CN114316171A - Preparation method of novel acylhydrazone bond gel through one-step crosslinking polymerization - Google Patents
Preparation method of novel acylhydrazone bond gel through one-step crosslinking polymerization Download PDFInfo
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- CN114316171A CN114316171A CN202210046678.8A CN202210046678A CN114316171A CN 114316171 A CN114316171 A CN 114316171A CN 202210046678 A CN202210046678 A CN 202210046678A CN 114316171 A CN114316171 A CN 114316171A
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Abstract
The invention provides a preparation method of novel acylhydrazone bond gel by one-step crosslinking polymerization. The method is characterized in that 1,3, 5-benzene trimethyl acyl chloride is used as a starting material and reacts with absolute ethyl alcohol to generate triethyl trimesate, and then the triethyl trimesate reacts with hydrazine hydrate to generate trimesoyl hydrazide. And finally, adopting trimesoyl hydrazine and aldehyde as organic monomers to construct a module, taking dimethyl sulfoxide as a solvent medium according to the Schiff base reaction principle and acylhydrazone covalent bonds as cross-linking points, and rapidly and directly synthesizing a series of novel acylhydrazone bond polymer gels at room temperature in one step. Compared with the existing preparation method of the acylhydrazone bond gel material, the novel acylhydrazone bond gel is completed through one-step crosslinking polymerization of organic monomers of hydrazide and aldehyde, the process that the prior acylhydrazone bond gel material is firstly designed and synthesized into a gel factor and then a crosslinking group is searched is omitted, and the design concept is more advanced and novel. The synthesis method is simple, low in cost, mild in condition, high in reaction rate and yield, and has good development and application potential in the aspect of intelligent materials.
Description
Technical Field
The invention relates to a preparation method of novel acylhydrazone bond gel by one-step crosslinking polymerization, belonging to the field of high polymer materials.
Background
The polymer gel is a gel system which is formed by three-dimensional or interpenetrating network structure with unique physical and chemical properties and a large amount of solvent through crosslinking polymer macromolecules. According to the crosslinking mode between polymer macromolecules, the gel can be divided into polymer physical gel and polymer chemical gel. The polymer physical gel is a cross-linking system formed by taking intermolecular forces (hydrogen bonds, van der waals forces and the like) as cross-linking points, has low strength and poor thermal stability and solvent stability, has good responsiveness to external environments (such as light, heat and the like), and easily realizes the reversible conversion and self-repairing processes of sol-gel. The polymer chemical gel is a cross-linked structure formed by taking static covalent bonds as cross-linking points among macromolecular chains, has high mechanical strength and thermal stability, and is difficult to self-repair once a network structure is damaged. Combining the environmental responsiveness of physical gel and the mechanical properties of chemical gel to form intelligent polymer gel with both excellent properties becomes a hot spot of current research.
Dynamic covalent bonds are a class of chemical bonds that can undergo reversible reactions. The dynamic covalent bond gel with physical gel reversibility and chemical gel stability can be obtained by applying the dynamic covalent bond to the synthesis of the polymer gel. Acylhydrazone linkages, which are typical of reversible covalent bonds, are obtained by the reaction of hydrazides with aldehydes or ketones and are widely used in controllable polymers. The acylhydrazone bond has the advantages of simple formation, mild reaction conditions, flexible and changeable product structure, biocompatibility and the like, and has potential application value in the fields of medicine and biology.
The acylhydrazone bond gel is polymer gel obtained by reaction of hydrazide and aldehyde or ketone, but most acylhydrazone bond gels are synthesized by firstly designing and synthesizing a gel factor, then searching a crosslinking group, and finally synthesizing through an initiator and a crosslinking agent to obtain the acylhydrazone bond polymer gel. At present, there are few reports on the rapid and direct synthesis of novel acylhydrazone bond polymer gels at room temperature by using hydrazides and aldehydes as organic monomers.
Disclosure of Invention
The invention aims to solve the technical problems of simple synthesis method, low cost, no catalyst, mild condition, high reaction rate and high yield of the acylhydrazone bond gel.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the novel acylhydrazone bond gel by one-step crosslinking polymerization comprises the following steps:
the method comprises the following steps: preparation of triethyl trimesate compound: feeding 1,3, 5-benzene tricarbochloride and absolute ethyl alcohol into a round-bottom flask according to the mass/volume g/mL ratio of 1:10-1:20, adding a little triethylamine, stirring at room temperature for reacting for 4-8 h, filtering after the reaction is finished, and recrystallizing with absolute ethyl alcohol to obtain triethyl trimesate;
step two: preparation of trimesoyl hydrazide compound: adding triethyl trimesate, hydrazine hydrate, absolute ethyl alcohol and tetrahydrofuran into a round-bottom flask according to the mass/volume g/mL ratio of 1:10-1:15, 1:10-1:20 and 1:10-1:20 respectively, heating and refluxing for 4-6 h under stirring, after the reaction is finished, carrying out reduced pressure distillation, washing the reaction product to be neutral by using distilled water, recrystallizing by using absolute ethyl alcohol, and filtering to obtain trimesoyl hydrazide;
step three: preparation of a novel acylhydrazone linkage gel: feeding trimesoyl hydrazide and aldehyde group organic monomers according to the molar ratio of 1:1 or 1:1.5, and calculating according to the content of amino groups in the trimesoyl hydrazide and aldehyde groups in the aldehyde;
firstly, weighing a certain amount of trimesoyl hydrazide in a 2-20 mL glass vial, adding dimethyl sulfoxide (DMSO), wherein the concentration of the solution is 0.04-0.4mmol/mL, and completely dissolving by ultrasonic; weighing a certain amount of aldehyde monomer in another 2-20 mL glass vial, adding DMSO solvent for dissolving, wherein the concentration of the solution is 0.04-0.4mmol/mL or 0.06-0.6 mmol/mL; under ultrasound, mixing DMSO solutions of two monomers, wherein the concentration is 0.01-0.20 mmol/mL, calculating according to the content of amino groups in trimesoyl hydrazide, gradually changing the mixed solution from a turbid solution to a light yellow transparent solution, standing at room temperature for 15-30 min to form a gel state, and transferring a fresh gel to an oven to heat and age for 12 h at 80 ℃; after aging, soaking and washing the gel with 15-30 mL of solvent for 24 h, and exchanging the solvent every 8 h for 3 times; finally freeze drying or subcritical CO at low temperature2The solvent was exchanged by soxhlet extractor to obtain pale yellow solid gel powder with a yield of 95-98%.
In the invention, the one-step crosslinking polymerization is that trimesoyl hydrazide and aldehyde organic monomer are directly condensed to form acylhydrazone bonds through Schiff base reaction.
In the invention, the molar ratio of the trimesoyl hydrazide to the aldehyde group organic monomer in the step three is 1:1 or 1:1.5, and the molar ratio is calculated according to the content of amino groups and aldehyde group.
In the invention, the aldehyde organic monomer in the step three is one or more compounds of o-phthalaldehyde, p-phthalaldehyde, m-phthalaldehyde, biphenyl phthalaldehyde and trimeldehyde.
In the invention, the concentration of the DMSO solution of the trimesoyl hydrazide monomer in the step three is 0.04-0.4 mmol/mL.
In the invention, the concentration of the DMSO solution of the aldehyde monomer in the step three is 0.04-0.4mmol/mL or 0.06-0.6 mmol/mL.
In the invention, the concentration of the DMSO mixed solution of the trimesoyl hydrazide and the aldehyde in the step three is 0.01-0.30 mmol/mL, and the calculation is carried out according to the content of amino groups in the trimesoyl hydrazide.
In the invention, the reaction temperature in the third step is room temperature.
In the invention, the reaction time in the step three is 15-30 min.
In the invention, the washing solvent is tetrahydrofuran and absolute ethyl alcohol respectively.
The beneficial effect of adopting above-mentioned technical scheme is:
1. compared with the existing preparation method of the acylhydrazone bond gel material, the novel acylhydrazone bond gel is prepared by one-step crosslinking polymerization of the organic monomers of the hydrazide and the aldehyde, so that the process of firstly designing and synthesizing a gel factor and then searching a crosslinking group of the existing acylhydrazone bond gel material is omitted, and the design concept is more advanced and novel.
2. Compared with the prior art, the preparation method of the acylhydrazone bond polymer gel has the advantages of simple synthesis method, mild conditions, quick reaction and high yield.
3. The novel acylhydrazone bond gel has good physical and chemical properties, can realize sol-gel conversion performance and room temperature self-healing function through temperature change, and has good application potential in the aspects of intelligent materials, biological medicines and the like.
4. The preparation method has the advantages of low raw material cost, high efficiency, rapidness, and good development and popularization.
Drawings
FIG. 1 is a scanning electron micrograph of three novel acylhydrazone-linked gels according to the present invention.
FIG. 2 is an infrared spectrum of three novel acylhydrazone-bonded gels of the present invention.
FIG. 3 is a NMR chart of three novel acylhydrazone bond gels of the present invention.
FIG. 4 is a diagram of the sol-gel transition of three novel acylhydrazone bond gels according to the present invention.
FIG. 5 is a graph showing the self-healing properties of three novel acylhydrazone bond gels of the present invention.
Detailed Description
The three novel acylhydrazone-bonded gels (BTH-BD, BTH-PD, BTH-BDD) of the present experiment are described in detail below with reference to the accompanying drawings and specific embodiments.
I) three novel acylhydrazone bond gels are subjected to structure and performance determination by adopting a Fourier transform infrared spectrometer (FTIR), a nuclear magnetic resonance analyzer (NMR), a Scanning Electron Microscope (SEM) and the like, and the sol-gel conversion performance and the self-healing function of the gel are researched.
Example 1
Synthesis of triethyl trimesate: weighing 4.53 g (17.0 mmol) of 1,3, 5-benzene tricarbochloride in a 150 mL round-bottom flask, adding 50 mL of absolute ethyl alcohol and 5-8 drops of triethylamine, stirring at room temperature for reacting for 6 h, stopping reaction to obtain a white solid, performing suction filtration, recrystallizing the solid with absolute ethyl alcohol, and filtering to obtain a white needle-shaped crystal; the synthetic route is shown below.
Example 2
Synthesis of trimesoyl hydrazide: weighing 1.47 g (5.0 mmol) of triethyl trimesate in a 150 mL round-bottom flask, adding 20 mL of 80% hydrazine hydrate, 30 mL of anhydrous ethanol and 30 mL of tetrahydrofuran, heating and refluxing for 6 h under stirring, distilling under reduced pressure to remove ethanol, cooling to separate out a large amount of white solid, carrying out suction filtration, washing with a large amount of water to neutrality, recrystallizing the solid with anhydrous ethanol, and filtering to obtain white solid powder; the synthetic route is shown below.
Example 3
Preparation of novel acylhydrazone bond Polymer gel (BTH-BD): weighing 100.5 mg (0.4 mmol) of trimesoyl hydrazide in a 10 mL glass vial, adding 4.0 mL of DMSO solvent, and performing ultrasonic treatment for 10 min to completely dissolve the trimesoyl hydrazide; further, 80.8 mg (0.6 mmol) of isophthalaldehyde was weighed into another 10 mL glass vial, and 4.0 mL of DMSO solvent was added thereto to completely dissolve the isophthalaldehyde. Slowly dripping a DMSO solution of m-phthalaldehyde into a DMSO solution of trimesoyl hydrazide under ultrasound, gradually changing the mixed solution from a turbid solution to a light green transparent solution, standing the mixed solution at room temperature for 30 min to form a gel state, and then transferring the newly prepared gel to an oven to heat and age at 80 ℃ for 12 h. After aging, the solvent in the vial is taken out, and the gel is soaked and washed with 15-30 mL of tetrahydrofuran for 24 h (the solvent is exchanged every 8 h for 3 times); soaking and washing the mixture for 24 hours by 15-30 mL of absolute ethyl alcohol (the solvent is exchanged every 8 hours in 3 times). Finally, freeze-drying at low temperature to obtain light yellow gel powder with the yield of 95 percent; the synthetic route is shown below.
Example 4
Preparation of a novel acylhydrazone linkage gel (BTH-PD): weighing 100.5 mg (0.4 mmol) of trimesoyl hydrazide in a 10 mL glass vial, adding 4.0 mL of DMSO solvent, and performing ultrasonic treatment for 10 min to completely dissolve the trimesoyl hydrazide; 80.4 mg (0.6 mmol) of terephthalaldehyde was weighed into another 10 mL glass vial, and 4.0 mL of DMSO solvent was added to completely dissolve the terephthalaldehyde. Slowly dripping a DMSO solution of terephthalaldehyde into a DMSO solution of trimesoyl hydrazide under ultrasound, gradually changing the mixed solution from a turbid solution to a light yellow transparent solution, standing the mixed solution at room temperature for 20 min to form a gel state, and then transferring the newly prepared gel to an oven to be heated and aged at 80 ℃ for 12 h. After aging, the solvent in the vial is taken out, and the gel is soaked and washed with 15-30 mL of tetrahydrofuran for 24 h (the solvent is exchanged every 8 h for 3 times); soaking and washing the mixture for 24 hours by 15-30 mL of absolute ethyl alcohol (the solvent is exchanged every 8 hours in 3 times). Finally, low-temperature freeze drying is carried out to obtain light yellow gel powder with the yield of 97 percent; the synthetic route is shown below.
Example 5
Preparation of a novel acylhydrazone bond gel (BTH-BDD): weighing 100.5 mg (0.4 mmol) of trimesoyl hydrazide in a 10 mL glass vial, adding 4.0 mL of DMSO solvent, and performing ultrasonic treatment for 10 min to completely dissolve the trimesoyl hydrazide; in another 10 mL glass vial, 126.2 mg (0.6 mmol) of biphenyldicarboxaldehyde was weighed out and dissolved completely in 4.0 mL of DMSO solvent. Slowly dripping a DMSO solution of biphenyldicarboxaldehyde into a DMSO solution of trimesoyl hydrazide under ultrasound, gradually changing the mixed solution from a turbid solution to a light yellow transparent solution, standing the mixed solution at room temperature for 15 min to form a gel state, and then transferring the newly prepared gel to an oven to be heated and aged at 80 ℃ for 12 h. After aging, the solvent in the vial is taken out, and the gel is soaked and washed with 15-30 mL of tetrahydrofuran for 24 h (the solvent is exchanged every 8 h for 3 times); soaking the mixture in 15-30 mL of absolute ethyl alcohol for 24 h (the solvent is exchanged every 8 h for 3 times). Finally using subcritical CO2Exchanging the solvent by a Soxhlet extractor to obtain light yellow gel powder with the yield of 98 percent; the synthetic route is shown below.
Example 6
And (3) converting the DMSO mixed solution of the trimesoyl hydrazide and the aldehyde monomer into gel.
II) the following examples are presented to perform structural characterization and performance studies of three novel acylhydrazone-linked gels.
Example 1
Three (BTH-BD, BTH-PD, BTH-BDD) materials were topographically characterized using a scanning electron microscope, as shown in FIG. 1. The result shows that gel particles are highly crosslinked and stacked layer by layer, the surface of the appearance is a three-dimensional porous structure, and the particle size is about 10-500 nm.
Example 2
The functional groups of three novel acylhydrazone bond gel (BTH-BD, BTH-PD and BTH-BDD) materials are characterized by infrared absorption spectrum, as shown in FIG. 2. The absorption peaks of N-H stretching vibration characteristics on amide groups in the three novel acylhydrazone bond gel materials are respectively 3430 cm-1、3441 cm-1、3437 cm-1Typical absorption peaks for stretching vibration of imine bond (C = N) were each located at 1548 cm-1、1543 cm-1、1548 cm-1To (3).
Example 3
Using solids13C NMR confirmed the structural information of three novel acylhydrazone bond gel (BTH-BD, BTH-PD, BTH-BDD) materials, as shown in FIG. 3. The signals at the chemical shifts of 164 ppm, 163 ppm and 169 ppm in the three novel acylhydrazone bond gel materials are resonance signals of carbon atoms in carbonyl groups, and the signals at the chemical shifts of 149 ppm, 149 ppm and 145 ppm are the resonance signals of carbon atoms in C = N.
Example 4
The sol-gel performance of three novel acylhydrazone bond gels (BTH-BD, BTH-PD, BTH-BDD) is shown in FIG. 4. Respectively weighing a certain amount of trimesoyl hydrazide and aldehyde monomers (in a molar ratio), adding the monomers into a double-neck round-bottom flask, and adding a certain amount of DMSO solution. Heating and stirring for reaction, and observing the gel-sol conversion process of the acylhydrazone bond gel through slow temperature rise and temperature fall changes. Research shows that the novel acylhydrazone bond gel can generate reversible sol-gel transformation under the heating condition, and the novel acylhydrazone bond gel is in a gel state when the temperature is lower than 150 ℃; when the temperature is more than 150 ℃, the gel is completely converted into the solution. The novel acylhydrazone bond gel can realize multiple possible transformation of gel-sol through the stimulus response of temperature change. The result shows that the novel acylhydrazone bond gel material has good temperature response performance.
Example 5
Three novel acylhydrazone bond gels (BTH-BD, BTH-PD, BTH-BDD) were investigated for their self-healing properties, as shown in FIG. 5. The three fresh gels are cut into two halves by a knife, the two halves of the fresh gels are closely contacted with each other, and the healing condition of the gels is observed every 12 hours. After 3 days, the incision of the gel is gradually reduced, after 4 days, the incision basically disappears, and after 5 days, the gel achieves the effect of complete healing. Research results show that the novel acylhydrazone bond gel material has strong self-healing performance at room temperature without external stimulation.
The above embodiments are only intended to illustrate the technical solution of the present invention, and are not intended to limit the present invention in any way, and any simple modification or equivalent replacement of some technical features according to the technical spirit of the present invention may be made without departing from the technical solution of the present invention, and the modifications or the replacement are within the scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the novel acylhydrazone bond gel by one-step crosslinking polymerization is characterized by comprising the following steps of: it comprises the following steps:
the method comprises the following steps: preparation of triethyl trimesate compound: feeding 1,3, 5-benzene tricarbochloride and absolute ethyl alcohol into a round-bottom flask according to the mass/volume g/mL ratio of 1:10-1:20, adding a little triethylamine, stirring at room temperature for reacting for 4-8 h, filtering after the reaction is finished, and recrystallizing with absolute ethyl alcohol to obtain triethyl trimesate;
step two: preparation of trimesoyl hydrazide compound: adding triethyl trimesate, hydrazine hydrate, absolute ethyl alcohol and tetrahydrofuran into a round-bottom flask according to the mass/volume g/mL ratio of 1:10-1:15, 1:10-1:20 and 1:10-1:20 respectively, heating and refluxing for 4-6 h under stirring, after the reaction is finished, carrying out reduced pressure distillation, washing the reaction product to be neutral by using distilled water, recrystallizing by using absolute ethyl alcohol, and filtering to obtain trimesoyl hydrazide;
step three: preparation of a novel acylhydrazone linkage gel: feeding trimesoyl hydrazide and aldehyde group organic monomers according to the molar ratio of 1:1 or 1:1.5, and calculating according to the content of amino groups in the trimesoyl hydrazide and aldehyde groups in the aldehyde;
firstly, weighing a certain amount of trimesoyl hydrazide in a 2-20 mL glass vial, adding dimethyl sulfoxide (DMSO), wherein the concentration of the solution is 0.04-0.4mmol/mL, and completely dissolving by ultrasonic; weighing a certain amount of aldehyde monomer in another 2-20 mL glass vial, adding DMSO solvent for dissolving, wherein the concentration of the solution is 0.04-0.4mmol/mL or 0.06-0.6 mmol/mL; under ultrasound, mixing DMSO solutions of two monomers, wherein the concentration is 0.01-0.20 mmol/mL, calculating according to the content of amino groups in trimesoyl hydrazide, gradually changing the mixed solution from a turbid solution to a light yellow transparent solution, standing at room temperature for 15-30 min to form a gel state, and transferring a fresh gel to an oven to heat and age for 12 h at 80 ℃; after aging, soaking and washing the gel with 15-30 mL of solvent for 24 h, and exchanging the solvent every 8 h for 3 times; finally freeze drying or subcritical CO at low temperature2The solvent was exchanged by soxhlet extractor to obtain pale yellow solid gel powder with a yield of 95-98%.
2. The method for preparing a one-step crosslinked and polymerized acylhydrazone bond gel according to claim 1, which is characterized in that: the one-step crosslinking polymerization is that trimesoyl hydrazide and aldehyde organic monomers are directly condensed to form acylhydrazone bonds through Schiff base reaction.
3. The method for preparing a one-step crosslinked and polymerized acylhydrazone bond gel according to claim 1, which is characterized in that: and step three, the molar ratio of the trimesoyl hydrazide to the aldehyde group organic monomer is 1:1 or 1:1.5, and the molar ratio is calculated according to the content of amino groups and aldehyde group.
4. The method for preparing a one-step crosslinked and polymerized acylhydrazone bond gel according to claim 1, which is characterized in that: and the aldehyde organic monomer in the step three is one or more compounds of o-phthalaldehyde, p-phthalaldehyde, m-phthalaldehyde, biphenyl phthalaldehyde and trimeldehyde.
5. The method for preparing a one-step crosslinked and polymerized acylhydrazone bond gel according to claim 1, which is characterized in that: and step three, the concentration of the DMSO solution of the trimesoyl hydrazide monomer is 0.04-0.4 mmol/mL.
6. The method for preparing a one-step crosslinked and polymerized acylhydrazone bond gel according to claim 1, which is characterized in that: and step three, the concentration of the DMSO solution of the aldehyde group monomer is 0.04-0.4mmol/mL or 0.06-0.6 mmol/mL.
7. The method for preparing a one-step crosslinked and polymerized acylhydrazone bond gel according to claim 1, which is characterized in that: and step three, the concentration of the DMSO mixed solution of the trimesoyl hydrazide and the aldehyde is 0.01-0.30 mmol/mL, and the calculation is carried out according to the content of amino groups in the trimesoyl hydrazide.
8. The method for preparing a one-step crosslinked and polymerized acylhydrazone bond gel according to claim 1, which is characterized in that: and the reaction temperature in the third step is room temperature.
9. The method for preparing a one-step crosslinked and polymerized acylhydrazone bond gel according to claim 1, which is characterized in that: and the reaction time in the third step is 15-30 min.
10. The method for preparing a one-step crosslinked and polymerized acylhydrazone bond gel according to claim 1, which is characterized in that: the washing solvent is tetrahydrofuran and absolute ethyl alcohol respectively.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114907278A (en) * | 2022-06-21 | 2022-08-16 | 武汉大学 | Preparation method of polymer based on acylhydrazone macrocycle |
| CN114907278B (en) * | 2022-06-21 | 2023-06-02 | 武汉大学 | Preparation method of acylhydrazone macrocyclic-based polymer |
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