Flame-retardant smoke-suppressing TPU fiber film material and preparation method thereof

Abstract

The application discloses a kind of flame-retardant smoke suppression TPU fiber membrane materials and preparation method thereof, comprising: preparation phytic acid derivative;Phytic acid derivative, natural antioxidant, inorganic carbon source are mixed uniformly with solvent, and composite flame retardant solution is obtained;TPU granules are added to composite flame retardant solution, heated and stirred, and composite spinning solution is formed;Composite spinning solution is used to carry out electrostatic spinning, and flame-retardant smoke suppression TPU fiber membrane material is obtained.The application introduces phytic acid derivative, natural antioxidant and inorganic carbon source in situ into TPU fiber membrane material by electrostatic spinning technology, improves the distribution uniformity of flame-retardant material and introduction amount, realizes the substantial improvement of flame-retardant performance, and preparation method is green and simple, low in cost, reduces the generation and release of harmful gas in its combustion process.

Description

Technical Field

[0001] This invention belongs to the field of flame retardant materials and relates to a flame retardant and smoke-suppressing TPU fiber membrane material and its preparation method. Background Technology

[0002] TPU is short for thermoplastic polyurethane elastomer, a polymer material formed by the reaction of diisocyanate molecules such as diphenylmethane diisocyanate (MDI) or toluene diisocyanate (TDI) with macromolecular polyols and low-molecular-weight polyols (chain extenders). Currently, TPU fiber films are widely used in medical and health, electronics, industry, and sports, possessing properties such as high strength, good toughness, aging resistance, and weather resistance. However, TPU is a flammable material. Upon heating, the physical cross-linking points composed of hydrogen bonds in the hard segments of TPU gradually fail, weakening the interactions between molecular chains, and the TPU changes from a network structure to a linear structure. As the temperature continues to rise, the urethane bonds in TPU decompose, forming short-chain molecules and small molecules such as isocyanates, alcohols, amines, and carbon dioxide. With further increases in temperature, the polyol soft segments in TPU begin to decompose, and the resulting small molecules diffuse into the flame zone above the polymer / air interface, mixing with air to form a flammable mixture. When the concentration and temperature of the mixture exceed the flammability threshold, the combustibles in the gas phase begin to burn. Some of the heat generated during combustion is fed back to the polymer surface, further exacerbating the thermal decomposition of TPU and producing more flammable debris, thus creating a vicious cycle.

[0003] TPU combustion is often accompanied by the formation of smoke, gases, and toxic / corrosive products. When TPU burns, it produces carbon monoxide, carbon dioxide, and nitrogen-containing volatiles (such as nitrogen oxides and hydrogen cyanide). Carbon monoxide is the main product, while nitrogen oxides and hydrogen cyanide can reach high concentrations under specific conditions. Related studies indicate that the hazard of the gases and smoke produced during combustion to TPU depends primarily on the concentration of decomposition products in the initial stage of combustion. If flame retardants can inhibit the initial combustion of TPU and reduce the concentration of toxic and harmful gaseous products in this stage, the fire hazard of TPU can be significantly reduced.

[0004] The aforementioned problems are currently typically addressed by adding flame retardants and smoke suppressants. Halogenated flame retardants are the most widely used due to their lower price and higher efficiency. However, halogenated flame retardants release toxic fumes during combustion, polluting the environment and harming human health. With increasingly stringent environmental standards, the use of some high-efficiency halogenated flame retardants has been prohibited or restricted, and halogen-free flame retardants are gaining increasing attention. Yin Shougen et al. from Tianjin University of Technology used ammonium polyphosphate and MXene to improve the flame retardancy of TPU fiber films, but the flame retardants they used were mostly inorganic materials, and the smoke suppression performance was not improved. Summary of the Invention

[0005] The purpose of this invention is to provide a flame-retardant and smoke-suppressing TPU fiber membrane material and its preparation method, which solves the problems of existing technologies releasing toxic fumes and having poor smoke suppression performance during combustion.

[0006] To achieve the above objectives, the present invention employs the following technical solution:

[0007] A method for preparing a flame-retardant and smoke-suppressing TPU fiber membrane material includes:

[0008] Preparation of phytic acid derivatives;

[0009] Phytic acid derivatives, natural antioxidants, inorganic carbon sources and solvents are mixed evenly to obtain a composite flame retardant solution.

[0010] TPU particles are added to the composite flame retardant solution, heated and stirred to form a composite spinning solution;

[0011] Flame-retardant and smoke-suppressing TPU fiber membrane material was obtained by electrospinning using a composite spinning solution.

[0012] Furthermore, the preparation process of the phytic acid derivative includes:

[0013] A phytic acid solution with a concentration of 50%–70% was heated to 120°C while stirring at 200 rpm and kept at that temperature for 2–4 hours. The temperature was then increased to 170°C and kept at that temperature for 3–6 hours to obtain the phytic acid derivative.

[0014] Furthermore, the phytic acid derivative includes one or more of the products obtained by heating phytic acid to remove one, two, and three water molecules.

[0015] The natural antioxidants include one or more of the following: flavonoids, tannins, vitamins, quinones, sterols, phenylpropanoids, coumarins, and enoic acids.

[0016] The inorganic carbon source includes one or more of graphite, expanded graphite, single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene, graphene oxide, and reduced graphene oxide.

[0017] Furthermore, the composite flame retardant solution comprises 1-4 parts of phytic acid derivative, 1-3 parts of natural antioxidant, 0.2-0.6 parts of inorganic carbon source, and 64.4-76.8 parts of solvent.

[0018] Furthermore, the solvent is water or an organic solvent, wherein the organic solvent is one or both of tetrahydrofuran and N,N-dimethylformamide.

[0019] Furthermore, the composite spinning solution includes 20-30 parts of TPU particles and 70-80 parts of composite flame retardant solution.

[0020] Furthermore, the TPU particles are polyether-type thermoplastic polyurethane elastomers.

[0021] Furthermore, the heating temperature is 60°C, the stirring rate is 200 r / min, and the stirring time is 3–5 h.

[0022] Furthermore, during the electrospinning process, the temperature is 20–50°C, the humidity is 20%–50%, the high voltage is +5–20KV, the low voltage is -1KV, the injection speed is 0.45–4.50mL / h, the rotation speed is 10–1000rpm, the plate distance is 5–20cm, and the electrospinning time is 6–24h.

[0023] A flame-retardant and smoke-suppressing TPU fiber membrane material prepared by the aforementioned method is characterized in that the total heat release per unit area of ​​the flame-retardant and smoke-suppressing TPU fiber membrane material is 1.50–1.92 MJ / m². 2 The heat release rate per unit area is 35.0–87.5 kW / m². 2 The smoke release rate is 1.27–2.33 m. 2 / s, with peak carbon dioxide emissions ranging from 0.07% to 0.22%.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] This invention provides a method for preparing a flame-retardant and smoke-suppressing TPU fiber membrane material, employing phytic acid derivatives, natural antioxidants, and inorganic carbon sources to synergistically improve the flame-retardant and smoke-suppressing properties of TPU. Phytic acid derivatives exhibit better water resistance and flame retardancy than phytic acid itself, and can act in both the condensed and gas phases of polymer combustion, enhancing the flame-retardant performance of the matrix. Natural antioxidants, as a class of natural, renewable, and pollution-free antioxidants, possess excellent free radical scavenging properties and can exert a flame-retardant effect by scavenging oxygen-containing groups. Inorganic carbon sources, due to their inherent plate-like physical barrier effect and high carbon content, impart good char-forming and smoke-suppressing properties to the polymer. This invention introduces phytic acid derivatives, natural antioxidants, and inorganic carbon sources in situ into the TPU fiber membrane material using electrospinning technology, improving the uniformity of flame-retardant material distribution and the amount introduced, achieving a significant improvement in flame-retardant performance. Furthermore, the preparation method is green, simple, and low-cost, reducing the generation and release of harmful gases during combustion.

[0026] This invention also provides a flame-retardant and smoke-suppressing TPU fiber membrane material, which has the advantages of being resistant to bending and having good flexibility, and the total heat release per unit area is 1.50~1.92MJ / m². 2 The heat release rate per unit area is 35.0–87.5 kW / m². 2 The smoke release rate is 1.27–2.33 m.2 The peak carbon dioxide emission is 0.07–0.22% per second. It can improve the flame retardant properties of thermoplastic polyurethane fiber films while reducing the generation and release of harmful gases during combustion. Compared with pure TPU fiber films, the total heat release per unit area is reduced by 10–30%, the heat release rate per unit area is reduced by 50–80%, the smoke release rate is reduced by 30–60%, and the peak carbon dioxide emission is reduced by 40–80%. Attached Figure Description

[0027] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0028] Figure 1 SEM image of the flame-retardant and smoke-suppressing TPU fiber membrane prepared in Example 1 of the present invention.

[0029] Figure 2 This is a SEM image of a pure TPU fiber membrane.

[0030] Figure 3 A comparison chart of the total heat release per unit area of ​​the pure TPU fiber membrane of the present invention and the flame-retardant and smoke-suppressing TPU fiber membrane prepared in Example 1.

[0031] Figure 4 A comparison chart of the heat release rate per unit area of ​​the pure TPU fiber membrane of the present invention and the flame-retardant and smoke-suppressing TPU fiber membrane prepared in Example 1.

[0032] Figure 5 A comparison chart of smoke release rates between the pure TPU fiber membrane of the present invention and the flame-retardant and smoke-suppressing TPU fiber membrane prepared in Example 1.

[0033] Figure 6 A comparison chart of CO2 content between the pure TPU fiber membrane of the present invention and the flame-retardant and smoke-suppressing TPU fiber membrane prepared in Example 1. Detailed Implementation

[0034] To enable those skilled in the art to understand the features and effects of the present invention, the terms and expressions used in the specification and claims are explained and defined in general below. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning understood by those skilled in the art regarding the present invention, and in case of conflict, the definitions in this specification shall prevail.

[0035] The theories or mechanisms described and disclosed herein, whether right or wrong, should not in any way limit the scope of the invention, that is, the contents of the invention can be implemented without being limited by any particular theory or mechanism.

[0036] In this document, all features defined by numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible sub-ranges and individual numerical values ​​(including integers and fractions) within those ranges.

[0037] In this article, unless otherwise specified, “contains,” “includes,” “containing,” “has,” or similar terms cover the meanings of “composed of” and “mainly composed of,” for example, “A contains a” covers the meanings of “A contains a and others” and “A contains only a.”

[0038] For the sake of brevity, not all possible combinations of the technical features in each implementation scheme or embodiment are described herein. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each implementation scheme or embodiment can be combined arbitrarily, and all possible combinations should be considered within the scope of this specification.

[0039] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0040] The following examples use instruments and equipment conventional in the art. Experimental methods in the following examples, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. All raw materials used in the following examples are conventional commercially available products with specifications conventional in the art. In this specification and the following examples, unless otherwise specified, "%" refers to weight percentage, "parts" refers to parts by weight, and "ratio" refers to weight proportion.

[0041] The present invention will now be described in further detail:

[0042] This invention provides a flame-retardant and smoke-suppressing TPU fiber membrane material and its preparation method, comprising the following steps:

[0043] Step 1: Add a phytic acid solution with a concentration of 50% to 70% to a four-necked flask, stir at 200 r / min and heat to 120°C, keep the temperature for 2 to 4 hours, then heat to 170°C and keep the temperature for 3 to 6 hours to obtain the phytic acid derivative.

[0044] Preferably, the phytic acid derivative includes one or more of the products obtained by heating phytic acid to remove one, two, or three water molecules.

[0045] Step 2: Mix 1-4 parts of phytic acid derivative, 1-3 parts of natural antioxidant, 0.2-0.6 parts of inorganic carbon source and 64.4-76.8 parts of solvent evenly to obtain a composite flame retardant solution.

[0046] Preferably, the natural antioxidants include one or more of flavonoids, tannins, vitamins, quinones, sterols, phenylpropanoids, coumarins, and enoic acids.

[0047] Preferably, the inorganic carbon source includes one or more of graphite, expanded graphite, single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene, graphene oxide, and reduced redox graphene.

[0048] Preferably, the solvent is water or an organic solvent.

[0049] More preferably, the organic solvent is one or both of tetrahydrofuran and N,N-dimethylformamide.

[0050] Step 3: Mix 20-30 parts of TPU granules with 70-80 parts of composite flame retardant solution, and stir magnetically at 60°C for 3-5 hours to form a composite spinning solution.

[0051] Preferably, the TPU particles are polyether-type thermoplastic polyurethane elastomers.

[0052] Step 4: Add the composite spinning solution into the syringe. At a temperature of 20-50℃ and a humidity of 20%-50%, set the electrospinning machine to a high voltage of +5-20KV, a low voltage of -1KV, an injection speed of 0.45-4.50mL / h, a rotation speed of 10-1000rpm, and a plate distance of 5-20cm, and perform electrospinning for 6-24 hours to obtain flame-retardant and smoke-suppressing TPU fiber membrane material.

[0053] The present invention will be further described in detail below with reference to specific embodiments:

[0054] Example 1:

[0055] This embodiment describes a method for preparing a flame-retardant and smoke-suppressing TPU fiber membrane material, including the following steps:

[0056] Step 1: Add a 70% phytic acid solution to a four-necked flask, stir at 200 r / min and heat to 120℃, keep the temperature for 2 h, then heat to 170℃ and keep the temperature for 3 h to obtain the phytic acid derivative.

[0057] Step 2: Mix 2 parts of phytic acid derivative, 2 parts of genistein (flavonoids), 0.2 parts of layered graphite and 75.8 parts of solvent evenly. The solvent is DMF and THF with a mass ratio of 1:1 to obtain a composite flame retardant solution.

[0058] Step 3: Mix 20 parts of TPU particles with the composite flame retardant solution and stir magnetically at 60°C for 3 hours to form a composite spinning solution.

[0059] Step 4: Add the composite spinning solution into the syringe. At a temperature of 20℃ and a humidity of 20%, set the electrospinning machine to a high voltage of 18KV / low voltage of -1KV, an injection speed of 1.35mL / h, a rotation speed of 30rpm, and a plate distance of 10cm. Perform electrospinning for 8 hours to obtain flame-retardant and smoke-suppressing TPU fiber membrane material.

[0060] Example 2:

[0061] This embodiment describes a method for preparing a flame-retardant and smoke-suppressing TPU fiber membrane material, including the following steps:

[0062] Step 1: Add a 70% phytic acid solution to a four-necked flask, stir at 200 r / min and heat to 120℃, keep the temperature for 4 h, then heat to 170℃ and keep the temperature for 5 h to obtain the phytic acid derivative.

[0063] Step 2: Mix 2 parts of phytic acid derivative, 3 parts of tannic acid (tannins), 0.4 parts of expanded graphite and 69.6 parts of solvent DMF evenly to obtain a composite flame retardant solution.

[0064] Step 3: Mix 25 parts of TPU particles with the composite flame retardant solution and stir magnetically at 60°C for 3 hours to form a composite spinning solution.

[0065] Step 4: Add the composite spinning solution into the syringe. At a temperature of 30℃ and a humidity of 30%, set the electrospinning machine to a high voltage of 14KV / low voltage of -1KV, an injection speed of 4.50mL / h, a rotation speed of 10rpm, and a plate distance of 5cm. Perform electrospinning for 6 hours to obtain flame-retardant and smoke-suppressing TPU fiber membrane material.

[0066] Example 3:

[0067] This embodiment describes a method for preparing a flame-retardant and smoke-suppressing TPU fiber membrane material, including the following steps:

[0068] Step 1: Add a 60% phytic acid solution to a four-necked flask, stir at 200 r / min and heat to 120℃, keep the temperature for 4 h, then heat to 170℃ and keep the temperature for 6 h to obtain the phytic acid derivative.

[0069] Step 2: Mix 3 parts of phytic acid derivative, 1 part of vitamin C (vitamin), 0.6 parts of single-walled carbon nanotubes and 65.4 parts of solvent THF evenly to obtain a composite flame retardant solution.

[0070] Step 3: Mix 30 parts of TPU particles with the composite flame retardant solution and stir magnetically at 60°C for 3 hours to form a composite spinning solution.

[0071] Step 4: Add the composite spinning solution into the syringe. At a temperature of 40℃ and a humidity of 40%, set the electrospinning machine to a high voltage of 12KV / low voltage of -1KV, an injection speed of 3.80mL / h, a rotation speed of 80rpm, and a plate distance of 15cm. Perform electrospinning for 10h to obtain flame-retardant and smoke-suppressing TPU fiber membrane material.

[0072] Example 4:

[0073] This embodiment describes a method for preparing a flame-retardant and smoke-suppressing TPU fiber membrane material, including the following steps:

[0074] Step 1: Add a 50% phytic acid solution to a four-necked flask, stir at 200 r / min and heat to 120℃, keep the temperature for 2 h, then heat to 170℃ and keep the temperature for 3 h to obtain the phytic acid derivative.

[0075] Step 2: Mix 2 parts of phytic acid derivative, 2 parts of anthraquinone (quinone), 0.2 parts of graphene and 75.8 parts of solvent water evenly to obtain a composite flame retardant solution.

[0076] Step 3: Mix 20 parts of TPU particles with the composite flame retardant solution and stir magnetically at 60°C for 4 hours to form a composite spinning solution.

[0077] Step 4: Add the composite spinning solution into the syringe. At a temperature of 30℃ and a humidity of 30%, set the electrospinning machine to a high voltage of 10KV / low voltage of -1KV, an injection speed of 3.45mL / h, a rotation speed of 100rpm, and a plate distance of 20cm. Perform electrospinning for 6 hours to obtain flame-retardant and smoke-suppressing TPU fiber membrane material.

[0078] Example 5:

[0079] This embodiment describes a method for preparing a flame-retardant and smoke-suppressing TPU fiber membrane material, including the following steps:

[0080] Step 1: Add a 55% phytic acid solution to a four-necked flask, stir at 200 r / min and heat to 120℃, keep the temperature for 4 h, then heat to 170℃ and keep the temperature for 5 h to obtain the phytic acid derivative.

[0081] Step 2: Mix 4 parts of phytic acid derivative, 1 part of sterol, 0.2 parts of graphene oxide and 69.8 parts of solvent evenly. The solvent is DMF and THF with a mass ratio of 1:1 to obtain a composite flame retardant solution.

[0082] Step 3: Mix 25 parts of TPU granules with the composite flame retardant solution and stir magnetically at 60°C for 5 hours to form a composite spinning solution.

[0083] Step 4: Add the composite spinning solution into the syringe. At a temperature of 35℃ and a humidity of 35%, set the electrospinning machine to a high voltage of 15KV / low voltage of -1KV, an injection speed of 2.25mL / h, a rotation speed of 200rpm, and a plate distance of 10cm. Perform electrospinning for 16h to obtain flame-retardant and smoke-suppressing TPU fiber membrane material.

[0084] Example 6:

[0085] This embodiment describes a method for preparing a flame-retardant and smoke-suppressing TPU fiber membrane material, including the following steps:

[0086] Step 1: Add a 65% phytic acid solution to a four-necked flask, stir at 200 r / min and heat to 120℃, keep the temperature for 4 h, then heat to 170℃ and keep the temperature for 6 h to obtain the phytic acid derivative.

[0087] Step 2: Mix 2 parts of phytic acid derivative, 3 parts of phenylpropanol, 0.6 parts of redox graphene with 64.4 parts of solvent evenly. The solvent is DMF and THF with a mass ratio of 1:1 to obtain a composite flame retardant solution.

[0088] Step 3: Mix 30 parts of TPU particles with the composite flame retardant solution and stir magnetically at 60°C for 5 hours to form a composite spinning solution.

[0089] Step 4: Add the composite spinning solution into the syringe. At a temperature of 40℃ and a humidity of 40%, set the electrospinning machine to a high voltage of 5KV / low voltage of -1KV, an injection speed of 0.90mL / h, a rotation speed of 400rpm, and a plate distance of 15cm. Perform electrospinning for 18h to obtain flame-retardant and smoke-suppressing TPU fiber membrane material.

[0090] Example 7:

[0091] This embodiment describes a method for preparing a flame-retardant and smoke-suppressing TPU fiber membrane material, including the following steps:

[0092] Step 1: Add a 70% phytic acid solution to a four-necked flask, stir at 200 r / min and heat to 120℃, keep the temperature for 2 h, then heat to 170℃ and keep the temperature for 3 h to obtain the phytic acid derivative.

[0093] Step 2: Mix 2 parts of phytic acid derivative, 2 parts of coumarin, 0.2 parts of layered graphite with 70.8 parts of solvent. The solvent is DMF and THF in a mass ratio of 1:1 to obtain a composite flame retardant solution.

[0094] Step 3: Mix 25 parts of TPU particles with the composite flame retardant solution and stir magnetically at 60°C for 3 hours to form a composite spinning solution.

[0095] Step 4: Add the composite spinning solution into the syringe. At a temperature of 45℃ and a humidity of 45%, set the electrospinning machine to a high voltage of 20KV / low voltage of -1KV, an injection speed of 0.90mL / h, a rotation speed of 600rpm, and a plate distance of 10cm. Perform electrospinning for 20h to obtain flame-retardant and smoke-suppressing TPU fiber membrane material.

[0096] Example 8:

[0097] This embodiment describes a method for preparing a flame-retardant and smoke-suppressing TPU fiber membrane material, including the following steps:

[0098] Step 1: Add a 70% phytic acid solution to a four-necked flask, stir at 200 r / min and heat to 120℃, keep the temperature for 2 h, then heat to 170℃ and keep the temperature for 4 h to obtain the phytic acid derivative.

[0099] Step 2: Mix 4 parts of phytic acid derivative, 3 parts of olefinic acid, 0.2 parts of graphene and 72.8 parts of solvent evenly. The solvent is DMF and THF with a mass ratio of 1:1 to obtain a composite flame retardant solution.

[0100] Step 3: Mix 20 parts of TPU particles with the composite flame retardant solution and stir magnetically at 60°C for 3 hours to form a composite spinning solution.

[0101] Step 4: Add the composite spinning solution into the syringe. At a temperature of 50℃ and a humidity of 50%, set the electrospinning machine to a high voltage of 5KV / low voltage of -1KV, an injection speed of 0.45mL / h, a rotation speed of 1000rpm, and a plate distance of 20cm. Perform electrospinning for 24h to obtain flame-retardant and smoke-suppressing TPU fiber membrane material.

[0102] Example 9:

[0103] This embodiment describes a method for preparing a flame-retardant and smoke-suppressing TPU fiber membrane material, including the following steps:

[0104] Step 1: Add a 70% phytic acid solution to a four-necked flask, stir at 200 r / min and heat to 120℃, keep the temperature for 2 h, then heat to 170℃ and keep the temperature for 3 h to obtain the phytic acid derivative.

[0105] Step 2: Mix 1 part phytic acid derivative, 2 parts genistein, 0.2 parts layered graphite with 76.8 parts solvent evenly. The solvent is DMF and THF in a mass ratio of 1:1 to obtain a composite flame retardant solution.

[0106] Step 3: Mix 20 parts of TPU particles with the composite flame retardant solution and stir magnetically at 60°C for 3 hours to form a composite spinning solution.

[0107] Step 4: Add the composite spinning solution into the syringe, and perform electrospinning for 8 hours at a temperature of 30℃, a humidity of 30%, a high voltage of 18KV / low voltage of -1KV, an injection speed of 1.35mL / h, a rotation speed of 30rpm, and a plate distance of 10cm to obtain flame-retardant and smoke-suppressing TPU fiber membrane material.

[0108] The performance of the flame-retardant and smoke-suppressing TPU fiber membrane material prepared in Example 1 of this invention:

[0109] Depend on Figures 1-2 It can be seen that, compared with pure TPU fibers, the TPU fibers in the flame-retardant and smoke-suppressing fiber membrane material prepared in Example 1 are thinner and have a rough surface with particulate matter, indicating that the flame retardant is successfully present in the fibers.

[0110] Depend on Figures 3-5 It is known that TPU fibers themselves have poor flame retardant and smoke suppression properties, and the total heat release per unit area of ​​pure TPU fiber membrane is 2.1383 MJ / m². 2 The heat release rate per unit area is 174.95 kW / m². 2 The smoke release rate was 3.1901 m. 2 / s, with a peak carbon dioxide release of 0.37%. Compared to pure TPU fiber membrane, the total heat release per unit area of ​​the flame-retardant and smoke-suppressing fiber membrane material prepared in Example 1 is 1.6574 MJ / m². 2 It decreased by 22.48%; the heat release rate per unit area was 53.23 kW / m². 2 It decreased by 69.57%; the smoke release rate was 1.5866m. 2 / s, a decrease of 50.27%; peak carbon dioxide emissions were 0.09%, a decrease of 75.68%.

[0111] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A process for the preparation of a flame retardant smoke suppressing TPU fibrous membrane material, characterized in that, include: Preparation of phytic acid derivatives; Phytic acid derivatives, natural antioxidants, inorganic carbon sources and solvents are mixed evenly to obtain a composite flame retardant solution. TPU particles are added to the composite flame retardant solution, heated and stirred to form a composite spinning solution; Flame-retardant and smoke-suppressing TPU fiber membrane material was obtained by electrospinning using a composite spinning solution. The preparation process of the phytic acid derivative includes: A phytic acid solution with a concentration of 50%~70% was heated to 120℃ while stirring at 200r / min and kept at this temperature for 2~4h. Then the temperature was raised to 170℃ and kept at this temperature for 3~6h to obtain phytic acid derivatives. The phytic acid derivatives include one or more of the products obtained by heating phytic acid to remove one, two, or three water molecules. The natural antioxidants include one or more of the following: flavonoids, tannins, vitamins, quinones, sterols, phenylpropanoids, coumarins, and enoic acids. The inorganic carbon source includes one or more of graphite, expanded graphite, single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene, graphene oxide, and reduced graphene oxide. The composite flame retardant solution comprises 1-4 parts of phytic acid derivative, 1-3 parts of natural antioxidant, 0.2-0.6 parts of inorganic carbon source, and 64.4-76.8 parts of solvent; The total heat release per unit area of ​​the flame-retardant and smoke-suppressing TPU fiber membrane material is 1.50~1.92 MJ / m². 2 The heat release rate per unit area is 35.0~87.5 kW / m². 2 The smoke release rate is 1.27~2.33m. 2 / s, with a peak carbon dioxide emission of 0.07~0.22%.

2. The preparation method of the flame-retardant and smoke-suppressive TPU fiber film material according to claim 1, characterized in that, The solvent is water or an organic solvent, and the organic solvent is one or both of tetrahydrofuran and N,N-dimethylformamide.

3. The preparation method of the flame-retardant and smoke-suppressive TPU fiber film material according to claim 1, characterized in that, The composite spinning solution includes 20-30 parts of TPU particles and 70-80 parts of composite flame retardant solution.

4. The preparation method of the flame-retardant and smoke-suppressive TPU fiber film material according to claim 1, characterized in that, The TPU particles are polyether-type thermoplastic polyurethane elastomers.

5. The preparation method of the flame-retardant and smoke-suppressive TPU fiber film material according to claim 1, characterized in that, The heating temperature is 60℃, the stirring rate is 200r / min, and the stirring time is 3~5h.

6. The method for preparing a flame-retardant and smoke-suppressing TPU fiber membrane material according to claim 1, characterized in that, During the electrospinning process, the temperature is 20~50℃, the humidity is 20%~50%, the high voltage is +5~20KV, the low voltage is -1KV, the injection speed is 0.45~4.50mL / h, the rotation speed is 10~1000rpm, the plate distance is 5~20cm, and the electrospinning time is 6~24h.

7. A flame-retardant and smoke-suppressing TPU fiber membrane material prepared by the preparation method according to any one of claims 1 to 6.

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