CN114907836A - Multistage photoresponse type fluorescent liquid crystal element, polymer thereof and preparation method thereof - Google Patents
Multistage photoresponse type fluorescent liquid crystal element, polymer thereof and preparation method thereof Download PDFInfo
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 30
- 229920000642 polymer Polymers 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 229920000106 Liquid crystal polymer Polymers 0.000 claims abstract description 17
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 207
- 239000007787 solid Substances 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 238000004440 column chromatography Methods 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 39
- -1 1-bromoalkane Chemical compound 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 238000010791 quenching Methods 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 238000000746 purification Methods 0.000 claims description 15
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 14
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 14
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- FBSFWRHWHYMIOG-UHFFFAOYSA-N methyl 3,4,5-trihydroxybenzoate Chemical compound COC(=O)C1=CC(O)=C(O)C(O)=C1 FBSFWRHWHYMIOG-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims description 9
- 230000001678 irradiating effect Effects 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- 230000000171 quenching effect Effects 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 8
- 229940095102 methyl benzoate Drugs 0.000 claims description 7
- 230000004298 light response Effects 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 claims description 6
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 5
- LEIMLDGFXIOXMT-UHFFFAOYSA-N trimethylsilyl cyanide Chemical compound C[Si](C)(C)C#N LEIMLDGFXIOXMT-UHFFFAOYSA-N 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 4
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 4
- 125000005997 bromomethyl group Chemical group 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- DCXZLBAXIGEGMA-UHFFFAOYSA-N cyclobutane-1,3-dicarbonitrile Chemical compound N#CC1CC(C#N)C1 DCXZLBAXIGEGMA-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000007106 1,2-cycloaddition reaction Methods 0.000 claims description 2
- 238000004639 Schlenk technique Methods 0.000 claims description 2
- 125000005036 alkoxyphenyl group Chemical group 0.000 claims description 2
- RJUIDDKTATZJFE-UHFFFAOYSA-N but-2-enoyl chloride Chemical compound CC=CC(Cl)=O RJUIDDKTATZJFE-UHFFFAOYSA-N 0.000 claims description 2
- 210000002858 crystal cell Anatomy 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 claims description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 claims description 2
- 125000005415 substituted alkoxy group Chemical group 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 239000000463 material Substances 0.000 abstract description 4
- 230000009456 molecular mechanism Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000006552 photochemical reaction Methods 0.000 abstract description 3
- 230000000638 stimulation Effects 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 45
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 22
- 239000003480 eluent Substances 0.000 description 20
- 238000000605 extraction Methods 0.000 description 15
- HRMRQTGUSWAVCV-UHFFFAOYSA-N (3,4,5-tridodecoxyphenyl)methanol Chemical compound CCCCCCCCCCCCOC1=CC(CO)=CC(OCCCCCCCCCCCC)=C1OCCCCCCCCCCCC HRMRQTGUSWAVCV-UHFFFAOYSA-N 0.000 description 6
- MQPGDDQRYPVBPH-UHFFFAOYSA-N 2-(3,4,5-tridodecoxyphenyl)acetonitrile Chemical compound C(CCCCCCCCCCC)OC=1C=C(C=C(C=1OCCCCCCCCCCCC)OCCCCCCCCCCCC)CC#N MQPGDDQRYPVBPH-UHFFFAOYSA-N 0.000 description 6
- PXFDQEJVDJTIIE-UHFFFAOYSA-N 5-(bromomethyl)-1,2,3-tridodecoxybenzene Chemical compound CCCCCCCCCCCCOC1=CC(CBr)=CC(OCCCCCCCCCCCC)=C1OCCCCCCCCCCCC PXFDQEJVDJTIIE-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 5
- DGXKEVFWHHGGJI-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]benzaldehyde Chemical compound OCCOCCOC1=CC=CC=C1C=O DGXKEVFWHHGGJI-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- AHSLFIRTZGMDDL-UHFFFAOYSA-N methyl 3,4,5-tridodecoxybenzoate Chemical compound CCCCCCCCCCCCOC1=CC(C(=O)OC)=CC(OCCCCCCCCCCCC)=C1OCCCCCCCCCCCC AHSLFIRTZGMDDL-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
- VFOKYTYWXOYPOX-PTNGSMBKSA-N (e)-2,3-diphenylprop-2-enenitrile Chemical compound C=1C=CC=CC=1C(/C#N)=C\C1=CC=CC=C1 VFOKYTYWXOYPOX-PTNGSMBKSA-N 0.000 description 1
- ZWKNLRXFUTWSOY-QPJJXVBHSA-N (e)-3-phenylprop-2-enenitrile Chemical compound N#C\C=C\C1=CC=CC=C1 ZWKNLRXFUTWSOY-QPJJXVBHSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001109 fluorescent polymer Polymers 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- 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
- C08F122/00—Homopolymers 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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
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Abstract
The invention relates to a multistage photoresponse type fluorescent liquid crystal element, a polymer thereof and a preparation method thereof, wherein the polymer is introduced into a polymer system to obtain a fluorescent liquid crystal polymer with multistage photoresponse characteristics. Firstly, separating and purifying photochemical reaction products of fluorescent liquid crystal elements under different light stimulation conditions, and determining a molecular mechanism of a multistage photoresponse process and control elements of the reaction of the molecular mechanism; and then the fluorescent liquid crystal element is introduced into a polymer system in the form of a polymer side group to prepare the fluorescent liquid crystal polymer with the multilevel photoresponse characteristic. Compared with the existing liquid crystal polymer material which is only converted between two states, the multistage photoresponse type fluorescent liquid crystal polymer which can be sequentially converted between multiple states has larger application prospect in the fields of information storage, anti-counterfeiting encryption, multicolor fluorescence sensing and the like.
Description
Technical Field
The invention belongs to the field of functional polymers, and relates to a multistage photoresponse type fluorescent liquid crystal element, a polymer thereof and a preparation method thereof
Background
The liquid crystal polymer integrates the advantages of the orientation ordered structure and the photoelectric responsiveness of liquid crystal, the excellent processability and the thermal stability of the polymer and the like, and shows wide application prospect in the field of stimulation response photoelectric materials. The photoresponse fluorescent liquid crystal polymer can be reversibly transformed into multiple properties such as a liquid crystal structure, a luminous color, a material shape and the like under the illumination condition, and has obvious application value in the fields of information storage, fluorescence sensing, liquid crystal display and the like, so that the design and synthesis of the multilevel photoresponse fluorescent liquid crystal polymer which can be sequentially transformed among multiple heterogeneous states have important significance.
Document 2, "yanan Zhu, Meiqing Zheng, Yuanyang Tu, and Xiao-Fang chen, superior molecular Fluorescent Polymers connecting α -Cyanostilbene Based stereosomes, Z/E-isomer Induced multiplex Reversible switching, macromolecules 2018,51, 3487-.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a multi-level light response type fluorescent liquid crystal element, a polymer thereof and a preparation method thereof, and the multi-level light response type fluorescent liquid crystal element is a trialkoxy cyano styrene liquid crystal element and a polymer thereof, and the multi-level light response type fluorescent liquid crystal polymer which can be sequentially and controllably converted among four states is obtained.
Technical scheme
A multi-level light response type fluorescent liquid crystal element and a polymer thereof are characterized in that the structural formula of the polymer is as follows:
a preparation method of the multistage photoresponse type fluorescent liquid crystal element and the polymer thereof is characterized by comprising the following steps:
step 1: dissolving methyl 3,4, 5-trihydroxybenzoate, 1-bromoalkane, tetrabutylammonium iodide and potassium carbonate in a molar ratio of 1:4:0.03:8 in N, N-dimethylformamide, and stirring at 80-85 ℃ for reacting overnight; after the reaction liquid is cooled to room temperature, adding water for quenching reaction, then extracting by using dichloromethane, and then separating and purifying by column chromatography to obtain a white solid 3,4, 5-trialkoxy methyl benzoate;
step 2: dissolving 1 time equivalent of 3,4, 5-trialkoxy methyl benzoate in dry tetrahydrofuran, slowly dripping 1.5 times equivalent of lithium aluminum hydride tetrahydrofuran solution at the temperature of 0 ℃, continuously stirring and reacting for 30-35 minutes, and then continuously reacting for 2-3 hours at room temperature; adding water to quench the reaction, extracting with dichloromethane, drying with anhydrous magnesium sulfate, and rotary evaporating to remove solvent to obtain white solid 3,4, 5-trialkoxy benzyl alcohol;
and step 3: dissolving 1 equivalent of 3,4, 5-trialkoxy benzyl alcohol in dichloromethane, slowly dropping 2 equivalents of phosphorus tribromide tetrahydrofuran solution at 0 ℃, and continuously stirring and reacting at room temperature for 3-4 h; after quenching the reaction with water, extracting with dichloromethane, drying over anhydrous magnesium sulfate and rotary evaporating to remove the solvent to obtain 5- (bromomethyl) -1,2, 3-trialkoxybenzene as a white solid;
and 4, step 4: dissolving 5- (bromomethyl) -1,2, 3-trialkoxybenzene and trimethylsilyl cyanide in a molar ratio of 1:2 in anhydrous acetonitrile, and stirring to react for 3-4 h at room temperature; adding water to quench the reaction, extracting with dichloromethane, and performing column chromatography separation and purification to obtain a white solid 3,4, 5-trialkoxyphenylacetonitrile;
and 5: dissolving 4-methoxybenzaldehyde and 3,4, 5-trialkoxyphenylacetonitrile with a molar ratio of 1:1 in absolute ethanol, adding 2 times of equivalent of sodium hydroxide ethanol solution, and stirring and reacting at 50-55 ℃ for 2-3 h; adding water to quench the reaction, extracting the reaction product by using dichloromethane, and then carrying out column chromatography separation and purification to obtain a yellow solid (Z) -3- (4-methoxyphenyl) -2- (3,4, 5-trialkoxy phenyl) acrylonitrile, namely a multistage photoresponse type fluorescent liquid crystal element;
step 6: dissolving 450-500 mg of (Z) -3- (4-methoxyphenyl) -2- (3,4, 5-trialkoxyphenyl) acrylonitrile solid in a dichloromethane solution, continuously irradiating for 30min by using a 365nm ultraviolet lamp, and then separating and purifying by column chromatography to obtain a yellow solid (E) -3- (4-methoxyphenyl) -2- (3,4, 5-trialkoxyphenyl) acrylonitrile, namely the cis-trans isomeric state of the fluorescent liquid crystal element;
and 7: 170-200 mg of (E) -3- (4-methoxyphenyl) -2- (3,4, 5-trialkoxyphenyl) acrylonitrile solid is taken to be dissolved in dichloromethane solution, an ultraviolet lamp with the wavelength of 365nm is used for continuously irradiating for 2-3 h, and then column chromatography separation and purification are carried out to obtain yellow solid 5,6, 7-trialkoxy-3-methoxyphenanthrene-9-carbonitrile, namely the intramolecular cyclization state of the fluorescent liquid crystal elements;
and 8: taking 120 mg-150 mg of (E) -3- (4-methoxyphenyl) -2- (3,4, 5-trialkoxyphenyl) acrylonitrile solid, pressing the solid on a glass slide to form a film, continuously irradiating the film for 1h by using a 365nm ultraviolet lamp, and then separating and purifying the film by column chromatography to obtain yellow solid (1R,2R,3S,4S) -2, 4-bis (4-methoxyphenyl) -1, 3-bis (3,4, 5-trialkoxyphenyl) cyclobutane-1, 3-dicarbonitrile, namely the intermolecular [2+2] cycloaddition state of the fluorescent liquid crystal element;
step 10: dissolving bromoalkyl alcohol, p-hydroxybenzaldehyde and potassium carbonate in a molar ratio of 1:1:2 in N, N-dimethylformamide, and stirring and reacting at 85-90 ℃ for 11-12 hours; pouring the reaction liquid into water, extracting by using dichloromethane, and then carrying out column chromatography separation and purification to obtain hydroxy-substituted alkoxybenzaldehyde of a yellow oily liquid;
step 11: dissolving terminal hydroxyl substituted alkoxy benzaldehyde and 3,4, 5-trialkoxy phenylacetonitrile in a molar ratio of 1:1 in absolute ethanol, adding 2 times of equivalent of tetrabutyl ammonium hydroxide solution, and stirring and reacting at 40-45 ℃ for 2-3 h; adding water, extracting with dichloromethane, and purifying by column chromatography to obtain yellow solid (Z) -3- (4-end hydroxyl alkoxyl phenyl) -2- (3,4, 5-trialkoxy phenyl) acrylonitrile;
step 12: dissolving (Z) -3- (4-hydroxyl-terminated alkoxyphenyl) -2- (3,4, 5-trialkoxyphenyl) acrylonitrile and triethylamine in a molar ratio of 1:3 in dichloromethane, and slowly dropping a dichloromethane solution of 3 times equivalent of (methyl) acryloyl chloride into the reaction solution under the ice bath condition; after the reaction is finished, pouring the reaction liquid into water, extracting with dichloromethane, and then separating and purifying by column chromatography to obtain a polymerizable monomer;
step 13: dissolving 300-350 mg of polymerizable monomer in tetrahydrofuran, adding 0.02 equivalent of 2, 2-azobisisobutyronitrile initiator, performing three freezing-vacuum-unfreezing cycles on the mixed solution in a dry Schlenk tube, keeping the mixed solution in a nitrogen atmosphere, and stirring and reacting for 8 hours at 75 ℃; and (4) separating and purifying by direct column chromatography to obtain the multi-stage light response type fluorescent liquid crystal polymer.
The Schlenk technique is as follows: after the reactants and the solvent are added into a dried Schlenk tube, the Schlenk tube is frozen by liquid nitrogen and then vacuumized, then unfreezed by introducing nitrogen gas, and then vacuumized after being frozen by liquid nitrogen again, so that the operations of freezing-unfreezing-freezing are repeated for many times.
All solution heating was done under constant temperature oil bath conditions.
Advantageous effects
The invention provides a multistage photoresponse type fluorescent liquid crystal element, a polymer thereof and a preparation method thereof. Firstly, separating and purifying photochemical reaction products of fluorescent liquid crystal elements under different light stimulation conditions, and determining a molecular mechanism of a multistage photoresponse process and control elements of the reaction of the molecular mechanism; and then the fluorescent liquid crystal element is introduced into a polymer system in the form of a polymer side group to prepare the fluorescent liquid crystal polymer with the multilevel photoresponse characteristic. Compared with the existing liquid crystal polymer material which is only converted between two states, the multistage photoresponse type fluorescent liquid crystal polymer which can be sequentially converted between multiple states has larger application prospect in the fields of information storage, anti-counterfeiting encryption, multicolor fluorescence sensing and the like.
Drawings
FIG. 1: the invention is a schematic diagram of the molecular structure and multilevel photoresponse change of the fluorescent liquid crystal element and the polymer thereof prepared by the method.
FIG. 2 is a schematic diagram: is a nuclear magnetic resonance hydrogen spectrum schematic diagram of the multi-stage photoresponse change process of the fluorescent liquid crystal element prepared in the embodiment 1 of the method.
FIG. 3: FIG. 3 is a schematic diagram of NMR spectra of the multi-stage photoresponsive fluorescent liquid crystal polymer prepared in example 2 of the present invention
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
the first embodiment is as follows:
dissolving 0.6g of methyl 3,4, 5-trihydroxybenzoate, 3.2g of 1-bromododecane, 33mg of tetrabutylammonium iodide and 3.6g of potassium carbonate in 30mL of N, N-dimethylformamide, and stirring at 80 ℃ for reacting overnight; after the reaction liquid is cooled to room temperature, 100mL of water is added, and then 50mL of water is used for extraction by dichloromethane for 2 times, and then the mixture is separated and purified by column chromatography (eluent is n-hexane: ethyl acetate ═ 5:1) to obtain 3,4, 5-tri (dodecyloxy) methyl benzoate as a white solid;
dissolving 2.1g of methyl 3,4, 5-tris (dodecyloxy) benzoate in 15mL of dry tetrahydrofuran, slowly dropping 4.3mL of lithium aluminum hydride tetrahydrofuran solution (1mol/L) at 0 ℃, continuously stirring for reaction for 30min, and then continuously stirring for reaction for 2h at room temperature; after quenching the reaction with 100mL of water, 50mL × 3 times of extraction with dichloromethane, drying over anhydrous magnesium sulfate and rotary evaporation to remove the solvent, 3,4, 5-tris (dodecyloxy) benzyl alcohol was obtained as a white solid;
dissolving 1.4g of 3,4, 5-tris (dodecyloxy) benzyl alcohol in 15mL of dichloromethane, slowly dropping 4.7mL of phosphorus tribromide tetrahydrofuran solution (1mol/L) at the temperature of 0 ℃, continuously stirring and reacting for 1h, and then continuously stirring and reacting for 3h at the room temperature; after quenching the reaction with water, 50mL × 3 times were extracted with dichloromethane, then dried over anhydrous magnesium sulfate and the solvent was removed by rotary evaporation to give 5- (bromomethyl) -1,2, 3-tris (dodecyloxy) benzene as a white solid;
dissolving 1.2g of 5- (bromomethyl) -1,2, 3-tris (dodecyloxy) benzene and 0.4mL of trimethylsilyl cyanide in 15mL of anhydrous acetonitrile, and stirring the mixture at room temperature for reaction for 3 hours; adding 100mL of water to quench the reaction, extracting with dichloromethane for 50mL multiplied by 3 times, and then performing column chromatography separation and purification (eluent is dichloromethane) to obtain 3,4, 5-tri (dodecyloxy) phenylacetonitrile as a white solid;
dissolving 0.5g of 4-methoxybenzaldehyde, 2.5g of 3,4, 5-tri (dodecyloxy) phenylacetonitrile and 0.3g of sodium hydroxide in 30mL of absolute ethanol, and stirring for reaction at 50 ℃ for 2 h; after the reaction solution was cooled to room temperature, 100mL of water was added, followed by extraction with dichloromethane for 50mL × 2 times, and further purification by column chromatography (eluent n-hexane: ethyl acetate ═ 10:1) gave (Z) -3- (4-methoxyphenyl) -2- (3,4, 5-tris (dodecyloxy) phenyl) acrylonitrile as a yellow solid;
dissolving 500mg of (Z) -3- (4-methoxyphenyl) -2- (3,4, 5-tris (dodecyloxy) phenyl) acrylonitrile in a dichloromethane solution, continuously irradiating the dichloromethane solution for 30min by using a 365nm ultraviolet lamp, and then performing column chromatography separation and purification on the obtained product (eluent is n-hexane: ethyl acetate ═ 5:1) to obtain yellow solid (E) -3- (4-methoxyphenyl) -2- (3,4, 5-tris (dodecyloxy) phenyl) acrylonitrile;
dissolving 200mg of (E) -3- (4-methoxyphenyl) -2- (3,4, 5-tri (dodecyloxy) phenyl) acrylonitrile in a dichloromethane solution, continuously irradiating the dichloromethane solution for 2h by using a 365nm ultraviolet lamp, and then separating and purifying the mixture by column chromatography (eluent is n-hexane: ethyl acetate: 10:1) to obtain 5,6, 7-tri (dodecyloxy) -3-methoxyphenanthrene-9-carbonitrile as a yellow solid;
pressing 150mg of (E) -3- (4-methoxyphenyl) -2- (3,4, 5-tridodecyloxy) phenyl acrylonitrile into a film on a glass slide, continuously irradiating the film for 1h by using a 365nm ultraviolet lamp, and then separating and purifying the film by column chromatography (eluent is n-hexane: ethyl acetate ═ 3:1) to obtain yellow solid (1R,2R,3S,4S) -2, 4-bis (4-methoxyphenyl) -1, 3-bis (3,4, 5-tridodecyloxy) phenyl) cyclobutane-1, 3-dicarbonitrile;
as can be seen from the multi-stage photoresponse change process in fig. 1 and the nmr hydrogen spectrum of each photochemical reaction product in fig. 2, the fluorescent mesogen prepared in this example 1 controllably generates a multi-stage photoresponse characteristic that can be sequentially changed between four states under the ultraviolet irradiation condition;
example two:
dissolving 1.5g of methyl 3,4, 5-trihydroxybenzoate, 8g of 1-bromododecane, 83mg of tetrabutylammonium iodide and 9g of potassium carbonate in 30mL of N, N-dimethylformamide, and stirring at 80 ℃ for reacting overnight; after the reaction liquid is cooled to room temperature, 200mL of water is added, then 100mL of water is used for extraction by dichloromethane for 2 times, and then the mixture is separated and purified by column chromatography (eluent is n-hexane: ethyl acetate ═ 5:1) to obtain 3,4, 5-tri (dodecyloxy) methyl benzoate as a white solid;
dissolving 5.3g of methyl 3,4, 5-tris (dodecyloxy) benzoate in 30mL of dry tetrahydrofuran, slowly dropping 10.8mL of lithium aluminum hydride tetrahydrofuran solution (1mol/L) at 0 ℃, continuously stirring for reaction for 30min, and then continuously stirring for reaction for 2h at room temperature; after quenching the reaction with 100mL of water, extracting 100mL × 3 times with dichloromethane, drying over anhydrous magnesium sulfate, and rotary evaporating to remove the solvent to obtain 3,4, 5-tris (dodecyloxy) benzyl alcohol as a white solid;
dissolving 3.5g of 3,4, 5-tris (dodecyloxy) benzyl alcohol in 20mL of dichloromethane, slowly dropping 12mL of phosphorus tribromide tetrahydrofuran solution (1mol/L) at the temperature of 0 ℃, continuously stirring and reacting for 1h, and then continuously stirring and reacting for 3h at the room temperature; after quenching the reaction with water, 100mL × 3 times of extraction with dichloromethane, followed by drying over anhydrous magnesium sulfate and rotary evaporation to remove the solvent, 5- (bromomethyl) -1,2, 3-tris (dodecyloxy) benzene was obtained as a white solid;
dissolving 3.0g of 5- (bromomethyl) -1,2, 3-tris (dodecyloxy) benzene and 1mL of trimethylsilyl cyanide in 20mL of anhydrous acetonitrile, and stirring at room temperature for reaction for 3 h; adding 100mL of water to quench the reaction, extracting with dichloromethane for 50mL multiplied by 3 times, and then performing column chromatography separation and purification (eluent is dichloromethane) to obtain 3,4, 5-tri (dodecyloxy) phenylacetonitrile as a white solid;
dissolving 15g of tetraethylene glycol and 9.8mL of triethylamine in 100mL of dichloromethane, then dissolving 3.6g of p-methylbenzenesulfonyl chloride in 20mL of dichloromethane, slowly dropwise adding the solution into the reaction solution, and stirring the solution at room temperature for reaction for 1 h; after the reaction is finished, 150mL of water is added, and then 100mL of water is extracted by dichloromethane for 2 times, and then the mixture is separated and purified by column chromatography (eluent is n-hexane: ethyl acetate 1:2) to obtain yellow oily liquid 2- (2- (2- (2- (4- (methylsulfonyl) phenoxy) ethoxy) ethane-1-alcohol;
dissolving 4.0g of 2- (2- (2- (2- (4- (methylsulfonyl) phenoxy) ethoxy) ethane-1-ol, 1.3g of p-hydroxybenzaldehyde and 3g of potassium carbonate in 150mL of N, N-dimethylformamide, and stirring to react at 85 ℃ for 12 hours; after the reaction solution is cooled to room temperature, 150mL of water is added, and then 100mL × 2 times of extraction is carried out by using dichloromethane, and then the extraction is carried out by column chromatography (eluent is methanol: ethyl acetate ═ 1:10), so as to obtain 4- (2- (2- (2- (2-hydroxyethoxy) ethoxy) benzaldehyde as yellow oily liquid;
dissolving 1.3g of 4- (2- (2- (2- (2-hydroxyethoxy) ethoxy) benzaldehyde, 2.8g of 3,4, 5-tri (dodecyloxy) phenylacetonitrile and 5mL of tetrabutylammonium hydroxide solution in 50mL of absolute ethanol, and stirring for reacting for 2h at 40 ℃; after the reaction solution was cooled to room temperature, 100mL of water was added, followed by extraction with dichloromethane 100mL × 2 times, and further purification by column chromatography (eluent dichloromethane: ethyl acetate ═ 10:1) gave (Z) -3- (4- (2- (2- (2-hydroxyethoxy) ethoxy) phenyl) -2- (3,4, 5-tris (dodecyloxy) phenyl) acrylonitrile as a yellow solid;
3.0g of (Z) -3- (4- (2- (2- (2- (2-hydroxyethoxy) ethoxy) phenyl) -2- (3,4, 5-tri (dodecyloxy) phenyl) acrylonitrile and 1.3mL of triethylamine are dissolved in 100mL of dichloromethane, stirred in an ice bath for 30min, then 1g of methacryloyl chloride is dissolved in 30mL of dichloromethane solution, and the reaction solution is slowly added dropwise under ice bath conditions, wherein the dropwise adding time is controlled to be 8 h; after the reaction is finished, 100mL of water is added, and then 100mL × 2 times of extraction is carried out by dichloromethane, and then the product is separated and purified by column chromatography (eluent is n-hexane: ethyl acetate ═ 5:1) to obtain yellow solid ethyl (Z) -2- (2- (2- (2- (4- (2-cyano-2- (3,4, 5-tri (dodecyloxy) phenyl) vinyl) phenoxy) ethoxy) methacrylate;
300mg of ethyl (Z) -2- (2- (2- (4- (2-cyano-2- (3,4, 5-tridodecyloxy) phenyl) vinyl) phenoxy) ethoxy) methacrylate was dissolved in 0.6mL of tetrahydrofuran, 1.6mg of 2, 2-azobisisobutyronitrile initiator was added, and then the mixed solution was subjected to three freeze-vacuum-thaw cycles in a dry Schlenk tube under nitrogen atmosphere and stirred at 75 ℃ for 8 h; and (4) performing direct column chromatography separation and purification (the eluent is dichloromethane) to obtain a yellow solid, namely the multistage photoresponse type liquid crystal polymer.
As can be seen from the nuclear magnetic resonance hydrogen spectrogram of the polymer in fig. 3, the polymer prepared in the embodiment 2 successfully introduces the multi-level photoresponse fluorescent liquid crystal cell, so as to obtain the multi-level photoresponse fluorescent liquid crystal polymer.
Example three:
1.1g of methyl 3,4, 5-trihydroxybenzoate, 5.8g of 1-bromododecane, 60mg of tetrabutylammonium iodide and 6.5g of potassium carbonate are dissolved in 50mL of N, N-dimethylformamide and reacted with stirring at 80 ℃ overnight; after the reaction liquid is cooled to room temperature, 150mL of water is added, then 100mL of water is used for extraction by dichloromethane for 2 times, and then the mixture is separated and purified by column chromatography (eluent is n-hexane: ethyl acetate ═ 5:1) to obtain 3,4, 5-tri (dodecyloxy) methyl benzoate as a white solid;
dissolving 3.8g of methyl 3,4, 5-tris (dodecyloxy) benzoate in 30mL of dry tetrahydrofuran, slowly dripping 8mL of lithium aluminum hydride tetrahydrofuran solution (1mol/L) at the temperature of 0 ℃, continuously stirring for reaction for 1 hour, and then continuously stirring for reaction for 2 hours at the room temperature; after quenching the reaction with 150mL of water, 100mL × 3 times of extraction with dichloromethane, drying over anhydrous magnesium sulfate and rotary evaporation to remove the solvent, 3,4, 5-tris (dodecyloxy) benzyl alcohol was obtained as a white solid;
dissolving 2.5g of 3,4, 5-tris (dodecyloxy) benzyl alcohol in 20mL of dichloromethane, slowly dripping 8mL of phosphorus tribromide tetrahydrofuran solution (1mol/L) at the temperature of 0 ℃, continuously stirring for reaction for 1h, and then continuously stirring for reaction for 3h at the room temperature; after quenching the reaction with water, 50mL × 3 times were extracted with dichloromethane, then dried over anhydrous magnesium sulfate and the solvent was removed by rotary evaporation to give 5- (bromomethyl) -1,2, 3-tris (dodecyloxy) benzene as a white solid;
2.2g of 5- (bromomethyl) -1,2, 3-tris (dodecyloxy) benzene and 0.7mL of trimethylsilyl cyanide are dissolved in 20mL of anhydrous acetonitrile and the reaction is stirred at room temperature for 3 h; adding 150mL of water to quench the reaction, extracting with dichloromethane for 100mL multiplied by 3 times, and then performing column chromatography separation and purification (eluent is dichloromethane) to obtain 3,4, 5-tri (dodecyloxy) phenylacetonitrile as a white solid;
dissolving 10.8g of tetraethylene glycol and 7mL of triethylamine in 100mL of dichloromethane, then dissolving 2.6g of p-methylbenzenesulfonyl chloride in 30mL of dichloromethane, slowly dropwise adding the solution into the reaction solution, and stirring the solution at room temperature for reaction for 1 h; after the reaction is finished, adding 180mL of water, extracting 50mL of water by using dichloromethane for 2 times, and then separating and purifying by column chromatography (eluent is n-hexane: ethyl acetate ═ 1:2) to obtain yellow oily liquid 2- (2- (2- (2- (4- (methylsulfonyl) phenoxy) ethoxy) ethane-1-alcohol;
2.9g of 2- (2- (2- (2- (4- (methylsulfonyl) phenoxy) ethoxy) ethane-1-ol, 1g of p-hydroxybenzaldehyde and 2.2g of potassium carbonate are dissolved in 150mL of N, N-dimethylformamide and stirred at 85 ℃ for reaction for 12 hours; after the reaction solution is cooled to room temperature, 180mL of water is added, and then 100mL × 2 times of extraction is carried out by using dichloromethane, and then the extraction is carried out by column chromatography (eluent is methanol: ethyl acetate ═ 1:10), so as to obtain 4- (2- (2- (2- (2-hydroxyethoxy) ethoxy) benzaldehyde as yellow oily liquid;
0.9g of 4- (2- (2- (2- (2-hydroxyethoxy) ethoxy) benzaldehyde, 2g of 3,4, 5-tris (dodecyloxy) phenylacetonitrile and 4.5mL of tetrabutylammonium hydroxide solution are dissolved in 40mL of absolute ethanol and stirred at 40 ℃ for 2 h; after the reaction solution was cooled to room temperature, 100mL of water was added, followed by extraction with dichloromethane 50mL × 2 times, and further purification by column chromatography (eluent dichloromethane: ethyl acetate ═ 10:1) gave (Z) -3- (4- (2- (2- (2-hydroxyethoxy) ethoxy) phenyl) -2- (3,4, 5-tris (dodecyloxy) phenyl) acrylonitrile as a yellow solid;
dissolving 2g of (Z) -3- (4- (2- (2- (2- (2-hydroxyethoxy) ethoxy) phenyl) -2- (3,4, 5-tris (dodecyloxy) phenyl) acrylonitrile and 0.9mL of triethylamine in 50mL of dichloromethane, stirring in ice bath for 30min, then dissolving 700mg of methacryloyl chloride in 45mL of dichloromethane solution, and slowly adding the reaction solution dropwise under ice bath conditions, wherein the dropwise adding time is controlled to be 8 h; after the reaction is finished, 100mL of water is added, and then 100mL × 2 times of extraction is carried out by dichloromethane, and then the product is separated and purified by column chromatography (eluent is n-hexane: ethyl acetate ═ 5:1) to obtain yellow solid ethyl (Z) -2- (2- (2- (2- (4- (2-cyano-2- (3,4, 5-tri (dodecyloxy) phenyl) vinyl) phenoxy) ethoxy) methacrylate;
500mg of (Z) -ethyl 2- (2- (2- (2- (4- (2-cyano-2- (3,4, 5-tris (dodecyloxy) phenyl) vinyl) phenoxy) ethoxy) methacrylate was dissolved in 1mL of tetrahydrofuran, and 2.8mg of 2, 2-azobisisobutyronitrile initiator was added, and then the mixed solution was subjected to three freeze-vacuum-thaw cycles in a dry Schlenk tube, kept under a nitrogen atmosphere, and stirred at 75 ℃ for reaction for 8 hours; and (4) performing direct column chromatography separation and purification (the eluent is dichloromethane) to obtain a yellow solid, namely the multistage photoresponse fluorescent liquid crystal polymer.
Claims (4)
1. A multi-stage photoresponse type fluorescent liquid crystal element and a polymer thereof are characterized in that the structural formula of the polymer is as follows:
2. a method for preparing the multistage photoresponse type fluorescent liquid crystal cell and the polymer thereof as claimed in claim 1, is characterized by comprising the following steps:
step 1: dissolving methyl 3,4, 5-trihydroxybenzoate, 1-bromoalkane, tetrabutylammonium iodide and potassium carbonate in a molar ratio of 1:4:0.03:8 in N, N-dimethylformamide, and stirring at 80-85 ℃ for reacting overnight; after the reaction liquid is cooled to room temperature, adding water for quenching reaction, then extracting by using dichloromethane, and then separating and purifying by column chromatography to obtain a white solid 3,4, 5-trialkoxy methyl benzoate;
step 2: dissolving 1 time equivalent of 3,4, 5-trialkoxy methyl benzoate in dry tetrahydrofuran, slowly dripping 1.5 times equivalent of lithium aluminum hydride tetrahydrofuran solution at 0 ℃, continuously stirring and reacting for 30-35 minutes, and continuously reacting for 2-3 hours at room temperature; adding water to quench the reaction, extracting with dichloromethane, drying with anhydrous magnesium sulfate, and rotary evaporating to remove solvent to obtain white solid 3,4, 5-trialkoxy benzyl alcohol;
and step 3: dissolving 1 equivalent of 3,4, 5-trialkoxy benzyl alcohol in dichloromethane, slowly dropping 2 equivalents of phosphorus tribromide tetrahydrofuran solution at 0 ℃, and continuously stirring and reacting at room temperature for 3-4 h; adding water to quench the reaction, extracting with dichloromethane, drying with anhydrous magnesium sulfate, and rotary evaporating to remove solvent to obtain white solid 5- (bromomethyl) -1,2, 3-trialkoxy benzene;
and 4, step 4: dissolving 5- (bromomethyl) -1,2, 3-trialkoxybenzene and trimethylsilyl cyanide in a molar ratio of 1:2 in anhydrous acetonitrile, and stirring to react for 3-4 h at room temperature; adding water to quench the reaction, extracting the reaction product by using dichloromethane, and then separating and purifying the reaction product by column chromatography to obtain a white solid 3,4, 5-trialkoxy phenylacetonitrile;
and 5: dissolving 4-methoxybenzaldehyde and 3,4, 5-trialkoxyphenylacetonitrile with a molar ratio of 1:1 in absolute ethanol, adding 2 times of equivalent of sodium hydroxide ethanol solution, and stirring and reacting at 50-55 ℃ for 2-3 h; adding water to quench the reaction, extracting the reaction product by using dichloromethane, and then carrying out column chromatography separation and purification to obtain a yellow solid (Z) -3- (4-methoxyphenyl) -2- (3,4, 5-trialkoxy phenyl) acrylonitrile, namely a multistage photoresponse type fluorescent liquid crystal element;
step 6: dissolving 450-500 mg of (Z) -3- (4-methoxyphenyl) -2- (3,4, 5-trialkoxyphenyl) acrylonitrile solid in a dichloromethane solution, continuously irradiating for 30min by using a 365nm ultraviolet lamp, and then separating and purifying by column chromatography to obtain a yellow solid (E) -3- (4-methoxyphenyl) -2- (3,4, 5-trialkoxyphenyl) acrylonitrile, namely the cis-trans isomeric state of the fluorescent liquid crystal element;
and 7: dissolving 170-200 mg of (E) -3- (4-methoxyphenyl) -2- (3,4, 5-trialkoxyphenyl) acrylonitrile solid in a dichloromethane solution, continuously irradiating for 2-3 h by using a 365nm ultraviolet lamp, and then separating and purifying by column chromatography to obtain a yellow solid 5,6, 7-trialkoxy-3-methoxyphenanthrene-9-carbonitrile, namely the intramolecular cyclization state of the fluorescent liquid crystal element;
and 8: taking 120 mg-150 mg of (E) -3- (4-methoxyphenyl) -2- (3,4, 5-trialkoxyphenyl) acrylonitrile solid, pressing the solid on a glass slide to form a film, continuously irradiating the film for 1h by using a 365nm ultraviolet lamp, and then separating and purifying the film by column chromatography to obtain yellow solid (1R,2R,3S,4S) -2, 4-bis (4-methoxyphenyl) -1, 3-bis (3,4, 5-trialkoxyphenyl) cyclobutane-1, 3-dicarbonitrile, namely the intermolecular [2+2] cycloaddition state of the fluorescent liquid crystal element;
step 10: the method comprises the following steps of dissolving bromoalkyl alcohol, p-hydroxybenzaldehyde and potassium carbonate in a molar ratio of 1:1:2 in N, N-dimethylformamide, and stirring and reacting at 85-90 ℃ for 11-12 hours; pouring the reaction liquid into water, extracting by using dichloromethane, and then carrying out column chromatography separation and purification to obtain hydroxy-substituted alkoxybenzaldehyde of a yellow oily liquid;
step 11: dissolving terminal hydroxyl substituted alkoxy benzaldehyde and 3,4, 5-trialkoxy phenylacetonitrile in a molar ratio of 1:1 in absolute ethanol, adding 2 times of equivalent of tetrabutyl ammonium hydroxide solution, and stirring and reacting at 40-45 ℃ for 2-3 h; adding water, extracting with dichloromethane, and purifying by column chromatography to obtain yellow solid (Z) -3- (4-end hydroxyl alkoxyl phenyl) -2- (3,4, 5-trialkoxy phenyl) acrylonitrile;
step 12: dissolving (Z) -3- (4-hydroxyl-terminated alkoxyphenyl) -2- (3,4, 5-trialkoxyphenyl) acrylonitrile and triethylamine in a molar ratio of 1:3 in dichloromethane, and slowly dropping a dichloromethane solution of 3 times equivalent of (methyl) acryloyl chloride into the reaction solution under the ice bath condition; after the reaction is finished, pouring the reaction liquid into water, extracting with dichloromethane, and then separating and purifying by column chromatography to obtain a polymerizable monomer;
step 13: dissolving 300-350 mg of polymerizable monomer in tetrahydrofuran, adding 0.02 equivalent of 2, 2-azobisisobutyronitrile initiator, performing three freezing-vacuum-unfreezing cycles on the mixed solution in a dry Schlenk tube, keeping the mixed solution in a nitrogen atmosphere, and stirring and reacting for 8 hours at 75 ℃; and (4) separating and purifying by direct column chromatography to obtain the multi-stage light response type fluorescent liquid crystal polymer.
3. The method of claim 2, wherein: the Schlenk technique is as follows: after the reactants and the solvent are added into a dry Schlenk tube, the Schlenk tube is frozen by liquid nitrogen and then vacuumized, then unfrozen by introducing nitrogen, and then vacuumized after being frozen by liquid nitrogen again, so that the operations of freezing-unfreezing-freezing are repeated for many times.
4. The method of claim 2, wherein: all solution heating was done under constant temperature oil bath conditions.
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