Intelligent protective compound fabric as well as preparation method and application thereof

Abstract

The invention discloses an intelligent protective compound fabric as well as a preparation method and application thereof, and relates to the technical field of materials. The intelligent protective composite fabric comprises a base fabric and a shear hardening coating which is self-assembled on the base fabric, wherein the whole shear hardening coating is of a nacreous layer imitating structure; the base fabric is one or more of Kevlar, ultra-high molecular weight polyethylene or carbon fibers; and the thickness of the shear hardening coating is 80 to 120 microns. The intelligent protective composite fabric has remarkable shear hardening capacity, has excellent flame retardance, thermal radiation shielding and impact protection performance, and can be widely applied to the field of fire protection.

Description

Technical Field

[0001] The present invention relates to the technical field of materials, and particularly to an intelligent protective composite fabric, a preparation method thereof, and an application thereof. Background Art

[0002] The performance requirements of fire-fighting fabrics in complex and extreme environments are extremely stringent. Fire-fighting protective clothing needs to simultaneously possess excellent impact resistance, flame retardancy, heat radiation isolation efficiency, and wearing comfort. However, traditional protective fabrics mostly adopt a single-performance design concept, resulting in deficiencies in their comprehensive protective efficiency. For example, although traditional polyester fire-fighting suits have good flame retardancy, their impact resistance and tear resistance are significantly insufficient. When encountering building collapses or high-impact loads during fire-fighting and rescue operations, polyester materials often cannot effectively resist impact energy, leading to material rupture and causing injuries to firefighters' bodies. In addition, the use of rigid protective clothing can improve mechanical strength, but it will sacrifice material flexibility, thereby affecting the operational flexibility of firefighters. Therefore, designing multifunctional composite fabrics with excellent flame retardancy, good mechanical properties, and comfort has become the research focus in the field of fire safety.

[0003] In summary, in the design of fire-fighting protective fabric composites, it is very necessary to achieve the coordinated improvement of impact resistance and flame retardancy. Summary of the Invention

[0004] The present invention aims to improve the deficiencies of traditional technologies and provides an intelligent protective composite fabric, a preparation method thereof, and an application thereof. This composite fabric has remarkable shear hardening ability and excellent flame retardancy, heat radiation shielding, and impact protection properties. Therefore, this composite fabric has broad application prospects in the field of fire-fighting protection.

[0005] The present invention adopts the following technical solutions:

[0006] An intelligent protective composite fabric, the intelligent protective composite fabric includes a base fabric and a shear hardening coating self-assembled on the base fabric, wherein the shear hardening coating as a whole has a nacre-like structure; the base fabric is one or more of Kevlar, ultra-high molecular weight polyethylene, or carbon fiber; the thickness of the shear hardening coating is 80 to 120 micrometers.

[0007] Furthermore, the shear hardening coating is made by dispersing metal nanosheets and shear hardening polyborosiloxane in an organic solvent at a temperature of 30 to 100 degrees Celsius and through a vacuum-assisted evaporation-induced technique; the concentration of the metal nanosheets is 0.4 to 0.8 grams per milliliter; the concentration of the shear hardening polyborosiloxane is 0.4 to 0.8 grams per milliliter.

[0008] Furthermore, the metal nanosheets are selected from one or more of magnesium hydroxide, titanium dioxide, or aluminum oxide.

[0009] Further, the shear-hardening polyborosiloxane is prepared by reacting silicone oil with a boride at a temperature of 30 to 400 °C; the mass ratio of the silicone oil to the boride is 30:1 to 4:1.

[0010] Further, the silicone oil is selected from one or more of hydroxy silicone oil, dimethyl silicone oil, or methyl silicone oil.

[0011] Further, the boride is selected from one or more of boric acid, boron chloride, or boron fluoride.

[0012] Further, the organic solvent is selected from one or more of ethanol, acetone, or n-hexane.

[0013] Further, the vacuum-assisted evaporation-induced process is carried out by evaporating for 1 to 100 hours at a temperature of 30 to 200 °C and a pressure of 1 to 100 Pa.

[0014] A method for preparing an intelligent protective composite fabric includes the following steps:

[0015] (1) Mix the silicone oil and the boride, and continuously stir them at a high temperature to make them react fully to construct dynamic boron-oxygen crosslinking bonds, obtaining a shear-hardening polyborosiloxane;

[0016] (2) Disperse the metal nanosheets in an organic solvent, and continuously stir to make them evenly dispersed, obtaining a metal nanosheet dispersion;

[0017] (3) Dissolve the shear-hardening polyborosiloxane obtained in step (1) in an organic solvent to obtain a shear-hardening polyborosiloxane solution;

[0018] (4) Blend the metal nanosheet dispersion obtained in step (2) with the shear-hardening polyborosiloxane solution obtained in step (3) to obtain a precursor liquid for vacuum-assisted evaporation-induced process;

[0019] (5) Cover the surface of the protective fabric with the precursor liquid obtained in step (4), place it in a vacuum degassing machine to evacuate the air, and carry out evaporation-induced and curing crosslinking until there is no liquid residue on the fabric surface;

[0020] (6) Cure the composite fabric obtained in step (5) in an oven to further crosslink the coating and the fabric, obtaining a composite fabric with a shear-hardening coating having a nacre-like structure.

[0021] The application of the above intelligent protective composite fabric in the field of fire protection.

[0022] The beneficial effects of the present invention are:

[0023] (1) The intelligent protective composite fabric of the present invention can provide a protective mechanism with a dynamic response strategy, and its core principle is to make adaptive adjustments according to the externally applied load. During daily wear, the fabric exhibits flexible characteristics to ensure comfort; while under impact load, the fabric exhibits shear hardening characteristics, thereby enhancing its impact resistance. Such a protective mechanism realizes an efficient and flexible self-intelligent protection function by real-time sensing and analyzing changes in the external environment.

[0024] (2) The intelligent protective composite fabric of the present invention has a shear hardening coating with a nacre-like structure, which has significant shear hardening characteristics and stable rheological properties, and is significantly superior to traditional composite fabrics in terms of bulletproof performance, and exhibits excellent high-energy dissipation effects.

[0025] (3) The intelligent protective composite fabric of the present invention has excellent flame retardant and heat radiation shielding characteristics.

[0026] (4) The preparation method of the intelligent protective composite fabric of the present invention is simple, scalable, capable of realizing large-scale production of the composite fabric, and the technology is mature and reliable. Brief Description of the Drawings

[0027] Figure 1 Schematic diagram of the intelligent protective composite fabric obtained from Example 9 to Example 12 of the present invention.

[0028] Figure 2 Scanning electron microscope image of the intelligent protective composite fabric prepared in Example 9 of the present invention.

[0029] Figure 3 Scanning electron microscope image of the nacre-like structure of the present invention.

[0030] Figure 4 Relationship curve between the storage modulus and frequency of the shear hardening polyborosiloxane obtained in Example 1.

[0031] Figure 5 Protective effects of the existing Kevlar fabric and the intelligent protective composite fabric prepared in Example 9 of the present invention under bullet penetration.

[0032] Figure 6 Limiting oxygen index test diagrams of the intelligent protective composite fabrics prepared in Comparative Example 1 and Example 9 to Example 11.

[0033] Figure 7 Shows the flame retardant effects of the commonly used fireproof clothing and the intelligent protective composite fabric prepared in Example 9 of the present invention.

[0034] Figure 8 Application scenarios of the intelligent protective composite fabric of the present invention. Detailed Description of the Invention

[0035] In order to make the objectives, technical solutions and advantages of the present invention more clear and understandable, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0036] Example 1:

[0037] The preparation method of the shear-hardening polyborosiloxane is as follows:

[0038] (1) Completely dissolve 2 grams of boric acid in 60 grams of hydroxy silicone oil;

[0039] (2) Stir the mixture obtained in step (1) at 160 °C for 2.5 hours until it reacts into a gel;

[0040] (3) Place the product obtained in step (2) in an oven at 30 °C to cool, and the shear-hardening polyborosiloxane is obtained.

[0041] Example 2:

[0042] The preparation method of the shear-hardening polyborosiloxane is as follows:

[0043] (1) Completely dissolve 3 grams of boric acid in 60 grams of hydroxy silicone oil;

[0044] (2) Stir the mixture obtained in step (1) at 160 °C for 2.5 hours until it reacts into a gel;

[0045] (3) Place the product obtained in step (2) in an oven at 30 °C to cool, and the shear-hardening polyborosiloxane is obtained.

[0046] Example 3:

[0047] The preparation method of the shear-hardening polyborosiloxane is as follows:

[0048] (1) Completely dissolve 6 grams of boric acid in 60 grams of hydroxy silicone oil;

[0049] (2) Stir the mixture obtained in step (1) at 160 °C for 2.5 hours until it reacts into a gel;

[0050] (3) Place the product obtained in step (2) in an oven at 30 °C to cool, and the shear-hardening polyborosiloxane is obtained.

[0051] Example 4:

[0052] The preparation method of the shear-hardening polyborosiloxane is as follows:

[0053] (1) Dissolve 15 g of boric acid completely in 60 g of hydroxy silicone oil;

[0054] (2) Stir the mixture obtained in step (1) at 160 °C for 2.5 h until it reacts into a jelly;

[0055] (3) Place the product obtained in step (2) in a drying oven at 30 °C to cool, and shear-hardening polyborosiloxane is obtained.

[0056] Example 5:

[0057] The preparation method of the shear-hardening coating is as follows:

[0058] (1) Dissolve 5 g of the shear-hardening polyborosiloxane obtained in Example 1 in 12.5 mL of ethanol at 30 °C and ultrasonically treat for 6 h;

[0059] (2) Disperse 5 g of magnesium hydroxide in 12.5 mL of ethanol at 30 °C and ultrasonically treat for 6 h;

[0060] (3) Mix the shear-hardening polyborosiloxane-ethanol solution obtained in step (1) and the magnesium hydroxide-ethanol dispersion obtained in step (2) in equal volume to obtain a shear-hardening coating for vacuum-assisted evaporation-induced.

[0061] Example 6:

[0062] The preparation method of the shear-hardening coating is as follows:

[0063] (1) Dissolve 10 g of the shear-hardening polyborosiloxane obtained in Example 1 in 12.5 mL of ethanol at 30 °C and ultrasonically treat for 6 h;

[0064] (2) Disperse 5 g of magnesium hydroxide in 12.5 mL of ethanol at 30 °C and ultrasonically treat for 6 h;

[0065] (3) Mix the shear-hardening polyborosiloxane-ethanol solution obtained in step (1) and the magnesium hydroxide-ethanol dispersion obtained in step (2) in equal volume to obtain a shear-hardening coating for vacuum-assisted evaporation-induced.

[0066] Example 7:

[0067] The preparation method of the shear-hardening coating is as follows:

[0068] (1) Dissolve 5 g of the shear-hardening polyborosiloxane obtained in Example 1 in 12.5 mL of ethanol at 30 °C and ultrasonically treat for 6 h;

[0069] (2) Disperse 10 g of magnesium hydroxide in 12.5 mL of ethanol at 30 °C and sonicate for 6 hours;

[0070] (3) Mix the shear-thickening polyborosiloxane-ethanol solution obtained in step (1) and the magnesium hydroxide-ethanol dispersion obtained in step (2) in equal volumes to obtain a shear-thickening coating for vacuum-assisted evaporation-induced.

[0071] Example 8:

[0072] The preparation method of the shear-thickening coating is as follows:

[0073] (1) Dissolve 10 g of the shear-thickening polyborosiloxane obtained in Example 1 in 12.5 mL of ethanol at 30 °C and sonicate for 6 hours;

[0074] (2) Disperse 10 g of magnesium hydroxide in 12.5 mL of ethanol at 30 °C and sonicate for 6 hours;

[0075] (3) Mix the shear-thickening polyborosiloxane-ethanol solution obtained in step (1) and the magnesium hydroxide-ethanol dispersion obtained in step (2) in equal volumes to obtain a shear-thickening coating for vacuum-assisted evaporation-induced.

[0076] Example 9:

[0077] The preparation method of the intelligent protective composite fabric with nacre-like structure is as follows:

[0078] (1) Cover the surface of a 5-cm side square Kevlar fabric with 25 mL of the shear-thickening coating obtained in Example 5, place it in a vacuum degassing machine for degassing, and carry out evaporation-induced and curing crosslinking for 24 hours until there is no liquid residue on the fabric surface, so as to form hydrogen bonds and dynamic borate bonds;

[0079] (2) Place the composite fabric obtained in step (1) in an oven at 100 °C for curing for 48 hours to further crosslink the coating and the fabric, and obtain an intelligent protective composite fabric with nacre-like structure.

[0080] Example 10:

[0081] The preparation method of the intelligent protective composite fabric with nacre-like structure is as follows:

[0082] (1) Cover the surface of a 5-cm side square Kevlar fabric with 25 mL of the shear-thickening coating obtained in Example 6, place it in a vacuum degassing machine for degassing, and carry out evaporation-induced and curing crosslinking for 24 hours until there is no liquid residue on the fabric surface, so as to form hydrogen bonds and dynamic borate bonds;

[0083] (2) Place the composite fabric obtained in step (1) in an oven at 100 °C for 48 hours to further crosslink the coating with the fabric, obtaining an intelligent protective composite fabric with a nacre-like structure.

[0084] Example 11:

[0085] The preparation method of the intelligent protective composite fabric with a nacre-like structure is as follows:

[0086] (1) Cover the surface of a 5-cm side square Kevlar fabric with 25 ml of the shear-thickening coating obtained in Example 7, place it in a vacuum degassing machine for degassing, and perform evaporation-induced and curing crosslinking for 24 hours until there is no liquid residue on the fabric surface, forming hydrogen bonds and dynamic borate bonds;

[0087] (2) Place the composite fabric obtained in step (1) in an oven at 100 °C for 48 hours to further crosslink the coating with the fabric, obtaining an intelligent protective composite fabric with a nacre-like structure.

[0088] Example 12:

[0089] The preparation method of the intelligent protective composite fabric with a nacre-like structure is as follows:

[0090] (1) Cover the surface of a 5-cm side square Kevlar fabric with 25 ml of the shear-thickening coating obtained in Example 8, place it in a vacuum degassing machine for degassing, and perform evaporation-induced and curing crosslinking for 24 hours until there is no liquid residue on the fabric surface, forming hydrogen bonds and dynamic borate bonds;

[0091] (2) Place the composite fabric obtained in step (1) in an oven at 100 °C for 48 hours to further crosslink the coating with the fabric, obtaining an intelligent protective composite fabric with a nacre-like structure.

[0092] Comparative Example 1:

[0093] The preparation method of the shear-thickening fabric in this example is as follows:

[0094] (1) Dissolve 5 g of the shear-thickening polyborosiloxane obtained in Example 1 in 25 ml of ethanol at 30 °C and sonicate for 6 hours;

[0095] (2) Cover the surface of a 5-cm side square Kevlar fabric with 25 ml of the shear-thickening polyborosiloxane-ethanol solution obtained in step (1), place it in a vacuum degassing machine for degassing, and perform evaporation-induced and curing crosslinking for 24 hours until there is no liquid residue on the fabric surface;

[0096] (3) The composite fabric obtained in step (2) is placed in an oven at 100 °C for curing for 48 hours to further crosslink the coating with the fabric, obtaining a shear-thickening fabric.

[0097] Figure 1 It is a schematic diagram of the intelligent protective composite fabric obtained in Examples 9 to 12 of the present invention. Among them, the upper layer is a shear-thickening coating with a nacre-like structure, and the lower layer is a Kevlar fabric.

[0098] Figure 2 and Figure 3 It is a scanning electron micrograph of the intelligent protective composite fabric prepared in Example 9 of the present invention and the nacre structure. From Figure 2 and Figure 3 it can be seen that the nacre specifically exhibits a "brick and mortar"-type layered structure. After the metal nanosheets and the shear-thickening polyborosiloxane are self-assembled, a "brick and mortar"-type layered structure as shown in Figure 3 is formed on the surface of the base fabric. This structure can effectively dissipate energy, thereby improving the protective performance of the composite fabric.

[0099] Figure 4 It is a relationship curve of the storage modulus and frequency of the shear-thickening polyborosiloxane obtained in Example 1. The storage modulus of the shear-thickening polyborosiloxane obtained in Example 1 is tested by the frequency scanning module of a rotational rheometer. From Figure 4 it can be seen that the storage modulus of the shear-thickening polyborosiloxane increases from 1.40 kPa at 0.1 Hz to 311.58 kPa at 100 Hz, showing significant shear-thickening characteristics. In addition, through long-term aging experiments, the storage modulus curve at the 24th month is basically the same as that at the 1st month, proving its stable rheological properties.

[0100] Figure 5 It is the protective effect of the existing Kevlar fabric and the intelligent protective composite fabric prepared in Example 9 of the present invention under bullet penetration. Through a ballistic test platform, the protective effects of Kevlar and the composite fabric are tested under bullet penetration at 68.26 m / s and 190.04 m / s respectively. From Figure 5 it can be seen that Kevlar is instantly penetrated under bullet penetration, while the composite fabric rebounds the bullet at a higher speed.

[0101] Figure 6 It is a test chart of the limiting oxygen index of the intelligent protective composite fabrics prepared in Comparative Example 1 and Examples 9 to 11. Among them, the limiting oxygen index is tested by a limiting oxygen index tester. From Figure 6It can be seen that the limiting oxygen indices of the composite fabric 1 prepared in Example 10, the composite fabric 2 prepared in Example 9, and the composite fabric 3 prepared in Example 11 are 26.0%, 28.5%, and 34.5% respectively, all of which are higher than 24.5% of the shear-hardening fabric prepared in Comparative Example 1.

[0102] Figure 7 The flame retardant effects of a commonly used fire-fighting suit and the intelligent protective composite fabric prepared in Example 9 of the present invention are shown. Figure 7 It can be seen that the fire-fighting suit was damaged after burning for 5 minutes and a large amount of smoke was generated. However, the composite fabric prepared in Example 9 of the present invention remained intact after burning for 60 minutes and no smoke was generated.

[0103] Figure 8 This is the application scenario of the intelligent protective composite fabric of the present invention. Figure 8 It can be seen that when the composite fabric is worn on the human body, it is soft without losing strength, which not only ensures the freedom of movement of the human body but also provides effective safety protection.

[0104] Those skilled in the art can easily understand that the above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, and improvements made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

[0105] The parts not detailed in the specification of the present invention belong to the well-known technologies in the art. The above embodiments are only for the purpose of describing the present invention and are not intended to limit the scope of the present invention. The scope of the present invention is defined by the appended claims. All equivalent replacements and modifications made without departing from the spirit and principles of the present invention shall be covered within the scope of the present invention.

Claims

1. An intelligent protective composite fabric, characterized in that: The intelligent protective composite fabric includes a base fabric and a shear-thickening coating self-assembled on the base fabric, wherein the shear-thickening coating has an overall nacre-like structure; the base fabric is one or more of Kevlar, ultra-high molecular weight polyethylene, or carbon fiber; the thickness of the shear-thickening coating is 80 to 120 microns.

2. The intelligent protection composite fabric according to claim 1, characterized in that: The shear-thickening coating is prepared by dispersing metal nanosheets and shear-thickening polyborosiloxane in an organic solvent at a temperature of 30 to 100 °C and then using a vacuum-assisted evaporation-induced technique; the concentration of the metal nanosheets is 0.4 to 0.8 grams per milliliter; the concentration of the shear-thickening polyborosiloxane is 0.4 to 0.8 grams per milliliter.

3. The intelligent protection composite fabric according to claim 2, wherein: The metal nanosheets are selected from one or more of magnesium hydroxide, titanium dioxide, or aluminum oxide.

4. The intelligent protective composite fabric according to claim 2, characterized in that: The shear-thickening polyborosiloxane is prepared by reacting silicone oil with a boride at a temperature of 30 to 400 °C; the mass ratio of silicone oil to boride is 30:1 to 4:

1.

5. The intelligent protective composite fabric according to claim 4, wherein: The silicone oil is selected from one or more of hydroxy silicone oil, dimethyl silicone oil, or methyl silicone oil.

6. The intelligent protective composite fabric according to claim 4, wherein: The boride is selected from one or more of boric acid, boron chloride, or boron fluoride.

7. The intelligent protective composite fabric according to claim 2, wherein: The organic solvent is selected from one or more of ethanol, acetone, or n-hexane.

8. The intelligent protective composite fabric according to claim 2, characterized in that: The vacuum-assisted evaporation-induced process is carried out by evaporating for 1 to 100 hours at a temperature of 30 to 200 °C and a pressure of 1 to 100 Pa.

9. A method for preparing the intelligent protective composite fabric according to any one of claims 1 to 8, characterized in that, It includes the following steps: Step 1: Mix silicone oil and a boride, and make them react fully by continuous stirring at high temperature to construct dynamic boron-oxygen cross-linking bonds to obtain shear-thickening polyborosiloxane; Step 2: Disperse metal nanosheets in an organic solvent and continuously stir to make them evenly dispersed to obtain a metal nanosheet dispersion; Step 3: Dissolve the shear-thickening polyborosiloxane obtained in Step 1 in an organic solvent to obtain a shear-thickening polyborosiloxane solution; Step 4: Blend the metal nanosheet dispersion obtained in Step 2 with the shear-thickening polyborosiloxane solution obtained in Step 3 to obtain a precursor liquid for vacuum-assisted evaporation-induced process; Step 5: Cover the surface of the base fabric with the precursor liquid obtained in Step 4, place it in a vacuum degassing machine to evacuate air, and carry out evaporation-induced and curing cross-linking until there is no liquid residue on the fabric surface; Step 6: Cure the composite fabric obtained in Step 5 in an oven to further cross-link the coating and the fabric to obtain a composite fabric with a nacre-like structure shear-thickening coating.

10. Application of the intelligent protective composite fabric according to any one of claims 1 to 8 in the field of fire protection.

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