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CN-121975068-A - Shape memory hydrogel with mechanical property and stimulus responsiveness and preparation method thereof

CN121975068ACN 121975068 ACN121975068 ACN 121975068ACN-121975068-A

Abstract

The invention discloses a shape memory hydrogel with mechanical property and stimulus response and a preparation method thereof, belonging to the technical field of shape memory hydrogels, and comprising the following raw materials, by weight, 20-25 parts of functional monomer UPyMA, 3-5 parts of maleic anhydride modified poly (vinyl alcohol-co-ethylene), 5-8 parts of dimethylaminoethyl methacrylate, 1-1.5 parts of composite reinforcing phase, 1.5-2 parts of polyethylene glycol diacrylate cross-linking agent, 0.6-0.8 part of ammonium persulfate initiator and 0.1-0.2 part of DMA (direct memory) accelerator. Through the mode, the shape memory hydrogel prepared by the invention has both mechanical properties and stimulus responsiveness.

Inventors

  • ZHANG HONGJI
  • XIE YU
  • LI YONGWEN

Assignees

  • 江南大学
  • 江苏德纳化学股份有限公司

Dates

Publication Date
20260505
Application Date
20260312

Claims (8)

  1. 1. The shape memory hydrogel with both mechanical properties and stimulus responsiveness is characterized by comprising, by weight, 20-25 parts of functional monomers UPyMA, 3-5 parts of maleic anhydride modified poly (vinyl alcohol-co-ethylene), 5-8 parts of dimethylaminoethyl methacrylate, 1-1.5 parts of a composite reinforcing phase, 1.5-2 parts of a polyethylene glycol diacrylate cross-linking agent, 0.6-0.8 part of an ammonium persulfate initiator and 0.1-0.2 part of a DMA (direct memory access) accelerator.
  2. 2. The shape memory hydrogel with both mechanical properties and stimulus responsiveness and preparation method according to claim 1, wherein the preparation method of the maleic anhydride modified poly (vinyl alcohol-co-ethylene) comprises the following steps: (1.1) adding 6-10 parts of dried poly (vinyl alcohol-co-ethylene) into 50 mL anhydrous DMF under the protection of nitrogen, and stirring at 60-70 ℃ until the poly (vinyl alcohol-co-ethylene) is completely dissolved to obtain a component A; (1.2) weighing 0.5-0.7 part of maleic anhydride, adding the maleic anhydride into 15-24 mL anhydrous DMF, stirring and dissolving, and then adding 0.05-0.08 part of p-toluenesulfonic acid catalyst to prepare a component B; (1.3) slowly adding the component B into the component A at the dropping speed of 0.5-1 mL/min, heating to 75-80 ℃ after the dropping is completed, and reacting for 3-5h while keeping nitrogen gas to be introduced; And (1.4) after the reaction is finished, naturally cooling to room temperature, pouring the reaction solution into absolute ethyl alcohol with the volume of 6-8 times for precipitation, standing for 0.5-1h, carrying out suction filtration, collecting the precipitate, washing the precipitate with absolute ethyl alcohol for 3-4 times, and carrying out vacuum drying to obtain the catalyst.
  3. 3. The shape memory hydrogel of claim 2, wherein the poly (vinyl alcohol-co-ethylene) has an ethylene content of 10-15% and a hydroxyl content of 85-90%.
  4. 4. The shape memory hydrogel with both mechanical properties and stimulus responsiveness of claim 3, wherein the preparation method of the composite reinforcement phase comprises the steps of: (2.1) adding 10-12 parts of carboxymethyl guar gum, 4-6 parts of sulfonated lignin and 1-2 parts of hydroxypropyl cellulose into 80 mL anhydrous acetone, and stirring at 35-42 ℃ for 30-40min to form a uniform suspension; (2.2) heating the suspension to 45-50 ℃, adding DBTDL, stirring for 10-15min, adding IPDI diluted by anhydrous acetone, and stirring and reacting for 1.5-2h under the conditions of constant temperature of 45-50 ℃ and rotation speed of 400-500 r/min; (2.3) recovering anhydrous acetone by reduced pressure distillation of the reaction solution, and drying the residual product to obtain the composite reinforced powder.
  5. 5. The shape memory hydrogel with both mechanical properties and stimulus responsiveness of claim 4, wherein the mass of DBTDL is 1-1.2% of the mass of IPDI.
  6. 6. The shape memory hydrogel with both mechanical properties and stimulus responsiveness according to claim 5, wherein the mass of IPDI is 10-15% of the total mass of CMG, SL and HPC, and the IPDI is diluted with anhydrous acetone in a volume ratio = 1:1.
  7. 7. A method of preparing a shape memory hydrogel having both mechanical properties and stimulus responsiveness according to claim 6, comprising the steps of: 1. The preparation method comprises the steps of pre-treating composite reinforcing powder, namely placing the composite reinforcing powder into a cavity of a plasma treatment instrument, vacuumizing to a background pressure of less than 1 Pa, introducing Ar and N 2 mixed gas for plasma treatment, wherein the plasma power is 30-40W, the mixed gas flow is 15-20 sccm, and the treatment time is 1-2min; 2. dissolving a functional monomer UPyMA in 200-500mL anhydrous DMSO at 55-60 ℃, and stirring until the functional monomer is completely dissolved to obtain a basic solution; 3. adding dimethylaminoethyl methacrylate and a PVA-co-PE hydrophilic-hydrophobic copolymer modified by maleic anhydride into the basic solution, and magnetically stirring for 20-30min at 55-60 ℃ to form a uniform solution; 4. Slowly adding the pretreated composite reinforcing phase DMSO dispersion liquid into the uniform solution, stirring while adding, and continuing stirring for 30-40min after adding; 5. Sequentially adding a polyethylene glycol diacrylate crosslinking agent and a DMA (direct memory access) accelerator, and magnetically stirring for 15-20min; 6. Then adding ammonium persulfate initiator, stirring for 5-10min, transferring the obtained mixture to a polytetrafluoroethylene mould, and reacting for 4-6h at 45-50 ℃; 7. And after the reaction is finished, taking out the product, soaking the product in deionized water for 24-48 hours, replacing the deionized water every 6 hours, and removing the residual solvent and unreacted monomers to obtain the target shape memory hydrogel.
  8. 8. A shape memory hydrogel having both mechanical properties and stimulus responsiveness prepared according to the method of claim 7.

Description

Shape memory hydrogel with mechanical property and stimulus responsiveness and preparation method thereof Technical Field The invention relates to the technical field of shape memory hydrogels, in particular to a shape memory hydrogel with mechanical properties and stimulus responsiveness and a preparation method thereof. Background Acid gas and alkaline gas widely exist in chemical production, environmental emission and other scenes, leakage of the acid gas and the alkaline gas not only aggravates environmental problems such as acid rain and haze, but also directly damages human health, such as irritation to respiratory tract mucous membrane, and high-concentration exposure can even cause fatal damage such as pulmonary edema. Because the gas is easy to diffuse rapidly and difficult to visually perceive in the early stage of leakage, the development of a novel technology capable of realizing rapid and visual detection of acid-base gas has great significance for environmental protection, industrial safety early warning and human health safety protection. Electrochemical methods based on metal oxides and porphyrins are widely used for the detection of acidic or basic gases, however, these techniques tend to exhibit low selectivity, which limits their effectiveness in complex environments. Compared with the fluorescent probe, the fluorescent probe realizes the rapid optical sensing of volatile acid-base gas by virtue of high selectivity and sensitivity and through solid-state platforms such as mesoporous silica, hydrogel and the like. However, such sensors rely heavily on optical readings, presenting significant difficulties in visual identification of micro or sudden gas leaks, limiting their reliability in real-time on-site monitoring. Based on the above, the invention designs the shape memory hydrogel with mechanical property and stimulus response and the preparation method thereof to solve the problems. Disclosure of Invention Aiming at the defects existing in the prior art, the invention provides the shape memory hydrogel with mechanical property and stimulus responsiveness and a preparation method thereof. In order to achieve the above purpose, the invention is realized by the following technical scheme: The shape memory hydrogel with mechanical property and stimulus response comprises the following raw materials, by weight, 20-25 parts of functional monomer UPyMA, 3-5 parts of poly (vinyl alcohol-co-ethylene) modified by maleic anhydride, 5-8 parts of dimethylaminoethyl methacrylate, 1-1.5 parts of composite reinforcing phase, 1.5-2 parts of polyethylene glycol diacrylate cross-linking agent, 0.6-0.8 part of ammonium persulfate initiator and 0.1-0.2 part of DMA (direct memory access) accelerator. Further, the preparation method of the poly (vinyl alcohol-co-ethylene) modified by maleic anhydride comprises the following steps: (1.1) adding 6-10 parts of dried poly (vinyl alcohol-co-ethylene) into 50 mL anhydrous DMF under the protection of nitrogen, and stirring at 60-70 ℃ until the poly (vinyl alcohol-co-ethylene) is completely dissolved to obtain a component A; (1.2) weighing 0.5-0.7 part of maleic anhydride, adding the maleic anhydride into 15-24 mL anhydrous DMF, stirring and dissolving, and then adding 0.05-0.08 part of p-toluenesulfonic acid catalyst to prepare a component B; (1.3) slowly adding the component B into the component A at the dropping speed of 0.5-1 mL/min, heating to 75-80 ℃ after the dropping is completed, and reacting for 3-5h while keeping nitrogen gas to be introduced; And (1.4) after the reaction is finished, naturally cooling to room temperature, pouring the reaction solution into absolute ethyl alcohol with the volume of 6-8 times for precipitation, standing for 0.5-1h, carrying out suction filtration, collecting the precipitate, washing the precipitate with absolute ethyl alcohol for 3-4 times, and carrying out vacuum drying to obtain the catalyst. Further, in the poly (vinyl alcohol-co-ethylene), the ethylene content is 10-15% and the hydroxyl content is 85-90%. Further, the preparation method of the composite reinforcing phase comprises the following steps: (2.1) adding 10-12 parts of carboxymethyl guar gum, 4-6 parts of sulfonated lignin and 1-2 parts of hydroxypropyl cellulose into 80 mL anhydrous acetone, and stirring at 35-42 ℃ for 30-40min to form a uniform suspension; (2.2) heating the suspension to 45-50 ℃, adding DBTDL, stirring for 10-15min, adding IPDI diluted by anhydrous acetone, and stirring and reacting for 1.5-2h under the conditions of constant temperature of 45-50 ℃ and rotation speed of 400-500 r/min; (2.3) recovering anhydrous acetone by reduced pressure distillation of the reaction solution, and drying the residual product to obtain the composite reinforced powder. Further, the DBTDL mass is 1-1.2% of the IPDI mass. Further, the mass of the IPDI is 10-15% of the total mass of the CMG, the SL and the HPC, and the IPDI is diluted by anhydrous acetone accord