Shape memory material and preparation method and application thereof

Abstract

The invention provides a shape memory material and a preparation method thereof. The method comprises the following steps: S1, mixing epoxy resin, glycidyl methacrylate, polyether amine, a photoinitiator and phosphorescent molecules; s2, the mixture obtained in the step S1 is heated and stirred to be dissolved, the mixture is injected into a mold, and a polymer film is obtained after a thermocuring reaction; and S3, heating the polymer film obtained in the step S2 to carry out photo-crosslinking treatment, and regulating and controlling the phosphorescence lifetime by controlling the photo-crosslinking time to obtain the shape memory material. The super-long phosphorescence function and the shape memory function are deeply integrated and cooperatively regulated and controlled.

Description

Technical Field

[0001] This invention relates to the field of shape memory materials technology, specifically to a shape memory material, its preparation method, and its application. Background Technology

[0002] Shape memory polymers are a class of smart materials capable of recovering their permanent shape from a temporary shape under external stimuli (such as heat, light, and electricity), showing broad application prospects in fields such as soft robotics, intelligent actuators, and biomedicine. However, with the continuous expansion of application scenarios, especially in extreme environments such as enclosed spaces, high temperatures, or miniaturization, how to monitor the dynamic deformation behavior of these materials in real time and intuitively has become a key technological challenge restricting their further development. Currently, observation is usually achieved using high-speed cameras or external sensors, but these methods are often difficult to implement in high-temperature, enclosed, or space-constrained environments, and increase the complexity and cost of the system.

[0003] To achieve intuitive monitoring of material behavior, researchers have attempted to incorporate luminescence properties into smart material systems. Among these, organic long-afterglow room-temperature phosphorescent materials have attracted considerable attention due to their long lifetime and large Stokes shift. However, current technologies often involve simply physically blending or modifying phosphorescent materials within a polymer matrix. The phosphorescence properties and the material's intelligent responses (such as shape memory effects) are often independent "island" functions, failing to produce a synergistic enhancement effect. For example, most existing luminescent shape memory materials can only achieve static luminescence or simple deformation indication, unable to accurately reflect dynamic deformation processes (such as changes in speed or angle) using changes in luminescence properties.

[0004] Furthermore, in the field of information encryption, existing phosphorescent-based anti-counterfeiting technologies are mostly limited to static, two-dimensional pattern displays. The encrypted information is fixed and singular, lacking encryption dimensions in three-dimensional space and dynamic response, resulting in limited security. Similarly, in circuit monitoring, there is a lack of intelligent coating materials that can be integrated with circuit components and provide direct, visual, and quantitative monitoring of heat generation. Summary of the Invention

[0005] The purpose of this invention is to provide a shape memory material, its preparation method, and its application, so as to deeply integrate and synergistically regulate the two functions of "ultra-long phosphorescence" and "shape memory", creating a new type of material whose phosphorescence properties can not only serve as a visible signal, but also as a sensitive probe for reporting information such as deformation and temperature of the material's internal state.

[0006] To achieve the above objectives, the present invention provides the following technical solution: A method for preparing shape memory materials, the method comprising the following steps: S1, a mixture of epoxy resin, glycidyl methacrylate, polyetheramine, photoinitiator and phosphorescent molecules; S2, The mixture obtained in step S1 is heated and stirred to dissolve, injected into a mold, and a polymer film is obtained after a thermosetting reaction; S3, the polymer film obtained in step S2 is heated to perform photocrosslinking treatment, and the phosphorescence lifetime is adjusted by controlling the photocrosslinking time to obtain the shape memory material.

[0007] To achieve the above objectives, the present invention also provides the following technical solutions: A shape memory material, the shape memory material being obtained by the method described above, and the phosphorescence lifetime of the shape memory material being adjustable between 2.36 and 5.87 s.

[0008] To achieve the above objectives, the present invention also provides the following technical solutions: The shape memory material obtained by the above method or the application of the above shape memory material is preferably used in high-temperature dynamic behavior visualization, 3D multi-information encryption or circuit heat generation status monitoring.

[0009] Other applicable fields will become apparent from the description provided in this invention.

[0010] The descriptions and specific examples in the invention summary are intended to be illustrative only and are not intended to limit the scope of the invention.

[0011] Compared with the prior art, the technical solution provided by the present invention has the following beneficial effects: 1. This invention prepares a series of shape memory materials with ultralong phosphorescence by controlling the degree of photocrosslinking of double bonds in the system. The phosphorescence lifetime ranges from 2.36 seconds to 5.87 seconds with a gradient response.

[0012] 2. The dynamic behavior (movement trend, movement speed, movement angle, etc.) of the shape memory material provided by the present invention at high temperature can be intuitively determined by visible phosphorescence afterglow, and its phosphorescence performance has extremely strong moisture resistance.

[0013] 3. Based on the synergistic regulation of temperature on afterglow and shape memory function, the shape memory material provided by the present invention can display multiple anti-counterfeiting functions in different shapes. At the same time, the shape memory material can be directly used as a coating material for conductive metal wires, and the afterglow performance can be used to visualize and quantitatively monitor the type of metal wire, circuit voltage, and circuit continuity. 4. This invention solves the problem that the optical and mechanical response functions of shape memory materials are independent and cannot work synergistically in the prior art. This invention aims to achieve real-time visual monitoring of the dynamic behavior of shape memory materials through phosphorescence afterglow, and to expand its application in the fields of multi-level information encryption and intelligent circuit monitoring and protection based on temperature-based synergistic regulation of both. Attached Figure Description

[0014] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For those skilled in the art, other solutions can be obtained based on these drawings without creative effort.

[0015] Figure 1 The phosphorescence spectra of the shape memory material obtained in Example 1 of this invention at different photocrosslinking times are shown. Figure 2 The phosphorescence lifetime of the shape memory material obtained in Example 1 of this invention under different photocrosslinking times; Figure 3 These are phosphorescence afterglow images of the shape memory material obtained in Example 1 of this invention at different photocrosslinking times; Figure 4 This is a visualization monitoring of the dynamic behavior of the 3D butterfly configuration of the shape memory material in Embodiment 2 of the present invention at different photocrosslinking times and at different temperatures. Figure 5 Encryption of multiple information regarding the body temperature response of the shape memory material in Embodiment 3 of the present invention; Figure 6 This invention encrypts multiple information regarding the shape memory material's response to different temperatures in Embodiment 3. Figure 7 For monitoring the heat generation of the circuit in Embodiment 4 of the present invention, which uses shape memory material to coat Cu and Cr20Ni80 metal wires; Figure 8 The circuit heat generation of the Cu and Cr20Ni80 series system coated with shape memory material in Embodiment 4 of the present invention can be used to identify the type of metal wire. Figure 9 This is a visual evaluation of the overheat protection function of the switch made of copper wire coated with shape memory material in Embodiment 4 of the present invention. Detailed Implementation

[0016] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. It should be understood that the specific embodiments described herein are only for illustration and explanation of the present invention and are not intended to limit the present invention.

[0017] Any specific numerical values ​​disclosed herein (including the endpoints of numerical ranges) are not limited to their exact values, but should be understood to also include values ​​close to the exact value, such as all possible values ​​within ±5% of the exact value. Furthermore, with respect to the disclosed numerical ranges, one or more new numerical ranges can be obtained by arbitrarily combining the endpoint values ​​of the range, the endpoint values ​​with specific point values ​​within the range, and the specific point values ​​themselves; these new numerical ranges should also be considered as specifically disclosed herein.

[0018] The terminology used in this invention is for the purpose of describing specific exemplary embodiments only and is not intended to be limiting. Unless the context clearly indicates otherwise, the singular forms “a,” “an,” and “the” as used herein are intended to include the plural forms as well. The terms “comprising,” “including,” “containing,” and “having” are inclusive and thus describe the presence of said features, elements, compositions, steps, integers, operations, and / or components, but do not exclude the presence or inclusion of one or more other features, integers, steps, operations, elements, components, and / or sets thereof. Although the open-ended term “comprising” should be understood as a non-limiting term used to describe and claim the various embodiments described in this invention, in some aspects it may instead be understood as a more restrictive and limiting term, such as “consisting of” or “essentially composed of.” Thus, for any given embodiment describing a composition, material, component, element, feature, integer, operation, and / or process step, the invention also particularly includes embodiments consisting of or substantially consisting of such compositions, materials, components, elements, features, integers, operations, and / or process steps. In the case of “consisting of…”, the alternative embodiments exclude any additional compositions, materials, components, elements, features, integers, operations and / or process steps. In the case of “essentially composed of…”, any additional compositions, materials, components, elements, features, integers, operations and / or process steps that substantially affect the essential and novel characteristics are excluded from such embodiments. However, any compositions, materials, components, elements, features, integers, operations and / or process steps that do not substantially affect the essential and novel characteristics may be included in the embodiments.

[0019] Any method steps, processes, and operations described in this invention should not be construed as necessarily requiring them to be performed in the specific order discussed or shown, unless explicitly specified. It should also be understood that, unless otherwise stated, additional or alternative steps may be used.

[0020] In this invention, except where expressly stated, any matters or issues not mentioned are directly applicable to those known in the art without any modification. Furthermore, any embodiment described in this invention can be freely combined with one or more other embodiments described in this invention, and the resulting technical solutions or concepts are considered part of the original disclosure or original record of this invention, and should not be regarded as new content not disclosed or anticipated by this invention, unless those skilled in the art consider the combination to be clearly unreasonable.

[0021] Unless otherwise stated, the terms used herein have the same meaning as commonly understood by those skilled in the art, and if a term is defined herein and its definition differs from the common understanding in the art, the definition herein shall prevail.

[0022] Unless otherwise stated, when % is mentioned in this document, it refers to wt%.

[0023] As can be seen from the foregoing background technology, the present invention aims to solve the following technical problems: 1. The "invisibility" problem of dynamic behavior in extreme environments: In environments such as high temperatures, where it is difficult to observe directly with the naked eye or where instruments are difficult to deploy, the dynamic behavior (such as deformation process, movement speed, and angle) of existing shape memory materials (such as those used in soft robots and micro actuators) cannot be monitored in real time and intuitively. 2. Static and low-dimensional problems of information encryption technology: Existing information encryption technologies based on luminescent materials are mostly static (fixed pattern) and two-dimensional, lacking dynamic responsiveness and three-dimensional spatial hiding ability. The encryption level is single and easy to be imitated or cracked. 3. The indirectness and complexity of circuit status monitoring: Monitoring the thermal state (such as local overheating, on / off state) of circuits, especially small or complex circuits, usually requires external sensors, which makes the system more complex, increases costs, and makes it impossible to achieve direct, visual quantitative assessment and early warning.

[0024] To address the problems existing in the prior art, the present invention provides the following technical solution: First aspect This invention provides a method for preparing shape memory materials, comprising the following steps: S1, mixing epoxy resin, glycidyl methacrylate, polyetheramine, photoinitiator, and phosphorescent molecules; S2, heating and stirring the mixture obtained in step S1 to dissolve it, injecting it into a mold, and obtaining a polymer film after a thermosetting reaction; S3, heating the polymer film obtained in step S2 to perform photocrosslinking treatment, and controlling the photocrosslinking time to regulate the phosphorescence lifetime to obtain the shape memory material.

[0025] It is worth noting that epoxy resin materials are often formed by the ring-opening polymerization of monomers with epoxy groups and amino-containing monomers, and are mostly T g Shape memory materials. In this epoxy resin-based shape memory material, the present invention introduces a large number of unreacted double bonds into the system by adding the monomer glycidyl methacrylate, thereby achieving synergistic regulation of the glass transition temperature and afterglow lifetime of the material by controlling the degree of photocrosslinking of the double bonds.

[0026] In some embodiments of the present invention, in step S1, the structural formula of the phosphorescent molecule is shown in any one of the following formulas (1) to (11): Equation (1) is , Equation (2) is , Equation (3) is , Equation (4) is , Equation (5) is , Equation (6) is , Equation (7) is , Equation (8) is , Equation (9) is , Equation (10) is , Equation (11) is , Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R in equations (1) to (11) above 10 R 11 Each of the following is independently selected from any one of alkyl chains, carboxylic acids, ester groups, aldehydes, ketones, and boric acids.

[0027] In some embodiments of the present invention, in step S1, the structure of the phosphorescent molecule is shown in formula (1) below: Equation (1) is R1 is independently selected from any one of alkyl chains, carboxylic acids, ester groups, aldehydes, ketones, and boric acids.

[0028] In some embodiments of the present invention, in step S1, the structure of the phosphorescent molecule is shown in the following formula (2): Equation (2) is R2 is independently selected from any one of alkyl chains, carboxylic acids, ester groups, aldehydes, ketones, and boric acids.

[0029] In some embodiments of the present invention, in step S1, the structure of the phosphorescent molecule is shown in the following formula (3): Equation (3) is R3 is independently selected from any one of alkyl chains, carboxylic acids, ester groups, aldehydes, ketones, and boric acids.

[0030] In some embodiments of the present invention, in step S1, the structure of the phosphorescent molecule is shown in the following formula (4): Equation (4) is R4 is independently selected from any one of alkyl chains, carboxylic acids, ester groups, aldehydes, ketones, and boric acids.

[0031] In some embodiments of the present invention, in step S1, the structure of the phosphorescent molecule is shown in the following formula (5): Equation (5) is R5 is independently selected from any one of alkyl chains, carboxylic acids, ester groups, aldehydes, ketones, and boric acids.

[0032] In some embodiments of the present invention, in step S1, the structure of the phosphorescent molecule is shown in the following formula (6): Equation (6) is R6 is independently selected from any one of alkyl chains, carboxylic acids, ester groups, aldehydes, ketones, and boric acids.

[0033] In some embodiments of the present invention, in step S1, the structure of the phosphorescent molecule is shown in the following formula (7): Equation (7) is R7 is independently selected from any one of alkyl chains, carboxylic acids, ester groups, aldehydes, ketones, and boric acids.

[0034] In some embodiments of the present invention, in step S1, the structure of the phosphorescent molecule is shown in the following formula (8): Equation (8) is R8 is independently selected from any one of alkyl chains, carboxylic acids, ester groups, aldehydes, ketones, and boric acids.

[0035] In some embodiments of the present invention, in step S1, the structure of the phosphorescent molecule is shown in the following formula (9): Equation (9) is R9 is independently selected from any one of alkyl chains, carboxylic acids, ester groups, aldehydes, ketones, and boric acids.

[0036] In some embodiments of the present invention, in step S1, the structure of the phosphorescent molecule is shown in the following formula (10): Equation (10) is R 10 It is independently selected from any one of alkyl chains, carboxylic acids, ester groups, aldehydes, ketones, and boric acids.

[0037] In some embodiments of the present invention, in step S1, the structure of the phosphorescent molecule is shown in the following formula (11): Equation (11) is R 11 It is independently selected from any one of alkyl chains, carboxylic acids, ester groups, aldehydes, ketones, and boric acids.

[0038] For phosphorescent molecules, their phosphorescent properties are often determined by their basic structure. The phosphorescent molecules with the above-mentioned molecular structure selected in this invention can endow the luminescent molecules with other properties, such as water solubility.

[0039] In some embodiments of the present invention, in step S1, the epoxy resin has the following structural formula 12: Equation 12 is , Wherein, R in Equation 12 12 The radical group is selected from aromatic or aliphatic groups. Epoxy resin materials include various types such as aromatic and aliphatic, and their composition is determined by reactive monomers containing diepoxy groups.

[0040] In some embodiments of the present invention, in step S1, the glycidyl methacrylate has the structural formula shown in Formula 13 below: Equation 13 is .

[0041] It is worth noting that adding the above-mentioned glycidyl methacrylate in step S1 can introduce a large number of unreacted double bonds into the epoxy material system, which can play an important role in the photocrosslinking process in the subsequent step S3.

[0042] In some embodiments of the present invention, in step S1, the polyetheramine has the structural formula shown in Formula 14 below:

[0043] In Equation 14, n can be any value from 1 to 12. Polyetheramine is used as a curing agent in the preparation of epoxy resins for thermosetting film formation.

[0044] In some embodiments of the present invention, in step S1, the epoxy resin is 1 part by weight, the glycidyl methacrylate is 2.4 parts by weight, the polyetheramine is 1 part by weight, the photoinitiator is 0.01 parts by weight, and the phosphorescent molecule is 0.001 parts by weight. Changing the ratio of epoxy resin, glycidyl methacrylate, and polyetheramine can prepare systems with different double bond contents, thereby achieving control over different glass transition temperature ranges. Only trace amounts of the photoinitiator and phosphorescent molecule are needed to achieve the desired effect.

[0045] In some embodiments of the present invention, in step S1, the photoinitiator is at least one of photoinitiator 2959 and photoinitiator TPO.

[0046] In some embodiments of the present invention, in step S2, the heating temperature is 80°C, the stirring speed is 500-1000 rpm, and the heating and stirring time is 15 min.

[0047] In some embodiments of the present invention, in step S2, the temperature of the thermosetting reaction is 80°C and the duration is 8 hours. The thermosetting temperature should not be too low or too high; too low a temperature will result in an excessively long curing time, while too high a temperature will easily generate a large number of bubbles.

[0048] In some embodiments of the present invention, in step S3, the heating temperature of the polymer film is 80°C, and the heating time is 60 seconds. A certain temperature is required to activate the polymer chains in the photocrosslinking process to carry out the double bond crosslinking reaction.

[0049] In some embodiments of the present invention, in step S3, the duration of the photocrosslinking treatment is 0.1 to 60 seconds. The photocrosslinking treatment time depends on the light intensity of the UV lamp.

[0050] Second aspect This invention provides a shape memory material obtained by the method described in the first aspect above, wherein the phosphorescence lifetime of the shape memory material is adjustable between 2.36 and 5.87 s. Exemplarily, the phosphorescence lifetime of the Cor-EP system can be any value selected from 2.4 s, 2.5 s, 2.8 s, 3 s, 3.5 s, 4 s, 4.5 s, or 5 s, or a range of any two of the aforementioned values, or any value within that range.

[0051] It is worth noting that the aforementioned shape memory materials achieve functional coupling, rather than simple superposition: traditional materials may simply mix luminescent substances into a matrix, where luminescence and deformation are two independent processes; the purpose of this invention is to precisely control both the phosphorescence lifetime and shape memory behavior (such as recovery speed and shape fixation) of the material simultaneously by sharing the key preparation parameter of "photocrosslinking." This creates an intrinsic and inseparable link between the two functions; The purpose of giving materials the ability to "self-report" is to enable them to report their dynamic processes (such as motion trends, instantaneous speed and angle changes) in real time and intuitively through the visible phosphorescence afterglow emitted by the materials themselves when performing shape memory functions (such as deformation recovery), without relying on external detection equipment. Using temperature as a "switch" for synergistic regulation aims to leverage this key stimulus to simultaneously and synergistically trigger changes in two functions: activating shape recovery and modulating phosphorescence intensity. It is this synergistic effect that has spurred a series of subsequent innovative applications.

[0052] In some embodiments of the present invention, the structure containing the above formula (1) is a corona-phenyl structure, and the phosphorescence lifetime of the corona-phenyl system (Cor-EP) can be any value among 2.4s, 2.5s, 2.8s, 3s, 3.5s, 4s, 4.5s or 5s.

[0053] Third aspect The present invention provides applications of shape memory materials obtained by the method in the first aspect above or the shape memory materials in the second aspect above, preferably applications in high-temperature dynamic behavior visualization, 3D multi-information encryption or circuit heat generation status monitoring.

[0054] In the field of monitoring, the shape memory material provided by this invention enables non-destructive, real-time, and visualized monitoring of the dynamic behavior of materials under extreme environments such as high temperature and confined spaces. This is crucial for in-service diagnostics of soft robots and micro actuators.

[0055] In the field of encryption, the shape memory material provided by this invention can construct a dynamic, three-dimensional, and reconfigurable multi-layered information encryption platform. Through the two keys of "3D shape hiding" and "temperature-controlled afterglow," the security level of information is greatly enhanced, overcoming the shortcomings of existing static, two-dimensional encryption technologies.

[0056] In the field of electronics, the shape memory material provided by this invention integrates visual monitoring and intelligent protection functions. It can not only intuitively display the thermal state of the circuit like a "visual thermocouple", but also actively cut off the circuit through the shape memory effect when overheating, thus achieving "visible" overheat protection.

[0057] It should be noted that, through the above-described scheme, this invention synergistically integrates ultra-long phosphorescence with shape memory function, achieving the following beneficial effects: 1. Real-time and visual monitoring of dynamic behavior at high temperatures is achieved: The material's own phosphorescence afterglow acts as a built-in "indicator light" that does not require an external power supply, which can intuitively display the entire deformation process (trend, speed, angle), making it particularly suitable for intelligent devices in extreme environments; 2. A dynamic and reconfigurable multi-layered information encryption platform was constructed: spatial encryption, which uses shape memory effect to fold and hide two-dimensional information in a three-dimensional structure; dynamic information change, which uses temperature to control the intensity of phosphorescence so that the information content presented during decryption changes with temperature, thus achieving multi-layered information encryption. 3. Provides an intuitive and visual circuit heat generation status monitoring solution: direct visualization, that is, by observing the change in afterglow intensity of the coating material, the circuit's on / off state, voltage level, and heat generation status can be directly determined; quantitative potential, that is, afterglow intensity is related to temperature, and has the potential to quantitatively monitor the circuit's thermal state; intelligent overheat protection, that is, combining shape memory function with thermal response, can produce intelligent circuit switches with visualized self-destruct or self-disconnection functions.

[0058] Example 1 This embodiment provides the preparation process of the above-mentioned shape memory material with ultra-long phosphorescence.

[0059] The purpose of this embodiment is to synthesize the aforementioned shape memory material system Cor-EP with ultralong phosphorescence.

[0060] The detailed steps of the preparation process provided in this embodiment are as follows: 1. Mixing: Epoxy resin, glycidyl methacrylate (GMA), and polyetheramine are mixed; wherein the mass ratio of epoxy resin, glycidyl methacrylate (GMA), and polyetheramine is 1:2.4:1.1, and the epoxy resin is 1 part by weight, the glycidyl methacrylate is 2.4 parts by weight, the polyetheramine is 1 part by weight, the photoinitiator is 0.01 parts by weight, and the phosphorescent molecule is 0.001 parts by weight; 2. Addition of additives: The mixture obtained in step 1 above is mixed with a photoinitiator and phosphorescent molecules; wherein, the amount of photoinitiator added is 1 wt% of the mass of the glycidyl methacrylate, and the amount of phosphorescent molecules added is 0.1 wt% of the mass of the glycidyl methacrylate; photoinitiator 2959 is used as the photoinitiator; 3. Dissolving and casting: The mixture obtained in step 2 above is heated and stirred to fully dissolve and mix the material system. The resulting solution is then poured into a silicone rubber mold. The heating temperature is 80℃, the stirring speed is 500~1000rpm, and the mixing time is 15 min. The size of the silicone rubber mold is 1*1*0.3 cm. 4. Thermal curing: The solution obtained in step 3 and introduced into the silicone rubber mold is subjected to a two-step thermal curing reaction, namely, thermal curing treatment at 80°C for 8 hours and then thermal curing treatment at 100°C for 2 hours to obtain a polymer film. 5. Photocrosslinking control: The polymer film obtained in step 4 is subjected to photocrosslinking reaction at 80°C. By controlling the duration of photocrosslinking, a series of the above-mentioned shape memory materials with different phosphorescence lifetimes are prepared.

[0061] Example 2 This embodiment applies the shape memory material obtained in Example 1 to dynamic behavior visualization monitoring.

[0062] The purpose of this embodiment is to verify that the dynamic behavior of the shape memory material obtained in Embodiment 1 during the shape recovery process can be monitored in real time and intuitively by phosphorescent afterglow.

[0063] This embodiment provides the following operation process to achieve dynamic behavior visualization monitoring: 1. Sample preparation: Cut the polymer film obtained in Example 1 into the following shapes: Figure 4 The butterfly shape shown is fixed into a temporary shape with the wings spread at 90°. 2. Differential treatment: The above-mentioned series of samples with different phosphorescence lifetimes were subjected to photocrosslinking treatment for different durations in water at 80℃ to obtain 3D butterflies with different wingspan angles. The photocrosslinking time and wingspan angle used for samples with different phosphorescence lifetimes are shown in Table 1 below. Table 1. Photocrosslinking time and wingspan angle used for samples with different phosphorescence lifetimes

[0064] 3. Triggering and Observation: Place these 3D butterflies on a heating platform at 35~200℃ to trigger their shape recovery. The entire recovery process can be directly observed and judged by the afterglow of the phosphorescence they emit. Specifically, it can be judged by how the wings of these 3D butterflies move, the speed of movement, and the final angle.

[0065] Example 3 This embodiment applies the aforementioned shape memory material to multiple information encryption.

[0066] The purpose of this embodiment is to demonstrate the application of the above-mentioned shape memory material in the field of information encryption.

[0067] The specific steps are as follows: 1. Localized control: The shape memory material, also known as the Cor-EP thin film, obtained in Example 1 was locally illuminated using photomask technology, with an illumination intensity of 100 mW / cm². 2 By controlling the degree of photocrosslinking in different regions, different phosphorescent patterns can be "written" onto the film; 2. 3D encryption: Utilizing the shape memory effect, this patterned film is folded or rolled into a 3D structure to further hide the information; 3. Decryption and Reading: When this 3D structure is heated, two effects occur simultaneously: 3.1 Shape Restoration: The 3D structure unfolds back into the original thin film, revealing hidden information; 3.2 Afterglow Changes: Temperature simultaneously modulates the phosphorescence intensity, causing changes in the pattern information; 3.3 By controlling the decryption temperature, multiple information can be read.

[0068] Example 4 This embodiment applies the above-mentioned shape memory material to circuit heat generation status monitoring and overheat protection.

[0069] The purpose of this embodiment is to demonstrate the application of the above-mentioned shape memory material as a smart coating material in the electronics field.

[0070] The detailed steps are as follows: 1. Coating metal wires: Pour the fully dissolved and mixed solution from step 3 of Example 1 into a mold, then put in copper wire and nickel-chromium wire, and use thermosetting to coat the copper wire and nickel-chromium wire in the form of a thin film with shape memory material, thereby producing Cor-EP-Cu and Cor-EP-Cr20Ni80; 2. Monitoring heat generation: Connect these two types of coated wires to the circuit; when current passes through, the metal wire heats up, and the heat is transferred to the coating material, changing its phosphorescence brightness; by monitoring the afterglow intensity, the heat generation status of the circuit can be monitored quantitatively and visually, and even different types of metal wires or circuit continuity can be distinguished. 3. Series identification: Copper wire and nickel-chromium wire are wound together to form a series system. Since the two have different resistances and generate different amounts of heat, phosphorescence can be used to visually identify which segment is which type of metal wire.

[0071] 4. Overheat Protection Switch: The aforementioned shape memory material, also known as Cor-EP material, coated with copper wire, is completely folded and photocrosslinked at 80°C to fix this folded shape; it is then connected to the circuit as a switch. Under normal circumstances, the circuit is conductive; when the circuit overheats, the heat triggers the shape memory effect, and the material returns to its original straight state, thus physically disconnecting the circuit; the entire process of overheat triggering and switching action can be directly visually monitored through changes in the phosphorescence of the material.

[0072] Next, taking the phosphorescent molecular halo benzene system Cor-EP as an example, please refer to the accompanying drawings in the specification of this invention: 1. Figure 1 These are the phosphorescence spectra of the Cor-EP system in Example 1 at different photocrosslinking times. Figure 1 The phosphorescence intensity of Cor-EP at different photocrosslinking times in the system of Example 1 is shown; 2. Figure 2 This is a phosphorescence lifetime diagram of the Cor-EP system in Example 1 at different photocrosslinking times. Figure 2 The phosphorescence lifetime of Cor-EP in Example 1 system with different photocrosslinking times is shown; 3. Figure 3 These are phosphorescence afterglow images of the Cor-EP system in Example 1 at different photocrosslinking times. Figure 3 The phosphorescence afterglow of Cor-EP at different photocrosslinking times in the system of Example 1 is shown; 4. Figure 4 This is a visualization of the dynamic behavior of the 3D butterfly configuration of Cor-EP at different photocrosslinking times in the Example 2 system at different temperatures. Figure 4 The visualization monitoring of the dynamic behavior of the 3D butterfly configuration of Cor-EP with different photocrosslinking times in Example 2 system at different temperatures was demonstrated. 5. Figure 5 This is a multi-encrypted image display of the body temperature response of the Cor-EP system in Example 3. Figure 5 This demonstrates the multi-layered information encryption of the body temperature response of the Cor-EP system in Example 3; 6. Figure 6 This is a multi-information encrypted image display of the different temperature responses of the Cor-EP system in Example 3. Figure 6 This demonstrates multiple information encryption methods for the Cor-EP system of Example 3 at different temperatures; 7. Figure 7 This is a display of circuit heat generation monitoring images for the Cor-EP-coated Cu and Cr20Ni80 metal wire system in Example 4. Figure 7 The circuit heat generation monitoring of the Cor-EP coated Cu and Cr20Ni80 metal wire system in Example 4 is demonstrated; 8. Figure 8This is a circuit heat generation diagram of the Cor-EP coated Cu and Cr20Ni80 series system in Example 4, showing the identifiable metal wire types. Figure 8 The circuit heat generation of the Cor-EP coated Cu and Cr20Ni80 series system in Example 4 is shown, and the type of metal wire can be identified; 9. Figure 9 This is a visual evaluation image of the overheat protection function of the switch prepared by the Cor-EP coated copper wire in Example 4. Figure 9 A visual evaluation of the overheat protection function of the switch prepared by the Cor-EP coated copper wire system in Example 4 is presented.

[0073] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims. Furthermore, specific examples have been used in the specification to illustrate the principles and implementation methods of the present invention. The above description of the embodiments is only for the purpose of helping to understand the method and core ideas of the present invention, and the content of this specification should not be construed as a limitation of the present invention.

Claims

1. A method for preparing shape memory materials, characterized in that, The method includes the following steps: S1, a mixture of epoxy resin, glycidyl methacrylate, polyetheramine, photoinitiator and phosphorescent molecules; S2, The mixture obtained in step S1 is heated and stirred to dissolve, injected into a mold, and a polymer film is obtained after a thermosetting reaction; S3, the polymer film obtained in step S2 is heated to perform photocrosslinking treatment, and the phosphorescence lifetime is adjusted by controlling the photocrosslinking time to obtain the shape memory material.

2. The method according to claim 1, characterized in that, In step S1, the structural formula of the phosphorescent molecule is shown in any one of the following formulas (1) to (11): Equation (1) is , Equation (2) is , Equation (3) is , Equation (4) is , Equation (5) is , Equation (6) is , Equation (7) is , Equation (8) is , Equation (9) is , Equation (10) is , Equation (11) is , Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R in equations (1) to (11) above 10 R 11 Each of the following is independently selected from any one of alkyl chains, carboxylic acids, ester groups, aldehydes, ketones, and boric acids.

3. The method according to claim 1, characterized in that, In step S1, the epoxy resin has the following structural formula 12: Wherein, R in Equation 12 12 The radical group is selected from aromatic or aliphatic compounds.

4. The method according to claim 1, characterized in that, In step S1, the structural formula of the glycidyl methacrylate is shown in Formula 13 below: 。 5. The method according to claim 1, characterized in that, In step S1, the structural formula of the polyetheramine is shown in Formula 14 below: ， In Equation 14, n is any value from 1 to 12.

6. The method according to claim 1, characterized in that, Step S1 has at least one of the following characteristics: The epoxy resin is 1 part by weight, the glycidyl methacrylate is 2.4 parts by weight, the polyetheramine is 1 part by weight, the photoinitiator is 0.01 parts by weight, and the phosphorescent molecule is 0.001 parts by weight. The photoinitiator is at least one of photoinitiator 2959 and photoinitiator TPO.

7. The method according to claim 1, characterized in that, Step S2 has at least one of the following characteristics: The heating temperature is 80℃, the stirring speed is 500-1000 rpm, and the heating and stirring time is 15 minutes. The thermosetting reaction is carried out at a temperature of 80°C for 8 hours.

8. The method according to claim 1, characterized in that, Step S3 has at least one of the following characteristics: The heating temperature for the polymer film is 80°C, and the heating time is 60 seconds. The duration of the photocrosslinking treatment is 0.1~60 s.

9. A shape memory material, characterized in that, The shape memory material is obtained by the method of any one of claims 1 to 8, and the phosphorescence lifetime of the shape memory material is adjustable between 2.36 and 5.87 s.

10. The application of the shape memory material obtained by the method of any one of claims 1 to 8 or the shape memory material as described in claim 9 is preferably used in high-temperature dynamic behavior visualization, 3D multi-information encryption or circuit heat generation status monitoring.

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