CN114907504A - Cross-linked chiral azobenzene polymer microsphere and intermediate and application thereof - Google Patents
Cross-linked chiral azobenzene polymer microsphere and intermediate and application thereof Download PDFInfo
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- CN114907504A CN114907504A CN202210472983.3A CN202210472983A CN114907504A CN 114907504 A CN114907504 A CN 114907504A CN 202210472983 A CN202210472983 A CN 202210472983A CN 114907504 A CN114907504 A CN 114907504A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 81
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000004005 microsphere Substances 0.000 title claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000004132 cross linking Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 10
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 13
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 230000006698 induction Effects 0.000 claims description 7
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 238000006359 acetalization reaction Methods 0.000 claims description 4
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 claims description 4
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 3
- 230000001939 inductive effect Effects 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 24
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 17
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical group [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 16
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- -1 styryl azobenzene Chemical compound 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000006378 damage Effects 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 239000012954 diazonium Substances 0.000 description 5
- 150000001989 diazonium salts Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 235000010288 sodium nitrite Nutrition 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- FCMCSZXRVWDVAW-UHFFFAOYSA-N 6-bromo-1-hexanol Chemical compound OCCCCCCBr FCMCSZXRVWDVAW-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 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
- 229910001516 alkali metal iodide Inorganic materials 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 3
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- SJWFXCIHNDVPSH-QMMMGPOBSA-N (2S)-octan-2-ol Chemical compound CCCCCC[C@H](C)O SJWFXCIHNDVPSH-QMMMGPOBSA-N 0.000 description 2
- PEXGTUZWTLMFID-UHFFFAOYSA-N 2-phenyldiazenylphenol Chemical compound OC1=CC=CC=C1N=NC1=CC=CC=C1 PEXGTUZWTLMFID-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 2
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 2
- 235000010703 Modiola caroliniana Nutrition 0.000 description 2
- 244000038561 Modiola caroliniana Species 0.000 description 2
- 229920003082 Povidone K 90 Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 2
- 150000008046 alkali metal hydrides Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Chemical group 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 150000008049 diazo compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
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- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
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- 239000000047 product Substances 0.000 description 2
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- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- LGZMUUBPTDRQQM-UHFFFAOYSA-N 10-Bromo-1-decanol Chemical compound OCCCCCCCCCCBr LGZMUUBPTDRQQM-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- WLODWTPNUWYZKN-UHFFFAOYSA-N 1h-pyrrol-2-ol Chemical class OC1=CC=CN1 WLODWTPNUWYZKN-UHFFFAOYSA-N 0.000 description 1
- SIJLYRDVTMMSIP-UHFFFAOYSA-N 4-Bromo-1-butanol Chemical compound OCCCCBr SIJLYRDVTMMSIP-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- GMXIEASXPUEOTG-UHFFFAOYSA-N 8-bromooctan-1-ol Chemical compound OCCCCCCCCBr GMXIEASXPUEOTG-UHFFFAOYSA-N 0.000 description 1
- 102100028292 Aladin Human genes 0.000 description 1
- 101710065039 Aladin Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
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- 230000002238 attenuated effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
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- 125000001309 chloro group Chemical group Cl* 0.000 description 1
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- 229920000891 common polymer Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 229920000075 poly(4-vinylpyridine) Polymers 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 239000011232 storage material Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/28—Condensation with aldehydes or ketones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/26—Nitrogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a cross-linking type chiral azobenzene polymer microsphere, an intermediate and application thereof, wherein the raw material of the cross-linking type chiral azobenzene polymer microsphere comprises a chiral polymer with a structure shown as a formula (I), and the cross-linking type chiral azobenzene polymer microsphere is obtained by mixing the raw materials and carrying out an acetal reaction; in formula (I), y: x is (0.1-50) to 1, a, b and c are independently selected from 2-15, R 1 Is cyano, C 1‑3 Alkyl or C 1‑3 The crosslinking type chiral azobenzene polymer microsphere not only can be obtained by polymerizing an achiral monomer, but also can recover the damaged chirality under the irradiation of visible light, thereby solving the technical problem that the chirality can be recovered only by high-temperature heating after the chirality is damaged in the prior art.
Description
Technical Field
The invention belongs to the technical field of functional polymer microspheres, and particularly relates to a polymer microsphere with controllable chirality and recoverable under visible light irradiation after chiral destruction, in particular to a cross-linked chiral azobenzene polymer microsphere and an intermediate and application thereof.
Background
Chiral polymer particles have received much attention as a special class of chiral materials due to their unique optical activities and large specific surface areas. Compared with common polymer particles, the chiral polymer particles have unique performance and potential application prospect in the fields of chiral identification, chiral separation and asymmetric catalysis. However, most of the chiral polymer particles reported in the past are directly prepared from chiral polymers or chiral helical polymers derived from chiral monomers, and the preparation methods have to use extremely high cost and limited kinds of chiral monomers, thereby limiting the preparation of the chiral polymer particles.
For this reason, there are currently available ways of preparing chiral-containing polymer particles from achiral monomers, specifically using: in the presence of chiral micromolecules, an initiator and a dispersing agent, styryl azobenzene achiral monomers are subjected to polymerization reaction in a solvent to obtain the chiral monodisperse azobenzene polymer microspheres.
However, it should be particularly noted that the above reported chiral polymer particles still have the following problems: after chiral destruction, the optical activity cannot be recovered in the absence of a chiral induction source, or after chiral destruction, the chirality can be recovered only by high-temperature heating, which seriously hinders further application of the chiral polymer particles.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a novel crosslinking type chiral azobenzene polymer microsphere which can be obtained by polymerizing an achiral monomer and can recover the damaged chirality under the irradiation of visible light.
The invention also provides an intermediate for preparing the cross-linked chiral azobenzene polymer microsphere.
The invention also provides a chiral material, which can be prepared by the crosslinked chiral azobenzene polymer microsphere, can realize the attenuation of chiral signals under the irradiation of ultraviolet light, can realize the recovery of the chiral signals under the irradiation of visible light, can be better applied to photoresponsive materials, and further increases the flexible applicability of the chiral azobenzene polymer microsphere in practice.
In order to achieve the purpose, the invention adopts a technical scheme that: a cross-linking type chiral azobenzene polymer microsphere is prepared through mixing raw materials, and carrying out acetal reaction;
in the formula (I), y: x is (0.1-50) to 1;
a. b and c are independently selected from 2-15, R 1 Is cyano, C 1-3 Alkyl or C 1-3 An alkoxy group.
According to some preferred and specific aspects of the invention, in formula (i), a, b, c are independently selected from 4, 5, 6, 7, 8, 9, 10.
According to some preferred and specific aspects of the invention, in formula (I), R 1 Is methyl, ethyl, methoxy or ethoxy.
According to some preferred aspects of the invention, in formula (i), y: x is (0.15-25): 1. Further, in formula (I), y: x is (0.15-15) to 1. Still further, in formula (I), y: x is (0.3-5): 1. In some embodiments of the invention, in formula (i), y: x ═ 0.3 to 3: 1. In some embodiments of the invention, in formula (i), y: x ═ 0.3 to 2: 1. In some embodiments of the invention, in formula (i), y: x ═ 0.3 to 1: 1.
Within the range, the invention can ensure better chirality and can also have chirality recovery under the irradiation of visible light.
According to some particular aspects of the invention, the structure of formula (i) is a combination of one or more compounds selected from the group consisting of:
according to some preferred aspects of the invention, the aldolisation reaction is carried out in the presence of aldehydes, including but not limited to formaldehyde.
According to some preferred aspects of the invention, the acetalization reaction is carried out in a first solvent in the presence of hydrochloric acid and formaldehyde.
According to some specific aspects of the invention, the first solvent includes, but is not limited to, petroleum ether.
According to some preferred aspects of the invention, the reaction temperature of the aldolisation reaction is in the range of 10-40 ℃. According to a particular aspect of the invention, the aldolisation reaction can be carried out at room temperature.
In some embodiments of the invention, the acetalization reaction is conducted under sealed conditions.
The invention provides another technical scheme that: an intermediate for preparing a cross-linked chiral azobenzene polymer microsphere, which is a chiral polymer with a structure shown in a formula (I):
in the formula (I), x, y, a, b, c and R 1 The definitions of (A) and (B) are as defined above.
The invention provides another technical scheme that: a method for preparing the intermediate, which comprises the following steps:
copolymerizing a compound shown in a formula (II) and a compound shown in a formula (III) in a second solvent in the presence of an initiator, a chiral induction source and a non-ionic dispersing agent to generate a chiral polymer with a structure shown in a formula (I);
in some preferred embodiments of the present invention, the mass ratio of the compound represented by the formula (II) to the compound represented by the formula (III) is 0.1-6: 1.
According to some specific aspects of the invention, the mass ratio of the compound represented by the formula (II) to the compound represented by the formula (III) is 1-6: 1.
According to some preferred aspects of the invention, the reaction temperature of the copolymerization is from 65 to 75 ℃.
In some embodiments of the invention, the copolymerization is carried out in an oxygen-free environment.
In some embodiments of the invention, the initiator is an azo initiator that is a combination of one or more selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, and dimethyl azobisisobutyrate.
In some embodiments of the invention, the chiral inducing source is a combination of one or more selected from chiral 2-octanol, chiral 2-hexanol, chiral 2-butanol
In some embodiments of the invention, the non-ionic dispersing agent is a combination of one or more selected from the group consisting of polyvinylpyrrolidone, poly 4-vinylpyridine, polyethylene glycol, and polyhydroxyethylmethacrylate.
In some embodiments of the invention, the second solvent is a combination of one or more selected from ethanol, methanol, propanol, butanol.
In the invention, in the initial stage of reaction, the compound shown in the formula (II) and the compound shown in the formula (III) form oligomer coalescence nucleation in the polymerization process, the oligomer coalescence nucleation is separated out from a solvent medium, relatively small nuclei are mutually coalesced to form polymer particles, and meanwhile, a dispersing agent existing in the system is adsorbed on the surfaces of the polymer particles to stabilize the particles; during the particle growth process, the polymer particles continuously capture the free small cores around, so that the particle size gradually increases, and the chiral polymer with the structure shown in the formula (I) is obtained under the action of the chiral induction source. According to the invention, the chiral polymer with the structure shown in the formula (I) can be a monodisperse polymer.
According to some preferred aspects of the invention, the compound of formula (iii) is prepared using the following synthetic route:
wherein n is 2-15, b and c are selected from n, and Y is chlorine or bromine.
In some embodiments of the present invention, the compound represented by formula (III-3) is a combination of one or more selected from the group consisting of 1-bromo-4-hydroxybutane, 1-bromo-6-hydroxyhexane, 1-bromo-8-hydroxyoctane, and 1-bromo-10-hydroxydecane.
In some embodiments of the present invention, the compound represented by formula (III-5) is prepared by reacting p-hydroxyphenylamine in a hydrochloric acid solution with an aqueous solution of sodium nitrite to obtain a diazonium salt solution of p-hydroxyphenylamine. Further, the reaction temperature was controlled to 0-5 ℃.
In some embodiments of the present invention, the compound represented by formula (III-4) is prepared by reacting a compound represented by formula (III-5) with phenol. Further, in the preparation process, phenol was dissolved in an aqueous sodium hydroxide solution, and then added dropwise to the aforementioned diazonium salt solution of p-hydroxyphenylamine, reacted, with the temperature of the reaction being controlled at 0-5 ℃.
In some embodiments of the present invention, the compound represented by formula (III-1) is prepared by reacting a compound represented by formula (III-4) with a compound represented by formula (III-3) in the presence of a base, in the presence of an alkali metal iodide, and in a third solvent.
Further, in the preparation of the compound represented by the formula (iii-1), the base is potassium carbonate, sodium bicarbonate, sodium hydroxide, etc., the alkali metal iodide is potassium iodide, sodium iodide, etc., and the third solvent includes, but is not limited to, N-Dimethylformamide (DMF).
Further, in the preparation of the compound represented by the formula (III-1), the reaction is controlled to be carried out at 75 to 85 ℃. According to a particular aspect of the invention, the controlled reaction is carried out under stirred reflux conditions.
In some embodiments of the present invention, the compound represented by formula (III) is prepared by reacting a compound represented by formula (III-1) with a compound represented by formula (III-2) in the presence of an alkali metal hydride and an alkali metal iodide in a fourth solvent.
Further, in the process of preparing the compound represented by the formula (iii), the alkali metal hydride includes, but is not limited to, sodium hydride, potassium hydride, etc., the alkali metal iodide may be potassium iodide, sodium iodide, etc., and the fourth solvent includes, but is not limited to, tetrahydrofuran, and may be anhydrous tetrahydrofuran.
Further, in the preparation of the compound represented by the formula (III), the reaction is controlled to be carried out at 45 to 55 ℃.
Further, in the production of the compound represented by the formula (iii), the compound represented by the formula (iii) is obtained in as high a yield as possible by controlling the amount of the raw material to be added and the separation means for post-treatment (for example, column chromatography, etc.), and the compound represented by the formula (iii) is isolated.
In some embodiments of the invention, the compounds of formula (II) are commercially available or may be prepared by conventional methods.
Preferably, the synthetic method of the compound shown in formula (II) of the invention can be used for preparing the diazo compound by taking nitrite and aniline compounds as raw materials; preparing azophenol compound by taking diazo compound and phenol as raw materials; preparing an azoalcohol compound by using an azophenol compound and a halohydrin compound as raw materials; the invention takes azo alcohol compound and p-halogen methyl styrene as raw materials to prepare styryl azobenzene achiral monomer, namely the compound shown in the formula (II). The reaction process can be represented as follows:
wherein a is selected from 2-15, R 1 Is cyano, C 1-3 Alkyl or C 1-3 Alkoxy, A is chlorine or bromine.
The invention provides another technical scheme that: the crosslinked chiral azobenzene polymer microsphere is applied to preparation of chiral materials, wherein the chiral materials realize the attenuation of chiral signals under the irradiation of ultraviolet light and the recovery of the chiral signals under the irradiation of visible light.
According to some preferred aspects of the invention, the chiral material is a photoresponsive material.
In some embodiments of the present invention, the photoresponsive material may be specifically an optical switch, an optical information storage material, and the like.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
in the research process, the inventor of the invention unexpectedly finds that when the compound shown as the formula (II) and the compound shown as the formula (III) are respectively used as achiral comonomers, chiral polymers with chirality can be copolymerized under the action of a chiral induction source, and terminal hydroxyl is introduced into a system, so that the characteristic of acetal crosslinking of the system is given. Particularly, after covalent crosslinking through an acetal reaction, the average size of the polyazo benzene polymer is reduced, other obvious changes do not exist, the chirality can be recovered through visible light illumination after being destroyed, and the technical problem that the chirality can be recovered only by high-temperature heating after being destroyed in the prior art is solved. In addition, the crosslinked chiral azobenzene polymer microsphere can not change the spherical shape of the azobenzene copolymer after the chirality is recovered, and the chirality of the azobenzene copolymer can be controlled by utilizing the controllability of the photoinduced property of the microsphere and adjusting the chirality of the azobenzene copolymer, so that the chirality of a chiral material can be controlled.
Drawings
FIG. 1 is a NMR spectrum of a monomer AzoMS in example 1;
FIG. 2 is a NMR spectrum of the monomer Azolols in example 2;
FIG. 3 is a diagram showing the appearance of a chiral polymer during polymerization at different monomer feed ratios;
FIG. 4A is a CD graph (A) of a chiral polymer after R-octanol induced polymerization at different monomer charge ratios;
FIG. 4B is a CD diagram (B) of a chiral polymer after S-octanol induced polymerization at different monomer charge ratios;
FIG. 5 is a graph showing the chiral recovery after chiral destruction of chiral polymers of different proportions after chiral fixation;
FIG. 6 is a hand cycle "on" and "off" CD test plot at a chiral fully recoverable scale;
FIG. 7 is a graph of the morphology of a chiral polymer after covalent cross-linking (a) and after ultraviolet (b) and visible light (c).
Detailed Description
In the following examples, the chemical reagents used were:
1-bromo-6-hydroxyhexane, Acros, 95%;
polyvinylpyrrolidone, PVPK90, J & K;
4-aminophenol, chinese petrochemical chemical agents limited, CP;
phenol, aladin, AR;
(R) - (-) -octanol, TCL, > 99%;
(S) - (+) -octanol, TCL, > 99%;
99.5% of methylene chloride, Jiangsu Qiangsheng functional chemistry GmbH;
anhydrous sodium sulfate, 98%, national drug group chemical reagents ltd;
ethyl acetate, 99.5%, Jiangsu Qiangsheng functional chemistry GmbH;
azobisisobutyronitrile (AIBN), chemically pure, Shanghai reagent IV plant, recrystallized twice before use;
petroleum ether, analytically pure, Jiangsu Qiangsheng functional chemistry GmbH;
p-chloromethylstyrene, 90%, Macklin, was purified using a short basic alumina column prior to use.
Concentrated hydrochloric acid, analytically pure, Jiangsu Qiangsheng functional chemistry GmbH;
aqueous formaldehyde solution, analytical grade, chemical reagents of the national pharmaceutical group, ltd.
Testing instruments and conditions:
CD spectrometer: j-1500 type of JASCO company of Japan, the test temperature is 25 ℃, a quartz cuvette with the caliber of 10mm is used, the scanning range is 250-600 nm, the scanning speed is 200nm/min, the bandwidth is 2nm, the response time is 2s, and the measuring optical distance is 1 nm;
nuclear magnetic resonance hydrogen spectrum ( 1 H-NMR): using a Bruker 300MHz NMR spectrometer with CDCl 3 With DMSO-d 6 The TMS is an internal standard, and the TMS is measured at room temperature;
SEM image: a cold field transmit HITACHI SU8010 shot was used.
The above-described scheme is further illustrated below with reference to specific examples; it is to be understood that these embodiments are provided to illustrate the general principles, essential features and advantages of the present invention, and the present invention is not limited in scope by the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.
Not specifically illustrated in the following examples, all starting materials are commercially available or prepared by methods conventional in the art.
Example 1: synthesis of achiral monomer containing styrene azobenzene (AzoMS)
Dissolving p-anisidine (12.3g,0.1mol) in 80mL of water at 0 ℃, adding 30mL of concentrated hydrochloric acid under stirring, and stirring for 30min at 0-5 ℃; dissolving sodium nitrite (7.0g,0.11mmol) in 30mL of deionized water, controlling the reaction temperature to be kept at 0-5 ℃, slowly dropwise adding a sodium nitrite solution into the reaction system for 30 minutes to finish dropwise adding; the temperature is kept at 0 ℃ all the time after the reaction is carried out for 1h, so that the diazonium salt solution of the p-methoxyaniline is obtained.
At a temperature of 0 deg.C, phenol (16.0g) was dissolved in 300mL of water, and NaOH (8.0g) and NaHCO were added 3 (8.4g), a phenol solution was obtained. The diazonium salt solution of p-anisidine obtained previously is then added dropwise to the above-mentioned phenol solution, with mechanical stirring, while still maintaining the temperature of 0 ℃. The solution gradually changed from colorless to yellow and finally to brown-yellow. And after the dropwise addition is finished for 30 minutes, reacting for 4 hours in the environment to obtain a yellowish turbid liquid, and performing suction filtration, water washing, drying, ethanol recrystallization, suction filtration and vacuum drying on the obtained turbid liquid to finally obtain the dark yellow compound 1.
Potassium carbonate (46.0g,0.33mol), compound 1(10.0g,0.044mol), 10mg of potassium iodide (KI), 100mL of DMF were added to a 500mL dry round bottom flask to dissolve, heated to 80 ℃ and stirred for 30 min; then 1-bromo-6-hydroxyhexane (11.9g,0.066mol) is dissolved in 30mL DMF, slowly added into a round-bottom flask, stirred and refluxed at 80 ℃, cooled to room temperature after 8h, extracted by ethyl acetate and water to obtain an oil phase, washed 3 times with saturated ammonium chloride, dried by anhydrous sodium sulfate, evaporated, recrystallized by petroleum ether and a small amount of tetrahydrofuran, and subjected to suction filtration, washing and drying to obtain compound 2.
p-Chloromethylstyrene (30.5mL) was dissolved in 50mL of anhydrous tetrahydrofuran in a 500mL dry round-bottom flask, stirred at room temperature, sodium hydride (3.6g, 0.061mol) was added and stirring was continued for 30min, then Compound 2 dissolved in 250mL of anhydrous tetrahydrofuran was added to the round-bottom flask, and 10mg of KI was added thereto and reacted at 50 ℃ for 24 hours. After the reaction was completed, it was cooled to room temperature and filtered with suction, and then the filtrate was extracted with anhydrous magnesium sulfate (MgSO) 4 ) Drying, filtering, rotary steaming, and performing column chromatography to obtain achiral monomer (AzoMS) containing styrene azobenzene [ i.e. the compound of formula (II) of the invention, wherein a is 6, R 1 Methoxy radical, its nuclear magnetic resonance hydrogen spectrum is shown in figure 1.
The reaction process is as follows:
example 2: synthesis of non-chiral monomer containing styrene hydroxy azobenzene (AzoOLS)
Dissolving p-hydroxyphenylamine (10.0g,0.091mol) in 1M hydrochloric acid solution (200mL) at 0 ℃, and stirring for 30min at 0-5 ℃; dissolving sodium nitrite (9.3g,0.11mmol) in 150mL of deionized water, controlling the reaction temperature to be kept at 0-5 ℃, slowly dropwise adding a sodium nitrite solution into the reaction system, and completing dropwise adding for 30 min; reacting for 30min, keeping the temperature at 0 ℃, adding 200mL of ice methanol, and reacting for 1h to obtain the diazonium salt solution of p-hydroxyphenylamine.
Phenol (8.6g) was dissolved in 3M aqueous sodium hydroxide (65mL) at a temperature of 0 ℃. Then slowly dropwise adding into the diazo salt solution of p-hydroxyphenylamine obtained before, mechanically stirring for 30min under the condition of keeping 0 ℃, and then moving to room temperature for reaction for 2 h. And (3) after the reaction is finished, performing rotary evaporation to remove redundant methanol, adjusting the pH value of the solution to be less than 5 by using concentrated hydrochloric acid, separating out mauve particles, performing suction filtration, washing, drying, recrystallization by using ethanol/water (1/2), performing suction filtration, and performing vacuum drying treatment to finally obtain mauve compound 1.
Potassium carbonate (9.7g,0.07mol), compound 1(5.0g,0.023mol), 10mg of potassium iodide (KI), 60mL of DMF were added into a 500mL dry round-bottom flask to dissolve, heated to 80 ℃ and stirred for 30 min; then 1-bromo-6-hydroxyhexane (10.6g,0.058mol) is dissolved in 30mL DMF, slowly added into a round-bottom flask, stirred and refluxed at 80 ℃, cooled to room temperature after 8h, extracted by ethyl acetate and water to obtain an oil phase, and the oil phase is washed with saturated ammonium chloride for 2 times, dried over anhydrous sodium sulfate, rotary evaporated and subjected to column chromatography to obtain compound 2.
p-Chloromethylstyrene (2.9mL) was dissolved in 20mL of anhydrous tetrahydrofuran in a 500mL dry round-bottom flask, stirred at room temperature, sodium hydride (1.2g, 0.05mol) was added and stirring was continued for 30min, then Compound 2 dissolved in 80mL of anhydrous tetrahydrofuran was added to the round-bottom flask and 10mg of KI was added thereto and reacted at 50 ℃ for 24 hours. After the reaction is finished, cooling the reaction product to room temperature, carrying out suction filtration, drying the filtrate by using anhydrous sodium sulfate, filtering, carrying out rotary evaporation and carrying out column chromatography to obtain an achiral monomer (AzoOLS) containing styrene hydroxy azobenzene (namely the compound shown in the formula (III), wherein b and c are both 6), and the nuclear magnetic resonance hydrogen spectrogram is shown in figure 2.
The reaction process is as follows:
example 3: preparation of chiral polymer by dispersion polymerization of non-chiral monomer containing styrene azobenzene
Adding the monomer AzoMS/Azolols obtained in example 1 and example 2, chiral octanol ((R) - (-) -octanol or (S) - (+) -octanol), initiator Azobisisobutyronitrile (AIBN), dispersant PVP-K90 and absolute ethyl alcohol into a 10mL ampoule bottle, performing three times of oxygen removal by using a double-row pipe after the sample addition is finished, sealing the bottle mouth after the oxygen removal is finished, and heating and stirring the mixture at 70 ℃ under argon for reaction for 20 hours; stopping the reaction to obtain a chiral polymer with chirality; wherein, the ratio of the achiral monomer (AzoMS/Azolols) containing the styrene azobenzene, the initiator, PVP-K90, the chiral octanol and the mass is as follows: 60: 0.7: 3: 0.5, the total amount of the non-chiral monomer (AzoMS/Azolols) containing styrene azobenzene is 60mg, the mass ratio of the two monomers (11/1, 6/1, 3/1, 7/5 and 1/1) is adjusted to obtain the copolymer polymers with different ratios, the solvent is ethanol, and the using amount of the solvent is 2.7 mL.
The synthesis of chiral polymer is as follows:
FIG. 3 is a graph of the morphology of chiral polymer obtained in the polymerization process at different feed ratios (polymerization time is 20 hours); FIGS. 4A and 4B show CD spectra of chiral polymers obtained at different ratios (4A for R-octanol induction and 4B for S-octanol induction).
The polymer particles prepared by the method are approximately microspherical, the size reaches micron level, the polymer particles have optical activity, the particle size of the polymer particles is uniformly distributed when the proportion of the comonomer is proper, the particle size distribution can show that the polymer particles have excellent monodispersity, and when the proportion of the comonomer is 7/5, the particle size and the dispersity of the obtained product are optimal; the optical activity of the polymer can be changed due to different proportions of the comonomers, and in some cases, the spiral stacking of the internal azobenzene units is damaged due to the strong hydrogen bonding formed by hydroxyl groups, so that the optical activity is changed.
Example 4: chiral fixation (namely preparing cross-linked chiral azobenzene polymer microspheres) and chiral recovery of chiral polymer obtained by copolymerization
Dispersing the chiral polymers obtained in example 3 in different proportions in dry 50mL beakers to prepare dilute dispersion solutions, then placing the dilute dispersion solutions in 1000mL beakers, placing small beakers respectively containing concentrated hydrochloric acid and formaldehyde solutions in the 1000mL beakers, sealing the 1000mL beakers, and reacting for 20 hours to obtain the chirally-fixed cross-linked chiral azobenzene polymer microspheres. And then dispersing the covalently crosslinked crosslinking chiral azobenzene polymer microspheres in ethanol, irradiating by ultraviolet light and visible light, and performing CD test after reaching a photostability.
FIG. 5 is a diagram showing the chiral recovery degree of a crosslinked chiral azobenzene polymer microsphere obtained after chiral fixation of a chiral polymer, and the chiral destruction of the crosslinked chiral azobenzene polymer microsphere according to the proportion of a comonomer;
FIG. 6 shows the spectrum of the chiral "ON" and "OFF" test CD under the chiral fully recoverable conditions;
as shown, the degree of chiral self-recovery gradually increased from complete failure to recover with increasing hydroxyl monomer content, and was fully recovered at the two monomer ratio 7/5; repeating the chiral "destruction" and "recovery" processes several times with the chiral polymer of monomer ratio 7/5, the absorption intensity associated with the pi-pi electron transition of the trans isomer in the chiral polymer decreased significantly (in the range of 320nm to 400 nm) under 365nm uv irradiation, and was accompanied by a gradual increase in the absorption intensity of the n-pi electron transition of the cis isomer (in the range of 400nm to 500 nm). Also, the absolute CD amplitude of the chiral polymer also decreased to zero with the trans isomer content, and the change in CD signal under 365nm light irradiation was attributable to the non-coplanar and curved structure of the cis-azo unit, which disrupted the helical stacking of the non-chiral coplanar trans-azo unit. And then irradiating by visible light, converting the cis-isomer into the trans-isomer, and inducing the unfixed azobenzene unit to reform a spiral structure by the fixed chiral azobenzene unit, wherein the chiral signal is recovered and is not obviously attenuated.
FIG. 7 is a graph showing the appearance of a chiral polymer after covalent crosslinking and after ultraviolet and visible light irradiation, which is a), b) and c) in sequence. After covalent crosslinking through an acetal reaction, the polyazobenzene polymer has no other obvious change except that the average size is reduced, which shows that the crosslinking reaction is generated inside the polyazobenzene polymer; after the ultraviolet irradiation, the internal helical structure is damaged, but the spherical shape is not damaged, the internal helical structure can be restored again by the visible light irradiation, and the spherical shape of the polyazobenzene polymer is not changed.
Comparative example 1
The existing polymer microsphere structure:
comparative example 2
The existing azobenzene crosslinked film structure:
through experimental verification, the products with the structures shown in the comparative examples 1 and 2 cannot recover the chiral function under the irradiation of visible light after the chirality is destroyed.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Claims (10)
1. A cross-linking type chiral azobenzene polymer microsphere is characterized in that raw materials of the cross-linking type chiral azobenzene polymer microsphere comprise chiral polymers with structures shown in a formula (I), and the cross-linking type chiral azobenzene polymer microsphere is obtained by mixing the raw materials and carrying out an acetal reaction;
in the formula (I), y: x is (0.1-50) to 1;
a. b and c are independently selected from 2-15, R 1 Is cyano, C 1-3 Alkyl or C 1-3 An alkoxy group.
2. The crosslinked chiral azobenzene polymer microsphere according to claim 1, wherein in formula (I), y: x is (0.3-5) to 1.
3. The crosslinked chiral azobenzene polymer microsphere according to claim 1, wherein the structure shown in formula (i) is one or more selected from the following compounds:
4. the crosslinked chiral azobenzene polymer microsphere according to claim 1, wherein the acetalization reaction is carried out in a first solvent in the presence of hydrochloric acid and aldehydes, wherein the first solvent comprises petroleum ether and the aldehydes comprise formaldehyde.
5. The crosslinked chiral azobenzene polymer microsphere according to claim 1, wherein the reaction temperature of the acetalization reaction is 10-40 ℃.
6. An intermediate for preparing cross-linked chiral azobenzene polymer microspheres, which is a chiral polymer having a structure represented by the formula (i) in claim 1.
7. A method for preparing the intermediate of claim 6, comprising:
copolymerizing a compound shown in a formula (II) and a compound shown in a formula (III) in a second solvent in the presence of an initiator, a chiral induction source and a non-ionic dispersing agent to generate a chiral polymer with a structure shown in a formula (I);
8. the process for the preparation of the intermediate according to claim 7, characterized in that the reaction temperature of the copolymerization is 65-75 ℃; and/or, the copolymerization is carried out in an oxygen-free environment.
9. The method for preparing an intermediate according to claim 7, wherein the initiator is an azo initiator, and the azo initiator is one or more selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, and dimethyl azobisisobutyrate; the chiral inducing source is one or more of chiral 2-octanol, chiral 2-hexanol and chiral 2-butanol; the non-ionic dispersing agent is one or more of polyvinylpyrrolidone, poly-4-vinylpyridine, polyethylene glycol and polyhydroxyethyl methacrylate; the second solvent is one or more selected from ethanol, methanol, propanol and butanol.
10. The application of the cross-linked chiral azobenzene polymer microsphere as claimed in any one of claims 1 to 5 in preparing chiral materials, wherein the chiral materials realize the attenuation of chiral signals under the irradiation of ultraviolet light and the recovery of chiral signals under the irradiation of visible light.
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| CN115725011B (en) * | 2022-10-18 | 2023-08-25 | 苏州大学 | Azobenzene polymer supermolecule assembly with controllable chirality and chiral regulation method thereof |
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