CN113121781A - Preparation method of self-repairable thermosetting film based on multi-component Ugi polymerization reaction and dynamic oxime urethane bond exchange - Google Patents
Preparation method of self-repairable thermosetting film based on multi-component Ugi polymerization reaction and dynamic oxime urethane bond exchange Download PDFInfo
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Abstract
The invention relates to a preparation method of a self-repairable thermosetting film based on multi-component Ugi polymerization reaction and dynamic oxime urethane bond exchange. The oxime urethane bond can carry out exchange reaction when being heated, so that the cured film has certain plasticity when being heated, self-repairing and repeated reprocessing can be realized, and the defects that the thermosetting resin is difficult to repair and is formed in one step after being damaged are overcome. Meanwhile, the polymer structure is highly designable, an intermediate does not need to be separated, and the reaction activity is high, so that the preparation efficiency and the environmental friendliness of the material are improved by introducing a multi-component reaction into the preparation process of the self-repairing material.
Description
Technical Field
The invention belongs to a preparation method of a self-repairable thermosetting film, relates to a preparation method of a self-repairable thermosetting film based on multi-component Ugi polymerization reaction and dynamic oxime urethane bond exchange, and particularly relates to synthesis of a macromolecular chain containing an oxime side chain based on multi-component Ugi polymerization reaction and preparation of a self-repairable thermosetting film containing a dynamic oxime urethane bond.
Background
With the development of the field of material science, polymers mainly include thermoplastics and thermosets. Thermoplastics are linear polymers that are easily recycled or reprocessed. However, their mechanical properties and solvent resistance are limited. Thermosets, on the other hand, generally consist of a three-dimensional network which is permanently cross-linked by covalent bonds. Unlike thermoplastics, they have better mechanical properties, dimensional stability and chemical resistance. However, once they are fully crosslinked, thermosets cannot be dissolved or melted, which makes them difficult to reprocess or recycle. Therefore, if thermosets have processing and recycling characteristics, their field of application will be expanded.
In recent years, dynamic covalent chemistry has provided a theoretical basis for the development of smart materials that have attracted a wide interest in the synthesis of self-healing, recyclable thermosets (covalent adaptive networks, CAN). The dynamically crosslinked network in CAN dissociate and recover under certain stimulus conditions (e.g., heat, uv, pH). CAN, which is based on a dissociative exchange mechanism (e.g., the Diels-Alder reaction), first breaks a chemical bond and then forms a new chemical bond at another location. However, chemical bonds in CAN based on association exchange mechanisms (dynamic exchange reactions) or vitrimers CAN form new chemical bonds with a constant degree of crosslinking upon cleavage, which CAN prevent sudden viscosity drops and maintain structural integrity during processing. In 2011, Leibler and his colleagues extended the field of dynamic covalent chemistry for the first time and thoroughly studied the performance differences between vitrimmers and other thermosets by adding a suitable transesterification catalyst to the epoxy network. Several exchangeable reactions have been developed so far, such as transesterification, transalkylation, imine exchange, disulfide bond exchange, transesterification of borate ester, transamination of vinyl group, carbamation, oxime-promoted carbamation, and the like. In 2017, the xuakang group developed a dynamic covalent chemistry based on an oxime-promoted carbamation reaction that produced dynamic poly (oxime-carbamate) without catalyst at room temperature with excellent mechanical properties and recyclability. As researchers find more and more dynamic covalent bonds, the field of application of dynamic covalent bonds would be greatly expanded if there were a general method of introducing dynamic covalent bonds into a crosslinked network.
In the field of organic chemistry, there is a well-known type of reaction, namely multi-component reaction (MCR), in which three or more reaction substrates are mixed together and the product is obtained directly by a one-pot process. To date, more and more multicomponent reactions have been found, such as the Biginelli reaction, Passerini reaction, Ugi reaction. During the reaction, intermediates do not need to be separated, and the final product contains fragments of each starting material, and this unique property determines the possibility of MCR with molecular structural design (side groups and repeating units can be designed) and efficient atom economy. And the byproduct is only water, so the method is very environment-friendly. Therefore, it is of interest to apply MCR in the field of polymer chemistry. In 2010, the Meier project group applied the Passerini three-component reaction (Passerini-3CR) to the synthesis of polymers and prepared a series of α, ω -diene compounds having the Passerini structure. In 2014, the Meier project group applied the Ugi four-component reaction (Ugi-4CR) to the synthesis of various substituted polyamides, systematically illustrating the application of Ugi-4CR in polymer chemistry. To our knowledge, there is no example of a vitrimer prepared by Ugi-4CR, and we propose a self-healing thermoset film with dynamic oxime urethane linkages.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a preparation method of a self-repairable thermosetting film based on multi-component Ugi polymerization reaction and dynamic oxime urethane bond exchange, which fully utilizes the advantages of the multi-component polymerization reaction and vitrimer, has faster relaxation time and higher mechanical strength, reduces the processing technology requirement of repair, and can reduce the cost of the prior synthesis technology.
Technical scheme
A preparation method of a self-repairable thermosetting film based on multi-component Ugi polymerization reaction and dynamic oxime urethane bond exchange is characterized by comprising the following steps:
step 1, synthesizing a macromolecular chain with oxime groups as side groups through a Ugi polymerization reaction:
step a: reacting polyether amine, methanol and isobutyraldehyde at room temperature under stirring; the molar ratio of the polyether amine to the isobutyraldehyde is 1:2.0-3.0, and the mass ratio of the methanol to the polyether amine monomer is 6-10: 1;
step b: at room temperature, sequentially adding tetrahydrofuran, 1, 6-diethylcyanohexane and levulinic acid into the system in the step 1, after the reaction is completed under stirring, rotationally evaporating the reaction liquid at the temperature of 30-50 ℃, removing the solvent, adding dichloromethane into the system, precipitating the polymer by using n-hexane, and then drying at 40 ℃ for 12 hours to obtain a polymer solid with a side group of a methyl carbonyl group;
the molar ratio of the 1, 6-diethylcyanohexane to the polyether amine is 1: 1-1.2, the molar ratio of the polyether amine to the levulinic acid is 1:2.0-3.0, and the mass ratio of the tetrahydrofuran to the polyether amine monomer is 3.0-5.0: 1;
step c: sequentially adding an alcohol solvent, deionized water, hydroxylamine hydrochloride, sodium acetate and the polymer solid with the side group of the methyl carbonyl obtained in the step b into a container, and carrying out reflux reaction at 100 ℃ for 6-8 hours;
the molar ratio of the polymer with the side group of the methyl carbonyl obtained from the hydroxylamine hydrochloride, the sodium acetate and the b1 is 10-15:5-8:1, and the mass ratio of the alcohol solvent to the deionized water is 2-3: 1;
step d: after the reaction is finished, extracting the organic phase for 3 times by using dichloromethane, washing the organic phase by using saturated saline solution, drying the organic phase by using anhydrous sodium sulfate, then removing the dichloromethane by rotary evaporation, controlling the temperature to be 30-50 ℃, and precipitating in normal hexane to obtain a high molecular chain solid with an oxime group as a side group;
dissolving a high molecular chain solid with side groups of oxime groups and a diisocyanate monomer in tetrahydrofuran, stirring for 1 hour at room temperature, pouring into a polytetrafluoroethylene mold, volatilizing a solvent in a fume hood at room temperature for one night, and post-curing for 12 hours at 80 ℃ in vacuum to obtain a self-repairable thermosetting film based on multi-component Ugi polymerization reaction and dynamic oxime urethane bond exchange;
the ratio of the functional groups of the macromolecular chain solid with the side group of oxime group and the diisocyanate is 1: 1.0-1.2.
The step a and the step c are that reactants are put into a container provided with a magnetic stirrer.
The polyetheramines in step 1 include, but are not limited to: polyetheramine D230, polyetheramine D400, polyetheramine D1000, or polyetheramine D2000.
The alcoholic solvent in step c includes but is not limited to: methanol or ethanol, and any combination thereof.
The diisocyanate monomers in step 2 include, but are not limited to: toluene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, or any one or combination thereof.
Advantageous effects
The invention provides a preparation method of a self-repairable thermosetting film based on multi-component Ugi polymerization reaction and dynamic oxime urethane bond exchange. The molecular weight of the polymer can be effectively regulated and controlled by regulating and controlling the molecular weight of the monomer. The oxime urethane bond can carry out exchange reaction when being heated, so that the cured film has 90 percent of repair efficiency when being heated, can realize self repair and repeated reprocessing, and solves the defects of difficult repair and one-step molding after the thermosetting resin is damaged. At the same time, there are many advantages to multicomponent polymerization reactions, such as: the polymer structure is highly designable, an intermediate does not need to be separated, and the reaction activity is high, so that the application of multi-component polymerization reaction in the field of materials can be widened by introducing the multi-component reaction into the preparation process of the self-repairing material, and an idea can be provided for the preparation of the novel polyamide vitrier.
The invention fully utilizes the advantages of multi-component polymerization reaction and vitrimer, simultaneously has faster relaxation time (40S at 170 ℃) and higher mechanical strength (stress is 8.75Mpa, strain is 255%), reduces the processing technology requirement of repair, and can reduce the cost of the prior synthesis technology.
The mechanical properties (a) of the self-healing thermoset film containing a dynamic oxime urethane bond are compared with the thermal properties (b) of D400-U in FIG. 3, wherein the storage modulus curve on the left and the loss tangent curve on the right show a Tg of about 34.1 ℃.
Drawings
FIG. 1: a synthetic route of a macromolecular chain with oxime groups as side groups is synthesized through Ugi polymerization;
FIG. 2: nuclear magnetic resonance hydrogen spectrogram of macromolecular chain with side group of oxime group
FIG. 3: comparing the thermal performance and the mechanical performance of the self-repairing thermosetting film containing the dynamic oxime urethane bond;
FIG. 4: the thermal weight loss curve of the self-repairing thermosetting film containing the dynamic oxime urethane bond;
FIG. 5: a reprocessing flow schematic diagram of the self-repairing thermosetting film containing the dynamic oxime urethane bond;
FIG. 6: a self-repairing process schematic diagram of the self-repairing thermosetting film containing the dynamic oxime urethane bond;
FIG. 7: the self-repairing thermosetting film containing dynamic oxime urethane bond has the shape memory performance.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
1. and (3) synthesizing a macromolecular chain with oxime groups as side groups through Ugi polymerization.
Example 1: to a vessel equipped with a magnetic stirrer were added 4.60g of polyetheramine D230, 20.00mL of methanol and 4.32g of isobutyraldehyde in this order at room temperature and reacted under rapid stirring for 1 hour, followed by adding 7.50mL of tetrahydrofuran, 2.72g of 1, 6-diethylcyanohexane and 6.96g of levulinic acid in this order to the system and reacted under rapid stirring for 48 hours. After the reaction is finished, the reaction solution is rotationally evaporated, and the temperature is controlled at 30-50 ℃. After the solvent is completely removed, adding a certain amount of dichloromethane into the system, precipitating the polymer by using normal hexane, and finally drying at 40 ℃ for 12 hours to obtain the polymer with the side group of the methyl carbonyl. Adding 80.00mL of ethanol, 40.00mL of deionized water, 1.80g of hydroxylamine hydrochloride, 3.39g of sodium acetate and 2.00g of polymer with a side group of methyl carbonyl into a container provided with a magnetic stirrer in sequence, carrying out reflux reaction for 6-8 hours at 100 ℃, extracting an organic phase for 3 times by using dichloromethane after the reaction is finished, washing the organic phase by using saturated saline solution, drying the organic phase by using anhydrous sodium sulfate, carrying out rotary evaporation to remove dichloromethane, controlling the temperature to be 30-50 ℃, and precipitating in normal hexane to obtain 1.62g of a high molecular chain with a side group of oxime (A).
Example 2: to a vessel equipped with a magnetic stirrer were added 4.00g of polyetheramine D400, 20.00mL of methanol and 2.16g of isobutyraldehyde in this order at room temperature and reacted under rapid stirring for 1 hour, followed by adding 7.50mL of tetrahydrofuran, 1.36g of 1, 6-diethylcyanohexane and 3.48g of levulinic acid in this order to the system and reacted under rapid stirring for 48 hours. After the reaction is finished, the reaction solution is rotationally evaporated, and the temperature is controlled at 30-50 ℃. After the solvent is completely removed, adding a certain amount of dichloromethane into the system, precipitating the polymer by using normal hexane, and finally drying at 40 ℃ for 12 hours to obtain the polymer with the side group of the methyl carbonyl. Adding 80.00mL of ethanol, 40.00mL of deionized water, 1.59g of hydroxylamine hydrochloride, 2.99g of sodium acetate and 2.00g of polymer with a side group of methyl carbonyl into a container provided with a magnetic stirrer in sequence, carrying out reflux reaction for 6-8 hours at 100 ℃, extracting an organic phase for 3 times by using dichloromethane after the reaction is finished, washing the organic phase by using saturated saline solution, drying the organic phase by using anhydrous sodium sulfate, carrying out rotary evaporation to remove dichloromethane, controlling the temperature to be 30-50 ℃, and precipitating in normal hexane to obtain 1.70g of a high molecular chain with a side group of oxime (B).
Example 3: to a vessel equipped with a magnetic stirrer were added 4.00g of polyetheramine D2000, 20.00mL of methanol and 0.521g of isobutyraldehyde in this order at room temperature and reacted under rapid stirring for 1 hour, followed by adding 7.50mL of tetrahydrofuran, 0.27g of 1, 6-diethylcyanohexane and 0.67g of levulinic acid in this order to the system and reacted under rapid stirring for 48 hours. After the reaction is finished, the reaction solution is rotationally evaporated, and the temperature is controlled at 30-50 ℃. After the solvent is completely removed, adding a certain amount of dichloromethane into the system, precipitating the polymer by using normal hexane, and finally drying at 40 ℃ for 12 hours to obtain the polymer with the side group of the methyl carbonyl. Adding 80.00mL of ethanol, 40.00mL of deionized water, 0.56g of hydroxylamine hydrochloride, 1.06g of sodium acetate and 2.00g of polymer with a side group of methyl carbonyl into a container provided with a magnetic stirrer in sequence, carrying out reflux reaction for 6-8 hours at 100 ℃, extracting an organic phase for 3 times by using dichloromethane after the reaction is finished, washing the organic phase by using saturated saline solution, drying the organic phase by using anhydrous sodium sulfate, carrying out rotary evaporation to remove dichloromethane, controlling the temperature to be 30-50 ℃, and precipitating in normal hexane to obtain 1.60g (C) of a high molecular chain with a side group of oxime.
2. Preparation of self-repairing thermosetting film containing dynamic oxime urethane bond
Dissolving 2.0g of macromolecular chain (A) with side group being oxime group and 0.48g of hexamethylene diisocyanate in 20mL of tetrahydrofuran, violently stirring for 1 hour at room temperature, pouring into a polytetrafluoroethylene mold, volatilizing the solvent in a fume hood overnight at room temperature, and post-curing for 12 hours at 80 ℃ in vacuum to obtain the self-repairing thermosetting film.
2.0g of macromolecular chain (B) with side group being oxime group and 0.38g of hexamethylene diisocyanate are dissolved in 20mL of tetrahydrofuran, stirred vigorously for 1 hour at room temperature, poured into a polytetrafluoroethylene mold, volatilized in a fume hood at room temperature overnight, and then post-cured for 12 hours at vacuum 80 ℃ to obtain the self-repairing thermosetting film.
2.0g of macromolecular chain (C) with side group being oxime group and 0.14g of hexamethylene diisocyanate are dissolved in 20mL of tetrahydrofuran, stirred vigorously for 1 hour at room temperature, poured into a polytetrafluoroethylene mold, volatilized in a fume hood at room temperature overnight, and then post-cured for 12 hours at vacuum 80 ℃ to obtain the self-repairing thermosetting film.
Claims (5)
1. A preparation method of a self-repairable thermosetting film based on multi-component Ugi polymerization reaction and dynamic oxime urethane bond exchange is characterized by comprising the following steps:
step 1, synthesizing a macromolecular chain with oxime groups as side groups through a Ugi polymerization reaction:
step a: reacting polyether amine, methanol and isobutyraldehyde at room temperature under stirring; the molar ratio of the polyether amine to the isobutyraldehyde is 1:2.0-3.0, and the mass ratio of the methanol to the polyether amine monomer is 6-10: 1;
step b: at room temperature, sequentially adding tetrahydrofuran, 1, 6-diethylcyanohexane and levulinic acid into the system in the step 1, after the reaction is completed under stirring, rotationally evaporating the reaction liquid at the temperature of 30-50 ℃, removing the solvent, adding dichloromethane into the system, precipitating the polymer by using n-hexane, and then drying at 40 ℃ for 12 hours to obtain a polymer solid with a side group of a methyl carbonyl group;
the molar ratio of the 1, 6-diethylcyanohexane to the polyether amine is 1: 1-1.2, the molar ratio of the polyether amine to the levulinic acid is 1:2.0-3.0, and the mass ratio of the tetrahydrofuran to the polyether amine monomer is 3.0-5.0: 1;
step c: sequentially adding an alcohol solvent, deionized water, hydroxylamine hydrochloride, sodium acetate and the polymer solid with the side group of the methyl carbonyl obtained in the step b into a container, and carrying out reflux reaction at 100 ℃ for 6-8 hours;
the molar ratio of the polymer with the side group of the methyl carbonyl obtained from the hydroxylamine hydrochloride, the sodium acetate and the b1 is 10-15:5-8:1, and the mass ratio of the alcohol solvent to the deionized water is 2-3: 1;
step d: after the reaction is finished, extracting the organic phase for 3 times by using dichloromethane, washing the organic phase by using saturated saline solution, drying the organic phase by using anhydrous sodium sulfate, then removing the dichloromethane by rotary evaporation, controlling the temperature to be 30-50 ℃, and precipitating in normal hexane to obtain a high molecular chain solid with an oxime group as a side group;
step 2, preparing the self-repairing thermosetting film containing the dynamic oxime urethane bond:
dissolving a high molecular chain solid with side groups of oxime groups and a diisocyanate monomer in tetrahydrofuran, stirring for 1 hour at room temperature, pouring into a polytetrafluoroethylene mold, volatilizing a solvent in a fume hood at room temperature for one night, and post-curing for 12 hours at 80 ℃ in vacuum to obtain a self-repairable thermosetting film based on multi-component Ugi polymerization reaction and dynamic oxime urethane bond exchange;
the ratio of the functional groups of the macromolecular chain solid with the side group of oxime group and the diisocyanate is 1: 1.0-1.2.
2. The preparation method of the self-repairable thermosetting film based on the multi-component Ugi polymerization reaction and the dynamic oxime urethane bond exchange as claimed in claim 1, wherein: the step a and the step c are that reactants are put into a container provided with a magnetic stirrer.
3. The preparation method of the self-repairable thermosetting film based on the multi-component Ugi polymerization reaction and the dynamic oxime urethane bond exchange as claimed in claim 1, wherein: the polyetheramines in step 1 include, but are not limited to: polyetheramine D230, polyetheramine D400, polyetheramine D1000, or polyetheramine D2000.
4. The preparation method of the self-repairable thermosetting film based on the multi-component Ugi polymerization reaction and the dynamic oxime urethane bond exchange as claimed in claim 1, wherein: the alcoholic solvent in step c includes but is not limited to: methanol or ethanol, and any combination thereof.
5. The preparation method of the self-repairable thermosetting film based on the multi-component Ugi polymerization reaction and the dynamic oxime urethane bond exchange as claimed in claim 1, wherein: the diisocyanate monomers in step 2 include, but are not limited to: toluene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, or any one or combination thereof.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115368559A (en) * | 2022-08-08 | 2022-11-22 | 烟台大学 | Hydrogen bond induced bio-based fluorescent polyamide and preparation method thereof |
| CN116574425A (en) * | 2023-06-08 | 2023-08-11 | 诺奇兄弟新材料(吴江)有限公司 | Finished product water-based paint and preparation method thereof |
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2021
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115368559A (en) * | 2022-08-08 | 2022-11-22 | 烟台大学 | Hydrogen bond induced bio-based fluorescent polyamide and preparation method thereof |
| CN115368559B (en) * | 2022-08-08 | 2023-12-22 | 烟台大学 | Hydrogen-bond-induced bio-based fluorescent polyamide and preparation method thereof |
| CN116574425A (en) * | 2023-06-08 | 2023-08-11 | 诺奇兄弟新材料(吴江)有限公司 | Finished product water-based paint and preparation method thereof |
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