CN105155252B - Fabric of surface carbon nanotubes flame retardant coating and preparation method thereof - Google Patents

Abstract

The invention discloses a fabric with a carbon nanotube flame-retardant coating on the surface and a preparation method thereof. The two surfaces of the fabric are covered with at least one combined coating formed by an aminated carbon nanotube layer and a carboxylated carbon nanotube layer, and in the combined coating, the aminated carbon nanotube layer and the carboxylated carbon nanotube layer are respectively used as Inner and outer layers. The preparation method comprises: preparing aminated carbon nanotube suspension and carboxylated carbon nanotube suspension. The fabric is fully soaked in a sufficient amount of aminated carbon nanotube suspension, washed in deionized water, and vacuum-dried; then fully soaked in a sufficient amount of carboxylated carbon nanotube suspension, washed in deionized water, and vacuum-dried; repeat The above steps are performed several times to obtain the fabric with the carbon nanotube flame retardant coating on the surface. The preparation method of the invention is simple and easy, has good controllability, and is suitable for industrialized production; the treated fabric has good flame retardancy, and has broad application prospects in the fields of home textiles, composite materials, and the like.

Description

Fabric with carbon nanotube flame retardant coating on surface and preparation method thereof

technical field

The invention relates to a fabric and a preparation method thereof, in particular to a fabric with a carbon nanotube flame-retardant coating on the surface and a preparation method thereof.

Background technique

Fiber fabrics such as cotton and linen are widely used in the field of home textiles, and also have very good application prospects in the field of composite materials. However, such fabrics are easy to burn, which brings potential hidden dangers to life and property safety. Therefore, flame-retardant treatment of fiber fabrics such as cotton and linen is one of the research topics that has attracted much attention in the industry. Researchers at home and abroad often use methods such as padding-baking, sol-gel or graft modification to treat cotton and hemp fiber fabrics with flame retardant treatment, which often requires complex chemical reaction processes or special equipment. In recent years, the application of the layer-by-layer assembly method in the flame retardant treatment of fabrics has aroused great interest in the industry due to its simple operation, flexibility and good stability. However, currently reported flame-retardant coatings for fiber fabrics such as cotton and hemp often have high mass content, and poor corrosion resistance and thermal stability. Therefore, how to use a simple and effective method to prepare flame-retardant coatings with low mass content, good corrosion resistance and good thermal stability is an urgent problem to be solved.

Contents of the invention

In order to overcome the problems in the background technology, the object of the present invention is to provide a fabric with a carbon nanotube flame-retardant coating on its surface and a preparation method thereof.

In order to achieve the above object, the technical solution adopted by the present invention to solve the technical problems is:

1. A fabric with a carbon nanotube flame-retardant coating on its surface:

Both surfaces of the fabric are covered with at least one combined coating formed by an aminated carbon nanotube layer and a carboxylated carbon nanotube layer, and in the combined coating, the aminated carbon nanotube layer and the carboxylated carbon nanotube layer are respectively as inner and outer layers.

The fabric is cotton fiber or hemp fiber fabric.

Two, a kind of preparation method of the fabric that surface contains carbon nanotube flame retardant coating, comprises the following steps:

1) preparing aminated carbon nanotube suspension and carboxylated carbon nanotube suspension;

2) Fully soak the fabric in a sufficient amount of aminated carbon nanotube suspension for 5 to 30 minutes, wash it twice in deionized water, and vacuum dry; then fully soak in a sufficient amount of carboxylated carbon nanotube suspension for 5 to 30 minutes , washed twice in deionized water, and dried in vacuum;

3) Repeat step 2) several times to obtain the fabric with the carbon nanotube flame retardant coating on the surface.

The aminated carbon nanotube suspension is prepared in the following manner: ultrasonically disperse the dry aminated carbon nanotube powder in an organic solvent until uniformly dispersed, add deionized water, continue ultrasonically until uniformly dispersed, and form a concentration of 0.1 to 1.0 mg/mL of homogeneously dispersed suspension of aminated carbon nanotubes.

The carboxylated carbon nanotube suspension is prepared in the following manner: ultrasonically disperse the dry carboxylated carbon nanotube powder in an organic solvent until uniformly dispersed, add deionized water, continue ultrasonically until uniformly dispersed, and form a concentration of 0.1 to 1.0 mg/mL of a homogeneously dispersed suspension of carboxylated carbon nanotubes.

The organic solvent is N,N-dimethylformamide, dioxane, tetrahydrofuran or ethyl acetate.

The fabric is cotton fiber or hemp fiber fabric.

The volume ratio of the organic solvent to deionized water is 5-1:1.

The present invention adopts the layer-by-layer assembly method to prepare, and the layer-by-layer assembly method can alternately deposit the multilayer film on the surface of the substrate by means of the physical adsorption of positive and negative charges polyelectrolyte. wide range.

Compared with background technology, the beneficial effect of the present invention is:

The invention adopts a simple layer-by-layer assembly method, utilizes carbon nanotubes with light weight, good corrosion resistance and excellent thermal stability, and absorbs carbon nanotubes layer by layer on the surface of fiber fabrics such as cotton and hemp to form a flame-retardant function. The non-toxic coating will have a good application prospect for improving the fire safety of fiber fabrics such as cotton and linen.

The preparation method of the present invention is simple and easy to implement, has good controllability, and is suitable for industrial production; the present invention makes full use of the surface properties of cotton fibers or hemp fibers and the performance characteristics of carbon nanotubes, and the treated fabric has good flame-retardant properties , has broad application prospects in the fields of home textiles and composite materials.

Description of drawings

Fig. 1 is the SEM photograph of the surface morphology of the ramie fabric containing the carbon nanotube flame retardant coating prepared in Example 2.

detailed description

The present invention will be described in further detail below in conjunction with the accompanying drawings and specific embodiments.

Aminated carbon nanotubes, carboxylated carbon nanotubes, N,N-dimethylformamide, dioxane, tetrahydrofuran, cotton fabrics and ramie fabrics used in the examples are all commercially available materials. Among them, aminated carbon nanotubes, amino content: 0.45wt%, purity: >95%, length: ~50μm, outer diameter: 8-15nm; carboxylated carbon nanotubes, carboxyl content: 2.00wt%, purity: >95 %, length: 10-30 μm, outer diameter: 10-20 nm.

Example 1:

(1) Add 48 mg of dry aminated carbon nanotube powder into 400 mL of dioxane, sonicate until uniformly dispersed, add 80 mL of deionized water, continue to sonicate until uniformly dispersed, and form 480 mL of uniformly dispersed dioxane with a concentration of 0.1 mg/mL Aminated carbon nanotube suspension.

(2) Add 48 mg of dry carboxylated carbon nanotube powder into 400 mL of dioxane, sonicate until uniformly dispersed, add 80 mL of deionized water, continue to sonicate until uniformly dispersed, and form 480 mL of uniformly dispersed carboxylated carbon nanotubes with a concentration of 0.1 mg/mL. Carboxylated carbon nanotube suspension.

(3) Soak the ramie fabric (length × width: 400mm × 90mm) in the aminated carbon nanotube suspension formed in step (1) for 5min, wash it twice with 500mL deionized water, and dry it in vacuum at 60°C; Soak the suspension of carboxylated carbon nanotubes formed in step (2) for 5 minutes, wash with 500 mL of deionized water twice, and dry under vacuum at 60°C.

(4) Repeat step (3) 20 times to obtain the fabric with the carbon nanotube flame retardant coating on the surface.

The flame retardant performance test results are shown in Table 1.

Example 2:

(1) Add 400 mg of dry aminated carbon nanotube powder into 600 mL of tetrahydrofuran, sonicate until uniformly dispersed, add 200 mL of deionized water, continue to sonicate until uniformly dispersed, and form 800 mL of uniformly dispersed aminated carbon with a concentration of 0.5 mg/mL nanotube suspension.

(2) Add 400 mg of dry carboxylated carbon nanotube powder into 600 mL of tetrahydrofuran, sonicate until uniformly dispersed, add 200 mL of deionized water, continue to sonicate until uniformly dispersed, and form 800 mL of uniformly dispersed carboxylated carbon with a concentration of 0.5 mg/mL nanotube suspension.

(3) Soak the ramie fabric (length × width: 400mm × 90mm) in the aminated carbon nanotube suspension formed in step (1) for 10min, wash it twice with 800mL deionized water, and dry it in vacuum at 60°C; Soak the carboxylated carbon nanotube suspension formed in step (2) for 10 min, wash with 800 mL of deionized water twice, and dry under vacuum at 60°C.

(4) Repeat step (3) 20 times to obtain the fabric with the carbon nanotube flame retardant coating on the surface.

The surface morphology is shown in Figure 1. The surface of the ramie fabric is covered with a multi-layer carbon nanotube network structure. The flame retardant performance test results are shown in Table 1.

Example 3:

(1) Add 1000mg of dry aminated carbon nanotube powder into 500mL N,N-dimethylformamide, sonicate until uniformly dispersed, add 500mL of deionized water, continue sonicating until uniformly dispersed, and form 1000mL with a concentration of 1.0mg/mL homogeneously dispersed suspension of aminated carbon nanotubes.

(2) Add 1000mg of dry carboxylated carbon nanotube powder into 500mL N,N-dimethylformamide, sonicate until uniformly dispersed, add 500mL deionized water, continue sonicating until uniformly dispersed, and form 1000mL with a concentration of 1.0mg/mL homogeneously dispersed suspension of carboxylated carbon nanotubes.

(3) Soak the ramie fabric (length × width: 400mm × 90mm) in the aminated carbon nanotube suspension formed in step (1) for 30min, wash it twice with 1000mL deionized water, and dry it in vacuum at 60°C; Soak the suspension of carboxylated carbon nanotubes formed in step (2) for 30 min, wash with 1000 mL of deionized water twice, and dry under vacuum at 60°C.

(4) Repeat step (3) 20 times to obtain the fabric with the carbon nanotube flame retardant coating on the surface.

The flame retardant performance test results are shown in Table 1.

Each embodiment of the present invention has carried out the flame retardant performance test, and the flame retardant performance test result of the fabric containing the carbon nanotube flame retardant coating on the surface of the gained is as shown in Table 1, wherein the blank sample does not contain the carbon nanotube flame retardant coating pure ramie fabric. Flame retardant performance test method: micro calorimeter (Govmark MCC-2, USA), the oxygen flow rate is set to 20mL/min, the nitrogen flow rate is set to 80mL/min, the sample is first kept at 100°C for 5min, and then the sample is heated at 1°C/sec The speed is heated up to 650 °C.

Table 1

In Table 1: PHRR: peak heat release rate, in W/g; THR: total heat release, in kJ/g.

Analysis of the data in Table 1 shows that the carbon nanotube flame-retardant coating of the present invention has a good flame-retardant effect on ramie fabrics, is simple and easy to implement, has good controllability, is suitable for industrial production, and has outstanding prospects and effects.

The above-mentioned embodiments are only used to explain the present invention, but not to limit the protection scope of the present invention. Any equivalent changes or modifications made within the spirit of the present invention and the protection scope of the claims are deemed to be within the protection scope of the present invention.

Claims (4)

1. A kind of 1. fabric of surface carbon nanotubes flame retardant coating, it is characterised in that：It is covered with least on two surfaces of fabric One layer of combination coating formed by aminated carbon nano tube layer and carboxylic carbon nano-tube layer, combine amination carbon nanometer in coating Tube layer and carboxylic carbon nano-tube layer are respectively as internal layer and outer layer；Described fabric is cotton fiber or hemp fabric；

   1) aminated carbon nano tube suspension and carboxylic carbon nano-tube suspension are prepared；

   Described carboxylic carbon nano-tube suspension is prepared in the following ways：Dry carboxylic carbon nano-tube powder is being had Ultrasound adds deionized water to dispersed in solvent, continues ultrasound to dispersed, it is 0.1~1.0mg/ to form concentration ML dispersed carboxylic carbon nano-tube suspension；

   Described aminated carbon nano tube suspension is prepared in the following ways：Dry aminated carbon nano tube powder is being had Ultrasound adds deionized water to dispersed in solvent, continues ultrasound to dispersed, it is 0.1~1.0mg/ to form concentration ML dispersed aminated carbon nano tube suspension；

   2) fabric is fully soaked into 5~30min in enough aminated carbon nano tube suspension, cleaned 2 times in deionized water, Vacuum drying；Then 5~30min is fully soaked in enough carboxylic carbon nano-tube suspension, 2 are cleaned in deionized water It is secondary, vacuum drying；

   3) repeat step 2) several times, obtain the fabric of described surface carbon nanotubes flame retardant coating.
2. 2. a kind of preparation method of the fabric of surface carbon nanotubes flame retardant coating, it is characterised in that comprise the following steps：

   1) aminated carbon nano tube suspension and carboxylic carbon nano-tube suspension are prepared；

   Described carboxylic carbon nano-tube suspension is prepared in the following ways：Dry carboxylic carbon nano-tube powder is being had Ultrasound adds deionized water to dispersed in solvent, continues ultrasound to dispersed, it is 0.1~1.0mg/ to form concentration ML dispersed carboxylic carbon nano-tube suspension；

   Described aminated carbon nano tube suspension is prepared in the following ways：Dry aminated carbon nano tube powder is being had Ultrasound adds deionized water to dispersed in solvent, continues ultrasound to dispersed, it is 0.1~1.0mg/ to form concentration ML dispersed aminated carbon nano tube suspension；

   2) fabric is fully soaked into 5~30min in enough aminated carbon nano tube suspension, cleaned 2 times in deionized water, Vacuum drying；Then 5~30min is fully soaked in enough carboxylic carbon nano-tube suspension, 2 are cleaned in deionized water It is secondary, vacuum drying；

   3) repeat step 2) several times, obtain the fabric of described surface carbon nanotubes flame retardant coating.
3. 3. a kind of preparation method of the fabric of surface carbon nanotubes flame retardant coating according to claim 2, its feature exist In：Described organic solvent is N,N-dimethylformamide, dioxane, tetrahydrofuran or ethyl acetate.
4. 4. a kind of preparation method of the fabric of surface carbon nanotubes flame retardant coating according to claim 2, its feature exist In：Described organic solvent and deionized water volume ratio are 5-1:1.