CN103266468A - Flame retardant conditioning method of intumescent flame retardant system on pure cotton fabrics - Google Patents

Abstract

The invention relates to a method for flame-retardant finishing of pure cotton fabrics by an intumescent flame-retardant system, comprising: stirring and dispersing montmorillonite and organic amine for 1-3 hours to obtain a dispersion liquid, then adding the dispersion liquid dropwise into fatty acid, adding a catalyst, At 160-210°C, under the condition of nitrogen protection, react for 4-7 hours, cool to obtain montmorillonite nanocomposites; heat the montmorillonite nanocomposites to 110-120°C, then add emulsifier and acetic acid, and keep warm for 15- After cooling for 30 minutes, add water to obtain a montmorillonite nanocomposite emulsion, then add resin crosslinking agent and ammonium polyphosphate, mix and disperse to obtain a flame-retardant finishing solution; pure cotton fabrics are dipped in the flame-retardant finishing solution, pre- Bake and bake to get flame retardant fabric. The invention overcomes the shortcomings of whitening and insufficient strength caused by the migration of ammonium polyphosphate with a high degree of polymerization on the surface of the fabric; overcomes the shortcomings of easy aggregation, migration and uneven dispersion of fine particles on the fabric.

Description

A method for flame-retardant finishing of pure cotton fabrics by an intumescent flame-retardant system

technical field

The invention belongs to the field of flame-retardant finishing methods, and in particular relates to a flame-retardant finishing method for pure cotton fabrics by an intumescent flame-retardant finishing system.

Background technique

Nanoscience and technology is an emerging high-tech field that emerged in the late 1980s. Its basic connotation is to study the manipulation of atoms or molecules to process materials within the space scale of 0.1-100nm, so as to prepare new materials with specific functions. Compared with conventional composite materials, montmorillonite nanocomposites have the following advantages: 1. The weight is lighter because of the low amount of inorganic substances added (organic soil mixed with 0.5wt% to 15wt% can significantly improve the performance of polymers); 2. .The mechanical properties are improved, and its nano-dispersed sheet structure strengthens the polymer in the two-dimensional direction; 3. Excellent gas barrier effect and certain flame retardant effect; 4. Does not affect the transparency of the material, and its dispersed sheet The thickness of the layer is about 1nm, which is equivalent to the wavelength of visible light, and the light wave can pass through directly; 5. The cost is low and the processing is convenient. It is precisely because of these advantages of montmorillonite nanocomposites that it has broad application prospects and has been extensively studied and valued by research institutions, governments and enterprises in various countries.

Phosphorus and nitrogen flame retardants are also called intumescent flame retardants. They do not contain halogens and do not use antimony oxide as a synergist. Intumescent flame retardants are generally composite flame retardants with P, N, and C elements as the core components. It is mainly composed of three parts: carbonization agent (carbon source), carbonization catalyst (acid source), expansion agent (gas source). The carbon source is a substance capable of forming an expanded porous carbon layer, and is generally a carbon-rich multifunctional (such as OH) carbon forming agent, such as pentaerythritol and its diacetal, triacetal, starch, etc. The availability of carbon sources is related to the carbon content and the number of active hydroxyl groups. The carbon source should react with the carbonization catalyst at a lower temperature than it decomposes itself or the polymer matrix.

Contents of the invention

The technical problem to be solved by the present invention is to provide a method for flame-retardant finishing of pure cotton fabrics by an intumescent flame-retardant system. The intumescent system composed of montmorillonite nanocomposites and ammonium polyphosphate synthesized by this method has a better flame-retardant effect , higher carbon formation rate; overcome the shortcomings of whitening and insufficient strength caused by the migration of ammonium polyphosphate with a high degree of polymerization on the surface of the fabric; overcome the problems of easy aggregation, migration and uneven dispersion of fine particles on the fabric Disadvantage: It overcomes the defect that the fabric feels severely stiff after flame-retardant finishing in the past.

A method for flame-retardant finishing of pure cotton fabrics by an intumescent flame-retardant system of the present invention, comprising:

(1) Stir and disperse montmorillonite and organic amine for 1-3 hours to obtain a dispersion liquid, then add the dispersion liquid dropwise to the fatty acid, add a catalyst, and react at 160-210°C for 4-7 hours under the condition of nitrogen protection, and cool. A montmorillonite nanocomposite material is obtained; wherein the molar ratio of fatty acid to organic amine is 1:0.52, and the mass percentage of montmorillonite in the composite material is 3-10%;

(2) Heat the above montmorillonite nanocomposite material to 110-120°C, then add emulsifier and acetic acid, keep warm for 15-30min, add water after cooling to obtain montmorillonite nanocomposite emulsion, then add resin crosslinking agent , ammonium polyphosphate, mixed and dispersed to obtain a flame-retardant finishing solution; the mass ratio of montmorillonite composite material, resin crosslinking agent, ammonium polyphosphate, emulsifier, acetic acid and water is (0.5-2): (0.4 ~1):(1-3):(0.1~0.3):(0.15~0.35):(10~15);

(3) Soak the pure cotton fabric in the flame-retardant finishing solution, pre-dry it, and bake it to obtain the flame-retardant fabric.

The organic amine in the step (1) is one of ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.

The fatty acid in the step (1) is one of stearic acid, oleic acid and capric acid.

The catalyst in the step (1) is an inorganic acid.

The inorganic acid is one of acetic acid, phosphoric acid and sulfuric acid.

The model of the emulsifier in the step (2) is T05 or OP10.

The amount of emulsifier in the step (2) is 10%-30% of the mass of the montmorillonite nanocomposite material.

The resin crosslinking agent in the step (2) is one of polyurethane resin, 2D resin, and formaldehyde-free anti-wrinkle resin TC.

In the step (2), the ammonium polyphosphate has a degree of polymerization greater than 1000.

In the step (2), by weight percentage, in the obtained flame retardant finishing liquid, 2% to 10% of montmorillonite nanocomposite material, 10% to 30% of ammonium polyphosphate (APP), and 4% to 30% of resin crosslinking agent 10%, emulsifier 0.5%~1.5% and water 40%~80%.

In the step (3), soak for 10-15 minutes, pre-bake at 80-100° C. for 5-10 minutes, and then bake at 150-180° C. for 3-8 minutes.

The preparation of montmorillonite nanocomposites is to fully disperse montmorillonite and organic amines first, so that the small molecules of organic amines enter the montmorillonite sheets, and then react with fatty acids under certain conditions to utilize the synthesized long carbon chain amide The distance between layers of montmorillonite is increased, so that the intercalated montmorillonite nanocomposite material is prepared.

Preparation of a new intumescent flame retardant system: heat and melt the montmorillonite nanocomposite material, add emulsifier and a small amount of acetic acid, add deionized water to fully disperse, add resin crosslinking agent, ammonium polyphosphate (polymerization degree) to the dispersion n>1000) water dispersion liquid, stir and disperse for a certain period of time to obtain a flame retardant finishing liquid.

The method of soaking-pad-drying is used for flame retardant finishing of pure cotton fabric, and the finished fabric has better flame retardant performance.

The present invention adopts a new method to synthesize montmorillonite nano-composite materials, and uses this kind of composite materials as the carbon forming agent of intumescent flame-retardant system for the first time, prepares flame-retardant finishing liquid, and performs flame-retardant finishing on cotton fabrics, Ultimately endow the fabric with better flame retardant properties.

Beneficial effect

1. The expansion system composed of montmorillonite nanocomposite material and ammonium polyphosphate synthesized by the present invention has better flame retardant effect and higher carbon formation rate;

2. The present invention overcomes the shortcomings of whitening and insufficient strength caused by the migration of ammonium polyphosphate with a high degree of polymerization on the surface of the fabric;

3. The present invention overcomes the disadvantages that fine particles are easy to gather, swim, and disperse unevenly on the fabric;

4. The present invention overcomes the defect that the hand feeling of the fabric after flame-retardant finishing is severely hardened in the past.

Description of drawings

Fig. 1 Diagram of flame retardant mechanism of fabric after flame retardant finishing.

Detailed ways

Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Example 1

(1) Preparation of stearic acid amide montmorillonite nanocomposites

Weigh 0.17mol of diethylenetriamine, put a certain amount of montmorillonite in a beaker, place it on a magnetic stirrer, stir and disperse for 3h, put 0.34mol of stearic acid into a four-necked round bottom flask, and heat up to 100°C After the stearic acid is completely melted, add a small amount of acetic acid as a catalyst, drop the dispersion of diethylenetriamine and montmorillonite into a four-necked bottle, raise the temperature to 160-180°C for 5 hours, and protect it under nitrogen. After the reaction is cooled, the stearic acid amide montmorillonite nanocomposite material is obtained.

(2) Preparation of flame retardant finishing liquid

Heat the synthesized montmorillonite nanocomposite material to 110°C, then add emulsifier and acetic acid, keep it warm for 30 minutes, add deionized water to fully emulsify after cooling to room temperature, and prepare montmorillonite nanocomposite emulsion, and add resin to the emulsion The cross-linking agent and ammonium polyphosphate are fully mixed, and dispersed with a high-speed disperser for 30 minutes to obtain a flame-retardant finishing solution. The mass ratio of montmorillonite composite material, resin crosslinking agent, ammonium polyphosphate, emulsifier, acetic acid and water is 1:1:3:0.3:0.15:15.

(3) Flame retardant finishing

The cotton poplin 4040×3372 is dipped in the above flame retardant finishing solution, dried in a blast oven at 80°C, and baked at 160°C.

(4) Vertical burning test

Use YG815 vertical method fabric combustion performance tester to test according to "GB/T5455-1997 Textile Combustion Performance Test Vertical Method", the afterburning time is 0s, the smoldering time is 0s, and the length of damaged carbon is 7.6cm.

Example 2

(1) Preparation of stearic acid amide montmorillonite nanocomposites

Weigh 0.17mol of diethylenetriamine, put a certain amount of montmorillonite in a beaker, place on a magnetic stirrer to stir and disperse for 3h, put 0.34mol of stearic acid into a four-necked round bottom flask, and heat up to 100°C After the stearic acid is completely melted, add a small amount of acetic acid as a catalyst, drop the dispersion of diethylenetriamine and montmorillonite into a four-necked bottle, raise the temperature to 160-180°C for 5 hours, and protect it under nitrogen. After the reaction is cooled, the stearic acid amide montmorillonite nanocomposite material is obtained.

(2) Preparation of flame retardant finishing liquid

Heat the synthesized montmorillonite nanocomposite material to 110°C, then add emulsifier and acetic acid, keep it warm for 30 minutes, add deionized water to fully emulsify after cooling to room temperature, and prepare montmorillonite nanocomposite material emulsion, and add resin to the emulsion The cross-linking agent and ammonium polyphosphate are fully mixed, and dispersed with a high-speed disperser for 30 minutes to obtain a flame-retardant finishing solution. The mass ratio of montmorillonite composite material, resin crosslinking agent, ammonium polyphosphate, emulsifier, acetic acid and water is 1:1:3:0.3:0.25:10.

(3) Flame retardant finishing

The cotton poplin 4040×3372 is dipped in the above flame retardant finishing solution, dried in a blast oven at 80°C, and baked at 160°C.

(4) Vertical burning test

Use YG815 vertical fabric combustion performance tester to test according to "GB/T5455-1997 Textile Combustion Performance Test Vertical Method", the afterburn time is 0s, the smoldering time is 0s, and the length of the damaged carbon is 3.2cm.

Example 3

(1) Preparation of stearic acid amide montmorillonite nanocomposites

Weigh 0.17mol of diethylenetriamine, put a certain amount of montmorillonite in a beaker, place on a magnetic stirrer to stir and disperse for 3h, put 0.34mol of stearic acid into a four-necked round bottom flask, and heat up to 100°C After the stearic acid is completely melted, add a small amount of acetic acid as a catalyst, drop the dispersion of diethylenetriamine and montmorillonite into a four-necked bottle, raise the temperature to 160-180°C for 5 hours, and protect it under nitrogen. After the reaction is cooled, the stearic acid amide montmorillonite nanocomposite material is obtained.

(2) Preparation of flame retardant finishing liquid

Heat the synthesized montmorillonite nanocomposite material to 110°C, then add emulsifier and acetic acid, keep it warm for 30 minutes, add deionized water to fully emulsify after cooling to room temperature, and prepare montmorillonite nanocomposite material emulsion, and add resin to the emulsion The cross-linking agent and ammonium polyphosphate are fully mixed, and dispersed with a high-speed disperser for 30 minutes to obtain a flame-retardant finishing solution. The mass ratio of montmorillonite composite material, resin crosslinking agent, ammonium polyphosphate, emulsifier, acetic acid and water is 0.5:1:3:0.3:0.15:15.

(3) Flame retardant finishing

Immerse cotton poplin 4040×3372 in the above-mentioned flame-retardant finishing solution, dry in a blast oven at 80°C, and bake at 160°C.

(4) Vertical burning test

Use the YG815 vertical method fabric combustion performance tester to test according to "GB/T5455-1997 Textile Combustion Performance Test Vertical Method", the afterburn time is 1.2s, the smoldering time is 0s, and the damaged carbon length is 9.7cm.

Example 4

(1) Preparation of stearic acid amide montmorillonite nanocomposites

Weigh 0.17mol of diethylenetriamine, put a certain amount of montmorillonite in a beaker, place on a magnetic stirrer to stir and disperse for 3h, put 0.34mol of stearic acid into a four-necked round bottom flask, and heat up to 100°C After the stearic acid is completely melted, add a small amount of acetic acid as a catalyst, drop the dispersion of diethylenetriamine and montmorillonite into a four-necked bottle, raise the temperature to 160-180°C for 5 hours, and protect it under nitrogen. After the reaction is cooled, the stearic acid amide montmorillonite nanocomposite material is obtained.

(2) Preparation of flame retardant finishing liquid

Heat the synthesized montmorillonite nanocomposite material to 110°C, then add emulsifier and acetic acid, keep it warm for 30 minutes, add deionized water to fully emulsify after cooling to room temperature, and prepare montmorillonite nanocomposite material emulsion, and add resin to the emulsion The cross-linking agent and ammonium polyphosphate are fully mixed, and dispersed with a high-speed disperser for 30 minutes to obtain a flame-retardant finishing solution. The mass ratio of montmorillonite composite material, resin crosslinking agent, ammonium polyphosphate, emulsifier, acetic acid and water is 2:1:1:0.3:0.35:15.

(3) Flame retardant finishing

Immerse cotton poplin 4040×3372 in the above-mentioned flame-retardant finishing solution, dry in a blast oven at 80°C, and bake at 160°C.

(4) Vertical burning test

Use YG815 vertical method fabric combustion performance tester to test according to "GB/T5455-1997 Textile Combustion Performance Test Vertical Method", the afterburning time is 3.6s, the smoldering time is 0s, and the damaged carbon length is 16.9cm.

Example 5

(1) Preparation of stearic acid amide montmorillonite nanocomposites

Weigh 0.17mol of diethylenetriamine, put a certain amount of montmorillonite in a beaker, place on a magnetic stirrer to stir and disperse for 3h, put 0.34mol of stearic acid into a four-necked round bottom flask, and heat up to 100°C After the stearic acid is completely melted, add a small amount of acetic acid as a catalyst, drop the dispersion of diethylenetriamine and montmorillonite into a four-necked bottle, raise the temperature to 160-180°C for 5 hours, and protect it under nitrogen. After the reaction is cooled, the stearic acid amide montmorillonite nanocomposite material is obtained.

(2) Preparation of flame retardant finishing liquid

Heat the synthesized montmorillonite nanocomposite material to 110°C, then add emulsifier and acetic acid, keep it warm for 30 minutes, add deionized water to fully emulsify after cooling to room temperature, and prepare montmorillonite nanocomposite material emulsion, and add resin to the emulsion The cross-linking agent and ammonium polyphosphate are fully mixed, and dispersed with a high-speed disperser for 30 minutes to obtain a flame-retardant finishing solution. The mass ratio of montmorillonite composite material, resin crosslinking agent, ammonium polyphosphate, emulsifier, acetic acid and water is 1:1:1.5:0.3:0.25:15.

(3) Flame retardant finishing

The cotton poplin 4040×3372 is dipped in the above flame retardant finishing solution, dried in a blast oven at 80°C, and baked at 160°C.

(4) Vertical burning test

Use the YG815 vertical method fabric combustion performance tester to test according to "GB/T5455-1997 Textile Combustion Performance Test Vertical Method".

Claims (9)

1. an expandable flame retardant system comprises the flame-retardant finishing method of pure cotton fabric:

(1) with imvite and organic amine dispersed with stirring 1-3h, get dispersion liquid, then dispersant liquid drop is added in the aliphatic acid, add catalyst, at 160-210 ℃, under the nitrogen protection condition, reaction 4～7h, cooling obtains Nano composite material of montmorillonite; Wherein the mol ratio of aliphatic acid and organic amine is 1:0.52, and the quality percentage composition of imvite in the composite is 3-10%;

(2) above-mentioned Nano composite material of montmorillonite is heated to 110-120 ℃, adds emulsifying agent and acetic acid then, insulation 15-30min, add water after the cooling, obtain the Nano composite material of montmorillonite emulsion, add resin cross-linking agent, ammonium polyphosphate again, mix, disperse, obtain fire retarding treating liquid; The mass ratio of montmorillonite composite material, resin cross-linking agent, ammonium polyphosphate, emulsifying agent, acetic acid and water is (0.5-2): (0.4～1): (1-3): (0.1～0.3): (0.15～0.35): (10～15);

(3) pure cotton fabric is flooded in fire retarding treating liquid, preliminary drying, bake, namely get flame-retardant textile.

2. a kind of expandable flame retardant system according to claim 1 is characterized in that the flame-retardant finishing method of pure cotton fabric: organic amine is a kind of in ethylenediamine, diethylenetriamine, triethylene tetramine, the tetraethylene pentamine in the described step (1).

3. a kind of expandable flame retardant system according to claim 1 is characterized in that the flame-retardant finishing method of pure cotton fabric: aliphatic acid is a kind of in stearic acid, oleic acid, the certain herbaceous plants with big flowers acid in the described step (1).

4. a kind of expandable flame retardant system according to claim 1 is characterized in that the flame-retardant finishing method of pure cotton fabric: catalyst is inorganic acid in the described step (1).

5. a kind of expandable flame retardant system according to claim 4 is characterized in that the flame-retardant finishing method of pure cotton fabric: described inorganic acid is a kind of in acetic acid, phosphoric acid, the sulfuric acid.

6. a kind of expandable flame retardant system according to claim 1 is characterized in that the flame-retardant finishing method of pure cotton fabric: the emulsifying agent model is T05 or OP10 in the described step (2); The emulsifying agent consumption is the 10%-30% of Nano composite material of montmorillonite quality.

7. a kind of expandable flame retardant system according to claim 1 is characterized in that the flame-retardant finishing method of pure cotton fabric: resin cross-linking agent is a kind of among polyurethane resin, 2D resin, the formaldehydeless crease-resistant resin TC in the described step (2).

8. a kind of expandable flame retardant system according to claim 1 is characterized in that the flame-retardant finishing method of pure cotton fabric: ammonium polyphosphate is that the degree of polymerization is greater than 1000 in the described step (2).

9. a kind of expandable flame retardant system according to claim 1 is characterized in that the flame-retardant finishing method of pure cotton fabric: dipping 10-15min in the described step (3), 80-100 ℃ of preliminary drying 5-10min at 150-180 ℃, bakes 3-8min then.

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