CN114479101A - Supramolecular gel composition - Google Patents
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Abstract
The invention discloses a supermolecular gel composition which is 5,5' - (pentane-1, 5-diacyl bis (oxy)) bis (N)1,N3-bis (6-butylamine pyridine-2-yl) isophthalamide as a first gel factor, and barbituric acid modified polyoxometalate as a second gel factor, and dissolving the mixture in chloroform at a molar ratio of 1: 0.9-1.1 to form a mixed system. The supermolecule gel composition has high thermal stability, good self-healing property and excellent mechanical property, and can be used as an adsorption material, a biological medicine material, a sensing and detecting material, an environmental response structure material and the like.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis and supermolecule science, relates to a supermolecule gel, and particularly relates to a supermolecule gel with high thermal stability, self-healing property and good mechanical property, and a preparation method of the gel.
Background
Supramolecular gels, a kind of functional soft materials, have recently received much attention from scientists because of their excellent properties. The supramolecular gel generally refers to a soft material with an ordered structure, which is self-assembled by organic small molecule gel factors in an organic solvent through a synergistic effect. The organic small molecule gel factor forms three-dimensional network structures with different structures through the interaction of non-covalent bonds such as hydrogen bond force, pi-pi bond acting force, van der waals force and the like, the three-dimensional network structures can wrap and fix a large number of organic solvent molecules to form organic gel structures, and special functional molecular groups are introduced into the gel factor structures, so that the characteristics of the supermolecule gel are utilized, and the excellent performances in certain aspects, such as good thermal reversibility and response to the external environment, are generated, so that the organic small molecule gel factor has wide application in the aspects of chemical sensing, nano templates, dynamic functional materials and the like.
Although the supramolecular gel has many excellent characteristics, the supramolecular gel has good application prospects in many fields, the preparation of related gel factors has contingency, randomness and complexity, and the formed gel has certain limitations, so that the practical application and potential application range of the supramolecular gel are greatly limited.
The following are several key issues facing current supramolecular gels.
1. It is difficult to purposefully prepare the high-efficiency gelator which can be directly used.
The designed and prepared potential gelator can not necessarily form stable gel well in a certain solvent, so that great randomness and contingency exist in the design and preparation of the gelator.
2. The method for optimizing the performance of the gel factor has complex steps and difficult process operation.
The method for optimizing the gel performance reported at present is to introduce specific functional groups into the molecular structure of the gel factor with high-efficiency gel capability and modify the geometric configuration of the gel factor. However, the chemical modification increases the complexity and difficulty of the process for preparing the gel, and consumes manpower, material resources and financial resources.
3. The organogels prepared tend to exhibit poor gelling properties.
This is because the acting force for forming the supramolecular gel is a non-covalent bond acting force with weak intermolecular hydrogen bond, pi-pi stacking acting force, van der waals force and the like, and the gel structure cannot adapt to the tiny change of the external environment, thus showing poor performance.
For example, the gel has poor thermal stability, the thermal movement of gel factors is easily accelerated by small rise of the environmental temperature, the non-covalent force action among the gel factors is weakened, the gel structure is damaged, and the gel is macroscopically represented as the liquefaction phenomenon of the gel.
As another example, gels generally have no self-healing properties, since the non-covalent bonds connecting the gels are generally irreversible, and changes in the structural units of the gel due to changes in external conditions, the irreversible connection renders the gel incapable of self-healing, and macroscopically incapable of repairing the structure of the damaged site.
Also for example, gels have poor mechanical properties, are poorly defined due to their irreversible non-covalent bonds that are unable to form a re-establishment of reversible dynamic crosslinks in the gel network, have a low degree of bonding and crosslinking, macroscopically behave as poor viscoelasticity, etc.
Due to these performance leaks, practical applications of the gel are greatly limited.
The thermal stability of the organogel is improved, and the application of the organogel as a functional soft material is greatly expanded; the self-healing performance is improved, the service life of the organogel can be prolonged, the use safety can be greatly improved, and the organogel has great application potential in multiple fields such as sensing and detection, drug release, drivers, tissue engineering and the like; the improvement of mechanical properties relates to a great breakthrough in the fields of environmental response structural materials and the like. Therefore, the preparation of the supermolecular gel with excellent performance, which is simple and easy to operate, has profound practical significance.
Disclosure of Invention
The invention aims to provide a supermolecule gel composition with high thermal stability, high self-healing property and excellent mechanical property.
The supramolecular gel composition is a mixed system formed by dissolving a first gelator and a second gelator in chloroform according to the molar ratio of 1: 0.9-1.1.
Wherein the first gelator is a compound with the following structural formula, chemical formula C57H64N12O10Chemical name 5,5' - (pentane-1, 5-diacylbis (oxy)) bis (N)1,N3-bis (6-butylamine pyridin-2-yl) isophthalamide.
The second gel factor is barbituric acid modified polyoxometalate with the following structural formula (C)21H33N2O6)2[(OCH2)3CNH]2(MnMo6O18)•[(C4H9)4N]3。
Wherein: POM is MnMo6O18TBA is (C)4H9)4N。
Furthermore, the supramolecular gel composition is a mixed system which is formed by dissolving the first gelator and the second gelator in chloroform and has the concentration of 10-30 mg/mL.
The invention also provides a specific preparation method of the supramolecular gel composition, which comprises the steps of adding the first gelator and the second gelator into chloroform as a solvent according to the molar ratio of 1: 0.9-1.1, carrying out ultrasonic combined heating treatment to enable the first gelator and the second gelator to be dissolved uniformly, and standing to form stable supramolecular gel.
Preferably, the standing time is not less than 3 hours.
More specifically, the first gelator of the present invention can be prepared by the following method.
1) And reacting 5- (benzyloxy) isophthalic acid with thionyl chloride to obtain 5- (benzyloxy) isophthaloyl dichloride.
2) Further reacting 5- (benzyloxy) isophthaloyl chloride with N- (6-aminopyridin-2-yl) butanamide in a chloroform solution of triethylamine to prepare 5- (benzyloxy) -N1,N3Bis (6-butylaminopyridin-2-yl) isophthalamide.
3) And then 5- (benzyloxy) -N1,N3Reaction of (6-butylaminopyridin-2-yl) isophthalamide in anhydrous methanol containing palladium on carbon and formic acid to give N1,N3-bis (6-butylamine pyridin-2-yl) -5-hydroxyisophthalamide.
4) And finally, with N1,N3Reacting (E) -bis (6-butylamine pyridine-2-yl) -5-hydroxyisophthalamide and 1, 5-dibromopentane in an acetone solution containing potassium carbonate and potassium iodide to prepare the target product 5,5' - (pentane-1, 5-diacyl bis (oxy)) bis (N)1,N3Bis (6-butylamine pyridin-2-yl) isophthalamide.
Wherein, in the step 1), the mol ratio of the 5- (benzyloxy) isophthalic acid to the thionyl chloride is preferably 1: 5-10.
In the step 2), the mol ratio of the 5- (benzyloxy) isophthaloyl dichloride, the N- (6-aminopyridine-2-yl) butanamide and the triethylamine is preferably 1: 2.1-2.3.
In the step 3), 5- (benzyloxy) -N1,N3The mol ratio of the (6-butylaminopyridin-2-yl) isophthalamide to the palladium carbon and the formic acid is preferably 1: 4-4.3: 1.1-1.3.
In the step 4), N1,N3The mol ratio of the (6-butylamine pyridine-2-yl) -5-hydroxyisophthalamide to the 1, 5-dibromopentane to the potassium carbonate and the potassium iodide is preferably 1: 0.3-0.5: 3-4: 1.3-1.5.
Further, the second gelator of the present invention is a barbituric acid-modified polyoxometalate hybrid disclosed in CN 112570025a of the applicant.
Compared with the common supermolecule gel in which the main intermolecular force is hydrogen bond force and van der waals force, the invention purposefully introduces polyoxometallate ion clusters into the second gel factor, reasonably utilizes the strong electrostatic interaction among the molecules, the cage-shaped rigid framework structure and the poor solubility of low-polarity solvents, greatly improves the thermal stability of the prepared gel through the combination of the first gel factor and the second gel factor, and forms the gel structure shown as the following.
In the structure, the first gelator and the second gelator have strong six-fold hydrogen bond effect among molecules and belong to non-covalent bond force, and the non-covalent bond force enables the prepared supramolecular gel to have good self-healing capability through the reversible dynamic bonding effect of the hydrogen bond among the molecules.
In addition, the first gelator and the second gelator have enhanced hydrogen bonding effect, greatly enhance the crosslinking complexity of the three-dimensional supramolecular network structure of the gel, and further enhance the mechanical property of the gel.
The first gelator and the second gelator can not form gel independently, and can only form a stable structure as shown above when the first gelator and the second gelator exist simultaneously, and a solution system of the first gelator and the second gelator can form a stable supramolecular gel composition which has uniqueness, singleness and irreplaceability.
The present invention also has the interesting finding that the first gel factor and the second gel factor, when present alone, do not form a gel and must be used in combination.
Furthermore, when the second gelator is replaced by bis 4- (12-barbituric acid) -tetradecyloxy-4-oxosuccinate which does not contain polyoxometallate but has a completely identical molecular structure, gel formation still fails, and various properties cannot be mentioned.
Wherein, the compound bis 4- (12-barbituric acid) -tetradecyloxy-4-oxosuccinate has the following structural formula.
Therefore, only when the first gelator and the second gelator exist simultaneously, the solution system can form the stable supramolecular gel material, and the formed supramolecular gel material has various excellent properties, so that the supramolecular gel material has uniqueness, singularity and irreplaceability.
The preparation method of the supramolecular gel composition is simple, the reaction condition is mild, the raw materials are easy to obtain, the prepared supramolecular gel composition has excellent thermal stability, the gel-sol phase transition temperature is far higher than the boiling point of a solvent, and the stability of the supramolecular gel composition in use in different environments is ensured. In addition, the supermolecule gel composition has good self-healing property, and is suitable for various functional materials needing high self-healing property. The supramolecular gel composition of the present invention also has superior mechanical properties and does not break when it is stretched.
Based on various excellent performances of the supramolecular gel composition, the supramolecular gel composition can be used as various functional soft materials such as an adsorption material, a biomedical material, a sensing and detecting material, an environmental response structure material and the like, so that various use requirements in different fields are met, and the supramolecular gel composition has a wide application prospect.
Drawings
FIG. 1 shows intermediate product N for preparing first gelator1,N3Nuclear magnetic resonance hydrogen spectrum of (6-butylamine pyridin-2-yl) -5-hydroxyisophthalamide.
FIG. 2 is a graph of the first gelator, 5' - (pentane-1, 5-diacylbis (oxy)) bis (N1,N3-bis (6-butylamine pyridin-2-yl) isophthalamide NMR spectrum.
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of a second gel factor, namely, a barbituric acid modified polyoxometalate hybrid.
Figure 4 is a graph comparing the supramolecular gel composition of the present invention with other products to form solutions.
Fig. 5 is a diagram of the self-healing process of the supramolecular gel composition of the invention.
Fig. 6 is a mechanical property test chart of the supramolecular gel composition of the invention.
Detailed Description
The following describes in detail a specific embodiment of the present invention with reference to the drawings, examples and comparative examples. The following examples and comparative examples are only for more clearly illustrating the technical aspects of the present invention so that those skilled in the art can well understand and utilize the present invention, and do not limit the scope of the present invention.
The names and abbreviations of the experimental methods, production processes, instruments and equipment related to the examples and comparative examples of the present invention are all conventional names in the art, and are clearly and clearly understood in the related fields of use, and those skilled in the art can understand the conventional process steps and apply the corresponding equipment according to the names, and implement the process according to the conventional conditions or the conditions suggested by the manufacturers.
The various starting materials and reagents used in the examples and comparative examples of the present invention are not particularly limited in terms of their sources, and are all conventional products commercially available.
Example 1: a first gelator is prepared.
5g of 5- (benzyloxy) isophthalic acid was added to 200mL of thionyl chloride, the temperature was raised to 45 ℃ to react for 8 hours, the reaction mixture was cooled to room temperature, and then dried under reduced pressure to obtain 5- (benzyloxy) isophthaloyl dichloride.
Weighing 3g of 5- (benzyloxy) isophthaloyl dichloride, 3.5g N- (6-aminopyridin-2-yl) butanamide and 2.1g of triethylamine, dissolving in 350mL of chloroform, reacting at 60 ℃ for 48h, cooling the reaction solution to room temperature, washing the reaction solution with distilled water, and performing vacuum spin-drying on the organic phase to obtain 5- (benzyloxy) -N1,N3Bis (6-butylaminopyridin-2-yl) isophthalamide.
3g of 5- (benzyloxy) -N1,N3Dissolving-bis (6-butylaminopyridin-2-yl) isophthalamide, 2.2g palladium carbon and 0.28g formic acid in 200mL absolute methanol, reacting at 40 ℃ for 72h, cooling the reaction solution to room temperature, washing the reaction solution with distilled water, and performing vacuum spin drying on the organic phase to obtain N1,N3-bis (6-butylamine pyridin-2-yl) -5-hydroxyisophthalamide.
FIG. 1 shows the above preparation N1,N3Nuclear magnetic resonance hydrogen spectrum of (6-butylamine pyridin-2-yl) -5-hydroxyisophthalamide. The solvent peaks are shown in the figure, all characteristic peaks of which give a clear assignment, and the spectrum does not contain any miscellaneous peaks, thus proving that the prepared compound has high purity.
Weighing 1.5g N1,N3Dissolving (6-butylamine pyridin-2-yl) -5-hydroxyisophthalamide, 0.3g of 1, 5-dibromopentane, 1.4g of potassium carbonate and 0.7g of potassium iodide in 200mL of acetone, reacting at 56 ℃ for 70 hours, filtering the reaction solution, drying the filtrate by spinning, recrystallizing the filtrate with dichloromethane, and drying in vacuum to obtain 5,5' - (pentane-1, 5-diacyl bis (oxy)) bis (N-butyl benzene1,N3Bis (6-butylamine pyridin-2-yl) isophthalamide, the first gelator.
FIG. 2 shows a NMR spectrum of the first gel factor. The solvent peaks are shown in the figure, all the characteristic peaks of which give a clear assignment, and the spectrum does not contain any impurity peaks, thus proving that the first gelator prepared has higher purity.
Example 2: a second gelator is prepared.
5g of diethyl ethylmalonate, 7g of 11-bromo-1-undecanol and 1.3g of sodium hydride are weighed and added into 350mL of N, N-dimethylformamide, stirred and reacted for 20h at the temperature of 60 ℃, the reaction solution is cooled to room temperature, the reaction solution is washed with distilled water, and the organic phase is subjected to pressure spin drying to obtain the 11-diethyl ethylmalonate-1-undecanol.
6g of 11-diethyl ethylmalonate-1-undecanol, 1g of urea and 0.8g of sodium hydride are dissolved in 250mL of N, N-dimethylformamide, stirred at 85 ℃ for reaction for 20 hours, the reaction solution is cooled to room temperature, the reaction solution is washed with distilled water, and organic phase is subjected to vacuum spin drying to obtain 12-barbituric acid-tetradecanol.
3g of 12-barbituric acid-tetradecanol, 1.2g of succinic anhydride and 2g of triethylamine are added into 200mL of chloroform, the mixture is stirred and reacted for 50 hours at 48 ℃, the reaction solution is decompressed and dried, and is recrystallized by methanol and dried in vacuum, so that 4- (12-barbituric acid) -tetradecyloxy-4-oxobutyric acid is obtained.
Weighing 2.5g of 4- (12-barbituric acid) -tetradecyloxy-4-oxobutyric acid and 2g of 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline, and 4g of a compound of the formula [ (C)4H9)4N]3(MnMo6O18)[(OCH2)3CNH2]2Dissolving the polyoxometalate in 400mL of acetonitrile, stirring at 55 ℃ for reaction for 70h, concentrating the reaction solution under reduced pressure, precipitating in dichloromethane, filtering and drying to obtain the barbituric acid modified polyoxometalate hybrid, namely the second gel factor.
FIG. 3 shows a NMR spectrum of the second gel factor. The solvent peaks are shown in the figure, all characteristic peaks of which give a clear assignment, and the spectrum does not contain any miscellaneous peaks, thus proving that the second gel factor prepared has higher purity.
Example 3.
Weighing 4.2mg of the first gelator and 10.8mg of the second gelator, adding the first gelator and the second gelator into a screw vial with 1mL of chloroform, heating and carrying out ultrasonic treatment until the first gelator and the second gelator are completely dissolved, naturally cooling to room temperature, and standing for 3h to prepare the stable supramolecular gel.
Comparative example 1.
The supramolecular gel was prepared as in example 3 by weighing 15mg of the first gelator without adding the second gelator and was found to be incapable of forming a gel.
Comparative example 2.
The supramolecular gel was prepared as in example 3 by weighing 15mg of the second gelator without adding the first gelator and was found to be incapable of forming a gel.
Comparative example 3.
8.9mg of the first gelator and 6.1mg of bis 4- (12-barbituric acid) -tetradecyloxy-4-oxosuccinate were weighed out, and supramolecular gel was prepared according to the method of example 3, and it was found that gel could not be formed.
Wherein the bis 4- (12-barbituric acid) -tetradecyloxy-4-oxosuccinate used has the following structural formula similar to the second gelator.
FIG. 4 records a state diagram of the preparation of supramolecular gel-forming products of example 3 and comparative examples 1-3. Wherein, fig. 4a is the supramolecular gel formed by example 3, fig. 4b is the solution formed by comparative example 1 when the first gelator is used alone, fig. 4c is the solution formed by comparative example 2 when the second gelator is used alone, and fig. 4d is the solution formed by comparative example 3 when the first gelator and bis 4- (12-barbituric acid) -tetradecyloxy-4-oxosuccinate are used.
Therefore, only when the first gelator and the second gelator exist at the same time, the solution system can form a stable supramolecular gel composition, and the method has uniqueness, uniqueness and irreplaceability.
Example 4.
Weighing 5mg of first gelator and 13mg of second gelator, adding the first gelator and the second gelator into a screw-mouth vial added with 1mL of chloroform, heating and carrying out ultrasonic treatment until the first gelator and the second gelator are completely dissolved, naturally cooling to room temperature, and standing for 3h to prepare the stable supramolecular gel.
Vials containing the supramolecular gels prepared in example 3 and example 4, respectively, were placed upside down in a vacuum oven and heated at a heating rate of 12 ℃/h, and the gel-sol phase transition temperature of the gel was measured as it slides down to the bottom of the vial under the influence of gravity. The results show that the gel-sol phase transition temperatures of examples 3 and 4 are 93 ℃ and 97 ℃, respectively, both exceed 93 ℃, and are well above the solvent's own boiling point.
Example 5.
Weighing 7mg of first gelator and 18mg of second gelator, adding the first gelator and the 18mg of second gelator into a screw-mouth vial added with 1mL of chloroform, heating and carrying out ultrasonic treatment until the first gelator and the second gelator are completely dissolved, naturally cooling to room temperature, and standing for 3h to prepare the stable supramolecular gel.
After the prepared supramolecular gel is cut into two halves by a small knife, the two halves are put back to the original position and are simultaneously and quickly placed in a sealed bag, after the supramolecular gel composition is placed for 24 hours at room temperature without any stimulation, the self-healing process diagram of the supramolecular gel composition shown in the figure 5 is observed, and the two gel blocks cut before are adhered together to form an integral gel block, which shows that the gel has good self-healing capacity.
Example 6.
Weighing 8mg of first gelator and 20mg of second gelator, adding the first gelator and the second gelator into a screw-mouth vial added with 1mL of chloroform, heating and carrying out ultrasonic treatment until the first gelator and the second gelator are completely dissolved, naturally cooling to room temperature, and standing for 3h to prepare the stable supramolecular gel.
A gel strip with the length of 1cm is cut from the prepared supramolecular gel, the two ends of the gel strip are clamped by forceps, the gel strip is stretched by uniform force, the mechanical property of the gel strip is observed, the test result is shown in figure 6, and the gel strip is not broken when stretched, which indicates that the gel composition has good mechanical property.
The above embodiments of the present invention are not intended to be exhaustive or to limit the invention to the precise form disclosed. Various changes, modifications, substitutions and alterations to these embodiments will be apparent to those skilled in the art without departing from the principles and spirit of this invention.
Claims (10)
1. A supramolecular gel composition is a mixed system formed by dissolving a first gelator and a second gelator in chloroform according to the molar ratio of 1: 0.9-1.1, wherein:
the first gelator is of formula C57H64N12O10Chemical name 5,5' - (pentane-1, 5-diacylbis (oxy)) bis (N)1,N3-bis (6-butylamine pyridin-2-yl) isophthalamide represented by the following general structural formula:
the second gel factor is barbituric acid modified polymetallic oxygen cluster hybrid with the following structural formula (C)21H33N2O6)2[(OCH2)3CNH]2(MnMo6O18)•[(C4H9)4N]3：
Wherein: POM is MnMo6O18TBA is (C)4H9)4N。
2. The supramolecular gel composition as claimed in claim 1, which is a mixed system of 10-30 mg/mL concentration formed by dissolving the first gelator and the second gelator in chloroform.
3. The supramolecular gel composition as claimed in claim 1, wherein said first gelator is prepared by the following method:
1) reacting 5- (benzyloxy) isophthalic acid with thionyl chloride to prepare 5- (benzyloxy) isophthaloyl dichloride;
2) further reacting 5- (benzyloxy) isophthaloyl chloride with N- (6-aminopyridin-2-yl) butanamide in a chloroform solution of triethylamine to prepare 5- (benzyloxy) -N1,N3-bis (6-butylaminopyridin-2-yl) isophthalamide;
3) and then 5- (benzyloxy) -N1,N3Reaction of (6-butylaminopyridin-2-yl) isophthalamide in anhydrous methanol containing palladium on carbon and formic acid to give N1,N3-bis (6-butyamine pyridin-2-yl) -5-hydroxyisophthalamide;
4) and finally, with N1,N3Reacting (6-butylamine pyridine-2-yl) -5-hydroxyisophthalamide and 1, 5-dibromopentane in an acetone solution containing potassium carbonate and potassium iodide to prepare the target product 5,5' - (pentane-1, 5-diacyl bis (oxy)) bis (N)1,N3-bis (6-butylamine pyridin-2-yl) isophthalamide.
4. The supramolecular gel composition as claimed in claim 3, wherein the molar ratio of 5- (benzyloxy) isophthalic acid to thionyl chloride in step 1) is 1: 5-10.
5. The supramolecular gel composition as claimed in claim 3, wherein the molar ratio of 5- (benzyloxy) isophthaloyl chloride, N- (6-aminopyridin-2-yl) butanamide and triethylamine in step 2) is 1: 2.1-2.3.
6. The supramolecular gel composition of claim 3, wherein 5- (benzyloxy) -N in step 3)1,N3The molar ratio of the (6-butylaminopyridin-2-yl) isophthalamide to the palladium-carbon to the formic acid is 1: 4 to 4.3: 1.1 to 1.3.
7. The supramolecular gel composition of claim 3, wherein N in step 4)1,N3The molar ratio of the (6-butylamine pyridine-2-yl) -5-hydroxyisophthalamide to the 1, 5-dibromopentane to the potassium carbonate to the potassium iodide is 1: 0.3-0.5: 3-4: 1.3-1.5.
8. The preparation method of the supramolecular gel composition as claimed in claim 1, wherein the first gelator and the second gelator are added into chloroform as a solvent according to a molar ratio of 1: 0.9-1.1, and the mixture is subjected to ultrasonic combined heating treatment to be uniformly dissolved and then is kept stand to form the stable supramolecular gel.
9. The method for the preparation of supramolecular gel composition according to claim 8, wherein said resting time is not less than 3 h.
10. Use of the supramolecular gel composition as claimed in claim 1 as an adsorbent material, biomedical material, sensing and detecting material, environmental responsive structural material.
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| CN112570025A (en) * | 2020-10-30 | 2021-03-30 | 中北大学 | Barbituric acid modified polymetallic oxygen cluster hybrid and preparation method thereof |
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