Preparation method and application of high-toughness ubiquinol supramolecular material

Abstract

The application relates to the technical field of high polymer materials, and particularly discloses a preparation method and application of high-toughness ubiquinol supramolecular material, which comprises eugenol, a polyamine, the polyamine is tetraethylenepentamine, and further comprises DL alpha-sulfoxide acid monomers; the molar ratio of the DL alpha-sulfoxide acid monomers, the eugenol and the tetraethylenepentamine is 5:2:1. The application prepares a ubiquinol solution through a high-temperature induction method, and the ubiquinol supramolecular material is prepared through a blending method together with the eugenol and the tetraethylenepentamine, so that the toughness of the ubiquinol is remarkably improved, the mechanical properties of the material are improved, the preparation process is simple, and the ubiquinol supramolecular material is suitable for large-scale production.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to the preparation of a supramolecular polymer material, particularly the preparation of a high-toughness polythiooctanoic acid supramolecular material. Background Technology

[0002] Polythioctic acid (PTA) is a dynamic polymer obtained by ring-opening polymerization of thioctic acid (TA) monomers. Its molecular chains are rich in dynamic disulfide bonds, giving PTA materials excellent thermoforming and self-healing capabilities. However, in practical applications, PTA materials suffer from insufficient mechanical properties, particularly poor fracture toughness. Furthermore, traditional PTA preparation methods (such as hot-press polymerization) are subject to stringent preparation conditions, poor process controllability, and difficulty in introducing other functional components to regulate its properties. To improve the mechanical properties of composite materials, existing technologies mainly employ nanocomposites and dual-network structures. While these methods can improve toughness, they often come at the cost of sacrificing material flexibility and self-healing efficiency. Additionally, nanoparticles are prone to aggregation, leading to insufficient overall performance of the composite material.

[0003] Supramolecular materials are a class of smart materials built upon non-covalent interactions (such as hydrogen bonding, metal coordination, host-guest interactions, and hydrophobic interactions). Due to their dynamic reversibility, these materials often exhibit unique properties such as stimulus responsiveness, self-healing, and shape memory, showing broad application prospects in soft robotics, biomedicine, and wearable devices. However, traditional supramolecular materials typically face bottlenecks such as insufficient mechanical strength, particularly poor toughness, which greatly limits their application in practical engineering. This invention, based on the molecular structure of PTA composite materials, introduces multiple materials to construct a supramolecular network and form supramolecular forces, including the biomass material eugenol and polyamines, to develop a method for preparing high-toughness polythiooctanoic acid supramolecular materials, thereby meeting the stringent requirements of polythiooctanoic acid composite materials in diverse application scenarios. Summary of the Invention

[0004] To address the above problems, this invention provides a method for preparing polythiooctanoic acid supramolecular materials, thereby improving the toughness of polythiooctanoic acid composite materials in various application scenarios.

[0005] The present invention adopts the following technical solution:

[0006] A high-toughness polythiooctanoic acid supramolecular material includes eugenol (Eg) and a polyamine, wherein the polyamine is tetraethylenepentamine (PA5).

[0007] Preferably, it further includes DLα-lipoic acid monomer (TA), wherein the molar ratio of DLα-lipoic acid monomer (TA), eugenol (Eg), and tetraethylenepentamine (PA5) is 5:2:1.

[0008] A method for preparing a high-toughness polythiooctanoic acid supramolecular material includes the following steps:

[0009] Step 1: First, weigh out the DLα-lipoic acid monomer, stir, and start the ring-opening polymerization reaction of the monomer to form a polylipoic acid solution;

[0010] Step 2: Add eugenol to the polythioctic acid solution for crosslinking to form a prepolymer solution with a dynamic disulfide bond network;

[0011] Step 3: Next, add tetraethylenepentamine to the prepolymer solution and stir to form a reaction solution;

[0012] Step 4: Pour the reaction solution into a polytetrafluoroethylene mold, dry it in an oven, and dry it at room temperature to form polythiooctanoic acid supramolecular material (PTAP).

[0013] Preferably, the stirring temperature of the DLα-lipoic acid monomer in step one is 140°C.

[0014] Preferably, in step two, eugenol is added to the polythioctic acid solution, and a crosslinking reaction is carried out at 140°C for 2 hours.

[0015] Preferably, in step three, tetraethylenepentamine is added to the prepolymer solution and stirred at 140°C for 2 hours.

[0016] Preferably, step four involves reacting at a high temperature of 140°C in an oven for 2 hours.

[0017] Preferably, step four involves drying at room temperature for 8 hours.

[0018] Preferably, step four involves drying at room temperature to form a 2 cm thick polythiooctanoic acid supramolecular material.

[0019] The above-mentioned application of a high-toughness polythiooctanoic acid supramolecular material in polymer materials.

[0020] The beneficial effects of this invention are:

[0021] This invention employs a supramolecular structure design strategy, combined with the molecular structure characteristics of thioctic acid, to prepare a polythioctic acid solution via a high-temperature induction method, and then co-prepares a polythioctic acid supramolecular material with eugenol and tetraethylenepentamine via a blending method.

[0022] The polythiooctanoic acid supramolecular material of this invention exhibits extremely high toughness. In tensile tests, when the molar ratios of the components TA:Eg:PA5 were adjusted to 5:2:1 and 5:2:2, the maximum fracture stress of the polythiooctanoic acid supramolecular material was significantly higher than that of pure PTA, reaching 25.76 MPa and 16.52 MPa, respectively, representing increases of 2425% and 1520%. This demonstrates significantly enhanced toughness. Furthermore, at a molar ratio of 5:2:1, the maximum fracture stress of the material reached nearly 24 times that of the pure sample.

[0023] This invention provides a method for preparing a high-toughness polythiooctanoic acid supramolecular material, which can significantly improve the toughness of polythiooctanoic acid and enhance the mechanical properties of the material. The preparation process is simple and suitable for large-scale production. Attached Figure Description

[0024] Figure 1 The image shows the infrared spectrum of the polythiooctanoic acid supramolecular material prepared in Example 1.

[0025] Figure 2 Images showing fracture toughness test data of polythiooctanoic acid composite materials prepared in Examples 1-2 and Comparative Example 1. Detailed Implementation

[0026] The technical solution of the present invention will now be described in detail through specific embodiments.

[0027] A high-toughness polythioctic acid supramolecular material includes eugenol (Eg), a polyamine, wherein the polyamine is tetraethylenepentamine (PA5), and also includes DLα-thioctic acid monomer (TA).

[0028] Example 1

[0029] (1) Weigh 5.15g of DLα-lipoic acid monomer and stir at 140°C for 1.5 hours to obtain a polylipoic acid solution. Add 2.06g of eugenol to the polylipoic acid solution and stir at 140°C for 2 hours to obtain a prepolymer solution. Add 0.945g of tetraethylenepentamine to the prepolymer solution and stir at 140°C for 1.5 hours to obtain a reaction solution. Cast the reaction solution into a polytetrafluoroethylene mold and place it in an oven at 140°C for 2 hours to obtain solution C;

[0030] (2) Cool solution C at room temperature for 8 hours to obtain polythiooctanoic acid supramolecular material.

[0031] Example 2

[0032] (1) Weigh 5.15g of DLα-lipoic acid monomer and stir at 140°C for 1.5 hours to obtain a polylipoic acid solution. Add 2.06g of eugenol to the polylipoic acid solution and stir at 140°C for 2 hours to obtain a prepolymer solution. Add 1.890g of tetraethylenepentamine to the prepolymer solution and stir at 140°C for 1.5 hours to obtain a reaction solution. Cast the reaction solution into a polytetrafluoroethylene mold and place it in an oven at 140°C for 2 hours to obtain solution C;

[0033] (2) Cool solution C at room temperature for 8 hours to obtain polythiooctanoic acid supramolecular material.

[0034] Comparative Example 1

[0035] 10g of DLα-lipoic acid monomer was stirred at 140°C for 1.5 hours to obtain a polylipoic acid solution. The solution was then cast into a polytetrafluoroethylene mold and cooled for 8 hours to obtain polylipoic acid.

[0036] Analysis and Conclusion

[0037] The polythiooctanoic acid supramolecular material prepared in Example 1 was subjected to infrared spectroscopy testing, and the test results are as follows: Figure 1 As shown. From Figure 1 It can be seen that 3430cm -1 The broadening due to hydrogen bond formation indicates OH bond vibration. Compared to PTA, PTAP is at 1701 cm⁻¹. -1 The peak weakens at 1593 cm⁻¹, indicating the consumption of carboxyl groups. -1 The peak at 619 cm⁻¹ represents the bending vibration of NH₄⁺, indicating the occurrence of a copolymerization reaction. -1 The tensile vibration of CS is enhanced compared to pure PTA, indicating that the double bond in eugenol has successfully reacted with the sulfur radical.

[0038] Figure 2 The images show stress-strain data of the materials in Examples 1-2 and Comparative Example 1 during fracture toughness testing. The results show that the maximum stress of pure polythioctic acid is very low, only 1.02 MPa, while in Examples 1-2, the maximum stress of the polythioctic acid supramolecular materials is significantly higher than that of pure polythioctic acid, with the maximum stress in Example 1 reaching as high as 25.76 MPa, an increase of 2425%. This stark contrast demonstrates that introducing a supramolecular structure can endow polythioctic acid with excellent toughness, thereby enabling its application in diverse scenarios.

[0039] The polythioctic acid and its composites from Examples 1-2 and Comparative Example 1 were subjected to fracture toughness tests. The test methods are as follows: tensile fracture tests were performed according to GB / T1040.2-2006 standard. Before the test, all test samples were pretreated for 24 hours at a specified room temperature (23±5)℃ and relative humidity (50±5)%, and the tests were also carried out under the same temperature and humidity conditions.

[0040] Results analysis:

[0041] Comparative Example 1 exhibits poor toughness, with a maximum fracture stress of only 1.02 MPa. This fails to meet the requirements for normal application scenarios.

[0042] In Example 1, when the molar ratio of TA:Eg:PA5 in the supramolecular system is 5:2:1, the toughness of the polythiooctanoic acid supramolecular material is improved, with the maximum fracture stress reaching 25.76 MPa, an increase of 2425%, demonstrating extremely high toughness.

[0043] In Example 2, when the molar ratio of TA:Eg:PA5 in the supramolecular system was 5:2:2, the toughness of the polythiooctanoic acid supramolecular material was improved, with the maximum fracture stress reaching 16.52 MPa, an increase of 1520%, demonstrating high toughness.

[0044] Detailed analysis of Examples 1-2 and various comparative experiments in this study reveals that the synergistic effect of eugenol and tetraethylenepentamine can prepare polythioctic acid ionomer gels with excellent mechanical properties. Compared with the example where the TA:Eg:PA5 molar ratio is 5:2:2, the maximum fracture stress of the material when the TA:Eg:PA5 molar ratio is 5:2:1 reaches nearly 24 times that of the pure sample. This is attributed to the synergistic effect of multiple supramolecular components. This precise material ratio improves the mechanical properties of the composite material, providing new possibilities for the diverse applications of polythioctic acid composites in specific fields. Therefore, the solution provided in this example is particularly suitable for applications with strict requirements for toughness, offering an effective technical approach for the high-performance development of polythioctic acid composites.

[0045] The above embodiments demonstrate the effectiveness of the technical ideas and methods proposed in this invention, aiming to clarify the implementation details of this invention, but are not intended to limit the scope of protection of this invention. Based on the principles disclosed in this invention, those skilled in the art may make various changes and modifications without departing from the spirit and scope of this invention. Therefore, all equivalent modifications and modifications made according to the principles of this invention should be covered within the scope of protection of this invention.

Claims

1. A method for preparing a high-toughness polythiooctanoic acid supramolecular material, characterized in that, Includes the following steps: Step 1: First, weigh out the DLα-lipoic acid monomer, stir, and start the ring-opening polymerization reaction of the monomer to form a polylipoic acid solution; Step 2: Add eugenol to the polythioctic acid solution for crosslinking to form a prepolymer solution with a dynamic disulfide bond network; Step 3: Next, add tetraethylenepentamine to the prepolymer solution and stir to form a reaction solution; Step 4: Pour the reaction solution into a polytetrafluoroethylene mold, dry it in an oven, and dry it at room temperature to form a polythiooctanoic acid supramolecular material; The molar ratio of DLα-lipoic acid monomer, eugenol, and tetraethylenepentamine is 5:2:

1.

2. The method for preparing a high-toughness polythiooctanoic acid supramolecular material according to claim 1, characterized in that, The stirring temperature for the DLα-lipoic acid monomer in step one is 140°C.

3. The method for preparing a high-toughness polythiooctanoic acid supramolecular material according to claim 1, characterized in that, In step two, eugenol is added to the polythioctic acid solution, and a cross-linking reaction is carried out at 140°C for 2 hours.

4. The method for preparing a high-toughness polythiooctanoic acid supramolecular material according to claim 1, characterized in that, In step three, tetraethylenepentamine is added to the prepolymer solution and stirred at 140°C for 2 hours.

5. The method for preparing a high-toughness polythiooctanoic acid supramolecular material according to claim 1, characterized in that, Step four involves reacting the sample in an oven at 140°C for 2 hours.

6. The method for preparing a high-toughness polythiooctanoic acid supramolecular material according to claim 1, characterized in that, Step four involves drying at room temperature for 8 hours.

7. The method for preparing a high-toughness polythiooctanoic acid supramolecular material according to claim 1, characterized in that, Step four involves drying at room temperature to form a 2 cm thick polythiooctanoic acid supramolecular material.

8. The application of the high-toughness polythiooctanoic acid supramolecular material prepared by any one of the preparation methods according to claims 1-7 in the toughening design of supramolecular materials.

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