An antibacterial and corrosion-resistant EVA liquid storage bag material and its preparation method

Abstract

The present invention provides an antibacterial and corrosion-resistant EVA liquid storage bag material and a preparation method thereof. The EVA liquid storage bag material is obtained by blending an antibacterial / corrosion-resistant filler with a core-shell structure with EVA. The preparation method is as follows: The antibacterial / corrosion-resistant filler with a core-shell structure is uniformly mixed with the EVA substrate; it is placed in a mixer for mixing, the mixing temperature is 110°C, the double-roll speed is 100 r / min, and it is mixed twice, with each mixing time being 10 min, thus obtaining the product. The present invention adopts an antibacterial / corrosion-resistant filler with a core-shell structure, with a modified sodium alginate aerogel loaded with silver nanoclusters as the core and polyurethane as the shell, achieving the effects of both antibacterial and corrosion resistance; the α-L-guluronic acid in the sodium alginate aerogel can chelate with the silver nanoclusters to form an "egg box" structure. On the one hand, the silver nanoclusters are loaded on the aerogel, which can greatly improve the nano-aggregation degree of the silver nanoclusters, achieve high-density loading, and the "egg box" makes the combination of the silver nanoclusters and the sodium alginate aerogel more firm, and can maintain long-term stability.

Description

Technical Field

[0001] The present invention relates to the field of medical materials, and particularly to an antibacterial and corrosion-resistant EVA liquid storage bag material and a preparation method thereof. Background Art

[0002] Ethylene-vinyl acetate copolymer (EVA) is a highly branched random copolymer obtained by copolymerization of non-polar ethylene monomer and polar vinyl acetate monomer. The introduction of VA monomer in the EVA copolymer chain segment increases the chain segment branching degree and affects the crystallization ability, resulting in a decrease in its crystallinity. EVA copolymer is a semi-crystalline copolymer composed of a crystalline phase and an amorphous phase; EVA copolymer can be used in fields such as packaging protection materials, sealing materials, medical catheters, insulating films and fittings, etc.; EVA copolymer is non-toxic and harmless, and has good performance in terms of optical properties, weather resistance, processability, flexibility, etc. However, it does not have antibacterial properties itself, and there are problems with poor material compatibility. At the same time, when used as a liquid storage bag material, it needs to have good chemical corrosion resistance. Therefore, the key research is to develop a suitable EVA material that can achieve long-term antibacterial and chemical corrosion resistance effects. Summary of the Invention

[0003] Technical problems to be solved: In view of the above technical problems, the present invention provides an antibacterial and corrosion-resistant EVA liquid storage bag material and a preparation method thereof. An antibacterial / corrosion-resistant filler with a core-shell structure is used, with a modified sodium alginate aerogel loaded with silver nanoclusters as the core and polyurethane as the shell, to achieve the effects of simultaneous antibacterial and corrosion resistance; the α-L-guluronic acid in the sodium alginate aerogel can chelate with silver nanoclusters to form an "egg box" structure. On the one hand, the silver nanoclusters are loaded on the aerogel, which can greatly improve the nano-aggregation degree of the silver nanoclusters, achieve high-density loading, and the "egg box" makes the combination of the silver nanoclusters and the sodium alginate aerogel more firm, capable of maintaining long-term stability. On the other hand, the silver nanoclusters play a protective role in the internal pores and wire diameters of the sodium alginate aerogel, greatly improving the mechanical properties of the sodium alginate.

[0004] Technical solution: An antibacterial and corrosion-resistant EVA liquid storage bag material, wherein the EVA liquid storage bag material is obtained by blending an antibacterial / corrosion-resistant filler with a core-shell structure with EVA; the mass ratio of the antibacterial / corrosion-resistant filler with a core-shell structure to EVA is (3 - 5):100.

[0005] Further, the preparation method of the antibacterial / corrosion-resistant filler with a core-shell structure is as follows:

[0006] Step 1: Take sodium alginate and stir it with water to obtain a 1.5 wt.% sodium alginate aqueous solution;

[0007] Step 2: Add 2wt.% ethylenediamine solution, mix and stir evenly to obtain a modified sodium alginate aqueous solution;

[0008] Step 3: Mix the aldehyde-modified nanocellulose solution, the silver ammonia solution and the glutathione solution and stir them thoroughly to react, thereby obtaining silver nanocluster micelles;

[0009] Step 4: Add the silver nanocluster micelles into the modified sodium alginate aqueous solution, ultrasonicate for 30-60 minutes, and then stand for 40 minutes;

[0010] Step 5: slowly pour into anhydrous ethanol solution to obtain modified sodium alginate wet gel loaded with silver nanoclusters, let stand for 1 hour, and filter;

[0011] Step 6: rinse with deionized water, pre-freeze for 24 hours, and freeze-dry to obtain modified sodium alginate aerogel loaded with silver nanoclusters;

[0012] Step 7: crushing the modified sodium alginate aerogel loaded with silver nanoclusters and passing it through a 400-mesh sieve to obtain aerogel particles;

[0013] Step 8: dissolving polyurethane in N,N-dimethylformamide to obtain a polyurethane solution, impregnating aerogel particles therein, and maintaining the solution under vacuum until bubbles escape;

[0014] Step 9: Take out and dry thoroughly to obtain the antibacterial / corrosion-resistant filler with a core-shell structure.

[0015] Furthermore, the mass ratio of the sodium alginate in step 1 to the ethylenediamine in step 2 is 10:1.

[0016] Furthermore, the preparation method of the aldehyde-modified nanocellulose in step 3 is as follows:

[0017] (1) Disperse cellulose in a mixed solution of sodium hydroxide, urea and thiourea, stir vigorously for 30 min, cool to -10 °C, and centrifuge at 11000 rpm for 20 min to obtain a cellulose solution;

[0018] (2) Slowly dripping deionized water into the cellulose solution while slowly stirring to obtain a milky white suspension, and washing the suspension with deionized water until the pH value is 7;

[0019] (3) Ultrasonication at 600 W for 30 min to obtain nanocellulose;

[0020] (4) adding sodium periodate to a 10 mg / mL nanocellulose solution, adjusting the pH value to 4.5, stirring at 40 °C for 4 h, and centrifuging and washing to obtain dialdehyde nanocellulose;

[0021] (5) Disperse dialdehyde nanocellulose in deionized water, add 25 wt% glutaraldehyde solution, stir and react at 70 °C for 30 min, and centrifuge and wash with deionized water to obtain aldehyde-functionalized nanocellulose.

[0022] Further, in the mixed solution of sodium hydroxide, urea and thiourea in step (1), the concentration of sodium hydroxide is 8 wt%, the concentration of urea is 8 wt%, and the concentration of thiourea is 6.5 wt%.

[0023] Further, in step (4), the mass ratio of sodium periodate to nanocellulose is 2:1.

[0024] Further, in step 3, the molar ratio of the aldehyde group content of aldehyde-functionalized nanocellulose, silver-ammonia complex ions in silver-ammonia solution and glutathione is 1:(3 - 8):(5 - 10).

[0025] Further, in step 4, the volume ratio of silver nanocluster micelles to modified sodium alginate aqueous solution is 1:(1 - 3).

[0026] Further, in step 8, the concentration of the polyurethane solution is 0.2 - 0.4 g / mL.

[0027] The preparation method of the above antibacterial and corrosion-resistant EVA liquid storage bag material includes the following steps:

[0028] (1) Mix the core-shell structured antibacterial / corrosion-resistant filler with the EVA substrate evenly;

[0029] (2) Place it in a mixer for mixing. The mixing temperature is 110 °C, the speed of the double rollers is 100 r / min, mix twice, and the mixing time for each time is 10 min to obtain the product. Beneficial effects

[0030] The present invention adopts a core-shell structured antibacterial / corrosion-resistant filler, with a modified sodium alginate aerogel loaded with silver nanoclusters as the core and polyurethane as the shell, to achieve the effects of simultaneous antibacterial and corrosion resistance.

[0031] In the sodium alginate aerogel of the present invention, α-L-guluronic acid can chelate with silver nanoclusters to form an "egg box" structure. On the one hand, loading silver nanoclusters on the aerogel can greatly improve the nano-aggregation degree of silver nanoclusters, realize high-density loading, and the "egg box" makes the combination of silver nanoclusters and sodium alginate aerogel more firm and can maintain long-term stability. On the other hand, silver nanoclusters play a protective role in the internal pores and wire diameter sizes of sodium alginate aerogel, greatly improving the mechanical properties of sodium alginate.

[0032] In the present invention, sodium alginate is modified with ethylenediamine to obtain -NH2. The -NH-CO-NH- bond formed by the reaction of polyurethane with -NH2 has a relatively high bond energy, enabling them to be tightly combined, increasing the contact area between the particles constituting the framework structure, and improving the stability of the overall structure of the aerogel.

[0033] Aerogels are brittle and fragile. By coating the aerogel with polyurethane and introducing the flexible molecular chains of polyurethane, the microscopic structure of the aerogel can be effectively protected, enhancing the flexibility and mechanical strength of the material. Moreover, the hydroxyl groups on the sodium alginate aerogel can form hydrogen bond interactions with the hydrophilic groups present on the hard segments of polyurethane, increasing the crosslinking density and having excellent anti-corrosion effects.

[0034] Using polyurethane as the shell in the present invention can also improve the dispersibility of the core-shell structure and its compatibility with EVA. Specific Embodiments Example 1

[0035] The preparation method of aldehyde-functionalized nanocellulose is as follows:

[0036] (1) Take cellulose and disperse it in a mixed solution of sodium hydroxide, urea, and thiourea. The concentration of sodium hydroxide in the mixed solution is 8 wt.%, the concentration of urea is 8 wt.%, and the concentration of thiourea is 6.5 wt.%. Stir vigorously for 30 min and then cool to -10°C. Centrifuge at 11000 rpm for 20 min to obtain a cellulose solution;

[0037] (2) Slowly drip deionized water into the cellulose solution while stirring slowly to obtain a milky white suspension. Wash the suspension with deionized water until the pH value is 7;

[0038] (3) Ultrasonic at an ultrasonic power of 600 W for 30 min to obtain nanocellulose;

[0039] (4) Add sodium periodate to a 10 mg / mL nanocellulose solution. The mass ratio of sodium periodate to nanocellulose is 2:1. Adjust the pH value to 4.5 and stir at 40°C for 4 h. Centrifuge and wash to obtain dialdehyde nanocellulose;

[0040] (5) Disperse the dialdehyde nanocellulose in deionized water, add a 25 wt.% glutaraldehyde solution, stir and react at 70°C for 30 min, and centrifuge and wash with deionized water to obtain aldehyde-functionalized nanocellulose. Example 2

[0041] The preparation method of the core-shell structured antibacterial / corrosion-resistant filler is as follows:

[0042] Step 1: Take 10 g of sodium alginate and stir it with water to obtain a 1.5 wt.% aqueous sodium alginate solution;

[0043] Step 2: Take 1 g of ethylenediamine, add water and stir to obtain a 2 wt.% ethylenediamine solution. Mix the sodium alginate aqueous solution and the ethylenediamine solution and stir evenly to obtain a modified sodium alginate aqueous solution;

[0044] Step 3: Mix the aldehyde-functionalized nanocellulose solution, silver ammonia solution and glutathione solution, and stir well to react to obtain silver nanocluster micelles; wherein, the molar ratio of the aldehyde group content of the aldehyde-functionalized nanocellulose, silver ammonia complex ions in the silver ammonia solution and glutathione is 1:5:7;

[0045] Step 4: Add the silver nanocluster micelles to the modified sodium alginate aqueous solution. The volume ratio of the silver nanocluster micelles to the modified sodium alginate aqueous solution is 1:1. After ultrasonic treatment for 50 min, let it stand for 40 min;

[0046] Step 5: Slowly pour it into an anhydrous ethanol solution to obtain a modified sodium alginate wet gel loaded with silver nanoclusters. Let it stand for 1 h and filter;

[0047] Step 6: Rinse with deionized water and pre-freeze for 24 h, and freeze-dry to obtain a modified sodium alginate aerogel loaded with silver nanoclusters;

[0048] Step 7: Crush the modified sodium alginate aerogel loaded with silver nanoclusters, and pass through a 400-mesh sieve to obtain aerogel particles;

[0049] Step 8: Dissolve polyurethane in N,N-dimethylformamide to obtain a polyurethane solution with a concentration of 0.3 g / mL. Immerse the aerogel particles in it and keep it under vacuum conditions until the bubbles escape;

[0050] Step 9: Take it out and dry it thoroughly to obtain a core-shell structured antibacterial / corrosion-resistant filler. Example 3

[0051] The preparation method of the core-shell structured antibacterial / corrosion-resistant filler is as follows:

[0052] Step 1: Take 10 g of sodium alginate, add water and stir to obtain a 1.5 wt.% sodium alginate aqueous solution;

[0053] Step 2: Take 1 g of ethylenediamine, add water and stir to obtain a 2 wt.% ethylenediamine solution. Mix the sodium alginate aqueous solution and the ethylenediamine solution and stir evenly to obtain a modified sodium alginate aqueous solution;

[0054] Step 3: Mix the aldehyde-functionalized nanocellulose solution, silver ammonia solution and glutathione solution, and stir well to react to obtain silver nanocluster micelles; wherein, the molar ratio of the aldehyde group content of the aldehyde-functionalized nanocellulose, silver ammonia complex ions in the silver ammonia solution and glutathione is 1:5:7;

[0055] Step 4: Add the silver nanocluster micelles into the modified sodium alginate aqueous solution. The volume ratio of the silver nanocluster micelles to the modified sodium alginate aqueous solution is 1:2. After ultrasonic treatment for 50 min, let it stand for 40 min;

[0056] Step 5: Slowly pour it into the anhydrous ethanol solution to obtain the modified sodium alginate wet gel loaded with silver nanoclusters. Let it stand for 1 h and then filter;

[0057] Step 6: Rinse with deionized water and then pre-freeze for 24 h, and freeze-dry to obtain the modified sodium alginate aerogel loaded with silver nanoclusters;

[0058] Step 7: Crush the modified sodium alginate aerogel loaded with silver nanoclusters and pass it through a 400-mesh sieve to obtain aerogel particles;

[0059] Step 8: Dissolve polyurethane in N,N-dimethylformamide to obtain a polyurethane solution with a concentration of 0.3 g / mL. Immerse the aerogel particles in it and keep it under vacuum conditions until the bubbles escape;

[0060] Step 9: Take it out and dry it thoroughly to obtain the core-shell structured antibacterial / corrosion-resistant filler. Example 4

[0061] The preparation method of the core-shell structured antibacterial / corrosion-resistant filler is as follows:

[0062] Step 1: Take 10 g of sodium alginate and stir it with water to obtain a 1.5 wt.% sodium alginate aqueous solution;

[0063] Step 2: Take 1 g of ethylenediamine and stir it with water to obtain a 2 wt.% ethylenediamine solution. Mix the sodium alginate aqueous solution and the ethylenediamine solution and stir evenly to obtain the modified sodium alginate aqueous solution;

[0064] Step 3: Mix the aldehyde-functionalized nanocellulose solution, silver ammonia solution and glutathione solution and stir them fully to react to obtain silver nanocluster micelles; wherein, the molar ratio of the aldehyde group content of the aldehyde-functionalized nanocellulose, silver ammonia complex ions in the silver ammonia solution and glutathione is 1:5:7;

[0065] Step 4: Add the silver nanocluster micelles into the modified sodium alginate aqueous solution. The volume ratio of the silver nanocluster micelles to the modified sodium alginate aqueous solution is 1:3. After ultrasonic treatment for 50 min, let it stand for 40 min;

[0066] Step 5: Slowly pour it into the anhydrous ethanol solution to obtain the modified sodium alginate wet gel loaded with silver nanoclusters. Let it stand for 1 h and then filter;

[0067] Step 6: Rinse with deionized water and then pre-freeze for 24 h, and freeze-dry to obtain the modified sodium alginate aerogel loaded with silver nanoclusters;

[0068] Step 7: Crush the modified sodium alginate aerogel loaded with silver nanoclusters, and pass through a 400-mesh sieve to obtain aerogel particles;

[0069] Step 8: Dissolve polyurethane in N,N-dimethylformamide to obtain a polyurethane solution with a concentration of 0.3 g / mL. Immerse the aerogel particles therein and keep them under vacuum conditions until the bubbles escape;

[0070] Step 9: Take it out and dry it thoroughly to obtain the antibacterial / corrosion-resistant filler with a core-shell structure. Example 5

[0071] The preparation method of the antibacterial / corrosion-resistant filler with a core-shell structure is as follows:

[0072] Step 1: Take 10 g of sodium alginate and stir it with water to obtain a 1.5 wt.% aqueous sodium alginate solution;

[0073] Step 2: Take 1 g of ethylenediamine and stir it with water to obtain a 2 wt.% ethylenediamine solution. Mix and stir the aqueous sodium alginate solution and the ethylenediamine solution evenly to obtain a modified aqueous sodium alginate solution;

[0074] Step 3: Mix the aldehyde-functionalized nanocellulose solution, silver ammonia solution and glutathione solution and stir them fully to react to obtain silver nanocluster micelles; wherein, the molar ratio of the aldehyde group content of aldehyde-functionalized nanocellulose, silver ammonia complex ions in the silver ammonia solution and glutathione is 1:5:7;

[0075] Step 4: Add the silver nanocluster micelles to the modified aqueous sodium alginate solution. The volume ratio of the silver nanocluster micelles to the modified aqueous sodium alginate solution is 1:2. After ultrasonic treatment for 50 min, let it stand for 40 min;

[0076] Step 5: Slowly pour it into an anhydrous ethanol solution to obtain a wet gel of modified sodium alginate loaded with silver nanoclusters, let it stand for 1 h, and filter;

[0077] Step 6: Rinse it with deionized water and pre-freeze it for 24 h, and then freeze-dry it to obtain a modified sodium alginate aerogel loaded with silver nanoclusters;

[0078] Step 7: Crush the modified sodium alginate aerogel loaded with silver nanoclusters, and pass through a 400-mesh sieve to obtain aerogel particles;

[0079] Step 8: Dissolve polyurethane in N,N-dimethylformamide to obtain a polyurethane solution with a concentration of 0.2 g / mL. Immerse the aerogel particles therein and keep them under vacuum conditions until the bubbles escape;

[0080] Step 9: Take it out and dry it thoroughly to obtain the antibacterial / corrosion-resistant filler with a core-shell structure. Example 6

[0081] The preparation method of the core-shell structured antibacterial / corrosion-resistant filler is as follows:

[0082] Step 1: Take 10 g of sodium alginate, add water and stir to obtain a 1.5 wt.% sodium alginate aqueous solution;

[0083] Step 2: Take 1 g of ethylenediamine, add water and stir to obtain a 2 wt.% ethylenediamine solution, mix the sodium alginate aqueous solution and the ethylenediamine solution and stir evenly to obtain a modified sodium alginate aqueous solution;

[0084] Step 3: mixing the aldehyde-modified nanocellulose solution, the silver-ammonia solution and the glutathione solution and stirring them thoroughly to obtain silver nanocluster micelles; wherein the molar ratio of the aldehyde content of the aldehyde-modified nanocellulose, the silver-ammonia complex ions in the silver-ammonia solution and the glutathione is 1:5:7;

[0085] Step 4: adding the silver nanocluster micelles to the modified sodium alginate aqueous solution, the volume ratio of the silver nanocluster micelles to the modified sodium alginate aqueous solution is 1:2, ultrasonically treating for 50 minutes and then standing for 40 minutes;

[0086] Step 5: slowly pour into anhydrous ethanol solution to obtain modified sodium alginate wet gel loaded with silver nanoclusters, let stand for 1 hour, and filter;

[0087] Step 6: rinse with deionized water, pre-freeze for 24 hours, and freeze-dry to obtain modified sodium alginate aerogel loaded with silver nanoclusters;

[0088] Step 7: crushing the modified sodium alginate aerogel loaded with silver nanoclusters and passing it through a 400-mesh sieve to obtain aerogel particles;

[0089] Step 8: dissolving polyurethane in N,N-dimethylformamide to obtain a polyurethane solution with a concentration of 0.4 g / mL, immersing aerogel particles therein, and maintaining the solution under vacuum until bubbles escape;

[0090] Step 9: Take out and dry thoroughly to obtain the antibacterial / corrosion-resistant filler with a core-shell structure. Example 7

[0091] The preparation method of the core-shell structured antibacterial / corrosion-resistant filler is as follows:

[0092] Step 1: Take 10 g of sodium alginate, add water and stir to obtain a 1.5 wt.% sodium alginate aqueous solution;

[0093] Step 2: Take 1 g of ethylenediamine, add water and stir to obtain a 2 wt.% ethylenediamine solution, mix the sodium alginate aqueous solution and the ethylenediamine solution and stir evenly to obtain a modified sodium alginate aqueous solution;

[0094] Step 3: Mix the aldehyde-functionalized nanocellulose solution, silver ammonia solution, and glutathione solution, and stir the mixture thoroughly to react, obtaining silver nanocluster micelles; wherein, the molar ratio of the aldehyde group content of the aldehyde-functionalized nanocellulose, silver ammonia complex ions in the silver ammonia solution, and glutathione is 1:5:7;

[0095] Step 4: Add the silver nanocluster micelles to the modified sodium alginate aqueous solution. The volume ratio of the silver nanocluster micelles to the modified sodium alginate aqueous solution is 1:2. After ultrasonic treatment for 30 min, let it stand for 40 min;

[0096] Step 5: Slowly pour it into an anhydrous ethanol solution to obtain a modified sodium alginate wet gel loaded with silver nanoclusters. Let it stand for 1 h and then filter;

[0097] Step 6: Rinse with deionized water and then pre-freeze for 24 h, and freeze-dry to obtain a modified sodium alginate aerogel loaded with silver nanoclusters;

[0098] Step 7: Crush the modified sodium alginate aerogel loaded with silver nanoclusters, and pass it through a 400-mesh sieve to obtain aerogel particles;

[0099] Step 8: Dissolve polyurethane in N,N-dimethylformamide to obtain a polyurethane solution with a concentration of 0.3 g / mL. Immerse the aerogel particles in it and keep them under vacuum conditions until the bubbles escape;

[0100] Step 9: Take it out and dry it thoroughly to obtain the core-shell structured antibacterial / corrosion-resistant filler. Example 8

[0101] The preparation method of the core-shell structured antibacterial / corrosion-resistant filler is as follows:

[0102] Step 1: Take 10 g of sodium alginate and stir it with water to obtain a 1.5 wt.% sodium alginate aqueous solution;

[0103] Step 2: Take 1 g of ethylenediamine and stir it with water to obtain a 2 wt.% ethylenediamine solution. Mix the sodium alginate aqueous solution and the ethylenediamine solution and stir them evenly to obtain a modified sodium alginate aqueous solution;

[0104] Step 3: Mix the aldehyde-functionalized nanocellulose solution, silver ammonia solution, and glutathione solution, and stir the mixture thoroughly to react, obtaining silver nanocluster micelles; wherein, the molar ratio of the aldehyde group content of the aldehyde-functionalized nanocellulose, silver ammonia complex ions in the silver ammonia solution, and glutathione is 1:5:7;

[0105] Step 4: Add the silver nanocluster micelles to the modified sodium alginate aqueous solution. The volume ratio of the silver nanocluster micelles to the modified sodium alginate aqueous solution is 1:2. After ultrasonic treatment for 60 min, let it stand for 40 min;

[0106] Step 5: Slowly pour it into an anhydrous ethanol solution to obtain a modified sodium alginate wet gel loaded with silver nanoclusters, let it stand for 1 h, and filter;

[0107] Step 6: Rinse with deionized water and then pre-freeze for 24 h, and freeze-dry to obtain a modified sodium alginate aerogel loaded with silver nanoclusters;

[0108] Step 7: Crush the modified sodium alginate aerogel loaded with silver nanoclusters, and pass it through a 400-mesh sieve to obtain aerogel particles;

[0109] Step 8: Dissolve polyurethane in N,N-dimethylformamide to obtain a polyurethane solution with a concentration of 0.3 g / mL. Immerse the aerogel particles in it and keep them under vacuum conditions until the bubbles escape;

[0110] Step 9: Take it out and dry it thoroughly to obtain the core-shell structured antibacterial / corrosion-resistant filler. Comparative Example 1

[0111] The difference between this example and Example 3 is that silver nanocluster micelles are not loaded, and silver ions are directly added, specifically as follows:

[0112] The preparation method of the core-shell structured antibacterial / corrosion-resistant filler is as follows:

[0113] Step 1: Take 10 g of sodium alginate and stir it with water to obtain a 1.5 wt.% sodium alginate aqueous solution;

[0114] Step 2: Take 1 g of ethylenediamine and stir it with water to obtain a 2 wt.% ethylenediamine solution. Mix the sodium alginate aqueous solution and the ethylenediamine solution and stir evenly to obtain a modified sodium alginate aqueous solution;

[0115] Step 3: Dissolve 7.8 mmol of sodium nitrate, 6.1 mmol of silver nitrate and 10 mmol of ammonium dihydrogen phosphate in 100 mL of distilled water to obtain a mixed aqueous solution;

[0116] Step 4: Add the mixed aqueous solution to the modified sodium alginate aqueous solution. The volume ratio of the mixed aqueous solution to the modified sodium alginate aqueous solution is 1:2. After ultrasonic treatment for 50 min, let it stand for 40 min;

[0117] Step 5: Slowly pour it into an anhydrous ethanol solution to obtain a modified sodium alginate wet gel loaded with silver ions, let it stand for 1 h, and filter;

[0118] Step 6: Rinse with deionized water and then pre-freeze for 24 h, and freeze-dry to obtain a modified sodium alginate aerogel loaded with silver ions;

[0119] Step 7: Crush the modified sodium alginate aerogel loaded with silver ions, and pass it through a 400-mesh sieve to obtain aerogel particles;

[0120] Step 8: dissolving polyurethane in N,N-dimethylformamide to obtain a polyurethane solution with a concentration of 0.3 g / mL, immersing aerogel particles therein, and maintaining the solution under vacuum until bubbles escape;

[0121] Step 9: Take out and dry thoroughly to obtain the antibacterial / corrosion-resistant filler with a core-shell structure. Comparative Example 2

[0122] The difference between this embodiment and embodiment 3 is that ethylenediamine is not used for modification, and the details are as follows:

[0123] The preparation method of the core-shell structured antibacterial / corrosion-resistant filler is as follows:

[0124] Step 1: Take 10 g of sodium alginate, add water and stir to obtain a 1.5 wt.% sodium alginate aqueous solution;

[0125] Step 2: mixing the aldehyde-modified nanocellulose solution, the silver-ammonia solution and the glutathione solution and stirring them thoroughly to obtain silver nanocluster micelles; wherein the molar ratio of the aldehyde content of the aldehyde-modified nanocellulose, the silver-ammonia complex ions in the silver-ammonia solution and the glutathione is 1:5:7;

[0126] Step 3: adding the silver nanocluster micelles to the sodium alginate aqueous solution, the volume ratio of the silver nanocluster micelles to the sodium alginate aqueous solution is 1:2, ultrasonically treating for 50 minutes and then standing for 40 minutes;

[0127] Step 4: slowly pour into anhydrous ethanol solution to obtain sodium alginate wet gel loaded with silver nanoclusters, let stand for 1 hour, and filter;

[0128] Step 5: rinse with deionized water and pre-freeze for 24 hours, and freeze-dry to obtain sodium alginate aerogel loaded with silver nanoclusters;

[0129] Step 6: crushing the sodium alginate aerogel loaded with silver nanoclusters and passing it through a 400-mesh sieve to obtain aerogel particles;

[0130] Step 7: dissolving polyurethane in N,N-dimethylformamide to obtain a polyurethane solution with a concentration of 0.3 g / mL, immersing aerogel particles therein, and maintaining the solution under vacuum until bubbles escape;

[0131] Step 8: Take out and dry thoroughly to obtain the antibacterial / corrosion-resistant filler with a core-shell structure. Comparative Example 3

[0132] The difference between this embodiment and embodiment 3 is that polyurethane is not used for coating, as follows:

[0133] The preparation method of the antibacterial / corrosion-resistant filler is:

[0134] Step 1: Take 10 g of sodium alginate, add water and stir to obtain a 1.5 wt.% sodium alginate aqueous solution;

[0135] Step 2: Take 1 g of ethylenediamine, add water and stir to obtain a 2 wt.% ethylenediamine solution, mix the sodium alginate aqueous solution and the ethylenediamine solution and stir evenly to obtain a modified sodium alginate aqueous solution;

[0136] Step 3: mixing the aldehyde-modified nanocellulose solution, the silver-ammonia solution and the glutathione solution and stirring them thoroughly to obtain silver nanocluster micelles; wherein the molar ratio of the aldehyde content of the aldehyde-modified nanocellulose, the silver-ammonia complex ions in the silver-ammonia solution and the glutathione is 1:5:7;

[0137] Step 4: adding the silver nanocluster micelles to the modified sodium alginate aqueous solution, the volume ratio of the silver nanocluster micelles to the modified sodium alginate aqueous solution is 1:2, ultrasonically treating for 50 minutes and then standing for 40 minutes;

[0138] Step 5: slowly pour into anhydrous ethanol solution to obtain modified sodium alginate wet gel loaded with silver nanoclusters, let stand for 1 hour, and filter;

[0139] Step 6: rinse with deionized water, pre-freeze for 24 hours, and freeze-dry to obtain modified sodium alginate aerogel loaded with silver nanoclusters;

[0140] Step 7: The modified sodium alginate aerogel loaded with silver nanoclusters is crushed and passed through a 400-mesh sieve to obtain aerogel particles.

[0141] The porosity, compressive strength and antibacterial effect of the core-shell structured antibacterial / corrosion-resistant filler of the above embodiment were measured, and the results are shown in Table 1 below:

[0142] Table 1

[0143]

[0144] After comprehensively comparing the various properties of the above embodiments, the antibacterial / corrosion-resistant filler with a core-shell structure prepared in Example 3 was selected for subsequent tests. Example 9

[0145] A method for preparing an antibacterial and corrosion-resistant EVA liquid storage bag material comprises the following steps:

[0146] (1) The core-shell structured antibacterial / corrosion-resistant filler and the EVA substrate are uniformly mixed at a mass ratio of 3:100;

[0147] (2) Knead in a kneader at a kneading temperature of 110°C, a two-roll speed of 100 r / min, and knead twice, with each kneading time being 10 min to obtain the product. Example 10

[0148] A method for preparing an antibacterial and corrosion-resistant EVA liquid storage bag material, comprising the following steps:

[0149] (1) Mix the core-shell structured antibacterial / corrosion-resistant filler and the EVA substrate with a mass ratio of 4:100 evenly;

[0150] (2) Knead in a kneader at a kneading temperature of 110°C, a two-roll speed of 100 r / min, and knead twice, with each kneading time being 10 min to obtain the product. Example 11

[0151] A method for preparing an antibacterial and corrosion-resistant EVA liquid storage bag material, comprising the following steps:

[0152] (1) Mix the core-shell structured antibacterial / corrosion-resistant filler and the EVA substrate with a mass ratio of 5:100 evenly;

[0153] (2) Knead in a kneader at a kneading temperature of 110°C, a two-roll speed of 100 r / min, and knead twice, with each kneading time being 10 min to obtain the product. Comparative Example 4

[0154] The difference between this example and Example 10 is that: the core-shell structured antibacterial / corrosion-resistant filler prepared in Comparative Example 1 is used. Specifically:

[0155] A method for preparing an antibacterial and corrosion-resistant EVA liquid storage bag material, comprising the following steps:

[0156] (1) Mix the core-shell structured antibacterial / corrosion-resistant filler and the EVA substrate with a mass ratio of 4:100 evenly;

[0157] (2) Knead in a kneader at a kneading temperature of 110°C, a two-roll speed of 100 r / min, and knead twice, with each kneading time being 10 min to obtain the product. Comparative Example 5

[0158] The difference between this example and Example 10 is that: the core-shell structured antibacterial / corrosion-resistant filler prepared in Comparative Example 2 is used. Specifically:

[0159] A method for preparing an antibacterial and corrosion-resistant EVA liquid storage bag material, comprising the following steps:

[0160] Mix the core-shell structured antibacterial / corrosion-resistant filler and the EVA substrate with a mass ratio of 4:100 evenly;

[0161] (2) Place it in a kneader for kneading. The kneading temperature is 110 °C, the rotational speed of the two-roll is 100 r / min, and knead twice, with each kneading time being 10 min, then it is obtained. Comparative Example 6

[0162] The difference between this example and Example 10 lies in: using the antibacterial / corrosion-resistant filler prepared in Comparative Example 3. Specifically:

[0163] A preparation method of an antibacterial and corrosion-resistant EVA liquid storage bag material, comprising the following steps:

[0164] (1) Mix the antibacterial / corrosion-resistant filler and the EVA substrate with a mass ratio of 4:100 evenly;

[0165] (2) Place it in a kneader for kneading. The kneading temperature is 110 °C, the rotational speed of the two-roll is 100 r / min, and knead twice, with each kneading time being 10 min, then it is obtained.

[0166] Corrosion resistance test: For the initial EVA liquid storage bag material and the EVA liquid storage bag materials after being soaked in 30% NaCl solution and 15% ammonia water for 6 months respectively, use a universal testing machine to test the tensile strength and elongation at break of the liquid storage bag materials prepared in each example. Take the average value of five specimens, the tensile speed is 50 mm / min, and the tensile error is less than ±0.5%. The results are shown in Table 2 below:

[0167] Table 2

[0168]

[0169] Use the oscillating flask method to determine the antibacterial rate of the liquid storage bag materials in each example, and calculate with the following formula:

[0170]

[0171] In the formula, A is the average number of colonies after oscillation of the specimen, and B is the average number of colonies before oscillation of the specimen.

[0172] Table 3

[0173] .

Claims

1. An antibacterial and corrosion-resistant EVA liquid storage bag material, characterized in that: The EVA liquid storage bag material is obtained by blending an antibacterial / corrosion-resistant filler with a core-shell structure and EVA; the mass ratio of the antibacterial / corrosion-resistant filler with a core-shell structure to EVA is (3-5):100; The preparation method of the antibacterial / corrosion-resistant filler of the core-shell structure is as follows: Step 1: Take sodium alginate, add water and stir to obtain a 1.5wt.% sodium alginate aqueous solution; Step 2: Add 2wt.% ethylenediamine solution, mix and stir evenly to obtain a modified sodium alginate aqueous solution; Step 3: Mix the aldehyde-modified nanocellulose solution, the silver ammonia solution and the glutathione solution and stir them thoroughly to react, thereby obtaining silver nanocluster micelles; Step 4: Add the silver nanocluster micelles into the modified sodium alginate aqueous solution, ultrasonicate for 30-60 minutes, and then stand for 40 minutes; Step 5: slowly pour into anhydrous ethanol solution to obtain modified sodium alginate wet gel loaded with silver nanoclusters, let stand for 1 hour, and filter; Step 6: rinse with deionized water, pre-freeze for 24 hours, and freeze-dry to obtain modified sodium alginate aerogel loaded with silver nanoclusters; Step 7: crushing the modified sodium alginate aerogel loaded with silver nanoclusters and passing it through a 400-mesh sieve to obtain aerogel particles; Step 8: dissolving polyurethane in N,N-dimethylformamide to obtain a polyurethane solution, impregnating aerogel particles therein, and maintaining the solution under vacuum until bubbles escape; Step 9: Take out and fully dry to obtain the antibacterial / corrosion-resistant filler with a core-shell structure; The preparation method of the aldehyde-modified nanocellulose in step 3 is as follows: Step (1): dispersing cellulose in a mixed solution of sodium hydroxide, urea and thiourea, stirring vigorously for 30 min, cooling to -10°C, and centrifuging at 11000 rpm for 20 min to obtain a cellulose solution; Step (2): slowly dripping deionized water into the cellulose solution while slowly stirring to obtain a milky white suspension, and washing the suspension with deionized water until the pH value is 7; Step (3): ultrasonically treating the mixture at an ultrasonic power of 600 W for 30 min to obtain nanocellulose; Step (4): adding sodium periodate to a 10 mg / mL nanocellulose solution, adjusting the pH value to 4.5, stirring at 40°C for 4 hours, and centrifuging and washing to obtain dialdehyde nanocellulose; Step (5): Disperse the dialdehyde nanocellulose in deionized water, add 25 wt% glutaraldehyde solution, stir and react at 70°C for 30 min, and wash by centrifugation with deionized water to obtain aldehyde-modified nanocellulose.

2. The antibacterial and corrosion-resistant EVA liquid storage bag material according to claim 1, characterized in that: The mass ratio of the sodium alginate in step 1 to the ethylenediamine in step 2 is 10:

1.

3. The antibacterial and corrosion-resistant EVA liquid storage bag material according to claim 1, characterized in that: In the mixed solution of sodium hydroxide, urea and thiourea in step (1), the concentration of sodium hydroxide, the concentration of urea and the concentration of thiourea are 8 wt %, 8 wt % and 6.5 wt %.

4. The antibacterial and corrosion-resistant EVA liquid storage bag material according to claim 1, characterized in that: In the step (4), the mass ratio of sodium periodate to nanocellulose is 2:

1.

5. The antibacterial and corrosion-resistant EVA liquid storage bag material according to claim 1, characterized in that: In the step 3, the molar ratio of the aldehyde content of the aldehyde-modified nanocellulose, the silver-ammonia complex ions in the silver-ammonia solution, and glutathione is 1:(3-8):(5-10).

6. The antibacterial and corrosion-resistant EVA liquid storage bag material according to claim 1, characterized in that: In step 4, the volume ratio of the silver nanocluster micelles to the modified sodium alginate aqueous solution is 1:(1-3).

7. The antibacterial and corrosion-resistant EVA liquid storage bag material according to claim 1, characterized in that: The concentration of the polyurethane solution in step 8 is 0.2-0.4 g / mL.

8. The method for preparing an antibacterial and corrosion-resistant EVA liquid storage bag material according to any one of claims 1 to 7, characterized in that: The following steps are involved: (1) Mixing the core-shell structured antibacterial / corrosion-resistant filler and the EVA substrate uniformly; (2) Place the mixture in a mixer and mix it at a mixing temperature of 110°C and a double-roll speed of 100 r / min. Mix it twice, with each mixing time being 10 min.

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