CN114891215B - Three-dimensional near-infrared photoinitiator and preparation method and application thereof - Google Patents
Three-dimensional near-infrared photoinitiator and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a three-dimensional near-infrared photoinitiator, which has a structure shown in a general formula (1), wherein M represents one or more of Li, na and K; x is more than or equal to 0 and less than or equal to 7; re represents one or more of Y, gd, yb and Sc; y is more than or equal to 1 and less than or equal to 6; ln is one or more of Er, tm, ho, eu, tb, sm, dy, ce and Nd; z is more than or equal to 0 and less than or equal to 50; PI is hydroxyl-containing: one or more of coumarin, phenothiazine, thioxanthone, benzophenone, anthraquinone, camphorquinone, iodonium salt and sulfonium salt; p is more than or equal to 2 and less than or equal to 9; m is more than or equal to 0 and less than or equal to 15; n is more than or equal to 3. The initiator with the three-dimensional configuration is excited to induce polymerization under low-power near infrared irradiation, so that the near infrared power required by curing of the photosensitive material and the thermal effect in the photopolymerization process are reduced, and the initiator is suitable for the fields of photocureable coatings, adhesives, composite materials, additive manufacturing and the like.
Description
Technical Field
The invention relates to the technical field of photoinitiators, in particular to a three-dimensional near-infrared photoinitiator and a preparation method and application thereof.
Background
The photopolymerization technology using ultraviolet light, electron beams, near infrared light and the like as energy sources has the characteristics of high efficiency, energy conservation, environmental protection, controllable time-space and the like. Among them, the near-infrared light polymerization technology uses high-penetrability and low-biotoxicity near-infrared light, and has attracted much attention in the research of the field of photopolymerization materials such as biomedical materials, coating materials and multi-material additive manufacturing.
The photoinitiation system is a key component in the photopolymerisable material, and a proper near-infrared light initiation system is required for introducing near-infrared light into the near-infrared light for polymerization. The up-conversion material (UCm) can absorb near infrared light energy and then up-convert to emit ultraviolet-visible light, so that the photoinitiator is excited to generate active species to induce the photosensitive material to polymerize, and the up-conversion material assisted photo-initiation system and the formed up-conversion material assisted photo-polymerization technology (UCAP) are suitable for a commercial ultraviolet light polymerization material system, and have wide raw material selection range and strong universality [ CN105330790A ]. In recent years, the UCAP technology has been applied to the fields of dental materials, deep photopolymerization, functional polymer synthesis, additive manufacturing, and the like.
However, a large number of experiments show that although the upconversion material auxiliary near-infrared light initiation system directly formed by UCm and a photoinitiator has good stability and universality, the limited upconversion luminous efficiency and initiation efficiency also greatly limit the application technical innovation of the upconversion material auxiliary near-infrared light initiation system in the fields of high-performance materials and functional materials.
In order to improve the initiation efficiency of the upconversion material assisted near infrared light initiation system, domestic scholars modify UCm surface silica, introduce active groups, then graft photoinitiators, and improve the light energy utilization rate, so that the high-efficiency near infrared polymerization reaction can be applied, but the efficiency is still not satisfactory.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a three-dimensional near-infrared photoinitiator and a preparation method and application thereof. According to the invention, the macromolecular free radical photoinitiator is chemically bonded to the up-conversion material by a click chemistry method, so that the stereostructure initiator with high initiation efficiency is prepared, and the method is expected to be applied to photopolymerization technology.
The technical scheme of the invention is as follows:
a steric near-infrared photoinitiator is disclosed, wherein the structure of the initiator is shown in general formula (1):
in the general formula (1), M x Re y F x+3y Z% Ln expressed as a rare earth doped up-conversion material; m represents one or more of metal elements Li, na and K; x is more than or equal to 0 and less than or equal to 7;
re represents one or more of rare earth elements Y, gd, yb and Sc; y is more than or equal to 1 and less than or equal to 6;
ln is one or more of Er, tm, ho, eu, tb, sm, dy, ce and Nd doped with rare earth elements; z is more than or equal to 0 and less than or equal to 50;
PI is hydroxyl-containing: one or more of coumarin, phenothiazine, thioxanthone, benzophenone, anthraquinone, camphorquinone, iodonium salt and sulfonium salt; preferably, PI is hydroxyl-containing: one of coumarin, thioxanthone, phenothiazine and anthraquinone;
p represents the chain length of the terminal olefine acid of the surface ligand of the up-conversion material, and p is more than or equal to 2 and less than or equal to 9;
m represents the number of repeating units of the photoresponse structure in the macroinitiator, and m is more than or equal to 0 and less than or equal to 15;
n represents the grafting amount of the macroinitiator, and n is more than or equal to 3.
Preferably, 1. Ltoreq. X. Ltoreq.3; y =1; z is more than or equal to 0.5 and less than or equal to 18; p is more than or equal to 6 and less than or equal to 9; m is more than or equal to 10 and less than or equal to 12.
A preparation method of a three-dimensional near-infrared photoinitiator adopts click chemistry of sulfydryl-alkyne to connect an up-conversion material with a photoresponse structure.
Further, the preparation method comprises the following steps:
(1) Reacting PI containing hydroxyl with bromopropyne to prepare triple-bond modified PI;
(2) Carrying out mercapto-alkyne click chemical reaction on the PI modified by triple bonds and the propanedithiol under the protection of deoxygenated nitrogen to prepare a macroinitiator;
(3) Mixing a macromolecular initiator and an up-conversion material containing a terminal group double bond ligand, adding a thermal initiator, and reacting under the protection of oxygen and nitrogen to prepare the three-dimensional near-infrared initiator.
In the step (1), the hydroxyl-containing PI is hydroxyl-containing: one or more of coumarin, phenothiazine, thioxanthone, benzophenone, anthraquinone, camphorquinone, iodonium salt and sulfonium salt.
In the step (1), the molar ratio of the hydroxyl-containing photoinitiator PI to the bromopropyne is 1.1-1.
In the step (2), the molar ratio of the triple-bond modified PI to the propanedithiol is 1.5-1; the molecular weight of the macroinitiator is 1100-10000; preferably, the macroinitiator has a molecular weight of 4900.
In the step (3), the mol ratio of the up-conversion material containing the terminal group double bond ligand to the macroinitiator is 1.1-1; the thermal initiator is a peroxide or an azo compound.
An application of a three-dimensional near-infrared photoinitiator in photocuring paint, photocuring ink, photocuring adhesive, photoresist, composite materials or additive manufacturing.
The specific application method comprises the following steps: mixing a three-dimensional near-infrared initiator and a photocuring reaction liquid, and irradiating and curing by a near-infrared laser light source, wherein the wavelength is 900-1100nm, and the energy density is 10 2 -10 6 mW/cm 2 ;
The photocuring reaction liquid is one or more of polyurethane acrylate, epoxy acrylate, sulfydryl/epoxy acrylate, polyester acrylate, sulfydryl/polyester acrylate, amino acrylate, epoxy resin, vinyl resin and sulfydryl monomers.
The beneficial technical effects of the invention are as follows:
the invention uses the macro-molecular initiator ligand, improves the active group density of the initiator, improves the luminous utilization rate of the up-conversion material, improves the initiation and polymerization efficiency of a photoinitiation system compared with the traditional titanocene photoinitiator, can further improve the polymerization depth, and enlarges the application field of photopolymerization.
The three-dimensional near infrared initiator disclosed by the invention is excited to induce polymerization under low-power near infrared irradiation, so that the using power of near infrared laser is reduced, the heat effect of a near infrared polymerization process is reduced, and the three-dimensional near infrared initiator is suitable for the fields of photosensitive materials, biological materials and the like which are sensitive to heat.
The three-dimensional near infrared initiator is based on covalent bonding of a macromolecular initiator or a photosensitizer and an up-conversion material, improves the luminous utilization rate of the up-conversion material, improves the initiation and polymerization efficiency of a photo-initiation system, can induce polymerization under low-power near infrared excitation, reduces the polymerization reaction temperature, is suitable for various polymerization systems, further improves the polymerization depth, can realize polymerization of ultra-thick layer materials, and expands the application field of photo-polymerization.
Drawings
FIG. 1 shows the synthesis scheme of triple bond modified AOEC obtained in example 1 of the present invention;
FIG. 2 is a synthetic route of a stereoconfiguration near infrared photoinitiator UCm @ POEC obtained in example 2 of the present invention;
FIG. 3 is a gel chromatogram of POEC which are molecular initiators of different molecular weights and are obtained in examples 2-5 of the present invention;
FIG. 4 is a synthetic route of a stereoconfiguration near-infrared photoinitiator UCm @ PTX obtained in example 6 of the present invention;
FIG. 5 is a synthetic route of a three-dimensional near infrared photoinitiator UCm @ PAQ obtained in example 7 of the present invention;
FIG. 6 is a thermogravimetric analysis chart of the stereotactic near-infrared photoinitiator UCm @ POEC obtained in example 2 of the present invention;
FIG. 7 is a real-time conversion rate curve of acrylate curing initiated by the stereo-configuration near infrared photoinitiator UCm @ POEC and the corresponding non-grafted blending system UCm & POEC obtained in example 2 of the present invention;
FIG. 8 is a real-time conversion curve of acrylate curing initiated by the stereoconfiguration near infrared initiator UCm @ POEC and the commercial titanocene initiator obtained in example 2 of the present invention.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
Example 1: the synthesis of the three-bond modified AOEC is carried out by the route shown in figure 1;
(1) 1.38g of 2, 4-dihydroxybenzaldehyde, 0.2mL of piperidine and 1.2mL of ethyl acetoacetate were dissolved in 20mL of anhydrous ethanol. The temperature is raised to 80 ℃ under the nitrogen atmosphere, and the reaction is carried out for 12h. After the reaction is finished, cooling to room temperature and spin-drying to obtain a solid crude product. Column chromatography purification (petroleum ether: ethyl acetate = 5) gave P2.
(2) 0.2g of P2, 0.12g of sodium acetate and 0.1g of hydroxylamine hydrochloride are dissolved in 15mL of absolute ethanol, the temperature is raised to 80 ℃ under the protection of nitrogen, and the reflux reaction is carried out for 4 hours. After the end, the solid crude product was cooled to room temperature and spin-dried. Purification by column chromatography (petroleum ether: ethyl acetate = 3) gave P3.
(3) Dissolving 0.22g of P3 in 10mL of THF, adjusting the temperature to 0 ℃ with ice water under the protection of nitrogen, adding 0.04g of NaH, keeping the temperature, stirring for 30min, dropwise adding 0.2mL of benzoyl chloride, stirring for 30min, adding 10mL of 5% sodium bicarbonate aqueous solution, quenching the reaction, extracting for three times with 10mL of dichloromethane, combining the dichloromethane, drying and filtering with anhydrous sodium sulfate, and performing rotary evaporation to obtain a crude product; column chromatography purification (petroleum ether: ethyl acetate = 5) gave P4.
(4) 0.32g of P4 and 0.3g of potassium carbonate are dissolved in 10mL of anhydrous DMF, 92 μ L of bromopropyne (the molar ratio of P4 to bromopropyne is 1.15) is added to a pipette, and the mixture is heated to 60 ℃ under the protection of nitrogen and reacted for 8h. After the reaction, 10mL of water and 10mL of dichloromethane are added for extraction three times, the dichloromethane is combined, dried and filtered by anhydrous sodium sulfate, and rotary distillation is carried out to obtain a crude product. Column chromatography purification (petroleum ether: ethyl acetate = 5) gave a triple bond modified AOEC.
Example 2:
the synthesis of a stereo-configuration near-infrared photoinitiator UCm @ POEC comprises the following steps: referring to fig. 2;
(1) 0.36g of AOEC from example 1, 220. Mu.L of propanedithiol, different molar amounts of peroxide BPO (0.01 mmol) were added to 20mL of tetrahydrofuran and dissolved by sonication; deoxidizing the solution for 15min, reacting at 70 ℃ for 5h under the protection of nitrogen, cooling to room temperature after the reaction is finished, and spin-drying to obtain a crude product; washing the crude product with methanol for 3 times, and drying at 50 ℃ to obtain POEC; the gel chromatogram of the POEC is shown in fig. 3, and as can be seen from fig. 3, the molecular weights of the prepared POECs were 1100, respectively.
(2) 0.995mmol of YbCl 3 ·6H 2 O and 0.005mmol of TmCl 3 ·6H 2 Adding 10mL of a mixed solvent of water and ethanol (the volume ratio of water to ethanol is 6; putting the reaction kettle into a high-temperature oven at 180 ℃, reacting for 24h, after the reaction is finished, cleaning for 3 times by using a mixed solvent, carrying out centrifugal precipitation at 6000rpm, and drying at 70 ℃ to obtain the double-bond modified upconversion material NaYbF with the surface ligand of undecylenic acid 4 :0.5%Tm。
(3) 10mg of the double-bond modified upconversion material NaYbF with the surface ligand of undecylenic acid prepared in the step (2) 4 Adding 0.5 percent of Tm into 10mL of anhydrous dimethylformamide, ultrasonically dispersing for 30min, then adding 0.04mmol of POEC prepared in the step (1) and 12mg of BPO into a dispersion, deoxidizing the solution for 15min, reacting for 12h at 70 ℃ under the protection of nitrogen, cooling to room temperature after the reaction is finished, centrifugally removing a supernatant, washing with DMF for 3 times, and drying to obtain a stereo-configuration near-infrared photoinitiator UCm @ POEC.
Examples 3 to 5
A three-dimensional configuration near infrared light initiator UCm @ POEC is synthesized, the synthesis method refers to example 2, and the difference is that in the step (1), the molar usage of peroxide BPO is respectively changed into 0.02mmol, 0.05mmol and 0.1mmol, and molecular initiators POECs with different molecular weights are prepared; the gel chromatogram of the molecular initiator POEC with different molecular weights is shown in FIG. 3, and it can be seen from FIG. 3 that the molecular weights of the prepared POECs are 2500, 4900 and 6300, respectively.
Example 6
A stereo-configuration near-infrared photoinitiator UCm @ PTX synthesis method comprises the following steps: referring to fig. 4;
(1) Slowly adding 0.42g of thiosalicylic acid into 20mL of concentrated sulfuric acid, stirring for 30min to dissolve the thiosalicylic acid, then slowly adding 1.07g of phenol in batches, heating the mixed solution to 75 ℃, reacting for 2h, stopping heating, continuously stirring at room temperature for 24h, after the reaction is finished, pouring the mixed solution into 200mL of ice water to generate a precipitate, and filtering to obtain a crude product; dissolving the solid with dioxane, adding into water to generate precipitate, filtering, and drying to obtain hydroxyl modified thioxanthone TX-OH.
(2) Dissolving 0.23g of TX-OH prepared in the step (1) and 0.3g of potassium carbonate in 10mL of anhydrous DMF, adding 95 mu L of bromopropyne (the molar ratio of TX-OH to bromopropyne is 1.2) into a pipette gun, heating to 60 ℃ under the protection of nitrogen, reacting for 8 hours, adding 10mL of water and 10mL of dichloromethane after the reaction is finished, extracting for three times, combining dichloromethane, drying and filtering anhydrous sodium sulfate, and performing rotary distillation to obtain a crude product; column chromatography purification (petroleum ether: ethyl acetate = 5) gave triple bond modified thioxanthone ATX.
(3) Adding 0.27g of ATX prepared in the step (2), 220 mu L of propanedithiol and 0.05mmol of peroxide BPO into 20mL of tetrahydrofuran, ultrasonically dissolving, deoxidizing the solution for 15min, reacting at 70 ℃ for 5h under the protection of nitrogen, cooling to room temperature after the reaction is finished, and performing spin drying to obtain a crude product; the crude product was washed 3 times with methanol and dried at 50 ℃ to give PTX.
(4) Double bond modified up-conversion material NaYbF with 10mg of surface ligand being undecylenic acid 4 Adding 0.5 percent of Tm into 10mL of anhydrous dimethylformamide, ultrasonically dispersing for 30min, then adding 0.02mmol of PTX and 12mg of BPO into the dispersion, deoxidizing the solution for 15min, reacting at 70 ℃ for 12h under the protection of nitrogen, cooling to room temperature after the reaction is finished, centrifuging to remove supernatant, washing with DMF for 3 times, and drying to obtain a stereoconfigurational initiator UCm @ PTX.
Example 7
The synthesis of a three-dimensional near-infrared photoinitiator UCm @ PAQ comprises the following steps: referring to fig. 5;
(1) Dissolving 0.22g of 2-hydroxyanthraquinone AQ-OH and 0.3g of potassium carbonate in 10mL of anhydrous DMF, adding 94 mu L of bromopropyne (the molar ratio of TX-OH to bromopropyne is 1.2) into a pipette gun, heating to 60 ℃ under the protection of nitrogen, reacting for 8 hours, adding 10mL of water and 10mL of dichloromethane after the reaction is finished, extracting for three times, combining dichloromethane, drying and filtering anhydrous sodium sulfate, and performing rotary distillation to obtain a crude product; column chromatography purification (petroleum ether: ethyl acetate = 2) gave triple bond-modified anthraquinone AAQ.
(2) Adding 0.26g of AAQ prepared in the step (1), 220 mu L of propanedithiol and 0.05mmol of diazotized AIBN into 20mL of tetrahydrofuran, ultrasonically dissolving, deoxidizing the solution for 15min, reacting at 70 ℃ for 5h under the protection of nitrogen, cooling to room temperature after the reaction is finished, and performing spin drying to obtain a crude product; washing the crude product with methanol for 3 times, and drying at 50 ℃ to obtain PAQ.
(3) 0.9mmol of ScCl 3 ·6H 2 O and 0.1mmol of TmCl 3 ·6H 2 O, 10mL of a mixed solvent of water and ethanol (volume ratio of water to ethanol is 6. Ending stirring, adding 8mmol NaF, continuing stirring for 30min, transferring into 50mL polytetrafluoroethylene high-pressure reaction kettle, and adding mixed solvent 25mL to about 2/3; putting the reaction kettle into a high-temperature oven at 180 ℃, reacting for 24h, cleaning for 3 times by using a mixed solvent after the reaction is finished, carrying out centrifugal precipitation at 6000rpm, and drying at 70 ℃ to obtain the double-bond modified upconversion material Na with the surface ligand of nonenoic acid 3 ScF 6 :10%Tm。
(4) 10mg of double bond modified upconversion material Na with surface ligand of nonenoic acid prepared in the step (3) 3 ScF 6 Adding 10 percent of Tm into 10mL of anhydrous dimethylformamide, ultrasonically dispersing for 30min, then adding 0.02mmol of PAQ and 12mg of BPO into the dispersion, deoxidizing the solution for 15min, reacting for 12h at 70 ℃ under the protection of nitrogen, cooling to room temperature after the reaction is finished, centrifugally removing supernatant, washing for 3 times by DMF, and drying to obtain a stereoconfiguration near-infrared photoinitiator UCm @ PAQ.
Test example:
(1) The stereo configuration near infrared light initiator UCm @ POEC obtained in example 2 and the non-grafted and blended UCm & POEC system initiate epoxy acrylate curing
As shown in fig. 6, based on the thermogravimetric test, the POEC grafting rate of the stereoconfiguration near infrared photoinitiator ucm @ POEC was determined to be 8wt.%. Therefore, at the same addition level, UCm was non-graft blended&POEC systems will have 92wt.% NaYbF depending on the grafting yield 4 0.5% Tm mixed with 8wt.% POEC.
Preparing a TMPTA and TPGDA mixed resin system (the mass ratio is 1&POEC or 3wt.% stereoconfigurational near infrared photoinitiator ucm @ POEC was placed in a brown glass bottle, mixed by ultrasonic dispersion until the photoinitiating system was uniformly distributed in the polymer matrix, and no precipitation was observed within 30 minutes before curing. Then, the photocuring sample is placed on a total reflection infrared platform, and the output power of the near infrared light is adjusted to 5.05W cm -2 For excitation of UCm. After irradiation, the infrared spectrum in the near infrared irradiation process is monitored, and a fitting conversion rate curve is calculated.
As shown in FIG. 7, under the same conditions, the initiation rate, polymerization rate and final conversion rate of the stereo-configuration near-infrared photoinitiator UCm @ POEC are all higher than those of a UCm & POEC blended initiation system, which shows that the novel stereo-configuration near-infrared initiator constructed by covalent grafting is beneficial to the polymerization reaction.
(2) The stereo configuration near infrared light initiator UCm @ POEC and Titanocene (Titanocene)/UCm obtained in the embodiment 2 initiate the curing of epoxy acrylate
According to the POEC grafting ratio of the stereo-configuration near infrared photoinitiator UCm @ POEC in the test example (1), under the same addition amount, the Titanocene (Titanocene)/UCm system is 92wt.% NaYbF 4 0.5% Tm and 8wt.% Titanocene.
3wt.% UCm/titanocene or 3wt.% stereo-configuration near infrared photoinitiator UCm @ poec was added to the mixed resin system of test example (1), placed in a brown glass bottle, mixed by ultrasonic dispersion until the photoinitiating system was uniformly distributed in the polymer matrix, and no precipitation was observed within 30 minutes before curing. Then, the light-cured sample is placed on a total reflection infrared platform, and the output power of the near infrared light is adjusted to 5.05W cm -2 For exciting UCm. After irradiation, the infrared spectrum during the near infrared irradiation process is monitored, and a fitted conversion rate curve is calculated.
As shown in figure 8, under the same condition, the initiation and polymerization rate of the stereo-configuration near-infrared initiator UCm @ POEC are higher than that of the traditional near-infrared initiation system of titanocene/UCm, the induction period is also reduced, and the polymerization reaction is facilitated.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by one skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A three-dimensional near-infrared photoinitiator is characterized in that the structure of the initiator is shown as a general formula (1):
in the general formula (1), M x Re y F x+3y Z% Ln as rare earth dopingA heteroupconverting material; m represents one or more of metal elements Li, na and K; x is more than or equal to 1 and less than or equal to 7;
re represents one or more of rare earth elements Y, gd, yb and Sc; y is more than or equal to 1 and less than or equal to 6;
ln is one or more of Er, tm, ho, eu, tb, sm, dy, ce and Nd doped with rare earth elements; z is more than or equal to 0.5 and less than or equal to 50;
PI is hydroxyl-containing: one or more of coumarin, phenothiazine, thioxanthone, benzophenone, anthraquinone, camphorquinone, iodonium salt and sulfonium salt;
2≤p≤9;0≤m≤15;n≥3。
2. the stereoconfigurational near-infrared photoinitiator according to claim 1, characterized in that 1. Ltoreq. X.ltoreq.3; y =1; z is more than or equal to 0.5 and less than or equal to 18; p is more than or equal to 6 and less than or equal to 9; m is more than or equal to 10 and less than or equal to 12.
3. A method for preparing the steric near-infrared photoinitiator according to claim 1, wherein the method for preparing the steric near-infrared photoinitiator is characterized in that the upconversion material is connected with the photoresponsive structure by adopting thiol-alkyne click chemistry.
4. The method of claim 3, comprising the steps of:
(1) Reacting PI containing hydroxyl with bromopropyne to prepare triple-bond modified PI;
(2) Carrying out mercapto-alkyne click chemical reaction on the PI modified by triple bonds and the propanedithiol under the protection of deoxygenated nitrogen to prepare a macroinitiator;
(3) Mixing a macromolecular initiator and an up-conversion material containing a terminal group double bond ligand, adding a thermal initiator, and reacting under the protection of oxygen and nitrogen to prepare the three-dimensional near-infrared initiator.
5. The method according to claim 4, wherein in the step (1), the hydroxyl group-containing PI is a hydroxyl group-containing PI: one or more of coumarin, phenothiazine, thioxanthone, benzophenone, anthraquinone, camphorquinone, iodonium salt and sulfonium salt.
6. The preparation method according to claim 4, wherein in the step (1), the molar ratio of the hydroxyl-containing photoinitiator PI to the bromopropyne is 1.
7. The method according to claim 4, wherein in the step (2), the molar ratio of the triple-bond-modified PI to the propanedithiol is 1; the molecular weight of the macroinitiator is 1100-10000.
8. The preparation method according to claim 4, wherein in the step (3), the molar ratio of the upconversion material containing the terminal double bond ligand to the macroinitiator is 1.1-1; the thermal initiator is a peroxide or an azo compound.
9. Use of the stereoconfigurational near-infrared photoinitiator according to claim 1 in photocuring coatings, photocuring inks, photocuring adhesives, photoresists or additive manufacturing.
10. The application of claim 9, wherein the stereoconfigurational near-infrared photoinitiator is cured by irradiation with a near-infrared laser source after being mixed with the photocuring reaction solution, and has a wavelength of 900-1100nm and an energy density of 10 2 -10 6 mW/cm 2 ;
The photocuring reaction liquid is one or more of polyurethane acrylate, epoxy acrylate, sulfydryl/epoxy acrylate, polyester acrylate, sulfydryl/polyester acrylate, amino acrylate, epoxy resin, vinyl resin and sulfydryl monomers.
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