A bulletproof and stab-proof composite material and preparation method thereof

Abstract

The invention discloses a bulletproof and stab-proof composite material and a preparation method thereof, and belongs to the technical field of bulletproof and stab-proof composite materials. A bulletproof and stab-proof composite material is composed of Kevlar fabric and STF fluid; the STF fluid is prepared by the following method: adding mesoporous silica to polyethylene glycol, adding modified xanthan gum after high-speed dispersion for 5-20 minutes, continuing high-speed dispersion, and then placing in a vacuum drying oven at 40-55°C for 12-24 hours to obtain the STF fluid; the Kevlar fabric is impregnated in the STF fluid to obtain a high-performance bulletproof and stab-proof composite material.

Description

Technical Field

[0001] The present invention relates to the technical field of bulletproof and stab-proof composite materials, and in particular to a bulletproof and stab-proof composite material and a preparation method thereof. Background Art

[0002] With the rapid development of economy and society, the technology of military and police equipment is becoming more and more advanced. Among them, bulletproof vests are a very important personal protective equipment, which plays an important role in protecting the lives and safety of soldiers and police and reducing the degree of casualties. The materials of lightweight bulletproof vests are mainly aramid 1414 and ultra-high molecular weight polyethylene fiber (UHMWPE) woven fabrics. The structure of bulletproof vests directly affects its protective performance. Changing the structure and processing method of bulletproof vests has an important impact on improving the performance of bulletproof vests.

[0003] Shear thickening fluid (STF) has the characteristic of rapidly increasing viscosity upon impact, and is used to improve the impact resistance of bulletproof and stab-proof clothing. A Chinese invention patent with publication number CN118996864A discloses a flexible protective material and a preparation method thereof, the flexible protective material comprising: a shear thickening fluid coating and a fabric combined, the shear thickening fluid coating comprising nanoparticles and a dispersing solvent, wherein the dispersing solvent comprises at least an acrylic acid block low molecular weight copolymer, but its stab resistance performance needs to be further improved. Summary of the invention

[0004] In view of the deficiencies in the prior art, an object of the present invention is to provide a bulletproof and stab-proof composite material and a preparation method thereof.

[0005] To achieve the above object, the present invention is implemented through the following technical solutions:

[0006] A bulletproof and stab-resistant composite material consisting of Kevlar fabric and STF fluid;

[0007] The STF fluid is prepared by the following method:

[0008] Mesoporous silica is added to PEG600, and modified xanthan gum is added after high-speed dispersion for 5-20 minutes, and high-speed dispersion is continued, and then placed in a vacuum drying oven at 40-55°C for 12-24 hours to obtain STF fluid;

[0009] The modified xanthan gum is prepared by grafting and copolymerizing xanthan gum with ((4-(phenylamino)phenyl)azanediyl)bis(2-hydroxypropane-3,1-diyl)bis(2-methylacrylate) and sodium tetradecene-1-sulfonate.

[0010] The modified xanthan gum is prepared by the following method:

[0011] Under a nitrogen atmosphere, xanthan gum, deionized water, and ((4-(phenylamino)phenyl)azanediyl)bis(2-hydroxypropane-3,1-diyl)bis(2-methylacrylate) are mixed and heated to 40-50°C; at the same time, sodium tetradecene-1-sulfonate solution and ammonium persulfate solution are slowly added dropwise for 10-30 minutes, and the graft copolymerization reaction is carried out for 2-3 hours to obtain modified xanthan gum.

[0012] The mass ratio of the deionized water, xanthan gum, ((4-(phenylamino)phenyl)azanediyl)bis(2-hydroxypropane-3,1-diyl)bis(2-methylacrylate), and sodium tetradecene-1-sulfonate solution is 100:25:(5-8):(15-20).

[0013] The mass ratio of the PEG600, mesoporous silica and modified xanthan gum is 100:(20-40):(3-5).

[0014] The mesoporous silica is prepared by the following method:

[0015] S1: Add anhydrous ethanol, octadecylamine and propane sultone into a reaction flask, protect with nitrogen, heat to 75±5°C, react for 6h, and post-treat to obtain sulfonated octadecylamine;

[0016] S2: Add anhydrous toluene, sulfonated octadecylamine, PEG600, and ethylenediamine into a three-necked flask equipped with a Dean-Stark water separator, stir under nitrogen protection, heat to 120±5°C for reaction, and post-treat to obtain a white flocculent solid, which is PEG600-SO 3 H block copolymer surfactant;

[0017] S3: Place PEG600-SO 3 The H block copolymer surfactant was dissolved in deionized water to prepare a solution with a concentration of 0.5-3.0 wt %, the pH of the solution was adjusted to 2.5±0.5 with HCl, and stirred at 50-60° C. for 2-3 h to form a uniform micellar solution;

[0018] S4: Slowly add TEOS to the micellar solution, stir at 45-55°C for 6-12h, cool to room temperature, stand, centrifuge, wash, and use ethanol / 0.1M HNO 3 The solution was extracted and vacuum dried to obtain mesoporous silica.

[0019] The TEOS is slowly added dropwise at a speed of 0.1-0.5 mL / min / 100 mL micelles, and the volume ratio of TEOS to micelle solution is (2.5-6):100.

[0020] The ethanol / 0.1M HNO 3The mixing volume ratio of the solution is 3:1, the extraction temperature is 35-45°C, and the extraction time is 10-14h.

[0021] A method for preparing a bulletproof and stab-proof composite material, characterized by comprising the following steps:

[0022] S1: Mix the STF fluid and anhydrous ethanol, stir and mix well to obtain a diluted solution of the STF fluid;

[0023] S2: Dip the Kevlar fabric into the diluent for 2-5 minutes, and take out the Kevlar fabric for pressing;

[0024] S3: Drying the impregnated fabric in a forced air oven to obtain a bulletproof and stab-proof composite material.

[0025] The weight ratio of the STF fluid to anhydrous ethanol is 1:(1.2-1.8).

[0026] The roller pressure of the pressing is 0.2-0.35MPa.

[0027] Due to the adoption of the above technical solution, the beneficial effects of the present invention include:

[0028] The present application provides a xanthan gum grafted with anti-ultraviolet functional groups and surface active functional groups, and prepares a novel PEG600-SO 3 H block copolymer surfactant, and a preparation process of mesoporous silica was developed using the surfactant. STF fluid was prepared by high-speed dispersion of mesoporous silica and modified xanthan gum with PEG600, and Kevlar fabric was immersed in the STF fluid to obtain a high-performance bulletproof and stab-proof composite material. DETAILED DESCRIPTION

[0029] The invention will be further described below in conjunction with the embodiments, but the invention is not limited to these embodiments.

[0030] Example 1 Preparation of ((4-(phenylamino)phenyl)azanediyl)bis(2-hydroxypropane-3,1-diyl)bis(2-methylacrylate):

[0031] Add 315g of glycidyl methacrylate and 184g of p-aminodiphenylamine into a reaction bottle, protect with nitrogen, stir and dissolve, heat to 90-95℃ for 4h, cool to room temperature, and obtain the product. The reaction equation is as follows:

[0032] .

[0033] Example 2 Preparation of modified xanthan gum:

[0034] Under a nitrogen atmosphere, 25 g of xanthan gum, 100 g of deionized water, and 5 g of ((4-(phenylamino)phenyl)azanediyl)bis(2-hydroxypropane-3,1-diyl)bis(2-methylacrylate) were stirred and mixed, and the temperature was raised to 40°C; at the same time, 15 g of sodium tetradecene-1-sulfonate solution (20 wt% aqueous solution) and 8 g of ammonium persulfate solution (0.05 mol / L) were slowly added dropwise for 5 min, and the graft copolymerization reaction was carried out for 3 h. The mixture was cooled to room temperature, 300 g of acetone was added, stirred and precipitated, and filtered to obtain modified xanthan gum.

[0035] Example 3 Preparation of modified xanthan gum:

[0036] Under a nitrogen atmosphere, 25 g of xanthan gum, 100 g of deionized water, and 6 g of ((4-(phenylamino)phenyl)azanediyl)bis(2-hydroxypropane-3,1-diyl)bis(2-methylacrylate) were stirred and mixed, and the temperature was raised to 45°C; at the same time, 18 g of sodium tetradecene-1-sulfonate solution (20 wt% aqueous solution) and 9 g of ammonium persulfate solution (0.05 mol / L) were slowly added dropwise for 5 min, and the graft copolymerization reaction was carried out for 2.5 h. The mixture was cooled to room temperature, 300 g of acetone was added, stirred and precipitated, and filtered to obtain modified xanthan gum.

[0037] Example 4 Preparation of modified xanthan gum:

[0038] Under a nitrogen atmosphere, 25 g of xanthan gum, 100 g of deionized water, and 8 g of ((4-(phenylamino)phenyl)azanediyl)bis(2-hydroxypropane-3,1-diyl)bis(2-methylacrylate) were stirred and mixed, and the temperature was raised to 50°C; at the same time, 20 g of sodium tetradecene-1-sulfonate solution (20 wt% aqueous solution) and 10 g of ammonium persulfate solution (0.05 mol / L) were slowly added dropwise for 5 min, and the graft copolymerization reaction was carried out for 2 h. The mixture was cooled to room temperature, 300 g of acetone was added, stirred and precipitated, and filtered to obtain modified xanthan gum.

[0039] Example 5 PEG600-SO 3 Preparation of H block copolymer surfactant:

[0040] Add 50 mL of anhydrous ethanol, 20 mmol of octadecylamine and 24 mmol of propane sultone into a reaction flask, stir, protect with nitrogen, heat to 75±5°C, react for 6 h, remove ethanol by rotary evaporation (40°C, -0.09 MPa) to obtain a viscous liquid, add 50 mL of icy ether, stir to precipitate a white solid, filter and vacuum dry (40°C, 12 h) to obtain sulfonated octadecylamine as white crystals;

[0041] 30 mL of anhydrous toluene, 10 mmol of sulfonated octadecylamine, 5 mmol of PEG600 and 3 mmol of ethylenediamine were added to a three-necked flask equipped with a Dean-Stark water separator, stirred under nitrogen protection, heated to 120±5°C for 24 h, and 5 mL of dry toluene was added every 6 h to prevent the system from being too viscous; the temperature was lowered to 60°C, and 10 mL of methanol was slowly added dropwise to quench the reaction; toluene was removed by rotary evaporation (50°C, -0.08 MPa) to obtain a yellow viscous liquid; the yellow viscous liquid was dissolved in 50 mL of deionized water, and dialyzed with a dialysis bag with a molecular weight cutoff of 3500 Da for 48 hours to remove unreacted PEG and ethylenediamine; a white flocculent solid was obtained after freeze drying (cold trap temperature: -50°C, vacuum degree <10 Pa) for 24 h; that is, PEG600-SO 3 H block copolymer surfactant.

[0042] Example 6 Preparation of mesoporous silica:

[0043] S1: PEG600-SO 3 The H block copolymer surfactant (prepared in Example 5) was dissolved in deionized water to prepare a solution with a concentration of 0.5 wt %, the pH of the solution was adjusted to 2.5 ± 0.5 with 0.1 M HCl, and stirred at 50 ° C for 3 h to form a uniform micellar solution;

[0044] S2: 12.5 mL of TEOS (tetraethyl orthosilicate) was slowly added to 500 mL of micellar solution at a rate of 0.5 mL / min; stirred at 45 °C for 12 h, cooled to room temperature, allowed to stand for 15 h, centrifuged at 8000 rpm for 15 min, washed alternately with anhydrous ethanol / deionized water 3 times (30 mL each time), and washed with 250 ml of anhydrous ethanol / 0.1 M HNO 3 Solution (anhydrous ethanol and 0.1MHNO 3 The solution was mixed in a volume ratio of 3:1) and extracted at 35°C for 14 h and dried in vacuo at 60°C for 24 h to obtain mesoporous silica microspheres with an average particle size of 82.3 nm, a dispersion coefficient of 2.79%, and a pore size of 4.1 nm (BET method).

[0045] Example 7 Preparation of mesoporous silica:

[0046] S1: PEG600-SO 3 The H block copolymer surfactant (prepared in Example 5) was dissolved in deionized water to prepare a solution with a concentration of 1.5 wt %, the pH of the solution was adjusted to 2.5 ± 0.5 with 0.1 M HCl, and stirred at 55 ° C for 2.5 h to form a uniform micellar solution;

[0047] S2: 20 mL of TEOS (tetraethyl orthosilicate) was slowly added to 500 mL of micellar solution at a rate of 1.5 mL / min; stirred at 50 °C for 8 h, cooled to room temperature, allowed to stand for 15 h, centrifuged at 8000 rpm for 15 min, washed alternately with anhydrous ethanol / deionized water 3 times (30 mL each time), and washed with 250 ml of anhydrous ethanol / 0.1 M HNO 3 Solution (anhydrous ethanol and 0.1MHNO 3 The solution was mixed in a volume ratio of 3:1) and extracted at 40°C for 12 h and dried in vacuo at 60°C for 24 h to obtain mesoporous silica with an average particle size of 59.4 nm, a dispersion coefficient of 2.53%, and a pore size of 3.5 nm (BET method).

[0048] Example 8 Preparation of mesoporous silica:

[0049] S1: PEG600-SO 3 The H block copolymer surfactant (prepared in Example 5) was dissolved in deionized water to prepare a solution with a concentration of 3.0 wt %, the pH of the solution was adjusted to 2.5 ± 0.5 with 0.1 M HCl, and stirred at 60 ° C for 2 h to form a uniform micellar solution;

[0050] S2: 30 mL of LTEOS (tetraethyl orthosilicate) was slowly added to 500 mL of micellar solution at a rate of 2.5 mL / min; stirred at 55 °C for 6 h, cooled to room temperature, allowed to stand for 15 h, centrifuged at 8000 rpm for 15 min, washed alternately with anhydrous ethanol / deionized water 3 times (30 mL each time), and washed with 250 ml of anhydrous ethanol / 0.1 M HNO 3 Solution (anhydrous ethanol and 0.1 M HNO 3 The solution was mixed in a volume ratio of 3:1) and extracted at 45°C for 10 h and dried in vacuo at 60°C for 24 h to obtain mesoporous silica with an average particle size of 45.8 nm, a dispersion coefficient of 2.28%, and a pore size of 3.1 nm (BET method).

[0051] Example 9 Preparation of bulletproof and stab-proof composite material:

[0052] S1: 20 g of mesoporous silica (prepared in Example 6) was added to 100 g of PEG600, and the mixture was dispersed at 800 rpm for 5 min; then 3 g of modified xanthan gum (prepared in Example 2) was added, and the mixture was dispersed at 800 rpm for 5 min, and then placed in a vacuum drying oven at 40° C. for 24 h to obtain an STF fluid;

[0053] S2: Mix 100 g of STF fluid with 120 g of anhydrous ethanol, stir and mix well to obtain a diluted solution of STF fluid;

[0054] S3: The Kevlar fabric is immersed in the diluent for 2 minutes, and the Kevlar fabric is taken out and rolled. The roller pressure is 0.2 MPa, and the roller is rolled 4 times, each time for 5 seconds;

[0055] S4: Dry the impregnated fabric in a forced air oven at 60° C. for 12 h to obtain a bulletproof and stab-proof composite material.

[0056] Example 10 Preparation of bulletproof and stab-proof composite material:

[0057] S1: 30 g of mesoporous silica (prepared in Example 7) was added to 100 g of PEG600, and the mixture was dispersed at 800 rpm for 10 min; then 4 g of modified xanthan gum (prepared in Example 3) was added, and the mixture was dispersed at 800 rpm for 10 min, and then placed in a vacuum drying oven at 50° C. for 15 h to obtain an STF fluid;

[0058] S2: Mix 100 g of STF fluid with 150 g of anhydrous ethanol, stir and mix well to obtain a diluted solution of STF fluid;

[0059] S3: The Kevlar fabric is immersed in the diluent for 4 minutes, and the Kevlar fabric is taken out and rolled. The roller pressure is 0.3 MPa, and the roller is rolled 4 times, each time for 5 seconds;

[0060] S4: Dry the impregnated fabric in a forced air oven at 60° C. for 12 h to obtain a bulletproof and stab-proof composite material.

[0061] Example 11 Preparation of bulletproof and stab-proof composite material:

[0062] S1: 40 g of mesoporous silica (prepared in Example 8) was added to 100 g of PEG600, and the mixture was dispersed at 800 rpm for 20 min; then 5 g of modified xanthan gum (prepared in Example 4) was added, and the mixture was dispersed at 800 rpm for 20 min, and then placed in a vacuum drying oven at 55° C. for 12 h to obtain an STF fluid;

[0063] S2: Mix 100 g of STF fluid with 180 g of anhydrous ethanol, stir and mix well to obtain a diluted solution of STF fluid;

[0064] S3: The Kevlar fabric is immersed in the diluent for 5 minutes, and the Kevlar fabric is taken out and rolled. The roller pressure is 0.35 MPa, and the roller is rolled 3 times, each time for 5 seconds;

[0065] S4: Dry the impregnated fabric in a forced air oven at 60° C. for 12 h to obtain a bulletproof and stab-proof composite material.

[0066] Comparative Example 1

[0067] The preparation process of the bullet-proof and stab-proof composite material is basically the same as that of Example 10, except that the modified xanthan gum prepared in Example 3 is replaced by unmodified xanthan gum.

[0068] Comparative Example 2

[0069] The preparation process of the bulletproof and stab-proof composite material is basically the same as that of Example 10, except that the modified xanthan gum prepared in Example 3 is replaced by the modified xanthan gum prepared by the following method:

[0070] Under a nitrogen atmosphere, 25 g of xanthan gum, 100 g of deionized water, and 6 g of ((4-(phenylamino)phenyl)azanediyl)bis(2-hydroxypropane-3,1-diyl)bis(2-methylacrylate) were stirred and mixed, and the temperature was raised to 45°C; 9 g of ammonium persulfate solution (0.05 mol / L) was slowly added dropwise for 5 min, and the graft copolymerization reaction was carried out for 2.5 h. The mixture was cooled to room temperature, 300 g of acetone was added, stirred, precipitated, and filtered to obtain modified xanthan gum.

[0071] Comparative Example 3

[0072] The preparation process of the bulletproof and stab-proof composite material is basically the same as that of Example 10, except that the modified xanthan gum prepared in Example 3 is replaced by the modified xanthan gum prepared by the following method:

[0073] Under nitrogen atmosphere, 25 g of xanthan gum, 100 g of deionized water, and 6 g of ultraviolet absorber (prepared by the method of step (1) of Example 1 of invention patent publication number CN119041239 A) were stirred and mixed, and the temperature was raised to 45°C; at the same time, 18 g of sodium tetradecene-1-sulfonate solution (20 wt% aqueous solution) and 9 g of ammonium persulfate solution (0.05 mol / L) were slowly added dropwise for 5 min, and the graft copolymerization reaction was carried out for 2.5 h. The mixture was cooled to room temperature, 300 g of acetone was added, stirred and precipitated, and filtered to obtain modified xanthan gum.

[0074] Comparative Example 4

[0075] The preparation process of the bulletproof and stab-proof composite material is basically the same as that of Example 10, except that the modified xanthan gum prepared in Example 3 is replaced by the modified xanthan gum prepared by the following method:

[0076] Under a nitrogen atmosphere, 25 g of xanthan gum, 100 g of deionized water, and 6 g of ((4-(phenylamino)phenyl)azanediyl)bis(2-hydroxypropane-3,1-diyl)bis(2-methylacrylate) were stirred and mixed, and the temperature was raised to 45°C; at the same time, 18 g of sodium styrene sulfonate (20 wt% aqueous solution) and 9 g of ammonium persulfate solution (0.05 mol / L) were slowly added dropwise for 5 min, and the graft copolymerization reaction was carried out for 2.5 h. The mixture was cooled to room temperature, 300 g of acetone was added, stirred and precipitated, and filtered to obtain modified xanthan gum.

[0077] Comparative Example 5

[0078] The preparation process of the bullet-proof and stab-proof composite material is basically the same as that of Example 10, except that the mesoporous silica prepared in Example 7 is replaced by commercially available 50 nm non-mesoporous silica (manufacturer: Avid Technology Huailai Co., Ltd.).

[0079] Comparative Example 6

[0080] The preparation process of the bullet-proof and stab-proof composite material is substantially the same as that of Example 10, except that the mesoporous silica prepared in Example 7 is replaced by silica prepared by the following method:

[0081] S1: Add 50 mL of anhydrous ethanol, 20 mmol of octadecylamine and 24 mmol of propane sultone into a reaction flask, stir, protect with nitrogen, heat to 75±5°C, react for 6 h, remove ethanol by rotary evaporation (40°C, -0.09 MPa) to obtain a viscous liquid, add 50 mL of icy ether, stir to precipitate a white solid, filter and vacuum dry (40°C, 12 h) to obtain sulfonated octadecylamine as white crystals;

[0082] S2: 30 mL of anhydrous toluene, 10 mmol of sulfonated octadecylamine, 5 mmol of PEG400, and 3 mmol of ethylenediamine were added to a three-necked flask equipped with a Dean-Stark water separator, stirred under nitrogen protection, heated to 120±5°C for 24 h, and 5 mL of dry toluene was added every 6 h to prevent the system from being too viscous; the temperature was lowered to 60°C, and 10 mL of methanol was slowly added dropwise to quench the reaction; toluene was removed by rotary evaporation (50°C, -0.08 MPa) to obtain a yellow viscous liquid; the yellow viscous liquid was dissolved in 50 mL of deionized water, and dialyzed with a dialysis bag with a molecular weight cutoff of 3500 Da for 48 h to remove unreacted PEG and ethylenediamine; freeze-dried (cold trap temperature: -50°C, vacuum degree <10 Pa) for 24 h to obtain a white flocculent solid; that is, PEG400-SO 3 H block copolymer surfactant;

[0083] S3: Place PEG400-SO 3 The H block copolymer surfactant was dissolved in deionized water to prepare a solution with a concentration of 1.5 wt %, the pH of the solution was adjusted to 2.5 ± 0.5 with 0.1 M HCl, and stirred at 55 °C for 2.5 h to form a uniform micellar solution;

[0084] S4: 20 mL of TEOS (tetraethyl orthosilicate) was slowly added to 500 mL of micellar solution at a rate of 1.5 mL / min; stirred at 50 °C for 8 h, cooled to room temperature, allowed to stand for 15 h, centrifuged at 8000 rpm for 15 min, washed alternately with anhydrous ethanol / deionized water 3 times (30 mL each time), and washed with 250 ml of ethanol / 0.1 M HNO 3 Solution (ethanol with 0.1 M HNO 3 The solution was mixed in a volume ratio of 3:1) and extracted at 40°C for 12 h and dried in vacuo at 60°C for 24 h to obtain mesoporous silica with an average particle size of 48.6 nm, a dispersion coefficient of 9.82%, and a pore size of 2.4 nm (BET method).

[0085] Comparative Example 7

[0086] The preparation process of the bullet-proof and stab-proof composite material is substantially the same as that of Example 10, except that the mesoporous silica prepared in Example 7 is replaced by silica prepared by the following method:

[0087] S1: Add 50 mL of anhydrous ethanol, 20 mmol of octadecylamine and 24 mmol of propane sultone into a reaction flask, stir, protect with nitrogen, heat to 75±5°C, react for 6 h, remove ethanol by rotary evaporation (40°C, -0.09 MPa) to obtain a viscous liquid, add 50 mL of icy ether, stir to precipitate a white solid, filter and vacuum dry (40°C, 12 h) to obtain sulfonated octadecylamine as white crystals;

[0088] S2: 30 mL of anhydrous toluene, 10 mmol of sulfonated octadecylamine, 5 mmol of PEG800, and 3 mmol of ethylenediamine were added to a three-necked flask equipped with a Dean-Stark water separator, stirred under nitrogen protection, heated to 120±5°C for 24 h, and 5 mL of dry toluene was added every 6 h to prevent the system from being too viscous; the temperature was lowered to 60°C, and 10 mL of methanol was slowly added dropwise to quench the reaction; toluene was removed by rotary evaporation (50°C, -0.08 MPa) to obtain a yellow viscous liquid; the yellow viscous liquid was dissolved in 50 mL of deionized water, and dialyzed with a dialysis bag with a molecular weight cutoff of 3500 Da for 48 h to remove unreacted PEG and ethylenediamine; freeze-dried (cold trap temperature: -50°C, vacuum degree <10 Pa) for 24 h to obtain a white flocculent solid; that is, PEG800-SO 3 H block copolymer surfactant;

[0089] S3: Place PEG800-SO 3 The H block copolymer surfactant was dissolved in deionized water to prepare a solution with a concentration of 1.5 wt %, the pH of the solution was adjusted to 2.5 ± 0.5 with 0.1 M HCl, and stirred at 55 °C for 2.5 h to form a uniform micellar solution;

[0090] S4: 20 mL of TEOS (tetraethyl orthosilicate) was slowly added to 500 mL of micellar solution at a rate of 1.5 mL / min; stirred at 50 °C for 8 h, cooled to room temperature, allowed to stand for 15 h, centrifuged at 8000 rpm for 15 min, washed alternately with anhydrous ethanol / deionized water 3 times (30 mL each time), and washed with 250 ml of ethanol / 0.1 M HNO 3 Solution (ethanol with 0.1 M HNO 3 The solution was mixed in a volume ratio of 3:1) and extracted at 40°C for 12 h and dried in vacuo at 60°C for 24 h to obtain mesoporous silica with an average particle size of 127.5 nm, a dispersion coefficient of 6.48%, and a pore size of 6.5 nm (BET method).

[0091] Comparative Example 8

[0092] The preparation process of the bullet-proof and stab-proof composite material is substantially the same as that of Example 10, except that the mesoporous silica prepared in Example 7 is replaced by silica prepared by the following method:

[0093] S1: PEG600-SO 3 The H block copolymer surfactant (prepared in Example 5) was dissolved in deionized water to prepare a solution with a concentration of 4 wt %, the pH of the solution was adjusted to 2.5 ± 0.5 with 0.1 M HCl, and stirred at 55° C. for 2.5 h to form a uniform micellar solution;

[0094] S2: 20 mL of TEOS (tetraethyl orthosilicate) was slowly added to 500 mL of micellar solution at a rate of 1.5 mL / min; stirred at 50 °C for 8 h, cooled to room temperature, allowed to stand for 15 h, centrifuged at 8000 rpm for 15 min, washed alternately with anhydrous ethanol / deionized water 3 times (30 mL each time), and washed with 250 ml of ethanol / 0.1 M HNO 3 Solution (ethanol with 0.1 M HNO 3 The solution was mixed in a volume ratio of 3:1) and extracted at 40°C for 12 h and dried in vacuo at 60°C for 24 h to obtain mesoporous silica with an average particle size of 55.3 nm, a dispersion coefficient of 2.39%, and a pore size of 2.6 nm (BET method).

[0095] Comparative Example 9

[0096] Preparation of bulletproof and stab-proof composite materials:

[0097] S1: 30 g of mesoporous silica (prepared in Example 7) was added to 100 g of PEG600, and the mixture was dispersed at 800 rpm for 10 min; the mixture was then placed in a vacuum drying oven at 50° C. for 15 h to obtain an STF fluid;

[0098] S2: Mix 100 g of STF fluid with 150 g of anhydrous ethanol, stir and mix well to obtain a diluted solution of STF fluid;

[0099] S3: The Kevlar fabric is immersed in the diluent for 4 minutes, and the Kevlar fabric is taken out and rolled, with a roller pressure of 0.3 MPa, and rolled 5 times, each time for 5 seconds;

[0100] S4: Dry the impregnated fabric in a forced air oven at 60° C. for 12 h to obtain a bulletproof and stab-proof composite material.

[0101] Comparative Example 10

[0102] Preparation of bulletproof and stab-proof composite materials:

[0103] S1: 30 g of mesoporous silica (prepared in Example 7) was added to 100 g of PEG600, and the mixture was dispersed at 800 rpm for 10 min; then 4 g of modified xanthan gum (prepared in Example 3) was added, and the mixture was dispersed at 800 rpm for 10 min, and then placed in a vacuum drying oven at 50° C. for 15 h to obtain an STF fluid;

[0104] S2: 100 g of STF fluid (shear thickening fluid prepared by the method of Example 1 of the invention patent publication number CN118996864A) is mixed with 150 g of anhydrous ethanol, and stirred to obtain a diluted solution of the STF fluid;

[0105] S3: The Kevlar fabric is immersed in the diluent for 4 minutes, and the Kevlar fabric is taken out and rolled, with a roller pressure of 0.3 MPa, and rolled 5 times, each time for 5 seconds;

[0106] S4: Dry the impregnated fabric in a forced air oven at 60° C. for 12 h to obtain a bulletproof and stab-proof composite material.

[0107] Comparative Example 11

[0108] The preparation process of the bullet-proof and stab-proof composite material is substantially the same as that of Example 10, except that the mesoporous silica prepared in Example 7 is replaced by silica prepared by the following method:

[0109] S1: The surfactant CTAB was dissolved in deionized water to prepare a solution with a concentration of 1.5 wt%, the pH of the solution was adjusted to 2.5 ± 0.5 with 0.1 M HCl, and stirred at 55 °C for 2.5 h to form a uniform micellar solution;

[0110] S2: 20 mL of TEOS (tetraethyl orthosilicate) was slowly added to 500 mL of micellar solution at a rate of 1.5 mL / min; stirred at 50 °C for 8 h, cooled to room temperature, allowed to stand for 15 h, centrifuged at 8000 rpm for 15 min, washed alternately with anhydrous ethanol / deionized water 3 times (30 mL each time), and washed with 250 ml of ethanol / 0.1 M HNO 3 Solution (ethanol with 0.1 M HNO 3 The solution was mixed in a volume ratio of 3:1) and extracted at 40°C for 12 h and dried in vacuo at 60°C for 24 h to obtain mesoporous silica with an average particle size of 65.8 nm, a dispersion coefficient of 7.85%, and a pore size of 4.9 nm (BET method).

[0111] The Kevlar fabric used in this application is plain Kevlar-29 with a surface density of 200g / m 2 , warp density 8.7ends / cm, weft density 8.7ends / cm, fabric thickness 0.38mm, purchased from DuPont (China) Co., Ltd., cut into 10cm×10cm specifications when used. The ethanol described in this application is all anhydrous ethanol.

[0112] The particle size, morphology and distribution state were observed using a transmission electron microscope (TEM). The particles were first ultrasonically dispersed in an ethanol solution, and a copper mesh was clamped with tweezers and shaken up and down in the solution for about 100 times to ensure that the particles were successfully attached to the copper mesh. Finally, the copper mesh was placed in an oven to bake to remove the ethanol solution.

[0113] The dynamic stab-proof performance of the bullet-proof and stab-proof composite materials prepared in Examples 9-11 and Comparative Examples 1-11 was tested before and after aging. The test results are shown in Table 1.

[0114] The dynamic stab resistance performance test method is as follows:

[0115] According to the US NIJ-0115.00 "Personal Armor Stab Test" test standard, the test was conducted on an Instron Dynatup 9250HV impact tester. The backing material consists of 4 layers of 6mm thick neoprene sponge, 1 layer of 30mm thick polyethylene closed-cell foam 33kg / m 2 , 2 layers of 6.5mm thick natural rubber, simulating the process of human body being stabbed. In this experiment, the total mass of the counterweight and the knife is 4.83kg, and it falls freely from a height of 507mm. When the test head passes through the test sample, the computer automatically outputs a series of related data such as impact load and energy change. Each sample test is repeated 5 times to obtain the average dynamic anti-stab force. During the test, the bulletproof and stab-proof composite fabric is cut into 10cm×10cm specifications and 9 layers are superimposed.

[0116] UV aging method: Cut the bulletproof and stab-proof composite material fabric into a specification of 10cm×10cm and place it in an aging box with 1000W high-pressure mercury lamp ultraviolet light and 80°C for continuous irradiation for 1000 hours.

[0117] The bulletproof test uses 1.1gFSP, and the test content is V50, which is the bullet velocity with a penetration probability of 50%. It is often used to analyze the difference in ballistic performance. During the test, the bulletproof and stab-proof composite fabric is cut into a specification of 10cm×10cm and 9 layers are stacked.

[0118] Table 1

[0119]

[0120] It can be seen from the data in Table 1 that the bulletproof and stab-resistant composite material prepared in the present application has excellent bulletproof and stab-resistant performance and anti-aging performance.

[0121] Comparative Examples 1 and 9 are bulletproof and stab-proof composite materials prepared by using unmodified xanthan gum and no xanthan gum, and their maximum stab load before aging is low and their anti-aging performance is poor. This shows that modified xanthan gum can be better compatible with polyethylene glycol and mesoporous silica by grafting anti-ultraviolet functional groups and surface active groups to form a more uniform STF fluid, which can significantly improve the interface compatibility of the composite material, reduce interface defects, and thus improve the overall mechanical properties and bulletproof and stab-proof performance of the material.

[0122] Comparative Example 2 is xanthan gum that is not modified with sodium tetradecene-1-sulfonate, and its maximum knife stab load before aging is only 860.5N; Comparative Example 4 is xanthan gum modified with sodium styrene sulfonate, and its maximum knife stab load before aging is only 880.3N. Compared with the rigid styrene sulfonate groups, the long-chain alkyl sulfonic acid groups in the xanthan gum modified with sodium tetradecene-1-sulfonate can form stronger chemical bonds with polyethylene glycol and mesoporous silica; the xanthan gum modified with sodium tetradecene-1-sulfonate can increase the interface roughness of the composite material by grafting long-chain alkyl sulfonic acid groups, which helps to further improve the interface bonding strength between the fabric and the STF fluid, thereby improving the overall stab resistance of the composite material.

[0123] Comparative Example 3 is a comparative example of using ketophenol antioxidant grafted xanthan gum, and its anti-ultraviolet aging performance is poor. The reason may be that ketophenol antioxidants mainly prevent photo-oxidative degradation of materials by absorbing ultraviolet energy; ketophenol antioxidants have relatively weak absorption capacity in the high-energy ultraviolet region, and their ability to terminate the free radical reaction of materials is not as good as the amine antioxidant prepared in Example 1 of the present application.

[0124] In STF fluid, mesoporous silica with high specific surface area can provide more active sites and enhance the interaction with polyethylene glycol and modified xanthan gum, thereby improving the shear thickening properties of the fluid. Therefore, when non-mesoporous silica is used to prepare STF fluid, its anti-puncture performance is poor, as shown in Comparative Example 5.

[0125] Comparative Examples 6 and 7 are PEG-SO prepared using PEG400 and PEG800, respectively. 3 H block copolymer surfactant, which is used as a template for the preparation of mesoporous silica; due to the low molecular weight of PEG400, the PEG-SO 3 The surface activity of H block copolymer surfactant is high, and the micelles formed are small, resulting in a smaller silica pore structure. The pore size distribution of small-pore mesoporous silica is narrow. Although it helps to improve the adsorption capacity and reactivity of the material, in stab-proof materials, this narrow pore size distribution may limit the uniform dispersion of the fluid when it is impacted, which will cause the local area of ​​the material to be unable to effectively absorb and disperse energy when it is stabbed, thereby reducing the stab-proof performance. PEG800 has a large molecular weight and low surface activity, and the micelles formed are larger. The data shows that the pore size and particle size of the mesoporous silica prepared by it are both large, and the stab-proof performance is poor. The reason is that the specific surface area of ​​large-pore mesoporous silica is relatively small, which limits its interaction with polyethylene glycol and modified xanthan gum, thereby affecting the shear thickening effect of the fluid.

[0126] Comparative Example 8 prepared small-pore mesoporous silica by increasing the concentration of the surfactant, and its stab-proof performance was poor. It can be seen from Comparative Examples 6, 7 and 8 that too large or too small mesopore diameters are not conducive to improving the stab-proof performance of the composite material.

[0127] Comparative Example 10 is a composite material prepared by using the shear thickening fluid of Example 1 of the invention patent publication number CN118996864A. As can be seen from Table 1, its puncture resistance and anti-aging properties are poor.

[0128] Comparative Example 11 is a mesoporous silica prepared using CTAB as a template, which has a high dispersion coefficient and a relatively large pore size, and the composite material prepared therefrom has poor puncture resistance.

[0129] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. However, any equivalent changes, modifications and evolutions made by ordinary technicians in the field without departing from the scope of the technical solution of the present invention by using the technical content disclosed above are all equivalent embodiments of the present invention. At the same time, any equivalent changes, modifications and evolutions made to the above embodiments based on the essential technology of the present invention are still within the protection scope of the technical solution of the present invention.

Claims

1. A bulletproof and stab-proof composite material, characterized in that: Composed of Kevlar fabric and STF fluid; The STF fluid is prepared by the following method: Mesoporous silica is added to PEG600, and modified xanthan gum is added after high-speed dispersion for 5-20 minutes, and high-speed dispersion is continued, and then placed in a vacuum drying oven at 40-55°C for 12-24 hours to obtain STF fluid; The modified xanthan gum is prepared by grafting and copolymerizing xanthan gum with ((4-(phenylamino)phenyl)azanediyl)bis(2-hydroxypropane-3,1-diyl)bis(2-methylacrylate) and sodium tetradecene-1-sulfonate; The mesoporous silica is prepared by the following method: S1: Add anhydrous ethanol, octadecylamine and propane sultone into a reaction flask, protect with nitrogen, heat to 75±5°C, react for 6h, and post-treat to obtain sulfonated octadecylamine; S2: Anhydrous toluene, sulfonated octadecylamine, PEG600 and ethylenediamine were added into a three-necked flask equipped with a Dean-Stark water separator, stirred under nitrogen protection, heated to 120±5°C for reaction, and post-treated to obtain a white flocculent solid, which is the PEG600-SO3H block copolymer surfactant; S3: dissolving the PEG600-SO3H block copolymer surfactant in deionized water to prepare a solution with a concentration of 0.5-3.0 wt%, adjusting the pH of the solution to 2.5±0.5 with HCl, and stirring at 50-60°C for 2-3h to form a uniform micellar solution; S4: Slowly add TEOS to the micelle solution, stir at 45-55°C for 6-12h, cool to room temperature, stand, centrifuge, wash, extract with ethanol / 0.1M HNO3 solution, and vacuum dry to obtain mesoporous silica.

2. The bulletproof and stab-proof composite material according to claim 1, characterized in that: The modified xanthan gum is prepared by the following method: Under a nitrogen atmosphere, xanthan gum, deionized water, and ((4-(phenylamino)phenyl)azanediyl)bis(2-hydroxypropane-3,1-diyl)bis(2-methylacrylate) are mixed and heated to 40-50°C; at the same time, sodium tetradecene-1-sulfonate solution and ammonium persulfate solution are slowly added dropwise for 10-30 minutes, and the graft copolymerization reaction is carried out for 2-3 hours to obtain modified xanthan gum.

3. The bulletproof and stab-proof composite material according to claim 2, characterized in that: The mass ratio of the deionized water, xanthan gum, ((4-(phenylamino)phenyl)azanediyl)bis(2-hydroxypropane-3,1-diyl)bis(2-methylacrylate), and sodium tetradecene-1-sulfonate solution is 100:25:(5-8):(15-20).

4. The bulletproof and stab-proof composite material according to claim 1, characterized in that: The mass ratio of the PEG600, mesoporous silica and modified xanthan gum is 100:(20-40):(3-5).

5. The bulletproof and stab-proof composite material according to claim 1, characterized in that: The TEOS is slowly added dropwise at a speed of 0.1-0.5 mL / min / 100 mL micelles, and the volume ratio of TEOS to micelle solution is (2.5-6):

100.

6. The bulletproof and stab-proof composite material according to claim 1, characterized in that: The mixing volume ratio of the ethanol / 0.1MHNO3 solution is 3:1, the extraction temperature is 35-45°C, and the extraction time is 10-14h.

7. A method for preparing the bulletproof and stab-proof composite material according to any one of claims 1 to 6, characterized in that: The following steps are involved: S1: Mix the STF fluid and anhydrous ethanol, stir and mix well to obtain a diluted solution of the STF fluid; S2: Dip the Kevlar fabric into the diluent for 2-5 minutes, and take out the Kevlar fabric for pressing; S3: Drying the impregnated fabric in a forced air oven to obtain a bulletproof and stab-proof composite material.

8. The method for preparing the bulletproof and stab-proof composite material according to claim 7, characterized in that: The weight ratio of the STF fluid to anhydrous ethanol is 1:(1.2-1.8).

9. The method for preparing the bulletproof and stab-proof composite material according to claim 8, characterized in that: The roller pressure of the pressing is 0.2-0.35MPa.

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