Modified flame retardant, flame-retardant modified coating adhesive, composite cloth and preparation method thereof

Abstract

The present disclosure provides a modified flame-retardant compound, a modified flame-retardant, a flame-retardant modified coating glue, a composite cloth and a preparation method thereof, and belongs to the technical field of flame retardants, wherein the structure of the modified flame-retardant compound is as follows: the compound shown in formula (I) is obtained by introducing a Si-(OMe)3 group in the compound shown in formula (II); wherein the structure of the compound shown in formula (II) is as follows: the P and Si elements in the compound shown in formula (I) have good flame-retardant capacity, and after being blended with a blending agent such as phosphoric acid, ammonium salt, magnesium salt, melamine and the like, the flame-retardant capacity and the binding fastness of the fabric fiber can be improved.

Description

TECHNICAL FIELD

[0001] The present disclosure belongs to the technical field of flame retardants, and particularly relates to a modified flame-retardant compound, a modified flame-retardant, a flame-retardant modified coating glue, a composite cloth and a preparation method thereof. BACKGROUND

[0002] Cotton, polyester and other fiber fabrics are widely used in various industries around the world, such as clothing, curtains, fabric furniture, and interior decoration of shopping malls, airports, entertainment venues, and vehicles. Fiber fabrics bring convenience to people's lives, but also pose a fire hazard due to their flammability. Current flame-retardant fabrics, such as fire suits, have flame-retardant properties, but poor heat insulation performance, and cannot effectively retard flame and insulate heat in fire scenes.

[0003] Therefore, it is of great significance to develop fabrics with good flame retardance and heat insulation. SUMMARY

[0004] To solve the above technical problems, the present disclosure provides a modified flame-retardant compound, a modified flame-retardant, a flame-retardant modified coating glue, a composite cloth, and a preparation method thereof, in order to at least partially solve the above technical problems.

[0005] To solve the above technical problems, the technical solutions provided by the present disclosure are as follows:

[0006] As a first aspect of the present disclosure, a modified flame-retardant compound is provided, which has a specific structure as shown in formula (I):

[0007]

[0008] The compound shown in formula (I) is a Si-(OMe)3 group introduced in the compound shown in formula (II);

[0009] The structure of the compound shown in formula (II) is as follows:

[0010]

[0011] As a second aspect of the present disclosure, a method for preparing the compound shown in formula (I) in the modified flame-retardant compound is provided, which comprises:

[0012] A compound reacting with a B compound to obtain the compound shown in formula (I)

[0013] As a third aspect of the present disclosure, a modified flame-retardant is provided, which comprises:

[0014] a mixture of the compound shown in formula (I) and the compound shown in formula (II); and

[0015] a blending agent selected from one or more of phosphoric acid, ammonium salt, magnesium salt, melamine is blended with the mixture;

[0016] wherein the structures of the compounds of formula (I) and formula (II) are as follows:

[0017]

[0018] The ammonium salt is ammonium chloride, and the magnesium salt is selected from one or more of magnesium chloride and magnesium sulfate.

[0019] As a fourth aspect of the present disclosure, a flame-retardant modified coating glue is provided, comprising the following components in parts by weight:

[0020]

[0021] wherein the sum of the parts by weight of all components is 100, and the modifier is selected from one or more of graphite, fiber, silicon oxide, calcium oxide, and titanium oxide.

[0022] As a fifth aspect of the present disclosure, a preparation method of a flame-retardant modified coating glue is provided, comprising:

[0023] A diluent is added to a reactor containing aqueous polyurethane, and stirring is performed until a vortex appears at the center of the liquid surface;

[0024] After slowly adding a wetting agent, a defoaming agent, and a dispersing agent into the reactor, an ammonium polyphosphate flame retardant and a char-forming agent are added into the reactor and mixed uniformly;

[0025] The modifier is then added to the mixed solution, and the mixture is again dispersed and stirred uniformly to obtain the flame-retardant modified coating glue.

[0026] As a sixth aspect of the present disclosure, a preparation method of a flame-retardant thermal-insulation composite cloth is provided, comprising:

[0027] A plurality of pieces of fabric to be treated are soaked in an aqueous solution of a modified flame retardant at 30-45°C, and after soaking and treatment, pre-drying is performed at 55-65°C, and drying is performed at 100-120°C to obtain a plurality of pieces of flame-retardant fabric, wherein the mass ratio of the modified flame retardant to water is 1:10-30;

[0028] The flame-retardant thermal-insulation composite cloth is obtained by coating the flame-retardant modified coating glue as a thermal-insulation layer on both sides of each piece of flame-retardant fabric;

[0029] A plurality of pieces of flame-retardant thermal-insulation composite cloth are stacked in sequence and adhered together by the viscosity of the flame-retardant modified coating glue, and after drying, a flame-retardant thermal-insulation composite cloth is obtained;

[0030] The fabric to be treated includes any one of cotton, non-woven fabric, polyester, fiber, and fiber fabric, and the plurality of sequentially stacked flame-retardant thermal insulation fabrics are different from each other.

[0031] The thickness of the thermal insulation layer is 0.1-2mm.

[0032] As a seventh aspect of the present disclosure, a flame-retardant thermal insulation composite fabric is provided, which is prepared by the above method.

[0033] Based on the above technical solution, the modified flame-retardant compound, the modified flame-retardant agent, the flame-retardant modified coating glue, the composite fabric and the preparation method thereof provided by the present disclosure at least have one of the following beneficial effects:

[0034] (1) According to the embodiment of the present disclosure, Si-(OMe)3 is introduced on the basis of the compound shown in formula (II) to obtain the compound shown in formula (I). The P and Si elements in the compound shown in formula (I) have good flame-retardant ability, and can be used as a flame-retardant agent.

[0035] (2) According to the embodiment of the present disclosure, the P and Si elements in the compounds shown in formula (I) and formula (II) have good flame-retardant ability, and the selected melamine and magnesium elements also have good flame-retardant properties. The compound shown in formula (I) and formula (II) are mixed with at least one of the co-blending agents of phosphoric acid, ammonium salt, magnesium salt, and melamine to obtain a modified flame-retardant agent. The modified flame-retardant agent improves the flame-retardant ability of the fabric and the bonding strength of the flame-retardant agent and the fabric.

[0036] (3) According to the embodiment of the present disclosure, by mixing the modifiers such as graphite, fiber, etc. having certain high-temperature resistance and flame-retardant properties, and the water-based polyurethane having good expansion ability, thermal insulation ability, adhesion ability and strong compatibility, and the ammonium polyphosphate flame-retardant agent, carbonation agent, wetting agent, defoaming agent, etc., the prepared flame-retardant modified coating glue has good thermal insulation ability and good flame-retardant properties.

[0037] (4) According to an embodiment of the present disclosure, a series of combined composite cloth is obtained by immersing a plurality of fabrics to be treated in a modified flame retardant, and then coating the modified flame retardant fabric on both sides with a flame-retardant modified coating glue, and then stacking and assembling the plurality of fabrics in sequence. The composite cloth formed has flame-retardant properties while basically maintaining softness, and in the case of direct flame burning, the composite cloth does not burn within a certain time, and after the composite cloth is away from the fire, there is no smoldering. On the other hand, the modified coating glue in the composite cloth can absorb a large amount of heat to change phase and foam and expand to form a porous carbonized layer that is tens of times thicker than the original coating layer. The porous carbonized layer absorbs a large amount of heat during foaming, so that the formed porous carbonized layer has high heat insulation performance and can form a heat insulation barrier, so that the composite cloth has flame-retardant properties and also has heat insulation capacity, and is expected to be applied to flame-retardant and heat-insulating scenes. BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1 The infrared spectrum of the modified flame-retardant compound in the embodiment of the present disclosure;

[0039] Figure 2 The infrared spectrum of the modified flame retardant in the embodiment of the present disclosure;

[0040] Figure 3 The thermogravimetric-differential thermal scanning curve of the modified flame retardant in the embodiment of the present disclosure;

[0041] Figure 4 The infrared spectrum of the flame-retardant modified coating glue in the embodiment of the present disclosure;

[0042] Figure 5 The thermogravimetric-differential thermal scanning curve of the flame-retardant modified coating glue in the embodiment of the present disclosure;

[0043] Figure 6 The schematic diagram of the vertical flame spray flame-retardant and heat-insulating composite cloth in the embodiment of the present disclosure;

[0044] Figure 7 The composite cloth back surface temperature-time change graph under the 1300°C flame in Example 1 of the present disclosure;

[0045] Figure 8 The composite cloth mass-time change graph in the cone calorimeter test in Example 1 of the present disclosure;

[0046] Figure 9A The scanning electron microscope graph of the flame-retardant modified coating glue of the composite cloth in Example 1 of the present disclosure under the 5 micron scale of the thick carbonized partial block-shaped area after spraying and burning;

[0047] Figure 9B The scanning electron microscope graph of the flame-retardant modified coating glue of the composite cloth in Example 1 of the present disclosure under the 5 micron scale of the thick carbonized partial block-shaped area after spraying and burning;

[0048] Figure 9C A scanning electron microscope image of the flame-retardant modified coating glue of the composite cloth in Embodiment 1 of the present disclosure in a carbonized partial layer structure region of 10 microns in scale after burning. DETAILED DESCRIPTION

[0049] In order to make the purpose, technical solutions and advantages of the present disclosure clearer and more apparent, the present disclosure is further described in detail below in combination with specific embodiments and with reference to the accompanying drawings.

[0050] In view of the problem that existing fabrics cannot simultaneously achieve high flame retardation and heat insulation performance, the present disclosure provides a modified flame-retardant compound, a modified flame-retardant agent, a flame-retardant modified coating glue, a composite cloth and a preparation method thereof. A compound shown in formula (I) is obtained by introducing a Si-(OMe)3 group into a compound shown in formula (II). The P and Si elements in the compound shown in formula (I) have good flame-retardant ability. The compound shown in formula (I) and the compound shown in formula (II) are blended with a co-blending agent such as phosphoric acid, an ammonium salt, a magnesium salt and melamine to obtain a modified flame-retardant agent. At the same time, a modified coating glue with flame-retardant performance is obtained by reacting a water-based polyurethane with good foaming expansion, flame-retardant performance and compatibility, a modifier, an ammonium polyphosphate flame-retardant agent, a carbon-forming agent and a defoaming agent. Finally, the modified flame-retardant agent and the flame-retardant modified coating glue are used to treat a fabric to be treated, so that the fabric has both flame-retardant performance and heat insulation performance.

[0051] Specifically, a first aspect of the present disclosure provides a modified flame-retardant compound, which has a specific structure as shown in formula (I): The compound shown in formula (I) is obtained by introducing a Si-(OMe)3 group into a compound shown in formula (II); wherein the structure of the compound shown in formula (II) is as follows:

[0052] In the embodiments of the present disclosure, a compound shown in formula (I) is obtained by introducing a Si-(OMe)3 group into a compound shown in formula (II). The P and Si elements in the compound shown in formula (I) have good flame-retardant ability, and the compound can be used as a flame-retardant agent.

[0053] According to the embodiments of the present disclosure, a second aspect of the present disclosure provides a method for preparing the compound shown in formula (I) in the modified flame-retardant agent, which comprises: reacting a compound A with a compound B to obtain the compound shown in formula (I)

[0054] Specifically, the method for preparing the compound shown in formula (I) is: mixing the compound A and the compound B to form a flame-retardant mixture under the condition of an organic solvent and a catalyst, adding a pH adjuster to the flame-retardant mixture, and reacting at a preset temperature to obtain the compound shown in formula (I). Wherein, the organic solvent is selected from methanol, and the catalyst is selected from calcium oxide; the molar ratio of the compound A to the compound B is 1:1-1:1.2, such as 1:1.02; the preset reaction temperature is 50-70℃, such as 60℃; and the pH adjuster adjusts the pH of the flame-retardant mixture to neutral, and the pH is 6-7.

[0055] For example: the compound A (91.7mL, 1mol) and CaO (16.8g, 0.3mol) are placed in a reactor for stirring. Then, 300mL of methanol solvent is added, and after installing a condenser and a thermometer, the reactor is placed in a water bath, preheated to 50℃, and then the compound B (242mL, 1.02mol) is added dropwise into the reactor, and the reaction temperature is controlled at 65℃ during the dropping process. After 30min of reaction, the reaction is stopped; after filtration and methanol washing, the compound shown in formula (I) is obtained, and the infrared spectrum of the compound shown in formula (I) is shown in the following figure: Figure 1 The specific reaction formula for obtaining the compound shown in formula (I) is as follows:

[0056]

[0057] The third aspect of the present disclosure provides a modified flame retardant, comprising: a mixture of the compound shown in formula (I) and the compound shown in formula (II); and a blending agent blended with the mixture, wherein the blending agent is selected from one or more of phosphoric acid, ammonium salt, magnesium salt, and melamine; the ammonium salt is ammonium chloride, and the magnesium salt is selected from one or more of magnesium chloride and magnesium sulfate, and the structures of the compound shown in formula (I) and the compound shown in formula (II) are as follows:

[0058]

[0059] According to the embodiments of the present disclosure, the Si and P elements in the compounds shown in formula (I) and formula (II) have good flame-retardant ability, and the selected melamine and magnesium element also have good flame-retardant property. By mixing the compounds shown in formula (I) and formula (II) with at least one blending agent selected from phosphoric acid, ammonium salt, magnesium salt, and melamine, a modified flame retardant is obtained. The modified flame retardant improves the flame-retardant ability of the fabric, and at the same time, the solubility between the blending agent such as phosphoric acid, ammonium chloride, and magnesium sulfate and the compounds shown in formula (I) and formula (II) is utilized to improve the combination firmness of the flame retardant and the fabric.

[0060] According to the embodiment of the present disclosure, the blending mass ratio of the blending agent to the mixture (including the compounds shown in formula (I) and formula (II)) is 1:20-50, and the mass ratio of the compound shown in formula (I) to the compound shown in formula (II) is 1:1-3. Within the above ratio range, the modified flame retardant has good flame retardancy. The blending mass ratio can be 1:20, 1:30, 1:40, 1:50, etc., and the mass ratio of the compound shown in formula (I) to the compound shown in formula (II) can be 1:1, 1:2, 1:3, etc.

[0061] Figure 2 The infrared spectrum of the modified flame retardant in the embodiment of the present disclosure is shown in Figure 3 The thermogravimetric-differential scanning curve of the modified flame retardant in the embodiment of the present disclosure is shown in

[0062] From Figure 3 It can be seen that in the process of gradually increasing the temperature, there is a certain mass loss, and at the same time, there is an obvious endothermic peak, which can indicate that the modified flame retardant has a certain endothermic capacity.

[0063] According to the embodiment of the present disclosure, the fourth aspect of the present disclosure provides a flame-retardant modified coating glue, which comprises the following components in the weight percentage: 1-10 parts of a modifier, 20-50 parts of water-based polyurethane, 20-50 parts of an ammonium polyphosphate flame retardant, 10-30 parts of a char-forming agent, 0.1-0.5 parts of a wetting agent, 0.1-0.5 parts of an antifoaming agent, 0.1-0.5 parts of a dispersing agent, 0.1-0.5 parts of an anti-settling agent, and 10-30 parts of a diluent; wherein the sum of the weight percentages of all components is 100, and the modifier is selected from at least one of graphite, fiber, silicon oxide, calcium oxide, and titanium oxide. The infrared spectrum of the obtained flame-retardant modified coating glue is shown in Figure 4 .

[0064] In the embodiment of the present disclosure, the selected water-based polyurethane has the characteristics of being easy to expand, heat-insulating, adhesive, and having good compatibility with the compounds shown in formula (I) and formula (II) and other components during the reaction process. The selected modifier has the characteristics of porous structure, high temperature resistance, and flame retardancy. The ammonium polyphosphate flame retardant has the characteristics of good flame retardancy and uniform mixing with the modifier and the water-based polyurethane. The water-based polyurethane is doped with the modifier, the ammonium polyphosphate flame retardant, the char-forming agent, etc., so as to prepare the flame-retardant modified coating glue. The flame-retardant modified coating glue has flame retardancy, heat insulation, and uniform dispersion of each component in the coating glue.

[0065] According to an embodiment of the present disclosure, the wetting agent is a combination of one or more of BYK-306, BYK-S706, BYK-361, BYK-359, and SN-4727A; the defoaming agent is a combination of one or more of SN-6710, silicone defoaming agent, mineral oil, and polyether; the charring agent is a combination of one or more of glucose, starch, sucrose, cyclodextrin, pentaerythritol, and dipentaerythritol; the dispersing agent is a combination of one or more of BYK-2150, BYK-330, BYK-341, BYK-307, BYK-2155, BYK-104S, SN-1728A, SN-1728, SN-1729, SN-1776, SN-1760, SN-1790A, SN-1791, SN-1790, SN-1792, and SN-1798; the anti-settling agent is a combination of one or more of polyamide wax, bentonite, and polyethylene wax; and the diluent is a combination of one or more of gasoline, water, methanol, dimethylbenzene, isopropyl alcohol, ethanol, ethyl acetate, and propylene glycol dimethyl ether.

[0066] Figure 5 A thermogravimetric-differential thermal scanning curve of the fire-retardant modified coating glue in the embodiment of the present disclosure.

[0067] It can be seen from Figure 5 that there is a certain mass loss during the gradual increase in temperature, and there are three obvious endothermic peaks, which can indicate that the fire-retardant modified coating glue has strong endothermic capacity.

[0068] According to an embodiment of the present disclosure, the fifth aspect of the present disclosure provides a preparation method of fire-retardant modified coating glue, comprising: adding a diluent into a reactor containing water-based polyurethane, stirring until vortex appears at the center of the liquid surface, so as to fully dissolve the water-based polyurethane; slowly adding a wetting agent, a defoaming agent, and a dispersing agent into the reactor, so as to mix the added wetting agent, defoaming agent, and dispersing agent uniformly; adding an ammonium polyphosphate fire retardant and a charring agent into the reactor and mixing uniformly; then adding a modifier into the mixed solution, and dispersing and stirring again to obtain the fire-retardant modified coating glue. Through the above-mentioned adding sequence, the water-based polyurethane, the modifier, the ammonium polyphosphate fire retardant, the charring agent, and the defoaming agent can be uniformly dispersed, which is helpful to obtain the fire-retardant modified coating glue with moderate viscosity and uniformly dispersed fire retardant.

[0069] According to the embodiment of the present disclosure, the sixth aspect of the present disclosure provides a preparation method of the flame-retardant thermal-insulation composite cloth, comprising: immersing a plurality of pieces of the fabric to be treated in the aqueous solution of the modified flame retardant in the above-mentioned embodiment at 30-45℃, carrying out pre-drying at 55-65℃ after the immersion treatment, and drying at 100-120℃ to obtain a plurality of pieces of the flame-retardant fabric; coating the flame-retardant modified coating glue in the above-mentioned embodiment on both sides of each piece of the flame-retardant fabric as the thermal-insulation layer to obtain the flame-retardant thermal-insulation fabric; then, stacking the plurality of pieces of the flame-retardant thermal-insulation fabric in sequence, connecting the plurality of pieces of the flame-retardant thermal-insulation fabric to each other by the viscosity of the flame-retardant modified coating glue, and obtaining the flame-retardant thermal-insulation composite cloth after drying, wherein the immersion treatment time is 10-40min, the pre-drying time is 20-60min, the drying time is 10-40min, and the mass ratio of the modified flame retardant to water is 1:10-30.

[0070] According to the embodiment of the present disclosure, the thickness of the thermal-insulation layer is 0.1-2mm, so that the composite cloth has higher thermal-insulation and air permeability while maintaining the softness of the composite cloth.

[0071] According to the embodiment of the present disclosure, the fabric to be treated comprises any one of cotton cloth, non-woven fabric, polyester, fiber cloth, and the plurality of pieces of the flame-retardant thermal-insulation fabric stacked in sequence are different from each other. For example, the flame-retardant thermal-insulation composite cloth is obtained by stacking cotton cloth, non-woven fabric, and polyester in sequence, or the flame-retardant thermal-insulation composite cloth is obtained by stacking cotton cloth, fiber cloth, and polyester in sequence.

[0072] In the embodiment of the present disclosure, immersing the plurality of pieces of the fabric to be treated at 30-45℃ helps to wet the fabric, so that the modified flame retardant is uniformly dispersed on the fabric to be treated; then, carrying out pre-drying at 55-65℃ helps the modified flame retardant to infiltrate into the fabric to be treated; finally, drying at 100-120℃ removes the excess water on the fabric to be treated.

[0073] According to the embodiment of the present disclosure, the seventh aspect of the present disclosure provides a flame-retardant thermal-insulation composite cloth, which is obtained by the preparation method of the thermal-insulation composite cloth in the above-mentioned embodiment.

[0074] In the embodiments of the present disclosure, a series of different flame-retardant thermal insulation composite fabrics are obtained by using the modified flame retardant and the flame-retardant modified coating glue in combination, and then assembling different fabrics to be treated. The formed flame-retardant thermal insulation composite fabric has flame-retardant properties while basically maintaining softness. In the case of direct flame burning, the composite fabric does not burn for a period of time and does not afterglow after moving away from the flame, indicating that the composite fabric has good flame-retardant properties. In addition, in the case of direct flame burning, the composite fabric can absorb a large amount of heat to change phase, and at the same time, foam and expand to form a porous carbonized layer that is tens of times thicker than the original flame-retardant modified coating glue. The porous structure of the carbonized layer improves the thermal insulation performance and forms a thermal insulation barrier. The fabric treated by the flame-retardant modified coating glue and the flame-retardant modifier effectively reduces the possibility of fire caused by the fabric, and the composite fabric is made into a fire-fighting suit, which has good thermal insulation performance to ensure the safety of firefighters.

[0075] Embodiment 1

[0076] The preparation process of the cotton-fiber fabric-non-woven fabric flame-retardant thermal insulation composite fabric is as follows:

[0077] (1) The actual modified flame retardant needs to be compounded with a certain proportion of water in application. The mass ratio of the modified flame retardant to water is 1:10-30. The cotton fabric is placed in the modified flame retardant aqueous solution for 20 min, the soaking temperature is controlled at 30°C, after the soaking treatment is completed, it is pre-dried at 60°C for 20 min, and then dried in a 100°C oven for 15 min; the fiber fabric is placed in the modified flame retardant solution for 40 min, the soaking temperature is controlled at 45°C, after the soaking treatment is completed, it is pre-dried at 60°C for 60 min, and then dried in a 120°C oven for 30 min; the non-woven fabric is placed in the modified flame retardant solution for 10 min, the soaking temperature is controlled at 30°C, after the soaking treatment is completed, it is pre-dried at 60°C for 20 min, and then dried in a 100°C oven for 10 min, to obtain three different flame-retardant fabrics. The modified flame retardant aqueous solution includes: 5 parts by weight of the compound shown in formula (I), 10 parts by weight of the compound shown in formula (II), 0.04 parts by weight of phosphoric acid, 0.1 parts by weight of melamine, and 200 parts by weight of water.

[0078] (2) The steps of heat insulation treatment of the corresponding flame-retardant fabric are as follows: the cotton cloth, fiber cloth and non-woven fabric containing the modified flame retardant are coated with 0.1-1.0 mm thick flame-retardant modified coating glue on both sides. The flame-retardant modified coating glue is prepared from the following raw materials in parts by weight: modifier (expanded graphite) 7 parts by weight, water-based polyurethane emulsion (E11 (trade name) of Jiangsu Xingfeng Chemical Technology Co., Ltd.) 45 parts by weight, ammonium polyphosphate 23 parts by weight, carbonization agent (pentaerythritol) 12 parts by weight, wetting agent (BYK-S706 (trade name) of BYK, Germany) 0.8 parts by weight, defoaming agent (mineral oil) 0.3 parts by weight, dispersing agent (BYK-2150 (trade name) of BYK, Germany) 0.4 parts by weight, anti-settling agent (bentonite) 0.5 parts by weight, and diluent (water) 11 parts by weight. At the same time, the flame-retardant modified coating glue is used for adhesion according to the order of cotton cloth-fiber cloth-non-woven fabric, i.e. to obtain the cotton cloth-fiber cloth-non-woven fabric flame-retardant heat-insulating composite cloth.

[0079] In order to further improve its heat insulation performance, the flame-retardant modified coating glue can be continuously coated on the front and back of the composite cloth, and the thickness can be 1-2 mm. After the coating is completely dried, the adhesion of the composite cloth is high, and it will not fall off or crack, while having good flexibility.

[0080] The flame-retardant heat-insulating composite cloth prepared in Example 1 is tested for flame-retardant heat-insulating performance, and the specific process is as follows:

[0081] First, the flame-retardant fabric prepared in step (1) in the example is directly determined by the vertical method, and the schematic diagram of the vertical flame spraying of the flame-retardant heat-insulating composite cloth is shown in Figure 6 .

[0082] Cotton cloth flame-retardant test: at 20℃, in an atmospheric environment, a cotton cloth with a size of 300cm×80cm is placed in a vertical combustion tester, ignited, and the afterflame time, afterglow time and carbonization length are tested, and 5 sets of parallel experiments are performed, and the specific experimental results are shown in Table 1.

[0083] Table 1. Vertical combustion test of cotton cloth flame-retardant fabric

[0084]

[0085] As shown in Table 1, the average afterflame time of the cotton cloth flame-retardant fabric is less than 0.1s, the average afterglow time is 0.8s, and the average carbonization length is 3.0mm.

[0086] Fiber cloth flame-retardant test: at 20℃, in an atmospheric environment, a fiber cloth with a size of 300cm×80cm is placed in a vertical combustion tester, ignited, and the afterflame time, afterglow time and damage length are tested, and 5 sets of parallel experiments are performed, and the specific experimental results are shown in Table 2.

[0087] Table 2. Vertical burning test of flame-retardant fabric

[0088]

[0089] As shown in Table 2, the average afterflame time of the flame-retardant fabric is less than 0.1 s, the average afterglow time is less than 0.1 s, and the average char length is 1 mm.

[0090] Flame-retardant test of non-woven fabric: at 20°C, in an atmospheric environment, cotton fibers with a size of 300 cm x 80 cm were placed in a vertical burning tester, ignited, and the afterflame time, afterglow time, and damage length were tested, with 5 parallel experiments. The specific experimental results are shown in Table 3.

[0091] Table 3. Vertical burning test of flame-retardant fabric

[0092]

[0093] As shown in Table 3, the average afterflame time of the flame-retardant fabric is less than 0.1 s, the average afterglow time is 1.0 s, and the average char length is 4.0 mm.

[0094] Flame-retardant and heat-insulating composite fabric test: at 20°C, in an atmospheric environment, a flame-retardant and heat-insulating composite fabric with a size of 30 cm x 30 cm was tested, with the outermost heat-insulating layer being 1.0 mm. Two metal clamps were used to fix the composite fabric, which was placed vertically on the safety table of the fume hood. The heat-insulating performance was tested using a 1300°C flame, with a test time of 5.0 min, and 5 parallel experiments were conducted. The corresponding data were obtained. When the 1200-1300°C butane spray gun flame was aimed at the front of the composite fabric, the surface fell in the outer flame area of the highest temperature of the flame, the coating foamed, the foaming height was 30 times higher than the original coating, and phase change occurred, the coating was converted into a porous carbonized layer, a large amount of heat was absorbed during the foaming process, and the back temperature was only 55°C. The temperature change of the back of the composite fabric during the combustion process is shown in Figure 7 After the composite fabric was removed from the flame, the average afterflame time of the front of the composite fabric was less than 0.1 s, and the average afterglow time was less than 0.1 s. The specific experimental results are shown in Table 4.

[0095] Table 4. Burning test of flame-retardant composite fabric

[0096]

[0097] Further, the mass loss of the composite fabric was measured using a cone calorimeter. The specific steps were as follows: at 25°C, in an atmospheric environment, a flame-retardant and heat-insulating composite fabric with a size of 12 cm x 12 cm was tested under a radiation intensity of 50 kw / m 2 for 15 min, with a mass loss of 1.5 g and a unit area mass loss rate of 0.116 g / m 2s, and the specific experimental results are shown in Figure 8

[0098] Through the comparison of experimental results, the composite cloth prepared by modifying the cotton, non-woven fabric, polyester, fiber and fiber cloth with the modified flame retardant and the flame retardant modified coating has good flame retardant and heat insulation capacity. The surface of the composite cloth will immediately change and absorb heat when it encounters fire, and at the same time, a carbonized layer (such as Figure 9A Figure 9B Figure 9C ) is formed. These carbonized layers have very good heat insulation performance. If it is applied to the field of textile fibers, it can effectively prevent the occurrence and spread of fire, significantly reduce the incidence of fire caused by plant fibers and the loss caused by fire; at the same time, it can be used as raw materials for protective equipment and fire rescue equipment, especially for the production of fireproof and heat-insulating fire suits. The composite cloth has strong flexibility, light weight, and comfortable non-woven fabric in the inner layer; when heated, its outer surface can foam and insulate most of the heat, providing a relatively heat-insulating system for firefighters' rescue operations, and maximizing the safety of firefighters' lives.

[0099] Example 2

[0100] The preparation steps of the polyester-fiber-polyester flame-retardant and heat-insulating composite cloth are as follows:

[0101] (1) The polyester is soaked in the modified flame retardant aqueous solution for 30 min, and the soaking temperature is controlled at 35°C. After the soaking treatment is completed, it is pre-dried at 60°C for 25 min, and then dried in an oven at 100°C for 20 min. The fiber is soaked in the modified flame retardant solution for 15 min, and the temperature is controlled at 40°C. After the soaking treatment is completed, it is pre-dried at 60°C for 25 min, and then dried in an oven at 100°C for 25 min. The fiber cloth is soaked in the modified flame retardant solution for 40 min, and the temperature is controlled at 45°C. After the soaking treatment is completed, it is pre-dried at 60°C for 60 min, and then dried in an oven at 120°C for 30 min. Three different flame-retardant fabric fibers are obtained. The modified flame retardant includes: 5 parts by weight of the compound shown in formula (I), 10 parts by weight of the compound shown in formula (II), 0.04 parts by weight of phosphoric acid, 0.1 parts by weight of melamine, and 200 parts by weight of water.

[0102] ​​​(2) The steps of heat insulation treatment of the corresponding flame-retardant fabric are as follows: the double sides of the polyester, the vinylon and the fiber cloth are coated with a 0.1-1.0 mm thick flame-retardant modified coating glue. The flame-retardant modified coating glue is prepared from the following raw materials in parts by weight: modifier (expanded graphite) 7 parts by weight, water-based polyurethane emulsion (E11 (trade name) of Jiangsu Xingfeng Chemical Technology Co., Ltd.) 45 parts by weight, ammonium polyphosphate 23 parts by weight, carbonization agent (pentaerythritol) 12 parts by weight, wetting agent (BYK-S706 (trade name) of BYK, Germany) 0.8 parts by weight, defoaming agent (mineral oil) 0.3 parts by weight, dispersing agent (BYK-2150 (trade name) of BYK, Germany) 0.4 parts by weight, anti-settling agent (bentonite) 0.5 parts by weight, and diluent (water) 11 parts by weight. At the same time, the flame-retardant modified coating glue is used for adhesion according to the order of polyester-vinylon-fiber cloth, i.e. to obtain the flame-retardant heat-insulating composite cloth of polyester-vinylon-fiber.

[0103] Flame-retardant heat-insulating composite cloth test: in the atmospheric environment at 20°C, the size of the flame-retardant heat-insulating composite cloth is 30 cm x 30 cm, and the outermost heat insulation layer is 1.0 mm. Two metal clamps are used to fix the composite cloth, which is vertically placed on the safety table of the fume hood. The heat insulation performance is tested by using a 1300°C flame, the test time is 5.0 min, and 5 groups of parallel experiments are carried out. The corresponding data are obtained. When the 1200-1300°C butane spray gun flame is aimed at the front of the composite cloth and sprayed, the surface falls in the outer flame area of the highest temperature of the flame, the coating foams under the heat, the foaming height is 30 times higher than that of the original coating, and at the same time, the phase change occurs, the coating is converted into a porous carbonized layer, a large amount of heat is absorbed during the foaming process, and finally the back temperature is only 67°C. After the composite cloth is away from the fire, the average afterburning time of the front of the composite cloth is less than 0.1 s, and the average smoldering time is less than 0.1 s. The specific experimental results are shown in Table 5.

[0104] Table 5. Flame-retardant composite cloth combustion test

[0105]

[0106] In order to further improve the heat insulation performance, the flame-retardant modified coating glue can be continuously coated on the front and back of the composite cloth, and the thickness can be coated to 1-2 mm. After the coating is completely dried, the adhesion is high, and it will not fall off and will not crack, while having good flexibility.

[0107] Example 3

[0108] (1) The cotton is placed in a modified flame retardant aqueous solution for 20 min, the soaking temperature is controlled at 30°C, after the soaking treatment is completed, it is pre-dried at 60°C for 20 min, and then dried in an oven at 100°C for 15 min; the Vilen is placed in a modified flame retardant solution for 15 min, the soaking temperature is controlled at 40°C, after the soaking treatment is completed, it is pre-dried at 60°C for 25 min, and then dried in an oven at 100°C for 25 min; the polyester is placed in a modified flame retardant solution for 30 min, the soaking temperature is controlled at 35°C, after the soaking treatment is completed, it is pre-dried at 60°C for 25 min, and then dried in an oven at 100°C for 20 min. Three different flame-retardant fabric fibers are obtained. The modified flame retardant includes: 5 parts by weight of the compound represented by formula (I), 10 parts by weight of the compound represented by formula (II), 0.04 parts by weight of phosphoric acid, 0.1 parts by weight of melamine, and 200 parts by weight of water.

[0109] (2) The corresponding flame-retardant fabric is subjected to heat insulation treatment as follows: the cotton cloth, Vilen and polyester are coated with a 0.1-1.0 mm thick flame-retardant modified coating glue on both sides; at the same time, the flame-retardant modified coating glue is used for adhesion, and the cotton cloth-Vilen-polyester is adhered in the order of cotton cloth-Vilen-polyester, to obtain a cotton cloth-Vilen-polyester flame-retardant heat-insulating composite cloth. The flame-retardant modified coating glue is prepared from the following raw materials in parts by weight: modifier (expanded graphite) 7 parts, water-based polyurethane emulsion (E11 (trade name) of Jiangsu Xingfeng Chemical Technology Co., Ltd.) 45 parts, ammonium polyphosphate 23 parts, carbonization agent (pentaerythritol) 12 parts, wetting agent (BYK-S706 (trade name) of Germany BYK brand) 0.8 parts, defoaming agent (mineral oil) 0.3 parts, dispersing agent (BYK-2150 (trade name) of Germany BYK brand) 0.4 parts, anti-settling agent (bentonite) 0.5 parts, and diluent (water) 11 parts.

[0110] Flame-retardant heat-insulating composite cloth test: in an atmospheric environment at 20°C, a flame-retardant heat-insulating composite cloth with a size of 30 cm x 30 cm, and a 1.0 mm outermost heat-insulating layer. Two metal clamps are used to fix the composite cloth, which is vertically placed on the safety table of the fume hood. The heat insulation performance is tested by using a 1300°C flame, the test time is 3.0 min, and 5 groups of parallel experiments are performed. The corresponding data is obtained. When the 1200-1300°C butane spray gun flame is aimed at the front of the composite cloth and burns, the surface falls in the highest temperature outer flame area of the flame, the coating is heated and foamed, the foaming height is 30 times higher than that of the original coating, and phase change occurs at the same time, the coating is converted into a porous carbonized layer, a large amount of heat is absorbed during the foaming process, and the back temperature is only 84°C. After leaving the fire, the average afterburning time of the front of the composite cloth is less than 0.1 s, and the average smoldering time is less than 0.1 s. The specific experimental results are shown in Table 6.

[0111] Table 6. Flame-retardant composite cloth combustion test

[0112]

[0113] In order to further improve its thermal insulation performance, the flame-retardant modified coating glue can be continuously coated on the front and back of the composite cloth, and the thickness can be coated 1-2mm. After the coating is completely dried, the adhesion is high, will not fall off, will not crack and has good flexibility.

[0114] The above specific embodiments further illustrate the purpose, technical solutions and beneficial effects of the present disclosure. It should be understood that the above description is only a specific embodiment of the present disclosure and is not intended to limit the present disclosure. Any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present disclosure shall be included in the protection scope of the present disclosure.

Claims

1. A method for preparing a modified flame retardant compound having a structure shown in formula (I) comprising: A compound with a B compound reacting to obtain a modified flame-retardant compound of the structure shown in formula (I) .

2. The method of claim 1, wherein, The method comprises: under the condition of organic solvent and catalyst, the compound A is mixed with the compound B to form a fire-retardant mixture, a pH regulator is added to the fire-retardant mixture, and the mixture is reacted at a preset temperature to obtain a modified fire-retardant compound with the structure shown in formula (I). Formula (I); Wherein: The organic solvent is selected from methanol, and the catalyst is selected from calcium oxide; The molar ratio of the compound A to the compound B is 1:1-1:1.2; The preset reaction temperature is 50-70℃; The pH regulator adjusts the pH of the flame retardant mixture to neutral, and the pH is 6-7. 3.A modified flame retardant comprising: A mixture of a modified flame retardant compound having a structure shown in formula (I) and a compound shown in formula (II); And A blending agent blended with the mixture, the blending agent being selected from one or more of phosphoric acid, ammonium salt, magnesium salt, melamine; Wherein, the structures of the compound shown in formula (I) and formula (II) are as follows: Formula (I); Formula (II); The ammonium salt is ammonium chloride, and the magnesium salt is selected from one or more of magnesium chloride and magnesium sulfate.

4. The modified flame retardant of claim 3, wherein, The blending mass ratio of the blending agent to the mixture is 1:20-50, and the mass ratio of the compound shown in formula (I) to the compound shown in formula (II) is 1:1-3. 5.A flame-retardant modified coating glue comprising the following components in parts by weight: A modifier 1-10 parts; A water-based polyurethane 20-50 parts; An ammonium polyphosphate flame retardant 20-50 parts; A carbonization agent 10-30 parts; A wetting agent 0.1-0.5 parts; An antifoaming agent 0.1-0.5 parts; A dispersing agent 0.1-0.5 parts; An anti-settling agent 0.1-0.5 parts; A diluent 10-30 parts; wherein, The sum of the parts by weight of all components is 100, and the modifier is selected from one or more of graphite, fiber, silicon oxide, calcium oxide, and titanium oxide; The ammonium polyphosphate flame retardant is the modified flame retardant according to any one of claims 3-4. 6.The flame-retardant modified coating glue according to claim 5, wherein: The wetting agent is a combination of one or more of BYK-306, BYK-S706, BYK-361, BYK-359, and SN-4727A; The antifoaming agent is a combination of one or more of SN-6710, silicone antifoaming agent, mineral oil, and polyether; The carbonization agent is a combination of one or more of glucose, starch, sucrose, cyclodextrin, pentaerythritol, and dipentaerythritol; The dispersing agent is a combination of one or more of BYK-2150, BYK-330, BYK-341, BYK-307, BYK-2155, BYK-104S, SN-1728A, SN-1728, SN-1729, SN-1776, SN-1760, SN-1790A, SN-1791, SN-1790, SN-1792, and SN-1798; The anti-settling agent is a combination of one or more of polyamide wax, bentonite, and polyethylene wax; The diluent is a combination of one or more of gasoline, water, methanol, dimethylbenzene, isopropyl alcohol, ethanol, ethyl acetate, and propylene glycol dimethyl ether. 7.A method for preparing the flame-retardant modified coating glue according to any one of claims 5-6, comprising: Adding a diluent to a reactor containing a water-based polyurethane and stirring until a vortex appears at the center of the liquid surface; After slowly adding wetting agent, defoaming agent and dispersing agent into the reactor, ammonium polyphosphate flame retardant and char-forming agent are added into the reactor and mixed uniformly; Then, the modifier is added into the mixed solution, and the mixture is dispersed and stirred again to obtain the flame-retardant modified coating glue.

8. A preparation method of flame-retardant thermal-insulation composite cloth, comprising: dipping a plurality of pieces of the fabric to be treated into the aqueous solution of the modified flame retardant according to any one of claims 3-4 at 30-45°C, pre-drying at 55-65°C after the dipping treatment, and drying at 100-120°C to obtain a plurality of pieces of flame-retardant fabric, wherein the mass ratio of the modified flame retardant to water is 1:10-30; coating the flame-retardant modified coating glue according to any one of claims 5-6 as the thermal-insulation layer on both sides of each piece of the flame-retardant fabric to obtain flame-retardant thermal-insulation fabric; stacking a plurality of pieces of the flame-retardant thermal-insulation fabric in sequence and adhering them together by the viscosity of the flame-retardant modified coating glue to obtain the flame-retardant thermal-insulation composite cloth after drying; wherein the fabric to be treated comprises any one of cotton cloth, non-woven fabric, polyester, vinylon, and fiber fabric, and the plurality of pieces of flame-retardant thermal-insulation fabric stacked in sequence are different from each other; the thickness of the thermal-insulation layer is 0.1-2 mm.

9. A fire-retardant insulating composite cloth, wherein, The flame-retardant thermal-insulation composite cloth is prepared by the method according to claim 8.

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