A high-strength collagen matrix multifunctional organic hydrogel and its preparation method

Abstract

The present invention discloses a preparation method of a high-strength collagen matrix multifunctional organic hydrogel. The collagen matrix is obtained by using leather preparation technology. Then, an organic solvent, a metal salt, an amphoteric ion compound, an ionic liquid, and metal nanoparticles are added to water to obtain a mixed solution. Subsequently, the collagen matrix and the mixed solution are added to a rotary drum, allowed to stand after reaction, and then the rotary drum is rotated continuously and dried to obtain the high-strength collagen matrix multifunctional organic hydrogel. The high-strength collagen matrix multifunctional organic hydrogel prepared by the present invention has excellent mechanical properties, puncture resistance, moisture retention, moisture regain, antibacterial properties, cold resistance, heat resistance, and stimulation response characteristics, can effectively sense changes in environmental temperature and humidity, and monitor physiological signals of the human body, and has great application potential and prospects in wearable electronic devices, human-computer interaction, and artificial intelligence.

Description

Technical Field

[0001] The present invention belongs to the technical field of hydrogel preparation, and particularly relates to a high-strength collagen matrix multifunctional organic hydrogel and a preparation method thereof. Background Art

[0002] Flexible electronic devices have broad application prospects, including applications in wearable sensors, energy storage devices, actuators, and soft robots, and thus have received increasing attention. Due to the stretchable three-dimensional polymer network and the aqueous environment for ion transport, electronic skins based on conductive hydrogels can convert external stimuli (such as strain or pressure) into detectable electrical signals. The conductivity of hydrogels can be obtained through electronic conduction, ion conduction, and electron-ion conduction. Some functional materials have been incorporated into the polymer network to design conductive hydrogels, including conductive polymers, metal ions, ionic liquids, and carbon nanotubes. Among them, ion-conductive hydrogels have attracted great attention due to their characteristics such as easy fabrication, low cost, and high conductivity.

[0003] From the perspective of practical applications, electronic skins not only need to have high conductivity, but also stretchability, high mechanical strength, and toughness to withstand relatively heavy mechanical loads. Although conductive hydrogels have solid-like properties due to the presence of a polymer network and fast ion transport in the liquid state, the applications of these materials are limited due to their relatively weak mechanical strength. Currently, hydrogels with high mechanical properties can only be prepared by microstructural adjustment or using synthetic polymers. In addition, another application challenge of traditional conductive hydrogels is poor water retention and freezing at lower temperatures. Specifically, hydrogels will dehydrate when exposed to environmental conditions for a short time, which greatly limits their applications under various environmental conditions. At the same time, when the environmental temperature is below the freezing point, the water molecules in the traditional conductive hydrogel network will even crystallize, thus severely limiting its application due to the reduction in flexibility and conductivity. Therefore, it is very necessary to develop hydrogel electronic skins that simultaneously have various properties such as good mechanical properties, conductivity, biocompatibility, water retention, cold resistance, and heat resistance. Summary of the Invention

[0004] The purpose of the present invention is to provide a preparation method of a high-strength collagen matrix multifunctional organic hydrogel, and this hydrogel has excellent mechanical properties, water retention, and stimulus response characteristics.

[0005] The technical solution adopted by the present invention is a method for preparing a high-strength collagen matrix multifunctional organic hydrogel. A collagen matrix is obtained by using leather preparation technology, and then an organic solvent, a metal salt, an amphoteric ion compound, an ionic liquid, and metal nanoparticles are added to water to obtain a mixed solution. Then, the collagen matrix and the mixed solution are added to a rotary drum, allowed to react and stand still, and then the rotary drum is rotated continuously and dried to obtain the high-strength collagen matrix multifunctional organic hydrogel.

[0006] The features of the present invention also lie in that

[0007] It is specifically implemented according to the following steps:

[0008] Step 1: Prepare a collagen matrix material;

[0009] Step 2: Prepare a high-strength collagen matrix multifunctional organic hydrogel, specifically:

[0010] Step 2.1, add 10.0 - 300.0 parts by mass of an organic solvent, 0.1 - 25.0 parts by mass of a metal salt, 0.1 - 50.0 parts by mass of an amphoteric ion compound, 0.1 - 50.0 parts by mass of an ionic liquid, and 0.1 - 10.0 parts by mass of metal nanoparticles to 10.0 - 500.0 parts by mass of water, continuously stir at room temperature for 1.0 h to obtain a mixed solution, and adjust the pH of the system to 2.5 - 6.5 with hydrochloric acid;

[0011] Step 2.2, add 10.0 - 150.0 parts by mass of the collagen matrix and the prepared mixed solution to a rotary drum, rotate at room temperature for 6.0 h and then stand still for 12.0 h, then continue to rotate at room temperature for 0.5 h, then take out the collagen matrix and dry it at room temperature for 2.0 h, and dry it at 25 - 50 °C for 1 - 12.0 h to obtain the high-strength collagen matrix multifunctional organic hydrogel.

[0012] In Step 1, specifically:

[0013] Step 1.1, mix fresh skin, water, sodium hypochlorite, and sodium hydroxide, add them to a leather drum, and run at 25 °C for 12 h to remove dirt on the skin and dissolve some soluble proteins on the skin;

[0014] The fresh skin is any one of sheepskin, pigskin, cowhide, and horsehide;

[0015] Step 1.2, mix fresh skin, water, and sodium carbonate, and add them to a roller, and run at 38 °C for 2 h to remove some sebum;

[0016] Step 1.3, mix fresh skin, water, and sodium sulfide, add them to a rotary drum, run at 25 °C for 1.5 h, and then continue to add sodium hydroxide and run at 25 °C for 6 h to remove the hair on the skin.

[0017] Step 1.4: Mix fresh skin, water and calcium hydroxide, add them into a drum, and run for 18 h at 25 °C to further disperse collagen fibers, remove fiber matrix, saponify grease, remove hair and epidermis;

[0018] Step 1.5: Mix fresh skin, water and lactic acid, add them into a drum, and run for 1 h at 30 °C to adjust the swelling state of the skin;

[0019] Step 1.6: Mix fresh skin, water, trypsin, protease, ammonium chloride, add them into a drum, and run for 1 h at 28 °C to further remove epidermis, hair roots, pigments, grease, elastin, myosin, etc., and disperse collagen fibers;

[0020] Step 1.7: Mix water and sodium chloride to prepare pickling solution, adjust its pH value to 5.0 with hydrochloric acid, then add fresh skin and pickling solution into a rotary drum, and run for 6 h at 25 °C. After standing overnight, collagen matrix material is obtained.

[0021] In Step 2, the organic solvent is one or more of methanol, ethanol, ethylene glycol, propanol, propylene glycol, and glycerol; the metal salt is one or more of NaCl, KCl, LiCl, MgCl2, CaCl2, and AlCl3.

[0022] In Step 2, the zwitterionic compound is one or more of betaine, dimethylglycine, alanine, sarcosine, and L-proline.

[0023] In Step 2, the ionic liquid is one or more of 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium acetate, 1,3-dimethylimidazolium iodide, 1,3-dimethylimidazolium methyl sulfate, 1,3-dimethylimidazolium trifluoroacetate, and 1-ethyl-3-methylimidazolium ethyl sulfate.

[0024] In Step 2, the metal nanoparticles are one or more of gold nanoparticles, silver nanoparticles, amino-functionalized gold nanoparticles, carboxyl-functionalized gold nanoparticles, sulfonated gold nanoparticles, amino-functionalized silver nanoparticles, carboxyl-functionalized silver nanoparticles, and sulfonated silver nanoparticles.

[0025] The beneficial effects of the present invention are as follows:

[0026] (1) The collagen matrix raw material used in the present invention is derived from animals, has the advantages of low price, renewable and biodegradable, can replace some synthetic materials, thus effectively saving fossil resources and protecting the ecological environment;

[0027] (2) The high-strength collagen matrix multifunctional organic hydrogel prepared by the present invention has excellent mechanical properties, puncture resistance, moisture retention, moisture regain, antibacterial properties, cold resistance, heat resistance, and stimulus response characteristics. It can effectively sense changes in environmental temperature and humidity, as well as monitor human physiological signals, and has great application potential and prospects in wearable electronic devices, human-computer interaction, and artificial intelligence. In addition, the method is simple to operate and the conditions are mild. Description of the Drawings

[0028] Figure 1 It is a photograph of the appearance of the high-strength collagen matrix multifunctional organic hydrogel prepared in Example 1.

[0029] Figure 2 It is a scanning electron microscope image of the top-layer goatskin prepared in Example 1;

[0030] Figure 3 It is a scanning electron microscope image of the high-strength collagen matrix multifunctional organic hydrogel prepared in Example 1;

[0031] Figure 4 It is a graph of the real-time current change of the high-strength collagen matrix multifunctional organic hydrogel prepared in Example 1 at different environmental temperatures;

[0032] Figure 5 It is a graph of the real-time current change of the high-strength collagen matrix multifunctional organic hydrogel prepared in Example 1 at different environmental humidities;

[0033] Figure 6 It is a graph of the real-time resistance change of the high-strength collagen matrix multifunctional organic hydrogel prepared in Example 1 at different finger bending angles. Detailed Description of the Invention

[0034] The present invention will be described in detail below with reference to the drawings and specific embodiments.

[0035] A method for preparing a high-strength collagen matrix multifunctional organic hydrogel of the present invention, first, a collagen matrix material is obtained by using leather preparation technology, and then an organic solvent, a metal salt, an amphoteric ionic compound, an ionic liquid, and metal nanoparticles are added to water to obtain a mixed solution. Then, the collagen matrix and the mixed solution are added to a drum, reacted for a period of time and then left to stand, the drum is rotated for a further period of time, and then the collagen matrix is taken out and dried at room temperature to obtain a high-strength collagen matrix multifunctional organic hydrogel.

[0036] Specifically, it is implemented according to the following steps:

[0037] Step 1: Prepare the collagen matrix material, specifically:

[0038] Step 1.1, Mix fresh skin, water, sodium hypochlorite and sodium hydroxide, add them into a leather drum, and run at 25 °C for 12 h to remove dirt on the skin and dissolve some soluble proteins on the skin;

[0039] The mass of sodium hypochlorite is 1.0% of the mass of fresh skin; the mass of sodium hydroxide is 0.1% of the mass of fresh skin, and the mass of water is 4 times the mass of fresh skin;

[0040] The fresh skin is any one of sheepskin, pigskin, cowhide, and horsehide;

[0041] Step 1.2, Mix fresh skin, water and sodium carbonate, and add them into a roller, and run at 38 °C for 2 h to remove some sebum;

[0042] The mass of sodium hypochlorite is 4.0% of the mass of fresh skin;

[0043] Step 1.3, Mix fresh skin, water and sodium sulfide, add them into a rotary drum, and run at 25 °C for 1.5 h. Then, continue to add sodium hydroxide and run at 25 °C for 6 h to remove hair on the skin;

[0044] The mass of sodium sulfide is 1.0% of the mass of fresh skin; the mass of sodium hydroxide is 0.09% of the mass of fresh skin,

[0045] Step 1.4, Mix fresh skin, water and calcium hydroxide, add them into a roller, and run at 25 °C for 18 h to further disperse collagen fibers, remove fiber matrix, saponify grease, remove hair and epidermis;

[0046] Step 1.5, Mix fresh skin, water and lactic acid, add them into a roller, and run at 30 °C for 1 h to adjust the swelling state of the skin;

[0047] The mass of lactic acid is 1.0% of the mass of fresh skin;

[0048] Step 1.6, Mix fresh skin, water, trypsin, protease, and ammonium chloride, add them into a roller, and run at 28 °C for 1 h to further remove epidermis, hair roots, pigments, grease, elastin, myosin, etc., and disperse collagen fibers;

[0049] The mass of trypsin is 0.15% of the mass of fresh skin; the mass of protease is 0.05% of the mass of fresh skin; the mass of ammonium chloride is 0.5% of the mass of fresh skin;

[0050] Step 1.7, Mix water and sodium chloride to prepare pickling liquor, adjust its pH value to 5.0 with hydrochloric acid, then add fresh skin and pickling liquor into a rotary drum, and run at 25 °C for 6 h. After standing overnight, collagen matrix material is obtained;

[0051] The mass of sodium chloride is 8.0% of the mass of water;

[0052] Step 2. Prepare a high-strength collagen matrix multifunctional organic hydrogel, specifically as follows:

[0053] Step 2.1. Add 10.0 - 300.0 parts by mass of an organic solvent, 0.1 - 25.0 parts by mass of a metal salt, 0.1 - 50.0 parts by mass of an amphoteric ion compound, 0.1 - 50.0 parts by mass of an ionic liquid, and 0.1 - 10.0 parts by mass of metal nanoparticles to 10.0 - 500.0 parts by mass of water. Continuously stir for 1.0 h at room temperature to obtain a mixed solution, and adjust the pH of the system to 2.5 - 6.5 with hydrochloric acid;

[0054] The organic solvent is one or more of methanol, ethanol, ethylene glycol, propanol, propylene glycol, and glycerol;

[0055] The metal salt is one or more of NaCl, KCl, LiCl, MgCl2, CaCl2, and AlCl3;

[0056] The amphoteric ion compound is one or more of betaine, dimethylglycine, alanine, sarcosine, and L-proline;

[0057] The ionic liquid is one or more of 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium acetate, 1,3-dimethylimidazolium iodide, 1,3-dimethylimidazolium methyl sulfate, 1,3-dimethylimidazolium trifluoroacetate, and 1-ethyl-3-methylimidazolium ethyl sulfate;

[0058] The metal nanoparticles are one or more of gold or silver nanoparticles and their amino-modified, carboxyl-modified, and sulfonated modified products.

[0059] Step 2.2. Add 10.0 - 150.0 parts by mass of the collagen matrix and the prepared mixed solution to a rotary drum. Rotate for 6.0 h at room temperature and then let it stand for 12.0 h. Then continue to rotate for 0.5 h at room temperature, and then take out the collagen matrix and dry it at room temperature for 2.0 h and at 25 - 50 °C for 1 - 12.0 h to obtain a high-strength collagen matrix multifunctional organic hydrogel.

[0060] The present invention combines the leather preparation and nanomanufacturing processes. Using natural animal skin with a hierarchical structure and a three-dimensional network structure as the substrate, functional fillers and organic solvents are introduced to prepare a multifunctional organic hydrogel. The natural animal skin can endow the hydrogel with extremely strong mechanical properties; the functional fillers can enhance the interaction between collagen fibers and endow the hydrogel with good electrical conductivity, sensing performance, antibacterial performance, cold resistance performance, etc.; the organic solvent can greatly improve the moisture retention performance and cold resistance performance of the hydrogel.

[0061] Example 1

[0062] Step 1: Prepare a collagen matrix material;

[0063] Step 1.1: Add fresh goat skin and a solution containing 100.0 wt% (calculated based on 4.0 times the weight of the fresh skin, the same below) water, 1.0 wt% sodium hypochlorite, and 0.1 wt% sodium hydroxide into a leather drum, and run it at 25 °C for 12 h to remove dirt on the skin and dissolve some soluble proteins on the skin;

[0064] Step 1.2: Add fresh goat skin and a solution composed of 100.0 wt% water and 4.0 wt% sodium carbonate into a roller, and run it at 38 °C for 2 h to remove some sebum;

[0065] Step 1.3: Add fresh goat skin and a solution containing 100.0 wt% water and 1.0 wt% sodium sulfide into a rotating drum, and run it at 25 °C for 1.5 h. Then, continue to add 0.09 wt% sodium hydroxide and operate at 25 °C for 6 h to remove hair on the skin;

[0066] Step 1.4: Add fresh goat skin and a solution composed of 100.0 wt% water and 3.0 wt% calcium hydroxide into a roller, and run it at 25 °C for 18 h to further disperse collagen fibers, remove fiber matrix, saponify grease, remove hair and epidermis;

[0067] Step 1.5: Add fresh goat skin and a solution composed of 100.0 wt% water and 1.0 wt% lactic acid into a roller, and run it at 30 °C for 1 h to adjust the swelling state of the skin;

[0068] Step 1.6: Add fresh goat skin and a solution containing 100.0 wt% water, 0.15 wt% trypsin, 0.05 wt% protease, and 0.5 wt% ammonium chloride into a roller, and run it at 28 °C for 1 h to further remove epidermis, hair roots, pigments, grease, elastin, myosin, etc., and disperse collagen fibers;

[0069] Step 1.7: Prepare a pickling solution with 100.0 wt% water and 8.0 wt% sodium chloride, and adjust its pH value to 5.0 with hydrochloric acid. Then add fresh goat skin and the pickling solution into a rotating drum, and run it at 25 °C for 6 h. After standing overnight, a collagen matrix material is obtained, which is the top layer of goat skin;

[0070] Step 2: Prepare a high-strength collagen matrix multifunctional organic hydrogel;

[0071] Step 2.1, Add 140.0 parts by mass of glycerol, 10.0 parts by mass of LiCl, 18.0 parts by mass of betaine, 5.0 parts by mass of 1-ethyl-3-methylimidazolium chloride, and 0.5 parts by mass of carboxylated silver nanoparticles to 350.0 parts by mass of water, and continuously stir for 1.0 h at room temperature to obtain a mixed solution;

[0072] Step 2.2, Add 100.0 parts by mass of top-layer goatskin and the prepared mixed solution to a drum, rotate at room temperature for 3.0 h and then let it stand for 12.0 h; then continue to rotate the drum at room temperature for 0.5 h, and dry at room temperature for 2.0 h, and dry in an oven at 40 °C for 6.0 h to obtain a high-strength collagen matrix multifunctional organic hydrogel.

[0073] Figure 1 It is the appearance diagram of the high-strength collagen matrix multifunctional organic hydrogel prepared in Example 1. It can be seen through observation that the prepared organic hydrogel can be bent as needed, indicating its good flexibility.

[0074] Figure 2 and 3 are the scanning electron microscope diagrams of the top-layer goatskin and the high-strength collagen matrix multifunctional organic hydrogel prepared in Example 1 respectively. It can be seen through observation that the functional filler is effectively filled between the fiber structures of the goatskin.

[0075] Figure 4 It is the real-time current change diagram of the high-strength collagen matrix multifunctional organic hydrogel prepared in Example 1 at different environmental temperatures. It can be seen through observation that the current of the organic hydrogel shows regular changes with the change of environmental temperature, indicating its good electrical conductivity and temperature sensing performance.

[0076] Figure 5 It is the real-time current change diagram of the high-strength collagen matrix multifunctional organic hydrogel prepared in Example 1 at different environmental humidities. It can be seen through observation that the current of the organic hydrogel shows regular changes with the change of environmental humidity, indicating its good electrical conductivity and humidity sensing performance.

[0077] Figure 6 It is the real-time resistance change diagram of the high-strength collagen matrix multifunctional organic hydrogel prepared in Example 1 when the finger is bent at different angles. It can be seen through observation that as the finger continues to bend and the bending angle changes, the current shows cyclic and regular changes, indicating its good electrical conductivity and strain sensing performance.

[0078] Example 2

[0079] Step 1, Prepare a collagen matrix material;

[0080] Step 1.1, Add fresh yellow cowhide and a solution containing 100.0 wt% (calculated as 4.0 times the weight of the fresh hide, the same below) water, 1.0 wt% sodium hypochlorite, and 0.1 wt% sodium hydroxide into a leather drum, and run it at 25 °C for 12 h to remove dirt on the hide and dissolve some soluble proteins on the hide;

[0081] Step 1.2, Add fresh yellow cowhide and a solution composed of 100.0 wt% water and 4.0 wt% sodium carbonate into a roller, and run it at 38 °C for 2 h to remove some sebum;

[0082] Step 1.3, Add fresh yellow cowhide and a solution containing 100.0 wt% water and 1.0 wt% sodium sulfide into a rotating drum, and run it at 25 °C for 1.5 h. Then, continue to add 0.09 wt% sodium hydroxide and operate at 25 °C for 6 h to remove hair on the hide;

[0083] Step 1.4, Add fresh yellow cowhide and a solution composed of 100.0 wt% water and 3.0 wt% calcium hydroxide into a roller, and run it at 25 °C for 18 h to further disperse collagen fibers, remove fiber matrix, saponify grease, remove hair and epidermis;

[0084] Step 1.5, Add fresh yellow cowhide and a solution composed of 100.0 wt% water and 1.0 wt% lactic acid into a roller, and run it at 30 °C for 1 h to adjust the swelling state of the hide;

[0085] Step 1.6, Add fresh yellow cowhide and a solution containing 100.0 wt% water, 0.15 wt% trypsin, 0.05 wt% protease, and 0.5 wt% ammonium chloride into a roller, and run it at 28 °C for 1 h to further remove epidermis, hair roots, pigments, grease, elastin, myosin, etc., and disperse collagen fibers;

[0086] Step 1.7, Prepare pickling solution with 100.0 wt% water and 8.0 wt% sodium chloride, and adjust its pH value to 5.0 with hydrochloric acid. Then, add fresh yellow cowhide and the pickling solution into a rotating drum, and run it at 25 °C for 6 h. After standing overnight, collagen matrix material is obtained, which is split yellow cowhide;

[0087] Step 2, Prepare a high-strength collagen matrix multifunctional organic hydrogel;

[0088] Step 2.1, Add 145.0 parts by mass of ethylene glycol, 12.5 parts by mass of KCl, 20.0 parts by mass of dimethylglycine, 4.0 parts by mass of 1-ethyl-3-methylimidazolium acetate, and 0.5 parts by mass of amino-functionalized gold nanoparticles into 350.0 parts by mass of water, and continuously stir at room temperature for 1.0 h to obtain a mixed solution;

[0089] Step 2.2, Add 100.0 parts by mass of split yellow cowhide and the prepared mixed solution into a rotary drum, rotate at room temperature for 4.0 h and then let it stand for 12.0 h; continue to rotate the rotary drum at room temperature for 0.5 h, take it out and dry at room temperature for 2.0 h. Then dry it in an oven at 40 °C for 6.0 h to obtain a high-strength collagen matrix multifunctional organic hydrogel.

[0090] Example 3

[0091] Step 1: Prepare a collagen matrix material;

[0092] Step 1.1, Add fresh sheepskin and a solution containing 100.0 wt% (calculated based on 4.0 times the weight of the fresh skin, the same below) water, 1.0 wt% sodium hypochlorite, and 0.1 wt% sodium hydroxide into a leather drum, and operate at 25 °C for 12 h to remove dirt on the skin and dissolve some soluble proteins on the skin;

[0093] Step 1.2, Add fresh sheepskin and a solution composed of 100.0 wt% water and 4.0 wt% sodium carbonate into a roller, and operate at 38 °C for 2 h to remove some sebum;

[0094] Step 1.3, Add fresh sheepskin and a solution containing 100.0 wt% water and 1.0 wt% sodium sulfide into a rotary drum, and operate at 25 °C for 1.5 h. Then, continue to add 0.09 wt% sodium hydroxide and operate at 25 °C for 6 h to remove hair on the skin;

[0095] Step 1.4, Add fresh sheepskin and a solution composed of 100.0 wt% water and 3.0 wt% calcium hydroxide into a roller, and operate at 25 °C for 18 h to further disperse collagen fibers, remove fiber matrix, saponify grease, remove hair and epidermis;

[0096] Step 1.5, Add fresh sheepskin and a solution composed of 100.0 wt% water and 1.0 wt% lactic acid into a roller, and operate at 30 °C for 1 h to adjust the swelling state of the skin;

[0097] Step 1.6, Add fresh sheepskin and a solution containing 100.0 wt% water, 0.15 wt% trypsin, 0.05 wt% protease, and 0.5 wt% ammonium chloride into a roller, and operate at 28 °C for 1 h to further remove epidermis, hair roots, pigments, grease, elastin, myosin, etc., and disperse collagen fibers;

[0098] Step 1.7: Prepare the pickling solution with 100.0 wt% water and 8.0 wt% sodium chloride, and adjust its pH value to 5.0 with hydrochloric acid. Then add the fresh sheepskin and the pickling solution to the drum, and run it at 25 °C for 6 h. After standing overnight, the collagen matrix material, i.e., split sheepskin, is obtained.

[0099] Step 2: Prepare a high-strength collagen matrix multifunctional organic hydrogel.

[0100] Step 2.1: Add 150.0 parts by mass of glycerol, 15.0 parts by mass of CaCl2, 22.0 parts by mass of alanine, 4.5 parts by mass of 1-ethyl-3-methylimidazolium chloride, and 0.5 parts by mass of carboxylated silver nanoparticles to 350.0 parts by mass of water, and continuously stir at room temperature for 1.0 h to obtain a mixed solution.

[0101] Step 2.2: Add 100.0 parts by mass of split sheepskin and the prepared mixed solution to the drum, rotate at room temperature for 4.0 h and then stand for 12.0 h; continue to rotate the drum at room temperature for 0.5 h, and then dry at room temperature for 2.0 h. Then dry in an oven at 40 °C for 6.0 h to obtain a high-strength collagen matrix multifunctional organic hydrogel.

[0102] Example 4

[0103] Step 1: Prepare the collagen matrix material.

[0104] Step 1.1: Add the fresh buffalo hide and a solution containing 100.0 wt% water (calculated as 4.0 times the weight of the fresh hide, the same below), 1.0 wt% sodium hypochlorite, and 0.1 wt% sodium hydroxide to the leather drum, and run it at 25 °C for 12 h to remove the dirt on the hide and dissolve some soluble proteins on the hide.

[0105] Step 1.2: Add the fresh buffalo hide and a solution composed of 100.0 wt% water and 4.0 wt% sodium carbonate to the drum, and run it at 38 °C for 2 h to remove some sebum.

[0106] Step 1.3: Add the fresh buffalo hide and a solution containing 100.0 wt% water and 1.0 wt% sodium sulfide to the drum, and run it at 25 °C for 1.5 h. Then, continue to add 0.09 wt% sodium hydroxide and operate at 25 °C for 6 h to remove the hair on the hide.

[0107] Step 1.4: Add the fresh buffalo hide and a solution composed of 100.0 wt% water and 3.0 wt% calcium hydroxide to the drum, and run it at 25 °C for 18 h to further disperse the collagen fibers, remove the fiber matrix, saponify the grease, remove the hair and epidermis.

[0108] Step 1.5: Add fresh buffalo hide and a solution composed of 100.0 wt% water and 1.0 wt% lactic acid into a drum, and run for 1 h at 30 °C to adjust the swelling state of the hide.

[0109] Step 1.6: Add fresh buffalo hide and a solution containing 100.0 wt% water, 0.15 wt% trypsin, 0.05 wt% protease, and 0.5 wt% ammonium chloride into the drum, run for 1 h at 28 °C, further remove epidermis, hair roots, pigments, grease, elastin, myosin, etc., and disperse collagen fibers.

[0110] Step 1.7: Prepare pickling liquor with 100.0 wt% water and 8.0 wt% sodium chloride, and adjust its pH value to 5.0 with hydrochloric acid. Then add fresh buffalo hide and the pickling liquor into a rotary drum, run for 6 h at 25 °C, and let it stand overnight to obtain a collagen matrix material, which is the top layer of buffalo hide.

[0111] Step 2: Prepare a high-strength collagen matrix multifunctional organic hydrogel.

[0112] Step 2.1: Add 155.0 parts by mass of ethylene glycol, 17.5 parts by mass of AlCl3, 24.0 parts by mass of sarcosine, 5.5 parts by mass of 1-ethyl-3-methylimidazolium acetate, and 0.5 parts by mass of carboxylated gold nanoparticles into 350.0 parts by mass of water, and continuously stir for 1.0 h at room temperature to obtain a mixed solution.

[0113] Step 2.2: Add 100.0 parts by mass of the top layer of buffalo hide and the prepared mixed solution into a rotary drum, rotate for 5.0 h at room temperature and then let it stand for 12.0 h; continue to rotate the drum for 0.5 h at room temperature and then dry for 2.0 h at room temperature. Then dry in an oven at 40 °C for 6.0 h to obtain a high-strength collagen matrix multifunctional organic hydrogel.

[0114] Example 5

[0115] Step 1: Prepare a collagen matrix material.

[0116] Step 1.1: Add fresh horse hide and a solution containing 100.0 wt% (calculated based on 4.0 times the weight of the fresh hide, the same below) water, 1.0 wt% sodium hypochlorite, and 0.1 wt% sodium hydroxide into a leather drum, run for 12 h at 25 °C to remove dirt on the hide and dissolve some soluble proteins on the hide.

[0117] Step 1.2: Add fresh horse hide and a solution composed of 100.0 wt% water and 4.0 wt% sodium carbonate into a drum, and run for 2 h at 38 °C to remove some sebum.

[0118] Step 1.3: Add fresh horsehide and a solution containing 100.0 wt% water and 1.0 wt% sodium sulfide into a rotating drum, and run it at 25 °C for 1.5 h. Then, continue to add 0.09 wt% sodium hydroxide and operate at 25 °C for 6 h to remove the hair on the hide.

[0119] Step 1.4: Add fresh horsehide and a solution composed of 100.0 wt% water and 3.0 wt% calcium hydroxide into a roller, and run it at 25 °C for 18 h to further disperse collagen fibers, remove fiber matrix, saponify grease, remove hair and epidermis.

[0120] Step 1.5: Add fresh horsehide and a solution composed of 100.0 wt% water and 1.0 wt% lactic acid into a roller, and run it at 30 °C for 1 h to adjust the swelling state of the hide.

[0121] Step 1.6: Add fresh horsehide and a solution containing 100.0 wt% water, 0.15 wt% trypsin, 0.05 wt% protease, and 0.5 wt% ammonium chloride into a roller, and run it at 28 °C for 1 h to further remove epidermis, hair roots, pigments, grease, elastin, myosin, etc., and disperse collagen fibers.

[0122] Step 1.7: Prepare pickling liquor with 100.0 wt% water and 8.0 wt% sodium chloride, and adjust its pH value to 5.0 with hydrochloric acid. Then, add fresh horsehide and the pickling liquor into a rotating drum, and run it at 25 °C for 6 h. After standing overnight, a collagen matrix material, i.e., the top layer of horsehide, is obtained.

[0123] Step 2: Prepare a high-strength collagen matrix multifunctional organic hydrogel.

[0124] Step 2.1: Add 110.0 parts by mass of glycerol, 20.0 parts by mass of NaCl, 26.0 parts by mass of betaine, 6.0 parts by mass of 1-ethyl-3-methylimidazolium chloride, and 0.5 parts by mass of amino-functionalized silver nanoparticles into 350.0 parts by mass of water, and continuously stir at room temperature for 1.0 h to obtain a mixed solution.

[0125] Step 2.2: Add 100.0 parts by mass of the top layer of horsehide and the prepared mixed solution into a rotating drum, rotate at room temperature for 6.0 h and then stand for 12.0 h. Continue to rotate the rotating drum at room temperature for 0.5 h and then dry at room temperature for 2.0 h. Then, dry it in an oven at 40 °C for 6.0 h to obtain a high-strength collagen matrix multifunctional organic hydrogel.

[0126] Based on structural design and functional integration, and by combining leather preparation technology and nanomachining processes, the present invention prepares a high-strength collagen matrix multifunctional organic hydrogel using collagen matrix, organic solvents, metal salts, zwitterionic compounds, ionic liquids, metal nanoparticles, etc. as raw materials. The collagen matrix organic hydrogel prepared by the present invention has excellent mechanical properties, puncture resistance, moisture retention, moisture regain, antibacterial properties, cold resistance, heat resistance, and stimulus response characteristics, and can effectively sense changes in environmental temperature and humidity, as well as monitor human physiological signals.

Claims

1. A preparation method of a high-strength collagen matrix multifunctional organic hydrogel, characterized in that, The implementation is specifically carried out according to the following steps: Step 1: Prepare a collagen matrix material; Step 2: Prepare a high-strength collagen matrix multifunctional organic hydrogel, specifically: Step 2.1, Add 10.0 - 300.0 parts by mass of an organic solvent, 0.1 - 25.0 parts by mass of a metal salt, 0.1 - 50.0 parts by mass of an amphoteric ion compound, 0.1 - 50.0 parts by mass of an ionic liquid, and 0.1 - 10.0 parts by mass of metal nanoparticles to 10.0 - 500.0 parts by mass of water, continuously stir for 1.0 h at room temperature to obtain a mixed solution, and adjust the pH of the system to 2.5 - 6.5 with hydrochloric acid; Step 2.2, Add 10.0 - 150.0 parts by mass of the collagen matrix and the prepared mixed solution to a rotary drum, rotate at room temperature for 6.0 h, then let it stand for 12.0 h, then continue to rotate at room temperature for 0.5 h, then take out the collagen matrix and dry it at room temperature for 2.0 h, and dry it at 25 - 50 °C for 1 - 12.0 h to obtain a high-strength collagen matrix multifunctional organic hydrogel.

2. The preparation method of a high-strength collagen matrix multifunctional organic hydrogel according to claim 1, wherein, In the said Step 1, specifically: Step 1.1, Mix fresh skin, water, sodium hypochlorite, and sodium hydroxide, add them to a leather drum, and operate at 25 °C for 12 h to remove dirt on the skin and dissolve some soluble proteins on the skin; The fresh skin is any one of sheepskin, pigskin, cowhide, and horsehide; Step 1.2, Mix fresh skin, water, and sodium carbonate, and add them to a roller, and operate at 38 °C for 2 h to remove part of the sebum; Step 1.3, Mix fresh skin, water, and sodium sulfide, add them to a rotary drum, operate at 25 °C for 1.5 h, then continue to add sodium hydroxide and operate at 25 °C for 6 h to remove hair on the skin; Step 1.4, Mix fresh skin, water, and calcium hydroxide, add them to a roller, and operate at 25 °C for 18 h to further disperse collagen fibers, remove fiber matrix, saponify grease, remove hair and epidermis; Step 1.5, Mix fresh skin, water, and lactic acid, add them to a roller, and operate at 30 °C for 1 h to adjust the swelling state of the skin; Step 1.6, Mix fresh skin, water, trypsin, protease, and ammonium chloride, add them to a roller, and operate at 28 °C for 1 h to further remove epidermis, hair roots, pigments, grease, elastin, and myosin, and disperse collagen fibers; Step 1.7, Mix water and sodium chloride to prepare a pickling solution, adjust its pH value to 5.0 with hydrochloric acid, then add fresh skin and the pickling solution to a rotary drum, and operate at 25 °C for 6 h, let it stand overnight to obtain a collagen matrix material.

3. The preparation method of a high-strength collagen matrix multifunctional organic hydrogel according to claim 1, characterized in that, In the said Step 2, the organic solvent is one or more of methanol, ethanol, ethylene glycol, propanol, propylene glycol, and glycerol; the metal salt is one or more of NaCl, KCl, LiCl, MgCl₂, and CaCl₂.

4. The preparation method of a high-strength collagen matrix multifunctional organic hydrogel according to claim 1, characterized in that, In the said Step 2, the amphoteric ion compound is one or more of betaine, dimethylglycine, alanine, sarcosine, and L-proline.

5. The preparation method of a high-strength collagen matrix multifunctional organic hydrogel according to claim 1, characterized in that, In the step 2, the ionic liquid is one or more of 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium acetate, 1,3-dimethylimidazolium iodide, 1,3-dimethylimidazolium methyl sulfate, 1,3-dimethylimidazolium trifluoroacetate, and 1-ethyl-3-methylimidazolium ethyl sulfate.

6. The preparation method of a high-strength collagen matrix multifunctional organic hydrogel according to claim 1, characterized in that, In the step 2, the metal nanoparticles are one or more of gold nanoparticles, silver nanoparticles, amino-functionalized gold nanoparticles, carboxyl-functionalized gold nanoparticles, sulfonic acid-functionalized gold nanoparticles, amino-functionalized silver nanoparticles, carboxyl-functionalized silver nanoparticles, and sulfonic acid-functionalized silver nanoparticles.

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