Universal polymer force-sensitive cross-linking agent based on combination of cross-linking functions of force-sensitive group and diaziridine, and preparation method and application of universal polymer force-sensitive cross-linking agent

Abstract

The invention discloses a universal polymer force-sensitive cross-linking agent based on combination of a force-sensitive group and a bis-aziridine cross-linking function, and a preparation method and application thereof. The cross-linking agent is prepared by esterification of the force-sensitive group and a bis-aziridine group. The method comprises the following steps: in a nitrogen environment, carrying out a reaction on a force sensitive group, 4-[3-(trifluoromethyl) diazo-3-yl] benzoic acid, 4-dimethylaminopyridine (DMAP) and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC-HCl) in anhydrous dichloromethane; and extracting the obtained mixture for three times, performing column chromatography purification on the obtained mixture on a silica gel column by using an eluent, and spin-drying to obtain a final product. The mechanical response sensitivity and structural stability of the material are remarkably improved, a mechanical force sensitive group introduction strategy suitable for various polymer systems is established, and a new technical path and theoretical support are provided for multifunctional design and wide application of the stress sensitive material.

Description

Technical Field

[0001] This invention relates to the field of stretchable polymer elastomer materials, and more particularly to a general-purpose polymeric force-sensitive crosslinking agent based on the combination of force-sensitive groups and bisacrylidine crosslinking function, as well as its preparation method and application. Background Technology

[0002] Materials are constantly subjected to various mechanical stresses, which accumulate over time and can lead to structural failure through progressive failure mechanisms. Localized stress concentrations can induce catastrophic failure without warning, even in the absence of visible defects.

[0003] Therefore, developing real-time stress monitoring technology capable of detecting critical stress states with high spatiotemporal resolution is crucial for ensuring structural integrity and preventing material failure.

[0004] Mechanical deformation of polymer materials typically begins with the application of macroscopic forces, generating stress at crosslinking and entanglement points, thus affecting their elasticity and deformation. In recent years, polymer systems incorporating mechanomolecules that produce an optical response proportional to applied stress have emerged as promising alternatives. These materials enable real-time visualization of complex stress distributions without the need for external power sources or data processing infrastructure.

[0005] Therefore, providing a force-sensitive crosslinking agent that can impart force-sensitive functionality to commercial polymer materials to meet the need for stress visualization during the stress process of commercial polymer materials is a technical problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0006] In view of this, the present invention provides a general polymeric force-sensitive crosslinking agent based on the combination of force-sensitive group and bisacrylidine crosslinking function, as well as its preparation method and application.

[0007] To solve the above-mentioned technical problems, the present invention adopts the following technical solution: A general-purpose polymeric crosslinking agent based on the combination of a mechanosensitive group and the crosslinking function of bisacrididine, wherein the crosslinking agent is prepared by esterification of the mechanosensitive group and the bisacrididine group.

[0008] Preferably, the crosslinking agent can be obtained by crosslinking various commercial polymer systems, thereby achieving the purpose of introducing mechanistic groups into commercial polymers; The commercial polymer system includes any one of the following: unsaturated polymers, SIS, styrene-butadiene rubber (SBS), polyethylene-ethylene acetate (EVA), polyurethane (PU), polylactic acid (PLA), polycaprolactone (PCL), polyimide (PI), epoxy resin (ER), polyacrylamide (PAM), and saturated polymers, polyolefins (PO), polystyrene (PS), polydimethylsiloxane (PDMS), and polyvinyl alcohol (PVA).

[0009] Preferably, the force-sensitive group includes any one of spiropyran, rhodamine, 1,2-dioxane, spiroxazine, and anthraceneyne.

[0010] Preferably, the method for preparing the crosslinked commercial polymer with force-sensitive function includes the following steps: Dissolve 1.0 g of the commercial polymer in 10 mL of tetrahydrofuran (THF) and stir until completely dissolved; Meanwhile, under similar conditions, ethylene propylene rubber (EPDM) and polyolefin elastomer (POE) were dissolved in 10 mL of toluene, and the dissolution process was carried out at 60 °C. After the polymer is completely dissolved, a crosslinking agent with a concentration of 1.0 wt% is added to the polymer solution. After vortex mixing, an oil pump is used to degas the air bubbles in the polymer solution, and then the degassed solution is poured into a 3 cm × 5 cm polytetrafluoroethylene (PTFE) mold. The solvent was evaporated at room temperature for 24 hours to remove most of the solvent, and then vacuum dried for 6 hours to completely remove the residual solvent. The solvent-free polymer film was then heated at 100 °C for 24 hours under nitrogen atmosphere to generate the corresponding cross-linked polymer film.

[0011] A method for preparing a universal polymeric crosslinking agent based on the combination of a mechanosensitive group and the crosslinking function of bisacrylidine includes the following steps: Step 1: Under nitrogen atmosphere, react the sensitizing group, 4-[3-(trifluoromethyl)diazonyl-3-yl]benzoic acid, 4-dimethylaminopyridine (DMAP) and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC-HCl) in anhydrous dichloromethane; Step 2: After the reaction is complete, the mixture is extracted three times with deionized water. The mixture is then purified by column chromatography on a silica gel column using a mixture of dichloromethane and petroleum ether as eluent. After evaporation, the final product is obtained.

[0012] Preferably, in step 1, 0.5 mmol of a lysinic group, 345 mg of 1.5 mmol of 4-[3-(trifluoromethyl)diazonyl-3-yl]benzoic acid, 183 mg of 1.5 mmol of 4-dimethylaminopyridine (DMAP) and 767 mg of 4.0 mmol of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC-HCl) are reacted in anhydrous dichloromethane under a nitrogen atmosphere.

[0013] Preferably, in step 1, the reaction is carried out in anhydrous dichloromethane under a nitrogen atmosphere for 24 hours.

[0014] Application of a general-purpose polymeric force-sensitive crosslinking agent based on the combination of force-sensitive groups and the crosslinking function of bisacrylidine, wherein the material exhibits visible optical changes when subjected to stress through the force-sensitive function.

[0015] Preferably, the material exhibits stable optical change properties during stretching.

[0016] Preferably, when the material is stretched under defective conditions, the stress distribution of the material is reflected through optical changes.

[0017] The present invention achieves the following technical effects compared to the prior art: (1) In this invention, a typical force-sensitive group is combined with a diacrylidine group. The force-sensitive group imparts force-sensitive properties to the material, and the universal crosslinking properties of the diacrylidine group expand the range of commercial polymers that the crosslinking agent can crosslink. (2) This invention prepares a general-purpose polymeric crosslinking agent based on the combination of a mechanosensitive group and the crosslinking function of bisacrylidine through a simple esterification reaction. It is not only simple to operate, but also easy to synthesize. (3) This invention can crosslink various commercial polymers through the universal crosslinking function of bisacrylidine; (3) The present invention uses a solution blending method to prepare commercially available force-sensitive polymer materials. The process is simple and easy to scale up. By controlling the content of the force-sensitive crosslinking agent, the mechanical properties of the material can be flexibly adjusted to meet the needs of different application scenarios. Attached Figure Description

[0018] Figure 1 The present invention provides a preparation route for a general polymeric crosslinking agent using spiropyran, rhodamine, 1,2-dioxane, spiroxazine, maleimide, spirothiran, azobenzene, and difluorenylsuccinate as the mechanosensitive groups, and spiropyran as an example. Figure 2 The proton NMR spectrum prepared in Example 1; Figure 3 The manufacturer, model, and structure of the commercial polymer prepared in Example 2; Figure 4 The molecular weight distribution of the commercial polymers prepared in Example 2 with different crosslinking agent contents is shown in the figure. Figure 5 Gel chromatograms of molecular weight distribution of commercial polymers prepared in Example 2 with different crosslinking agent contents; Among them, (a) PMMA-PnBA-PMMA; (b) SBS; (c) SIS; (d) EVA; (e) PU; (f) SEBS; (g) PS; (h) EPDM; Figure 6Stress-strain curves of various polymer films prepared in Example 2; Figure 7 The graph shows the color changes of various polymer films prepared in Example 2 during the stretching process; Figure 8 The graphs show the color changes of various polymer films prepared in Example 2 under different pressures. Figure 9 The color change diagram of three types of PMMA-PnBA-PMMA (LA2140, LA2330, LA4285) films with a crosslinking agent content of 1wt% prepared in Example 2 during the stretching process; Among them, (a) LA2140; (b) LA2330; (c) LA4285; Figure 10 The graph shows the correspondence between the ABAQUS finite element simulation results and the color change during the stretching process of the PMMA-PnBA-PMMA (LA2330 model) film with a crosslinking agent content of 1 wt% prepared in Example 2. Figure 11 This image shows the application method and effect diagram of a general-purpose polymer crosslinking agent based on the crosslinking function of a force-sensitive group and bisacrylidine. Detailed Implementation

[0019] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. 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.

[0020] This invention discloses a general-purpose polymer crosslinking agent based on the combination of a mechanosensitive group and the crosslinking function of bisacrylidine. The crosslinking agent is prepared by esterification of the mechanosensitive group and the bisacrylidine group.

[0021] Crosslinking agents can be obtained by crosslinking various commercial polymer systems, thereby achieving the purpose of introducing mechanosensitive groups into commercial polymers; The commercial polymer systems include: unsaturated polymers, SIS, styrene-butadiene rubber (SBS), polyethylene-ethylene acetate (EVA), polyurethane (PU), polylactic acid (PLA), polycaprolactone (PCL), polyimide (PI), epoxy resin (ER), polyacrylamide (PAM), and any one of saturated polymers, polyolefins (PO), polystyrene (PS), polydimethylsiloxane (PDMS), and polyvinyl alcohol (PVA).

[0022] The sensitizing groups include, but are not limited to, spiropyran, rhodamine, 1,2-dioxane, spiroxazine, and anthracene.

[0023] The preparation method of a crosslinked commercial polymer with force-sensitive function includes the following steps: Dissolve 1.0 g of the commercial polymer in 10 mL of tetrahydrofuran (THF) and stir until completely dissolved; Meanwhile, under similar conditions, ethylene propylene rubber (EPDM) and polyolefin elastomer (POE) were dissolved in 10 mL of toluene, and the dissolution process was carried out at 60 °C. After the polymer is completely dissolved, a crosslinking agent with a concentration of 1.0 wt% is added to the polymer solution. After vortex mixing, an oil pump is used to degas the air bubbles in the polymer solution, and then the degassed solution is poured into a 3 cm × 5 cm polytetrafluoroethylene (PTFE) mold. The solvent was evaporated at room temperature for 24 hours to remove most of the solvent, and then vacuum dried for 6 hours to completely remove the residual solvent. The solvent-free polymer film was then heated at 100 °C for 24 hours under nitrogen atmosphere to generate the corresponding cross-linked polymer film.

[0024] This invention also discloses a method for preparing a universal polymeric crosslinking agent based on the combination of a mechanosensitive group and the crosslinking function of bisacrylidine, comprising the following steps: Step 1: Under nitrogen atmosphere, 0.5 mmol of a hydroxyl group, 345 mg (1.5 mmol) of 4-[3-(trifluoromethyl)diazonyl-3-yl]benzoic acid, 183 mg (1.5 mmol) of 4-dimethylaminopyridine (DMAP), and 767 mg (4.0 mmol) of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC-HCl) were reacted in anhydrous dichloromethane. The reaction was carried out in anhydrous dichloromethane under nitrogen atmosphere for 24 hours.

[0025] Step 2: After the reaction is complete, the resulting mixture is extracted three times with deionized water. The resulting mixture is then purified by column chromatography on a silica gel column using a dichloromethane:petroleum ether mixed eluent, and the final product is obtained after evaporation to dryness.

[0026] The present invention also discloses the application of a general polymeric force-sensitive crosslinking agent based on the combination of force-sensitive groups and the crosslinking function of bisacrylidine. The material exhibits visible optical changes when subjected to stress through the force-sensitive function.

[0027] The material exhibits stable optical properties during stretching.

[0028] When a material is stretched under defective conditions, the stress distribution on the material is revealed through optical changes.

[0029] Example 1: Preparation of a general-purpose polymer force-sensitive crosslinking agent, taking spiropyran as an example 191 mg (0.5 mmol) spiropyran (SP), 345 mg (1.5 mmol) 4-[3-(trifluoromethyl)diazonyl-3-yl]benzoic acid, 183 mg (1.5 mmol) 4-dimethylaminopyridine (DMAP) and 767 mg (4.0 mmol) 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC-HCl) were reacted in anhydrous dichloromethane under a nitrogen atmosphere for 24 hours. After the reaction, the resulting mixture was extracted three times with deionized water. The resulting mixture was then purified by column chromatography on a silica gel column using a dichloromethane:petroleum ether eluent at a ratio of 10:3 (v / v). After evaporation to dryness, a purple solid was obtained as the final product, with a yield of approximately 43%. Figure 1-2 As shown.

[0030] Example 2: Preparation of commercially available polymer films with force-sensitive functions by solvent method 1.0 g of the commercial polymer was dissolved in 10 mL of tetrahydrofuran (THF) and stirred until completely dissolved. Simultaneously, ethylene propylene diene monomer (EPDM) and polyolefin elastomer (POE) were dissolved in 10 mL of toluene under similar conditions at 60 °C.

[0031] After the polymer is completely dissolved, a crosslinking agent with a concentration of 1.0 wt% is added to the polymer solution to ensure that it is completely dispersed in the solution.

[0032] After vortex mixing, the air bubbles in the polymer solution are degassed using an oil pump, and then the degassed solution is poured into a 3 cm × 5 cm polytetrafluoroethylene (PTFE) mold. The solvent is evaporated at room temperature for 24 hours to remove most of the solvent, and then vacuum dried for 6 hours to completely remove the residual solvent.

[0033] The solvent-free polymer film was then heated at 100 °C for 24 hours under nitrogen atmosphere to generate the corresponding cross-linked polymer film, such as... Figure 3-5 As shown.

[0034] Application Example 1: Uniaxial tensile tests were conducted on various commercial polymer films prepared in Example 2 with a 1 wt% crosslinking agent content. The results are as follows: Figure 6-8 As shown.

[0035] Application Example 2: The color changes of three types of PMMA-PnBA-PMMA films (LA2140, LA2330, and LA4285) with 1 wt% crosslinking agent content prepared in Example 2 during the stretching process were analyzed using RGB colorimetry to establish a quantitative relationship between color and stress. The results are as follows: Figure 9 As shown.

[0036] Application Example 3: The PMMA-PnBA-PMMA (LA2330 type) film prepared in Example 2 with a 1wt% crosslinking agent content was cut into rectangular films with a size of 4cm × 2cm, and a circular hole with a diameter of 1.2cm was made in the middle. The prepared samples were subjected to uniaxial tensile tests, and a quantitative relationship was established between the RGB values ​​of the color change at different positions and the tensile strain. At the same time, stress finite element simulation was performed using ABAQUS, and the stress simulation results were correlated with the tensile color change. The results are as follows. Figure 10 As shown.

[0037] in, Figure 11 This image shows the application method and effect diagram of a general-purpose polymer crosslinking agent based on the crosslinking function of a force-sensitive group and bisacrylidine.

[0038] The above description is merely a preferred embodiment of the present invention and does not constitute any limitation on the technical scope of the present invention. Therefore, any minor modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention shall still fall within the scope of the technical solution of the present invention.

Claims

1. A universal polymeric crosslinking agent based on the combination of a mechanosensitive group and the crosslinking function of bisacrylidine, characterized in that, The crosslinking agent is prepared by esterification of a methionine group with a diazinon group.

2. The universal polymeric crosslinking agent based on the combination of a mechanosensitive group and the crosslinking function of bisacrididine according to claim 1, characterized in that, The crosslinking agent can be obtained by crosslinking various commercial polymer systems, thereby achieving the purpose of introducing mechanistic groups into commercial polymers; The commercial polymer system includes any one of the following: unsaturated polymers, SIS, styrene-butadiene rubber (SBS), polyethylene-ethylene acetate (EVA), polyurethane (PU), polylactic acid (PLA), polycaprolactone (PCL), polyimide (PI), epoxy resin (ER), polyacrylamide (PAM), and saturated polymers, polyolefins (PO), polystyrene (PS), polydimethylsiloxane (PDMS), and polyvinyl alcohol (PVA).

3. The universal polymeric crosslinking agent based on the combination of a mechanosensitive group and the crosslinking function of bisacrididine according to claim 1, characterized in that, The sensitizing group includes any one of spiropyran, rhodamine, 1,2-dioxane, spiroxazine, and anthraceneyne.

4. The universal polymeric crosslinking agent based on the combination of a mechanosensitive group and the crosslinking function of bisacrididine according to claim 1, characterized in that, The method for preparing the crosslinked commercial polymer with force-sensitive function includes the following steps: Dissolve 1.0 g of the commercial polymer in 10 mL of tetrahydrofuran (THF) and stir until completely dissolved; Meanwhile, under similar conditions, ethylene propylene rubber (EPDM) and polyolefin elastomer (POE) were dissolved in 10 mL of toluene, and the dissolution process was carried out at 60 °C. After the polymer is completely dissolved, a crosslinking agent with a concentration of 1.0 wt% is added to the polymer solution. After vortex mixing, an oil pump is used to degas the air bubbles in the polymer solution, and then the degassed solution is poured into a 3 cm × 5 cm polytetrafluoroethylene (PTFE) mold. The solvent was evaporated at room temperature for 24 hours to remove most of the solvent, and then vacuum dried for 6 hours to completely remove the residual solvent. The solvent-free polymer film was then heated at 100 °C for 24 hours under nitrogen atmosphere to generate the corresponding cross-linked polymer film.

5. A method for preparing a universal polymeric crosslinking agent based on the combination of a mechanosensitive group and the crosslinking function of bisacrylidine, characterized in that, Includes the following steps: Step 1: Under nitrogen atmosphere, react the sensitizing group, 4-[3-(trifluoromethyl)diazonyl-3-yl]benzoic acid, 4-dimethylaminopyridine (DMAP) and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC-HCl) in anhydrous dichloromethane; Step 2: After the reaction is complete, the mixture is extracted three times with deionized water. The mixture is then purified by column chromatography on a silica gel column using a mixture of dichloromethane and petroleum ether as eluent. After evaporation, the final product is obtained.

6. The method for preparing a universal polymeric crosslinking agent based on the combination of a mechanosensitive group and the crosslinking function of bisacrylidine according to claim 5, characterized in that, In step 1, under a nitrogen atmosphere, 0.5 mmol of a lysinic group, 345 mg of 1.5 mmol of 4-[3-(trifluoromethyl)diazonyl-3-yl]benzoic acid, 183 mg of 1.5 mmol of 4-dimethylaminopyridine (DMAP), and 767 mg of 4.0 mmol of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC-HCl) are reacted in anhydrous dichloromethane.

7. The method for preparing a universal polymeric crosslinking agent based on the combination of a mechanosensitive group and the crosslinking function of bisacrylidine according to claim 5, characterized in that, In step 1, the reaction is carried out in anhydrous dichloromethane under nitrogen atmosphere for 24 hours.

8. An application of a general-purpose polymeric crosslinking agent based on the combination of a mechanosensitive group and the crosslinking function of bisacrylidine, characterized in that, The material exhibits visible optical changes when subjected to stress through a force-sensitive function.

9. The application of a general-purpose polymeric crosslinking agent based on the combination of a mechanosensitive group and the crosslinking function of bisacrididine according to claim 8, characterized in that, The material exhibits stable optical change properties during stretching.

10. The application of a general-purpose polymeric crosslinking agent based on the combination of a mechanosensitive group and the crosslinking function of bisacrylidine according to claim 8, characterized in that, The material is stretched under defective conditions, and the stress distribution of the material is reflected through optical changes.

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