:
(3) adding MX into the aqueous solution of the precipitate (I) -b; said MX, wherein M is selected from potassium or sodium, X-Selected from hexafluorophosphate or hexafluoroantimonate; adjusting the pH value of the obtained solution to 9.0-9.2 by adding sodium carbonate and sodium hydroxide, reacting, and separating out a precipitate to obtain the alpha-aminoketone-stilbene sulfonium salt compound:
4. the production method according to claim 3, characterized in that: in the step (1), the catalyst is selected from palladium acetate/tri (o-methylphenyl) phosphine or tetrakis (triphenylphosphine) palladium dichloride; and/or the presence of a gas in the gas,
in the step (1), the reaction temperature is 60-150 ℃, and the reaction time is 6-24 h; and/or the presence of a gas in the gas,
in the step (1), the solvent is selected from acetonitrile, tetrahydrofuran or N, N-dimethylformamide; and/or the presence of a gas in the gas,
in the step (2), the reaction temperature is 40-80 ℃, and the reaction time is 5-24 h; and/or the presence of a gas in the gas,
in the step (3), the reaction temperature is 25-30 ℃, and the reaction time is 30-40 min.
5. A method for preparing α -aminoketone-stilbene sulfonium salt compound according to claim 1, which comprises the following steps: which comprises the following steps:
(1) containing R1Reacting substituted benzylthio substituted styrene with alpha-amino ketone substituted bromobenzene in a solvent under the action of a catalyst to obtain a stilbene conjugate (I) -a:
(2) and dissolving the stilbene conjugate (I) -a and water with equivalent weight in acetonitrile solution, adding dimethyl sulfate for reaction, and filtering to obtain a precipitate (I) -b:
(3) dissolving the precipitate (I) -b in an equivalent amount of an aqueous sodium hydroxide solution, adjusting the pH of the resulting solution to 9.0 by adding sodium carbonate in portions, reacting, extracting, and drying to obtain a sulfonium salt intermediate (I) -c:
(4) adding MX into the sulfonium salt intermediate (I) -c, wherein M is selected from potassium ion or sodium ion, and X-Selected from trifluoromethanesulfonyl or tetrafluoroborate; precipitating to obtain alpha-aminoketone-diphenylethyleneSulfonium salt compounds:
6. the method of claim 5, wherein: in the step (1), the catalyst is selected from one of palladium acetate/tri (o-methylphenyl) phosphine or tetra (triphenylphosphine) palladium dichloride; and/or the presence of a gas in the gas,
in the step (1), the reaction temperature is 60-150 ℃, and the reaction time is 6-24 h; and/or the presence of a gas in the gas,
in the step (1), the solvent is selected from one of acetonitrile, tetrahydrofuran or N, N-dimethylformamide; and/or the presence of a gas in the gas,
in the step (2), the reaction temperature is 40-80 ℃, and the reaction time is 5-24 h; and/or the presence of a gas in the gas,
in the step (3), the reaction temperature is 25-30 ℃, and the reaction time is 30-40 min.
7. Use of an α -aminoketone-stilbenethinylsulfonium compound as defined in claim 1 as a radiation-curing photoinitiator.
8. Use according to claim 7, characterized in that: the light source of the radiation curing photoinitiator is selected from one of ultraviolet light and visible light.
9. Use according to claim 8, characterized in that: the radiation curing photoinitiator comprises 0.01-30 parts by weight of alpha-aminoketone-stilbene sulfonium salt compound and 100 parts by weight of ethylenically unsaturated compound.
10. Use according to claim 9, characterized in that: the radiation curing photoinitiator comprises 0.5-10 parts by weight of alpha-aminoketone-stilbene sulfonium salt compounds and 100 parts by weight of ethylenically unsaturated compounds.
11. Use according to claim 9, characterized in that: the ethylenically unsaturated compound refers to a compound or mixture in which the ethylenic bonds are crosslinked by radical polymerization.
12. Use according to claim 11, characterized in that: the ethylenically unsaturated compound is selected from a monomer, an oligomer or a prepolymer, or a mixture or a copolymer of the three, or an aqueous dispersion of the three.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1376662A (en) * | 2002-04-04 | 2002-10-30 | 湘潭大学 | Free radical and cation hybridized trigger for optical solidification and its preparing process and application |
| CN101943862A (en) * | 2010-09-17 | 2011-01-12 | 同济大学 | Sulfonium salt photo-acid generator using stilbene as main body and preparation method thereof |
| CN102958909A (en) * | 2010-06-28 | 2013-03-06 | 巴斯夫欧洲公司 | Metal free bleaching composition |
| CN103012227A (en) * | 2013-01-04 | 2013-04-03 | 同济大学 | Sulfonium salt photo-acid generator having high photo-acid generation quantum yield, and preparation method and application thereof |
-
2019
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1376662A (en) * | 2002-04-04 | 2002-10-30 | 湘潭大学 | Free radical and cation hybridized trigger for optical solidification and its preparing process and application |
| CN102958909A (en) * | 2010-06-28 | 2013-03-06 | 巴斯夫欧洲公司 | Metal free bleaching composition |
| CN101943862A (en) * | 2010-09-17 | 2011-01-12 | 同济大学 | Sulfonium salt photo-acid generator using stilbene as main body and preparation method thereof |
| CN103012227A (en) * | 2013-01-04 | 2013-04-03 | 同济大学 | Sulfonium salt photo-acid generator having high photo-acid generation quantum yield, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 双支化D-π-A结构硫鎓盐型阳离子光聚合引发剂的制备及其性能的研究;任强等;《 2013 年全国高分子学术论文报告会》;20131231;P68 * |
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