CN112552897A - Triaryl ethylene photochromic material, method and application as 3D printing ink - Google Patents
Triaryl ethylene photochromic material, method and application as 3D printing ink Download PDFInfo
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- CN112552897A CN112552897A CN202011419723.7A CN202011419723A CN112552897A CN 112552897 A CN112552897 A CN 112552897A CN 202011419723 A CN202011419723 A CN 202011419723A CN 112552897 A CN112552897 A CN 112552897A
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- photochromic material
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- 239000000463 material Substances 0.000 title claims abstract description 64
- 238000010146 3D printing Methods 0.000 title claims abstract description 36
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000005977 Ethylene Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 150000001491 aromatic compounds Chemical class 0.000 claims description 10
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 10
- -1 nitro, carboxyl Chemical group 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 7
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical group 0.000 claims description 6
- 125000001151 peptidyl group Chemical group 0.000 claims description 6
- 229920001184 polypeptide Chemical group 0.000 claims description 6
- 108090000765 processed proteins & peptides Chemical group 0.000 claims description 6
- 102000004196 processed proteins & peptides Human genes 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 238000007639 printing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 150000008366 benzophenones Chemical class 0.000 claims description 4
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical group CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 238000007239 Wittig reaction Methods 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 125000004386 diacrylate group Chemical group 0.000 claims description 3
- NWWQVENFTIRUMF-UHFFFAOYSA-N diphenylphosphanyl 2,4,6-trimethylbenzoate Chemical compound CC1=CC(C)=CC(C)=C1C(=O)OP(C=1C=CC=CC=1)C1=CC=CC=C1 NWWQVENFTIRUMF-UHFFFAOYSA-N 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 2
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000004044 response Effects 0.000 abstract description 5
- 230000006870 function Effects 0.000 abstract description 3
- 230000005055 memory storage Effects 0.000 abstract description 2
- 238000007363 ring formation reaction Methods 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- MKYQPGPNVYRMHI-UHFFFAOYSA-N Triphenylethylene Chemical group C=1C=CC=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 MKYQPGPNVYRMHI-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- DHTQKXHLXVUBCF-UHFFFAOYSA-N diethyl phenyl phosphate Chemical compound CCOP(=O)(OCC)OC1=CC=CC=C1 DHTQKXHLXVUBCF-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 2
- NLWBJPPMPLPZIE-UHFFFAOYSA-N methyl 4-(bromomethyl)benzoate Chemical compound COC(=O)C1=CC=C(CBr)C=C1 NLWBJPPMPLPZIE-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- ACYSYNIYTMHNSY-UHFFFAOYSA-N 1-(diethoxyphosphorylmethyl)-4-iodobenzene Chemical compound CCOP(=O)(OCC)CC1=CC=C(I)C=C1 ACYSYNIYTMHNSY-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005811 Corey-Fuchs synthesis reaction Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001562 benzopyrans Chemical class 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000001988 diarylethenes Chemical class 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000004961 triphenylmethanes Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
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- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
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Abstract
The invention relates to a triaryl ethylene photochromic material, a method and application as 3D printing ink, which is a quick response triaryl ethylene photochromic material which can be optically controlled in real time, has good memory storage function and excellent erasability. The triaryl ethylene photochromic material containing the unsaturated polymerizable group derivative is applied to the field of 3D printing, and a photochromic three-dimensional structure with a good surface and a micro-architecture complex geometric shape is obtained by a 3D printing technology. The synthetic method has simple process, the obtained product is easy to purify, and the triaryl ethylene has no cis-trans isomerism, can generate a cyclization reaction under ultraviolet irradiation to form a closed ring structure, has photochromic property, and the synthesized photochromic material has good stability.
Description
Technical Field
The invention belongs to the field of color-changing materials, and particularly relates to a triaryl ethylene photochromic material, a method and application as 3D printing ink.
Background
Photochromic materials are materials that can undergo reversible physical or chemical changes when excited by a light source, thereby changing color and other physical properties. (H.Diirr, H.Bouas-latex. pure and Applied Chemistry,2001) the photochromic phenomenon can occur in both inorganic and organic compounds, and organic photochromic compounds are gradually becoming the main research objects of photochromic materials due to the characteristics of easy modification, good fatigue resistance and the like determined by the structure. (MINKIN V I.I. chemical reviews,2004) organic photochromic materials are mainly the following: spiropyrans, spirooxazines, benzopyrans, azos, fulgides, triphenylmethanes, and diarylethenes. However, most of the traditional organic photochromic materials have the problems of complex design and synthesis, high material cost and the like. The triphenylethylene photochromic material has a simple synthetic route and excellent photochromic performance, and is a triphenylethylene derivative with excellent photochromic performance obtained by introducing para-chlorine atoms on two benzene rings on the same side of triphenylethylene in photochromic materials Ou and the like with potential application values. (Ou D, Chemical Science,2016.), however, this kind of new material has a narrow application range, and can only be used to simply make photochromic thin films, and this kind of small molecule material often exists in a crystal or powder state, and is difficult to be applied to various complicated model constructions. Therefore, the series of materials still have some defects in light control precision materials and the like and are required to be further improved. However, 3D printing technology provides new capabilities to impart complex geometries to the device with precisely defined microarchitectures to meet individual needs and requirements to fabricate complex three-dimensional geometries. Simple planar or tubular geometries compared to conventional devices, such as actuator and spin-on photochromic film fabrication, casting or extrusion, 3D printing can not only meet the requirements of macroscopic complex shapes, but also meet the various conformational changes caused by external stimuli. Therefore, these 3D printed photochromic materials may be applied in a wide variety of fields including tissue engineering, soft robotics, nanodevices, optical engineering, metamaterials, and many others, providing future trends and opportunities.
In the present invention, a derivative containing an unsaturated polymerizable group is introduced into a triarylethylene-based photochromic material. Due to the polymerizability of the derivatives, the derivatives can be well connected with 3D printing. Therefore, the photochromic material not only has good information storage function and quick response of excellent erasability, but also can obtain a photochromic three-dimensional structure with a complex geometric shape of an excellent surface and a micro-architecture by a 3D printing technology, and the series of photochromic materials can be used in a plurality of fields (the same as the application range of the first paragraph). At the same time, considerable yield, cheap and readily available raw materials and mild synthesis conditions will also give this class of materials greater market potential.
Disclosure of Invention
The technical problem to be solved is as follows:
in order to avoid the defects of the prior art, the invention provides a triaryl ethylene photochromic material, a method and application as 3D printing ink, the triaryl ethylene photochromic material is quick-response triaryl ethylene photochromic 3D printing ink which can be controlled by light in real time, has good memory and storage functions and excellent erasability, and is used for light-operated sensing, anti-counterfeiting, protection, optical information storage, optical engineering, special materials and many other fields. It is another object of the present invention to provide two effective synthesis methods (Corey-fuchs reaction and wittig reaction) for the above-mentioned triarylethylene photochromic material containing unsaturated polymerizable group derivative, which have simple process, high yield and easy purification, and can adjust the photochromic property, light-emitting wavelength and the like of the final product by introducing different functional groups. The third purpose of the invention is to apply the triaryl ethylene photochromic material containing unsaturated polymerizable group derivatives to the field of 3D printing, and obtain a photochromic three-dimensional structure with a complex geometric shape with an excellent surface and a microarchitecture by a 3D printing technology.
The technical scheme of the invention is as follows: a triaryl ethylene photochromic material is characterized in that: the molecular general formula is:
the further technical scheme of the invention is as follows: r0When unsaturated polymerizable groups are present, the following structure is selected:
the further technical scheme of the invention is as follows: r4Is alkyl, alkoxy, ester group, peptidyl, polypeptide group, aromatic group or aromatic heterocyclic ring.
The further technical scheme of the invention is as follows: r5, R6 and R7 are hydrogen atoms, alkyl, halogen, cyano, alkoxy, nitro, carboxyl, ester groups, amino, hydroxyl, peptidyl, polypeptide, aromatic groups or same or different substituent groups in aromatic heterocycles.
The further technical scheme of the invention is as follows: r1 is an aromatic heterocycle selected from the following structures, which may be the same or different:
wherein, the dotted line represents a connecting part, and the R8, R9, R10, R11, R12, R13 and R14 groups are the same or different and are selected from any one of hydrogen atoms, alkyl, halogen, alkoxy, nitro, amino, aldehyde groups, cyano and aryl; r15 is selected from any one of hydrogen atom, alkyl, alkoxy, nitro and aryl.
The further technical scheme of the invention is as follows: r2 and R3 are hydrogen atoms, alkyl, halogen, cyano, alkoxy, nitro, carboxyl, amino, hydroxyl, peptidyl, polypeptide, aryl or aromatic heterocycle.
A preparation method of triaryl ethylene photochromic material comprises the following steps: the method is characterized by comprising the following specific steps:
the method comprises the following steps: an aromatic ring, an aromatic heterocycle and derivatives thereof with one end containing a formaldehyde substituent are subjected to a Corey-Funchs reaction to synthesize a dibromo substituent intermediate; providing an aromatic ring, an aromatic heterocycle or a derivative thereof with one end containing a formaldehyde substituent, and cooling to 0 ℃ in a dichloromethane solution under the action of triphenylphosphine and carbon tetrabromide to react for 16h to obtain a dibromo substituent; wherein, one end of the aromatic ring, the aromatic heterocycle or the derivative thereof contains a formaldehyde substituent, and the molar ratio of triphenylphosphine to carbon tetrabromide is 1: 2: 5;
step two: the target product is obtained by carrying out Suzuki reaction on the obtained dibromo substituent and an aromatic compound or a heterocyclic compound containing boric acid or pinacol borate, placing the dibromo substituent and the aromatic compound or the heterocyclic compound containing the boric acid or pinacol borate in a tetrahydrofuran solution, and heating to 50 ℃ for reaction under the action of palladium potassium carbonate catalysis to obtain the triaryl ethylene photochromic material containing the unsaturated polymerizable group; wherein, the mol ratio of the dibromo substituent, the aromatic compound or heterocyclic compound containing boric acid or pinacol borate and potassium carbonate is 1: 1: 3.
a preparation method of triaryl ethylene photochromic material comprises the following steps: the method is characterized by comprising the following specific steps:
the aromatic compound or heterocyclic compound containing phosphoric acid diethyl ester group and benzophenone derivative are dissolved in tetrahydrofuran solution, under the action of potassium tert-butoxide and at room temperature, triaryl ethylene photochromic material containing unsaturated polymerizable group is obtained by Wittig reaction.
Wherein the molar ratio of aromatic compound or heterocyclic compound containing phosphoric acid diethyl ester group, benzophenone derivative and potassium tert-butoxide is 1: 1: 3.
the application of the triaryl ethylene photochromic material as the 3D printing ink is characterized by comprising the following specific steps:
the method comprises the following steps: directly using the triaryl ethylene photochromic material as 3D printing ink;
or mixing a monomer of polyethylene glycol (glycol) diacrylate (molecular weight 575) and the triaryl ethylene photochromic material according to the mass fraction of 20: 1, uniformly mixing, adding 2-80% of tetrahydrofuran THF solution and 5 wt% of photoinitiator diphenyl- (2,4, 6-trimethylbenzoyl) oxyphosphorus TPO, and fully and uniformly stirring to obtain 3D printing ink;
step two: printing the 3D printing ink obtained in the step one on a customized high-resolution-based 3D printing system to form a complex three-dimensional structure; the exposure time was 2 seconds, and the thickness of each layer was 50 mm;
step three: after printing is finished, removing unreacted monomers and crosslinking agents on the surface of the printed 3D structure by using a rubber suction ball;
step four: the structure was post-cured in a UV oven.
Advantageous effects
The invention has the beneficial effects that: the traditional photochromic material has low yield, poor decoration and complex synthesis, the synthesis method of the invention has simple process, the obtained product is easy to purify, because the triaryl ethylene has no cis-trans isomerism, the triaryl ethylene can generate cyclization reaction under ultraviolet irradiation to form a closed ring structure, the photochromic material has photochromic property, and the synthesized photochromic material has good stability (can be stored at room temperature for more than 2 years and can also keep the original photochromic property), fast response speed (can achieve the color change effect by ultraviolet irradiation for 5 seconds) and excellent erasability (can be recovered to the original color under visible light and can be repeatedly used for hundreds of times).
The triaryl ethylene photochromic material containing the unsaturated polymerizable group derivative is directly applied to the field of 3D printing or is applied to the field of 3D printing after being blended with other 3D printing materials according to a certain proportion (the mass ratio is 1: 10000 to 10000: 1), and the polymerizability of the unsaturated group can be well combined with the traditional 3D printing materials, so that the obtained material can obtain a photochromic three-dimensional structure with a complex geometric shape with an excellent surface and a micro-architecture by a 3D printing technology, and is applied to light-operated materials, optical information storage, wearable devices, chemical biological detection, biological imaging, anti-counterfeiting, facility protection, optical engineering, special materials and many other fields.
To further illustrate the features and technical content of the present invention, please refer to the following drawings related to the present invention, which are for reference and illustration only and are not intended to limit the present invention.
Drawings
FIG. 1 is a comparison of before and after solution photochromism and UV absorption spectra of the product of example 1 of the present invention;
fig. 2 and 3 are comparative images before and after the 3D printing material of the product of example 1 of the present invention is photochromic.
Detailed Description
The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
The present invention will be further illustrated by the following specific examples, but the present invention is not limited to these specific examples.
3D printing ink monomer synthesis example 1:
the method comprises the following steps: synthesis of intermediate ylide reagent 4-methyl formate diethyl phenylphosphate
A250 ml flask was charged with methyl 4-bromomethylbenzoate (4.60g, 20.06mmol) and triethyl phosphite (10.00g, 60.18 mmol). The flask was initially suspended and heated above 80 ℃ on a magnetic stirrer to reflux. After 12 hours of reflux, it was cooled to room temperature and the excess triethyl phosphite was removed by distillation under reduced pressure. After cooling, solid is separated out from the residual stock solution, and the solid is washed by normal hexane, filtered and dried to obtain 5.05g of the ylide reagent 4-methyl formate diethyl phenylphosphate with the yield of 87.94%.
Failure case (1)
A250 ml flask was charged with methyl 4-bromomethylbenzoate (2.30g, 10.03mmol) and triethyl phosphite (5.00g, 30.09 mmol). The flask was initially suspended and heated to 50 ℃ on a magnetic stirrer, after 12 hours, cooled to room temperature and excess triethyl phosphite removed by distillation under reduced pressure. And (3) after cooling, precipitating a solid in the residual stock solution, washing with n-hexane, filtering and drying to obtain the ylide reagent 4-methyl formate diethyl phenylphosphate. The reaction failed due to insufficient heating temperature.
Step two: synthesis of intermediate methyl formate triaryl ethylene
Diethyl 4-carboxylate phenylphosphate (5.00g, 17.47mmol) was added to a three-necked flask, nitrogen was purged and the appropriate amount of Tetrahydrofuran (THF) was added, and potassium tert-butoxide (5.88g, 52.40mmol) was added. After the potassium tert-butoxide dissolved, 4-difluorobenzophenone (5.72g, 26.20mmol) was added and the reaction was stopped after 12 h. The mother liquor obtained in the reaction was transferred to a separatory funnel, and dichloromethane and saturated brine were added for extraction. After the organic layer was dried over anhydrous sodium sulfate, excess solvent was removed by a rotary evaporator. Then purifying by silica gel column chromatography, wherein the eluent is a mixed solution of n-hexane and dichloromethane with the volume ratio of 8.5: 1.5. Methyl formate triaryl ethylene 4.2g was obtained as a pale yellow solid in 68.63% yield.
Step three: synthesis of intermediate benzylhydroxytriarylethene
Intermediate methyl formate triarylethylene (4.00g, 11.42mmol) was dissolved in 100ml dichloromethane under anhydrous nitrogen blanket and cooled to-78 ℃. Diisobutylaluminum hydride (47ml, 1M solution in n-hexane) was then slowly added dropwise and after 3 hours of continuous stirring, the temperature was raised to 0 ℃. Quenched with distilled water. Then transferred to a separatory funnel and extracted by adding dichloromethane and water. The organic layer was dried over anhydrous magnesium sulfate and then spin-dried using a rotary evaporator to obtain 3.2g of benzylhydroxytriarylethylene as a white solid with a yield of 86.95%.
Step four: target products example 1 Synthesis of methyl methacrylate group-containing triaryl ethylene (Structure shown below)
Methacryloyl chloride (500mg, 4.78mmol) was dissolved in dichloromethane under nitrogen at 0 ℃ and then the intermediate benzylhydroxytriarylethylene (1.54g, 4.78mmol) and triethylamine (968.05mg, 9.57mmol) were added, stirred for 12 hours, quenched with 1M dilute hydrochloric acid, transferred to a separatory funnel and extracted with dichloromethane and water. The organic layer was dried over anhydrous magnesium sulfate, spin-dried with a rotary evaporator, and then purified by silica gel column chromatography, and the eluent was a mixed solution of dichloromethane and n-hexane in a volume ratio of 1: 1. 1.15g of a transparent oily liquid was obtained as triarylethylene containing methyl methacrylate groups, yield 61.58%.
Failure case (2)
Methacryloyl chloride (500mg, 4.78mmol) was dissolved in dichloromethane under nitrogen at 0 ℃ and then the intermediate benzylhydroxytriarylethylene (1.54g, 4.78mmol) was added, stirred for reaction for 12 hours, then quenched with 1M dilute hydrochloric acid, transferred to a separatory funnel and extracted with dichloromethane and water. And drying the organic layer by anhydrous magnesium sulfate, then carrying out spin drying by using a rotary evaporator, and then purifying by using a silica gel column chromatography method, wherein eluent is a mixed solution of dichloromethane and n-hexane in a volume ratio of 1:1, and a product is not obtained. The reaction does not produce a product due to the absence of triethylamine, which provides a basic environment.
3D printing ink monomer synthesis example 2:
the method comprises the following steps: synthesis of intermediate iodotriaryl ethylene
To a two-necked round-bottomed flask containing bis (4-fluorophenyl) methanone (0.502g,2.0mmol) and diethyl (4-iodobenzyl) phosphonate (0.456g,2.0mmol) was added degassed tetrahydrofuran (30mL) under an argon atmosphere. After cooling to 0 deg.C, potassium tert-butoxide (0.672g,6mmol) was added. After stirring under argon for 12 hours, the mixture was poured into 95% ethanol (150mL) and stirred for another 1 hour. The white precipitate formed was collected by filtration. The precipitate was dissolved in dichloromethane and washed 3 times with water. The organic layer was dried over anhydrous magnesium sulfate. After evaporation of the filtrate, the residue is purified by steam diffusion recrystallization from hexane to a concentrated dichloromethane solution of the product to yield a white powder iodotriaryl ethylene product.
Step two: target product example 2 Alkynyltriaryl ethylene
Potassium carbonate (7.72mmol,1.07g) was added to a solution of trimethylsilyltriarylethylene (2.57mmol,1g) in methanol (20ml) and dichloromethane (10ml) (v/v ═ 2:1), stirred at room temperature for 12h, and the resulting mixture was treated with water and extracted with ether. The combined organic layers were washed with brine and then dried over magnesium sulfate. Removing the solvent, and obtaining the pure product of the alkynyltriarylethylene by decompression careful distillation or silica gel column chromatography purification.
3D printing example 3:
mixing a monomer of polyethylene glycol (diol) diacrylate (molecular weight 575) and the target product of the example 1, namely methyl methacrylate triaryl ethylene, according to the mass fraction of 20: 1, adding a certain amount of Tetrahydrofuran (THF) solution and 5 wt% of photoinitiator diphenyl- (2,4, 6-trimethylbenzoyl) oxyphosphorus (TPO) into the mixture, and fully and uniformly stirring the mixture to obtain the 3D printing ink. The prepared 3D ink is then printed on a custom high resolution based 3D printing system to print complex three dimensional structures. The exposure time was 2 seconds and the thickness of each layer was 50 mm. After printing is finished, unreacted monomers and crosslinking agents on the surface of the printed 3D structure are removed by using a rubber suction ball. Finally, the structure was post-cured in a UV oven.
TABLE 1 UV absorption wavelength of maximum discoloration and stimulus response conditions for the final products in the examples
| Compound (I) | Effect of photochromic generation | Ultraviolet absorption peak (lambda/nm) |
| Example 1 | Obvious photochromism | 450 |
| Example 2 | |
460 |
| Example 3 | |
480 |
Note: the ultraviolet absorption spectrum was measured by marine optics QE65 pro.
In summary, the present invention relates to a triaryl ethylene-containing photochromic material, which has excellent photochromic properties and good erasability, and is suitable for use as a photoswitch, a memory storage material (write many), and the like. In addition, the material can be used as 3D printing ink, can successfully print out a photochromic three-dimensional structure with a complex geometric shape and an excellent surface and a micro-architecture in a 3D mode, and is suitable for light-operated sensing, anti-counterfeiting, camouflage, protection, optical information storage, optical engineering, special materials and many other fields. As described above, the person skilled in the art can make other various corresponding changes and modifications according to the technical solution and the technical idea of the present invention, and all such changes and modifications should fall within the protection scope of the claims of the present invention.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (9)
1. A triaryl ethylene photochromic material is characterized in that: the molecular general formula is:
2. the triarylethylene-based photochromic material of claim 1, wherein: r0When unsaturated polymerizable groups are present, the following structure is selected:
3. the triarylethylene-based photochromic material of claim 2, wherein: r4Is alkyl, alkoxy, ester group, peptidyl, polypeptide group, aromatic group or aromatic heterocyclic ring.
4. The triarylethylene-based photochromic material of claim 2, wherein: r5, R6 and R7 are hydrogen atoms, alkyl, halogen, cyano, alkoxy, nitro, carboxyl, ester groups, amino, hydroxyl, peptidyl, polypeptide, aromatic groups or same or different substituent groups in aromatic heterocycles.
5. The triarylethylene-based photochromic material of claim 1, wherein: r1 is an aromatic heterocycle selected from the following structures, which may be the same or different:
wherein, the dotted line represents a connecting part, and the R8, R9, R10, R11, R12, R13 and R14 groups are the same or different and are selected from any one of hydrogen atoms, alkyl, halogen, alkoxy, nitro, amino, aldehyde groups, cyano and aryl; r15 is selected from any one of hydrogen atom, alkyl, alkoxy, nitro and aryl.
6. The triarylethylene-based photochromic material of claim 1, wherein: r2 and R3 are hydrogen atoms, alkyl, halogen, cyano, alkoxy, nitro, carboxyl, amino, hydroxyl, peptidyl, polypeptide, aryl or aromatic heterocycle.
7. A process for producing the triarylethylene-based photochromic material according to any one of claims 1 to 6, which comprises: the method is characterized by comprising the following specific steps:
the method comprises the following steps: an aromatic ring, an aromatic heterocycle and derivatives thereof with one end containing a formaldehyde substituent are subjected to a Corey-Funchs reaction to synthesize a dibromo substituent intermediate; providing an aromatic ring, an aromatic heterocycle or a derivative thereof with one end containing a formaldehyde substituent, and cooling to 0 ℃ in a dichloromethane solution under the action of triphenylphosphine and carbon tetrabromide to react for 16h to obtain a dibromo substituent; wherein, one end of the aromatic ring, the aromatic heterocycle or the derivative thereof contains a formaldehyde substituent, and the molar ratio of triphenylphosphine to carbon tetrabromide is 1: 2: 5;
step two: the target product is obtained by carrying out Suzuki reaction on the obtained dibromo substituent and an aromatic compound or a heterocyclic compound containing boric acid or pinacol borate, placing the dibromo substituent and the aromatic compound or the heterocyclic compound containing the boric acid or pinacol borate in a tetrahydrofuran solution, and heating to 50 ℃ for reaction under the action of palladium potassium carbonate catalysis to obtain the triaryl ethylene photochromic material containing the unsaturated polymerizable group; wherein, the mol ratio of the dibromo substituent, the aromatic compound or heterocyclic compound containing boric acid or pinacol borate and potassium carbonate is 1: 1: 3.
8. a process for producing the triarylethylene-based photochromic material according to any one of claims 1 to 6, which comprises: the method is characterized by comprising the following specific steps:
the aromatic compound or heterocyclic compound containing phosphoric acid diethyl ester group and benzophenone derivative are dissolved in tetrahydrofuran solution, under the action of potassium tert-butoxide and at room temperature, triaryl ethylene photochromic material containing unsaturated polymerizable group is obtained by Wittig reaction.
Wherein the molar ratio of aromatic compound or heterocyclic compound containing phosphoric acid diethyl ester group, benzophenone derivative and potassium tert-butoxide is 1: 1: 3.
9. the application of the triaryl ethylene photochromic material of any one of claims 1 to 6 as 3D printing ink is characterized by comprising the following specific steps:
the method comprises the following steps: directly using the triaryl ethylene photochromic material as 3D printing ink;
or mixing a monomer of polyethylene glycol (glycol) diacrylate (molecular weight 575) and the triaryl ethylene photochromic material according to the mass fraction of 20: 1, uniformly mixing, adding 2-80% of tetrahydrofuran THF solution and 5 wt% of photoinitiator diphenyl- (2,4, 6-trimethylbenzoyl) oxyphosphorus TPO, and fully and uniformly stirring to obtain 3D printing ink;
step two: printing the 3D printing ink obtained in the step one on a customized high-resolution-based 3D printing system to form a complex three-dimensional structure; the exposure time was 2 seconds, and the thickness of each layer was 50 mm;
step three: after printing is finished, removing unreacted monomers and crosslinking agents on the surface of the printed 3D structure by using a rubber suction ball;
step four: the structure was post-cured in a UV oven.
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| CN115404721A (en) * | 2022-06-21 | 2022-11-29 | 西北工业大学 | Preparation and application of photoresponse thermal printing paper |
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