Preparation method of autocatalytic dual-dynamic network multifunctional material

Abstract

The invention discloses a preparation method of an autocatalytic dual-dynamic network multifunctional material, and relates to a preparation method of a multifunctional material. The problems that an existing multifunctional material is complex in molecular design and high in synthesis difficulty, and cannot have multiple functions, self-repairing capacity and environmental adaptability at the same time are solved. Lipoic acid, epoxy resin and dimethylaminoethyl methacrylate are mixed and heated for a reaction, and the autocatalytic double-dynamic-network multifunctional material is obtained. The preparation method is used for preparing the self-catalytic double-dynamic network multifunctional material.

Description

Technical Field

[0001] The invention relates to a method for preparing a multifunctional material. Background Art

[0002] With the continuous advancement of science and technology and the rapid development of industry, the demand for new materials is growing. Especially in the fields of aerospace, automobile manufacturing, electronic products, construction and so on, the performance requirements for materials are getting higher and higher. Although traditional materials have met these needs to a certain extent, they still have many shortcomings in terms of multifunctionality, self-healing ability, environmental adaptability, and degradable and recyclable properties.

[0003] The few multifunctional materials on the market are difficult to popularize in practical applications due to the complex molecular design process and high preparation cost. The ideal multifunctional material should be prepared by simple and low-energy methods using raw materials from simple sources. However, the preparation of current multifunctional materials requires complex structural design and synthesis processes to obtain the required raw materials, and the preparation environment requirements are strict. The complexity of these structures and the increase in the difficulty of synthesis also increase the cost.

[0004] In view of this, the development of a new 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] The present invention aims to solve the problems that existing multifunctional materials have complex molecular design, high synthesis difficulty, and cannot simultaneously possess multifunctionality, self-repairing ability and environmental adaptability, and further provides a method for preparing a self-catalytic dual dynamic network multifunctional material.

[0006] A method for preparing an autocatalytic dual dynamic network multifunctional material is carried out according to the following steps:

[0007] At room temperature and in an air atmosphere, lipoic acid, epoxy resin and dimethylaminoethyl methacrylate are mixed to obtain a mixture, the mixture is reacted at a temperature of 50° C. to 130° C. in an 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 lipoic acid to epoxy resin is 1:(0.01-1); the molar ratio of lipoic acid to dimethylaminoethyl methacrylate is 1:(0.01-1);

[0009] When the molar ratio of the epoxy resin to lipoic 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 the present invention are:

[0011] The present invention utilizes copolymerization of thioctic acid and dimethylaminoethyl methacrylate as the polymer backbone of the soft segment and improves the autocatalytic effect (the autocatalytic effect is higher than the ordinary catalytic effect), the carboxyl group of thioctic acid reacts with epoxy resin to form a rigid cross-linked structure, and successfully prepares an autocatalytic dual dynamic network multifunctional material, and the high-density dual dynamic network (disulfide bond and dynamic ester bond) gives the material excellent self-repairing ability. By systematically adjusting the feed ratio of thioctic acid, epoxy resin and dimethylaminoethyl methacrylate, the preparation of structural adhesive materials (shear strength), hot melt adhesive materials (shear strength), elastomeric materials (tensile test), and pressure-sensitive adhesive materials (peel strength) can be simply achieved.

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

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

[0014] Figure 2 This is a comparison chart of the overlap tensile shear test of the self-catalytic dual dynamic network multifunctional material prepared in Example 1;

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

[0016] Figure 4 Schematic diagram of the 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 light transmittance 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 placed for 24 hours, and e is a 3D printed square cup immersed in water for 24 hours;

[0017] Figure 5 A schematic diagram of the self-repairing performance of the self-catalytic dual-dynamic network multifunctional material prepared in Example 3;

[0018] Figure 6 Schematic diagram of the impact resistance of the self-catalytic dual dynamic network multifunctional materials prepared in Examples 3, 4 and 5. DETAILED DESCRIPTION

[0019] Specific implementation method 1: This implementation method is a method for preparing an autocatalytic dual dynamic network multifunctional material, which is carried out according to the following steps:

[0020] At room temperature and in an air atmosphere, lipoic acid, epoxy resin and dimethylaminoethyl methacrylate are mixed to obtain a mixture, the mixture is reacted at a temperature of 50° C. to 130° C. in an 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 lipoic acid to epoxy resin is 1:(0.01-1); the molar ratio of lipoic acid to dimethylaminoethyl methacrylate is 1:(0.01-1);

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

[0023] In this embodiment, after the reaction 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 it is used, or placed in a specific mold for cooling and molding.

[0024] In this embodiment, there is no specific order for adding materials when weighing and mixing the samples, and the samples do not need to be stirred evenly before heating and reacting.

[0025] The beneficial effects of this embodiment are:

[0026] This embodiment uses thioctic acid and dimethylaminoethyl methacrylate copolymerization as the polymer backbone of the soft segment and improves the autocatalytic effect (the autocatalytic effect is higher than the ordinary catalytic effect). The carboxyl group of thioctic acid reacts with epoxy resin to form a rigid cross-linked structure, and successfully prepares an autocatalytic dual dynamic network multifunctional material. The high-density dual dynamic network (disulfide bond and dynamic ester bond) gives the material excellent self-repairing ability. By systematically adjusting the feed ratio of thioctic acid, epoxy resin and dimethylaminoethyl methacrylate, the preparation of structural adhesive materials (shear strength), hot melt adhesive materials (shear strength), elastomeric materials (tensile test), and pressure-sensitive adhesive materials (peel strength) can be simply achieved.

[0027] The preparation method of 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 and promote technological progress and sustainable development of related industries.

[0028] Specific embodiment 2: This embodiment differs from specific embodiment 1 in that the mixture is stirred for reaction for >5 min at a temperature of 50°C to 130°C, a rotation speed of 50 r / min to 1500 r / min and an air atmosphere. The rest is the same as specific embodiment 1.

[0029] Specific embodiment 3: This embodiment is different from specific embodiment 1 or 2 in that: the mixture is stirred and reacted for 5 min to 120 min at a temperature of 80°C to 130°C, a rotation speed of 50 r / min to 1500 r / min and an air atmosphere, and then the reaction is continued for 5 min to 120 min at a temperature of 50°C to 70°C. The rest is the same as specific embodiment 1 or 2.

[0030] Specific embodiment 4: This embodiment differs from specific embodiments 1 to 3 in that the mixture is stirred and reacted for 90 min to 120 min at a temperature of 130° C., a rotation speed of 400 r / min to 1500 r / min and an air atmosphere, and then the reaction is continued for 60 min to 120 min at a temperature of 70° C. The rest is the same as specific embodiments 1 to 3.

[0031] Specific embodiment 5: This embodiment differs from specific embodiments 1 to 4 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 and in an air atmosphere, and then transferred to a temperature of 50°C to 70°C and continued to react for 5 min to 120 min. The rest is the same as specific embodiments 1 to 4.

[0032] Specific embodiment 6: This embodiment is different from specific embodiments 1 to 5 in that the lipoic acid is DL-α-lipoic acid, R-(+)-lipoic acid or (±)-α-lipoic acid (racemic). Other aspects are the same as specific embodiments 1 to 5.

[0033] Specific embodiment 7: This embodiment is different from specific embodiments 1 to 6 in that the epoxy resin is bisphenol A type epoxy resin. The rest is the same as specific embodiments 1 to 6.

[0034] Specific embodiment 8: This embodiment differs from specific embodiments 1 to 7 in that: 10 mmol lipoic acid, 10 mmol epoxy resin and 0.5 mmol to 1.5 mmol dimethylaminoethyl methacrylate are mixed at room temperature and in air atmosphere to obtain a mixture. The rest is the same as specific embodiments 1 to 7.

[0035] Specific embodiment 9: This embodiment differs from specific embodiments 1 to 8 in that: 14 mmol lipoic acid, 6 mmol epoxy resin and 0.9 mmol to 2.4 mmol dimethylaminoethyl methacrylate are mixed at room temperature and in air atmosphere to obtain a mixture. The rest is the same as specific embodiments 1 to 8.

[0036] Specific embodiment 10: This embodiment differs from specific embodiments 1 to 9 in that 8 mmol lipoic acid, 2 mmol epoxy resin and 0.64 mmol dimethylaminoethyl methacrylate are mixed at room temperature and in air atmosphere to obtain a mixture. The rest is the same as specific embodiments 1 to 9.

[0037] The following examples are used to verify the beneficial effects of the present invention:

[0038] Embodiment 1:

[0039] A method for preparing an autocatalytic dual dynamic network multifunctional material is carried out according to the following steps:

[0040] At room temperature and in an air atmosphere, 10 mmol of lipoic acid, 10 mmol of epoxy resin and 1.5 mmol of dimethylaminoethyl methacrylate were mixed to obtain a mixture, and the mixture was stirred and reacted for 1.5 hours at a temperature of 130°C, a rotation speed of 400 r / min and in an air atmosphere, and then transferred to an electric heated blast drying oven at a temperature of 70°C, and continued to react for 1 hour, and finally naturally cooled to room temperature to obtain a self-catalytic dual dynamic network multifunctional material;

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

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

[0043] Embodiment 2:

[0044] A method for preparing an autocatalytic dual dynamic network multifunctional material is carried out according to the following steps:

[0045] At room temperature and in an air atmosphere, 10 mmol of lipoic acid, 10 mmol of epoxy resin and 0.5 mmol of dimethylaminoethyl methacrylate were mixed to obtain a mixture, and the mixture was stirred and reacted for 1.5 hours at a temperature of 130°C, a rotation speed of 400 r / min and in an air atmosphere, and then transferred to an electric heated blast drying oven at a temperature of 70°C, and continued to react for 1 hour, and finally naturally cooled to room temperature to obtain a self-catalytic dual dynamic network multifunctional material;

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

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

[0048] Embodiment 3:

[0049] A method for preparing an autocatalytic dual dynamic network multifunctional material is carried out according to the following steps:

[0050] At room temperature and in an air atmosphere, 14 mmol of lipoic acid, 6 mmol of epoxy resin and 1.48 mmol of dimethylaminoethyl methacrylate were mixed to obtain a mixture, which was first heated to 130°C at a speed of 400 r / min and poured into a rectangular polytetrafluoroethylene mold, then reacted for 1.5 hours at a temperature of 130°C and in an air atmosphere, and then transferred to an electric heated blast drying oven at a temperature of 70°C, and continued to react for 1 hour, and finally naturally cooled to room temperature to obtain a self-catalytic dual dynamic network multifunctional material;

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

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

[0053] Embodiment 4:

[0054] A method for preparing an autocatalytic dual dynamic network multifunctional material is carried out according to the following steps:

[0055] At room temperature and in an air atmosphere, 14 mmol of lipoic acid, 6 mmol of epoxy resin and 2.4 mmol of dimethylaminoethyl methacrylate were mixed to obtain a mixture, which was first heated to 130°C at a speed of 400 r / min and poured into a rectangular polytetrafluoroethylene mold, then reacted for 1.5 hours at a temperature of 130°C and in an air atmosphere, and then transferred to an electric heated blast drying oven at a temperature of 70°C, and continued to react for 1 hour, and finally naturally cooled to room temperature to obtain a self-catalytic dual dynamic network multifunctional material;

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

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

[0058] Embodiment 5:

[0059] A method for preparing an autocatalytic dual dynamic network multifunctional material is carried out according to the following steps:

[0060] At room temperature and in an air atmosphere, 14 mmol of lipoic acid, 6 mmol of epoxy resin and 0.9 mmol of dimethylaminoethyl methacrylate were mixed to obtain a mixture, which was first heated to 130°C at a speed of 400 r / min and poured into a rectangular polytetrafluoroethylene mold, then reacted for 1.5 hours at a temperature of 130°C and in an air atmosphere, and then transferred to an electric heated blast drying oven at a temperature of 70°C, and continued to react for 1 hour, and finally naturally cooled to room temperature to obtain a self-catalytic dual dynamic network multifunctional material;

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

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

[0063] The self-catalytic dual dynamic network multifunctional material prepared in Example 1 was selected for Fourier transform infrared spectroscopy test. The Fourier transform infrared spectroscopy test method is as follows: the self-catalytic dual dynamic network multifunctional material is subjected to a spectral range of 400 to 4000 cm -1 The measurements were carried out at room temperature using a Fourier transform infrared microscope (Thermo Fisher SCIENTIFIC, model: Nicolet iN10) in attenuated total reflectance mode. Figure 1 This is the Fourier transform infrared spectrum of the self-catalytic dual dynamic network multifunctional material prepared in Example 1; as can be seen from the figure, epoxy resin-E44 has a peak at 3500 cm -1 The broad peak at 1700 cm is the hydroxyl peak. The hydroxyl peak is significantly broadened on the multifunctional material obtained in Example 1, which is attributed to the ring-opening reaction between the carboxyl group of lipoic acid and the epoxy group of the epoxy resin to form hydroxyl groups; -1 The peaks at 1730 cm-1 and 1730 cm-2 belong to the carboxyl group of lipoic acid. -1 The carbon-carbon double bond peak of dimethylaminoethyl methacrylate is shifted to 1740 cm-1 on the multifunctional material of Example 1. -1 , indicating that the carboxyl group basically reacts with the epoxy group, and the carbon-carbon double bond polymerizes to the main chain of lipoic acid. The Fourier transform infrared spectrum test results of the self-catalytic dual dynamic network multifunctional material prepared in Example 1 show that lipoic acid and dimethylaminoethyl methacrylate undergo polymerization to form an autocatalytic system, and under the autocatalytic system, lipoic acid and epoxy resin undergo efficient cross-linking reaction.

[0064] The self-catalytic dual-dynamic network multifunctional material prepared in Example 1 was selected for overlap tensile shear test. The specific test method of the overlap tensile shear test is as follows: the self-catalytic dual-dynamic network multifunctional material prepared in Example 1 was reheated to 130°C, and dripped on a substrate (glass, 304 stainless steel, pure aluminum, pure copper, black walnut and polytetrafluoroethylene), and another substrate was overlapped and bonded, and pressure was applied with a clamp to fix it (the clamp was fixed with external force until it cooled, and the excess amount would be squeezed out by the applied external force), and then placed in an electric blast drying oven at a temperature of 70°C to continue the reaction for 1 hour, and finally transferred to room temperature and air environment, and naturally cooled to room temperature. Figure 2 The comparison chart of the overlap tensile shear test of the self-catalytic dual-dynamic network multifunctional material prepared in Example 1 is as follows; it can be seen from the figure that the tensile shear strengths of Example 1 for glass, 304 stainless steel, pure aluminum, pure copper, black walnut and polytetrafluoroethylene are 11.24MPa, 12.03MPa, 5.69MPa, 9.74MPa, 5.59MPa and 0.73MPa respectively, and Example 1 has excellent adhesion properties to many materials.

[0065] The self-catalytic dual-dynamic network multifunctional material prepared in Example 2 was selected for shape memory testing. The specific method of the shape memory test is: at 60°C, the rectangular self-catalytic dual-dynamic network multifunctional material is twisted and deformed by external force, taken out, cooled to room temperature and then the external force is removed, and the material cooled to room temperature is placed back in 60°C water to restore its properties. Figure 3 Schematic diagram of the shape memory of the self-catalytic dual dynamic network multifunctional material prepared in Example 2; Figure 3 It can be seen that the rectangular multifunctional material of Example 2 can be twisted and deformed due to external force at 60°C, and can maintain its shape after cooling. After being placed back in an environment of 60°C, it will quickly and spontaneously restore its original shape, indicating that Example 2 has 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 method of 3D printing was as follows: 3D printing was performed using a food dual-head printer, and the self-catalytic dual-dynamic network multifunctional material was placed in the barrel of the food dual-head printer (model: FOODBOT-D1). Parameter selection: the extrusion barrel nozzle was selected to be 0.84 mm, the height of the first printed layer was 0.8 mm, the height of the remaining printed layers except the first layer was 0.7 mm, the filling density was 90%, the printing speed was 7 mm / s, and then the self-catalytic dual-dynamic network multifunctional material was melt-extruded and printed at a temperature of 90°C. Figure 4 Schematic diagram of the 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 light transmission 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 placed for 24 hours, and e is a 3D printed square cup immersed in water 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 permeability under light, and the 3D printed square cup model does not leak after being filled with water and placed for 24 hours, and does not swell / dissolve after being sunk to the bottom of the water for 24 hours, and 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 test method for the self-healing performance is: the self-catalytic dual-dynamic network multifunctional material is prepared into a thin film, a scratch is made on the film, and then placed in an oven at a constant temperature of 50°C for 3 hours, and then the scratch repair is observed using a microscope. Figure 5 Schematic diagram of the self-healing performance of the self-catalytic dual-dynamic network multifunctional material prepared in Example 3; 0s represents the moment a scratch is just applied to the material, and the scratch basically disappears after repair in Example 3, indicating excellent self-healing ability.

[0068] The self-catalytic dual-dynamic network multifunctional materials prepared in Example 3, Example 4, and Example 5 were selected for impact resistance test. The specific test method for impact resistance is: the self-catalytic dual-dynamic network multifunctional material is prepared into a square film with a size of 100mm×100mm×0.4mm, and the film is placed on a film pendulum impact testing machine and clamped, and measured according to GB / T8809-2015. During the test, a hemispherical punch impacts and passes through the film sample, and the machine displays the energy consumed by the punch, which is the anti-pendulum impact energy of the film sample. Figure 6 Schematic diagram of the impact resistance of the self-catalytic dual-dynamic network multifunctional materials prepared in Examples 3, 4 and 5; it can be seen from the figure that the impact resistance of Example 3, Example 4 and Example 5 are 0.4J, 0.45J and 0.3J respectively, but the film of Example 4 is brittle. Taking all factors into consideration, the film of Example 3 has excellent comprehensive performance.

Claims

1. A method for preparing an autocatalytic dual dynamic network multifunctional material, characterized in that It is carried out in the following steps: At room temperature and in an air atmosphere, lipoic acid, epoxy resin and dimethylaminoethyl methacrylate are mixed to obtain a mixture, the mixture is reacted at a temperature of 50° C. to 130° C. in an air atmosphere, and finally naturally cooled to room temperature to obtain a self-catalytic dual dynamic network multifunctional material; When the molar ratio of lipoic acid to epoxy resin is 1:(0.01-1); the molar ratio of lipoic acid to dimethylaminoethyl methacrylate is 1:(0.01-1); When the molar ratio of the epoxy resin to lipoic acid is 1:(0.01-1); the molar ratio of the epoxy resin 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 >5 min at a temperature of 50° C. to 130° C., a rotation speed of 50 r / min to 1500 r / min and 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 is stirred and reacted for 5 min to 120 min at a temperature of 80° C. to 130° C., a rotation speed of 50 r / min to 1500 r / min and an air atmosphere, and then the reaction is continued for 5 min to 120 min at a temperature of 50° C. to 70° C.

4. 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 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 is 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 At a rotation speed of 50 r / min to 1500 r / min, the mixture is heated to 80°C to 130°C and poured into a mold, then reacted for 5min to 120min at a temperature of 80°C to 130°C and in an air atmosphere, and then transferred to a temperature of 50°C to 70°C and continued to react for 5min to 120min.

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

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

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

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

Images