CN115975394A - Preparation method and application of organic dye based on indane-1, 3-dione derivative - Google Patents
Preparation method and application of organic dye based on indane-1, 3-dione derivative Download PDFInfo
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- UHKAJLSKXBADFT-UHFFFAOYSA-N 1,3-indandione Chemical class C1=CC=C2C(=O)CC(=O)C2=C1 UHKAJLSKXBADFT-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 14
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000975 dye Substances 0.000 claims description 77
- 238000010146 3D printing Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 5
- 238000003512 Claisen condensation reaction Methods 0.000 claims description 3
- 238000006000 Knoevenagel condensation reaction Methods 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 238000005262 decarbonization Methods 0.000 claims description 3
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical group N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- 238000007039 two-step reaction Methods 0.000 claims description 3
- 239000000178 monomer Substances 0.000 abstract description 23
- 229920005989 resin Polymers 0.000 abstract description 19
- 239000011347 resin Substances 0.000 abstract description 19
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 abstract description 16
- 238000000016 photochemical curing Methods 0.000 abstract description 10
- 239000000654 additive Substances 0.000 abstract description 7
- 230000000996 additive effect Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000002835 absorbance Methods 0.000 abstract description 6
- 238000001723 curing Methods 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 5
- 238000005286 illumination Methods 0.000 abstract description 5
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 abstract description 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003086 colorant Substances 0.000 abstract description 3
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 abstract description 3
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 10
- 239000007787 solid Substances 0.000 description 8
- 238000004949 mass spectrometry Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000000399 optical microscopy Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- -1 amine salt Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- YAJKDGXVZVCTKQ-UHFFFAOYSA-N cyclopenta[b]naphthalene-1,3-dione Chemical class C1=CC=C2C=C3C(=O)CC(=O)C3=CC2=C1 YAJKDGXVZVCTKQ-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- VSEAAEQOQBMPQF-UHFFFAOYSA-N morpholin-3-one Chemical compound O=C1COCCN1 VSEAAEQOQBMPQF-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
The invention discloses a preparation method and application of an organic dye based on indan-1, 3-dione derivatives, and relates to the technical field of photocuring. The organic dye prepared by the method has photochemical properties such as high absorbance, high oxidation-reduction property and the like, can emit fluorescence of different colors, is a pure organic fluorescent micromolecule, and can achieve high photoinitiation efficiency and meanwhile part of organic dye molecules have an unusual photobleaching phenomenon. The dye molecule is combined with iodide salt and ammonium salt to be directly used as a three-component photoinitiation system in photocuring, under the illumination of a 405nm LED, a resin monomer trimethylolpropane triacrylate TMPTA (or a hexanediol diacrylate HDDA monomer and the like is used) can be polymerized to obtain a photopolymerisable product with smooth and flat surface, high color purity and high fluorescence, and the photopolymerisable product has important application prospect in the technical fields of additive manufacturing, ultraviolet light curing coating preparation and photoresist. Especially in additive manufacturing.
Description
Technical Field
The invention relates to the technical field of photocuring, in particular to a preparation method and application of an organic dye based on indan-1, 3-dione derivatives.
Background
The photo-induced high polymer polymerization is used as a novel photo-curing technology and has important application prospects in the fields of additive manufacturing, ultraviolet curing coatings, photoresist and the like. Currently, the industry layout and upgrade for accelerated photocuring is also in all countries of the world. In the photo-induced polymer polymerization technology, the selection of the light source is very important because it directly affects the polymerization efficiency of the polymer monomer. The photoinitiation efficiency of photopolymer polymerisation based on blue, deep blue light sources is still not satisfactory for commercial applications compared to green and red light sources which have already been put to commercial use. Therefore, the development of commercially applicable blue light and deep blue light-based photo-induced polymer polymerization technology has been an important research area concerned by the academia and related industries. Of the current scientific research, the Light Emitting Diode (LED) with a wavelength of 405nm is the most widely studied.
In the photo-induced polymer polymerization, how to select a light source with a proper wavelength to match with a high-efficiency photoinitiator is the biggest bottleneck of current research. In the design research of the photoinitiator, the synthesis of a novel organic photoinitiation system is the most important research strategy for realizing high-efficiency photocuring. However, for most organic dye molecules, it is difficult to achieve high conversion of resin, high fluorescence activity and good color of products at the same time due to weak light absorption property and triplet formation and photobleaching occurring during photopolymerization. In addition, the corresponding initiation aid also needs to be doped into a suitable organic dye molecule, namely a photoinitiator, to form an efficient photoinitiation system. Commercialization of photoinitiated systems is yet to be developed. The use of push-pull organic dye molecules (push-pull dyes) is a reliable strategy to achieve high efficiency photopolymer polymerisation. In addition, compared with the traditional organic dye molecules, the fluorescent dye has great advantages in realizing blue light absorption and color purity. In addition, the moderate photoinitiation capability of the composite material enables the composite material to be effectively applied to Stereolithography (SLA) and Digital Light Processing (DLP) 3D printing, and the composite material shows good polymerization stability and operability. Therefore, the development of the push-pull type organic dye molecules with high fluorescence has very important practical significance.
Disclosure of Invention
Based on the above, in order to solve the problems that organic dye molecules are difficult to realize high conversion rate, high fluorescence activity and good color of resin at the same time, the invention provides an organic dye based on indane-1, 3-dione derivatives and application thereof, and the specific technical scheme is as follows:
a preparation method of an organic dye comprises the following steps:
s1, obtaining indan-1, 3-dione and derivative EA thereof, wherein the EA comprises EA1, EA2 and EA3;
s2, increasing the photochemical activity of indan-1, 3-dione and derivatives EA thereof, and reacting D1, D2, D3, D4, D5 and D6 with EA obtained in S1 to obtain an organic dye or reacting ED with EA2 obtained in S1 to obtain the organic dye.
Preferably, the EA is obtained by: EA1 is obtained through two-step reaction of claisen condensation and decarbonization of a sodium salt intermediate; or adding a malononitrile group to the indane-1, 3-dione, and optionally adding a cyano group to EA1 by Knoevenagel condensation to obtain EA2 and EA3.
Preferably, the reaction formula of the process for obtaining EA is as follows:
preferably, D1, D2, D3, D4, D5, D6 respectively correspond to the following structures:
preferably, D1, D2, D3, D4, D5, D6 are each reacted with EA as follows:
preferably, the ED includes ED1 and ED2, and the structural formula of ED1 is:
the structural formula of ED3 is: />
Preferably, the reaction of ED with EA2 is as follows:
the invention also provides an application of the organic dye in a photocuring three-component photoinitiation system.
In addition, an application of the organic dye in 3D printing with a three-component photoinitiation system of an iodonium salt and an ammonium salt is provided.
The organic dye in the scheme has photochemical properties such as high absorbance, high oxidation-reduction property and the like, can emit fluorescence of different colors, is a pure organic fluorescent micromolecule, and can achieve high photoinitiation efficiency and meanwhile part of organic dye molecules have an unusual photobleaching phenomenon. The dye molecule is combined with iodide salt and ammonium salt to be directly used as a three-component photoinitiation system in photocuring, under the illumination of a 405nm LED, a resin monomer trimethylolpropane triacrylate TMPTA (or a hexanediol diacrylate HDDA monomer and the like is used) can be polymerized to obtain a photopolymerisable product with smooth and flat surface, high color purity and high fluorescence, and the photopolymerisable product has important application prospect in the technical fields of additive manufacturing, ultraviolet light curing coating preparation and photoresist. Especially in additive manufacturing.
Drawings
FIG. 1 is a plot of double bond conversion versus time in a resin monomer (TMPTA) under 405nm LED illumination using a three component initiation system based on dyes 1-11, iodonium salts, ammonium salts;
FIG. 2 is a UV absorbance spectrum of dyes 1-11;
FIG. 3 is a top plan view of a three-component photoinitiation system based on example dye 8, iodide salt, and ammonium salt, after 3D printing of resin monomer (TMPTA) by stereolithography, the resulting product was observed by digital optical microscopy;
FIG. 4 is a side view of a three-component photo-initiation system based on example dye 8, iodide salt, and ammonium salt, in 3D form, after stereolithographic 3D printing of resin monomer (TMPTA), the resulting product is observed by digital optical microscopy;
FIG. 5 is a top plan view of a three-component photoinitiation system based on example dye 9, iodide salt, and ammonium salt, after stereolithography 3D printing of resin monomer (TMPTA), the resulting product was observed by digital optical microscopy;
FIG. 6 is a side view of a three-component photoinitiation system based on example dye 9, iodide salt, and ammonium salt, in 3D form, after stereolithographic 3D printing of resin monomer (TMPTA), and digital optical microscopy of the resulting product;
FIG. 7 is a top plan view of a three-component photoinitiation system based on example dye 9, iodide salt, and ammonium salt, wherein resin monomer (TMPTA) is added to silicon filler and subjected to stereolithography 3D printing, and the resulting product is observed by a digital optical microscope;
FIG. 8 is a 3D side view of a three-component photoinitiation system based on example dye 9, iodide salt, and ammonium salt, wherein resin monomer (TMPTA) is added to silicon filler and stereolithography 3D printing is performed, and the resulting product is observed by a digital optical microscope.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to embodiments thereof. It should be understood that the detailed description and specific examples, while indicating the scope of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The preparation method of the organic dye in one embodiment of the invention comprises the following steps:
s1, obtaining indan-1, 3-dione and derivative EA thereof, wherein the EA comprises EA1, EA2 and EA3;
s2, increasing the photochemical activity of indan-1, 3-dione and derivatives EA thereof, and reacting D1, D2, D3, D4, D5 and D6 with EA obtained in S1 to obtain an organic dye or reacting ED with EA2 obtained in S1 to obtain the organic dye.
In one embodiment, the method for obtaining EA is: EA1 is obtained through two-step reaction of claisen condensation and decarbonization of a sodium salt intermediate; or adding a malononitrile group on the indane-1, 3-dione, and selectively adding a cyano group on the EA1 through Knoevenagel condensation to obtain EA2 and EA3.
In one embodiment, the process for obtaining EA has the following reaction formula:
in one embodiment, D1, D2, D3, D4, D5, and D6 respectively correspond to the following structures:
in one embodiment, D1, D2, D3, D4, D5, D6 are each reacted with EA as follows:
in one embodiment, the ED includes ED1 and ED2, and the ED1 has a structural formula:
the structural formula of ED3 is: />
In one embodiment, the formula for ED and EA2 is as follows:
the invention also provides an application of the organic dye in a photocuring three-component photoinitiation system.
In addition, an application of the organic dye in 3D printing of a three-component photoinitiation system of the organic dye and an iodide salt and an ammonium salt is provided.
The organic dye in the scheme has photochemical properties such as high absorbance, high oxidation-reduction property and the like, can emit fluorescence of different colors, is a pure organic fluorescent micromolecule, can achieve high light initiation efficiency, and simultaneously effectively avoids the common photobleaching phenomenon of organic dye molecules. The dye molecule is combined with iodide salt and ammonium salt to be directly used as a three-component photoinitiation system in photocuring, under the illumination of a 405nm LED, a resin monomer trimethylolpropane triacrylate TMPTA (or a hexanediol diacrylate HDDA monomer and the like is used) can be polymerized to obtain a photopolymerisable product with smooth and flat surface, high color purity and high fluorescence, and the photopolymerisable product has important application prospect in the technical fields of additive manufacturing, ultraviolet light curing coating preparation and photoresist. Especially in additive manufacturing.
Embodiments of the present invention will be described in detail below with reference to specific examples.
The 11 1H-cyclopenta [ b ] naphthalene-1, 3 (2H) -dione derivatives obtained in this application have the following structural formula:
the 11 structural formulas represent 11 organic dyes prepared in the application, and are marked as dye 1, dye 2, dye 3, dye 4, dye 5, dye 6, dye 7, dye 8, dye 9, dye 10 and dye 11.
Example 1:
the structural formula of dye 1 is as follows:
the preparation method of the dye 1 comprises the following steps:
in a 100mL round-bottom flask, 2-butoxy-4- (diethylamine) benzaldehyde (0.456 g,1.8mmol, M = 249.35g/mol), 2- (3-oxo-2, 3-dihydro-1H-cyclopenta [ b ] naphthalene-1-methylene) malononitrile (0.445g, 1.8mmol, M = 244.25g/mol) and 40mL of absolute ethanol (ethanol) as a solvent were sequentially added, and after thorough mixing, several drops of N, N-Diisopropylethylamine (DIPEA) were added. Then heating the uniformly mixed solution to 90 ℃ and refluxing for 30min until the color of the mixture turns to dark red; cooling the solution to room temperature after 15min until precipitation is obtained;
filtering out insoluble dark red solid, washing with ethanol or pentane for several times, and drying in vacuum to obtain 0.744g of dark brown solid, namely the dye 1 described in the embodiment 1 of the application. And the yield of example 1 was 87%.
The dye 1 obtained in example 1 is subjected to mass spectrometry, and the theoretical value MW of the mass spectrometry is 476.2333, and the M/z is 476.2336 ([ M + H + ]) actually measured; 1H NMR (400mhz, cdcl3) δ:9.08 (d, J =13.0hz, 2h), 8.84 (s, 1H), 8.24 (s, 1H), 8.10-7.93 (m, 2H), 7.68-7.57 (m, 2H), 6.44 (dd, J =9.5,2.2hz, 1h), 6.00 (d, J =2.2hz, 1h), 4.07 (t, J =6.4hz, 2h), 3.54 (q, J =7.1hz, 4h), 1.99-1.86 (m, 2H), 1.56 (d, J =13.1hz, 4h), 1.30 (t, J =7.1hz, 6h), 1.02 (t, J =7.4hz, 3h); 13C NMR (101MHz, CDCl3) delta: 164.57,164.15,156.25,142.62,139.01,135.97,135.19,134.11,130.40,129.84,128.90,128.67,125.40,123.35,122.53,116.85,114.08,105.74,92.62,77.32,77.00,76.69,68.63,45.46,30.89,19.35,13.83,12.88.
Example 2:
the structural formula of dye 2 is as follows:
the preparation method of the dye 2 comprises the following steps:
4- (diethylamine) benzaldehyde (0.272g, 1.8mmol, M = 149.19g/mol), 2- (3-oxo-2, 3-dihydro-1H-cyclopenta [ b ] naphthalene-1-methylene) malononitrile (0.445g, 1.8mmol, M = 244.25g/mol) are added in sequence into a 100mL round-bottomed flask, 40mL of absolute ethanol (ethanol) is added as a solvent, and after thorough mixing, a plurality of drops of N, N-Diisopropylethylamine (DIPEA) are added; then heating the uniformly mixed solution to 90 ℃ and refluxing for 30min until the color of the mixture turns to dark red, and cooling the solution to room temperature after 15min until precipitates.
Filtering out insoluble dark red solid, washing with ethanol or pentane for several times, and drying in vacuum to obtain 0.459g of dark brown solid, namely the dye 2 in the embodiment 2 of the application. And the yield of example 2 was 68%.
Dye 2 of example 2 is subjected to mass spectrometry, and the theoretical value MW of the mass spectrometry is 376.1444, and the measured M/z is 375.1372 ([ M + H + ]); 1H NMR (300MHz, CDCl3). Delta.9.14 (s, 1H), 8.65-8.28 (m, 4H), 8.06 (s, 2H), 7.66 (s, 2H), 6.79 (s, 2H), 3.23 (s, 6H); theoretical values of element analysis are C25H17N3O, C80.0, H11.2 and O4.3; the results show that the catalyst is C79.8, H11.3 and O4.5.
Example 3:
the structural formula of dye 8 is as follows:
the preparation method of the dye 8 comprises the following steps:
in a 100mL round-bottom flask, 4- (dimethylamine) benzaldehyde (0.272g, 1.8mmol, M = 149.19g/mol), 2- (3-oxo-2, 3-dihydro-1H-cyclopenta [ b ] naphthalene-1-methylene) malononitrile (0.445g, 1.8mmol, M = 244.25g/mol) were sequentially added, and 40mL of absolute ethanol (ethanol) was added as a solvent, and after thorough mixing, paraoxonitrilic ring (morpholinone) was added in several drops.
Then heating the uniformly mixed solution to 90 ℃ and refluxing for 30min until the color of the mixture turns to dark red, and cooling the solution to room temperature after 15min until a precipitate is separated out.
Insoluble dark red solid is filtered, washed with ethanol or ether for several times, and dried under vacuum to obtain 0.658g red solid, which is dye 8 with 79% yield of example 3.
Dye 8 is subjected to mass spectrometry, and the mass spectrum theoretical value MW of 463.2129 is actually measured to be M/z of 463.2126 ([ M + H + ]); 1H NMR (400mhz, cdcl3) δ:2.92 (s, 6H), 3.47-3.52 (m, 4H), 3.72-3.77 (m, 4H), 5.42 (brs, 1H), 5.63 (d, 1h, j =3.9 hz), 6.68 (d, 2h, j =8.5 hz), 7.25 (d, 2h, j =8.5 hz), 7.44-7.52 (m, 2H), 7.74 (s, 1H), 7.79 (d, 1h, j =7.8 hz), 7.84 (d, 1h, j =7.8 hz), 8.16 (s, 1H); 1H NMR (400MHz, DMSO-d 6) delta: 2.85 (s, 6H), 3.44-3.54 (m, 2H), 3.69-3.78 (m, 6H), 5.49 (s, 1H), 6.68 (d, 2H, J =8.9 Hz), 7.12 (d, 2H, J =8.9 Hz), 7.50-7.58 (m, 2H), 7.78 (s, 1H), 7.89 (d, 1H, J =8.6 Hz), 7.98 (d, 1H, J =8.6 Hz), 8.04 (s, 1H), 8.97 (s, 1H); 13C NMR (100MHz, DMSO-d 6) delta: 48.0,49.1,51.5,59.3,65.9,112.4,117.5,119.0,119.8,120.2,127.2,128.0,129.0,129.8,129.9,131.9,133.3,133.6,134.4,135.3,149.9,153.3,160.2,185.9.
Example 4:
the structural formula of the dye 9 is as follows:
in a 100mL round-bottomed flask, 4- (dimethylamine) benzaldehyde (0.77g, 5.15mmol, M = 149.19g/mol), 2- (3-oxo-2, 3-dihydro-1H-cyclopenta [ b ] naphthalene-1-methylene) malononitrile (1.25g, 5.15mmol, M = 244.25g/mol) and 40mL of absolute ethanol (ethanol) as a solvent were sequentially added, and after thorough mixing, p-oxazaprinine (morpholine) was added in several drops.
Heating the uniformly mixed solution to 90 ℃ and refluxing for 30min until the color of the mixture turns to dark red, and cooling the solution to room temperature after 15min until precipitates.
Insoluble dark red solid is filtered, washed by ethanol or ether for a plurality of times, and dried in vacuum to obtain 0.452g of red solid, namely the dye 9, and the yield of the embodiment is 14%.
Performing mass spectrometry on the dye 9, and actually measuring M/z:461.2333 ([ M + H + ]) according to a mass spectrometry theoretical value MW: 461.2336; 1H NMR (400 MHz, acetone-d 6) δ:1.68-1.80 (m, 6H), 2.90 (s, 6H), 3.58-3.87 (m, 4H), 5.59 (d, 2h, j = 4.8hz), 6.71 (d, 2h, j = 8.8hz), 7.23 (d, 2h, j = 8.8hz), 7.48-7.61 (m, 2H), 7.74 (s, 1H), 7.93 (dd, 2h, j =13.7hz, j = 7.5hz), 8.20 (s, 1H); 1H NMR (400mhz, cdcl3) δ:1.72-1.75 (m, 6H), 2.90 (s, 6H), 3.50-3.57 (m, 2H), 3.62-3.68 (m, 2H), 5.57-5.60 (m, 2H), 6.67 (d, 2h, j = 8.5hz), 7.25 (d, 2h, j = 8.5hz), 7.40-7.48 (m, 2H), 7.71 (s, 1H), 7.77 (d, 1h, j =7.6 hz), 7.82 (d, 1h, j =7.6 hz), 8.18 (s, 1H); 13C NMR (100MHz, CDCl3) delta: 25.4,40.2,40.4,49.8,54.2,80.2,110.9,112.4,120.5,120.9,123.5,124.1,127.2,127.9,128.4,129.5,130.1,131.9,133.3,133.7,134.8,136.2,153.6,157.3,160.1,160.2,187.2.
The present application is to provide the following application examples.
Application example:
preparing a three-component photoinitiation system, and implementing and characterizing photoinitiation high polymer polymerization:
weighing resin monomers with any mass, then weighing 0.1% of dye, 2% of iodized salt and 2% of ammonium salt according to the mass ratio of the resin monomers (TMPTA), pouring the weighed three components into the weighed resin monomers in sequence, and fully stirring to obtain the photo-induced high polymer polymerization system.
The structural formula of the iodide salt is as follows:
the structural formula of the amine salt is:
Taking out a plurality of drops from the obtained photo-induced high molecular polymerization system by a dropper, dropping the drops on one polypropylene film, and covering the other polypropylene film to ensure that the photo-induced high molecular polymerization system can be uniformly dispersed.
Irradiating the prepared photo-induced high polymer polymerization system by using a 405nm light emitting diode (light intensity: 110 mW. Cm-2) at room temperature, and simultaneously monitoring the peak position change of a wave band of-1630 cm-1 in an infrared absorption spectrum in real time by using a real-time Fourier transform infrared absorption spectrometer, namely the change of C = C double bonds in the resin monomer TMPTA.
The conversion rate of the double bond of the polymer resin monomer at a certain time is calculated according to the following formula:
conversion (%) = (initial peak-current peak)/initial peak × 100
The curve of the relationship between the conversion rate of the polymer resin monomer (TMPTA) and the illumination time induced by the three-component system based on 11 related organic dye fluorescent small molecules of the invention is shown in FIG. 1.
The ultraviolet light absorption property (i.e. absorbance) of the related organic dye fluorescent micromolecules is obtained by characterization and calculation of an ultraviolet-visible photometer (see figure 2).
The maximum ultraviolet absorption wavelength, the maximum absorbance, the absorbance at 405nm and the resin monomer conversion rate of the related four organic dye fluorescent small molecules in examples 1 to 4 are shown in Table 1:
table 1 photochemical parameters of the dyes and the final conversion of the resin monomers during the corresponding photopolymers.
Table 1:
application example 2:
implementation and characterization of 3D printing
The photo-induced high molecular polymerization system of the three-component photoinitiation system based on the dye 8 (or 9) obtained in example three was dropped into a 2mm thick glass container made by hand, and then placed in a Stereolithography (SLA) 3D printer having a 405nm laser diode as an excitation light source for 3D printing. The printing pattern is an English character "KES". The printed product is observed by a digital Optical Microscope (digital Optical Microscope), and has the characteristics of smoothness, clear characters, high resolution and the like. The observations for the printed products based on the dye 8 system are shown in fig. 3 (plane), 4 (three-dimensional). The observations for the printed products based on the dye 9 system are shown in fig. 5 (plane), 6 (three-dimensional).
The photo-induced high polymer polymerization system of the three-component light initiation system based on the dye 9 is added with the silicon filler with the mass ratio of 20 percent, and the photochemical composite material with higher strength and smooth and flat surface can be obtained through the three-dimensional curing molding 3D printing process after full stirring. The observation results by the digital light microscope are shown in fig. 7 (plane) and fig. 8 (three-dimensional).
As can be seen from the 3D printing product of the embodiment, the photoinduced high polymer system of the three-component photoinitiation system based on the organic dye fluorescent micromolecule can be directly used as a 3D printing material, and the 3D printing product with smooth surface and color and fluorescence can be obtained. Simultaneously, the 3D printing process has the advantages of easiness in control, high speed and the like. Based on the above advantages, the technical advantages of such photo-induced high molecular polymerization system will be based on advanced level if it is applied to the preparation of ultraviolet light curing coating and photoresist.
The above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same. While the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: modifications may be made to the embodiments described above, or equivalents may be substituted for some or all of the features thereof without departing from the spirit and scope of the invention as defined by the claims; but such modifications or substitutions are intended to be included within the scope of the present invention as defined in the appended claims.
Claims (9)
1. A process for the preparation of organic dyes based on indan-1, 3-dione derivatives, characterized in that it comprises the following steps:
s1, obtaining indan-1, 3-dione and derivative EA thereof, wherein the EA comprises EA1, EA2 and EA3;
s2, increasing the photochemical activity of indan-1, 3-dione EA, and reacting D1, D2, D3, D4, D5 and D6 with EA obtained in S1 to obtain an organic dye or reacting ED with EA2 obtained in S1 to obtain the organic dye.
2. The method of claim 1, wherein the EA is obtained by: EA1 is obtained through two-step reaction of claisen condensation and decarbonization of a sodium salt intermediate; or adding a malononitrile group to the indane-1, 3-dione, and optionally adding a cyano group to EA1 by Knoevenagel condensation to obtain EA2 and EA3.
3. The method of claim 2, wherein the EA is obtained according to the following reaction scheme:
4. the method according to claim 1, wherein each of D1, D2, D3, D4, D5 and D6 corresponds to the following structure:
5. the method of claim 1, wherein D1, D2, D3, D4, D5, D6 are each reacted with EA according to the following formula:
6. the preparation method according to claim 1, wherein the ED comprises ED1 and ED2, and the ED1 has the formula:
the structural formula of ED3 is: />
7. The method of claim 6, wherein the reaction of ED with EA2 is as follows:
8. use of an organic dye according to any one of embodiments 1 to 7 in a photo-cured three-component photo-initiation system.
9. Use of an organic dye according to any one of embodiments 1 to 7 in 3D printing with a three-component photoinitiation system comprising an iodide salt and an ammonium salt.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1076927A (en) * | 1992-03-10 | 1993-10-06 | 三菱化成株式会社 | 1,2-indane-1,3-derovatives and contain the weedicide of this derivative as activeconstituents |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1076927A (en) * | 1992-03-10 | 1993-10-06 | 三菱化成株式会社 | 1,2-indane-1,3-derovatives and contain the weedicide of this derivative as activeconstituents |
Non-Patent Citations (3)
| Title |
|---|
| PIGOT, CORENTIN 等: "New push-pull dyes based on 2-(3-oxo-2, 3-dihydro-1H-cyclopenta[b]naphthalene-1-ylidene)malononitrile: An amine-directed synthesis", DYES AND PIGMENTS, vol. 175, pages 108182 * |
| PIGOT, CORENTIN 等: "Unprecedented Nucleophilic Attack of Piperidine on the Electron Acceptor during the Synthesis of Push-Pull Dyes by a Knoevenagel Reaction", HELVETICA CHIMICA ACTA, vol. 102, no. 12, pages 1900229 * |
| SUN, KE 等: "Novel push-pull dyes derived from 1H-cyclopenta[b]naphthalene-1, 3(2H)-dione as versatile photoinitiators for photopolymerization and their related applications: 3D printing and fabrication of photocomposites", CATALYSTS, vol. 10, no. 10, pages 1196 * |
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