A flame-retardant spandex fabric and its preparation method

Abstract

The present invention relates to a flame-retardant spandex fabric and a preparation method thereof, characterized in that the fabric can be prepared by the following method: First, react aminophenyl-POSS with acryloyl chloride to obtain aminophenyl-POSS containing double bonds; crosslink zinc oxide powder with KH-570 crosslinking agent to obtain a crosslinked nano-level zinc oxide solution; then, polymerize aminophenyl-POSS containing double bonds with the crosslinked nano-level zinc oxide solution to obtain a modified solution; finish the spandex fabric in the modified solution to obtain the flame-retardant spandex fabric. The initial limiting oxygen index of the flame-retardant spandex fabric prepared by the present invention reaches more than 31%, belonging to the range of flame-retardant materials; after 5 times of washing, its limiting oxygen index does not decrease significantly and still reaches more than 29%.

Description

Technical Field

[0001] The present invention belongs to the technical field of fabric preparation, and particularly relates to a flame-retardant spandex fabric and a preparation method thereof. Background Art

[0002] With the progress of technology and the textile industry, the variety of textiles has been continuously increasing, and their application scope and quantity have increased significantly, covering many fields from people's daily life to industry, transportation, and military. Subsequently, fires spreading due to the lack of flame-retardant performance of textiles have been increasing day by day. Therefore, how to endow textiles with flame-retardant performance has attracted the attention and emphasis of all mankind.

[0003] Spandex fabric is a fabric woven from spandex fibers. Spandex fiber is short for polyurethane fiber and is a kind of elastic fiber. Spandex has excellent elasticity, its strength is 2-3 times higher than that of natural rubber filaments, its linear density is finer, and it is more resistant to chemical degradation. Spandex has good acid and alkali resistance, sweat resistance, seawater resistance, dry cleaning resistance, and abrasion resistance. Therefore, spandex can be used for clothing that needs to be stretchable to meet comfort requirements.

[0004] However, spandex fabric belongs to flammable fabric, and it emits a pungent odor when burning, which greatly limits the application scope of spandex. Therefore, endowing spandex fabric with excellent flame-retardant performance is the key development direction that researchers will focus on in the future.

[0005] Literature research shows that the flame-retardant performance of spandex fabric has received extensive attention. Currently, the main method for preparing flame-retardant spandex fabric is to soak the spandex fabric in a prepared flame-retardant solution to endow the fabric with high-efficiency flame-retardant performance; for example, Chinese Patent Application No. 201310280105.2 discloses a preparation method of flame-retardant spandex fabric, which is prepared by the following method: soaking the spandex fabric in a soaking solution containing a flame retardant, which is a compound of triethyl phosphate, methanol, and octabromoether solution in proportion; taking out the soaked fabric and drying it naturally to obtain the flame-retardant spandex fabric. There are still many deficiencies in the research on the flame-retardant performance of the flame-retardant spandex fabric prepared by this method. Because the flame retardant adheres to the fiber surface and absorbs the heat in the combustion area, dilutes and isolates the air during fabric combustion, thereby preventing combustion. This makes the flame retardant wash off after multiple washes, and the flame-retardant ability of the fiber also weakens accordingly; at the same time, adding the flame retardant on the surface of the spandex fabric also makes the fabric feel astringent and not soft. Therefore, it is necessary to continuously improve the existing flame-retardant process of spandex fabric and develop a preparation method with simple method, convenient operation, and low cost to produce spandex fabric with excellent flame-retardant performance. Summary of the Invention

[0006] Aiming at the above drawbacks existing in the prior art, the purpose of the present invention is to provide a flame-retardant spandex fabric and a preparation method thereof.

[0007] The object of the present invention is to provide a flame-retardant spandex fabric, which can be prepared by the following method: First, react amine phenyl-POSS with acryloyl chloride to obtain amine phenyl-POSS containing double bonds; crosslink zinc oxide powder with KH-570 crosslinking agent to obtain a crosslinked nano-level zinc oxide solution; then, polymerize the amine phenyl-POSS containing double bonds with the crosslinked nano-level zinc oxide solution to obtain a modified solution; finish the finishing of the spandex fabric in the modified solution to obtain the flame-retardant spandex fabric.

[0008] Another object of the present invention is to provide a preparation method of a flame-retardant spandex fabric, and the specific method comprises the following steps:

[0009] (1) Reaction of amine phenyl-POSS and acryloyl chloride: Under ice bath conditions, dissolve 5-7 g of amine phenyl-POSS and 1-2 g of triethylamine in 150 mL of tetrahydrofuran in a four-necked flask, stir in the ice bath and protect with N2, dissolve 4-6 g of acryloyl chloride in 100 mL of tetrahydrofuran, and drop the tetrahydrofuran solution containing acryloyl chloride into the tetrahydrofuran solution containing amine phenyl-POSS and triethylamine at a dropping rate of 1-3 drops / second. After dropping, keep the reaction at a constant temperature in the ice bath. After the reaction is completed, carry out vacuum filtration, rotary evaporation, and drying to obtain amine phenyl-POSS containing double bonds.

[0010] Preferably, the reaction time is: 10-14 h.

[0011] (2) Zinc oxide crosslinking modification: Grind zinc oxide powder to obtain nano-level zinc oxide particles; dissolve KH-570 crosslinking agent in dimethylformamide; add the obtained zinc oxide particles to the dimethylformamide solution containing KH-570 crosslinking agent, stir and react, the reaction temperature is: 60-80 °C, and the reaction time is: 3-5 h to obtain a crosslinked nano-level zinc oxide solution.

[0012] Preferably, the particle size range is 600-1500 nanometers.

[0013] Preferably, the dosage ratio of the KH-570 crosslinking agent (g) to dimethylformamide (mL) is: 1:10-20; the dosage ratio of the nano zinc oxide (g) to the dimethylformamide solution (mL) containing KH-570 crosslinking agent is: 1:10-20.

[0014] (3) Preparation of the modified solution: Dissolve the double-bond-containing aminophenyl-POSS obtained in step (1) and the cross-linked nano-zinc oxide solution obtained in step (2) in an appropriate amount of deionized water to prepare a monomer solution. Dissolve ammonium persulfate in deionized water to prepare an ammonium persulfate aqueous solution for standby. Then, under stirring conditions, control the temperature at 79 - 81 °C, and simultaneously drop the prepared monomer solution and the ammonium persulfate aqueous solution into a four-necked flask containing a certain amount of deionized water. Control the dropping time within 2 - 3 h. After the dropping is completed, keep the temperature for 3 - 4 h. Finally, cool to obtain the modified solution.

[0015] Preferably, the volume-mass ratio of the double-bond-containing aminophenyl-POSS (g) obtained in step (1), the cross-linked nano-zinc oxide solution (mL) obtained in step (2), and ammonium persulfate (g) is: 1∶10 - 20∶0.1 - 0.2.

[0016] (4) Preparation of the flame-retardant spandex fabric: Dilute the modified solution obtained in step (3) 10 - 12 times with tap water to obtain a diluted solution. Adjust the pH of the diluted solution to 5.0 - 5.5 with 10% hydrochloric acid. Immerse the spandex fabric in the diluted solution at 90 - 100 °C for 30 - 60 minutes. After the immersion, rinse with tap water 3 - 5 times and dry to obtain the flame-retardant spandex fabric.

[0017] Preferably, the dosage ratio of the spandex fabric (g) to the diluted solution (mL) is: 1∶30 - 50.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] (1) The present invention realizes grafting a polymer containing organosilicon and inorganic oxide particles on the surface of the spandex fabric, and this method significantly improves the flame retardancy of the spandex fabric.

[0020] (2) The inventors of the present application unexpectedly found that the initial limiting oxygen index of the flame-retardant spandex fabric prepared by the present invention reaches more than 31%, belonging to the range of flame-retardant materials; after 5 times of water washing, its limiting oxygen index does not decrease significantly and still reaches more than 29%.

[0021] (3) The present invention prepares a polymer containing organosilicon and inorganic oxide particles through a polymerization reaction. The polymer containing organosilicon and inorganic oxide particles is an excellent flame retardant. Therefore, the prepared spandex fabric also has excellent flame retardancy.

[0022] (4) The inventors of the present application unexpectedly found that a chemical reaction between the polymer containing organosilicon and inorganic oxide particles and the spandex fabric can achieve a firm combination of the two; further discovery: after the spandex fabric is washed with water multiple times, its flame retardancy is still not weakened.

[0023] (5) The flame-retardant spandex fabric prepared by the method of the present invention has strong flame retardancy, a simple overall production process, a low price, and little environmental pollution during the production process. Specific Embodiments

[0024] The following examples and comparative examples illustrate the present invention in detail.

[0025] Sources of main raw materials: The KH-570 crosslinking agent (chemical name: γ-methacryloxypropyltrimethoxysilane) was purchased from Wuhan Hualun Organosilicon Co., Ltd.; the purchased flame-retardant spandex fabric was purchased from Xinxiang Zhuocheng Special Textiles Co., Ltd.; amino-phenyl-POSS was purchased from Shanghai Macklin Biochemical Technology Co., Ltd., and its molecular structure is as follows:

[0026]

[0027] Example 1

[0028] A preparation method of a flame-retardant spandex fabric in this example, the preparation method includes the following steps:

[0029] (1) Reaction of amino-phenyl-POSS with acryloyl chloride: Under ice bath conditions, 6 g of amino-phenyl-POSS and 1.5 g of triethylamine were dissolved in 150 mL of tetrahydrofuran in a four-necked flask, stirred in an ice bath and protected by passing N2, 5 g of acryloyl chloride was dissolved in 100 mL of tetrahydrofuran, and the tetrahydrofuran solution containing acryloyl chloride was added dropwise to the tetrahydrofuran solution containing amino-phenyl-POSS and triethylamine, with a dropping rate of 2 drops / second. After the dropping was completed, the reaction was carried out at a constant temperature in an ice bath for a reaction time of 12 h. After the reaction was completed, filtration was carried out under reduced pressure, rotary evaporation was carried out, and drying was carried out to obtain amino-phenyl-POSS containing double bonds.

[0030] (2) Zinc oxide crosslinking modification: The zinc oxide powder was ground to obtain zinc oxide particles with a particle size of 1000-1400 nanometers; 1 g of KH-570 crosslinking agent was dissolved in 15 mL of dimethylformamide; 1 g of the prepared zinc oxide particles was added to 15 mL of the dimethylformamide solution containing the KH-570 crosslinking agent, and stirred for reaction at a reaction temperature of 70 °C and a reaction time of 4 h to obtain a crosslinked nano-level zinc oxide solution.

[0031] (3) Preparation of the modified liquid: Dissolve 1 g of the double-bond-containing aminophenyl-POSS prepared in step (1) and 15 mL of the crosslinked nano-zinc oxide solution prepared in step (2) in 100 mL of deionized water to prepare a monomer solution. Dissolve 0.15 g of ammonium persulfate in 100 mL of deionized water to prepare an ammonium persulfate aqueous solution for standby. Then, under stirring conditions, control the temperature at 80 °C, and simultaneously drop the prepared monomer solution and the ammonium persulfate aqueous solution into a four-necked flask containing 50 mL of deionized water. The dropping time is controlled within 2.5 h. After the dropping is completed, keep warm for 3.5 h. Finally, cool to obtain the modified liquid.

[0032] (4) Preparation of the flame-retardant spandex fabric: Dilute the modified liquid prepared in step (3) 11 times with tap water to obtain a diluted liquid. Adjust the pH of the diluted liquid to 5.3 with 10% hydrochloric acid. At 95 °C, immerse the spandex fabric in the diluted liquid. The dosage ratio of the spandex fabric (g) to the diluted liquid (mL) is 1:40, and the immersion time is 45 minutes. After the immersion is completed, rinse 4 times with tap water and dry to obtain the flame-retardant spandex fabric.

[0033] Example 2

[0034] A preparation method of a flame-retardant spandex fabric in this example, the preparation method includes the following steps:

[0035] (1) Reaction of aminophenyl-POSS and acryloyl chloride: Under ice bath conditions, dissolve 5 g of aminophenyl-POSS and 1 g of triethylamine in 150 mL of tetrahydrofuran in a four-necked flask. Stir in the ice bath and protect with N2. Dissolve 4 g of acryloyl chloride in 100 mL of tetrahydrofuran, and drop the tetrahydrofuran solution containing acryloyl chloride into the tetrahydrofuran solution containing aminophenyl-POSS and triethylamine at a dropping rate of 1 drop / second. After the dropping is completed, carry out constant-temperature reaction in the ice bath, and the reaction time is 10 h. After the reaction is completed, carry out vacuum filtration, rotary evaporation, and drying to obtain double-bond-containing aminophenyl-POSS.

[0036] (2) Zinc oxide crosslinking modification: Grind the zinc oxide powder to obtain zinc oxide particles with a particle size of 600 - 1000 nanometers; dissolve 1 g of KH-570 crosslinking agent in 10 mL of dimethylformamide; add 1 g of the prepared zinc oxide particles to 10 mL of the dimethylformamide solution containing KH-570 crosslinking agent, stir and react, the reaction temperature is 60 °C, and the reaction time is 3 h to obtain a crosslinked nano-zinc oxide solution.

[0037] (3) Preparation of the modified solution: Dissolve 1 g of the double-bond-containing aminophenyl-POSS prepared in step (1) and 10 mL of the crosslinked nano-zinc oxide solution prepared in step (2) in 100 mL of deionized water to prepare a monomer solution. Dissolve 0.1 g of ammonium persulfate in 100 mL of deionized water to prepare an ammonium persulfate aqueous solution for standby. Then, under stirring conditions, control the temperature at 79 °C, and simultaneously drop the prepared monomer solution and the ammonium persulfate aqueous solution into a four-necked flask containing 50 mL of deionized water. The dropping time is controlled within 2 h. After the dropping is completed, keep warm for 3 h. Finally, cool to obtain the modified solution.

[0038] (4) Preparation of the flame-retardant spandex fabric: Dilute the modified solution prepared in step (3) 10 times with tap water to obtain a diluted solution. Adjust the pH of the diluted solution to 5.0 with 10% hydrochloric acid. At 90 °C, immerse the spandex fabric in the diluted solution. The dosage ratio of the spandex fabric (g) to the diluted solution (mL) is 1:30, and the immersion time is 30 minutes. After the immersion is completed, rinse 3 times with tap water and dry to obtain the flame-retardant spandex fabric.

[0039] Example 3

[0040] A preparation method of a flame-retardant spandex fabric in this example, the preparation method includes the following steps:

[0041] (1) Reaction of aminophenyl-POSS and acryloyl chloride: Under ice bath conditions, dissolve 7 g of aminophenyl-POSS and 2 g of triethylamine in 150 mL of tetrahydrofuran in a four-necked flask. Stir in the ice bath and protect with N2. Dissolve 6 g of acryloyl chloride in 100 mL of tetrahydrofuran. Drop the tetrahydrofuran solution containing acryloyl chloride into the tetrahydrofuran solution containing aminophenyl-POSS and triethylamine at a dropping rate of 3 drops / second. After the dropping is completed, carry out a constant-temperature reaction in the ice bath. The reaction time is 14 h. After the reaction is completed, carry out vacuum filtration, rotary evaporation, and drying to obtain double-bond-containing aminophenyl-POSS.

[0042] (2) Zinc oxide crosslinking modification: Grind the zinc oxide powder to obtain zinc oxide particles with a particle size of 900 - 1500 nanometers; dissolve 1 g of KH-570 crosslinking agent in 20 mL of dimethylformamide; add 1 g of the prepared zinc oxide particles to 20 mL of the dimethylformamide solution containing the KH-570 crosslinking agent, stir and react. The reaction temperature is 80 °C, and the reaction time is 5 h to obtain a crosslinked nano-zinc oxide solution.

[0043] (3) Preparation of the modified solution: Dissolve 1 g of the double-bond-containing aminophenyl-POSS prepared in step (1) and 20 mL of the cross-linked nano-sized zinc oxide solution prepared in step (2) in 100 mL of deionized water to prepare a monomer solution. Dissolve 0.2 g of ammonium persulfate in 100 mL of deionized water to prepare an ammonium persulfate aqueous solution for standby. Then, under stirring conditions, control the temperature at 81 °C, and simultaneously dropwise add the prepared monomer solution and the ammonium persulfate aqueous solution into a four-necked flask containing 50 mL of deionized water. The dropping time is controlled within 3 h. After the dropping is completed, keep the temperature for 4 h. Finally, cool it to obtain the modified solution.

[0044] (4) Preparation of the flame-retardant spandex fabric: Dilute the modified solution prepared in step (3) 12 times with tap water to obtain a diluted solution. Adjust the pH of the diluted solution to 5.5 with 10% hydrochloric acid. At 100 °C, immerse the spandex fabric in the diluted solution. The dosage ratio of the spandex fabric (g) to the diluted solution (mL) is 1:50, and the immersion time is 60 minutes. After the immersion is completed, rinse it 5 times with tap water and then dry it to obtain the flame-retardant spandex fabric.

[0045] Comparative Example A

[0046] Taking Example 1 as a comparison, in this comparative example, reduce "6 g of aminophenyl-POSS" in step (1) to "0.6 g of aminophenyl-POSS", and implement other preparation methods according to the preparation method of Example 1.

[0047] Comparative Example B

[0048] Taking Example 1 as a comparison, in this comparative example, increase "6 g of aminophenyl-POSS" in step (1) to "30 g of aminophenyl-POSS", and implement other preparation methods according to the preparation method of Example 1.

[0049] Comparative Example C

[0050] Taking Example 1 as a comparison, in this comparative example, reduce "1 g of KH-570 cross-linking agent" in step (2) to "0.1 g of KH-570 cross-linking agent", and implement other preparation methods according to the preparation method of Example 1.

[0051] Comparative Example D

[0052] Taking Example 1 as a comparison, in this comparative example, increase "1 g of KH-570 cross-linking agent" in step (2) to "5 g of KH-570 cross-linking agent", and implement other preparation methods according to the preparation method of Example 1.

[0053] Comparative Example E

[0054] Taking Example 1 as a comparison, in this comparative example, in step (3), the dosage ratio of "the spandex fabric (g) to the diluent (mL) is: 1∶40" is changed to "the dosage ratio of the spandex fabric (g) to the diluent (mL) is: 1∶5", and other preparation methods are implemented according to the preparation method of Example 1.

[0055] Comparative Example F

[0056] Taking Example 1 as a comparison, in this comparative example, in step (3), the dosage ratio of "the spandex fabric (g) to the diluent (mL) is: 1∶40" is changed to "the dosage ratio of the spandex fabric (g) to the diluent (mL) is: 1∶200", and other preparation methods are implemented according to the preparation method of Example 1.

[0057] Performance evaluation example:

[0058] In order to better detect the flame retardancy of the spandex fabric prepared in the present invention, the flame retardant properties of the spandex fabrics prepared in the above Specific Examples 1-3 and Comparative Examples A-F of the present invention and the purchased flame retardant spandex fabric are tested. The test method adopts the oxygen index test method, that is, in accordance with GB / T 5454-1997 "Textiles - Burning performance - Oxygen index method", and the spandex fabric is subjected to standard washing with reference to the washing method of the color fastness to washing tester in GB / T 20944.1-2007. The test results are shown in Table 1.

[0059] Table 1 Flame retardancy test results of the spandex fabrics prepared in Examples 1-3 and Comparative Examples A-F and the purchased spandex fabric before and after 5 washes

[0060]

[0061] The limiting oxygen index LOI is one of the important indicators of flame retardant materials. Generally, materials with a limiting oxygen index greater than 28% are all flame retardant materials. It can be seen from Table 1 that the initial limiting oxygen index of the flame retardant spandex fabric prepared in the present invention reaches more than 31%, belonging to the range of flame retardant materials; after 5 washes, its limiting oxygen index does not decrease significantly and still reaches more than 29%. When not washed or washed 5 times, the flame retardant performance of the flame retardant spandex fabric prepared in the present invention is slightly higher than that of the purchased flame retardant spandex fabric. In addition, the limiting oxygen indexes of the spandex fabrics prepared in Comparative Examples A-F are all small, which indicates that: the dosage of amine phenyl-POSS, the dosage of KH-570 crosslinking agent, and the dosage ratio of the fabric to the diluent all have important influences on the flame retardant performance of the spandex fabric. The flame retardancy experiment test shows that: the flame retardant spandex fabric prepared in the present invention has a good flame retardant effect and is a qualified flame retardant spandex fabric.

Claims

1. A preparation method of a flame-retardant spandex fabric, characterized in that, The preparation method is as follows: Dilute the modified liquid 10 - 12 times with tap water to obtain a diluted liquid. Adjust the pH of the diluted liquid to 5.0 - 5.5 with 10% hydrochloric acid. Immerse the spandex fabric in the diluted liquid at 90 - 100 °C for 30 - 60 minutes. After immersion, rinse it 3 - 5 times with tap water and dry it to obtain the flame-retardant spandex fabric. Among them, the initial limiting oxygen index of the flame-retardant spandex fabric is higher than 31%, and after 5 times of water washing, its limiting oxygen index is higher than 29%. The dosage ratio of the spandex fabric to the diluted liquid is 1 g∶(30 - 50) mL. The preparation method of the modified liquid is as follows: Dissolve the double-bond-containing aminophenyl-POSS and the cross-linked nano-sized zinc oxide solution in an appropriate amount of deionized water to prepare a monomer solution. Dissolve ammonium persulfate in deionized water to prepare an ammonium persulfate aqueous solution for standby. Then, under stirring conditions, control the temperature at 79 - 81 °C, and simultaneously dropwise add the prepared monomer solution and the ammonium persulfate aqueous solution into a four-necked flask containing a certain amount of deionized water. The dropping time is controlled within 2 - 3 h. After dropping, keep warm for 3 - 4 h. Finally, cool it to obtain the modified liquid. The volume-mass ratio of the double-bond-containing aminophenyl-POSS, the cross-linked nano-sized zinc oxide solution, and ammonium persulfate is 1 g∶(10 - 20) mL∶(0.1 - 0.2) g. The preparation method of the double-bond-containing aminophenyl-POSS is as follows: Under ice bath conditions, dissolve 5 - 7 g of aminophenyl-POSS and 1 - 2 g of triethylamine in 150 mL of tetrahydrofuran in a four-necked flask. Stir in the ice bath and protect with N2. Dissolve 4 - 6 g of acryloyl chloride in 100 mL of tetrahydrofuran. Dropwise add the tetrahydrofuran solution containing acryloyl chloride into the tetrahydrofuran solution containing aminophenyl-POSS and triethylamine at a dropping rate of 1 - 3 drops / second. After dropping, react at a constant temperature in the ice bath. After the reaction is completed, perform vacuum filtration, rotary evaporation, and drying to obtain the double-bond-containing aminophenyl-POSS.

2. The preparation method of a flame-retardant spandex fabric according to claim 1, characterized in that, The reaction time is 10 - 14 h.

3. The preparation method of a flame-retardant spandex fabric according to claim 1, characterized in that, The preparation method of the cross-linked nano-sized zinc oxide solution is as follows: Grind the zinc oxide powder to obtain nano-sized zinc oxide particles with a particle size. Dissolve the KH-570 cross-linking agent in dimethylformamide. Add the prepared zinc oxide particles to the dimethylformamide solution containing the KH-570 cross-linking agent and stir to react. The reaction temperature is 60 - 80 °C, and the reaction time is 3 - 5 h to obtain the cross-linked nano-sized zinc oxide solution. The dosage ratio of the KH-570 cross-linking agent to dimethylformamide is 1 g∶(10 - 20) mL; the dosage ratio of the nano-sized zinc oxide to the dimethylformamide solution containing the KH-570 cross-linking agent is 1 g∶(10 - 20) mL.

4. The preparation method of a flame-retardant spandex fabric according to claim 3, characterized in that, The particle size range is 600 - 1500 nanometers.

5. A flame-retardant spandex fabric, characterized in that, It is prepared by using the preparation method of a flame-retardant spandex fabric according to any one of claims 1 - 4.

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