Preparation method of a self-catalytic dual dynamic network multifunctional material

Abstract

The application discloses a preparation method of a self-catalytic double dynamic network multifunctional material and relates to a preparation method of a multifunctional material. The application aims at solving the problems of complex molecular design, high synthesis difficulty, incapability of simultaneously possessing multifunction, self-repairing capability and environmental adaptability of the existing multifunctional material. Sulfur ointment, epoxy resin and dimethylaminoethyl methacrylate are mixed and heated to react to obtain the self-catalytic double dynamic network multifunctional material. The application is used for the preparation of the self-catalytic double dynamic network multifunctional material.

Description

Technical Field

[0001] This invention relates to a method for preparing multifunctional materials. Background Technology

[0002] With the continuous advancement of science and technology and the rapid development of industry, the demand for new materials is increasing. This is especially true in fields such as aerospace, automobile manufacturing, electronics, and construction, where the performance requirements for materials are becoming increasingly stringent. While traditional materials have met these demands to some extent, they still have many shortcomings in terms of multifunctionality, self-healing capabilities, environmental adaptability, and biodegradability and recyclability.

[0003] The few existing multifunctional materials on the market are difficult to popularize in practical applications due to their complex molecular design processes and high preparation costs. Ideally, multifunctional materials should be prepared using readily available raw materials through simple and low-energy pathways. However, current multifunctional material preparation requires complex structural design and synthesis processes to obtain the necessary raw materials, and the preparation environment demands stringent requirements. This increased complexity and difficulty in synthesis further increases costs.

[0004] Therefore, developing a new type of multifunctional material that integrates multiple functions, which can not only meet the needs of modern industry for high-performance materials, but also have self-healing capabilities, has become an important research direction in the field of materials science. Summary of the Invention

[0005] This invention aims to address the problems of complex molecular design and high synthesis difficulty of existing multifunctional materials, which cannot simultaneously possess multifunctionality, self-healing ability, and environmental adaptability. It provides a method for preparing self-catalytic dual dynamic network multifunctional materials.

[0006] A method for preparing a self-catalytic dual-dynamic network multifunctional material, comprising the following steps:

[0007] Thioctic acid, epoxy resin and dimethylaminoethyl methacrylate were mixed at room temperature and in air atmosphere to obtain a mixture. The mixture was reacted at a temperature of 50℃~130℃ in air atmosphere and finally naturally cooled to room temperature to obtain a self-catalytic dual dynamic network multifunctional material.

[0008] When the molar ratio of thioctic acid to epoxy resin is 1:(0.01~1); when the molar ratio of thioctic acid to dimethylaminoethyl methacrylate is 1:(0.01~1);

[0009] The molar ratio of the epoxy resin to thioctic acid is 1:(0.01-1); the molar ratio of the epoxy resin to dimethylaminoethyl methacrylate is 1:(0.01-1).

[0010] The beneficial effects of this invention are:

[0011] This invention utilizes the copolymerization of lipoic acid and dimethylaminoethyl methacrylate as the polymer backbone for the soft segment and enhances the autocatalytic effect (the autocatalytic effect is higher than that of ordinary catalysis). The carboxyl groups of lipoic acid react with epoxy resin to form a rigid cross-linked structure, successfully preparing an autocatalytic dual-dynamic network multifunctional material. The high-density dual-dynamic network (disulfide bonds and dynamic ester bonds) endows the material with excellent self-healing ability. By systematically adjusting the feed ratio of lipoic acid, epoxy resin, and dimethylaminoethyl methacrylate, structural adhesive materials (shear strength), hot melt adhesive materials (shear strength), elastomer materials (tensile test), and pressure-sensitive adhesive materials (peel strength) can be easily prepared.

[0012] The preparation method of this invention is simple and has high production efficiency. The self-catalytic dual-dynamic network multifunctional material proposed in this invention provides a novel, environmentally friendly material preparation method with broad application prospects. The materials prepared by this method are expected to play an important role in multiple fields, promoting technological progress and sustainable development in related industries. Attached Figure Description

[0013] Figure 1 Fourier transform infrared spectrum of the self-catalytic dual dynamic network multifunctional material prepared in Example 1;

[0014] Figure 2 Comparison of overlapping tensile shear tests performed on the self-catalytic dual dynamic network multifunctional material prepared in Example 1;

[0015] Figure 3 This is a schematic diagram of the shape memory of the self-catalytic dual dynamic network multifunctional material prepared in Example 2;

[0016] Figure 4 The diagram shows a 3D printed model of the self-catalytic dual dynamic network multifunctional material prepared in Example 1. a is a 3D printed butterfly, b is a 3D printed butterfly sample with light transmission, c is a 3D printed square cup, d is a 3D printed square cup filled with water and left for 24 hours, and e is a 3D printed square cup submerged in water and soaked for 24 hours.

[0017] Figure 5 This is a schematic diagram illustrating the self-healing properties of the self-catalytic dual dynamic network multifunctional material prepared in Example 3;

[0018] Figure 6 This is a schematic diagram illustrating the impact resistance of the self-catalytic dual dynamic network multifunctional materials prepared in Examples 3, 4, and 5. Detailed Implementation

[0019] Specific Implementation Method 1: This implementation method is a preparation method of a self-catalytic dual dynamic network multifunctional material, which is carried out according to the following steps:

[0020] Thioctic acid, epoxy resin and dimethylaminoethyl methacrylate were mixed at room temperature and in air atmosphere to obtain a mixture. The mixture was reacted at a temperature of 50℃~130℃ in air atmosphere and finally naturally cooled to room temperature to obtain a self-catalytic dual dynamic network multifunctional material.

[0021] When the molar ratio of thioctic acid to epoxy resin is 1:(0.01~1); when the molar ratio of thioctic acid to dimethylaminoethyl methacrylate is 1:(0.01~1);

[0022] The molar ratio of the epoxy resin to thioctic acid is 1:(0.01-1); the molar ratio of the epoxy resin to dimethylaminoethyl methacrylate is 1:(0.01-1).

[0023] After the reaction in this embodiment is completed, a dual-dynamic network multifunctional material is obtained. The dual-dynamic network multifunctional material can be cooled and stored, and then heated when needed, or placed in a specific mold to cool and form.

[0024] In this embodiment, there is no specific order of adding the sample during weighing and mixing, and the sample does not need to be stirred evenly before heating and reacting.

[0025] The beneficial effects of this embodiment are:

[0026] This embodiment utilizes the copolymerization of lipoic acid and dimethylaminoethyl methacrylate as the polymer backbone for the soft segment and enhances the autocatalytic effect (the autocatalytic effect is higher than that of ordinary catalysis). The carboxyl groups of lipoic acid react with epoxy resin to form a rigid cross-linked structure, successfully preparing an autocatalytic dual-dynamic network multifunctional material. The high-density dual-dynamic network (disulfide bonds and dynamic ester bonds) endows the material with excellent self-healing ability. By systematically adjusting the feed ratio of lipoic acid, epoxy resin, and dimethylaminoethyl methacrylate, structural adhesive materials (shear strength), hot melt adhesive materials (shear strength), elastomer materials (tensile test), and pressure-sensitive adhesive materials (peel strength) can be easily prepared.

[0027] The preparation method described in this embodiment is simple and has high production efficiency. The self-catalytic dual-dynamic network multifunctional material proposed in this embodiment provides a novel, environmentally friendly material preparation method with broad application prospects. The materials prepared by this method are expected to play an important role in multiple fields, promoting technological progress and sustainable development in related industries.

[0028] Specific Implementation Method Two: This implementation method differs from Specific Implementation Method One in that the mixture is stirred and reacted for more than 5 minutes at a temperature of 50℃~130℃, a rotation speed of 50r / min~1500r / min, and in an air atmosphere. Everything else is the same as in Specific Implementation Method One.

[0029] Specific Implementation Method Three: This implementation method differs from Specific Implementation Method One or Two in that: the mixture is stirred and reacted for 5 min to 120 min at a temperature of 80℃~130℃, a rotation speed of 50 r / min~1500 r / min, and in an air atmosphere, and then the reaction is continued for another 5 min to 120 min at a temperature of 50℃~70℃. Everything else is the same as in Specific Implementation Method One or Two.

[0030] Specific Implementation Method Four: This implementation method differs from Specific Implementation Methods One to Three in that: the mixture is stirred and reacted for 90 to 120 minutes at a temperature of 130°C, a rotation speed of 400 to 1500 r / min, and in an air atmosphere, and then the reaction is continued for another 60 to 120 minutes at a temperature of 70°C. Everything else is the same as in Specific Implementation Methods One to Three.

[0031] Specific Implementation Method Five: This implementation method differs from Specific Implementation Methods One to Four in that: the mixture is heated to 80°C to 130°C at a rotation speed of 50 r / min to 1500 r / min, poured into a mold, and then reacted for 5 min to 120 min at a temperature of 80°C to 130°C in an air atmosphere. The mixture is then transferred to a temperature of 50°C to 70°C and reacted for another 5 min to 120 min. Everything else is the same as in Specific Implementation Methods One to Four.

[0032] Specific Implementation Method Six: This implementation method differs from Specific Implementation Methods One to Five in that the lipoic acid mentioned is DL-α-lipoic acid, R-(+)-lipoic acid, or (±)-α-lipoic acid (racemic). Everything else is the same as in Specific Implementation Methods One to Five.

[0033] Specific Implementation Method Seven: This implementation method differs from Specific Implementation Methods One to Six in that the epoxy resin used is a bisphenol A type epoxy resin. Everything else is the same as in Specific Implementation Methods One to Six.

[0034] Specific Implementation Method Eight: This implementation method differs from Specific Implementation Methods One to Seven in that: 10 mmol of lipoic acid, 10 mmol of epoxy resin, and 0.5 mmol to 1.5 mmol of dimethylaminoethyl methacrylate are mixed at room temperature and in an air atmosphere to obtain a mixture. Everything else is the same as in Specific Implementation Methods One to Seven.

[0035] Specific Implementation Method Nine: This implementation method differs from Specific Implementation Methods One to Eight in that: 14 mmol of lipoic acid, 6 mmol of epoxy resin, and 0.9 mmol to 2.4 mmol of dimethylaminoethyl methacrylate are mixed at room temperature and in an air atmosphere to obtain a mixture. Everything else is the same as in Specific Implementation Methods One to Eight.

[0036] Specific Implementation Method Ten: This implementation method differs from Specific Implementation Methods One to Nine in that: 8 mmol of lipoic acid, 2 mmol of epoxy resin, and 0.64 mmol of dimethylaminoethyl methacrylate are mixed at room temperature and in an air atmosphere to obtain a mixture. Everything else is the same as in Specific Implementation Methods One to Nine.

[0037] The beneficial effects of the present invention are verified using the following embodiments:

[0038] Example 1:

[0039] A method for preparing a self-catalytic dual-dynamic network multifunctional material, comprising the following steps:

[0040] 10 mmol of lipoic acid, 10 mmol of epoxy resin and 1.5 mmol of dimethylaminoethyl methacrylate were mixed at room temperature and in air atmosphere to obtain a mixture. The mixture was stirred and reacted for 1.5 h at 130 °C and 400 r / min in air atmosphere. Then it was transferred to an electric heating drying oven at 70 °C and reacted for another 1 h. Finally, it was naturally cooled to room temperature to obtain a self-catalytic dual dynamic network multifunctional material.

[0041] The lipoic acid mentioned is DL-α-lipoic acid;

[0042] The epoxy resin mentioned is epoxy resin-E44.

[0043] Example 2:

[0044] A method for preparing a self-catalytic dual-dynamic network multifunctional material, comprising the following steps:

[0045] 10 mmol of lipoic acid, 10 mmol of epoxy resin and 0.5 mmol of dimethylaminoethyl methacrylate were mixed at room temperature and in air atmosphere to obtain a mixture. The mixture was stirred and reacted for 1.5 h at 130 °C and 400 r / min in air atmosphere. Then it was transferred to an electric heating drying oven at 70 °C and reacted for another 1 h. Finally, it was naturally cooled to room temperature to obtain a self-catalytic dual dynamic network multifunctional material.

[0046] The lipoic acid mentioned is DL-α-lipoic acid;

[0047] The epoxy resin mentioned is epoxy resin-E44.

[0048] Example 3:

[0049] A method for preparing a self-catalytic dual-dynamic network multifunctional material, comprising the following steps:

[0050] 14 mmol of lipoic acid, 6 mmol of epoxy resin and 1.48 mmol of dimethylaminoethyl methacrylate were mixed at room temperature and in air atmosphere to obtain a mixture. The mixture was first heated to 130°C at a speed of 400 r / min and poured into a rectangular polytetrafluoroethylene mold. The mixture was then reacted at 130°C and in air atmosphere for 1.5 h. The mixture was then transferred to an electric heating drying oven at 70°C and reacted for another h. Finally, the mixture was allowed to cool naturally to room temperature to obtain a self-catalyzing dual dynamic network multifunctional material.

[0051] The lipoic acid mentioned is DL-α-lipoic acid;

[0052] The epoxy resin mentioned is epoxy resin-E44.

[0053] Example 4:

[0054] A method for preparing a self-catalytic dual-dynamic network multifunctional material, comprising the following steps:

[0055] 14 mmol of lipoic acid, 6 mmol of epoxy resin and 2.4 mmol of dimethylaminoethyl methacrylate were mixed at room temperature and in air atmosphere to obtain a mixture. The mixture was first heated to 130°C at a speed of 400 r / min and poured into a rectangular polytetrafluoroethylene mold. The mixture was then reacted at 130°C in air atmosphere for 1.5 h. The mixture was then transferred to an electric heating drying oven at 70°C and reacted for another h. Finally, the mixture was allowed to cool naturally to room temperature to obtain a self-catalyzing dual dynamic network multifunctional material.

[0056] The lipoic acid mentioned is DL-α-lipoic acid;

[0057] The epoxy resin mentioned is epoxy resin-E44.

[0058] Example 5:

[0059] A method for preparing a self-catalytic dual-dynamic network multifunctional material, comprising the following steps:

[0060] 14 mmol of lipoic acid, 6 mmol of epoxy resin and 0.9 mmol of dimethylaminoethyl methacrylate were mixed at room temperature and in air atmosphere to obtain a mixture. The mixture was first heated to 130°C at a speed of 400 r / min and poured into a rectangular polytetrafluoroethylene mold. The mixture was then reacted at 130°C in air atmosphere for 1.5 h. The mixture was then transferred to an electric heating drying oven at 70°C and reacted for another h. Finally, the mixture was allowed to cool naturally to room temperature to obtain a self-catalyzing dual dynamic network multifunctional material.

[0061] The lipoic acid mentioned is DL-α-lipoic acid;

[0062] The epoxy resin mentioned is epoxy resin-E44.

[0063] The self-catalytic dual-dynamic network multifunctional material prepared in Example 1 was subjected to Fourier transform infrared spectroscopy. The specific method for Fourier transform infrared spectroscopy was as follows: the self-catalytic dual-dynamic network multifunctional material was subjected to Fourier transform infrared spectroscopy at 400–4000 cm⁻¹. -1 In attenuated total reflection mode, the test was conducted at room temperature using a Fourier transform micro-infrared spectrometer (Thermo Fisher SCIENTIFIC, model: Nicolet iN10). Figure 1 The Fourier transform infrared spectrum of the self-catalytic dual dynamic network multifunctional material prepared in Example 1 is shown in the figure. As can be seen from the figure, epoxy resin-E44 exhibits a high Fourier transform infrared spectrum at 3500 cm⁻¹. -1 The broad peak at 1700 cm⁻¹ is a hydroxyl peak. This hydroxyl peak is significantly broadened in the multifunctional material obtained in Example 1, which is attributed to the ring-opening reaction between the carboxyl group of thioctic acid and the epoxy group of the epoxy resin to form hydroxyl groups; -1 The peak at the carboxyl group of lipoic acid and 1730 cm⁻¹ -1 The carbon-carbon double bond peak belonging to dimethylaminoethyl methacrylate shifted to 1740 cm⁻¹ in the multifunctional material of Example 1. -1 This indicates that the carboxyl group reacts primarily with the epoxy group, and the carbon-carbon double bond polymerizes onto the lipoic acid backbone. Fourier transform infrared spectroscopy results of the self-catalytic dual-dynamic network multifunctional material prepared in Example 1 show that lipoic acid undergoes a polymerization reaction with dimethylaminoethyl methacrylate to form a self-catalytic system. Under this self-catalytic system, lipoic acid undergoes a highly efficient cross-linking reaction with epoxy resin.

[0064] The self-catalytic dual dynamic network multifunctional material prepared in Example 1 was subjected to an overlap tensile shear test. The specific test method for the overlap tensile shear test was as follows: The self-catalytic dual dynamic network multifunctional material prepared in Example 1 was reheated to 130°C and dropped onto a substrate (glass, 304 stainless steel, pure aluminum, pure copper, black walnut wood, and polytetrafluoroethylene). Another substrate was overlapped and bonded together, and pressure was applied using clamps to fix it (the clamps applied external force to fix it until it cooled, and the excess amount was squeezed out by the applied external force). Then, it was placed in an electric heating drying oven at 70°C to continue the reaction for 1 hour. Finally, it was transferred to a room temperature and air environment and allowed to cool naturally to room temperature. Figure 2 The figure shows a comparison of the lap tensile shear test results of the self-catalytic dual dynamic network multifunctional material prepared in Example 1. As can be seen from the figure, the tensile shear strengths of Example 1 on glass, 304 stainless steel, pure aluminum, pure copper, black walnut wood and polytetrafluoroethylene are 11.24 MPa, 12.03 MPa, 5.69 MPa, 9.74 MPa, 5.59 MPa and 0.73 MPa, respectively, showing excellent adhesion properties to many materials.

[0065] The self-catalytic dual dynamic network multifunctional material prepared in Example 2 was subjected to shape memory testing. The specific method of shape memory testing was as follows: at 60°C, the rectangular self-catalytic dual dynamic network multifunctional material was twisted by external force to deform it. After being taken out and cooled to room temperature, the external force was removed. The material cooled to room temperature was then placed back into water at 60°C to restore its properties. Figure 3 This is a schematic diagram of the shape memory of the self-catalytic dual dynamic network multifunctional material prepared in Example 2; (The diagram is from...) Figure 3 It can be seen that the rectangular multifunctional material of Example 2 can be twisted and deformed by external force at 60°C. After cooling, it can maintain its shape. After being placed back into the 60°C environment, it will quickly and spontaneously recover its original shape, indicating that Example 2 has a good shape memory ability.

[0066] The self-catalytic dual dynamic network multifunctional material prepared in Example 1 was selected for 3D model printing. The specific 3D printing method was as follows: 3D printing was performed using a food dual-head printer. The self-catalytic dual dynamic network multifunctional material was placed in the barrel of the food dual-head printer (model: FOODBOT-D1). The parameters were selected as follows: the nozzle of the extrusion barrel was 0.84 mm, the height of the first layer was 0.8 mm, the height of the remaining layers was 0.7 mm, the fill density was 90%, and the printing speed was 7 mm / s. Then, the self-catalytic dual dynamic network multifunctional material was melt-extruded and printed at a temperature of 90°C. Figure 4 This is a schematic diagram of the 3D printing model of the self-catalytic dual dynamic network multifunctional material prepared in Example 1. a is a 3D printed butterfly, b is a translucent image of the 3D printed butterfly sample, c is a 3D printed square cup, d is a 3D printed square cup filled with water and left for 24 hours, and e is a 3D printed square cup submerged in water and soaked for 24 hours. Figure 4 It can be seen that the self-catalytic dual dynamic network multifunctional material prepared in Example 1 can print high-precision complex patterns. The 3D printed butterfly has a certain degree of translucency under light irradiation. The 3D printed square cup model does not leak water after being filled with water and placed for 24 hours. It does not swell or dissolve after being submerged in water for 24 hours. It has good sealing and solvent resistance.

[0067] The self-catalytic dual dynamic network multifunctional material prepared in Example 3 was selected for self-healing performance testing. The specific testing method for self-healing performance was as follows: the self-catalytic dual dynamic network multifunctional material was prepared into a thin film, a scratch was made on the film, and it was placed in an oven at 50°C for 3 hours. Then, the scratch repair was observed using a microscope. Figure 5 This is a schematic diagram of the self-healing performance of the self-catalytic dual dynamic network multifunctional material prepared in Example 3; 0s represents the scratch just applied to the material. After repair in Example 3, the scratch basically disappeared, demonstrating excellent self-healing ability.

[0068] The self-catalytic dual-dynamic network multifunctional materials prepared in Examples 3, 4, and 5 were selected for impact resistance testing. The specific test method for impact resistance was as follows: the self-catalytic dual-dynamic network multifunctional material was prepared into a square film with a size of 100mm×100mm×0.4mm. The film was placed on a thin film pendulum impact tester and clamped. According to GB / T8809-2015, during the test, a hemispherical punch impacted and passed through the film sample. The energy consumed by the punch was displayed by the machine, which is the pendulum impact resistance energy of the film sample. Figure 6 The figure shows the impact resistance of the self-catalytic dual dynamic network multifunctional materials prepared in Examples 3, 4 and 5. As can be seen from the figure, the impact resistance of Examples 3, 4 and 5 is 0.4J, 0.45J and 0.3J, respectively. However, the film of Example 4 is brittle. Considering all factors, the film of Example 3 has excellent comprehensive performance.

Claims

1. A method for preparing a self-catalytic dual-dynamic network multifunctional material, characterized in that: Follow these steps: Thioctic acid, epoxy resin and dimethylaminoethyl methacrylate were mixed at room temperature and in air atmosphere to obtain a mixture. The mixture was reacted at a temperature of 50℃~130℃ in air atmosphere and finally naturally cooled to room temperature to obtain a self-catalytic dual dynamic network multifunctional material. The molar ratio of thioctic acid to epoxy resin is 1:(0.01~1); the molar ratio of thioctic acid to dimethylaminoethyl methacrylate is 1:(0.01~1).

2. The method for preparing a self-catalytic dual dynamic network multifunctional material according to claim 1, characterized in that... The mixture is stirred and reacted for more than 5 minutes at a temperature of 50℃~130℃, a rotation speed of 50r / min~1500r / min and in an air atmosphere.

3. The method for preparing a self-catalytic dual dynamic network multifunctional material according to claim 1, characterized in that... The mixture was stirred and reacted for 5 min to 120 min at a temperature of 80℃ to 130℃, a rotation speed of 50 r / min to 1500 r / min and in an air atmosphere, and then the reaction was continued for 5 min to 120 min at a temperature of 50℃ to 70℃.

4. The method for preparing a self-catalytic dual dynamic network multifunctional material according to claim 1, characterized in that... The mixture was stirred and reacted for 90 to 120 minutes at a temperature of 130°C, a rotation speed of 400 to 1500 r / min and an air atmosphere, and then the reaction was continued for 60 to 120 minutes at a temperature of 70°C.

5. The method for preparing a self-catalytic dual dynamic network multifunctional material according to claim 1, characterized in that... The mixture is heated to 80℃~130℃ at a rotation speed of 50r / min~1500r / min and poured into a mold. The mixture is then reacted at 80℃~130℃ in an air atmosphere for 5min~120min. The mixture is then transferred to a temperature of 50℃~70℃ and the reaction continues for 5min~120min.

6. The method for preparing a self-catalytic dual dynamic network multifunctional material according to claim 1, characterized in that... The lipoic acid mentioned is DL-α-lipoic acid or R-(+)-lipoic acid.

7. The method for preparing a self-catalytic dual dynamic network multifunctional material according to claim 1, characterized in that... The epoxy resin is a bisphenol A type epoxy resin.

8. The method for preparing a self-catalytic dual dynamic network multifunctional material according to claim 1, characterized in that... At room temperature and in an air atmosphere, 10 mmol of lipoic acid, 10 mmol of epoxy resin and 0.5 mmol to 1.5 mmol of dimethylaminoethyl methacrylate were mixed to obtain a mixture.

9. The method for preparing a self-catalytic dual-dynamic network multifunctional material according to claim 1, characterized in that... At room temperature and in an air atmosphere, 14 mmol of lipoic acid, 6 mmol of epoxy resin and 0.9 mmol to 2.4 mmol of dimethylaminoethyl methacrylate were mixed to obtain a mixture.

10. The method for preparing a self-catalytic dual dynamic network multifunctional material according to claim 1, characterized in that... At room temperature and in an air atmosphere, 8 mmol of lipoic acid, 2 mmol of epoxy resin and 0.64 mmol of dimethylaminoethyl methacrylate were mixed to obtain a mixture.

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