Colored spun yarn and preparation method thereof

Abstract

The invention discloses a color-spun yarn and a preparation method thereof. The method comprises the following steps: 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, p-phenylenediamine and a modified monomer are reacted to form polyamic acid, the polyamic acid is then blended with a modified filler to obtain a spinning solution, the spinning solution is then imidized under high temperature conditions to obtain a reinforced fiber, the reinforced fiber is dyed to obtain a dyed fiber, the dyed fiber is subjected to opening, carding, drawing, roving and spinning processes to obtain a pretreated yarn, the pretreated yarn is soaked in water, taken out and dried to obtain a color-spun yarn, when the pretreated fiber is soaked in water, siloxane on a side chain of a polyimide molecule and siloxane on a surface of the modified filler are hydrolyzed and condensed, so that the bonding degree of adjacent dyed fibers is improved, and the modified monomer is an elastic monomer, the modified monomer contains a cage-type silsesquioxane structure, the cage-type silsesquioxane structure contains a large amount of long-chain alkyl groups, the molecular gap of the polyimide can be increased, and thus the mechanical properties of the material are increased.

Description

Technical Field

[0001] The invention relates to the technical field of color spun yarn preparation, and in particular to a color spun yarn and a preparation method thereof. Background Art

[0002] Color spinning means dyeing the fiber into colored fiber first, and then mixing two or more fibers of different colors fully to spin into yarn with unique color mixing effect. Human beings have a long history of using fiber materials. From natural fibers such as cotton, linen, silk, wool to synthetic fibers such as nylon, acrylic, Teflon, etc., they have always been important thermal insulation materials for humans. Although synthetic fiber materials were born relatively late, their high performance, high strength, high precision and other characteristics are not possessed by natural fiber materials. However, synthetic fiber materials do not have more advantages in thermal insulation performance. The reason is that synthetic fibers spun by traditional methods do not have a three-dimensional network structure, and their porosity and specific surface area are low. The thermal insulation effect is not significantly improved compared with natural fibers. However, polyimide fibers are different. The fabrics prepared from polyimide fibers have good windproof and thermal insulation effects, but their own strength is limited. They are easily damaged by external forces during use, which affects normal use. Summary of the invention

[0003] The purpose of the present invention is to provide a colored spun yarn and a preparation method thereof, which solves the problem of low mechanical properties of the colored spun yarn at present.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] A method for preparing a colored spun yarn comprises the following steps:

[0006] 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, p-phenylenediamine, modified monomer and N,N-dimethylacetamide were mixed evenly, stirred for 3-5 hours at a speed of 120-150r / min and a temperature of 40-45°C, cooled to 0°C, stirred for 40-45 hours, modified filler was added, stirred for 3-5 hours to obtain a spinning solution, and the spinning solution was passed through 100 holes under a nitrogen pressure of 0.3-0.35MPa. The fibers are squeezed into a coagulation bath through a spinneret with a diameter of 75 microns, and then kept warm for 1 hour at 100°C, 280°C and 350°C respectively to obtain reinforced fibers, the reinforced fibers are dyed respectively to obtain dyed fibers, the dyed fibers are subjected to opening, carding, drawing, roving and spinning processes to obtain pretreated yarns, the pretreated yarns are immersed in water, kept warm for 3-5 hours at 40-50°C, taken out and dried to obtain colored spun yarns.

[0007] The dosage ratio of the 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, p-phenylenediamine, modified monomer, N,N-dimethylacetamide and modified filler is 60mmol:50mmol:10mmol:60mL:5g.

[0008] Further, the modified monomer is prepared by the following steps:

[0009] Step A1: uniformly mix hexadecyltrimethoxysilane, isopropanol, sodium hydroxide and deionized water, introduce nitrogen protection, react for 4-6 hours at a speed of 120-150 r / min and a temperature of 80-90° C., cool to 20-25° C., react for 10-15 hours to obtain intermediate 1, uniformly mix intermediate 1, triethylamine, methyldichlorosilane and tetrahydrofuran, react for 3-5 hours at a speed of 150-200 r / min and a temperature of 0° C., heat to 20-25° C., react for 18-20 hours to obtain intermediate 2;

[0010] Step A2: Mix intermediate 2, Custer catalyst, propylene alcohol and toluene uniformly, introduce nitrogen protection, react for 10-15 hours at a speed of 120-150 r / min and a temperature of 80-90° C. to obtain intermediate 3; mix acrylic acid, diethanolamine, dicyclohexylcarbodiimide and DMF, react for 3-5 hours at a speed of 120-150 r / min and a temperature of 40-50° C. to obtain intermediate 4;

[0011] Step A3: The intermediate 4, 3-mercaptopropyltrimethoxysilane, benzophenone and DMF are mixed evenly, and reacted for 1-1.5 hours under irradiation of 365nm ultraviolet light to obtain intermediate 5. The intermediate 3, intermediate 5, polytetramethylene furan ether diol, isophorone diisocyanate and toluene are mixed evenly, and nitrogen is introduced for protection. At a speed of 120-150r / min and a temperature of 75-80°C, the reaction is carried out for 2-3 hours, and ethylenediamine is added, and the reaction is continued for 1-2 hours to obtain a modified monomer.

[0012] Furthermore, the molar ratio of hexadecyltrimethoxysilane, isopropanol, sodium hydroxide and deionized water 24mmol:16mL:16mmol:1mL, intermediate 1, triethylamine and methyldichlorosilane described in step A1 is 1:2.1:2.

[0013] Furthermore, the molar ratio of the intermediate 2 and propenol described in step A2 is 1:2, the amount of the Custer catalyst used is 0.5‰ of the mass of propenol, and the molar ratio of acrylic acid, diethanolamine and dicyclohexylcarbodiimide is 1:1:1.1.

[0014] Furthermore, the molar ratio of intermediate 4 and 3-mercaptopropyltrimethoxysilane described in step A3 is 1:1, the amount of benzophenone is 0.3% of the mass of intermediate 4, the molar ratio of intermediate 3, intermediate 5, polytetramethylene glycol, isophorone diisocyanate and ethylenediamine is 1:1:5:8.2:2, and the molecular weight of polytetramethylene glycol is 1000.

[0015] Further, the modified filler is prepared by the following steps:

[0016] Step B1: carboxymethyl cellulose, diethanolamine, dicyclohexylcarbodiimide and DMF are mixed, and the mixture is reacted for 3-5 hours at a speed of 120-150 r / min and a temperature of 40-50° C., epichlorohydrin and boron trifluoride etherate are added, the mixture is heated to 65-70° C., the mixture is reacted for 2-3 hours, a sodium hydroxide solution is added, and the mixture is reacted for 3-5 hours to obtain pretreated cellulose;

[0017] Step B2: pretreated cellulose, 4-aminoimidazole and DMF are mixed uniformly, and reacted for 6-8 hours at a speed of 120-150 r / min and a temperature of 60-70° C. to obtain modified cellulose, and the pretreated fiber is dissolved in DMF, zinc chloride and methanol are added, and reacted for 4-6 hours at a speed of 60-80 r / min and a temperature of 70-80° C. to obtain a precursor;

[0018] Step B3: Mix the precursor, acryloyl chloride, triethylamine and DMF, react for 3-5 hours at a speed of 60-80r / min and a temperature of 30-40°C to obtain a modified precursor, mix the modified precursor, Custer catalyst and DMF, stir for 2-2.5 hours at a speed of 120-150r / min and a temperature of 40-50°C, add triethoxysilane, raise the temperature to 100°C, and react for 20-25 hours to obtain a modified filler.

[0019] Furthermore, the amount ratio of the carboxyl group on the carboxymethyl cellulose, diethanolamine, dicyclohexylcarbodiimide, epichlorohydrin, boron trifluoride etherate and sodium hydroxide solution in step B1 is 10 mmol: 10 mmol: 12 mmol: 20 mmol: 0.3 g: 20 mL, and the mass fraction of the sodium hydroxide solution is 25%.

[0020] Furthermore, the molar ratio of the epoxy group on the pretreated cellulose in step B2 to 4-aminoimidazole is 1:1.1, and the amount ratio of the modified cellulose, DMF, zinc chloride and methanol is 0.5 g:5 mL:10 mmol:30 mL.

[0021] Furthermore, the amount ratio of the precursor, acryloyl chloride and triethylamine described in step B3 is 1g:5mL:3g, the molar ratio of the double bond on the modified precursor and triethoxysilane is 1:1.1, and the amount of Custer catalyst is 1‰ of the mass of triethoxysilane.

[0022] Beneficial effects of the present invention: A colored spun yarn prepared by the present application is formed by reacting 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, p-phenylenediamine and a modified monomer to form polyamic acid, which is then blended with a modified filler to obtain a spinning solution, and the spinning is then imidized under high temperature conditions to obtain a reinforced fiber, and the reinforced fiber is dyed to obtain a dyed fiber, and the dyed fiber is subjected to opening, carding, drawing, roving and spinning processes to obtain a pretreated yarn, and the pretreated yarn is soaked in water, taken out and dried to obtain a colored spun yarn, and the modified monomer is hydrolyzed and polymerized with hexadecyltrimethoxysilane as a raw material to form sodium hexadecylcyclotetrasiloxane tetrasilanol to obtain an intermediate 1, and the intermediate 1 is reacted with dimethyldichlorosilane so that the sodium silanol and dimethyldichlorosilane on the intermediate 1 are reacted. The chlorine atom site on methyldichlorosilane is reacted to obtain intermediate 2, intermediate 2 is reacted with acryl alcohol so that the Si-H bond on intermediate 2 reacts with the double bond on acryl alcohol to obtain intermediate 3, acrylic acid and diethanolamine are reacted under the action of dicyclohexylcarbodiimide so that the carboxyl group on acrylic acid and the secondary amine on diethanolamine undergo a dehydration reaction to obtain intermediate 4, intermediate 4 is reacted with 3-mercaptopropyltrimethoxysilane under light so that the double bond on intermediate 4 reacts with the mercapto group on 3-mercaptopropyltrimethoxysilane to obtain intermediate 5, intermediate 3, intermediate 5, polytetramethylene glycol and isophorone diisocyanate are reacted to form a polyurethane prepolymer, and then ethylenediamine is used to extend the chain to form an amino end cap to obtain a modified monomer.

[0023] The modified filler is prepared by using carboxymethyl cellulose and diethanolamine as raw materials, and reacting the carboxyl group on the carboxymethyl cellulose with the secondary amine on the diethanolamine under the action of dicyclohexylcarbodiimide, then adding epichlorohydrin to react the epoxy group on the epichlorohydrin with the hydroxyl group, and forming a new epoxy group under the action of a sodium hydroxide solution to obtain pretreated cellulose, reacting the pretreated cellulose with 4-aminoimidazole to react the epoxy group on the pretreated cellulose with the amino group on the 4-aminoimidazole to obtain modified cellulose, reacting the modified cellulose with zinc chloride to form an imidazole-zinc complex to obtain a precursor, reacting the precursor with acryloyl chloride to react the acyl chloride group on the acryloyl chloride with the hydroxyl group on the precursor to graft double bonds on the surface to obtain a modified precursor, reacting the modified precursor with triethoxysilane to react the double bond on the modified precursor with the SiH bond on the triethoxysilane to obtain a modified filler.

[0024] When the pretreated fiber is immersed in water, the siloxane on the side chain of the polyimide molecule and the siloxane on the surface of the modified filler undergo hydrolysis and condensation, thereby improving the bonding degree of adjacent dyed fibers. At the same time, the modified monomer is an elastic monomer, and the modified monomer contains a cage-type silsesquioxane structure. The cage-type silsesquioxane structure contains a large number of long-chain alkyl groups, which can increase the molecular gap of the polyimide, thereby increasing the mechanical properties of the material. At the same time, it is coated with the modified filler to form a double-layer core-shell structure, further improving the mechanical properties of the color-spun yarn. The composite structure of imidazole zinc and cellulose can increase the elasticity of the color-spun yarn and cooperate with the modified monomer to improve the toughness of the color-spun yarn. DETAILED DESCRIPTION

[0025] 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.

[0026] Example 1

[0027] A method for preparing a colored spun yarn comprises the following steps:

[0028] 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, p-phenylenediamine, modified monomer and N,N-dimethylacetamide are mixed uniformly, stirred for 3 hours at a speed of 120 r / min and a temperature of 40°C, then cooled to 0°C and stirred for 40 hours, modified filler is added and stirred for 3 hours to obtain a spinning solution, the spinning solution is squeezed into a coagulation bath through a spinneret with 100 holes and a diameter of 75 microns under a nitrogen pressure of 0.3 MPa, and then kept warm for 1 hour at temperatures of 100°C, 280°C and 350°C to obtain a reinforced fiber, the reinforced fiber is dyed to obtain a dyed fiber, the dyed fiber is subjected to opening, carding, drawing, roving and spinning processes to obtain a pretreated yarn, the pretreated yarn is immersed in water, kept warm for 3 hours at a temperature of 40°C, taken out and dried to obtain a colored spun yarn.

[0029] The dosage ratio of the 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, p-phenylenediamine, modified monomer, N,N-dimethylacetamide and modified filler is 60mmol:50mmol:10mmol:60mL:5g.

[0030] The modified monomer is prepared by the following steps:

[0031] Step A1: Hexadecyltrimethoxysilane, isopropanol, sodium hydroxide and deionized water are mixed uniformly, nitrogen is introduced for protection, and the mixture is reacted at a speed of 120 r / min and a temperature of 80° C. for 4 hours, then the mixture is cooled to 20° C. and reacted for 10 hours to obtain intermediate 1; intermediate 1, triethylamine, methyldichlorosilane and tetrahydrofuran are mixed uniformly, the mixture is reacted at a speed of 150 r / min and a temperature of 0° C. for 3 hours, then the mixture is heated to 20° C. and reacted for 18 hours to obtain intermediate 2;

[0032] Step A2: Intermediate 2, Custer catalyst, propylene alcohol and toluene were mixed uniformly, nitrogen was introduced for protection, and the mixture was reacted at a speed of 120 r / min and a temperature of 80° C. for 10 h to obtain intermediate 3; acrylic acid, diethanolamine, dicyclohexylcarbodiimide and DMF were mixed, and the mixture was reacted at a speed of 120 r / min and a temperature of 40° C. for 3 h to obtain intermediate 4;

[0033] Step A3: Intermediate 4, 3-mercaptopropyltrimethoxysilane, benzophenone and DMF were mixed evenly, and reacted under 365nm ultraviolet light for 1h to obtain intermediate 5. Intermediate 3, intermediate 5, polytetramethylene glycol, isophorone diisocyanate and toluene were mixed evenly, nitrogen was introduced for protection, and the reaction was carried out at a speed of 120r / min and a temperature of 75°C for 2h. Ethylenediamine was added and the reaction was continued for 1h to obtain a modified monomer.

[0034] The molar ratio of hexadecyltrimethoxysilane, isopropanol, sodium hydroxide and deionized water 24mmol:16mL:16mmol:1mL, intermediate 1, triethylamine and methyldichlorosilane described in step A1 is 1:2.1:2.

[0035] The molar ratio of intermediate 2 and propenol described in step A2 is 1:2, the amount of Custer catalyst used is 0.5‰ of the mass of propenol, and the molar ratio of acrylic acid, diethanolamine and dicyclohexylcarbodiimide is 1:1:1.1.

[0036] The molar ratio of intermediate 4 and 3-mercaptopropyltrimethoxysilane described in step A3 is 1:1, the amount of benzophenone is 0.3% of the mass of intermediate 4, the molar ratio of intermediate 3, intermediate 5, polytetramethylene glycol, isophorone diisocyanate and ethylenediamine is 1:1:5:8.2:2, and the molecular weight of polytetramethylene glycol is 1000.

[0037] The modified filler is prepared by the following steps:

[0038] Step B1: carboxymethyl cellulose, diethanolamine, dicyclohexylcarbodiimide and DMF are mixed, and reacted for 3 hours at a speed of 120 r / min and a temperature of 40° C., epichlorohydrin and boron trifluoride etherate are added, the temperature is raised to 65° C., the reaction is carried out for 2 hours, and a sodium hydroxide solution is added and the reaction is carried out for 3 hours to obtain pretreated cellulose;

[0039] Step B2: pretreated cellulose, 4-aminoimidazole and DMF were mixed evenly, and reacted for 6 hours at a speed of 120 r / min and a temperature of 60° C. to obtain modified cellulose, and the pretreated fiber was dissolved in DMF, zinc chloride and methanol were added, and reacted for 4 hours at a speed of 60 r / min and a temperature of 70° C. to obtain a precursor;

[0040] Step B3: Mix the precursor, acryloyl chloride, triethylamine and DMF, and react at a speed of 60 r / min and a temperature of 30°C for 3 hours to obtain a modified precursor; mix the modified precursor, Custer catalyst and DMF, and stir at a speed of 120 r / min and a temperature of 40°C for 2 hours, then add triethoxysilane, raise the temperature to 100°C, and react for 20 hours to obtain a modified filler.

[0041] The amount ratio of the carboxyl group on the carboxymethyl cellulose, diethanolamine, dicyclohexylcarbodiimide, epichlorohydrin, boron trifluoride etherate and sodium hydroxide solution in step B1 is 10 mmol: 10 mmol: 12 mmol: 20 mmol: 0.3 g: 20 mL, and the mass fraction of the sodium hydroxide solution is 25%.

[0042] The molar ratio of the epoxy group on the pretreated cellulose and 4-aminoimidazole in step B2 is 1:1.1, and the amount ratio of the modified cellulose, DMF, zinc chloride and methanol is 0.5 g:5 mL:10 mmol:30 mL.

[0043] The amount ratio of the precursor, acryloyl chloride and triethylamine described in step B3 is 1g:5mL:3g, the molar ratio of the double bond on the modified precursor and triethoxysilane is 1:1.1, and the amount of Custer catalyst used is 1‰ of the mass of triethoxysilane.

[0044] Example 2

[0045] A method for preparing a colored spun yarn comprises the following steps:

[0046] 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, p-phenylenediamine, modified monomer and N,N-dimethylacetamide are mixed uniformly, stirred for 4 hours at a speed of 120 r / min and a temperature of 43°C, then cooled to 0°C and stirred for 43 hours, modified filler is added and stirred for 4 hours to obtain a spinning solution, the spinning solution is squeezed into a coagulation bath through a spinneret with 100 holes and a diameter of 75 microns under a nitrogen pressure of 0.3 MPa, and then kept warm for 1 hour at temperatures of 100°C, 280°C and 350°C respectively to obtain a reinforced fiber, the reinforced fiber is dyed respectively to obtain a dyed fiber, the dyed fiber is subjected to opening, carding, drawing, roving and spinning processes to obtain a pretreated yarn, the pretreated yarn is immersed in water, kept warm at a temperature of 45°C for 4 hours, taken out and dried to obtain a colored spun yarn.

[0047] The dosage ratio of the 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, p-phenylenediamine, modified monomer, N,N-dimethylacetamide and modified filler is 60mmol:50mmol:10mmol:60mL:5g.

[0048] The modified monomer is prepared by the following steps:

[0049] Step A1: Hexadecyltrimethoxysilane, isopropanol, sodium hydroxide and deionized water are mixed uniformly, nitrogen is introduced for protection, and the mixture is reacted at a speed of 120 r / min and a temperature of 85° C. for 5 hours, then the mixture is cooled to 20° C. and reacted for 13 hours to obtain intermediate 1; intermediate 1, triethylamine, methyldichlorosilane and tetrahydrofuran are mixed uniformly, the mixture is reacted at a speed of 150 r / min and a temperature of 0° C. for 4 hours, then the mixture is heated to 23° C. and reacted for 19 hours to obtain intermediate 2;

[0050] Step A2: Intermediate 2, Custer catalyst, propylene alcohol and toluene were mixed uniformly, nitrogen was introduced for protection, and the mixture was reacted at a speed of 120 r / min and a temperature of 85° C. for 13 h to obtain intermediate 3; acrylic acid, diethanolamine, dicyclohexylcarbodiimide and DMF were mixed, and the mixture was reacted at a speed of 120 r / min and a temperature of 45° C. for 4 h to obtain intermediate 4;

[0051] Step A3: The intermediate 4, 3-mercaptopropyltrimethoxysilane, benzophenone and DMF were mixed evenly, and the reaction was carried out for 1.5 hours under the irradiation of 365nm ultraviolet light to obtain the intermediate 5. The intermediate 3, intermediate 5, polytetramethylene furan ether diol, isophorone diisocyanate and toluene were mixed evenly, and nitrogen was introduced for protection. At a speed of 120r / min and a temperature of 78°C, the reaction was carried out for 2.5 hours. Ethylenediamine was added and the reaction was continued for 1.5 hours to obtain the modified monomer.

[0052] The molar ratio of hexadecyltrimethoxysilane, isopropanol, sodium hydroxide and deionized water 24mmol:16mL:16mmol:1mL, intermediate 1, triethylamine and methyldichlorosilane described in step A1 is 1:2.1:2.

[0053] The molar ratio of intermediate 2 and propenol described in step A2 is 1:2, the amount of Custer catalyst used is 0.5‰ of the mass of propenol, and the molar ratio of acrylic acid, diethanolamine and dicyclohexylcarbodiimide is 1:1:1.1.

[0054] The molar ratio of intermediate 4 and 3-mercaptopropyltrimethoxysilane described in step A3 is 1:1, the amount of benzophenone is 0.3% of the mass of intermediate 4, the molar ratio of intermediate 3, intermediate 5, polytetramethylene glycol, isophorone diisocyanate and ethylenediamine is 1:1:5:8.2:2, and the molecular weight of polytetramethylene glycol is 1000.

[0055] The modified filler is prepared by the following steps:

[0056] Step B1: carboxymethyl cellulose, diethanolamine, dicyclohexylcarbodiimide and DMF are mixed, and the mixture is reacted for 4 hours at a speed of 120 r / min and a temperature of 45° C., epichlorohydrin and boron trifluoride etherate are added, the mixture is heated to 68° C., the mixture is reacted for 3 hours, a sodium hydroxide solution is added, and the mixture is reacted for 4 hours to obtain pretreated cellulose;

[0057] Step B2: pretreated cellulose, 4-aminoimidazole and DMF were mixed evenly, and reacted for 7 hours at a speed of 120 r / min and a temperature of 65° C. to obtain modified cellulose; the pretreated fiber was dissolved in DMF, zinc chloride and methanol were added, and reacted for 5 hours at a speed of 60 r / min and a temperature of 75° C. to obtain a precursor;

[0058] Step B3: Mix the precursor, acryloyl chloride, triethylamine and DMF, and react at a speed of 60 r / min and a temperature of 35°C for 4 hours to obtain a modified precursor. Mix the modified precursor, Custer catalyst and DMF, and stir at a speed of 120 r / min and a temperature of 45°C for 2.5 hours. Then, add triethoxysilane, raise the temperature to 100°C, and react for 23 hours to obtain a modified filler.

[0059] The amount ratio of the carboxyl group on the carboxymethyl cellulose, diethanolamine, dicyclohexylcarbodiimide, epichlorohydrin, boron trifluoride etherate and sodium hydroxide solution in step B1 is 10 mmol: 10 mmol: 12 mmol: 20 mmol: 0.3 g: 20 mL, and the mass fraction of the sodium hydroxide solution is 25%.

[0060] The molar ratio of the epoxy group on the pretreated cellulose and 4-aminoimidazole in step B2 is 1:1.1, and the amount ratio of the modified cellulose, DMF, zinc chloride and methanol is 0.5 g:5 mL:10 mmol:30 mL.

[0061] The amount ratio of the precursor, acryloyl chloride and triethylamine described in step B3 is 1g:5mL:3g, the molar ratio of the double bond on the modified precursor and triethoxysilane is 1:1.1, and the amount of Custer catalyst used is 1‰ of the mass of triethoxysilane.

[0062] Example 3

[0063] A method for preparing a colored spun yarn comprises the following steps:

[0064] 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, p-phenylenediamine, modified monomer and N,N-dimethylacetamide were mixed uniformly, stirred for 5 hours at a speed of 150 r / min and a temperature of 45°C, then cooled to 0°C and stirred for 45 hours, modified filler was added and stirred for 5 hours to obtain a spinning solution, the spinning solution was squeezed into a coagulation bath through a spinneret with 100 holes and a diameter of 75 microns under a nitrogen pressure of 0.35 MPa, and then kept warm for 1 hour at temperatures of 100°C, 280°C and 350°C respectively to obtain a reinforced fiber, the reinforced fiber was dyed respectively to obtain a dyed fiber, the dyed fiber was subjected to opening, carding, drawing, roving and spinning processes to obtain a pretreated yarn, the pretreated yarn was immersed in water, kept warm at a temperature of 50°C for 5 hours, taken out and dried to obtain a colored spun yarn.

[0065] The dosage ratio of the 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, p-phenylenediamine, modified monomer, N,N-dimethylacetamide and modified filler is 60mmol:50mmol:10mmol:60mL:5g.

[0066] The modified monomer is prepared by the following steps:

[0067] Step A1: Hexadecyltrimethoxysilane, isopropanol, sodium hydroxide and deionized water are mixed uniformly, nitrogen is introduced for protection, and the mixture is reacted for 6 hours at a speed of 150 r / min and a temperature of 90° C., then the mixture is cooled to 25° C. and reacted for 15 hours to obtain intermediate 1; intermediate 1, triethylamine, methyldichlorosilane and tetrahydrofuran are mixed uniformly, the mixture is reacted for 5 hours at a speed of 200 r / min and a temperature of 0° C., then the mixture is heated to 25° C. and reacted for 20 hours to obtain intermediate 2;

[0068] Step A2: Mix intermediate 2, Custer catalyst, propylene alcohol and toluene uniformly, introduce nitrogen protection, react for 15 hours at a speed of 150 r / min and a temperature of 90° C. to obtain intermediate 3; mix acrylic acid, diethanolamine, dicyclohexylcarbodiimide and DMF, react for 5 hours at a speed of 150 r / min and a temperature of 50° C. to obtain intermediate 4;

[0069] Step A3: Intermediate 4, 3-mercaptopropyltrimethoxysilane, benzophenone and DMF were mixed evenly, and reacted under 365nm ultraviolet light for 1.5h to obtain intermediate 5. Intermediate 3, intermediate 5, polytetramethylene glycol, isophorone diisocyanate and toluene were mixed evenly, nitrogen was introduced for protection, and the reaction was carried out at a speed of 150r / min and a temperature of 80°C for 3h. Ethylenediamine was added and the reaction was continued for 2h to obtain a modified monomer.

[0070] The molar ratio of hexadecyltrimethoxysilane, isopropanol, sodium hydroxide and deionized water 24mmol:16mL:16mmol:1mL, intermediate 1, triethylamine and methyldichlorosilane described in step A1 is 1:2.1:2.

[0071] The molar ratio of intermediate 2 and propenol described in step A2 is 1:2, the amount of Custer catalyst used is 0.5‰ of the mass of propenol, and the molar ratio of acrylic acid, diethanolamine and dicyclohexylcarbodiimide is 1:1:1.1.

[0072] The molar ratio of intermediate 4 and 3-mercaptopropyltrimethoxysilane described in step A3 is 1:1, the amount of benzophenone is 0.3% of the mass of intermediate 4, the molar ratio of intermediate 3, intermediate 5, polytetramethylene glycol, isophorone diisocyanate and ethylenediamine is 1:1:5:8.2:2, and the molecular weight of polytetramethylene glycol is 1000.

[0073] The modified filler is prepared by the following steps:

[0074] Step B1: carboxymethyl cellulose, diethanolamine, dicyclohexylcarbodiimide and DMF are mixed, and the mixture is reacted for 5 hours at a speed of 150 r / min and a temperature of 50° C., epichlorohydrin and boron trifluoride etherate are added, the mixture is heated to 70° C., the mixture is reacted for 3 hours, a sodium hydroxide solution is added, and the mixture is reacted for 5 hours to obtain pretreated cellulose;

[0075] Step B2: pretreated cellulose, 4-aminoimidazole and DMF were mixed evenly, and reacted at a speed of 150 r / min and a temperature of 70° C. for 8 h to obtain modified cellulose, and the pretreated fiber was dissolved in DMF, zinc chloride and methanol were added, and reacted at a speed of 80 r / min and a temperature of 80° C. for 6 h to obtain a precursor;

[0076] Step B3: Mix the precursor, acryloyl chloride, triethylamine and DMF, and react at a speed of 80 r / min and a temperature of 40°C for 5 hours to obtain a modified precursor. Mix the modified precursor, Custer catalyst and DMF, and stir at a speed of 150 r / min and a temperature of 50°C for 2.5 hours, then add triethoxysilane, raise the temperature to 100°C, and react for 25 hours to obtain a modified filler.

[0077] The amount ratio of the carboxyl group on the carboxymethyl cellulose, diethanolamine, dicyclohexylcarbodiimide, epichlorohydrin, boron trifluoride etherate and sodium hydroxide solution in step B1 is 10 mmol: 10 mmol: 12 mmol: 20 mmol: 0.3 g: 20 mL, and the mass fraction of the sodium hydroxide solution is 25%.

[0078] The molar ratio of the epoxy group on the pretreated cellulose and 4-aminoimidazole in step B2 is 1:1.1, and the amount ratio of the modified cellulose, DMF, zinc chloride and methanol is 0.5 g:5 mL:10 mmol:30 mL.

[0079] The amount ratio of the precursor, acryloyl chloride and triethylamine described in step B3 is 1g:5mL:3g, the molar ratio of the double bond on the modified precursor and triethoxysilane is 1:1.1, and the amount of Custer catalyst used is 1‰ of the mass of triethoxysilane.

[0080] Comparative Example 1

[0081] Compared with Example 1, no modified monomer was added in this comparative example, and the remaining steps were the same.

[0082] Comparative Example 2

[0083] Compared with Example 1, this comparative example did not add intermediate 3, and the remaining steps were the same.

[0084] Comparative Example 3

[0085] Compared with Example 1, this comparative example did not add intermediate 5, and the remaining steps were the same.

[0086] Comparative Example 4

[0087] Compared with Example 1, this comparative example uses nanocellulose instead of the precursor, and the other steps are the same.

[0088] Comparative Example 5

[0089] Compared with Example 1, this comparative example uses a precursor instead of a modified filler, and the remaining steps are the same.

[0090] The colored spun yarns obtained in Examples 1-3 and Comparative Examples 1-5 were combined into 6 yarns and tested in accordance with the standard of GB / T3916-2013 using an XL-1 yarn strength and elongation tester and a constant-speed elongation test method. The clamping distance was 500 mm and the stretching speed was 500 mm / min. The test results are shown in the following table.

[0091]

[0092]

[0093] It can be seen from the above table that the present application has good mechanical strength.

[0094] 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 method for preparing a colored spun yarn, characterized in that: The specific steps include: After mixing and stirring 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, p-phenylenediamine, a modified monomer and N,N-dimethylacetamide, a modified filler is added, stirred to obtain a spinning solution, the spinning solution is spun and kept at high temperature to obtain a reinforced fiber, the reinforced fibers are dyed respectively to obtain a dyed fiber, the dyed fiber is subjected to opening, carding, drawing, roving and spinning processes to obtain a pretreated yarn, the pretreated yarn is soaked in water, soaked, taken out and dried to obtain a colored spun yarn; The usage ratio of the 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, p-phenylenediamine, modified monomer, N,N-dimethylacetamide and modified filler is 60mmol:50mmol:10mmol:60mL:5g; The modified monomer is prepared by the following steps: Step A1: Hexadecyltrimethoxysilane, isopropanol, sodium hydroxide and deionized water are mixed and reacted to obtain intermediate 1, and intermediate 1, triethylamine, methyldichlorosilane and tetrahydrofuran are mixed and reacted to obtain intermediate 2; Step A2: The intermediate 2, the Custer catalyst, propylene alcohol and toluene are uniformly mixed, and nitrogen is introduced for protection to react to obtain the intermediate 3; acrylic acid, diethanolamine, dicyclohexylcarbodiimide and DMF are mixed and reacted to obtain the intermediate 4; Step A3: intermediate 4, 3-mercaptopropyltrimethoxysilane, benzophenone and DMF are mixed for reaction to obtain intermediate 5, intermediate 3, intermediate 5, polytetramethylene glycol, isophorone diisocyanate and toluene are uniformly mixed, nitrogen is introduced for protection, reaction is carried out, ethylenediamine is added, and the reaction is continued to obtain a modified monomer; The modified filler is prepared by the following steps: Step B1: Carboxymethyl cellulose, diethanolamine, dicyclohexylcarbodiimide and DMF are mixed for reaction, epichlorohydrin and boron trifluoride ether are added, the temperature is raised for reaction, sodium hydroxide solution is added for reaction, and pretreated cellulose is obtained; Step B2: pretreated cellulose, 4-aminoimidazole and DMF are mixed and reacted to obtain modified cellulose, the pretreated fiber is dissolved in DMF, zinc chloride and methanol are added, and reacted to obtain a precursor; Step B3: The precursor, acryloyl chloride, triethylamine and DMF are mixed and reacted to obtain a modified precursor. The modified precursor, Custer catalyst and DMF are mixed and stirred, and triethoxysilane is added. The temperature is raised to react to obtain a modified filler.

2. The method for preparing a colored spun yarn according to claim 1, characterized in that: The molar ratio of hexadecyltrimethoxysilane, isopropanol, sodium hydroxide and deionized water 24mmol:16mL:16mmol:1mL described in step A1, intermediate 1, triethylamine and methyldichlorosilane is 1:2.1:

2.

3. The method for preparing a colored spun yarn according to claim 1, characterized in that: The molar ratio of the intermediate 2 and acryl alcohol described in step A2 is 1:2, and the molar ratio of acrylic acid, diethanolamine and dicyclohexylcarbodiimide is 1:1:1.

1.

4. The method for preparing a colored spun yarn according to claim 1, characterized in that: The molar ratio of intermediate 4 and 3-mercaptopropyltrimethoxysilane described in step A3 is 1:1, and the molar ratio of intermediate 3, intermediate 5, polytetramethylene glycol, isophorone diisocyanate and ethylenediamine is 1:1:5:8.2:

2.

5. The method for preparing a colored spun yarn according to claim 1, characterized in that: The amount ratio of the carboxyl group on the carboxymethyl cellulose, diethanolamine, dicyclohexylcarbodiimide, epichlorohydrin, boron trifluoride etherate and sodium hydroxide solution in step B1 is 10mmol:10mmol:12mmol:20mmol:0.3g:20mL.

6. The method for preparing a colored spun yarn according to claim 1, characterized in that: The molar ratio of the epoxy group on the pretreated cellulose and 4-aminoimidazole in step B2 is 1:1.1, and the amount ratio of the modified cellulose, DMF, zinc chloride and methanol is 0.5 g:5 mL:10 mmol:30 mL.

7. The method for preparing a colored spun yarn according to claim 1, characterized in that: The amount ratio of the precursor, acryloyl chloride and triethylamine described in step B3 is 1g:5mL:3g, and the molar ratio of the double bond on the modified precursor and triethoxysilane is 1:1.

1.

8. A colored spun yarn, characterized in that: Prepared according to any one of claims 1 to 7.

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