High-toughness anti-puncture tarpaulin material and preparation method thereof

Abstract

The invention discloses a high-toughness anti-puncture tarpaulin material and a preparation method thereof, and relates to the field of tarpaulin materials, and the tarpaulin material is composed of a fiber base cloth and a protective coating located on the surface of the fiber base cloth. The fiber base cloth is prepared from polyester fibers with good puncture resistance and cotton fibers with good toughness. A waterborne polyurethane coating used by the protective coating is prepared from the following raw materials in parts by weight: 50 to 60 parts of waterborne polyurethane emulsion, 10 to 15 parts of functional filler, 0.5 to 1.0 part of mildew preventive, 1.2 to 1.4 parts of antioxidant, 3.7 to 3.9 parts of defoaming agent, 1.4 to 1.6 parts of dispersing agent and 1.5 to 1.7 parts of flatting agent. Functional diisocyanate synthesized by preparing the waterborne polyurethane emulsion comprises a thiophene ring, a benzotriazole structure and a polysiloxane chain, and the ultraviolet resistance and the high temperature resistance of the tarpaulin material are improved. The synthesized functional filler comprises carbon nanotubes, DOPO and fluorine-containing alkane long chains, so that the strength, flame retardance and waterproofness of the tarpaulin material are improved.

Description

Technical Field

[0001] The invention relates to the field of tarpaulin materials, and in particular to a high-toughness puncture-resistant tarpaulin material and a preparation method thereof. Background Art

[0002] Tarpaulin is a waterproof material with high strength, good toughness and softness. The materials used to make tarpaulin are diverse, mainly including polyester, nylon, cotton, Oxford cloth and polyester fiber. With the improvement of people's living standards, the scope of use of tarpaulin is getting wider and wider, and the requirements for puncture resistance, toughness, waterproof breathability, flame retardancy and strength are getting higher and higher. Tarpaulin made of polyester fiber is widely used in outdoor products, such as tents, parasols, etc. Polyester tarpaulin is often treated with polyurethane coating to improve its durability. Polyester fiber has good puncture resistance, but poor breathability. Waterborne polyurethane coating is highly environmentally friendly, but not waterproof enough. Adding small molecule flame retardants, UV inhibitors and other additives to waterborne polyurethane coatings is conducive to improving flame retardancy and UV resistance, but small molecule additives have problems of poor dispersion compatibility and migration failure. Adding nanoparticle fillers such as carbon nanotubes helps to improve the mechanical properties of polyurethane coatings, but carbon nanotubes are easy to aggregate into bundles in the coating and have poor stability.

[0003] Therefore, it is necessary to develop a suitable modification method to solve the problems encountered in the actual use of polyester tarpaulins and the polyurethane coatings used therein, so as to meet the increasingly high usage demands. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides a high-toughness puncture-resistant tarpaulin material and a preparation method thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A high-toughness, puncture-resistant tarpaulin material, comprising a fiber-based fabric and a protective coating on the surface thereof; the fiber-based fabric is obtained by spinning and weaving polyester fibers and cotton fibers; the protective coating is obtained by coating a water-based polyurethane coating on the upper and lower surfaces of the fiber-based fabric, the water-based polyurethane coating comprising the following raw materials in parts by weight: 50-60 parts of water-based polyurethane emulsion, 10-15 parts of functional filler, 0.5-1.0 parts of mildewcide, 1.2-1.4 parts of antioxidant, 3.7-3.9 parts of defoamer, 1.4-1.6 parts of dispersant, and 1.5-1.7 parts of leveling agent; the mildewcide is pentachlorophenol, the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1, the defoamer is an organosilicon defoamer, the dispersant is a polyurethane dispersant, and the leveling agent is a polyester-modified polydimethylsiloxane solution;

[0007] The aqueous polyurethane emulsion comprises the following raw materials in parts by weight: 25-35 parts of polyether polyol, 10-15 parts of toluene diisocyanate, 5-10 parts of functional diisocyanate, 2.5-3.5 parts of ethylene glycol, 10-15 parts of DMF, 0.9-1.1 parts of dimethylol butyric acid, 0.5-1.0 parts of catalyst, 1.5-2.0 parts of end-capping agent, 1.2-1.8 parts of triethylamine and 30-40 parts of deionized water; the polyether polyol is polytetramethylene ether glycol, the catalyst is stannous octoate, and the end-capping agent is pentaerythritol triacrylate;

[0008] The preparation of the high-toughness puncture-resistant tarpaulin material comprises the following steps:

[0009] Step S1: spinning and weaving polyester fiber and cotton fiber in a mass ratio of 2:1 to obtain a fiber-based fabric;

[0010] Step S2: adding polyether polyol, functional diisocyanate, ethylene glycol and DMF into a reaction kettle, starting stirring, adding dimethylolbutyric acid after 30 minutes, continuing stirring and heating to 50-60° C., adding a catalyst, stirring for 40-50 minutes, heating to 70-80° C., reacting at a constant temperature for 5-6 hours, adding a capping agent, stirring for 5 minutes, cooling to 50° C., adding triethylamine, continuing stirring for 30 minutes, cooling to room temperature, adding deionized water and stirring for 10-15 minutes, to obtain an aqueous polyurethane emulsion;

[0011] Step S3: After the water-based polyurethane emulsion and the functional filler are mixed and stirred for 30-40 minutes, a mildew inhibitor, an antioxidant, a defoaming agent, a dispersant and a leveling agent are added and stirred for 15-20 minutes to obtain a water-based polyurethane coating;

[0012] Step S4: coating the upper and lower surfaces of the fiber-based fabric with a water-based polyurethane coating with a coating thickness of 1-1.2 mm to form a protective coating, and then heating at 50-60° C. for 1.5-2 h to obtain a high-toughness puncture-resistant tarpaulin material.

[0013] The functional diisocyanate is prepared by the following steps:

[0014] Step A1: 3-(5-nitrothiophene-2-yl)acrylic acid is added to DMF, and dichlorothionyl is added under stirring, and the mixture is refluxed and stirred at 50° C. for 4-5 hours to obtain an acyl chloride product; 4-nitro-1H-1,2,3-benzotriazole, potassium carbonate and dimethyl sulfoxide are added to a flask to obtain a mixed solution 1, and then the acyl chloride product is added to dimethyl sulfoxide to obtain a mixed solution 2, and the mixed solution 2 is slowly added dropwise to the mixed solution 1 in an ice-water bath at 0° C. After the addition is completed, the mixture is heated to 40° C. and stirred at a constant temperature for 10 hours to obtain a dinitro product;

[0015] Further, the dosage ratio of 3-(5-nitrothiophene-2-yl)acrylic acid, DMF, and dichlorothionyl is 0.1 mol: 60-70 mL: 0.12-0.15 mol; the dosage ratio of 4-nitro-1H-1,2,3-benzotriazole, potassium carbonate, and dimethyl sulfoxide is 0.1 mol: 0.015 mol: 35-45 mL; the dosage ratio of the acyl chloride product and dimethyl sulfoxide is 0.1 mol: 65-75 mL; the dosage ratio of the mixed solution 1 and the mixed solution 2 is 40-50 mL: 70-80 mL;

[0016] During the reaction of step A1, the carboxyl group of 3-(5-nitrothiophene-2-yl)acrylic acid reacts with thionyl chloride to generate an acyl chloride product; the secondary amino group of 4-nitro-1H-1,2,3-benzotriazole reacts with the acyl chloride product to generate a dinitro product containing a carbon-carbon double bond;

[0017] Step A2: Add toluene, hydrogenated silicone oil, hydroquinone, and cis-dichlorobis(pyridyl)platinum into a three-necked flask, stir and introduce nitrogen protection, slowly add the dinitro product, slowly raise the temperature to 70-80° C., stir and react for 3-4 hours, and evacuate to obtain a silicon-containing product;

[0018] Further, the usage ratio of the dinitro product, toluene, hydrogen-containing silicone oil, hydroquinone and cis-dichlorobis(pyridyl)platinum is 1-1.5 mol: 150 ml: 40-50 g: 0.5 mol: 0.015-0.020 mol;

[0019] During the reaction of step A2, the hydrogen-containing silicone oil reacts with the dinitro product under the catalysis of cis-dichlorobis(pyridyl)platinum, and the SiH bond and the C=C bond are added to generate a silicon-containing product;

[0020] Step A3: Add the silicon-containing product and toluene to a three-necked flask, heat it to 45°C, start reflux stirring, then add sodium dithionite, and reflux stirring to react for 1 hour to obtain a diamino product; add xylene to a four-necked flask, pass nitrogen, and add the diamino product and triphosgene successively under stirring at 75°C. After the addition is completed, heat it to 125°C and continue to react for 3.5 hours to obtain a functional diisocyanate;

[0021] Further, the usage ratio of silicon-containing product, toluene, and sodium dithionite is 40-42 g: 125-135 mL: 0.2 mol; the usage ratio of xylene, diamino product, and triphosgene is 150 mL: 38-40 g: 0.2 mol;

[0022] During the reaction of step A3, the nitro group of the silicon-containing product is reduced to an amino group to obtain a diamino product; the amino group of the diamino product reacts with triphosgene to generate chloroamide, which is then heated to dehydrochlorinate to generate a functional diisocyanate.

[0023] The functional filler is prepared by the following steps:

[0024] Step B1: add p-nitrobenzaldehyde to toluene, start reflux stirring, then add DOPO, raise the temperature to 100-110°C, reflux stirring and react for 3-4h to obtain a hydroxyl product;

[0025] Furthermore, the dosage ratio of p-nitrobenzaldehyde, toluene, and DOPO is 0.1 mol:75-85 mL:0.1 mol;

[0026] During the reaction of step B1, the aldehyde group of p-nitrobenzaldehyde and DOPO undergo an addition reaction to generate a hydroxyl product;

[0027] Step B2: Add the hydroxyl product, pyridine, triethylamine and dimethyl sulfoxide into a flask to obtain a mixed solution a, then add nonafluorovaleryl chloride into dimethyl sulfoxide to obtain a mixed solution b, slowly dropwise add the mixed solution b into the mixed solution a in an ice-water bath at 0°C, after the dropwise addition is completed, heat to 40°C, stir and react at a constant temperature for 8-10h, and distill under reduced pressure to obtain a nitro product; add the nitro product and toluene into a three-necked flask, heat to 45°C, start reflux and stir, then add sodium dithionite, and reflux and stir to react for 1h to obtain an amino product;

[0028] Furthermore, the dosage ratio of the hydroxyl product, pyridine, triethylamine and dimethyl sulfoxide is 0.1 mol: 0.01-0.013 mol: 0.1 mol: 80-90 mL; the dosage ratio of nonafluorovaleryl chloride and dimethyl sulfoxide is 0.1 mol: 55-65 mL; the dosage ratio of the mixed solution a and the mixed solution b is 85-95 mL: 60-70 mL; the dosage ratio of the nitro product, toluene and sodium dithionite is 0.1 mol: 155 mL: 0.1 mol;

[0029] During the reaction of step B2, the alcoholic hydroxyl group of the hydroxyl product reacts with nonafluorovaleryl chloride to generate a nitro product; the nitro group of the nitro product is reduced to an amino group to obtain an amino product;

[0030] Step B3: Add short multi-walled carbon nanotubes to the mixed acid, start stirring, reflux at 100-120°C for 1.5-2.5h, dilute, filter, wash, and dry in an oven at 110°C for 6-8h to obtain surface carboxyl carbon nanotubes; add the surface carboxyl carbon nanotubes to DMF, add dichlorothionyl under stirring, reflux and stir at 50°C for 4-5h, filter, wash, and dry to obtain an acyl chloride intermediate;

[0031] Furthermore, the amount ratio of carbon nanotubes to mixed acid is 10-15 g: 100-120 mL; the mixed acid is prepared by mixing concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1, and the mass fractions of concentrated sulfuric acid and concentrated nitric acid are both 98%; the amount ratio of surface carboxylated carbon nanotubes, DMF and dichlorothionyl is 8-10 g: 150 mL: 0.2-0.3 mol;

[0032] In the reaction process of step B3, the carbon nanotubes are treated with mixed acid to obtain surface carboxylated carbon nanotubes; the carboxyl groups of the surface carboxylated carbon nanotubes react with thionyl chloride to generate acyl chloride product 1;

[0033] Step B4: Add the amino product, potassium carbonate and dimethyl sulfoxide into a flask to obtain a mixed solution c, then add the acyl chloride product 1 into dimethyl sulfoxide to obtain a mixed solution d, slowly dropwise add the mixed solution d into the mixed solution c in an ice-water bath at 0°C, after the dropwise addition is completed, heat to 40°C, and stir the mixture at a constant temperature for 10 hours to obtain a functional filler;

[0034] Further, the dosage ratio of the amino product, potassium carbonate and dimethyl sulfoxide is 0.1 mol: 0.015 mol: 160-170 mL; the dosage ratio of the acyl chloride product 1 and dimethyl sulfoxide is 10-12 g: 155-165 mL; the dosage ratio of the mixed solution a and the mixed solution b is 165-175 mL: 160-170 mL;

[0035] During the reaction of step B4, the amino group of the amino product reacts with the acyl chloride product 1 to generate a functional filler.

[0036] Beneficial effects of the invention: The invention discloses a high-toughness puncture-resistant tarpaulin material, comprising a fiber-based fabric and a protective coating on the surface thereof; the protective coating is obtained by coating a water-based polyurethane coating on the upper and lower surfaces of the fiber-based fabric, and the water-based polyurethane coating comprises raw materials: water-based polyurethane emulsion, functional filler, mildew inhibitor, antioxidant, etc.; the water-based polyurethane emulsion comprises the following raw materials: polyether polyol, toluene diisocyanate, functional diisocyanate, ethylene glycol, etc. The fiber-based fabric is obtained by spinning and weaving polyester fiber and cotton fiber, and the polyester fiber has good puncture resistance and meets the use requirements of the puncture resistance of the tarpaulin material; the cotton fiber is slender and tough, not easy to break, and meets the high toughness requirements of the tarpaulin material, and the cotton fiber has good air permeability and is not easy to generate static electricity, which makes up for the shortcomings of polyester fiber, so that the tarpaulin material has good air permeability and antistatic properties, and is highly comfortable to use.

[0037] The functional diisocyanate synthesized for the preparation of protective coating contains thiophene ring, benzotriazole structure and polysiloxane chain. The introduction of thiophene ring not only broadens the ultraviolet absorption range, but also increases the molar absorption coefficient and enhances the ultraviolet absorption function; benzotriazole structure is a very effective ultraviolet absorption group with high chemical stability. When ultraviolet rays are irradiated to the surface of the fabric, it can absorb the energy of ultraviolet rays and convert it into heat energy or harmless radiation to prevent the fabric from fading; polysiloxane chain contains Si-O-Si bond and Si-C bond with high bond energy, which requires high energy to break, so that the thermal stability of functional diisocyanate is improved; functional diisocyanate participates in the reaction to synthesize modified polyurethane emulsion, and thiophene ring and benzotriazole structure with synergistic anti-ultraviolet performance and polysiloxane chain with high thermal stability are grafted into polyurethane, so that the modified polyurethane emulsion has stable ultraviolet resistance and thermal stability, and improves the ultraviolet resistance and high temperature resistance of tarpaulin materials.

[0038] Functional fillers used in preparing protective coatings contain carbon nanotubes, DOPO and long chains of fluorinated alkanes. The DOPO structure can dehydrate and degrade the burning surface of the polymer to form a carbon layer when the matrix burns. At the same time, the phosphorus-containing derivatives produced cover the surface of the polymer, isolate the combustible gas, block heat transfer, form a physical shield, and prevent the combustion from continuing; the long chain of fluorinated alkanes has strong hydrophobicity, which makes the coating highly waterproof, making the tarpaulin material not easily contaminated by water-soluble pollutants and keeping the surface clean; carbon nanotubes have the size of nanoparticles, high mechanical strength and good flexibility. After the surface of carbon nanotubes is modified by compounds containing structures such as DOPO, it is not easy to aggregate into bundles or entangle, and the dispersion in the coating matrix is ​​enhanced, so that the dispersion of DOPO small molecules with flame retardant properties in the coating is enhanced. Adding functional fillers can enhance the strength, flame retardancy and waterproofness of tarpaulin materials. DETAILED DESCRIPTION

[0039] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0040] Example 1: A functional diisocyanate, the preparation of which comprises the following steps:

[0041] Step A1: 3-(5-nitrothiophene-2-yl)acrylic acid is added to DMF, and dithionyl chloride is added under stirring, and the mixture is refluxed and stirred at 50°C for 4 hours to obtain an acyl chloride product; 4-nitro-1H-1,2,3-benzotriazole, potassium carbonate and dimethyl sulfoxide are added to a flask to obtain a mixed solution 1, and then the acyl chloride product is added to dimethyl sulfoxide to obtain a mixed solution 2, and the mixed solution 2 is slowly added dropwise to the mixed solution 1 under a 0°C ice-water bath. After the addition is completed, the mixture is heated to 40°C and stirred at a constant temperature for 10 hours to obtain a dinitro product; the dosage ratio of 3-(5-nitrothiophene-2-yl)acrylic acid, DMF and dithionyl chloride is 0.1 mol:60 mL:0.12 mol; the dosage ratio of 4-nitro-1H-1,2,3-benzotriazole, potassium carbonate and dimethyl sulfoxide is 0.1 mol:0.015 mol l:35mL; the dosage ratio of acyl chloride product and dimethyl sulfoxide is 0.1mol:65mL; ​​the dosage ratio of mixed solution 1 and mixed solution 2 is 40mL:70mL;

[0042] Step A2: Add toluene, hydrogen-containing silicone oil, hydroquinone, and cis-dichlorobis(pyridyl)platinum into a three-necked flask, stir and introduce nitrogen protection, slowly add the dinitro product, slowly raise the temperature to 70° C., stir and react for 3 hours, and evacuate to obtain a silicon-containing product; the amount ratio of the dinitro product, toluene, hydrogen-containing silicone oil, hydroquinone and cis-dichlorobis(pyridyl)platinum is 1 mol:150 ml:40 g:0.5 mol:0.015 mol;

[0043] Step A3: Add the silicon-containing product and toluene to a three-necked flask, heat to 45°C, start reflux stirring, then add sodium dithionite, and reflux stirring to react for 1 hour to obtain a diamino product; add xylene to a four-necked flask, pass nitrogen, add the diamino product and triphosgene successively under stirring at 75°C, after the addition is completed, heat to 125°C and continue to react for 3.5 hours to obtain a functional diisocyanate; the amount ratio of the silicon-containing product, toluene, and sodium dithionite is 40g:125mL:0.2mol; the amount ratio of xylene, diamino product, and triphosgene is 150mL:38g:0.2mol.

[0044] Example 2: A functional diisocyanate, the preparation of which comprises the following steps:

[0045] Step A1: 3-(5-nitrothiophene-2-yl)acrylic acid is added to DMF, and dithionyl chloride is added under stirring, and the mixture is refluxed and stirred at 50°C for 4.5 hours to obtain an acyl chloride product; 4-nitro-1H-1,2,3-benzotriazole, potassium carbonate and dimethyl sulfoxide are added to a flask to obtain a mixed solution 1, and then the acyl chloride product is added to dimethyl sulfoxide to obtain a mixed solution 2, and the mixed solution 2 is slowly added dropwise to the mixed solution 1 under a 0°C ice-water bath. After the addition is completed, the mixture is heated to 40°C and stirred at a constant temperature for 10 hours to obtain a dinitro product; the dosage ratio of 3-(5-nitrothiophene-2-yl)acrylic acid, DMF and dithionyl chloride is 0.1 mol:65 mL:0.13 mol; the dosage ratio of 4-nitro-1H-1,2,3-benzotriazole, potassium carbonate and dimethyl sulfoxide is 0.1 mol:0.015 mol l:40mL; the dosage ratio of acyl chloride product and dimethyl sulfoxide is 0.1mol:70mL; the dosage ratio of mixed solution 1 and mixed solution 2 is 45mL:75mL;

[0046] Step A2: Add toluene, hydrogen-containing silicone oil, hydroquinone, and cis-dichlorobis(pyridyl)platinum into a three-necked flask, stir and introduce nitrogen protection, slowly add the dinitro product, slowly raise the temperature to 75°C, stir and react for 3.5 hours, and evacuate to obtain a silicon-containing product; the dosage ratio of the dinitro product, toluene, hydrogen-containing silicone oil, hydroquinone and cis-dichlorobis(pyridyl)platinum is 1.3 mol:150 ml:45 g:0.5 mol:0.017 mol;

[0047] Step A3: Add the silicon-containing product and toluene to a three-necked flask, heat to 45°C, start reflux stirring, then add sodium dithionite, and reflux stirring to react for 1 hour to obtain a diamino product; add xylene to a four-necked flask, pass nitrogen, and add the diamino product and triphosgene successively under stirring at 75°C. After the addition is completed, heat to 125°C and continue to react for 3.5 hours to obtain a functional diisocyanate; the amount ratio of the silicon-containing product, toluene, and sodium dithionite is 41g:130mL:0.2mol; the amount ratio of xylene, diamino product, and triphosgene is 150mL:39g:0.2mol.

[0048] Example 3: A functional diisocyanate, the preparation of which comprises the following steps:

[0049] Step A1: 3-(5-nitrothiophene-2-yl)acrylic acid is added to DMF, and dichlorothionyl is added under stirring, and the mixture is refluxed and stirred at 50°C for 5 hours to obtain an acyl chloride product; 4-nitro-1H-1,2,3-benzotriazole, potassium carbonate and dimethyl sulfoxide are added to a flask to obtain a mixed solution 1, and then the acyl chloride product is added to dimethyl sulfoxide to obtain a mixed solution 2, and the mixed solution 2 is slowly added dropwise to the mixed solution 1 under a 0°C ice-water bath. After the addition is completed, the mixture is heated to 40°C and stirred at a constant temperature for 10 hours to obtain a dinitro product; the dosage ratio of 3-(5-nitrothiophene-2-yl)acrylic acid, DMF and dichlorothionyl is 0.1 mol:70 mL:0.15 mol; the dosage ratio of 4-nitro-1H-1,2,3-benzotriazole, potassium carbonate and dimethyl sulfoxide is 0.1 mol:0.015 mol l:45mL; the dosage ratio of acyl chloride product and dimethyl sulfoxide is 0.1mol:75mL; the dosage ratio of mixed solution 1 and mixed solution 2 is 50mL:80mL;

[0050] Step A2: Add toluene, hydrogen-containing silicone oil, hydroquinone, and cis-dichlorobis(pyridyl)platinum into a three-necked flask, stir and introduce nitrogen protection, slowly add the dinitro product, slowly raise the temperature to 80° C., stir and react for 4 hours, and evacuate to obtain a silicon-containing product; the amount ratio of the dinitro product, toluene, hydrogen-containing silicone oil, hydroquinone and cis-dichlorobis(pyridyl)platinum is 1.5 mol: 150 ml: 50 g: 0.5 mol: 0.020 mol;

[0051] Step A3: Add the silicon-containing product and toluene to a three-necked flask, heat to 45°C, start reflux stirring, then add sodium dithionite, and reflux stirring to react for 1 hour to obtain a diamino product; add xylene to a four-necked flask, pass nitrogen, and add the diamino product and triphosgene successively under stirring at 75°C. After the addition is completed, heat to 125°C and continue to react for 3.5 hours to obtain a functional diisocyanate; the amount ratio of the silicon-containing product, toluene, and sodium dithionite is 42g:135mL:0.2mol; the amount ratio of xylene, diamino product, and triphosgene is 150mL:40g:0.2mol.

[0052] Embodiment 4: A functional filler, the preparation of which comprises the following steps:

[0053] Step B1: add p-nitrobenzaldehyde to toluene, start reflux stirring, then add DOPO, heat to 100°C, reflux stirring and react for 3 hours to obtain a hydroxyl product; the dosage ratio of p-nitrobenzaldehyde, toluene and DOPO is 0.1 mol:75 mL:0.1 mol;

[0054] Step B2: Add the hydroxyl product, pyridine, triethylamine and dimethyl sulfoxide into a flask to obtain a mixed solution a, then add nonafluoropentanoyl chloride into dimethyl sulfoxide to obtain a mixed solution b, slowly dropwise add the mixed solution b into the mixed solution a in an ice-water bath at 0°C, after the dropwise addition is completed, heat to 40°C, stir and react at a constant temperature for 8 hours, and distill under reduced pressure to obtain a nitro product; add the nitro product and toluene into a three-necked flask, heat to 45°C, start reflux stirring, then add sodium dithionite, and reflux stirring and react for 1 hour to obtain an amino product; the amount ratio of the hydroxyl product, pyridine, triethylamine and dimethyl sulfoxide is 0.1 mol: 0.01 mol: 0.1 mol: 80 mL; the amount ratio of nonafluoropentanoyl chloride ... l:55mL; the dosage ratio of mixed solution a and mixed solution b is 85mL:60mL; the dosage ratio of nitro product, toluene and sodium dithionite is 0.1mol:155mL:0.1mol;

[0055] Step B3: Add short multi-walled carbon nanotubes to the mixed acid, start stirring, reflux at 100°C for 1.5 hours, dilute, filter, wash, and dry in a 110°C oven for 6 hours to obtain surface carboxylated carbon nanotubes; add the surface carboxylated carbon nanotubes to DMF, add dithionyl chloride while stirring, reflux and stir at 50°C for 4 hours, filter, wash with water, and dry to obtain an acyl chloride intermediate; the amount ratio of carbon nanotubes to the mixed acid is 10g:100mL; the mixed acid is prepared by mixing concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1, and the mass fractions of concentrated sulfuric acid and concentrated nitric acid are both 98%; the amount ratio of surface carboxylated carbon nanotubes, DMF and dithionyl chloride is 8-10g:150mL:0.2mol;

[0056] Step B4: Add the amino product, potassium carbonate and dimethyl sulfoxide into a flask to obtain a mixed solution c, then add the acyl chloride product 1 to dimethyl sulfoxide to obtain a mixed solution d, slowly drop the mixed solution d into the mixed solution c in an ice-water bath at 0°C, and after the dropwise addition is completed, heat the mixture to 40°C and stir the mixture at a constant temperature for 10 hours to obtain a functional filler; the amount ratio of the amino product, potassium carbonate and dimethyl sulfoxide is 0.1 mol: 0.015 mol: 160 mL; the amount ratio of the acyl chloride product 1 and dimethyl sulfoxide is 10 g: 155 mL; the amount ratio of the mixed solution a and the mixed solution b is 165 mL: 160 mL.

[0057] Embodiment 5: A functional filler, the preparation of which comprises the following steps:

[0058] Step B1: add p-nitrobenzaldehyde to toluene, start reflux stirring, then add DOPO, heat to 105°C, reflux stirring and react for 3.5 hours to obtain a hydroxyl product; the dosage ratio of p-nitrobenzaldehyde, toluene and DOPO is 0.1 mol:80 mL:0.1 mol;

[0059] Step B2: Add the hydroxyl product, pyridine, triethylamine and dimethyl sulfoxide into a flask to obtain a mixed solution a, then add nonafluoropentanoyl chloride into dimethyl sulfoxide to obtain a mixed solution b, slowly drop the mixed solution b into the mixed solution a in an ice water bath at 0°C, after the dropwise addition is completed, heat to 40°C, stir and react at constant temperature for 9 hours, and distill under reduced pressure to obtain a nitro product; add the nitro product and toluene into a three-necked flask, heat to 45°C, start reflux stirring, then add sodium dithionite, and reflux stirring and react for 1 hour to obtain an amino product; the amount ratio of the hydroxyl product, pyridine, triethylamine and dimethyl sulfoxide is 0.1 mol:0.012 mol:0.1 mol:85 mL; the amount ratio of nonafluoropentanoyl chloride ... l:60mL; the dosage ratio of mixed solution a and mixed solution b is 90mL:65mL; ​​the dosage ratio of nitro product, toluene and sodium dithionite is 0.1mol:155mL:0.1mol;

[0060] Step B3: Add short multi-walled carbon nanotubes to the mixed acid, start stirring, reflux at 110°C for 2.0h, dilute, filter, wash, and dry in an oven at 110°C for 7h to obtain surface carboxylated carbon nanotubes; add the surface carboxylated carbon nanotubes to DMF, add dithionyl chloride while stirring, reflux and stir at 50°C for 4.5h, filter, wash with water, and dry to obtain an acyl chloride intermediate; the amount ratio of carbon nanotubes to the mixed acid is 13g:110mL; the mixed acid is prepared by mixing concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1, and the mass fractions of concentrated sulfuric acid and concentrated nitric acid are both 98%; the amount ratio of surface carboxylated carbon nanotubes, DMF and dithionyl chloride is 9g:150mL:0.25mol;

[0061] Step B4: Add the amino product, potassium carbonate and dimethyl sulfoxide into a flask to obtain a mixed solution c, then add the acyl chloride product 1 to dimethyl sulfoxide to obtain a mixed solution d, slowly drop the mixed solution d into the mixed solution c in an ice-water bath at 0°C, and after the dropwise addition is completed, heat the mixture to 40°C and stir the mixture at a constant temperature for 10 hours to obtain a functional filler; the amount ratio of the amino product, potassium carbonate and dimethyl sulfoxide is 0.1 mol: 0.015 mol: 165 mL; the amount ratio of the acyl chloride product 1 and dimethyl sulfoxide is 11 g: 160 mL; the amount ratio of the mixed solution a and the mixed solution b is 170 mL: 165 mL.

[0062] Embodiment 6: A functional filler, the preparation of which comprises the following steps:

[0063] Step B1: add p-nitrobenzaldehyde to toluene, start reflux stirring, then add DOPO, heat to 110°C, reflux stirring and react for 4 hours to obtain a hydroxyl product; the dosage ratio of p-nitrobenzaldehyde, toluene and DOPO is 0.1 mol:85 mL:0.1 mol;

[0064] Step B2: Add the hydroxyl product, pyridine, triethylamine and dimethyl sulfoxide into a flask to obtain a mixed solution a, then add nonafluoropentanoyl chloride into dimethyl sulfoxide to obtain a mixed solution b, slowly drop the mixed solution b into the mixed solution a in an ice water bath at 0°C, after the dropwise addition is completed, heat to 40°C, stir and react at constant temperature for 10 hours, and distill under reduced pressure to obtain a nitro product; add the nitro product and toluene into a three-necked flask, heat to 45°C, start reflux stirring, then add sodium dithionite, and reflux stirring and react for 1 hour to obtain an amino product; the amount ratio of the hydroxyl product, pyridine, triethylamine and dimethyl sulfoxide is 0.1 mol:0.013 mol:0.1 mol:90 mL; the amount ratio of nonafluoropentanoyl chloride ... l:65mL; ​​the dosage ratio of mixed solution a and mixed solution b is 95mL:70mL; the dosage ratio of nitro product, toluene and sodium dithionite is 0.1mol:155mL:0.1mol;

[0065] Step B3: Add short multi-walled carbon nanotubes to the mixed acid, start stirring, reflux at 120°C for 2.5 hours, dilute, filter, wash, and dry in an oven at 110°C for 8 hours to obtain surface carboxylated carbon nanotubes; add the surface carboxylated carbon nanotubes to DMF, add dithionyl chloride while stirring, reflux and stir at 50°C for 5 hours, filter, wash with water, and dry to obtain an acyl chloride intermediate; the amount ratio of carbon nanotubes to the mixed acid is 15g:120mL; the mixed acid is prepared by mixing concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1, and the mass fractions of concentrated sulfuric acid and concentrated nitric acid are both 98%; the amount ratio of surface carboxylated carbon nanotubes, DMF and dithionyl chloride is 10g:150mL:0.3mol;

[0066] Step B4: Add the amino product, potassium carbonate and dimethyl sulfoxide into a flask to obtain a mixed solution c, then add the acyl chloride product 1 to dimethyl sulfoxide to obtain a mixed solution d, slowly drop the mixed solution d into the mixed solution c in an ice-water bath at 0°C, and after the dropwise addition is completed, heat the mixture to 40°C and stir the mixture at a constant temperature for 10 hours to obtain a functional filler; the amount ratio of the amino product, potassium carbonate and dimethyl sulfoxide is 0.1 mol: 0.015 mol: 170 mL; the amount ratio of the acyl chloride product 1 and dimethyl sulfoxide is 12 g: 165 mL; the amount ratio of the mixed solution a and the mixed solution b is 175 mL: 170 mL.

[0067] Embodiment 7: A high-toughness, puncture-resistant tarpaulin material, comprising a fiber-based fabric and a protective coating on the surface thereof; the fiber-based fabric is obtained by spinning and weaving polyester fibers and cotton fibers; the protective coating is obtained by coating a water-based polyurethane coating on the upper and lower surfaces of the fiber-based fabric, the water-based polyurethane coating comprising the following raw materials in parts by weight: 50 parts of water-based polyurethane emulsion, 10 parts of functional filler, 0.5 parts of mildewproof agent, 1.2 parts of antioxidant, 3.7 parts of defoamer, 1.4 parts of dispersant, and 1.5 parts of leveling agent; the mildewproof agent is pentachlorophenol, the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1, the defoamer is an organosilicon defoamer, the dispersant is a polyurethane dispersant, and the leveling agent is a polyester-modified polydimethylsiloxane solution;

[0068] The aqueous polyurethane emulsion comprises the following raw materials in parts by weight: 25 parts of polyether polyol, 10 parts of toluene diisocyanate, 5 parts of functional diisocyanate, 2.5 parts of ethylene glycol, 10 parts of DMF, 0.9 parts of dimethylolbutyric acid, 0.5 parts of catalyst, 1.5 parts of end-capping agent, 1.2 parts of triethylamine and 30 parts of deionized water; the polyether polyol is polytetramethylene ether glycol, the catalyst is stannous octoate, and the end-capping agent is pentaerythritol triacrylate;

[0069] The preparation of the high-toughness puncture-resistant tarpaulin material comprises the following steps:

[0070] Step S1: spinning and weaving polyester fiber and cotton fiber in a mass ratio of 2:1 to obtain a fiber-based fabric;

[0071] Step S2: Add polyether polyol, toluene diisocyanate, the functional diisocyanate obtained in Example 1, ethylene glycol and DMF into a reaction kettle, start stirring, add dimethylolbutyric acid after 30 minutes, continue stirring and heat to 50°C, then add a catalyst, stir for 40 minutes, heat to 70°C, react at constant temperature for 5 hours, add a blocking agent, stir for 5 minutes, cool to 50°C, add triethylamine, continue stirring for 30 minutes, cool to room temperature, add deionized water and stir for 10 minutes to obtain an aqueous polyurethane emulsion;

[0072] Step S3: After mixing the waterborne polyurethane emulsion and the functional filler obtained in Example 4 for 30 minutes, a mildew preventer, an antioxidant, a defoamer, a dispersant and a leveling agent are added and stirred for 15 minutes to obtain a waterborne polyurethane coating;

[0073] Step S4: coating the upper and lower surfaces of the fiber-based fabric with a water-based polyurethane coating with a coating thickness of 1 mm to form a protective coating, and then heating at 50° C. for 1.5 h to obtain a high-toughness puncture-resistant tarpaulin material.

[0074] Embodiment 8: A high-toughness, puncture-resistant tarpaulin material, comprising a fiber-based fabric and a protective coating on the surface thereof; the fiber-based fabric is obtained by spinning and weaving polyester fibers and cotton fibers; the protective coating is obtained by coating a water-based polyurethane coating on the upper and lower surfaces of the fiber-based fabric, the water-based polyurethane coating comprising the following raw materials in parts by weight: 55 parts of water-based polyurethane emulsion, 13 parts of functional filler, 0.8 parts of mildewcide, 1.3 parts of antioxidant, 3.8 parts of defoamer, 1.5 parts of dispersant, and 1.6 parts of leveling agent; the mildewcide is pentachlorophenol, the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1, the defoamer is an organosilicon defoamer, the dispersant is a polyurethane dispersant, and the leveling agent is a polyester-modified polydimethylsiloxane solution;

[0075] The aqueous polyurethane emulsion comprises the following raw materials in parts by weight: 30 parts of polyether polyol, 13 parts of toluene diisocyanate, 8 parts of functional diisocyanate, 3.0 parts of ethylene glycol, 13 parts of DMF, 1.0 parts of dimethylolbutyric acid, 0.8 parts of catalyst, 1.8 parts of end-capping agent, 1.5 parts of triethylamine and 35 parts of deionized water; the polyether polyol is polytetramethylene ether glycol, the catalyst is stannous octoate, and the end-capping agent is pentaerythritol triacrylate;

[0076] The preparation of the high-toughness puncture-resistant tarpaulin material comprises the following steps:

[0077] Step S1: spinning and weaving polyester fiber and cotton fiber in a mass ratio of 2:1 to obtain a fiber-based fabric;

[0078] Step S2: Add polyether polyol, toluene diisocyanate, the functional diisocyanate obtained in Example 2, ethylene glycol and DMF into a reaction kettle, start stirring, add dimethylolbutyric acid after 30 minutes, continue stirring and heat to 55°C, then add a catalyst, stir for 45 minutes, heat to 75°C, react at constant temperature for 5.5 hours, add a capping agent, stir for 5 minutes, cool to 50°C, add triethylamine, continue stirring for 30 minutes, cool to room temperature, add deionized water and stir for 13 minutes to obtain an aqueous polyurethane emulsion;

[0079] Step S3: After mixing the waterborne polyurethane emulsion and the functional filler obtained in Example 5 for 35 minutes, a mildew preventer, an antioxidant, a defoamer, a dispersant and a leveling agent are added and stirred for 18 minutes to obtain a waterborne polyurethane coating;

[0080] Step S4: coating the upper and lower surfaces of the fiber-based fabric with a water-based polyurethane coating with a coating thickness of 1.1 mm to form a protective coating, and then heating at 55° C. for 1.8 h to obtain a high-toughness puncture-resistant tarpaulin material.

[0081] Embodiment 9: A high-toughness, puncture-resistant tarpaulin material, comprising a fiber-based fabric and a protective coating on the surface thereof; the fiber-based fabric is obtained by spinning and weaving polyester fibers and cotton fibers; the protective coating is obtained by coating a water-based polyurethane coating on the upper and lower surfaces of the fiber-based fabric, the water-based polyurethane coating comprising the following raw materials in parts by weight: 60 parts of water-based polyurethane emulsion, 15 parts of functional filler, 1.0 parts of mildew inhibitor, 1.4 parts of antioxidant, 3.9 parts of defoamer, 1.6 parts of dispersant, and 1.7 parts of leveling agent; the mildew inhibitor is pentachlorophenol, the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1, the defoamer is an organosilicon defoamer, the dispersant is a polyurethane dispersant, and the leveling agent is a polyester-modified polydimethylsiloxane solution;

[0082] The aqueous polyurethane emulsion comprises the following raw materials in parts by weight: 35 parts of polyether polyol, 15 parts of toluene diisocyanate, 10 parts of functional diisocyanate, 3.5 parts of ethylene glycol, 15 parts of DMF, 1.1 parts of dimethylolbutyric acid, 1.0 parts of catalyst, 2.0 parts of end-capping agent, 1.8 parts of triethylamine and 40 parts of deionized water; the polyether polyol is polytetramethylene ether glycol, the catalyst is stannous octoate, and the end-capping agent is pentaerythritol triacrylate;

[0083] The preparation of the high-toughness puncture-resistant tarpaulin material comprises the following steps:

[0084] Step S1: spinning and weaving polyester fiber and cotton fiber in a mass ratio of 2:1 to obtain a fiber-based fabric;

[0085] Step S2: Add polyether polyol, toluene diisocyanate, the functional diisocyanate obtained in Example 3, ethylene glycol and DMF into a reaction kettle, start stirring, add dimethylolbutyric acid after 30 minutes, continue stirring and heat to 60°C, add catalyst, stir for 50 minutes, heat to 80°C, react at constant temperature for 6 hours, add end-capping agent, stir for 5 minutes, cool to 50°C, add triethylamine, continue stirring for 30 minutes, cool to room temperature, add deionized water and stir for 15 minutes to obtain water-based polyurethane emulsion;

[0086] Step S3: After mixing the waterborne polyurethane emulsion and the functional filler obtained in Example 6 for 40 minutes, a mildew preventer, an antioxidant, a defoamer, a dispersant and a leveling agent are added and stirred for 20 minutes to obtain a waterborne polyurethane coating;

[0087] Step S4: coating the upper and lower surfaces of the fiber-based fabric with a water-based polyurethane coating with a coating thickness of 1.2 mm to form a protective coating, and then heating at 60° C. for 2 h to obtain a high-toughness puncture-resistant tarpaulin material.

[0088] Comparative Example 1: Compared with Example 9, the functional diisocyanate is replaced with toluene diisocyanate, and the rest is exactly the same as Example 9 to obtain a high-toughness puncture-resistant tarpaulin material.

[0089] Comparative Example 2: Compared with Example 9, the functional filler is replaced with the surface carboxylated carbon nanotubes obtained in Step B3 of Example 6, and the rest is exactly the same as Example 9 to obtain a high-toughness puncture-resistant tarpaulin material.

[0090] The high-toughness puncture-resistant tarpaulin material prepared by the present invention is further tested for its effect, and the test results are as follows.

[0091] In order to test the high-toughness puncture-resistant tarpaulin material prepared by the present invention, the tensile strength is measured according to GB / T1040-1992 "Plastic Tensile Test Method";

[0092] High temperature resistance test method: After the high-toughness puncture-resistant tarpaulin materials obtained in Examples 7-9 and Comparative Examples 1-2 were placed in an air oven at 200°C for 48 hours, the tensile strength retention rate after treatment at 200°C was measured according to GB / T1040-1992 "Plastic Tensile Test Method";

[0093] Anti-ultraviolet performance test method: The tarpaulin materials obtained in Examples 7-9 and Comparative Examples 1-2 were cut into 100mm×100mm samples, and then placed in an ultraviolet accelerated aging test box, with 8 UVA-340 ultraviolet lamps of 40 watts each, and the lamps were 2cm away from the samples. The samples were aged for 240h, and the tensile strength retention rate after ultraviolet aging was measured:

[0094] Waterproof property test method: The contact angle of the high-toughness puncture-resistant tarpaulin materials obtained in Examples 7-9 and Comparative Examples 1-2 was measured using a static contact angle tester. The volume of the water droplet taken during the measurement was 5 μL, and 5 different positions were selected on the surface of the same material sample to be tested for measurement. The test was conducted five times in parallel, and the final average value was taken as the contact angle value. The larger the contact angle, the stronger the hydrophobicity and the better the waterproof property.

[0095] The limiting oxygen index was determined according to GB / T5454-1997 "Oxygen Index Method for Textile Combustion Performance Test", and the results are recorded in Table 1;

[0096] Table 1: Test results

[0097]

[0098] According to the data in Table 1, the high-toughness puncture-resistant tarpaulin material prepared by the present invention has good strength, high temperature resistance, UV resistance, waterproofness and flame retardancy. Comparison between Example 9 and Comparative Example 1 shows that the use of functional diisocyanates introduced with thiophene rings, benzotriazole and polysiloxane chains improves the UV resistance and high temperature resistance of the tarpaulin material. Comparison between Example 9 and Comparative Example 2 shows that the use of carbon nanotubes introduced with DOPO and fluorinated alkane long chains as fillers improves the flame retardancy and waterproofness of the tarpaulin material.

[0099] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. A high-toughness puncture-resistant tarpaulin material, characterized in that: It comprises a fiber-based fabric and a protective coating on the surface thereof; the fiber-based fabric is obtained by spinning and weaving polyester fibers and cotton fibers; the protective coating is obtained by coating a water-based polyurethane coating on the upper and lower surfaces of the fiber-based fabric, and the water-based polyurethane coating comprises the following raw materials in parts by weight: 50-60 parts of water-based polyurethane emulsion, 10-15 parts of functional filler, 0.5-1.0 parts of mildewproof agent, 1.2-1.4 parts of antioxidant, 3.7-3.9 parts of defoaming agent, 1.4-1.6 parts of dispersant, and 1.5-1.7 parts of leveling agent; The aqueous polyurethane emulsion comprises the following raw materials in parts by weight: 25-35 parts of polyether polyol, 10-15 parts of toluene diisocyanate, 5-10 parts of functional diisocyanate, 2.5-3.5 parts of ethylene glycol, 10-15 parts of DMF, 0.9-1.1 parts of dimethylolbutyric acid, 0.5-1.0 parts of catalyst, 1.5-2.0 parts of end-capping agent, 1.2-1.8 parts of triethylamine and 30-40 parts of deionized water; The functional diisocyanate is prepared by the following steps: Step A1: 3-(5-nitrothiophene-2-yl)acrylic acid is added to DMF, and dichlorothionyl is added under stirring, and the mixture is refluxed and stirred at 50° C. for 4-5 hours to obtain an acyl chloride product; 4-nitro-1H-1,2,3-benzotriazole, potassium carbonate and dimethyl sulfoxide are added to a flask to obtain a mixed solution 1, and then the acyl chloride product is added to dimethyl sulfoxide to obtain a mixed solution 2, and the mixed solution 2 is slowly added dropwise to the mixed solution 1 in an ice-water bath at 0° C. After the addition is completed, the mixture is heated to 40° C. and stirred at a constant temperature for 10 hours to obtain a dinitro product; Step A2: Add toluene, hydrogenated silicone oil, hydroquinone, and cis-dichlorobis(pyridyl)platinum into a three-necked flask, stir and introduce nitrogen protection, slowly add the dinitro product, slowly raise the temperature to 70-80° C., stir and react for 3-4 hours, and evacuate to obtain a silicon-containing product; Step A3: Add the silicon-containing product and toluene to a three-necked flask, heat to 45°C, start reflux stirring, then add sodium dithionite, and reflux stirring to react for 1 hour to obtain a diamino product; add xylene to a four-necked flask, pass nitrogen, and add the diamino product and triphosgene successively under stirring at 75°C. After the addition is completed, heat to 125°C and continue to react for 3.5 hours to obtain a functional diisocyanate.

2. The high-toughness puncture-resistant tarpaulin material according to claim 1, characterized in that: In step A1, the usage ratio of 3-(5-nitrothiophene-2-yl)acrylic acid, DMF and dichlorothionyl is 0.1 mol: 60-70 mL: 0.12-0.15 mol; the usage ratio of 4-nitro-1H-1,2,3-benzotriazole, potassium carbonate and dimethyl sulfoxide is 0.1 mol: 0.015 mol: 35-45 mL; the usage ratio of acyl chloride product and dimethyl sulfoxide is 0.1 mol: 65-75 mL; the usage ratio of mixed solution 1 and mixed solution 2 is 40-50 mL: 70-80 mL.

3. The high-toughness puncture-resistant tarpaulin material according to claim 1, characterized in that: In step A2, the usage ratio of dinitro product, toluene, hydrogenated silicone oil, hydroquinone and cis-dichlorobis(pyridyl)platinum is 1-1.5 mol:150 ml:40-50 g:0.5 mol:0.015-0.020 mol; in step A3, the usage ratio of silicon-containing product, toluene and sodium dithionite is 40-42 g:125-135 mL:0.2 mol; the usage ratio of xylene, diamino product and triphosgene is 150 mL:38-40 g:0.2 mol.

4. The high-toughness puncture-resistant tarpaulin material according to claim 1, characterized in that: The functional filler is prepared by the following steps: Step B1: add p-nitrobenzaldehyde to toluene, start reflux stirring, then add DOPO, raise the temperature to 100-110°C, reflux stirring and react for 3-4h to obtain a hydroxyl product; Step B2: Add the hydroxyl product, pyridine, triethylamine and dimethyl sulfoxide into a flask to obtain a mixed solution a, then add nonafluorovaleryl chloride into dimethyl sulfoxide to obtain a mixed solution b, slowly dropwise add the mixed solution b into the mixed solution a in an ice-water bath at 0°C, after the dropwise addition is completed, heat to 40°C, stir and react at a constant temperature for 8-10h, and distill under reduced pressure to obtain a nitro product; add the nitro product and toluene into a three-necked flask, heat to 45°C, start reflux stirring, then add sodium dithionite, and reflux stirring and react for 1h to obtain an amino product; Step B3: Add short multi-walled carbon nanotubes to the mixed acid, start stirring, reflux at 100-120° C. for 1.5-2.5 hours, dilute, filter, wash, and dry in an oven at 110° C. for 6-8 hours to obtain surface carboxyl carbon nanotubes; add the surface carboxyl carbon nanotubes to DMF, add dichlorothionyl under stirring, reflux and stir at 50° C. for 4-5 hours, filter, wash with water, and dry to obtain the acyl chloride product 1; Step B4: Add the amino product, potassium carbonate and dimethyl sulfoxide into a flask to obtain a mixed solution c, then add the acyl chloride product 1 into dimethyl sulfoxide to obtain a mixed solution d, slowly drop the mixed solution d into the mixed solution c in an ice-water bath at 0°C, after the dropwise addition is completed, heat to 40°C, stir and react at a constant temperature for 10 hours to obtain a functional filler.

5. The high-toughness puncture-resistant tarpaulin material according to claim 4, characterized in that: In step B1, the usage ratio of p-nitrobenzaldehyde, toluene and DOPO is 0.1 mol:75-85 mL:0.1 mol.

6. The high-toughness puncture-resistant tarpaulin material according to claim 4, characterized in that: In step B2, the usage ratio of the hydroxyl product, pyridine, triethylamine and dimethyl sulfoxide is 0.1 mol: 0.01-0.013 mol: 0.1 mol: 80-90 mL; the usage ratio of nonafluorovaleryl chloride and dimethyl sulfoxide is 0.1 mol: 55-65 mL; the usage ratio of mixed solution a and mixed solution b is 85-95 mL: 60-70 mL; the usage ratio of the nitro product, toluene and sodium dithionite is 0.1 mol: 155 mL: 0.1 mol.

7. The high-toughness puncture-resistant tarpaulin material according to claim 4, characterized in that: In step B3, the amount ratio of carbon nanotubes to mixed acid is 10-15g:100-120mL; the mixed acid is prepared by mixing concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1, and the mass fractions of concentrated sulfuric acid and concentrated nitric acid are both 98%; the amount ratio of surface carboxylated carbon nanotubes, DMF and dichlorothionyl is 8-10g:150mL:0.2-0.3mol.

8. The high-toughness puncture-resistant tarpaulin material according to claim 4, characterized in that: In step B4, the usage ratio of the amino product, potassium carbonate and dimethyl sulfoxide is 0.1 mol: 0.015 mol: 160-170 mL; the usage ratio of the acyl chloride product 1 and dimethyl sulfoxide is 10-12 g: 155-165 mL; the usage ratio of the mixed solution a and the mixed solution b is 165-175 mL: 160-170 mL.

9. The high-toughness puncture-resistant tarpaulin material according to claim 1, characterized in that: The mildew preventer is pentachlorophenol, the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1, the defoamer is an organosilicon defoamer, the dispersant is a polyurethane dispersant, and the leveling agent is a polyester-modified polydimethylsiloxane solution; the polyether polyol is polytetramethylene ether glycol, the catalyst is stannous octoate, and the capping agent is pentaerythritol triacrylate.

10. The method for preparing a high-toughness puncture-resistant tarpaulin material according to claim 1, characterized in that: The steps include: Step S1: spinning and weaving polyester fiber and cotton fiber in a mass ratio of 2:1 to obtain a fiber-based fabric; Step S2: adding polyether polyol, functional diisocyanate, ethylene glycol and DMF into a reaction kettle, starting stirring, adding dimethylolbutyric acid after 30 minutes, continuing stirring and heating to 50-60° C., adding a catalyst, stirring for 40-50 minutes, heating to 70-80° C., reacting at a constant temperature for 5-6 hours, adding a capping agent, stirring for 5 minutes, cooling to 50° C., adding triethylamine, continuing stirring for 30 minutes, cooling to room temperature, adding deionized water and stirring for 10-15 minutes, to obtain an aqueous polyurethane emulsion; Step S3: After the water-based polyurethane emulsion and the functional filler are mixed and stirred for 30-40 minutes, a mildew inhibitor, an antioxidant, a defoaming agent, a dispersant and a leveling agent are added and stirred for 15-20 minutes to obtain a water-based polyurethane coating; Step S4: coating the upper and lower surfaces of the fiber-based fabric with a water-based polyurethane coating with a coating thickness of 1-1.2 mm to form a protective coating, and then heating at 50-60° C. for 1.5-2 h to obtain a high-toughness puncture-resistant tarpaulin material.

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