Dehydroabietylamine epoxy resin-based Vitrimer, preparation method thereof and application of dehydroabietylamine epoxy resin-based Vitrimer in preparation of shape memory foam
By preparing dehydroabieamine epoxy resin-based Vitrimer at room temperature, the complex process problems caused by high-temperature curing are solved, and the renewable and environmentally friendly substitution of epoxy resin materials is achieved. It has shape memory and self-repair properties, and is suitable for buffering, shock absorption, thermal and sound insulation and other applications.
Patent Information
- Application Number
- CN202510492632.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-18
- Publication Date
- 2025-07-29
AI Technical Summary
The prior art requires high temperature curing during the preparation of vitrimer, resulting in cumbersome process, which limits its promotion and application. The existing epoxy resin materials lack renewable and environmentally friendly alternative petroleum-based materials.
The preparation method of dehydroabieamine epoxy resin-based Vitrimer was used to cure at room temperature. By reacting dehydroabieamine with epoxy chloride and NaOH treatment, combined with triethanolamine catalyst, an epoxy resin with dynamic covalent bond was prepared, and then mixed with bis(3-aminopropyl)amine to achieve room temperature curing.
The preparation of dehydroabieamine epoxy resin-based Vitrimer cured at room temperature is realized, which reduces production costs and imparts shape memory and self-repair performance to the material through dynamic covalent bonds. It is suitable for buffering, shock absorption, thermal insulation and sound insulation and other fields.
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Figure CN120383724A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of preparation of modified materials, and particularly relates to a dehydroabietylamine epoxy resin-based Vitrimer, a preparation method thereof, and an application thereof in the preparation of shape memory foams. Background Art
[0002] With the increasing depletion of petroleum resources and the enhancement of people's awareness of environmental protection, finding pollution-free and renewable resources to replace petroleum-based chemicals has become an inevitable trend of green sustainable development. Rosin, as a natural biomass resource, has the advantages of being green and environmentally friendly, rich in annual output, renewable, biodegradable, etc., and contains a stable rigid structure in itself, thus having the potential to replace petrochemical aromatic ring raw materials to prepare functional polymer materials. While reducing the generation of plastic waste, it can also provide a new way to alleviate the petroleum crisis. Dehydroabietylamine is a derivative of rosin, and its molecular formula contains a tricyclic hydro-phenanthrene structure, and this rigid cyclic structure makes dehydroabietylamine have good structural stability.
[0003] In recent years, the modification of epoxy resin materials has become a research hotspot, among which rosin derivatives are introduced into the epoxy resin system to prepare rosin-modified epoxy resin materials. Introducing dynamic covalent bonds into the structure of thermosetting resins can not only endow them with special properties such as shape memory, reprocessability, reparability, and degradability, but also improve the thermal stability and mechanical properties of the materials. Such materials are named Vitrimer. In the prior art, the curing of Vitrimer often needs to be carried out in a high-temperature environment during the preparation process, which makes the required conditions of the preparation process relatively high, resulting in cumbersome steps and restricting further popularization and application. Summary of the Invention
[0004] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a dehydroabietylamine epoxy resin-based Vitrimer, a preparation method thereof, and an application thereof in the preparation of shape memory foams. The dehydroabietylamine epoxy resin-based Vitrimer prepared by the present invention can be cured at room temperature without heating, and its preparation method is simple, which can reduce production costs. The foam with shape memory obtained based on the dehydroabietylamine epoxy resin-based Vitrimer has good application prospects in aspects such as buffering and shock absorption, heat insulation and sound insulation.
[0005] To achieve the above purpose, the technical solution adopted by the present invention is as follows: The first purpose of the present invention is to provide a preparation method of a dehydroabietylamine epoxy resin-based Vitrimer, comprising the following steps: (1) Epoxidize dehydroabietylamine (DHAA) with excessive epichlorohydrin (ECH), and then carry out ring closure with NaOH. The obtained product is purified to obtain dehydroabietylamine epoxy resin (DGDHAA). Specifically, the process is as follows: Dissolve dehydroabietylamine (DHAA) in excessive epichlorohydrin (ECH) to obtain a reaction solution. Heat the reaction solution to 45 °C and react for 150 h under constant temperature stirring. After the reaction is completed, add aqueous solutions of tetrabutylammonium bromide (TBAB) and NaOH to continue the reaction for 1.5 - 3 h. Cool to room temperature. Wash the obtained product with distilled water, let it stand and separate into layers. Separate and take the oily product and dry it to obtain a mixture. The mixture is separated and purified to obtain dehydroabietylamine epoxy resin (DGDHAA). Preferably, the purification method is as follows: Dissolve the mixture in acetone, filter to remove the white powder insoluble in acetone (unreacted TBAB) to obtain a filtrate. The filtrate is concentrated and the above steps are repeated at least once. The obtained material is dried to obtain dehydroabietylamine epoxy resin (DGDHAA).
[0006] (2) Mix dehydroabietylamine epoxy resin (DGDHAA), bis(3-aminopropyl)amine (BAPA) and the catalyst triethanolamine (TEOA), and after curing at room temperature, dehydroabietylamine epoxy resin-based Vitrimer is obtained. Both BAPA and TEOA are liquids at room temperature, forming a homogeneous single phase and being well mixed. The curing time of the liquid material at room temperature is about one week. The addition amount of the catalyst triethanolamine is 1 - 10 wt% of the total mass of DGDHAA and BAPA. As the amount of added triethanolamine increases, its catalytic effect enhances, but when it exceeds a certain amount, its catalytic effect weakens. Further preferably, the addition amount of triethanolamine is 3.8 wt%.
[0007] The second object of the present invention is to provide a dehydroabietylamine epoxy resin-based Vitrimer, which is prepared by the preparation method in the above first object.
[0008] The third object of the present invention is to provide a shape memory foam. The raw materials for preparing the shape memory foam include the dehydroabietylamine epoxy resin-based Vitrimer as described in the above second object. The preparation method of the shape memory foam includes the following steps: Mix dehydroabietylamine epoxy resin, bis(3-aminopropyl)amine, a catalyst and a foaming agent evenly to obtain a mixed material. After the mixed material is pre-cured at room temperature and then foamed, a shape memory foam is obtained. Preferably, the mixed material further includes a foam stabilizer, and the foam stabilizer can be N,N-dimethylbenzylamine. The pre-curing time is 0.5 - 2 h, and further preferably 1 h.
[0009] Further, the foaming agent is NaHCO3; NaHCO3 is a solid at room temperature and its decomposition temperature is about 50 °C. In order to make the dehydroabietylamine epoxy resin Vitrimer foam evenly and react fully, it decomposes relatively fast at temperatures above 100 °C. To make the foam material foam evenly and react fully, preferably, the heating temperature is 120 °C to obtain a stable carbon dioxide gas flow, so that the pores in the obtained product are evenly distributed.
[0010] Compared with the prior art, the beneficial effects of the present invention are as follows: The dehydroabietylamine epoxy resin-based Vitrimer prepared by the present invention can be cured at room temperature without high-temperature curing, which can simplify the curing process and reduce the production cost; moreover, the main raw material used in the present invention is dehydroabietylamine, which is a derivative of the natural biomass resource rosin and is expected to replace petroleum-based chemicals, providing a new way to alleviate the petroleum crisis.
[0011] The dehydroabietylamine epoxy resin-based Vitrimer prepared by the present invention reacts through the epoxy groups in the dehydroabietylamine epoxy resin and the amino groups in bis(3-aminopropyl)amine, introducing -C-N- dynamic covalent bonds into the product structure. Due to the introduction of dynamic covalent bonds, such materials have reversibility and certain temperature responsiveness, that is, they can be reversibly and controllably between breakage and bonding at high temperatures, so that the materials have excellent shape memory and self-healing properties.
[0012] The shape memory foam prepared based on the dehydroabietylamine epoxy resin-based Vitrimer of the present invention contains a large number of tricyclic hydro-phenanthrene structures in its molecules due to the use of dehydroabietylamine raw materials. This rigid ring structure makes the foam have good structural stability. In addition, the foam has shape memory properties and has good application prospects in related fields such as shock absorption, heat insulation, sound insulation, and packaging. Description of the Drawings
[0013] Figure 1 It is a synthetic route diagram of the preparation method of dehydroabietylamine epoxy resin; Figure 2 It is an appearance diagram of the products obtained after curing dehydroabietylamine epoxy resin (DGDHAA) and bis(3-aminopropyl)amine (BAPA) in different proportions; Figure 3 It is a scanning electron microscope diagram of the shape memory foam; Figure 4 It is an FT-IR spectrum diagram of dehydroabietylamine (DHAA) and dehydroabietylamine epoxy resin (DGDHAA); Figure 5 It is for dehydroabietylamine (DHAA) and dehydroabietylamine epoxy resin (DGDHAA) 1 1H NMR spectrum diagram and 1313C NMR spectrum; Figure 6 For the self - healing process of dehydroabietylamine epoxy - based Vitrimer; Figure 7 For the shape - memory process of dehydroabietylamine epoxy - based Vitrimer; Figure 8 The shape - memory process of shape - memory foam. Detailed implementation manners
[0014] The following examples are used to further illustrate the present invention, so that those skilled in the art can better understand the present invention and be able to implement it, but the examples given do not limit the present invention.
[0015] In the following examples, the dehydroabietylamine was purchased from Guangdong Weisida Chemical Co., Ltd.; other raw materials and reagents are all commercially available products unless otherwise specified.
[0016] Examples A preparation method of dehydroabietylamine epoxy - based Vitrimer, comprising the following steps: (1) Preparation of dehydroabietylamine epoxy resin, and its synthetic route is as Figure 1 shown. The steps are as follows: Add 5.7 g of dehydroabietylamine (0.02 mol), 22.32 g of epichlorohydrin (0.66 mol) and 1 mL of H2O into a 250 - mL single - necked flask, add a magnetic stirrer for magnetic stirring, heat to 45 °C and maintain for 150 h. After the reaction is completed, add 0.08 g of tetrabutylammonium bromide (TBAB) and 15 g of 30% NaOH aqueous solution to the crude product. After the dropping is completed, continue the reaction for 3 h. Solid salt precipitates, filter to remove it to obtain the filtrate, add 200 ml of distilled water for washing, let it stand for layering to obtain the oily organic layer, dry it with anhydrous magnesium sulfate, and finally remove epichlorohydrin (ECH) by vacuum drying to obtain dehydroabietylamine epoxy resin (DGDHAA).
[0017] (2) Mix the prepared dehydroabietylamine epoxy resin (DGDHAA) with bis(3 - aminopropyl)amine (BAPA) at different molar ratios (R = 1.4:1, 1.2:1, 1.1:1, 0.8:1, 0.6:1) and add 3.8 wt% of triethanolamine (TEOA) based on the total weight. After stirring evenly, place it in a mold and cure at room temperature for one week to obtain dehydroabietylamine epoxy - based Vitrimer. The product appearance diagram is as Figure 2 shown.
[0018] Application examples A preparation method of shape - memory foam, comprising the following steps: The dehydroabietylamine epoxy resin (DGDHAA) and bis(3-aminopropyl)amine were fully mixed at different molar ratios (R = 0.6:1, 0.8:1, 1:1), and 3.8 wt % of triethanolamine (TEOA) and 20% of NaHCO3 based on the total weight were added to obtain a mixture. After the mixture was pre-cured at room temperature for 1 h, it was placed in an oven at 120 °C for foaming for 3 h to obtain a shape memory foam material. The scanning electron micrograph of the product is as shown in Figure 3 which can be seen that the obtained foam material has a rich porous structure.
[0019] Structure Characterization The FT-IR spectra of dehydroabietylamine (DHAA) and dehydroabietylamine epoxy resin (DGDHAA) are as shown in Figure 4 which. It can be seen that a peak of the epoxy group appears at 968 cm -1 in DGDHAA, indicating that the preparation method provided by the present invention makes dehydroabietylamine react with epichlorohydrin to form an epoxy group.
[0020] The 1 1H NMR spectra and 13 13C NMR spectra of dehydroabietylamine (DHAA) and dehydroabietylamine epoxy resin (DGDHAA) are as shown in Figure 5 which. As shown in the 1 1H NMR spectrum, after the epoxidation reaction of DHAA with epichlorohydrin, characteristic peaks of hydrogen in the epoxy group appear at δ 2.5 and δ 2.7 (peaks a and b in DGDHAA). The number of hydrogens and the chemical shift of the characteristic hydrogens in the synthesized product are similar to those of the target product, indicating the synthesis of the target product DGDHAA. 13 As shown in the
[0021] 13C NMR spectrum, after the epoxidation reaction of DHAA with epichlorohydrin, a new peak of carbon in the epoxy group is found at δ 62 and δ 68 (peaks a, b in DGDHAA). This indicates the successful preparation of DGDHAA. 1 In summary, through the analysis of infrared, 13 1H NMR and
[0022] Self-healing Performance and Shape Memory Performance The dehydroabietylamine epoxy resin-based Vitrimer prepared by the present invention has reversibility and certain temperature responsiveness due to the introduction of dynamic covalent bonds, so it has self-healing and shape memory properties.
[0023] Scratches were made on the sample and the initial morphology of the scratches was photographed under a microscope. Then it was heated in an oven at 80 °C for 1 h, as shown in Figure 6Observation under the microscope revealed that the width of the scratch significantly narrowed and became shallower. After continuous heating overnight, the scratch was basically completely repaired, indicating that the sample has self-healing properties.
[0024] The dehydroabietylamine epoxy-based Vitrimer, initially in the shape of a rectangular thin sheet, as Figure 7 shown in (a) and (b), was wrapped with aluminum foil and twisted into the desired shape such as "V" under external force. After heating in an 85 °C oven for 1 h and cooling to room temperature, the shape of the film was permanently transformed into "V", as Figure 7 shown in (c). Because the dynamic covalent bond exchange reaction induced during the heating process causes the rearrangement of the topological structure of the crosslinked network, the shape of the sample can be permanently changed under external force. The new shape can stably exist below 80 °C. After the shape is changed, it still has good shape memory performance. Above T g above, when twisted into any shape under external force, it can spontaneously return to the original shape, as Figure 7 shown in (d) and (e). This process can be repeated multiple times without obvious changes.
[0025] The foam sample was heated at a temperature higher than T g for about 15 min; the sample would become soft, and it was extruded and deformed while it was hot. After cooling, even when the external force was removed, the shape remained fixed. At this time, it was put into the oven at T g again for 15 min, and the deformed shape could still spontaneously return to the original shape. After recovery, when heated above T g temperature again, under external force, a new shape could also be pressed out. The new shape could still spontaneously return to the original shape above T g temperature, as Figure 8 shown. This process can be repeated multiple times without obvious changes.
[0026] Obviously, the described embodiments are part of the embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.
Claims
1. A preparation method of dehydroabietylamine epoxy resin-based Vitrimer, characterized in that: It includes the following steps: (1) React dehydroabietylamine with excessive epichlorohydrin to prepare dehydroabietylamine epoxy resin; (2) Mix dehydroabietylamine epoxy resin, bis(3-aminopropyl)amine and a catalyst evenly, and after curing at room temperature, dehydroabietylamine epoxy resin-based Vitrimer is obtained.
2. The preparation method of the dehydroabietylamine epoxy resin-based Vitrimer according to claim 1, characterized in that: The process of step (1) is: heat and stir dehydroabietylamine and excessive epichlorohydrin, then add an aqueous solution of tetrabutylammonium bromide and NaOH thereto and continue the reaction, and separate and purify the obtained product to obtain dehydroabietylamine epoxy resin.
3. The preparation method of the dehydroabietylamine epoxy resin-based Vitrimer according to claim 1, characterized in that: The catalyst is triethanolamine.
4. The preparation method of the dehydroabietylamine epoxy resin-based Vitrimer according to claim 1, characterized in that: The time for curing at room temperature is 6 - 8 days.
5. A dehydroabietylamine epoxy resin-based Vitrimer, characterized in that: The dehydroabietylamine epoxy resin-based Vitrimer is prepared by the preparation method described in any one of claims 1 to 4.
6. A preparation method of shape memory foam, characterized in that: The raw materials for preparing the shape memory foam include the dehydroabietylamine epoxy resin-based Vitrimer described in claim 5, and the preparation method of the shape memory foam includes the following steps: Mix dehydroabietylamine epoxy resin, bis(3-aminopropyl)amine, a catalyst and a foaming agent evenly to obtain a mixed material; after the mixed material is pre-cured at room temperature, it is foamed to obtain a shape memory foam.
7. The preparation method of the dehydroabietylamine epoxy resin-based Vitrimer foam according to claim 6, characterized in that: The foaming agent is NaHCO3.
8. The preparation method of the dehydroabietylamine epoxy resin-based Vitrimer foam according to claim 6, characterized in that: The mixed material further includes a foam stabilizer.
9. The preparation method of the dehydroabietylamine epoxy resin-based Vitrimer foam according to claim 6, characterized in that: The time for pre-curing is 0.5 - 2 h.
10. The preparation method of the dehydroabietylamine epoxy resin-based Vitrimer foam according to claim 6, characterized in that: The temperature for foaming is 100 - 130 °C.