CN107778386A - Organic micromolecule catalyst for visible light catalytic polymerisation and preparation method thereof - Google Patents
Organic micromolecule catalyst for visible light catalytic polymerisation and preparation method thereof Download PDFInfo
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- CN107778386A CN107778386A CN201710997774.XA CN201710997774A CN107778386A CN 107778386 A CN107778386 A CN 107778386A CN 201710997774 A CN201710997774 A CN 201710997774A CN 107778386 A CN107778386 A CN 107778386A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 title abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 9
- 101710141544 Allatotropin-related peptide Proteins 0.000 claims abstract description 7
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims abstract description 7
- 238000005859 coupling reaction Methods 0.000 claims abstract description 6
- FDVVCYDXKLQMPI-UHFFFAOYSA-N 3,7-diphenyl-10h-phenothiazine Chemical class C=1C=C2NC3=CC=C(C=4C=CC=CC=4)C=C3SC2=CC=1C1=CC=CC=C1 FDVVCYDXKLQMPI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000004391 aryl sulfonyl group Chemical group 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 53
- 150000001875 compounds Chemical class 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 8
- 125000004185 ester group Chemical group 0.000 claims description 8
- 229910052711 selenium Inorganic materials 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 5
- 150000003254 radicals Chemical class 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 125000001424 substituent group Chemical class 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- 239000003999 initiator Substances 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- 239000011630 iodine Substances 0.000 claims 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- -1 perfluoroalkyl iodides Chemical class 0.000 abstract description 11
- 238000009826 distribution Methods 0.000 abstract description 9
- 238000005286 illumination Methods 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 229920001519 homopolymer Polymers 0.000 abstract description 2
- 230000000977 initiatory effect Effects 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 239000000376 reactant Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- MXFYYFVVIIWKFE-UHFFFAOYSA-N dicyclohexyl-[2-[2,6-di(propan-2-yloxy)phenyl]phenyl]phosphane Chemical compound CC(C)OC1=CC=CC(OC(C)C)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 MXFYYFVVIIWKFE-UHFFFAOYSA-N 0.000 description 12
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 10
- 238000013019 agitation Methods 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 235000010290 biphenyl Nutrition 0.000 description 7
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 229940125782 compound 2 Drugs 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
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- 230000003595 spectral effect Effects 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 230000005059 dormancy Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229910052755 nonmetal Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010257 thawing Methods 0.000 description 3
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 2
- PQMFVUNERGGBPG-UHFFFAOYSA-N (6-bromopyridin-2-yl)hydrazine Chemical compound NNC1=CC=CC(Br)=N1 PQMFVUNERGGBPG-UHFFFAOYSA-N 0.000 description 2
- APSMUYYLXZULMS-UHFFFAOYSA-N 2-bromonaphthalene Chemical class C1=CC=CC2=CC(Br)=CC=C21 APSMUYYLXZULMS-UHFFFAOYSA-N 0.000 description 2
- VGUWZCUCNQXGBU-UHFFFAOYSA-N 3-[(4-methylpiperazin-1-yl)methyl]-5-nitro-1h-indole Chemical compound C1CN(C)CCN1CC1=CNC2=CC=C([N+]([O-])=O)C=C12 VGUWZCUCNQXGBU-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HMKZOOYZHIBQOJ-UHFFFAOYSA-N (4-ethoxycarbonylphenoxy)boronic acid Chemical compound CCOC(=O)C1=CC=C(OB(O)O)C=C1 HMKZOOYZHIBQOJ-UHFFFAOYSA-N 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- WSEFYHOJDVVORU-UHFFFAOYSA-N 10-phenylphenothiazine Chemical class C12=CC=CC=C2SC2=CC=CC=C2N1C1=CC=CC=C1 WSEFYHOJDVVORU-UHFFFAOYSA-N 0.000 description 1
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000004768 bromobenzenes Chemical class 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 239000004744 fabric Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 150000002390 heteroarenes Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 150000007529 inorganic bases Chemical group 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
-
- 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
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention belongs to technical field of polymer chemistry, specially a kind of organic micromolecule catalyst for visible light catalytic polymerisation and preparation method thereof.The organic micromolecule catalyst of the present invention is 3,7 diphenyl phenothiazine compounds.The catalyst can be made by two step coupling reactions, the reachable visible-range of its UV absorption, and have the advantages that luminous power is strong, dosage is low, available under a variety of visible light sources, be easy to regulation and control reaction " ON/OFF ", suitable for the active free radical polymerization system of various photocontrols.Reacted under conditions of room temperature, visible ray illumination, obtain polymer.Initiation system includes RAFT, ATRP, aryl sulfonyl chloride and perfluoroalkyl iodides etc..It is controllable, narrow molecular weight distribution that relative molecular weight can be obtained under conditions of illumination（Methyl）Acrylate or（Methyl）The homopolymer or copolymer of acrylamide.
Description
Technical field
The invention belongs to technical field of polymer chemistry, and in particular to non-metal optical catalyst and preparation method thereof and should
With.
Background technology
Controllable free-radical polymerisation（CRP）There is very far-reaching development in Macroscopic single crystal.Light-operated active free radical polymerization
（photo-CRP）With the outside stimulus by " light ", "ON"/"Off" quickly starts and stopped obtaining the energy of Quality Initiative growth
Power, the synthesis strategy of this more " green " are applied in important active free radical polymerization method, such as reversible addition-disconnected
Split chain tra nsfer（RAFT）Polymerization, atom transferred free radical（ATRP）Polymerization etc..
The photochemical catalyst that the living free radical polymerization of visible light-inducing uses is concentrated mainly on ruthenium（Ru）And iridium（Ir）
Deng the complex of transition metal, this kind of catalyst can produce redox reaction by absorption/release photon, so as to efficiently
Catalytic polymerization.However, these transient metal complexes also have many shortcomings as catalyst, the post processing of polymerizate is answered
Miscellaneous, used most of catalyst is not easy to remove completely from product after reaction.In addition, the polymeric material prepared due to
Metal residual and exist toxicity or trigger polymer degradation reaction.Therefore, design that will not to residue in polymer and can efficient
The non-metal optical oxidation reduction catalyst tool of ground catalytic activity radical polymerization is of great significance.
Phenthazine is a kind of conventional photoelectric material, is a kind of heteroaromatic compound containing electron rich N and S, and it has
There is preferable redox reversible.Hawker groups are by 10- phenyl phenthazine（Periodical number：J. Am. Chem. Soc. 2014,
136,16096-16101, patent publication No.：US20170240660 A1）Photocatalyst applications are in light-operated ATRP.
10- phenyl phenthazine polymerize by Matyjaszewski seminar for acrylonitrile compound（Periodical number：ACS Macro
Lett. 2015, 4, 192−196）.Johnson seminar（Periodical number：ACS Macro Lett. 2015, 4, 566−
569）The RAFT that same catalyst is used for photocontrol polymerize.
However, 10- phenyl phenothiazine compounds are in UV light region（Less than 360 nm）Absorb substantially, more than 360 nm
The visible region absorption of wave-length coverage is very faint, is not used to effective progress in visible region catalytic polymerization.
As can be seen here, designed by deriving to phenthazine available under visible ray, absorption spectrum is wide, the efficient light of catalytic polymerization effect
Catalyst tool is of great significance.
The present invention develops the significant visible ray oxidation reduction catalyst of a kind of catalytic effect, available for visible photocontrol
ATRP, RAFT, perfluoroalkyl iodides and aryl sulfonyl chloride trigger the active free radical polymerization of system.
The content of the invention
The invention aims to solve the deficiencies in the prior art, there is provided a kind of for visible light catalytic polymerisation
Organic micromolecule catalyst and preparation method thereof.
Organic micromolecule catalyst provided by the invention, is 3,7- diphenyl phenothiazine compounds, its structure such as following formula
(I）It is shown：
,
Wherein, Z is sulphur atom or selenium atom；R is hydrogen atom, alkyl or ester group；R ' be hydrogen atom, aryl it is polysubstituted or single
Substituted radical, substituent are halogen atom, hydrogen atom, alkyl or alkoxy.
The present invention also provides above-mentioned organic micromolecule catalyst（3,7- diphenyl phenothiazine compounds）Preparation method,
Comprise the following steps that：
Step（1）, in a heated condition, in a solvent, will be such as formula（III）Shown compound with such as formula（II）Shown phenyl
Boric acid carries out coupling reaction, is made such as formula（IV）Shown photochemical catalyst intermediate；
Formula（III）In, Z is sulphur atom or selenium atom；
Formula（II）In, R is hydrogen atom, alkyl or ester group；
Wherein, the reaction time is 0.5 ~ 8 hour；Formula（III）Compound and formula（II）The mol ratio of phenylboric acid is 1:1~4；Instead
It is 20 ~ 150 DEG C to answer temperature.
Step（2）, in a heated condition, will be such as formula in a solvent（IV）Shown midbody compound is coupled
Reaction, it is made such as formula（I）Shown photochemical catalyst；
Formula（IV）In, Z is sulphur atom or selenium atom；
R is hydrogen atom, alkyl or ester group；
Formula（IV）In, X is chlorine atom or bromine atoms；R ' is hydrogen atom, the polysubstituted or monosubstituted group of aryl, and substituent is halogen
Plain atom, hydrogen atom, alkyl or alkoxy.
Wherein, the reaction time is 0.5 ~ 8 hour；Reaction temperature is 20 ~ 150 DEG C.
In the present invention, described solvent is organic solvent and/or inorganic solvent.
Described organic solvent can be single organic solvent, or the organic solvent of mixing.
Described solvent is selected from the one or more of toluene, N,N-dimethylformamide, toluene, 1,4- dioxane and water
The mixed solvent of solvent.
Above-mentioned photochemical catalyst provided by the invention, the reachable visible-range of its UV absorption；And there is luminous power
By force, dosage it is low, available under a variety of visible light sources, be easy to regulation and control reaction " ON/OFF " the advantages that, suitable for various photocontrols
Active free radical polymerization system.
Above-mentioned photochemical catalyst provided by the invention can be used for preparing polymer under visible light.Specifically, in room temperature
（10–40℃）Condition, it is seen that light illumination（Such as LED or electricity-saving lamp CFL are light source）Under conditions of reacted,
Obtain polymer.
Wherein, the light source of described visible ray can be purple light, blue light, green glow, the one or more of mixed white light.Specifically
For, can be sunlight, LED light, CFL lamps light or FSL lamp light etc..
When preparing polymer, system is triggered to include RAFT, ATRP, aryl sulfonyl chloride and perfluoroalkyl iodides etc..In illumination
Under conditions of can to obtain relative molecular weight controllable, narrow molecular weight distribution（Methyl）Acrylate or（Methyl）Acrylamide it is equal
Polymers or copolymer.
Compared with prior art, its advantage is the present invention：
The present invention obtains a series of novel photochemical catalyst of structures by reacting in step and step by step（I）.The synthesis technique of the present invention
Simply, efficiently, yield is high, and meets atom economy principle.The photochemical catalyst of the present invention is used to prepare polymer under visible ray.
Brief description of the drawings
Fig. 1 is the monocrystalline figure of compound 6.
Fig. 2 is compound 71H NMR。
Fig. 3 is the ultra-violet absorption spectrum of compound 7.
Fig. 4 is the GPC spectrograms of application example 3.
Embodiment
With reference to embodiment, the present invention is described in further detail.
It will be understood to those of skill in the art that the following example is merely to illustrate the present invention, and it should not be regarded as limiting this hair
Bright scope.In the examples where no specific technique or condition is specified, according to the technology or condition described by document in the art
Or carried out according to product description.The unreceipted production firm person such as agents useful for same, instrument, it is that can be obtained by buying
Conventional products.
Raw material of the present invention can be prepared or obtained by commercially available prod by the known method of this area.
The conventional method of 3,7- diphenyl phenothiazine compounds synthesis of the invention explained further below, but the present invention 3,
The preparation method of 7- diphenyl phenothiazine compounds is not limited to this.
The method for synthesizing the photochemical catalyst of the present invention is as follows：
Intermediate（IV）Synthesis is as follows：
Step 1, by formula（III）The compound and formula of structure（II）The phenylboric acid class compound of structure in appropriate solvent, have/
Without catalysts conditions, organic/inorganic alkali, heating response.After the completion of reaction, washed or recrystallized with appropriate solvent and prepare 3,
7- diphenyl phenothiazine compounds（IV）, it is specific to react as follows：
Formula（III）In, Z is sulphur atom or selenium atom；
Formula（II）In, R is hydrogen atom, alkyl or ester group;
Step（2）, in a heated condition, in a solvent, with/without catalysts conditions, organic/inorganic alkali will be such as formula（IV）It is shown
Midbody compound carry out coupling reaction, be made such as formula（I）Shown photochemical catalyst；
Formula（IV）In, Z is sulphur atom or selenium atom；R is hydrogen atom, alkyl or ester group；Formula（IV）In, X is that chlorine atom or bromine are former
Son；R ' is hydrogen atom, the polysubstituted or monosubstituted group of aryl, and substituent is halogen atom, hydrogen atom, alkyl or alkoxy.
In reaction, catalyst does not make concrete regulation, is often palladium, tetra-triphenylphosphine palladium or palladium bichloride.Alkali is not made specifically
Regulation, often it is inorganic base or organic base.Solvent does not make concrete regulation, be often ethanol, acetone, methanol, water, ethyl acetate, chloroform,
Dichloromethane,N,NOne or more of solvents in-dimethylformamide, tetrahydrofuran, toluene, 1,4- dioxane, acetonitrile
Mixed solvent, reaction temperature do not make concrete regulation, preferably 90 ~ 150 DEG C；Reaction time does not make concrete regulation, is often 0.5 ~ 8
Hour.The washed leaching solid of evaporation solvent after reaction completely.Product recrystallizes or washing separation solvent does not make concrete regulation,
Often it is methanol and mixed solvent, the ethanol of toluene.
Formula（III）And formula（IV）Compound be it is known, it is commercially available or can be prepared by known method.
In reaction, for 1 mol formula（III）Compound, formula（II）The dosage of compound is preferably 1.2 ~ 2 mol.Instead
The yield answered is often greater than 90%.For 1 mol formula（IV）Compound, formula（VI）The dosage of compound is preferably 1.2 ~ 2 mol.
The yield of reaction is often greater than 90%.
There is no specific requirement for the drying means present invention of product of the present invention, drying can be used, spontaneously dried, infrared lamp
The drying means such as lower drying.
The present invention is described in detail with reference to part specific embodiment.These embodiments are merely to illustrate the present invention,
Rather than limitation the scope of the present invention.Preparation scheme in embodiment is only preferred scheme, but the invention is not limited in excellent
Select preparation scheme.
Part I synthetic example
First, formula（IV）The synthesis of photochemical catalyst intermediate
Embodiment 1：Synthesize 3,7- diphenyl -10H- phenthazine（Compound 1）
The bromo- 10H- phenthazine of 3,7- bis- is added in 100 mL Schleck bottles（5 mmol, 1.77 g）, tetra-triphenylphosphine palladium
（0.135 mmol, 156 mg）, phenylboric acid（15 mmol, 1.83 g）And Anhydrous potassium carbonate（15 mmol, 2.07 g）
Afterwards, toluene is added（25 mL）, Isosorbide-5-Nitrae-dioxane（25 mL）And water（1ml）, under nitrogen atmosphere, 110 DEG C are reacted 8 hours.It is cold
But to room temperature, 100 ml water are added, after being extracted with 100 ml ethyl acetate, with anhydrous sodium sulfate drying, after removing solvent under reduced pressure
Recrystallized with toluene and methanol, washed after filtering with a small amount of ethanol, obtain the g of yellow solid 1.47, be dried in vacuo product 3,7- hexichol
Base -10H- phenthazine（Compound 1）, yield 84%.Fusing point：275.5–276.7℃.
Spectral data is：1H NMR (400 MHz, DMSO-d 6) δ: 8.85 (br, 1H), 7.58–7.60 (m,
4H), 7.39–7.43 (m, 4H), 7.25–7.34 (m, 6H), 6.78 (d, J = 8.3 Hz, 2H); 13C NMR
(100 MHz, DMSO-d 6) δ: 141.4, 139.6, 134.2, 129.3, 127.3, 126.4, 126.2, 124.6,
117.3, 115.3。
Embodiment 2：Double (4- the butyl phenyls) -10H- phenthazine of 3,7-（Compound 2）
The bromo- 10H- phenthazine of 3,7- bis- is added in 100 milliliters of Schleck bottles（5 mmol, 1.77 g）, tetra-triphenylphosphine palladium
（0.135 mmol, 156 mg）,（4- butyl phenyls）Boric acid（15 mmol, 2.65 g）And Anhydrous potassium carbonate（15 mmol,
2.07 g）Afterwards, toluene is added（25 mL）, Isosorbide-5-Nitrae-dioxane（25 mL）And water（1 ml）, under nitrogen atmosphere, 110 DEG C of reactions 8
Hour.Room temperature is cooled to, adds 100 ml water, after being extracted with 100 ml ethyl acetate, with anhydrous sodium sulfate drying, solvent is evaporated off
Recrystallized with toluene and methanol, washed after filtering with a small amount of ethanol afterwards, obtain the g of yellow solid 1.81, be dried in vacuo product 3,7- is double
(4- butyl phenyls) -10H- phenthazine（Compound 2）, yield 78%.Fusing point：281.3–282.7℃.
Spectral data is：1H NMR (400 MHz, Acetone-d6) δ: 8.04 (br, 1H), 7.49–7.57
(m, 4H), 7.25–7.31 (m, 8H), 6.81 (d, J = 8.2 Hz, 2H), 2.63–2.67 (m, 4H),
1.59–1.67 (m, 4H), 1.30–1.41(m, 4H), 0.95 (t, J = 7.3 Hz, 6H); 13C NMR (100
MHz, DMSO-d6) δ: 141.4, 141.2, 137.0, 134.2, 129.2, 126.0, 124.4, 117.8,
117.2, 115.2, 34.9, 33.6, 22.2, 14.3; HRMS (TOF ES+): m/z calcd for C32H34NS+
[M+H]+, 464.2406; found, 464.2410。
Embodiment 3：Synthesize double (4- (tert-butyl group) the phenyl) -10H- phenthazine of 3,7-（Compound 3）
The bromo- 10H- phenthazine of 3,7- bis- is added in 100 milliliters of Schleck bottles（5 mmol, 1.77 g）, four triphenylphosphines
Palladium（0.135 mmol, 156 mg）, (4- (tert-butyl group) phenyl) boric acid（15 mmol, 2.65 g）And Anhydrous potassium carbonate（15
mmol, 2.07 g）Afterwards, toluene is added（25 mL）, Isosorbide-5-Nitrae-dioxane（25 mL）And water（1 mL）, under nitrogen atmosphere, 110
DEG C reaction 8 hours.It is cooled to room temperature, adds 100 mL water, after being extracted with 100 mL ethyl acetate, with anhydrous sodium sulfate drying,
Recrystallized with toluene and methanol after solvent is evaporated off, washed after filtering with a small amount of ethanol, obtain the g of yellow solid 1.88, vacuum drying production
Double (4- the butyl phenyls) -10H- phenthazine of product 3,7-（Compound 3）, yield 81%.Fusing point：320.0–319.5℃.
Embodiment 4：Synthesize 4,4'- (10H- phenthazine -3,7- diyls) dibenzoic acid diethylester（Compound 4）
The bromo- 10H- phenthazine of 3,7- bis- is added in 100 milliliters of Schleck bottles（5 mmol, 1.77 g）, tetra-triphenylphosphine palladium
（0.135 mmol, 156 mg）, (4- (ethoxy carbonyl) phenyl) boric acid (15 mmol, 2.91 g）And Anhydrous potassium carbonate
（15 mmol, 2.07 g）Afterwards, toluene is added（25 mL）, Isosorbide-5-Nitrae-dioxane（25 mL）And water（1 mL）, in blanket of nitrogen
Under, 110 DEG C are reacted 8 hours.Room temperature is cooled to, adds 100 mL water, after being extracted with 100 mL ethyl acetate, uses anhydrous sodium sulfate
Dry, recrystallized with toluene and methanol after solvent is evaporated off, washed after filtering with a small amount of ethanol, obtain the g of yellow solid 2.03, vacuum is done
Double (4- the butyl phenyls) -10H- phenthazine of dry product 3,7-（Compound 4）, yield 82%.Fusing point：198.2–200.2℃.
Spectral data is：1H NMR (400 MHz, DMSO-d6) δ: 9.03 (br, 1H), 7.96–7.99 (m,
4H), 7.75–7.77 (m, 4H), 7.42 (dd, J = 8.3, 2.1 Hz, 2H), 7.36 (d, J = 2.1 Hz,
2H), 6.78 (d, J = 8.3 Hz, 2H), 4.33 (q, J = 7.1 Hz, 4H), 1.34 (t, J = 7.1 Hz,
6H)。
2nd, photochemical catalyst formula（I）Synthesis
Embodiment 5：Synthesize 10- (4- butyl phenyls) -3,7- diphenyl -10H- phenthazine（Compound 5）
NaO is added in the Schleck equipped with magnetic agitationtBu（134 mg, 1.4mmol）, compound 1（351 mg, 1
mmol）, RuPhos Precat（14 mg, 0.02 mmol, 2 mol%）And RuPhos（8mg, 0.02 mmol, 2
Mol%）.Bottle is vacuumized and backfilled 3 times with nitrogen, then adds dry Isosorbide-5-Nitrae-dioxane（1 mL）.It is eventually adding 4- fourths
Bromide benzene（298 mg, 1.4 mmol）.Then it reacts 5 hours in 110 DEG C of oil bath.Then bottle is cooled to room temperature,
Diluted with ethyl acetate, with water, salt water washing, use MgSO4Dry, and use column chromatography（0.5% ethyl acetate/petroleum ether）It is pure
Change.Product is dried under reduced pressure, obtains 458 mg yellow solids（95% yield）.Fusing point：65.1–67.2℃.
Embodiment 6：Synthesize double (4- the butyl phenyls) -10- phenyl -10H- phenthazine of 3,7-（Compound 6）
NaO is added in the Schleck equipped with magnetic agitationtBu（134 mg, 1.4 mmol）, compound 2（463.2 mg, 1
mmol）, RuPhos Precat（14 mg, 0.02 mmol, 2 mol%）And RuPhos（8 mg, 0.02 mmol, 2
Mol%）.Bottle is vacuumized and backfilled 3 times with nitrogen, then adds dry Isosorbide-5-Nitrae-dioxane（1 mL）.It is eventually adding bromobenzene
（219.8 mg, 1.4 mmol）.Then the bottle is stirred 5 hours in 110 DEG C of oil bath.Then bottle is cooled to room
Temperature, diluted with ethyl acetate, with water, salt water washing, MgSO4Dry, and use column chromatography（1% toluene/petroleum ether）Purifying.Will
Product is dried under reduced pressure, and obtains 521.5 mg yellow solids（97% yield）.Fusing point：78.5–80.2℃.
Spectral data is：1H NMR (400 MHz,Acetone-d6) δ: 7.73–7.77 (m, 2H), 7.60–
7.64 (m, 1H), 7.49 –7.52 (m, 5H), 7.35–7.35 (m, 2H), 7.24– 7.26 (m, 4H),
7.18– 7.21 (m, 2H), 6.26 (d, J = 8.6 Hz, 2H), 2.64 (t, J = 7.6 Hz, 4H), 1.58–
1.66 (m, 4H), 1.33–1.42 (m, 4H), 0.94 (t, J = 7.4 Hz, 6H); 13C N MR (100 MHz,
Acetone-d6) δ: 143.0, 141.7, 140.9, 136.8, 135.4, 131.1, 130.9, 128.9, 128.6,
126.0,125.2, 124.4, 120.0, 116.2, 34.9, 33.6, 22.1, 13.3; IR (neat, cm-1):
3022, 2954, 2924, 2854, 1589, 1475, 1382, 1308, 1254, 1153, 1072, 938, 880,
807, 733, 699, 673, 616, 589, 530, 501; HRMS (TOF ES+): m/z ca lcd for C38H36NS+ [M]+, 539.2647; found, 539.2640。
Embodiment 7：Synthesize double (4- the butyl phenyls) -10H- phenthazine of 10- ([1,1'- biphenyl] -4- bases) -3,7-（Chemical combination
Thing 7）
4- bromo biphenyls are added in the Schleck equipped with magnetic agitation（326 mg, 1.4 mmol）, NaOtBu（134 mg, 1.4
mmol）, compound 2（463.2 mg, 1 mmol）, RuPhos Precat（14 mg, 0.02 mmol, 2 mol%）With
RuPhos（8 mg, 0.02 mmol, 2 mol%）.Bottle is vacuumized and backfilled 3 times with nitrogen, then adds dry Isosorbide-5-Nitrae-dioxy
Six rings（1 mL）.Then the bottle is stirred 5 hours in 110 DEG C of oil bath.Then bottle is cooled to room temperature, with acetic acid second
Ester dilutes, with water, salt water washing, MgSO4Dry, and use column chromatography（1% toluene/petroleum ether）Purifying.By product under reduced pressure
Dry, obtain 592mg green solids（96% yield）.Fusing point：133.0–134.6℃.
Spectral data is：1H NMR (400 MHz, DMSO-d6) δ: 8.00 (d, J = 8.0 Hz, 2H),
7.81 (d, J = 7.6 Hz, 2H), 7.39–7.58 (m, 11H), 7.22–7.26 (m, 6H), 6.29 (d, J =
8.6 Hz, 2H), 2.59 (t, J = 7.7 Hz, 4H), 1.52–1.60 (m, 4H), 1.29–1.36 (m, 4H),
0.90 (t, J = 7.3 Hz, 6H); 13C NMR (100 MHz, DMSO-d6) δ: 142.8, 141. 8, 140.3,
139.7, 136.6, 135.3, 131.0, 129.7, 129.5, 129.2, 128.3, 127.3, 126.4, 126.3,
125.8, 124.8, 12 0.4, 117.0, 34.9, 33.4, 22.2,14.2 ; IR (neat, cm-1): 3025,
2923, 2859, 1631, 1468, 1379, 1308, 1288, 1 252, 1103, 843, 810, 728, 699,
471; HRMS (TOF ES+): m/z calcd for C44H42NS+ [M+H]+, 616.3032; found, 616.3029。
Embodiment 8：Synthesize double (4- butyl phenyls) -10- (naphthalene -2- the bases) -10H- phenthazine of 3,7-（Compound 8）
2- bromonaphthalenes are added in the Schleck equipped with magnetic agitation（290 mg, 1.4 mmol）, NaOtBu（134mg, 1.4
mmol）, compound 2（463.2 mg, 1 mmol）, RuPhos Precat（14 mg, 0.02 mmol, 2 mol%）With
RuPhos（8 mg, 0.02 mmol, 2 mol%）.Bottle is vacuumized and backfilled 3 times with nitrogen, then adds dry Isosorbide-5-Nitrae-dioxy
Six rings（1 mL）.Then the bottle is stirred 5 hours in 110 DEG C of oil bath.Then bottle is cooled to room temperature, with acetic acid second
Ester dilutes, with water, salt water washing, MgSO4Dry, and use column chromatography（1% toluene/petroleum ether）Purifying.By product under reduced pressure
Dry, obtain 561mg greenish yellow solids（95% yield）.Fusing point：85.1–86.7℃.
HRMS (TOF ES+): m/z calcd for C42H40NS+ [M+H]+, 590.2876; found,
590.2874.
Embodiment 9：Synthesize double (4- butyl phenyls) -10- (- 1- the bases) -10H- phenthazine of 3,7-（Compound 9）
The 2- bromonaphthalenes in embodiment 8 are replaced to be reacted to obtain 685 mg orange solids with 1- bromos（95% yield）.Fusing point：
116.4–118.0℃。
Embodiment 10：Synthesize 3,7,10- tri- (4- (tert-butyl group) phenyl) -10H- phenthazine（Compound 10）
4- tert-butyl group bromobenzenes are added in the Schleck equipped with magnetic agitation（298 mg, 1.4 mmol）, NaOtBu（134 mg,
1.4 mmol）, compound 2（463.2 mg, 1 mmol）, RuPhos Precat（14 mg, 0.02 mmol, 2 mol%）With
RuPhos（8 mg, 0.02 mmol, 2 mol%）.Bottle is vacuumized and backfilled 3 times with nitrogen, then adds dry Isosorbide-5-Nitrae-dioxy
Six rings（1 mL）.Then the bottle is stirred 5 hours in 110 DEG C of oil bath.Then bottle is cooled to room temperature, with acetic acid second
Ester dilutes, and with water, salt water washing, uses MgSO4Dry, and use column chromatography（1% toluene/petroleum ether）Purifying.Product is being depressurized
Lower drying, obtain 555 mg green solids（94% yield）.Fusing point：281.1–282.8℃.
Embodiment 11：Synthesize 4,4'- (10- ([1,1'- biphenyl] -4- bases) -10H- phenthazine -3,7- diyls) hexichol first
Diethyl phthalate（Compound 11）
4- bromo biphenyls are added in the Schleck equipped with magnetic agitation（326 mg, 1.4 mmol）, NaOtBu（134 mg, 1.4
mmol）, compound 3（496 mg, 1 mmol）, RuPhos Precat（14 mg, 0.02 mmol, 2 mol %）With
RuPhos（8 mg, 0.02 mmol, 2 mol%）.Bottle is vacuumized and backfilled 3 times with nitrogen, then adds dry Isosorbide-5-Nitrae-dioxy
Six rings（1 mL）.Then the bottle is stirred 5 hours in 110 DEG C of oil bath.Then bottle is cooled to room temperature, with acetic acid second
Ester dilutes, with water, salt water washing, MgSO4Dry, and use column chromatography（1% ethyl acetate/petroleum ether）Purifying.Product is being subtracted
Drying is depressed, obtains 589 mg green solids（91% yield）.
HRMS (TOF ES+): m/z calcd for C42H40NS+ [M+H]+, 648.220; found,
648.2204.
Embodiment 12：Synthesize 4,4'- (10- (naphthalene -2- bases) -10H- phenthazine -3,7- diyls) dibenzoic acid diethylester（Chemical combination
Thing 12）
The 4- bromo biphenyls in embodiment 10 are replaced to be reacted to obtain 577 mg green solids with 2- bromonaphthalenes（93% yield）.1H
NMR (400 MHz, DMSO-d6) δ: 8.26 (d, J = 8.6 Hz, 1H), 8.04–8.11 (m, 3H), 7.94–
7.96 (m, 4H), 7.49–7.72 (m, 9H), 6.18 (d, J = 8.5 Hz, 2H), 4.31 (q, J = 7.0
Hz, 4H), 1.31 (t, J = 6.9 Hz, 6H)。
Intermediate structure synthesized by the present invention is as shown in table 1：
The intermediate structure formula of table 1（Lower section numeral is embodiment compound number）
。
Photocatalyst structure synthesized by the present invention is as shown in table 2：
The photocatalyst structure formula of table 2（Lower section numeral is embodiment compound number）
。
The photocatalysis effect of Part II the compounds of this invention
By the present invention in that with invention non-metal optical catalyst, under visible light, respectively to three class living radical primosomes
System（ATRP, RAFT and perfluoroalkyl iodides）, with（Methyl）Acrylate or（Methyl）Acrylic acid amides are monomer, are carried out light-operated
Active free radical polymerization.
As a result show that the catalyst used in the present invention is changed into excitation state under illumination effect from ground state.Urging in excitation state
With dormancy kind redox reaction can occur for agent, so as to generate alkyl diradical, further trigger the chain of monomer to increase instead
Should.In addition, the photochemical catalyst in oxidation state, can occur again with living chain redox reaction generation ground state catalyst with
And dormancy kind.Reversible balance between this dormancy kind and growing chain free radical causes polymerization system to have controllability, and finally
Obtain homopolymer and block copolymer.
Application Example 1
Methyl methacrylate is added in the bottle equipped with magnetic stir bar（206 μ L, 2.00 mmol）, compound 5（0.1
Mol%）And DMA（1 mL）.Reactant mixture is freezed into-pumping-defrosting-nitrogen backfill circulation three times.Injected by syringe
α-bromo-acid ethyl ester（0.02 mmol）.Reactant is stirred vigorously under the irradiation of 13 W purple LEDs, while uses compressed air
Cool down to keep environment temperature.Reaction is carried out 24 h, pass through1The conversion ratio for the MMA that H NMR are surveyed is 52%, sample volume
Than for 7:The mixing liquid precipitate of 3 first alcohol and water three times, is dried under vacuum to constant weight, obtains white powder.GPC measures polymerization
The molecular weight of thingM n=6223 and molecular weight distributionM w/M n = 1.26.The above-mentioned white PMMA of 75 mg are taken to trigger as macromolecular
Agent, methyl acrylate will be added in the bottle equipped with magnetic agitation（91 μ L, 1.00 mmol）, compound 7（0.1 mol%）With
DMF（1 mL）.Reactant mixture is freezed into-pumping-defrosting-nitrogen backfill circulation three times.It is acute under the irradiation of 13 W white led lamps
Strong reaction stirred, while cooled down with compressed air to keep environment temperature.Reaction is carried out 4 h, pass through1What H NMR were surveyed
MA conversion ratio is the molecular weight that 63%, GPC measures polymerM n=12158 and molecular weight distributionM w/M n = 1.57。
Application Example 2
N-butyl acrylate will be added in bottle equipped with magnetic stir bar（286 μ L, 2.00 mmol）, paratoluensulfonyl chloride
（0.02 mmol）, compound 8（0.1 mol%）And DMF（1 mL）.Reactant mixture is freezed into-pumping-defrosting-nitrogen time
Fill out circulation three times.Reactant is stirred vigorously under blue LED lamp irradiation, while is cooled down with compressed air to keep environment temperature.
Reaction is carried out 5 h, pass through1What H NMR were surveyednBA conversion ratio is 54%, and sample volume ratio is 10:1 acetone and
The mixing liquid precipitate of ether three times, is dried under vacuum to constant weight.GPC measures the molecular weight of polymerM n =7265 and molecular weight point
ClothM w/M n = 1.50.Take the above-mentioned P of 100 mgnBA will be equipped with magnetic agitation bottle and add as macromole evocating agentN,N- two
Methacrylamide（113 μ L, 1.00 mmol）, compound 7（0.1 mol%）And DMF（1 mL）.Reactant mixture is cold
Jelly-pumping-defrosting-nitrogen backfill circulation is three times.Reactant is stirred vigorously under the irradiation of 13 W white led lamps, while with compressing
Air is cooled down to keep environment temperature.Reaction is carried out 4 h, pass through1The conversion ratio for the DMA that H NMR are surveyed measures for 85%, GPC
To the molecular weight of polymerM n =20175 and molecular weight distributionM w/M n = 1.77。
Application Example 3
Methyl acrylate will be added in bottle equipped with magnetic stir bar（181 μ L, 2.00 mmol）, 2- (((own sulfenyl) sulphur
Generation) thio) ethyl propionate（0.02 mmol）, compound 9（0.1 mol%）And DMSO（1 mL）.Reactant mixture is cold
Jelly-pumping-defrosting-nitrogen backfill circulation is three times.Reactant is stirred vigorously under blue LED lamp irradiation, while uses compressed air
Cool down to keep environment temperature.Reaction is carried out 2h, pass through1The conversion ratio for the MA that H NMR are surveyed is 54%, sample volume ratio
For 10:The mixing liquid precipitate of 1 first alcohol and water three times, is dried under vacuum to constant weight.GPC measures the molecular weight of polymerM n
=4647 and molecular weight distributionM w/M n = 1.19.The above-mentioned PMA of 58 mg are taken as macromole evocating agent, by equipped with magnetic agitation
Added in bottlenBA（143 μ L, 1.00 mmol）, compound 7（0.1 mol%）And DMF（1 mL）.By reactant mixture with three
Secondary freezing-pumping-defrosting thaw cycles degassing.Then bottle is backfilled with nitrogen, acutely stirred under the irradiation of 13 W white led lamps
Reactant is mixed, while is cooled down with compressed air to keep environment temperature.Reaction is carried out 3 h, pass through1What H NMR were surveyednBA's
Conversion ratio is the molecular weight that 90%, GPC measures polymerM n=13940 and molecular weight distributionM w/M n = 1.41。
Application Example 4
Methyl acrylate will be added in bottle equipped with magnetic agitation（181 μ L, 2.00 mmol）, perfluor butyl iodide（0.02
mmol）, compound 11（0.1 mol%）And DMSO（1 mL）.By reactant mixture freezing freezing-pumping-defrosting solution three times
Freeze circulating degasification.Reactant is stirred vigorously under white led lamps irradiation, while is cooled down with compressed air to keep environment temperature.
Reaction is carried out 10 h, pass through1 The conversion ratio for the MA that H NMR are surveyed is 62%, and sample volume ratio is 10:1 acetone and
The mixing liquid precipitate of ether three times, is dried under vacuum to constant weight.GPC measures the molecular weight of polymerM n=7432 and molecular weight
DistributionM w/M n = 1.43.The above-mentioned PMA of 104 mg are taken to be equipped with magnetic stirring bar bottle and add as macromole evocating agent
NiPAm（113 mg, 1.00 mmol）, compound 7（0.1 mol%）And DMSO（1 mL）.Reactant mixture use is cold three times
Jelly-pumping-defrosting thaw cycles degassing.Reactant is stirred vigorously under the irradiation of 13 W white led lamps, at the same it is cold with compressed air
But to keep environment temperature.Reaction is carried out 3 h, pass through1The conversion ratio for the NiPAm that H NMR are surveyed measures poly- for 90%, GPC
The molecular weight of compoundM n=16543 and molecular weight distributionM w/Mn = 1.56。
General principle, principal character and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (10)
1. it is 3,7- diphenyl phenothiazine compounds a kind of organic molecule photochemical catalyst, its structure such as following formula (I）It is shown：
,
Wherein, Z is sulphur atom or selenium atom；R is hydrogen atom, alkyl or ester group；R ' be hydrogen atom, aryl it is polysubstituted or single
Substituted radical, substituent are halogen atom, hydrogen atom, alkyl or alkoxy.
2. the preparation method of organic molecule photochemical catalyst as claimed in claim 1, it is characterised in that concretely comprise the following steps：
Step（1）, in a heated condition, in a solvent, will be such as formula（III）Shown compound with such as formula（II）Shown phenyl
Boric acid carries out coupling reaction, is made such as formula（IV）Shown photochemical catalyst intermediate；Its reaction equation is：
Formula（III）In, Z is sulphur atom or selenium atom；
Formula（II）In, R is hydrogen atom, alkyl or ester group；
Step（2）, in a heated condition, will be such as formula in a solvent（IV）Shown midbody compound carries out coupling reaction,
It is made such as formula（I）Shown photochemical catalyst；Its reaction equation is：
Formula（IV）In, Z is sulphur atom or selenium atom；
R is hydrogen atom, alkyl or ester group；
Formula（IV）In, X is chlorine atom or bromine atoms；R ' is hydrogen atom, the polysubstituted or monosubstituted group of aryl, and substituent is halogen
Plain atom, hydrogen atom, alkyl or alkoxy.
3. preparation method according to claim 2, it is characterised in that step（1）In, the reaction time is 0.5 ~ 8 hour；Formula
（III）Compound and formula（II）The mol ratio of phenylboric acid is 1:1~4；Reaction temperature is 20 ~ 150 DEG C.
4. preparation method according to claim 2, it is characterised in that step（2）In, the reaction time is 0.5 ~ 8 hour；Instead
It is 20 ~ 150 DEG C to answer temperature.
5. preparation method according to claim 2, it is characterised in that described solvent is organic solvent and/or inorganic molten
Agent.
6. preparation method according to claim 5, it is characterised in that described solvent is toluene, N, N- dimethyl formyls
Amine, toluene, 1,4- dioxane and water one or more of solvents mixed solvent.
7. organic molecule photochemical catalyst as claimed in claim 1 prepares the application in polymer under visible light.
8. the application described in claim 7, it is characterised in that the light source of described visible ray is purple light, blue light, green glow, is mixed
The one or more of white light.
9. application according to claim 7, it is characterised in that the light source of described visible ray be sunlight, LED light,
CFL lamps light or FSL lamp light.
10. application according to claim 7, it is characterised in that for initiator system it is RAFT, ATRP, perfluoroalkyl
The active free radical polymerization of iodine or aryl sulfonyl chloride.
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| CN115521478A (en) * | 2022-11-28 | 2022-12-27 | 广东工业大学 | Lanthanide MOF material for acidic pH sensing and preparation method and application thereof |
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