CN111675723A - High-temperature-resistant spirooxazine photochromic compound and preparation method and application thereof - Google Patents
High-temperature-resistant spirooxazine photochromic compound and preparation method and application thereof Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 235000010288 sodium nitrite Nutrition 0.000 claims description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 238000007336 electrophilic substitution reaction Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims 3
- 238000002845 discoloration Methods 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 abstract description 4
- 238000005562 fading Methods 0.000 abstract description 4
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- 239000003086 colorant Substances 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 8
- 229940125890 compound Ia Drugs 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
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- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- C07D498/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
- C07D498/20—Spiro-condensed systems
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Abstract
The invention discloses a high-temperature-resistant spirooxazine photochromic compound and a preparation method and application thereof, belonging to the technical field of organic functional materials. The invention aims to develop a high-temperature-resistant spirooxazine photochromic compound. The spirooxazine photochromic compound has good photo-thermal stability, easy dissolution, high temperature resistance and high discoloration and fading speed. Meanwhile, the preparation method is convenient for later-stage processing and application, and the plastic master batch is prepared by blending the slurry prepared from the spirooxazine photochromic compound and plastics and has various colors.
Description
Technical Field
The invention relates to a high-temperature-resistant spirooxazine photochromic compound and a preparation method and application thereof, belonging to the technical field of organic functional materials.
Background
Photochromic is a phenomenon that the absorption wavelength of photochromic powder in a powder, a solvent or resin is changed in a visible light region under the excitation of sunlight or ultraviolet light, so that the color is changed. Such materials, which have received much attention, have started from the 1956 application possibility of hirschberg to photochromic materials for optical recording storage. Hitherto, photochromic materials are widely used in the fields of photochromic glasses, photochromic plastics, coatings, anti-counterfeiting, textiles, optical information storage, optical regulation, optical switches, optical device materials, optical information gene materials, modified gene chip materials and the like.
Spirooxazine-based photochromic compounds are receiving attention due to excellent discoloration and fading rates. The improvement of the stability of the open ring state of spirooxazines is still under investigation. At present, few reports of the spirooxazine photochromic compounds which are stable outdoors for a long time and have high temperature resistance are provided. The indene condensed naphthol derivative has high melting point and higher decomposition temperature, so that the indene condensed naphthol derivative can resist high temperature relatively, and meanwhile, the photo-thermal stability of the structure is improved due to the conjugated structure of a plurality of benzene rings. Therefore, the invention provides a high-temperature resistant spirooxazine photochromic compound based on indeno-fused naphthol.
Disclosure of Invention
The invention aims to develop a high-temperature-resistant spirooxazine photochromic compound, which has the advantages of good photo-thermal stability, easy dissolution, high temperature resistance, high discoloration and fading speed and convenience for later-stage processing and application.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
a high-temperature resistant spirooxazine photochromic compound has the following molecular structure:
wherein, R1, R2, R3 and R4 are hydrogen, C1-C6 alkyl (CmH2m +1, m ═ 1,2,3,4,5,6), alkoxy and halogen; r5, R6 is one of hydrogen, C1-C6 alkyl (CmH2m +1, m ═ 1,2,3,4,5, 6).
A preparation method of a high-temperature-resistant spirooxazine photochromic compound comprises the following steps:
the first step is as follows: electrophilic substitution of compound M1 with sodium nitrite produces M2 compound, the reaction formula is as follows:
the second step is that: compound M2 and indoline were reacted in a solvent to synthesize compound M3, of the formula:
the third step: compound M3 is reacted with a halohydrocarbon under basic conditions to produce compound I, according to the formula:
as a preferred example, the nitrosating agent used in the first step is sodium nitrite, used in a quantity and in a molar ratio of compound M4 of (1.0 to 1.5): 1, the catalyst is dilute sulfuric acid with the concentration of 10-98 percent, the reaction temperature is-20-10 ℃, and the reaction time is 1-12 h.
As a preferred example, the molar ratio of compound M2 and indoline used in the second step is 1: (1.0-2.0), the protective gas of the reaction is nitrogen or argon, the used solvent is methanol, ethanol, n-butanol or isopropanol, the reaction temperature is 50-120 ℃, and the reaction time is 0.5-24 h.
As a preferable example, the hydrogen-withdrawing agent used in the third step is sodium hydride, calcium hydride or potassium tert-butoxide, the amount of the hydrogen-withdrawing agent used is 1.0 to 3.0 equivalents, the halohydrocarbon used is one or more of chloride, bromide and iodide of C1 to C6 alkyl, the amount of the halide added is 1.0 to 3.0 equivalents, the reaction solvent is one or more of tetrahydrofuran, 1, 4-dioxane, toluene or N, N-dimethylformamide, the reaction temperature is-20 to 80 ℃, and the reaction time is 1 to 18 hours.
As a preferred example, the photochromic compound is applied to the preparation of plastic master batches.
A plastic master batch prepared from a high-temperature-resistant spirooxazine photochromic compound comprises the following components in percentage by mass: 50-90% of plastic; 10-50% of slurry made of photochromic compound.
As a preferable example, the plastic in the plastic master batch is one or a combination of more of PET, PC, PVC, PP, PMMA and PU, the solid content of the slurry prepared from the photochromic compound is 1-20%, and the melting temperature is 200-300 ℃.
As a preferable example, the plastic master batch is applied to the fields of color-changing glasses, automobile and train window films and building window films.
The invention has the beneficial effects that: the spirooxazine photochromic compound prepared by the method disclosed by the invention has the advantages of great improvement on photo-thermal stability, high temperature resistance, easiness in dissolution, high discoloration and fading speed of the spirooxazine photochromic compound, high melting point and decomposition temperature of the compound, convenience for later-stage processing and application, and various colors.
Drawings
FIG. 1: changing the ultraviolet visible light absorption spectrum of a photochromic target compound Ia before and after ultraviolet light irradiation in an ethyl acetate solution (1 x 10 < -4 > mol/L); (wherein, the lines with squares and dots represent the changes in the UV-VIS absorption spectra of the compound Ia before and after the photochromism.)
FIG. 2: blending the color-changing powder and plastic, and preparing PET plastic master batch by melt extrusion without 365nm ultraviolet excitation;
FIG. 3: blending the color-changing powder and plastic, and melting and extruding the prepared PET plastic master batch a (schematic diagram after 365nm ultraviolet light excitation;
FIG. 4: a nuclear magnetic resonance hydrogen spectrum characteristic map of Ia;
FIG. 5: and the nuclear magnetic resonance carbon spectrum characterization map of Ia.
Detailed Description
In order to make the technical means, the original characteristics, the achieved purpose and the efficacy of the invention easily understood, the invention is further described with reference to the following embodiments.
Example one
Example 1 synthesis of photochromic compound Ia:
the first step is as follows: synthesis of M2a, reaction formula:
adding M1a (2.921g, 0.010mol) into a 50ml four-neck bottle, adding a 5% sodium hydroxide aqueous solution, magnetically stirring, completely dissolving, cooling to-5 ℃, then adding NaNO2(0.760g, 0.011mol), slowly dripping 40% dilute sulfuric acid solution under vigorous stirring for 1h, after the addition is finished, continuously stirring at 0 ℃ for reaction for 42h (TCL monitoring), and naturally heating to room temperature after the reaction is finished. And (3) directly filtering the reaction solution, washing the reaction solution to be neutral, and drying the reaction solution in vacuum to obtain M2 a. Yield: 86 percent.
The second step is that: synthesis of M3a, reaction formula:
adding M2a (2.571g, 0.008mol) into a 50ml four-mouth bottle, adding 25ml ethanol solvent, magnetically stirring, heating to 90 ℃, completely dissolving, keeping a reflux state, slowly dropwise adding an ethanol solution of indoline (1.731g, 0.010mol) under the protection of argon, and finishing dropwise adding for 1 hour. After the addition, refluxing reaction is continued for 3h at 90 ℃ (monitoring by TCL), after the reaction is finished, ethanol of the reaction solution is spin-dried, and then petroleum ether/ethyl acetate (4: 1) column chromatography is carried out, and the M3a is obtained after spin-drying. Yield: 72 percent.
The third step: ia, the reaction formula is as follows:
adding M3a (4.766g, 0.010mol) into a 100ml four-mouth bottle, adding 60ml of N, N-dimethylformamide solvent, magnetically stirring at normal temperature for 20min for complete dissolution, then cooling to 0 ℃, then adding sodium hydrogen (0.600g, 0.025mol), finally slowly dripping methyl iodide (3.549g, 0.025mol), continuing stirring at 0 ℃ for reaction for 10h (TCL monitoring) after the addition is finished, filtering the reaction solution after the reaction is finished, carrying out rotary evaporation on the filtrate, and recrystallizing petroleum ether/dichloromethane (6: 1) to obtain the target product Ia. Yield: and (3.5).
As shown in FIG. 4, the NMR hydrogen spectrum characterization data for Ia is: 1H NMR (400MHz, CDCl 3): (ppm)8.06(s, 1H), 7.61(s, 1H), 7.50(s, 1H), 7.44(s, 1H), 7.40(s, 1H), 7.24(s, 1H), 7.11(s, 1H), 6.9(s, 1H), 6.88(s, 1H), 6.52(s, 1H), 6.51(s, 1H), 3.73(d, 6H), 2.85(s, 3H), 1.73(s, 6H), 1.39(s, 6H).
As shown in FIG. 5, the NMR carbon spectrum characterization data of Ia is: 13C NMR (400MHz, CDCl 3): 150.7, 150.7, 145.6, 145.4, 141.9, 141.2, 136.5, 131.7, 128.9, 128.4, 127.9, 127.9, 126.7, 126.5, 126.3, 125.7, 124.9, 122.0, 117.6, 112.7, 106.0, 104.2, 100.7, 56.3, 56.3, 43.9, 33.4, 31.4, 31.4, 29.6, 18.4, 18.4.
The formula of the PET plastic master batch prepared from the prepared photochromic compound Ia comprises the following components: PET: 70%, paste made of photochromic compound: 30 percent; the solid content of the photochromic compound Ia slurry is 10 percent, the melt extrusion temperature is 275 ℃, wherein the decomposition temperature of the PET plastic is known to be 283-306 ℃, and the plastic master batch prepared by high-temperature melt extrusion can change color, remove ultraviolet rays and return to a colorless state after being irradiated by ultraviolet rays.
The melting points and TGA decomposition temperatures (10%) of the photochromic compound Ia and the fluorenylspirooxazine photochromic compound adopting the following structure are compared as shown in the table I:
watch 1
As can be seen from the table I, compared with spirooxazine photochromic compounds with small molecular weight such as fluoreno spirooxazine and the like, the photochromic compound Ia prepared by the method has higher melting point, higher decomposition temperature and higher high temperature resistance, and is suitable for being used in a plastic master batch system.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. A high-temperature-resistant spirooxazine photochromic compound is characterized in that the molecular structure is as follows:
wherein, R1, R2, R3 and R4 are hydrogen, C1-C6 alkyl (CmH2m +1, m ═ 1,2,3,4,5,6), alkoxy and halogen; r5, R6 is one of hydrogen, C1-C6 alkyl (CmH2m +1, m ═ 1,2,3,4,5, 6).
2. A preparation method of a high-temperature-resistant spirooxazine photochromic compound is characterized by comprising the following steps:
the first step is as follows: electrophilic substitution of compound M1 with sodium nitrite produces M2 compound, the reaction formula is as follows:
the second step is that: compound M2 and indoline were reacted in a solvent to synthesize compound M3, of the formula:
the third step: compound M3 is reacted with a halohydrocarbon under basic conditions to produce compound I, according to the formula:
3. the method for preparing the high temperature resistant spirooxazine photochromic compound of claim 7, wherein: the nitrosating reagent used in the first step is sodium nitrite, used in a molar ratio with respect to compound M4 of (1.0 to 1.5): 1, the catalyst is dilute sulfuric acid with the concentration of 10-98 percent, the reaction temperature is-20-10 ℃, and the reaction time is 1-12 h.
4. The method for preparing the high temperature resistant spirooxazine photochromic compound of claim 7, wherein: the molar ratio of the compound M2 to indoline used in the second step is 1: (1.0-2.0), the protective gas of the reaction is nitrogen or argon, the used solvent is methanol, ethanol, n-butanol or isopropanol, the reaction temperature is 50-120 ℃, and the reaction time is 0.5-24 h.
5. The method for preparing the high temperature resistant spirooxazine photochromic compound of claim 7, wherein: the hydrogen removing reagent used in the third step is sodium hydride, calcium hydride or potassium tert-butoxide, the dosage of the hydrogen removing reagent is 1.0 to 3.0 equivalents, the used halohydrocarbon is one or more of C1 to C6 alkyl chloride, bromide and iodide, the dosage of the halide is 1.0 to 3.0 equivalents, the reaction solvent is tetrahydrofuran, 1, 4-dioxane, toluene or N, N-dimethylformamide, the reaction temperature is-20 to 80 ℃, and the reaction time is 1 to 18 hours.
6. The high temperature resistant spirooxazine photochromic compound of claim 1, wherein: the photochromic compound is applied to preparing plastic master batches.
7. A plastic master batch prepared based on the high-temperature-resistant spirooxazine photochromic compound of claim 7, wherein the plastic master batch comprises the following components in percentage by mass: 50-90% of plastic; 10-50% of slurry made of photochromic compound.
8. The plastic masterbatch prepared from high temperature resistant spirooxazine photochromic compound as claimed in claim 8, wherein the plastic in the plastic masterbatch is one or more of PET, PC, PVC, PP, PMMA, PU, the solid content of the slurry prepared from photochromic compound is 1-20%, and the melting temperature is 200-300 ℃.
9. The plastic master batch prepared from the high-temperature-resistant spirooxazine photochromic compound as claimed in claim 4, wherein the plastic master batch is applied to the fields of photochromic glasses, automobile and train window films and building window films.
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