A high syndiotactic halogen-containing polar α-olefin polymer material and its application
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-06-02
- Publication Date
- 2026-08-14
AI Technical Summary
[0004]本发明旨在解决现有技术中极性α-烯烃单体配位聚合催化剂易失活、立构规整度低，以及形状记忆与自修复功能难以在同一材料体系中集成调控的技术问题，提供一类具有高间规立构规整度的含卤素极性α-烯烃聚合物材料，并实现其形状记忆性能与自修复性能的按需调控
[0015]1. 首次实现了含卤素极性α-烯烃单体的高间规立构选择性聚合，间规立构规整度rrrr＞99％，显著优于现有极性烯烃聚合体系，填补了高间规含卤素极性α-烯烃聚合物的技术空白。
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Abstract
Description
Technical Field
[0001] This invention relates to a highly syndiotactic halogen-containing polar α-olefin polymer material and its applications. The polymer material has shape memory properties or a combination of shape memory and self-healing properties, and belongs to the field of polymer material technology. Background Technology
[0002] Shape memory polymers are intelligent polymer materials that can recover their original shape from a temporarily fixed shape under external stimuli such as heat, light, and electricity. They are currently used in aerospace, flexible electronics, and biomedical devices. Self-healing polymers are polymer materials that can autonomously or under external stimuli heal cracks or repair fractures after being damaged, effectively extending service life and reducing maintenance costs. Existing shape memory polymers mainly involve systems such as polyurethane, polycaprolactone, cross-linked polyethylene, and epoxy resin. Their shape memory effect mostly relies on entropic elastic recovery driven by glass transition or melt transition, which has problems such as narrow transition temperature control range, insufficient recovery stress, and single function. Existing self-healing polymers are mainly based on reversible covalent bonds or supramolecular interactions. Although they can achieve multiple repairs, they generally have limitations such as cumbersome synthesis steps, insufficient mechanical strength, and harsh repair conditions. More importantly, few polymer materials can currently achieve high stereoregularity while simultaneously possessing the controllable integration of polar functional group introduction and shape memory / self-healing functions.
[0003] Halogen-containing polar α-olefin polymers possess potential applications in the field of functional polymers due to the flame retardancy, surface polarity, and chemical modification sites imparted by their halogen atoms. The polar groups can also improve interfacial compatibility with biological tissues or electronic devices. However, the coordination polymerization of these monomers has long faced the following technical challenges: firstly, the polar groups readily coordinate with electrophilic metal centers, leading to catalyst deactivation; secondly, the stereoselectivity of α-olefin polymerization is difficult to control, with the synthesis of highly syndiotactic polymers being particularly challenging. Currently, research reports on highly syndiotactic halogen-containing polar α-olefin polymers are extremely limited, and materials possessing both shape memory and self-healing properties have not yet been publicly disclosed. Rare earth metal catalysts, due to their unique electronic structure and coordination mode, exhibit unique advantages in the tolerance and stereoselectivity control of polar monomers. Previous studies have shown that fluorene-based rare earth dialkyl complexes in [Ph3C][B(C6F5)4] / Al i The Bu3 co-catalyst system can efficiently catalyze the high syndiotactic polymerization of monomers such as styrene and conjugated dienes, but extending this catalytic system to halogen-containing polar α-olefin monomers and further achieving precise control of polymer intelligent functions is still a technological gap. Summary of the Invention
[0004] This invention aims to address the technical problems in existing technologies, such as the easy deactivation and low stereoregularity of polar α-olefin monomer coordination polymerization catalysts, and the difficulty in integrating and controlling shape memory and self-healing functions within the same material system. It provides a class of halogen-containing polar α-olefin polymer materials with high syndiotactic stereoregularity, and enables on-demand control of their shape memory and self-healing properties. To achieve the above objectives, this invention provides the following technical solutions:
[0005] 1. A highly syndiotactic halogenated polar α-olefin polymer material A with shape memory properties, characterized in that the polymer material is synthesized by catalytic polymerization of monomer 1 using a rare earth metal catalytic system; the monomer 1 is 4-chlorophenylbut-3-en-1-yl sulfide, with the structure shown in formula (I): 4-Cl—C6H4—S—CH2—CH2—CH=CH2; the syndiotactic stereoregularity of the polymer material is greater than 99% in terms of rrrr, and the number average molecular weight is 1.8×10 4 ~3.0×10 4 The polymer material has a shape memory fixation rate of >99% and a shape recovery rate of >65%, with recovery conditions of 30-40℃ and a recovery time of 5-15 s.
[0006] 2. A highly syndiotactic halogen-containing polar α-olefin polymer material B possessing both shape memory and self-healing properties, characterized in that the polymer material is synthesized by monomer 2 via a rare earth metal catalytic system; the monomer 2 is 4-bromophenylbut-3-en-1-yl sulfide, with the structure shown in formula (II): 4-Br—C6H4—S—CH2—CH2—CH=CH2; the syndiotactic stereoregularity of the polymer material is greater than 99% (in terms of rrrr), and the number-average molecular weight is 1.8 × 10⁻⁶. 4 ~3.0×10 4 The polymer material has a molecular weight distribution of 1.2–1.9 g / mol; its shape memory fixation rate is >99%, its shape recovery rate is >97%, and its recovery conditions are 40–45℃ and recovery time is 5–15 s; its self-healing efficiency is >90%, and its repair conditions are 60℃ and repair time is 1–4 h.
[0007] 3. The polymer material according to claim 1 or 2, characterized in that the main catalyst of the rare earth metal catalytic system is a fluorene-based rare earth metal bis(alkyl) complex with the general formula [2,7-(R1)2-9-R2-C]. 13 [H6]Sc(CH2SiMe3)2(THF)(1-4), with [Ph3C][B(C6F5)4] and Al as co-catalysts. i Bu3.
[0008] 4. The polymer material according to claim 3, characterized in that the main catalyst is selected from at least one of the following complexes: 1: R1 = R2 = H; 2: R1 = H, R2 = t Bu;3:R1= SiMe3, R2=H;4:R1= SiMe3, R2= t Bu.
[0009] 5. The polymer material according to claim 1 or 2, characterized in that the number-average molecular weight of the polymer material is 1.8 × 10⁻⁶. 4 ~3.0×10 4 g / mol, with a molecular weight distribution of 1.2–1.9.
[0010] 6. The polymer material according to claim 1 or 2, characterized in that the syndiotactic stereoregularity of the polymer material is greater than 99% in terms of rrr.
[0011] 7. The polymer material according to claim 1 or 2, characterized in that the halogen atoms in monomer 1 and monomer 2 are Cl and Br, respectively, and the polar groups are both thioethers.
[0012] 8. An application of the polymer material according to claim 1 or 2, characterized in that the polymer material is used in the fields of smart devices, flexible electronics or medical materials.
[0013] 9. The application according to claim 8, characterized in that the polymer material of claim 1 is used for smart molded devices that do not require self-healing, and the polymer material of claim 2 is used for fragile flexible electronics or medical consumables. For smart molded devices requiring self-healing, polymer materials possessing both self-healing and shape memory properties are preferentially used in the fields of fragile flexible electronics and medical consumables.
[0014] Compared with the prior art, the present invention has the following beneficial effects:
[0015] 1. For the first time, highly syndiotactic stereoselective polymerization of halogen-containing polar α-olefin monomers was achieved, with syndiotactic stereoregularity > 99%, which is significantly better than existing polar olefin polymerization systems, filling the technological gap in highly syndiotactic halogen-containing polar α-olefin polymers.
[0016] 2. By simply replacing halogen atoms in the monomer structure, it is possible to conveniently control the shape memory function from a single shape memory function to a dual shape memory-self-repair function under the same catalytic system, providing a new molecular strategy for the functional design of smart polymer materials.
[0017] 3. The obtained polymer materials have excellent shape memory properties: the shape recovery rate of chlorinated polymers is >65%, the shape recovery rate of bromine polymers is >97%, and the recovery temperature is close to the human body temperature (30-45℃), which has good potential for biomedical applications.
[0018] 4. Brominated polymers also have a self-healing efficiency of >90%, mild repair conditions (60℃, 1-4 h), no need for external repair agents or complex irritants, and have good practical value.
[0019] 5. The polymer has a narrow molecular weight distribution (1.2-1.9), and the material properties are uniform and stable; the rare earth catalytic system has good tolerance to polar groups, the polymerization process is controllable, the catalyst has high activity, and it has good reproducibility and large-scale application prospects. Attached Figure Description
[0021] Figure 1 The rare earth metal catalyst [2,7-(R1)2-9-R2-C] in Example 1 13 The 1H NMR spectrum of H6]Sc(CH2SiMe3)2(THF)(1), 1:R1= R2= H.
[0022] Figure 2 The above is the 1H NMR spectrum of monomer 1 in Example 2.
[0023] Figure 3 The above is the 1H NMR spectrum of monomer 2 in Example 3.
[0024] Figure 4 The rare earth metal catalytic system in Example 4 was used to catalyze the polymerization of monomer 1, and the 1H NMR spectrum of polymer A was obtained.
[0025] Figure 5 The rare earth metal catalytic system in Example 4 was used to catalyze the polymerization of monomer 1, and the carbon NMR spectrum of polymer A was obtained.
[0026] Figure 6 The DSC curve of polymer A was obtained by catalyzing the polymerization of monomer 1 using the rare earth metal catalytic system in Example 4.
[0027] Figure 7 The rare earth metal catalytic system in Example 4 was used to catalyze the polymerization of monomer 1, resulting in polymer A with its molecular weight and molecular weight distribution.
[0028] Figure 8 The rare earth metal catalytic system in Example 4 was used to catalyze the polymerization of monomer 1, resulting in the shape memory curve of polymer A.
[0029] Figure 9 The rare earth metal catalytic system in Example 5 was used to catalyze the polymerization of monomer 2, and the 1H NMR spectrum of polymer B was obtained.
[0030] Figure 10 The rare earth metal catalytic system in Example 5 was used to catalyze the polymerization of monomer 2, and the carbon NMR spectrum of polymer B was obtained.
[0031] Figure 11 The DSC curve of polymer B was obtained by catalyzing the polymerization of monomer 2 using the rare earth metal catalytic system in Example 5.
[0032] Figure 12 The rare earth metal catalytic system in Example 5 was used to catalyze the polymerization of monomer 2, resulting in the molecular weight and molecular weight distribution of polymer B.
[0033] Figure 13 The rare earth metal catalytic system in Example 5 was used to catalyze the polymerization of monomer 2, resulting in the shape memory curve of polymer B.
[0034] Figure 14 The self-healing curve of polymer B is obtained by polymerizing monomer 2 using the rare earth metal catalytic system in Example 5.
[0035] Detailed Implementation: In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described below in conjunction with the embodiments.
[0036] The main reagent information mentioned in the following examples is shown in Table 1, and the main instruments and equipment are shown in Table 2.
[0037] Table 1 n-Hexane Analytical Pure Bailingwei Chemical Technology Co., Ltd. Solvent distillation system Toluene Analytical Pure Beijing Chemical Plant Solvent distillation system Tetrahydrofuran Analytical Pure Bailingwei Chemical Technology Co., Ltd. Solvent distillation system Nitrogen 99.999% Helium --- Calcium hydride Analytical Pure Anaiji Chemical --- Anhydrous ethanol Analytical Pure Beijing Chemical Plant --- Flu Analytical purity 99% Tianjin Zancheng Technology --- <![CDATA[Al i Bu3]]> 1.0M in toluene Tianjin Zancheng Technology --- <![CDATA[[Ph3C][B(C6F5)4]]]> Analytical purity 98% Anaiji Chemical --- Scandium trichloride Analytical purity 99.9% Strem Chemicals --- n-BuLi 2.5M in hexane Anaiji Chemical --- <![CDATA[LiCH2SiMe3]]> 1.0M in hexane Anaiji Chemical --- methanol Analytical Pure Beijing Chemical Plant --- petroleum ether Analytical Pure Beijing Chemical Plant --- dichloromethane Analytical Pure Beijing Chemical Plant --- Ethyl acetate Analytical Pure Beijing Chemical Plant --- D-chloroform 99.9% Anaiji Chemical --- Diethyl ether Analytical purity 99% Beijing Chemical Plant <![CDATA[CaH2 distillation]]> 4-Chlorothiophenol 98% Anaiji Chemical --- 4-Fluorothiophenol 98% Anaiji Chemical --- 4-Bromo-1-butene 98% Anaiji Chemical --- Table 2 Rotary evaporator N-100DG-29 Shanghai Airong Instrument Co., Ltd. glove box LABstar 1250 / 1000 German company MBRAUN vacuum pump RV3, RV5, RV8 BOC Edwards (UK) Electronic balance BS223S / BS124S Beijing Sartorius Scientific Instruments Co., Ltd. Nuclear magnetic resonance spectrometer AVANCE 400 BRUKER, Sweden Thermostatic magnetic stirrer DF-101 Gongyi Yuhua Instrument Co., Ltd. Cryogenic cooling circulation pump DL-1510 Ningbo Xinzhi Biotechnology Co., Ltd. refrigerator FCD-270CSN Qingdao Haier Group Vacuum drying oven DHG-9240A Shanghai Feiyue Experimental Instruments Co., Ltd. Gel permeation chromatography WATERS 1515 WATERS Company, USA Combined X-ray diffractometer Ultima Ⅳ Rigaku Intelligent weight analyzer IGA100C Hiden, UK Fully automated surface area and micropore analyzer ASIQM000-1-MP American CANTA Scanning electron microscope JSM-7500F Hitachi Corporation Thermodynamic Analysis System DSC DSC-60 Shimadzu Corporation of Japan Thermodynamic Analysis System DTG DTG-60 Shimadzu Corporation of Japan
[0038] Implementation Example 1
[0039] Synthesis of Rare Earth Metal Catalyst 1: 0.9 g (6.0 mmol) of ScCl3 was weighed and placed in a 100 mL Schlenk tube. Approximately 40 mL of THF was added, and the mixture was evacuated and then placed in a glove box. The mixture was refluxed at 100 °C for 12 h. After reflux, the reaction apparatus was evacuated back into the glove box, and the THF was removed to obtain a white solid, ScCl3(THF)3. A certain amount of toluene was added to ScCl3(THF)3, and the mixture was placed in a refrigerator for later use. Next, 1.18 g (6.0 mmol) of fluorene ligand was weighed into a single-necked flask and dissolved in anhydrous diethyl ether. The flask was then refrigerated. After cooling, 2.5 Mn-BuLi (2.5 mL, 6.0 mmol) was added dropwise to the ligand, and the reaction was allowed to proceed for 2 h. After the reaction, the solvent was removed, and a certain amount of toluene was added to dissolve the ligand. The flask was then refrigerated. After a period of refrigeration, the solution was slowly added dropwise to the toluene solution of ScCl3(THF)3. After the addition was complete, the reaction was allowed to proceed at room temperature for 12 h. Next, 1.13 g (12.0 mmol) of LiCH₂TMS was weighed and placed in an isotope flask. Toluene was added, and the flask was refrigerated. After a period of time, a toluene solution of lithium salt was added dropwise to the above reaction system, and the reaction was carried out at room temperature for 16 h. After the reaction was completed, the toluene was dried under vacuum, and hex was added to remove the lithium salt. The solution was dried under vacuum, and n-hexane was added to just dissolve the solid. The solution was then placed in a refrigerator for freezing and crystallization. Finally, the precipitated solid was collected to obtain a light yellow solid (1.3 g, yield = 52%).
[0040] The rare earth metal catalyst 1 prepared in this embodiment was subjected to the following tests: Nuclear magnetic resonance detection: NMR spectrum (H1N) of the polymerization product prepared in this embodiment.
[0041] Example 2
[0042] Under nitrogen protection, 0.25 mol (1 equivalent) of 4-chlorophenyl sulfide was added to a dry reaction vessel equipped with a magnetic stir bar. The flask was purged with nitrogen three times, and dry tetrahydrofuran (250 mL) was added with stirring at 0 °C. Under nitrogen protection, 0.46 mol (1.1 equivalent) of NaH (60% dispersed in mineral oil) was added in portions, and the mixture was stirred at 0 °C for 30 min. Subsequently, 0.325 mol (1.3 equivalent) of 4-bromo-1-butene was added, and the reaction mixture was stirred at room temperature for 12 h. After the reaction was complete, ice water was added dropwise to the mixture at 0 °C. The product was extracted with diethyl ether (3 × 50 mL), the combined organic layers were dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The crude residue was purified by silica gel chromatography, eluting with petroleum ether / ethyl acetate (20:1) to give monomer 1.
[0043] The monomer 1 prepared in this embodiment was subjected to the following tests: Nuclear magnetic resonance detection: NMR spectrum (H1N) of the polymer product prepared in this embodiment.
[0044] Implementation Example 3
[0045] Under nitrogen protection, 0.25 mol (1 equivalent) of 4-bromophenyl sulfide was added to a dry reaction vessel equipped with a magnetic stir bar. The flask was purged with nitrogen three times, and dry tetrahydrofuran (250 mL) was added with stirring at 0°C. Under nitrogen protection, 0.46 mol (1.1 equivalent) of NaH (60% dispersed in mineral oil) was added in portions, and the mixture was stirred at 0°C for 30 minutes. Subsequently, 0.325 mol (1.3 equivalent) of 4-bromo-1-butene was added, and the reaction mixture was stirred at room temperature for 12 hours. After the reaction was complete, ice water was added dropwise to the mixture at 0°C. The product was extracted with diethyl ether (3 × 50 mL), the combined organic layers were dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The crude residue was purified by silica gel chromatography, eluting with petroleum ether / ethyl acetate (20:1) to give monomer 2.
[0046] The monomer 2 prepared in this embodiment was subjected to the following tests: Nuclear magnetic resonance detection: NMR spectrum (H1N) of the polymer product prepared in this embodiment.
[0047] Example 4
[0048] The polymerization reaction was carried out in a glove box. 10 μL of rare earth metal catalyst 1 was weighed into a 25 mL round-bottom flask, dissolved in 3 mL of toluene, and then 100 μL of Al was added to the solution. i Add 10 μL of co-catalyst [Ph3C][B(C6F5)4] and stir for 5 minutes. During this time, weigh 2 mmol of monomer 1 into a small centrifuge tube and add 50 μL of Al. i Bu3 was used to remove any water and impurities that might be present in the monomer. The monomer was then added to the reaction system all at once and allowed to react at room temperature for a period of time. After the reaction was complete, the reaction solution was quickly poured into 100 mL of methanol to stop the reaction. A solid was observed to precipitate. After stirring for 20 minutes, the solid was filtered and collected. The product was then dried in a vacuum oven to constant weight to obtain polymer A. The calculated yield was 99%.
[0049] The polymer A prepared in this embodiment was tested as follows: (1) Nuclear magnetic resonance detection was performed to test the 1H NMR spectrum and 1C NMR spectrum of the polymer. The syndiotactic selectivity of the polymer was determined to be >99% by the 1C NMR spectrum.
[0050] (2) GPC detection: The integral of the GPC detection results of the polymer product prepared in this embodiment shows that the number average molecular weight M of the polymer product is... n =18000, molecular weight distribution M w / M n = 1.37.
[0051] (3) Shape memory curve detection: Dynamic mechanical analysis (DMA) was used to test the shape memory curve of polymer A, and the shape fixation rate R of polymer A at 40℃ was obtained. f =99.9%, Shape recovery rate R r =65.5%.
[0052] Example 5
[0053] The polymerization reaction was carried out in a glove box. 10 μL of rare earth metal catalyst 1 was weighed into a 25 mL round-bottom flask, dissolved in 3 mL of toluene, and then 100 μL of Al was added to the solution. i Add 10 μL of co-catalyst [Ph3C][B(C6F5)4] and stir the solution for 5 minutes. During this time, weigh 2 mmol of monomer 2 into a small centrifuge tube and add 50 μL of Al. i Bu3 was used to remove any water and impurities that might be present in the monomer. The monomer was then added to the reaction system all at once and allowed to react at room temperature for a period of time. After the reaction was complete, the reaction solution was quickly poured into 100 mL of methanol to stop the reaction. A solid was observed to precipitate. After stirring for 20 minutes, the solid was filtered and collected. The product was then dried in a vacuum oven to constant weight to obtain polymer B. The calculated yield was 92%.
[0054] The following tests were performed on polymer A prepared in this embodiment:
[0055] (1) Nuclear magnetic resonance detection: The 1H NMR spectrum and 1C NMR spectrum of the polymer were tested, and the syndiotactic selectivity of the polymer was determined by the 1C NMR spectrum > 99%.
[0056] (2) GPC detection: The integral of the GPC detection results of the polymer product prepared in this embodiment shows that the number average molecular weight M of the polymer product is... n = 19000, molecular weight distribution M w / M n = 1.28.
[0057] (3) Shape memory curve detection: Dynamic mechanical analysis (DMA) was used to test the shape memory curve of polymer A, and the shape fixation rate R of polymer A at 40℃ was obtained. f =99.9%, Shape recovery rate R r =97.3%.
[0058] (4) Shape recovery curve test: The dumbbell-shaped sample was cut in the middle, the cut surfaces were joined together and placed in a 60℃ oven for healing for 1-4 hours. Tensile tests were performed before and after healing. The elongation at break was used as the self-repair efficiency evaluation index. Repair efficiency = (elongation at break after healing / original elongation at break) × 100%. After 3 hours of repair, the elongation at break recovered to 100%.
Claims
1. A high syndiotactic halogen-containing polar α-olefin polymer material with shape memory properties, characterized in that, The polymer material is obtained by catalytic polymerization of monomer 1 through a rare earth metal catalytic system; the monomer 1 is 4-chlorophenylbut-3-en-1-yl sulfide, and its structure is shown in formula (Ⅰ): 4-Cl—C6H4—S—CH2—CH2—CH=CH2; The syndiotactic stereoregularity of the polymer material is greater than 99% (in terms of rrrr), and the number-average molecular weight is 1.8 × 10 4 ~3.0×10 4 The polymer material has a shape memory fixation rate of ≥99% and a shape recovery rate of ≥65%, with recovery conditions of 30–40℃ and a recovery time of 5–15 s.
2. A highly syndiotactic halogen-containing polar α-olefin polymer material possessing both shape memory and self-healing properties, characterized in that, The polymer material is formed by the catalytic polymerization of monomer 2 through a rare earth metal catalytic system; the monomer 2 is 4-bromophenylbut-3-en-1-yl sulfide, and its structure is shown in formula (II): 4-Br—C6H4—S—CH2—CH2—CH=CH2; The syndiotactic stereoregularity of the polymer material is greater than 99% (in terms of rrrr), and the number-average molecular weight is 1.8 × 10 4 ~3.0×10 4 The polymer material has a molecular weight distribution of 1.2–1.9 g / mol; its shape memory fixation rate is >99%, its shape recovery rate is >97%, and its recovery conditions are 40–45℃ and recovery time is 5–15 s; its self-healing efficiency is >90%, and its repair conditions are 60℃ and repair time is 1–4 h.
3. The polymer material according to claim 1 or 2, characterized in that, The main catalyst of the rare earth metal catalytic system is a fluorene-based rare earth metal bis(alkyl) complex, with the structure shown in the general formula [2,7-(R1)2-9-R2-C]. 13 [H6]Sc(CH2SiMe3)2(THF)(1-4), with [Ph3C][B(C6F5)4] and Al as co-catalysts. i Bu3.
4. The polymer material according to claim 3, characterized in that, The main catalyst is selected from at least one of the following complexes: 1: R1 = R2 = H; 2: R1 = H, R2 = t Bu; 3: R1= SiMe3, R2 =H; 4: R1 = SiMe3, R2 = t Bu.
5. The polymer material according to claim 1 or 2, characterized in that, The number-average molecular weight of the polymer material is 1.8 × 10⁻⁶. 4 ~3.0×10 4 g / mol, with a molecular weight distribution of 1.2–1.
9.
6. The polymer material according to claim 1 or 2, characterized in that, The syndiotactic stereoregularity of the polymer material is greater than 99% in terms of rrr.
7. The polymer material according to claim 1 or 2, characterized in that, The halogen atoms in monomer 1 and monomer 2 are Cl and Br, respectively, and the polar groups in both monomers are thioethers.
8. An application of the polymer material according to claim 1 or 2, characterized in that, The polymer material is used in the fields of smart devices, flexible electronics, or medical materials.
9. The application according to claim 8, characterized in that, The polymer material of claim 1 is used for smart molded devices that do not require self-healing, and the polymer material of claim 2 is used for fragile flexible electronics or medical consumables. For smart molded devices requiring self-healing, polymer materials possessing both self-healing and shape memory properties are preferentially used in the fields of fragile flexible electronics and medical consumables.