CN112961274A - Preparation method and application of photoresponse organic gel capable of being used at 80 DEG C - Google Patents
Preparation method and application of photoresponse organic gel capable of being used at 80 DEG C Download PDFInfo
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Abstract
The invention provides a preparation method and application of a photoresponse organic gel capable of being used at 80 ℃; the preparation method of the photoresponse gel without adding the cross-linking agent comprises the following steps: heating a ruthenium-containing monomer and a benzonitrile-containing monomer in 1, 2-propylene glycol for reaction to obtain an initial mixed solution; mixing a comonomer, an initiator and 1, 2-propylene glycol, and then mixing with the initial mixed solution to obtain a prepolymer solution; and heating and polymerizing the prepolymer solution in the dark to obtain the photoresponse gel without adding the crosslinking agent. The application also provides a preparation method of the external cross-linking agent photoresponse gel. The application can realize reversible transformation of gel-sol by switching of illumination and light-resistant heating conditions, and is used for material remodeling. Meanwhile, based on the color difference of the photoresponse unit in ligand coordination and dissociation, the gel prepared by the external cross-linking agent can realize reversible writing and erasing of different patterns through control of illumination and light-proof heating conditions, and is expected to be used for information storage and anti-counterfeiting.
Description
Technical Field
The invention relates to the technical field of photoresponse polymer materials, in particular to a preparation method and application of a photoresponse organic gel without an external cross-linking agent or an external cross-linking agent.
Background
The hydrogel has great potential in biomedical engineering, and can be used in the fields of tissue engineering, health care, electronic skin, soft robots and the like. However, the limitation of the existing hydrogels is the lack of long-term stability, water molecules cannot be stably immobilized in the polymer network during application, causing the hydrogel to dehydrate and dry. Meanwhile, the hydrogel is dried at high temperature, so that the shape and mechanical properties of the hydrogel are greatly changed, and the application range and practical application scene of the hydrogel are limited. Therefore, it is a challenge to design gel materials with long-term stability and heat resistance to maintain good performance at high temperatures.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of organogel without an external cross-linking agent and a preparation method of organogel with an external cross-linking agent, the organogel prepared by the method can be used as a photoresponse gel material which can be used at 80 ℃, the problems of easy volatilization, lack of heat resistance and the like of the conventional gel material are solved, and the organogel still has good photoresponse performance at higher temperature.
In view of the above, the present application provides a method for preparing a photoresponsive gel without adding a cross-linking agent, comprising the following steps:
heating a ruthenium-containing monomer and a benzonitrile-containing monomer in 1, 2-propylene glycol for reaction to obtain an initial mixed solution;
dissolving a comonomer and an initiator in 1, 2-propylene glycol, and mixing with the initial mixed solution to obtain a prepolymer solution;
and heating and polymerizing the prepolymer solution in the dark to obtain the photoresponse gel without adding the crosslinking agent.
The application also provides a preparation method of the external cross-linking agent photoresponse gel, which comprises the following steps:
heating a ruthenium-containing monomer and a benzonitrile-containing monomer in 1, 2-propylene glycol for reaction to obtain an initial mixed solution;
dissolving a comonomer, an initiator and a crosslinking agent in 1, 2-propylene glycol, and mixing with the initial mixed solution to obtain a prepolymer solution;
and heating and polymerizing the prepolymer solution in the dark to obtain the additional cross-linking agent organogel.
Preferably, the comonomer is acrylamide and the initiator is azobisisobutyronitrile.
Preferably, the structural formula of the ruthenium-containing monomer is shown as a formula (I), and the structural formula of the benzonitrile-containing monomer is shown as a formula (II);
preferably, the preparation method of the ruthenium-containing monomer specifically comprises the following steps:
A) dissolving potassium hydroxide in dimethyl sulfoxide, heating and stirring, adding ethanolamine, and adding 4-chloro-2, 2,6 '', 2 '' -terpyridine for reaction;
B) reacting the product obtained in the step A) with acryloyl chloride in the presence of triethylamine;
C) mixing the product obtained in step B) with RuCl3▪3H2Heating and refluxing O for reaction;
D) reacting the product obtained in the step C) with 2, 2-bipyridyl in the presence of lithium chloride and triethylamine;
E) and D) refluxing and heating the product obtained in the step D) and silver nitrate in a solvent, and dropwise adding a saturated ammonium hexafluorophosphate solution after the reaction is stopped to obtain the ruthenium-containing monomer.
Preferably, the preparation method of the benzonitrile containing monomer comprises the following steps:
A) 4-hydroxy benzonitrile, potassium carbonate and potassium iodide are subjected to primary reaction in a solvent, 3-chloro-1-propanol is dissolved in the solvent, and the mixture is added into a product obtained by the primary reaction for reaction;
B) reacting the reactant obtained in the step A) with acryloyl chloride in the presence of triethylamine to obtain a benzonitrile monomer.
Preferably, when the concentration of the gel monomer is 0.6mol/L, the molar ratio of the ruthenium-containing monomer to the benzonitrile-containing monomer is not more than 1: 20; when the concentration of the gel monomer is 1mol/L, the molar ratio of the ruthenium-containing monomer to the benzonitrile-containing monomer is 1: 10-1: 20; the molar ratio of the comonomer to the initiator is (79-89): 1; the gel monomer is the ruthenium-containing monomer, the benzonitrile-containing monomer and the comonomer.
Preferably, when the concentration of the gel monomer is 1mol/L, the molar ratio of the ruthenium-containing monomer to the benzonitrile-containing monomer is 1: 10-1: 20, and the concentration of the crosslinking agent is 0.001-0.001 mol/L; the gel monomer is the ruthenium-containing monomer, the benzonitrile-containing monomer and the comonomer.
The application also provides a method for gel remodeling, which comprises the following steps:
irradiating the organogel without the addition of the cross-linking agent prepared by the preparation method of claim 1 under an LED light source to obtain sol;
the sol was heated in the dark, protected from light, and the gel was re-formed.
The application also provides a method for realizing writing and erasing of gel patterns, which comprises the following steps:
placing a photomask with a pattern right above the external cross-linking agent organic gel prepared by the preparation method of claim 2 for illumination to obtain gel with a pattern;
and heating the gel with the pattern in a dark place to erase the pattern.
The application provides a preparation method of photoresponse organic gel without an external cross-linking agent and with the external cross-linking agent, the organogel is prepared by using a ruthenium-containing monomer and a benzonitrile-containing monomer in 1, 2-propanediol without adding a crosslinking agent and without adding a crosslinking agent, the monomers can generate coordination under the dark heating condition, and the coordination bond between ruthenium in the ruthenium-containing monomer and benzonitrile in the benzonitrile-containing monomer after the irradiation with light can be broken, the 1, 2-propylene glycol can replace the position of the original ligand to be coordinated with ruthenium, so the formation and the dissociation of the coordination bond between the ruthenium-containing ligand and the benzonitrile-containing monomer can be controlled by heating away from light and switching the illumination condition, meanwhile, as the 1, 2-propylene glycol used for preparing the gel is a high-boiling-point organic solvent and is not easy to volatilize, therefore, the organogel prepared by the method has good light response performance under high temperature conditions.
Furthermore, the organogel provided by the application can directly form gel under the condition of not adding a cross-linking agent by adjusting the monomer concentration and the proportion of the ruthenium-containing complex monomer and the benzonitrile-containing monomer, and can realize reversible transformation of gel-sol through switching of illumination and light-shielding heating conditions, so that the organogel is used for material remodeling. Based on the color difference of the photoresponse unit in ligand coordination and dissociation, the organogel prepared by the external cross-linking agent can realize reversible writing and erasing of different patterns by controlling illumination and light-proof heating conditions, and is expected to be used for information storage and anti-counterfeiting.
Drawings
FIG. 1 is a NMR spectrum of a ruthenium-containing monomer A prepared in example 1;
FIG. 2 is a NMR spectrum of benzonitrile monomer B prepared in example 2;
FIG. 3 shows the organogel formation without addition of cross-linking agent at different monomer concentrations and different ratios of ruthenium and benzonitrile monomers in example 3;
FIG. 4 is a diagram of an example of organogel remodeling without the addition of a crosslinking agent;
FIG. 5 is a diagram of an example of photopatterning of an organogel with the addition of a crosslinking agent;
FIG. 6 is a graph of the change in weight of organogels and hydrogels at 80 ℃;
FIG. 7 is a schematic diagram of organogel remodeling without the addition of a crosslinking agent.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Aiming at the problems of easy volatilization and lack of heat resistance of organogel in the prior art, the application uses 1, 2-propylene glycol which has high boiling point and low volatility to replace solvent-water in the traditional hydrogel, and compounds a photoresponse unit ruthenium ligand and a benzonitrile-containing ligand into a gel network to prepare the photoresponse organogel which can be used at 80 ℃. Furthermore, the gel can be directly formed under the condition of not adding a cross-linking agent by adjusting the monomer concentration and the proportion of the ruthenium complex-containing monomer and the benzonitrile-containing monomer, and the reversible transformation of the gel-sol can be realized through the switching of the illumination and the light-proof heating conditions, so that the gel-sol can be used for material remodeling. Meanwhile, based on the color difference of the photoresponse unit in ligand coordination and dissociation, the gel prepared by the external cross-linking agent can realize reversible writing and erasing of different patterns by controlling illumination and light-proof heating conditions, and is expected to be used for information storage and anti-counterfeiting. Therefore, the invention can be used as a photoresponse gel material which can be used at 80 ℃, solves the problems of easy volatilization, lack of heat resistance and the like of the conventional gel material, and has good photoresponse performance at higher temperature. Specifically, the application firstly provides a preparation method of organogel without adding a cross-linking agent, which comprises the following steps:
heating a ruthenium-containing monomer and a benzonitrile-containing monomer in 1, 2-propylene glycol for reaction to obtain an initial mixed solution;
dissolving a comonomer and an initiator in 1, 2-propylene glycol, and mixing with the initial mixed solution to obtain a prepolymer solution;
and heating and polymerizing the prepolymer solution in the dark to obtain the photoresponse gel without adding the crosslinking agent.
In the process of preparing the organic gel without adding the cross-linking agent, firstly, dissolving a ruthenium-containing ligand and a benzonitrile-containing monomer in a solvent 1, 2-propylene glycol, stirring in a dark place, and stirring at 80-120 ℃ for 10-15 h to obtain an initial mixed solution; in the present application, the preparation method of the ruthenium-containing monomer specifically comprises:
A) dissolving potassium hydroxide in dimethyl sulfoxide, heating and stirring, slowly adding ethanolamine dropwise, and then adding 4-chloro-2, 2,6 '', 2 '' -terpyridine for reaction;
B) reacting the product obtained in the step A) with acryloyl chloride in the presence of triethylamine;
C) mixing the product obtained in step B) with RuCl3▪3H2Reacting O in a solvent;
D) reacting the product obtained in the step C) with 2, 2-bipyridyl in the presence of lithium chloride and triethylamine;
E) and D) reacting the product obtained in the step D) with silver nitrate in a solvent, and adding ammonium hexafluorophosphate solution after the reaction is stopped to obtain the ruthenium-containing monomer.
The preparation method of the benzonitrile monomer comprises the following steps:
A) 4-hydroxy benzonitrile, potassium carbonate and potassium iodide are subjected to primary reaction in a solvent, 3-chloro-1-propanol is dissolved in N, N-dimethylformamide, added into the reactants, and the reaction is continued.
B) Reacting the reactant obtained in the step A) with acryloyl chloride in the presence of triethylamine to obtain a benzonitrile monomer.
And after the initial mixed solution is obtained, dissolving a comonomer, an initiator and 1, 2-propylene glycol in the initial mixed solution, mixing the mixture with the initial mixed solution, and heating the mixture at 80-100 ℃ in a dark place for 10-15 hours to obtain the organic gel without the addition of the crosslinking agent. The ruthenium-containing monomer, the benzonitrile-containing monomer and the comonomer are referred to as gel monomers in this application, and when the gel monomer concentration is 0.6mol/L, the molar ratio of the ruthenium-containing monomer and the benzonitrile-containing monomer capable of satisfying the gel forming condition is not more than 1:20, more specifically 1: 20; when the concentration of the gel monomer is 1mol/L, the molar ratio of the ruthenium-containing monomer and the benzonitrile-containing monomer which can meet the gelling condition is 1: 10-1: 20; the comonomer is specifically selected from acrylamide, the initiator is specifically selected from azobisisobutyronitrile, and the molar ratio of the comonomer to the initiator is (79-89): 1.
in the preparation process of the organogel without adding a crosslinking agent, coordination bonds between ruthenium-containing monomers and benzonitrile-containing monomers are used as crosslinking points of a gel system to form a gel network in the presence of a gel substrate, so that the organogel is obtained.
The application also provides a preparation method of the additional cross-linking agent organogel, which comprises the following steps:
heating a ruthenium-containing monomer and a benzonitrile-containing monomer in 1, 2-propylene glycol for reaction to obtain an initial mixed solution;
dissolving a comonomer, an initiator and a crosslinking agent in 1, 2-propylene glycol, and mixing with the initial mixed solution to obtain a prepolymer solution;
and heating and polymerizing the prepolymer solution in the dark to obtain the additional cross-linking agent organogel.
In the preparation process of the external cross-linking agent organogel, firstly, a ruthenium-containing monomer and a benzonitrile-containing monomer are dissolved in 1, 2-propylene glycol, and the mixture is stirred away from light and is stirred for 10-15 hours at 80-120 ℃ to obtain an initial mixed solution.
After the initial mixed liquid is obtained, dissolving a comonomer, an initiator and a crosslinking agent in 1, 2-propylene glycol, mixing with the initial mixed liquid, and heating for 10-15 hours at 80-100 ℃ in a dark place to obtain the external crosslinking agent organogel. The ruthenium-containing monomer, the benzonitrile-containing monomer and the comonomer are referred to as gel monomers, when the concentration of the gel monomers is 1mol/L, the molar ratio of the ruthenium-containing ligand to the benzonitrile-containing monomer is 1: 10-1: 20, and the system can form enough cross-linking points in the molar ratio range so as to generate gel; the comonomer is specifically selected from acrylamide, and the concentration of the cross-linking agent is 0.001-0.001 mol/L.
In the add-on crosslinker organogel, the ruthenium-containing monomer and the benzonitrile-containing monomer provide coordination crosslinking, and the covalent crosslinking agent also provides covalent crosslinking, thereby providing the add-on crosslinker organogel.
The application also provides a gel remodeling method, which specifically comprises the following steps:
irradiating the organic gel without the additional cross-linking agent under an LED light source to obtain sol;
the sol was heated in the dark, protected from light, and the gel was re-formed.
In the gel remodeling process, the organogel without the addition of the cross-linking agent is placed at 80-100 ℃ and under 455nm LED light source irradiation for 1-3 hours, coordination cross-linking and dissociation between ruthenium and benzonitrile units can realize the conversion from the gel to the sol, and then the organogel is placed in a dark environment at 80-100 ℃ for 8-15 hours, and coordination bonds are formed, so that gel remodeling can be realized. A detailed schematic diagram is shown in fig. 7.
The organogel without the external cross-linking agent only uses the coordination bond between the ruthenium-containing monomer and the benzonitrile-containing monomer as the only cross-linking point in the gel system. When heating in the dark, namely the coordination bond is formed, the gel can be formed by the existence of the crosslinking point in the system; when irradiated by light with a certain wavelength, the coordination bond between the ruthenium-containing monomer and the benzonitrile-containing monomer of the ruthenium-containing monomer is broken, that is, no crosslinking point exists in the system, that is, the sol is obtained.
The application also provides a method for realizing pattern conversion by using the gel, which comprises the following steps:
placing a photomask containing a pattern right above the prepared additional cross-linking agent organic gel for illumination to obtain gel with the pattern;
and heating the gel with the pattern in a dark place to erase the pattern.
The above method utilizes an external crosslinker organogel to achieve patterning and erasure, more specifically:
a photomask containing a pattern is placed right above the external cross-linking agent organic gel and is illuminated by an LED light source with the wavelength of 455nm, so that a preset pattern can be generated on the gel; placing the gel with the written pattern into a sealed small glass bottle, and placing the sealed small glass bottle in a 100 ℃ drying oven to be heated in a dark place for 1-3 hours, so that the pattern can be erased; the resulting gel can be used for the next patterning, and then a different pattern can be written. When the concentration of the gel monomer is 1mol/L, the concentration of the ruthenium-containing monomer is 0.00002-0.002 mol/L, and the patterning effect is more remarkable.
In addition to the coordination crosslinks provided by the ruthenium-containing monomer and the benzonitrile-containing monomer, the organogel system with the addition of a crosslinking agent also has covalent crosslinks provided by a covalent crosslinking agent. When the photomask is used for patterning, the parts which are not irradiated by light in the system are in a coordination state with the benzonitrile monomer and present a color, while the parts which are exposed to the light are irradiated to cause the breakage of coordination crosslinking between ruthenium and benzonitrile monomer, but because the covalent crosslinking still exists in the system, the gel sol transformation does not occur, but because the coordination bonds are in a breakage state, the color presented by the irradiated parts is different. Thus a preset pattern can be created on the gel using a mask and light. In addition, since the coordination bond between ruthenium and benzonitrile monomers can be reformed by heating, and after the coordination cross-linking of the illuminated site generating the pattern is reformed, i.e. no difference from the non-illuminated site, the pattern can be erased after the patterned gel is placed at a high temperature for a period of time. A detailed schematic diagram is shown in fig. 7.
For further understanding of the present invention, the following examples are provided to illustrate the preparation and application of the organogel of the present invention, and the scope of the present invention is not limited by the following examples.
Example 1 synthesis of ruthenium-containing monomer a:
1) adding 7mmol of potassium hydroxide into 20mL of dimethyl sulfoxide, stirring and heating to 65 ℃, slowly dropwise adding 7.4mmol of ethanolamine into the solution, stirring the system at 65 ℃ for 30min, then adding 3.7mmol of 4-chloro-2, 2,6 '', 2 '' -terpyridine into the system, stirring at 65 ℃ for reaction for 2d, and stopping the reaction; cooling the reaction liquid to room temperature, pouring the reaction liquid into 20ml of deionized water, extracting the crude product by using dichloromethane, drying the obtained product by using anhydrous sodium sulfate, filtering the obtained product, performing suction filtration and washing on the reaction liquid to obtain a crude product, collecting an oil phase, removing a solvent by rotary evaporation to obtain the crude product, and recrystallizing the crude product by using ethyl acetate to obtain a light yellow solid;
2) dissolving 4.7mol of the final product in the step 1) in 40mL of anhydrous dichloromethane, adding 9.8mol of triethylamine at 0 ℃ under the nitrogen atmosphere, stirring at 0 ℃ for 30min, slowly adding 6.71mmol of acryloyl chloride into the system, stirring the reaction solution at 0 ℃ for 2h, and then stirring at room temperature for 21 h; after the reaction is stopped, adding 20ml of deionized water to quench the reaction, separating liquid, washing with dichloromethane for 3 times, washing all collected dichloromethane with 5-6 ml of saturated saline water, and removing the solvent by rotary evaporation to obtain a crude product; purifying the crude product by silica gel column chromatography, wherein the eluent is ethyl acetate and petroleum ether to obtain a product;
3) 1mmol of the final product of step 2) and 1.0mmol of RuCl3▪3H2Dissolving O in 150ml of absolute ethyl alcohol, and heating and refluxing the mixture for 3 hours; cooling the reaction liquid to room temperature, carrying out suction filtration, washing with ethanol and diethyl ether, and drying in a vacuum drying oven to obtain a product;
4) dissolving 0.32mmol of the final product in the step 3), 0.32mmol of 2, 2-bipyridine and 2.4mmol of lithium chloride in a mixed solvent of 20mL of ethanol and water =3:1, bubbling nitrogen for 10min, adding 0.64mmol of triethylamine under the nitrogen atmosphere, and refluxing for 21h in a dark place; cooling the reaction liquid to room temperature, filtering, and purifying the crude product by silica gel column chromatography, wherein the eluent is dichloromethane and methanol to obtain mauve solid;
5) dissolving 0.3mmol of the final product in the step 4) and 0.6mmol of silver nitrate in 16mL of mixed solvent of acetone and water =3:1, bubbling nitrogen for 10min, refluxing overnight in the dark, filtering the hot reaction solution, reducing the solvent to 4mL by a rotary evaporator of the crude product, slowly dropwise adding saturated ammonium hexafluorophosphate solution to separate out brown yellow precipitate until the precipitate does not increase any more, washing with ice water, collecting the precipitate, and drying for 24h at 50 ℃ in a vacuum drying oven. Thus obtaining the final ruthenium-containing monomer. The nuclear magnetic spectrum is shown in FIG. 1.
Example 2 synthesis of benzonitrile monomer B:
1) dissolving 10mmol of 4-hydroxybenzonitrile, 10mmol of potassium carbonate and 0.6mmol of potassium iodide in 20ml of N, N-dimethylformamide, stirring the reaction solution at 110 ℃ for 30min, then dissolving 11mol of 3-chloro-1-propanol in 10ml of N, N-dimethylformamide, slowly dripping the solution into the system, stirring the solution at 110 ℃ for 24h, stopping the reaction, filtering the reaction mixture, washing residues with dichloromethane, removing the solvent by a rotary evaporator to obtain a crude product, drying the crude product, purifying the crude product by silica gel column chromatography, and eluting with petroleum ether and ethyl acetate to obtain colorless oily liquid;
2) dissolving 5.64mmol of the final product in the step 1) and 8.64mmol of triethylamine in 40mL of anhydrous dichloromethane, stirring at room temperature for 10min, then slowly dropwise adding 8.64mmol of acryloyl chloride into the system at 0 ℃ in a nitrogen atmosphere, stirring the reaction solution at 0 ℃ for 2h, stirring at room temperature for 21h, after the reaction is stopped, adding 20mL of deionized water to quench the reaction, separating, washing dichloromethane with water for 3 times, washing all collected dichloromethane with 5-6 mL of saturated common salt solution, removing the solvent by rotary evaporation to obtain a crude product, purifying the crude product by silica gel column chromatography, wherein eluents are ethyl acetate and petroleum ether, and drying at 40 ℃ for 24h in a vacuum drying oven. Thus obtaining the final benzonitrile monomer. The nuclear magnetic spectrum is shown in FIG. 2.
Example 3 preparation of a gel without addition of crosslinker (sample 1mol/L monomer, 1% ruthenium-containing monomer, 10% benzonitrile-containing monomer as an example):
1) dissolving 0.02mmol of ruthenium-containing monomer A and 0.2mmol of benzonitrile-containing monomer B in 100. mu.l of 1, 2-propanediol, and stirring for 12h at 100 ℃ in the dark;
2) dissolving 1.78mmol of acrylamide and 0.02mmol of azobisisobutyronitrile into 100 mu l of 1, 2-propylene glycol, adding into the system 1), and stirring and mixing uniformly;
3) and (3) injecting the mixed solution into a reaction mould, and heating for 12 hours at 80 ℃ in a dark place to obtain the organic gel without the addition of the cross-linking agent. The gelling condition is shown in figure 3; in FIG. 3, when the concentration of the gel monomer is 0.6mol/L (left diagram) and 1mol/L (right diagram), the ratio of the ruthenium-containing monomer to the benzonitrile-containing monomer is 0: 20. 1: 0. 1: 5. 1: 10. 1: gel formation of sample 20.
Example 4 preparation of a gel with an external crosslinker (sample containing 1mol/L of monomer, 0.2% of ruthenium-containing monomer, 4% of benzonitrile-containing monomer as an example):
1) dissolving 0.004mmol of ruthenium-containing monomer A and 0.08mmol of benzonitrile-containing monomer B in 100 mu l of 1, 2-propanediol, and stirring for 12h at 100 ℃ in the dark;
2) dissolving 1.92mmol of acrylamide, 0.02mmol of azodiisobutyronitrile and 0.04mmol of polyethylene glycol diacrylate in 100 mu l of 1, 2-propylene glycol, adding into the system 1), and stirring and mixing uniformly;
3) and (3) injecting the mixed solution into a reaction mould, and heating for 12 hours at 80 ℃ in a dark place to obtain the external cross-linking agent organogel. See in particular the first sample in fig. 5.
Example 5
The method for realizing the remodeling without adding the cross-linking agent gel comprises the following steps: placing a piece of gel with the size of 1cm multiplied by 1mm without adding a cross-linking agent under the irradiation of an LED light source with the temperature of 80 ℃ and the thickness of 455nm for 1h, wherein the transformation from gel to sol can be realized due to the coordination cross-linking dissociation between ruthenium and benzonitrile units; and transferring the obtained sol into another mold, placing the mold in the dark at 100 ℃ for 12h, and re-forming coordinate bonds to realize gel remodeling. See in particular fig. 4.
Example 6
The method for writing and erasing the pattern by adding the crosslinking agent gel comprises the following steps: placing a photomask containing a pattern right above the gel with the external cross-linking agent, and illuminating by using an LED light source with the wavelength of 455nm, wherein the preset pattern can be generated on the gel due to the difference of the colors of a broken part of an illumination coordination bond and an un-illuminated part; putting the gel written with the pattern into a sealed small glass bottle, putting the sealed small glass bottle into a drying oven at 100 ℃ and heating the sealed small glass bottle in the dark for 1 hour, and then re-forming coordinate bonds at the illumination position to erase the pattern; the resulting gel can be used for the next patterning, and then a different pattern can be written. See in particular fig. 5.
Example 7
Method for determining the weight change of organogel and hydrogel at 80 ℃: the monomer concentration is 1mol/L, the ruthenium monomer content is 1%, the benzonitrile monomer content is 10%, the organic gel and the hydrogel with the same volume of the added cross-linking agent are placed in an oven at the temperature of 80 ℃, and the percentage of the gel weight to the initial weight after different time intervals is measured. The experiment was repeated three times and the weighing results averaged. Specifically, as shown in fig. 6, it can be seen from fig. 6 that the gel weight loss of the organogel is significantly better than that of the hydrogel at 80 ℃.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of a photoresponse gel without an external cross-linking agent comprises the following steps:
heating a ruthenium-containing monomer and a benzonitrile-containing monomer in 1, 2-propylene glycol for reaction to obtain an initial mixed solution;
dissolving a comonomer and an initiator in 1, 2-propylene glycol, and mixing with the initial mixed solution to obtain a prepolymer solution;
and heating and polymerizing the prepolymer solution in the dark to obtain the photoresponse gel without adding the crosslinking agent.
2. A preparation method of an external cross-linking agent photoresponse gel comprises the following steps:
heating a ruthenium-containing monomer and a benzonitrile-containing monomer in 1, 2-propylene glycol for reaction to obtain an initial mixed solution;
dissolving a comonomer, an initiator and a crosslinking agent in 1, 2-propylene glycol, and mixing with the initial mixed solution to obtain a prepolymer solution;
and heating and polymerizing the prepolymer solution in the dark to obtain the additional cross-linking agent organogel.
3. The method according to claim 1 or 2, wherein the comonomer is acrylamide and the initiator is azobisisobutyronitrile.
4. The preparation method of claim 1 or 2, wherein the structural formula of the ruthenium-containing monomer is shown as formula (I), and the structural formula of the benzonitrile-containing monomer is shown as formula (II);
5. the method according to claim 4, wherein the ruthenium-containing monomer is prepared by a method comprising:
A) dissolving potassium hydroxide in dimethyl sulfoxide, heating and stirring, adding ethanolamine, and then adding 4-chloro-2, 2,6 ', 2' -terpyridine for reaction;
B) reacting the product obtained in the step A) with acryloyl chloride in the presence of triethylamine;
C) mixing the product obtained in step B) with RuCl3·3H2Heating and refluxing O for reaction;
D) reacting the product obtained in the step C) with 2, 2-bipyridyl in the presence of lithium chloride and triethylamine;
E) and D) refluxing and heating the product obtained in the step D) and silver nitrate in a solvent, and dropwise adding a saturated ammonium hexafluorophosphate solution after the reaction is stopped to obtain the ruthenium-containing monomer.
6. The method according to claim 4, wherein the method for preparing the benzonitrile monomer comprises:
A) 4-hydroxy benzonitrile, potassium carbonate and potassium iodide are subjected to primary reaction in a solvent, 3-chloro-1-propanol is dissolved in the solvent, and the mixture is added into a product obtained by the primary reaction for reaction;
B) reacting the reactant obtained in the step A) with acryloyl chloride in the presence of triethylamine to obtain a benzonitrile monomer.
7. The method according to claim 1, wherein the molar ratio of the ruthenium-containing monomer to the benzonitrile-containing monomer is not more than 1: 20; when the concentration of the gel monomer is 1mol/L, the molar ratio of the ruthenium-containing monomer to the benzonitrile-containing monomer is 1: 10-1: 20; the molar ratio of the comonomer to the initiator is (79-89): 1; the gel monomer is the ruthenium-containing monomer, the benzonitrile-containing monomer and the comonomer.
8. The preparation method according to claim 2, wherein when the concentration of the gel monomer is 1mol/L, the molar ratio of the ruthenium-containing monomer to the benzonitrile-containing monomer is 1:10 to 1:20, and the concentration of the crosslinking agent is 0.001 to 0.001 mol/L; the gel monomer is the ruthenium-containing monomer, the benzonitrile-containing monomer and the comonomer.
9. A method of gel remodeling comprising the steps of:
irradiating the organogel without the addition of the cross-linking agent prepared by the preparation method of claim 1 under an LED light source to obtain sol;
the sol was heated in the dark, protected from light, and the gel was re-formed.
10. A method of achieving gel pattern writing and erasing, comprising the steps of:
placing a photomask with a pattern right above the external cross-linking agent organic gel prepared by the preparation method of claim 2 for illumination to obtain gel with a pattern;
and heating the gel with the pattern in a dark place to erase the pattern.
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