A dyed anti-slip and wear-resistant carpet and its preparation method

Abstract

The present invention discloses a dyed, anti-slip and wear-resistant carpet and a preparation method thereof, relating to the technical field of plastics. The dyed, anti-slip and wear-resistant carpet prepared by the present invention is obtained by weaving modified aramid fibers into a fabric, then coating a dyeing film, and finally laminating with a film. The modified aramid fibers are obtained by reacting imidazole aramid fibers with modified carbon nanotubes. The imidazole aramid fibers are prepared from isophthaloyl chloride and 2-(4-aminophenyl)-5-aminobenzimidazole as raw materials, using N,N-dimethylacetamide as a solvent, through low-temperature solution polycondensation, and then wet-dry spinning to enhance the anti-slip and wear resistance of the carpet. The dyeing film is a modified aromatic polyisocyanate, which is obtained by reacting resorcinol diglycidyl ether, N-methylethanolamine with polymethylene polyphenyl polyisocyanate and then modifying with polyethylene glycol monomethyl ether to improve the color fastness.

Description

Technical Field

[0001] The present invention relates to the technical field of carpets, and specifically to a dyed anti-slip and wear-resistant carpet and a preparation method thereof. Background Technique

[0002] Carpets have changed from commonly used floor decorations in hotels to commonly used items in families, and they have both aesthetic and practical functions; carpets are generally made of natural fibers such as cotton, linen, silk, wool, or chemical synthetic fibers, and are ground coverings woven, tufted, or woven by hand or mechanical processes.

[0003] Generally, carpets made of cotton and linen can only meet the general needs of people's lives, but they often have poor wear resistance, and the dyeability and color fastness of aramid fiber fabrics for cationic dyes are often poor. Therefore, it is very promising to research and invent a dyed anti-slip and wear-resistant carpet with both wear resistance and dyeability. Summary of the Invention

[0004] The purpose of the present invention is to provide a dyed anti-slip and wear-resistant carpet and a preparation method thereof to solve the problems raised in the above background technique.

[0005] To solve the above technical problems, the present invention provides the following technical solution: A dyed anti-slip and wear-resistant carpet is obtained by weaving modified aramid fibers into a fabric, then coating a dyeing film, and finally laminating with a film; the modified aramid fiber is obtained by reacting imidazole aramid fiber with modified carbon nanotubes; the dyeing film is a modified aromatic polyisocyanate.

[0006] Preferably, the imidazole aramid fiber is prepared by using isophthaloyl chloride and 2-(4-aminophenyl)-5-aminobenzimidazole as raw materials, using N,N-dimethylacetamide as a solvent, and performing dry-wet spinning after low-temperature solution polycondensation; the modified carbon nanotube is obtained by reacting carboxylated carbon nanotubes with hydroxypiperidine derivatives.

[0007] Preferably, the film is nitrile rubber.

[0008] Preferably, the modified aromatic polyisocyanate is obtained by reacting resorcinol diglycidyl ether, N-methylethanolamine with polymethylene polyphenyl polyisocyanate and then modifying with polyethylene glycol monomethyl ether.

[0009] Preferably, a preparation method of a dyed anti-slip and wear-resistant carpet includes the following specific steps:

[0010] (1) Under a nitrogen atmosphere, N,N-dimethylacetamide, lithium chloride, and 2-(4-aminophenyl)-5-aminobenzimidazole were mixed in a mass ratio of 1:30:100 - 120. After stirring and dissolving, the temperature was lowered to -3~-5°C, and the reaction was carried out for 30~40 min. During this period, isophthaloyl chloride, which is 20~30 times the mass of N,N-dimethylacetamide, was added in three portions, and the reaction was continued for 30~40 min. Then, lithium hydroxide, which is 20~30 times the mass of N,N-dimethylacetamide, was added to obtain an imidazole aramid resin melt solution. The imidazole aramid resin melt solution was centrifuged and then charged into a reaction tank for degassing, followed by wet spinning to obtain imidazole aramid fibers.

[0011] (2) A hydroxyl piperidine derivative and carboxylated carbon nanotubes were mixed in a mass ratio of 8~12:1. After stirring evenly, the temperature was raised to 90~110°C, and concentrated sulfuric acid, which is 0.004~0.006 times the mass of the hydroxyl piperidine derivative, was added dropwise at a rate of 1~3 mL / min. The reaction was carried out for 12~16 h, followed by centrifugation and washing with deionized water 8~10 times, and then drying to obtain modified carbon nanotubes.

[0012] (3) The imidazole aramid fibers were immersed in N,N-dimethylacetamide, and modified carbon nanotubes, which are 0.2~0.6 times the mass of the imidazole aramid fibers, were added. The temperature was raised to 90~110°C, and the mixture was stirred and reacted at 200~500 rpm for 12~16 h. After fishing out, it was washed 3~5 times with deionized water and dried to obtain modified aramid fibers. The modified aramid fibers were subjected to doubling, spinning, and weaving to obtain a modified aramid fiber fabric with a gram weight of 120~180 g / m 2 of the modified aramid fiber fabric;

[0013] (4) A modified aromatic polyisocyanate, glacial acetic acid, and an aqueous hydroxyl acrylate emulsion PA-4000 were mixed in a mass ratio of 100:1:400~800. After stirring evenly, it was coated on the surface of the modified aramid fiber fabric and cured at 170~190°C for 30~50 min to obtain a modified aramid fiber fabric coated with a dyeing film;

[0014] (5) Nitrile rubber was put into a mixer and kneaded for 5~7 min. Then, a plasticizer vegetable oil, which is 0.005~0.006 times the mass of the nitrile rubber, was added and kneaded continuously. When the temperature of the mixer reached 70~80°C, it was discharged and left to stand at room temperature for 24~48 h. Then, it was put into an open mill, and a vulcanization accelerator DTDM, which is 0.005 times the mass of the nitrile rubber, was added. It was kneaded for 15~25 min, discharged and left to stand at room temperature for 20~30 h. Then, it was placed on a flat vulcanizer, the vulcanization temperature was 150°C, and the time was 5~8 min. After discharging and standing for 24 h, a nitrile rubber sheet was obtained.

[0015] (6) Bond the film to the modified aramid fiber fabric coated with the dyeing film and place it in a press at a temperature of 140 - 160 °C for 3 - 6 min, then cool to room temperature to obtain the dyed anti-slip and wear-resistant carpet.

[0016] Preferably, in the above step (1): During wet spinning, transfer the prepared spinning solution to the spinneret of a metal needle. The anode is a copper wire, the cathode is an ITO glass, the distance between the spinneret and the ITO is 8 - 10 cm, the flow rate is 1.0 mL / h, and under the conditions of a relative humidity of 40 - 50% and a temperature of 22 - 28 °C, adjust the voltage between the two electrodes to 12 - 14 kV.

[0017] Preferably, in the above step (2): The preparation method of the hydroxypiperidine derivative is as follows: Under an ice bath, mix 3,4,5,6 - tetra(benzyloxy)-1,2 - cyclohexanediol and dichloromethane in a mass ratio of 1:40 - 50, then add triethylamine, a desiccant with the same mass as 3,4,5,6 - tetra(benzyloxy)-1,2 - cyclohexanediol, stir evenly, and then dropwise add ethylsulfonyl chloride with a mass 0.6 - 0.8 times that of 3,4,5,6 - tetra(benzyloxy)-1,2 - cyclohexanediol at a rate of 1 - 3 mL / min. React for 4 - 6 h, terminate the reaction with saturated sodium carbonate solution, then add aminoethylbenzene with a mass 7 - 9 times that of 3,4,5,6 - tetra(benzyloxy)-1,2 - cyclohexanediol, raise the temperature to 85 - 95 °C, react for 16 - 18 h, terminate the reaction with deionized water, extract with dichloromethane, rotary evaporate, and then separate and purify by silica gel chromatography column. The eluent is ethyl acetate and petroleum ether with a volume ratio of 1:4. Then add methanol with a mass 40 - 60 times that of 3,4,5,6 - tetra(benzyloxy)-1,2 - cyclohexanediol, trifluoroacetic acid with the same mass as 3,4,5,6 - tetra(benzyloxy)-1,2 - cyclohexanediol, and palladium - carbon catalyst with a mass 0.2 - 0.3 times that of 3,4,5,6 - tetra(benzyloxy)-1,2 - cyclohexanediol. React with hydrogen at room temperature for 48 - 56 h, and finally filter and adjust the pH to 6.8 - 7.2 with sodium hydroxide, separate and purify to obtain the hydroxypiperidine derivative.

[0018] Preferably, in the above step (2): The preparation method of the carboxylated carbon nanotubes is as follows: Mix carbon nanotubes, concentrated sulfuric acid, and concentrated nitric acid in a mass ratio of 1:28 - 30:8 - 10, carry out condensation reflux and ultrasonic treatment at 60 - 80 kHz for 6 - 8 h, filter by suction and wash 8 - 10 times successively with deionized water and acetone, and finally dry at 95 - 105 °C to obtain the carboxylated carbon nanotubes.

[0019] Preferably, in the above step (4), the preparation method of the modified aromatic polyisocyanate is as follows: under a nitrogen atmosphere, resorcinol diglycidyl ether and N,N-dimethylacetamide are mixed at a mass ratio of 1:3 to 5, cooled to 8 to 10 °C, and N-methylethanolamine with a mass 0.25 to 0.35 times that of resorcinol diglycidyl ether is added, and the reaction is carried out for 30 to 40 min to obtain solution A; polymethylene polyphenyl polyisocyanate and N,N-dimethylacetamide are mixed at a mass ratio of 1:0.75 to 0.85, stirred evenly and then heated to 48 to 52 °C, and solution A with a mass 0.2 to 0.3 times that of polymethylene polyphenyl polyisocyanate is added dropwise at a rate of 1 to 3 mL / min. After the dropwise addition is completed, the reaction is carried out for 2 to 4 h, and then polyethylene glycol monomethyl ether with the same mass as polymethylene polyphenyl polyisocyanate is added, and the reaction is continued for 1 to 3 h, and then cooled to room temperature to obtain the modified aromatic polyisocyanate.

[0020] Preferably, in the above step (4), the thickness of the dyeing film is 8 to 10 μm.

[0021] Compared with the prior art, the beneficial effects achieved by the present invention are as follows:

[0022] The dyed anti-slip and wear-resistant carpet prepared by the present invention is obtained by weaving modified aramid fibers into a fabric, then coating a dyeing film, and finally laminating with a film.

[0023] The modified aramid fiber is prepared by reacting imidazole aramid fiber with modified carbon nanotubes. The imidazole aramid fiber is prepared by using isophthaloyl chloride and 2-(4-aminophenyl)-5-aminobenzimidazole as raw materials, using N,N-dimethylacetamide as a solvent, and through low-temperature solution polycondensation, followed by dry-wet spinning. The modified carbon nanotubes are prepared by reacting carboxylated carbon nanotubes with hydroxypiperidine derivatives. Hydrogen bonds are formed between the imidazole aramid fiber and the modified carbon nanotubes, which are connected to the surface of the imidazole aramid fiber to form a convex structure, increasing the surface area and making the surface of the modified aramid fiber rough, enhancing the anti-slip and wear resistance of the carpet.

[0024] However, the molecular chain of the imidazole aramid fiber is a regular and rigid structure, and its dyeability is poor. Therefore, a dyeing film is coated on the modified aramid fabric. The dyeing film is a modified aromatic polyisocyanate, which is prepared by reacting resorcinol diglycidyl ether, N-methylethanolamine with polymethylene polyphenyl polyisocyanate and then modifying with polyethylene glycol monomethyl ether. While having active epoxy groups, the modified aromatic polyisocyanate can not only form hydrogen bonds on the surface of the modified aramid fiber, increasing the wear resistance and thus enhancing the color fastness, but also has an affinity for cationic dyes, can form unstable compounds with dyes in the dyeing solution, react with the fiber, break the hydrogen bonds between aramid macromolecules, enabling the dyes to enter the fiber interior to achieve the purpose of dyeing and improving the color fastness. Detailed implementation mode

[0025] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0026] In order to more clearly illustrate the method provided by the present invention, the following examples are used for detailed description. The test methods for each index of the dyed anti-slip wear-resistant carpets prepared in the examples and comparative examples are as follows:

[0027] Wear resistance: Cut the dyed anti-slip wear-resistant carpets prepared in the examples and comparative examples into the same size, and use a GX-5028-DIN abrasion tester to test the wear resistance of the heat-resistant wear-resistant carpets obtained in the examples and the products of the comparative examples.

[0028] Dye uptake rate: Dilute the blank dye solution and the residual dye solutions after dyeing in the examples and comparative examples by the same multiple, measure the absorbance at the maximum absorption wavelength of the dye with a UV-1900PC type ultraviolet-visible spectrophotometer, and calculate the dye uptake rate.

[0029] Dye uptake rate =

[0030] In the formula: A0 - Absorbance of the blank solution diluted by n0 times

[0031] A i —— Absorbance of the residual dye solution after dyeing diluted by n i times

[0032] Color fastness: After soaping the dyed anti-slip wear-resistant carpets prepared in the examples and comparative examples according to GB / T 3921, measure the K / S value.

[0033] Example 1

[0034] (1) Under a nitrogen atmosphere, N,N-dimethylacetamide, lithium chloride, and 2-(4-aminophenyl)-5-aminobenzimidazole were mixed at a mass ratio of 1:30:100. After stirring and dissolving, the temperature was lowered to -3°C, and the reaction was carried out for 30 min. During this period, isophthaloyl chloride, which is 20 times the mass of N,N-dimethylacetamide, was added in three portions, and the reaction was continued for 30 min. Then, lithium hydroxide, which is 20 times the mass of N,N-dimethylacetamide, was added to obtain a molten solution of imidazole aramid resin. The molten solution of imidazole aramid resin was centrifuged and then charged into a reaction tank for degassing. Wet spinning was carried out. The prepared spinning solution was transferred to a spinneret with a metal needle. The anode was a copper wire, and the cathode was an ITO glass. The distance between the spinneret and the ITO was 8 cm, the flow rate was 1.0 mL / h, and under the conditions of a relative humidity of 40% and a temperature of 22°C, the voltage between the two electrodes was adjusted to 12 kV to obtain imidazole aramid fibers.

[0035] (2) Under an ice bath, 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol and dichloromethane were mixed at a mass ratio of 1:40. Then, triethylamine, which is equal in mass to 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol, was added as a drying agent. After stirring evenly, ethanesulfonyl chloride, which is 0.6 times the mass of 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol, was added dropwise at a rate of 1 mL / min, and the reaction was carried out for 4 h. The reaction was terminated with saturated sodium carbonate solution. Then, aminoethylbenzene, which is 7 times the mass of 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol, was added, and the temperature was raised to 85°C, and the reaction was carried out for 16 h. The reaction was terminated with deionized water, and extraction was carried out with dichloromethane, followed by rotary evaporation. Then, separation and purification were carried out using a silica gel chromatography column, and the eluent was ethyl acetate and petroleum ether with a volume ratio of 1:4. Then, methanol, which is 40 times the mass of 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol, trifluoroacetic acid, which is equal in mass to 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol, and palladium-carbon catalyst, which is 0.2 times the mass of 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol, were added. Hydrogen was introduced at room temperature for a reaction of 48 h. Finally, filtration was carried out and the pH was adjusted to 6.8 with sodium hydroxide for separation and purification to obtain a hydroxy piperidine derivative. Carbon nanotubes, concentrated sulfuric acid, and concentrated nitric acid were mixed at a mass ratio of 1:28:8, and the mixture was refluxed under condensation and ultrasonicated at 60 kHz for 6 h. Suction filtration was carried out, and washing was carried out 8 times successively with deionized water and acetone. Finally, drying was carried out at 95°C to obtain carboxylated carbon nanotubes. The hydroxy piperidine derivative and the carboxylated carbon nanotubes were mixed at a mass ratio of 8:1. After stirring evenly, the temperature was raised to 90°C, and concentrated sulfuric acid, which is 0.004 times the mass of the hydroxy piperidine derivative, was added dropwise at a rate of 1 mL / min, and the reaction was carried out for 12 h. Centrifugation was carried out and washing was carried out 8 times with deionized water, and then drying was carried out to obtain modified carbon nanotubes.

[0036] (3) Immerse the imidazole aramid fiber in N,N-dimethylacetamide, add modified carbon nanotubes with a mass 0.2 times that of the imidazole aramid fiber, heat up to 90 °C, stir and react at 200 rpm for 12 h, fish out, wash 3 times with deionized water and dry to obtain the modified aramid fiber; After doubling the twist, spinning and weaving of the modified aramid fiber, a modified aramid fiber fabric with a gram weight of 120 g / m 2 is obtained;

[0037] (4) Under a nitrogen atmosphere, mix resorcinol diglycidyl ether and N,N-dimethylacetamide in a mass ratio of 1:3, cool down to 8 °C, add N-methylethanolamine with a mass 0.25 times that of resorcinol diglycidyl ether, and react for 30 min to obtain solution A; Mix polymethylene polyphenyl polyisocyanate and N,N-dimethylacetamide in a mass ratio of 1:0.75, stir evenly, heat up to 48 °C, and dropwise add solution A with a mass 0.2 times that of polymethylene polyphenyl polyisocyanate at a rate of 1 mL / min. After the dropping is completed, react for 2 h, then add polyethylene glycol monomethyl ether with the same mass as polymethylene polyphenyl polyisocyanate, continue to react for 1 h, cool to room temperature to obtain the modified aromatic polyisocyanate; Mix the modified aromatic polyisocyanate, glacial acetic acid and the aqueous hydroxy acrylic emulsion PA-4000 in a mass ratio of 100:1:400, stir evenly and coat on the surface of the modified aramid fiber fabric with a thickness of 8 μm, and cure at 170 °C for 30 min to obtain the modified aramid fiber fabric coated with a dyeing film;

[0038] (5) Put the nitrile rubber into the internal mixer, mix for 5 min, add plasticizer vegetable oil with a mass 0.005 times that of the nitrile rubber, continue to mix. When the temperature of the internal mixer reaches 70 °C, discharge and let it stand at room temperature for 24 h, then put it into the open mill, add accelerator DTDM with a mass 0.005 times that of the nitrile rubber, roll for 15 min, discharge and let it stand at room temperature for 20 h, then place it on the flat vulcanizer, the vulcanization temperature is 150 °C, the time is 5 min, discharge and let it stand for 24 h to obtain the nitrile rubber sheet;

[0039] (6) Bond the sheet with the modified aramid fiber fabric coated with a dyeing film and place it in a laminator at a temperature of 140 °C, laminate for 3 min, cool to room temperature to obtain the dyed, non-slip and wear-resistant carpet.

[0040] Example 2

[0041] (1) Under a nitrogen atmosphere, N,N-dimethylacetamide, lithium chloride, and 2-(4-aminophenyl)-5-aminobenzimidazole were mixed in a mass ratio of 1:30:110. After stirring and dissolving, the temperature was lowered to -4°C, and the reaction was carried out for 35 minutes. During this period, isophthaloyl chloride, which is 25 times the mass of N,N-dimethylacetamide, was added in three portions, and the reaction was continued for 35 minutes. Then, lithium hydroxide, which is 25 times the mass of N,N-dimethylacetamide, was added to obtain a molten solution of imidazole aramid resin. The molten solution of imidazole aramid resin was centrifuged and then charged into a reaction tank for degassing. Wet spinning was carried out. The prepared spinning solution was transferred to a spinneret with a metal needle. The anode was a copper wire, and the cathode was an ITO glass. The distance between the spinneret and the ITO was 9 cm, the flow rate was 1.0 mL / h, and under the conditions of a relative humidity of 45% and a temperature of 26°C, the voltage between the two electrodes was adjusted to 13 kV to obtain imidazole aramid fibers.

[0042] (2) Under an ice bath, 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol and dichloromethane were mixed in a mass ratio of 1:45. Then, triethylamine, which is equal in mass to 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol, as a desiccant, was added. After stirring evenly, ethylsulfonyl chloride, which is 0.7 times the mass of 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol, was added dropwise at a rate of 2 mL / min. The reaction was carried out for 5 hours, and the reaction was terminated with saturated sodium carbonate solution. Then, aminoethylbenzene, which is 8 times the mass of 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol, was added, and the temperature was raised to 90°C. The reaction was carried out for 17 hours, and the reaction was terminated with deionized water and extracted with dichloromethane. Rotary evaporation was carried out, and then separation and purification were carried out using a silica gel chromatography column. The eluent was ethyl acetate and petroleum ether with a volume ratio of 1:4. Then, methanol, which is 50 times the mass of 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol, trifluoroacetic acid, which is equal in mass to 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol, and palladium-carbon catalyst, which is 0.25 times the mass of 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol, were added. Hydrogen was introduced at room temperature for a reaction of 52 hours. Finally, filtration was carried out and the pH was adjusted to 7.0 with sodium hydroxide for separation and purification to obtain a hydroxy piperidine derivative. Carbon nanotubes, concentrated sulfuric acid, and concentrated nitric acid were mixed in a mass ratio of 1:29:9. Condensation reflux and ultrasonic treatment were carried out at 70 kHz for 7 hours. Filtration was carried out and washed successively with deionized water and acetone 9 times. Finally, drying was carried out at 100°C to obtain carboxylated carbon nanotubes. The hydroxy piperidine derivative and the carboxylated carbon nanotubes were mixed in a mass ratio of 10:1. After stirring evenly, the temperature was raised to 100°C, and concentrated sulfuric acid, which is 0.005 times the mass of the hydroxy piperidine derivative, was added dropwise at a rate of 2 mL / min. The reaction was carried out for 14 hours, centrifuged and washed 9 times with deionized water, and dried to obtain modified carbon nanotubes.

[0043] (3) Immerse the imidazole aramid fiber in N,N-dimethylacetamide, add modified carbon nanotubes with a mass 0.4 times that of the imidazole aramid fiber, heat up to 100 °C, stir and react at 400 rpm for 14 h, fish out and wash 4 times with deionized water and dry to obtain the modified aramid fiber; after the modified aramid fiber undergoes double twisting, spinning, and weaving, a modified aramid fiber fabric with a grammage of 160 g / m 2 is obtained;

[0044] (4) Under a nitrogen atmosphere, mix resorcinol diglycidyl ether and N,N-dimethylacetamide at a mass ratio of 1:4, cool down to 9 °C, add N-methylethanolamine with a mass 0.3 times that of resorcinol diglycidyl ether, and react for 35 min to obtain solution A; mix polymethylene polyphenyl polyisocyanate and N,N-dimethylacetamide at a mass ratio of 1:0.8, stir evenly and heat up to 50 °C, and dropwise add solution A with a mass 0.25 times that of polymethylene polyphenyl polyisocyanate at a rate of 2 mL / min. After the dropping is completed, react for 3 h, then add polyethylene glycol monomethyl ether with the same mass as polymethylene polyphenyl polyisocyanate, and continue to react for 2 h. Cool to room temperature to obtain the modified aromatic polyisocyanate; mix the modified aromatic polyisocyanate, glacial acetic acid, and aqueous hydroxyl acrylic emulsion PA-4000 at a mass ratio of 100:1:600, stir evenly and coat on the surface of the modified aramid fiber fabric with a thickness of 9 μm, and cure at 180 °C for 40 min to obtain the modified aramid fiber fabric coated with a dyeing film;

[0045] (5) Put nitrile rubber into a kneader, knead for 6 min, add plasticizer vegetable oil with a mass 0.0055 times that of nitrile rubber, continue to knead. When the temperature of the kneader reaches 75 °C, discharge and let stand at room temperature for 36 h, then put into an open mill, add accelerator DTDM with a mass 0.005 times that of nitrile rubber, and roll for 20 min. Discharge and let stand at room temperature for 25 h, then place on a flat vulcanizer, the vulcanization temperature is 150 °C, the time is 6 min, discharge and let stand for 24 h to obtain a nitrile rubber sheet;

[0046] (6) Bond the sheet and the modified aramid fiber fabric coated with a dyeing film and place them in a press, the temperature is 150 °C, press for 4 min, cool to room temperature to obtain a dyed, non-slip and wear-resistant carpet.

[0047] Example 3

[0048] (1) Under a nitrogen atmosphere, N,N-dimethylacetamide, lithium chloride, and 2-(4-aminophenyl)-5-aminobenzimidazole were mixed at a mass ratio of 1:30:120. After stirring and dissolving, the temperature was lowered to -5°C, and the reaction was carried out for 40 min. During this period, isophthaloyl chloride, which is 30 times the mass of N,N-dimethylacetamide, was added in three portions, and the reaction was continued for 40 min. Then, lithium hydroxide, which is 30 times the mass of N,N-dimethylacetamide, was added to obtain an imidazole aramid resin melt solution. The imidazole aramid resin melt solution was centrifuged and then charged into a reaction tank for degassing. Wet spinning was carried out. The prepared spinning solution was transferred to a spinneret with a metal needle. The anode was a copper wire, and the cathode was an ITO glass. The distance between the spinneret and the ITO was 10 cm, the flow rate was 1.0 mL / h, and under the conditions of a relative humidity of 50% and a temperature of 28°C, the voltage between the two electrodes was adjusted to 14 kV to obtain imidazole aramid fibers;

[0049] (2) Under an ice bath, 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol and dichloromethane were mixed at a mass ratio of 1:50. Then, triethylamine, which is the same mass as 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol, as a desiccant, was added. After stirring evenly, ethylsulfonyl chloride, which is 0.8 times the mass of 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol, was added dropwise at a rate of 3 mL / min, and the reaction was carried out for 6 h. The reaction was terminated with saturated sodium carbonate solution. Then, aminoethylbenzene, which is 9 times the mass of 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol, was added, and the temperature was raised to 95°C, and the reaction was carried out for 18 h. The reaction was terminated with deionized water, and extraction was carried out with dichloromethane, followed by rotary evaporation. Then, separation and purification were carried out using a silica gel chromatography column, and the eluent was ethyl acetate and petroleum ether with a volume ratio of 1:4. Then, methanol, which is 60 times the mass of 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol, trifluoroacetic acid, which is the same mass as 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol, and palladium on carbon catalyst, which is 0.3 times the mass of 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol, were added. Hydrogen was introduced at room temperature for reaction for 56 h. Finally, filtration was carried out and the pH was adjusted to 7.2 with sodium hydroxide for separation and purification to obtain a hydroxypiperidine derivative; Carbon nanotubes, concentrated sulfuric acid, and concentrated nitric acid were mixed at a mass ratio of 1:30:10, and the mixture was refluxed under condensation and ultrasonicated at 80 kHz for 8 h. Filtration was carried out and the product was washed successively with deionized water and acetone 10 times. Finally, it was dried at 105°C to obtain carboxylated carbon nanotubes; The hydroxypiperidine derivative and carboxylated carbon nanotubes were mixed at a mass ratio of 12:1. After stirring evenly, the temperature was raised to 110°C, and concentrated sulfuric acid, which is 0.006 times the mass of the hydroxypiperidine derivative, was added dropwise at a rate of 3 mL / min, and the reaction was carried out for 16 h. Centrifugation was carried out and the product was washed with deionized water 10 times and then dried to obtain modified carbon nanotubes;

[0050] (3) Immerse the imidazole aramid fiber in N,N-dimethylacetamide, add modified carbon nanotubes with a mass 0.6 times that of the imidazole aramid fiber, heat up to 110 °C, stir and react at 500 rpm for 16 h, take it out, wash it 5 times with deionized water and dry it to obtain the modified aramid fiber; after doubling the twist, spinning and weaving of the modified aramid fiber, a modified aramid fiber fabric with a gram weight of 180 g / m 2 is obtained;

[0051] (4) Under a nitrogen atmosphere, mix resorcinol diglycidyl ether and N,N-dimethylacetamide at a mass ratio of 1:5, cool down to 10 °C, add N-methylethanolamine with a mass 0.35 times that of resorcinol diglycidyl ether, and react for 40 min to obtain Solution A; mix polymethylene polyphenyl polyisocyanate and N,N-dimethylacetamide at a mass ratio of 1:0.85, stir evenly and heat up to 52 °C, and dropwise add Solution A with a mass 0.3 times that of polymethylene polyphenyl polyisocyanate at a rate of 3 mL / min. After the dropping is completed, react for 4 h, then add polyethylene glycol monomethyl ether with the same mass as polymethylene polyphenyl polyisocyanate, and continue to react for 3 h. Cool to room temperature to obtain the modified aromatic polyisocyanate; mix the modified aromatic polyisocyanate, glacial acetic acid and aqueous hydroxyl acrylic emulsion PA-4000 at a mass ratio of 100:1:800, stir evenly and coat it on the surface of the modified aramid fiber fabric with a thickness of 10 μm, and cure it at 190 °C for 50 min to obtain the modified aramid fiber fabric coated with a dyeing film;

[0052] (5) Put the nitrile rubber into a mixer, mix for 7 min, add plasticizer vegetable oil with a mass 0.06 times that of the nitrile rubber, continue to mix. When the temperature of the mixer reaches 80 °C, discharge it and let it stand at room temperature for 48 h, then put it into an open mill, add accelerator DTDM with a mass 0.006 times that of the nitrile rubber, roll for 25 min, discharge it and let it stand at room temperature for 30 h, then place it on a flat vulcanizer, the vulcanization temperature is 150 °C, the time is 8 min, discharge it and let it stand for 24 h to obtain the nitrile rubber film;

[0053] (6) Bond the film with the modified aramid fiber fabric coated with a dyeing film and place it in a press, the temperature is 160 °C, press for 6 min, cool to room temperature to obtain the dyed, non-slip and wear-resistant carpet.

[0054] Comparative Example 1

[0055] The prescription composition of Comparative Example 1 is the same as that of Example 2. The difference in the manufacturing method of this dyed, non-slip and wear-resistant carpet from that of Example 2 is only that the modified carbon nanotubes are only carboxylated carbon nanotubes.

[0056] Comparative Example 2

[0057] The prescription composition of Comparative Example 2 is the same as that of Example 2. The difference in the manufacturing method of this dyed anti-slip and wear-resistant carpet from that of Example 2 is only that the modified aramid fiber is only imidazole aramid fiber.

[0058] Comparative Example 3

[0059] The prescription composition of Comparative Example 3 is the same as that of Example 2. The difference in the manufacturing method of this dyed anti-slip and wear-resistant carpet from that of Example 2 is only that the dyeing film is only polyisocyanate.

[0060] Comparative Example 4

[0061] The prescription composition of Comparative Example 4 is the same as that of Example 2. The difference in the manufacturing method of this dyed anti-slip and wear-resistant carpet from that of Example 2 is only that the dyed anti-slip and wear-resistant carpet is obtained by directly laminating the fabric woven from modified aramid fiber with a film.

[0062] Effect Example

[0063] The following Table 1 gives the performance analysis results of the dyed anti-slip and wear-resistant carpets of Examples 1 to 3 and Comparative Examples 1 to 4 of the present invention:

[0064]

[0065] It can be clearly found by comparing the experimental data of the examples and comparative examples in Table 1 that the dyed anti-slip and wear-resistant carpets prepared in Examples 1, 2, and 3 have excellent anti-slip and wear resistance and dyeability.

[0066] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Examples 1, 2, 3, it can be found that using isophthaloyl chloride and 2-(4-aminophenyl)-5-aminobenzimidazole as raw materials, N,N-dimethylacetamide as a solvent, through low-temperature solution polycondensation, and then wet-dry spinning to obtain imidazole aramid fiber, the modified carbon nanotubes prepared by reacting carboxylated carbon nanotubes with hydroxypiperidine derivatives, hydrogen bonds are formed between the imidazole aramid fiber and the modified carbon nanotubes, connecting to the surface of the imidazole aramid fiber to form a convex structure, which increases the surface area and makes the surface of the modified aramid fiber rough, enhancing the anti-slip and wear resistance of the carpet;

[0067] From the comparison of the experimental data of Example 1, Example 2, Example 3 and Comparative Example 4, it can be found that after the reaction of resorcinol diglycidyl ether, N-methylethanolamine and polymethylene polyphenyl polyisocyanate, and then modified with methoxypolyethylene glycol, the modified aromatic polyisocyanate has active epoxy groups. At the same time, the modified aromatic polyisocyanate can not only form hydrogen bonds on the surface of the modified aramid fiber, increase the wear resistance and thus enhance the color fastness, but also has an affinity for cationic dyes, can combine with the dyes in the dye solution to form unstable compounds, and react with the fibers to break the hydrogen bonds between the aramid macromolecules, enabling the dyes to enter the interior of the fibers, achieving the purpose of dyeing and improving the color fastness.

[0068] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention. Any reference signs in the claims should not be construed as limiting the claims involved.

Claims

1. A dyed, anti-slip and wear-resistant carpet, characterized in that, The dyed anti-slip and wear-resistant carpet is prepared by weaving modified aramid fibers into a fabric, then coating it with a dyeing film, and finally laminating it with a film; the modified aramid fiber is prepared by reacting imidazole aramid fiber with modified carbon nanotubes; the dyeing film is a modified aromatic polyisocyanate; the imidazole aramid fiber is prepared by using isophthaloyl chloride and 2-(4-aminophenyl)-5-aminobenzimidazole as raw materials, N,N-dimethylacetamide as a solvent, through low-temperature solution polycondensation, and then wet-dry spinning; the modified carbon nanotubes are prepared by reacting carboxylated carbon nanotubes with hydroxypiperidine derivatives; the modified aromatic polyisocyanate is prepared by reacting resorcinol diglycidyl ether, N-methylethanolamine with polymethylene polyphenyl polyisocyanate, and then modifying it with polyethylene glycol monomethyl ether.

2. The stain-resistant, non-slip and wear-resistant carpet according to claim 1, wherein The film is a nitrile rubber film.

3. A preparation method of a dyed, anti-slip and wear-resistant carpet, characterized in that, The preparation method of the dyed anti-slip and wear-resistant carpet includes the following specific steps: (1) Under a nitrogen atmosphere, N,N-dimethylacetamide, lithium chloride and 2-(4-aminophenyl)-5-aminobenzimidazole are mixed in a mass ratio of 1:30:100-120, stirred and dissolved, then cooled to -3 to -5 °C, reacted for 30 to 40 min, during which isophthaloyl chloride 20 to 30 times the mass of N,N-dimethylacetamide is added in three portions, continue to react for 30 to 40 min, and then lithium hydroxide 20 to 30 times the mass of N,N-dimethylacetamide is added to obtain an imidazole aramid resin melt solution; the imidazole aramid resin melt solution is centrifuged and then charged into a reaction tank for defoaming, and wet spinning is carried out to obtain imidazole aramid fibers; (2) The hydroxypiperidine derivative and carboxylated carbon nanotubes are mixed in a mass ratio of 8-12:1, stirred evenly and then heated to 90-110 °C, and concentrated sulfuric acid 0.004-0.006 times the mass of the hydroxypiperidine derivative is added dropwise at a rate of 1-3 mL / min, reacted for 12-16 h, centrifuged and washed with deionized water 8-10 times, and dried to obtain modified carbon nanotubes; (3) Immerse the imidazole aramid fiber in N,N-dimethylacetamide, add modified carbon nanotubes in an amount of 0.2 to 0.6 times the mass of the imidazole aramid fiber, heat up to 90 to 110 °C, stir and react at 200 to 500 rpm for 12 to 16 h, fish out, wash with deionized water 3 to 5 times and dry to obtain the modified aramid fiber; after the modified aramid fiber is doubled-twisted, spun, and woven, a modified aramid fiber fabric with a grammage of 120 to 180 g / m 2 is obtained; (4) Under a nitrogen atmosphere, resorcinol diglycidyl ether and N,N-dimethylacetamide were mixed at a mass ratio of 1:3 to 5, then cooled to 8 - 10 °C, and N-methylethanolamine with a mass 0.25 - 0.35 times that of resorcinol diglycidyl ether was added, followed by reacting for 30 - 40 min to obtain solution A; polymethylene polyphenyl polyisocyanate and N,N-dimethylacetamide were mixed at a mass ratio of 1:0.75 to 0.85, stirred evenly and then heated to 48 - 52 °C, and solution A with a mass 0.2 - 0.3 times that of polymethylene polyphenyl polyisocyanate was added dropwise at a rate of 1 - 3 mL / min. After the dropwise addition was completed, the reaction was carried out for 2 - 4 h, then polyethylene glycol monomethyl ether with the same mass as polymethylene polyphenyl polyisocyanate was added, and the reaction continued for 1 - 3 h. After cooling to room temperature, a modified aromatic polyisocyanate was obtained; the modified aromatic polyisocyanate, glacial acetic acid, and aqueous hydroxy acrylic emulsion PA-4000 were mixed at a mass ratio of 100:1:400 to 800, stirred evenly and then coated on the surface of the modified aramid fiber fabric, and cured at 170 - 190 °C for 30 - 50 min to obtain a modified aramid fiber fabric coated with a dyeing film; (5) Nitrile rubber was put into a kneader and kneaded for 5 - 7 min, then plasticizer vegetable oil with a mass 0.005 - 0.006 times that of nitrile rubber was added and kneading continued. When the temperature of the kneader reached 70 - 80 °C, the material was discharged and left to stand at room temperature for 24 - 48 h, then put into an open mill, accelerator DTDM with a mass 0.005 times that of nitrile rubber was added, and it was kneaded and refined for 15 - 25 min. After discharging and leaving to stand at room temperature for 20 - 30 h, it was placed on a flat vulcanizer, the vulcanization temperature was 150 °C, the time was 5 - 8 min, and after discharging and leaving to stand for 24 h, a nitrile rubber sheet was obtained; (6) The sheet was laminated with the modified aramid fiber fabric coated with a dyeing film and placed in a laminator at a temperature of 140 - 160 °C and laminated for 3 - 6 min, then cooled to room temperature to obtain a dyed, non-slip and wear-resistant carpet.

4. The preparation method of a dyed, anti-slip and wear-resistant carpet according to claim 3, characterized in that In the above step (1): During wet spinning, the prepared spinning solution was transferred to the spinneret of a metal needle. The anode was a copper wire, the cathode was ITO glass, the distance between the spinneret and ITO was 8 - 10 cm, the flow rate was 1.0 mL / h, and under the conditions of a relative humidity of 40 - 50% and a temperature of 22 - 28 °C, the voltage between the two electrodes was adjusted to 12 - 14 kV.

5. The preparation method of a dyed, anti-slip and wear-resistant carpet according to claim 3, characterized in that, In the above step (2): The preparation method of the hydroxypiperidine derivative is as follows: Under an ice bath, 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol and dichloromethane are mixed at a mass ratio of 1:40 - 50, and then triethylamine, which is the same mass as 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol, as a desiccant, is added. After stirring evenly, ethylsulfonyl chloride, which is 0.6 - 0.8 times the mass of 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol, is added dropwise at a rate of 1 - 3 mL / min. The reaction is carried out for 4 - 6 h, and the reaction is terminated with saturated sodium carbonate solution. Then, aminoethylbenzene, which is 7 - 9 times the mass of 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol, is added, and the temperature is raised to 85 - 95 °C. The reaction is carried out for 16 - 18 h, and the reaction is terminated with deionized water and extracted with dichloromethane. After rotary evaporation, it is separated and purified by a silica gel chromatography column. The eluent is ethyl acetate and petroleum ether with a volume ratio of 1:

4. Then, methanol, which is 40 - 60 times the mass of 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol, trifluoroacetic acid, which is the same mass as 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol, and palladium-carbon catalyst, which is 0.2 - 0.3 times the mass of 3,4,5,6-tetra(benzyloxy)-1,2-cyclohexanediol, are added. Hydrogen is introduced at room temperature for reaction for 48 - 56 h. Finally, it is filtered and the pH is adjusted to 6.8 - 7.2 with sodium hydroxide, and then separated and purified to obtain the hydroxypiperidine derivative.

6. The preparation method of a dyed, anti-slip and wear-resistant carpet according to claim 3, wherein, In the above step (2): The preparation method of the carboxylated carbon nanotubes is as follows: Carbon nanotubes, concentrated sulfuric acid, and concentrated nitric acid are mixed at a mass ratio of 1:28 - 30:8 - 10, and then subjected to condensation reflux and ultrasonic treatment at 60 - 80 kHz for 6 - 8 h. After suction filtration, it is washed 8 - 10 times successively with deionized water and acetone, and finally dried at 95 - 105 °C to obtain the carboxylated carbon nanotubes.

7. The preparation method of a dyed, anti-slip and wear-resistant carpet according to claim 3, characterized in that, In the above step (4): The thickness of the dyeing film is 8 - 10 μm.

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