Fireproof flame-retardant spinning yarn and preparation method thereof

Abstract

The invention discloses a fireproof flame-retardant spinning yarn and a preparation method thereof, and relates to the technical field of spinning yarns. When the fireproof flame-retardant spinning yarn is prepared, benzyl benzoate is used as a core material, chitosan is used as a wall material, and pentenedialdehyde is used as a cross-linking agent to prepare an anti-mite microcapsule; carrying out condensation polymerization on ethylene glycol, a hydroxyl-terminated siloxane oligomer, the functionalized DOPO and dimethyl terephthalate to prepare functionalized polyester; the functional polyester and the anti-mite microcapsules are prepared into a spinning solution, and the polyester fiber is prepared through electrostatic spinning; reacting cotton fibers with maleic anhydride and o-phenylenediamine in sequence to obtain modified cotton fibers; polyester fibers and modified cotton fibers are blended in a spinning machine to prepare blended yarns, and the blended yarns are post-treated with chloroplatinic acid to prepare the fireproof flame-retardant spun yarns. The fireproof flame-retardant spinning yarn prepared by the invention has excellent anti-mite, flame-retardant and mechanical properties.

Description

Technical Field

[0001] The invention relates to the technical field of spinning yarns, in particular to a fire-resistant and flame-retardant spinning yarn and a preparation method thereof. Background Art

[0002] Dust mites are one of the important factors affecting the hygiene of the home environment and human health. The corpses, feces and other excrement produced by them are harmful to human skin health and can easily cause diseases including asthma, allergic rhinitis and dermatitis. In the home environment, household textiles such as soft furniture and bedding are loose and porous and have residual human dandruff, which provides suitable living conditions for dust mites. They are the main pathogenic medium of diseases transmitted by dust mites. Therefore, the development of anti-mite home textiles is of great significance. Existing anti-mite home textiles and related research mostly use fabric pore size control, chemical and natural anti-mite fiber blending and post-finishing methods. This type of anti-mite textiles has the problems of poor comfort, small range of raw material options and poor durability.

[0003] In addition, most of the textiles used in daily life are flammable or combustible. The fibers are decomposed by heat under high temperature conditions to produce combustible gases. The combustible gases then react chemically with oxygen and continue to release heat. The heat generated will promote the cycle of this process until the fibers are completely decomposed. If the fire is not put out in time, it will cause the fire to spread. Certain firefighting measures can be taken for small-scale fire spread, but in the case of fierce fire, people may not be able to leave the fire scene in time, which will inevitably cause great losses to people's personal and property safety. It can be seen that textiles with flame retardant functions are important to our lives.

[0004] Based on the above problems, the present application has developed a spinning yarn with excellent anti-mite and flame retardant properties to protect people's life, health and property safety. Summary of the invention

[0005] The purpose of the present invention is to provide a fire-retardant spun yarn and a preparation method thereof, so as to solve the problems existing in the prior art.

[0006] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0007] A fire-retardant spun yarn, wherein the fire-retardant spun yarn is prepared by using benzyl benzoate as a core material, chitosan as a wall material, and glutaraldehyde as a crosslinking agent to prepare anti-mite microcapsules; ethylene glycol, terminal hydroxyl siloxane oligomers, functionalized DOPO and dimethyl terephthalate are polycondensed to prepare functionalized polyester; the functionalized polyester and the anti-mite microcapsules are prepared into a spinning solution, and polyester fibers are prepared by electrostatic spinning; polyester fibers and modified cotton fibers are blended in a spinning machine to prepare blended yarns, and the blended yarns are post-treated with chloroplatinic acid to prepare the fire-retardant spun yarns;

[0008] The terminal hydroxyl siloxane oligomer is prepared by ring-opening polymerization of tetramethylcyclotetrasiloxane and end-capping with 1,3-bis(3-hydroxypropyl)tetramethyldisiloxane;

[0009] The functionalized DOPO is prepared by reacting diethanolamine and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide;

[0010] The modified cotton fiber is prepared by reacting pre-modified cotton fiber and o-phenylenediamine;

[0011] The pre-modified cotton fiber is prepared by reacting cotton fiber and maleic anhydride.

[0012] A method for preparing a fire-retardant spun yarn, the method comprising the following preparation steps:

[0013] (1) chitosan and 4% to 6% acetic acid aqueous solution are mixed uniformly in a mass ratio of 1:(20 to 30) to prepare a chitosan acetic acid solution; under the conditions of 10 to 30° C. and 300 to 500 r / min stirring, 0.4 to 0.5 times the mass of the chitosan acetic acid solution of benzyl benzoate solution is uniformly added dropwise to the chitosan acetic acid solution within 10 minutes, and then 0.1 to 0.2 times the mass of the chitosan acetic acid solution of glutaraldehyde is added, and the reaction is continued with stirring for 4 to 5 hours, centrifuged, washed with anhydrous ethanol for 3 to 5 times, and dried at -40 to -30° C. for 36 to 40 hours to prepare anti-mite microcapsules;

[0014] (2) adding diethanolamine and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in a molar ratio of 1:1 to tetrahydrofuran (10 to 12 times the mass of diethanolamine), then adding triethylamine (0.03 to 0.05 times the mass of diethanolamine), stirring at 300 to 500 r / min and 50 to 60° C. for 3 to 4 hours, and drying at 50 to 60° C. for 8 to 10 hours under vacuum conditions to obtain functionalized DOPO; adding ethylene glycol, terminal hydroxyl siloxane oligomer, functionalized DOPO, antimony trioxide, and trimethyl phosphate in a mass ratio of 1:1. The mixture is uniformly mixed with 1:(0.3-0.4):(0.3-0.4):(0.02-0.04):(0.05-0.07), and dimethyl terephthalate with a molar amount of 3-4 times of ethylene glycol is added, and the mixture is placed in a polycondensation reactor, and stirred at 270-280°C and 300-500r / min for 1-2h, and the pressure is reduced to 50-100Pa, and the stirring reaction is continued for 1-2h. After cooling to room temperature, the mixture is discharged, washed with deionized water for 3-5 times, and dried at 50-60°C for 7-8h under vacuum conditions to obtain a functional polyester.

[0015] (3) mixing the functionalized polyester, anti-mite microcapsules and dichloromethane in a mass ratio of 1:(0.04-0.06):(6-7), stirring at 10-30° C. and 300-500 r / min for 20-30 min to prepare a spinning solution; loading the spinning solution into a micro pump, using an ice plate covered with aluminum foil as a receiving device, and performing electrospinning in an electrospinning device to obtain polyester fibers;

[0016] (4) immersing the cotton fiber in a maleic anhydride solution, ultrasonically oscillating at 70-80° C. for 5-6 hours, taking it out, and drying it at 50-60° C. for 8-10 hours under vacuum conditions to obtain pre-modified cotton fiber; immersing the pre-modified cotton fiber in an o-phenylenediamine solution, ultrasonically oscillating at 80-90° C. for 12-14 hours, taking it out, washing it 3-5 times with a hydrochloric acid aqueous solution with a molar concentration of 2 mol / L, and drying it at 50-60° C. for 8-10 hours under vacuum conditions to obtain modified cotton fiber;

[0017] (5) Spinning polyester fiber and modified cotton fiber in a spinning machine at a blending ratio of 3:2 to obtain a blended yarn; immersing the blended yarn in a catalyst solution, ultrasonically oscillating at 70-80° C. for 5-6 hours, taking it out, and drying it at 50-60° C. for 8-10 hours under vacuum conditions to obtain a fire-retardant spun yarn.

[0018] As an optimization, the chitosan in step (1) has a deacetylation degree of 93% and a weight average molecular weight of 85 kDa.

[0019] As an optimization, the preparation method of the benzyl benzoate solution in step (1) is: benzyl benzoate, Tween 80, and anhydrous ethanol are mixed uniformly in a mass ratio of 1: (0.3-0.5): (3-4) to prepare a benzyl benzoate solution.

[0020] As an optimization, the reaction process of the functionalized DOPO in step (2) is:

[0021]

[0022] As an optimization, the preparation method of the terminal hydroxyl siloxane oligomer in step (2) is as follows: tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide and dimethyl sulfoxide are mixed uniformly in a mass ratio of 1:(0.01-0.03):(0.01-0.03), stirred and reacted at 65-75°C and 300-500r / min for 20-22min, 1,3-bis(3-hydroxypropyl)tetramethyldisiloxane in an amount of 0.2-0.3 times the mass of tetramethylcyclotetrasiloxane is added, the stirring reaction is continued for 8-10min, the temperature is cooled to room temperature, and the terminal hydroxyl siloxane is washed with a mixture of equal volumes of deionized water and toluene, the mixture is allowed to stand for stratification, the aqueous phase is removed, the washing is repeated 3-5 times, the organic phase is placed in a drying oven, and dried at 50-60°C for 8-10h under vacuum conditions to obtain the terminal hydroxyl siloxane oligomer.

[0023] As an optimization, the process parameters of the electrospinning in step (3) are as follows: adjusting the receiving distance to 16-18 cm, the voltage during spinning to 23-25 ​​kV, the propulsion rate to 0.6-0.7 mL / h, the ambient temperature to 10-30° C., and the spinning humidity to 50%-60%.

[0024] As an optimization, the preparation method of the maleic anhydride solution in step (4) is: maleic anhydride, p-benzoquinone, and N,N-dimethylformamide are uniformly mixed in a mass ratio of 1:(0.03-0.05):(16-20) to prepare a maleic anhydride solution.

[0025] As an optimization, the preparation method of the o-phenylenediamine solution in step (4) is: o-phenylenediamine and a hydrochloric acid aqueous solution with a molar concentration of 4 mol / L are uniformly mixed in a mass ratio of 1:(14-16) to prepare an o-phenylenediamine solution.

[0026] As an optimization, the cotton fiber in step (4) is specifically kapok fiber, with a length of 28 to 36 mm and a linear density of 1.6 to 2.2 dtex.

[0027] As an optimization, the preparation method of the catalyst solution in step (5) is: chloroplatinic acid and N,N-dimethylformamide are uniformly mixed in a mass ratio of 1:(40-50) to prepare a catalyst solution.

[0028] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0029] In the preparation of the fire-retardant spinning yarn, the invention uses benzyl benzoate as the core material, chitosan as the wall material, and glutaraldehyde as the crosslinking agent to prepare the anti-mite microcapsule; tetramethylcyclotetrasiloxane is ring-opened polymerized and end-capped with 1,3-bis(3-hydroxypropyl)tetramethyldisiloxane to prepare the terminal hydroxyl siloxane oligomer; diethanolamine and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are reacted to prepare the functionalized DOPO; ethylene glycol and terminal hydroxyl siloxane are reacted to prepare the functionalized DOPO; Functionalized polyester is prepared by condensation polymerization of oxalane oligomers, functionalized DOPO and dimethyl terephthalate; functionalized polyester and anti-mite microcapsules are prepared into spinning solution, and polyester fiber is prepared by electrostatic spinning; cotton fiber and maleic anhydride are reacted to obtain pre-modified cotton fiber; pre-modified cotton fiber and o-phenylenediamine are reacted to obtain modified cotton fiber; polyester fiber and modified cotton fiber are blended in a spinning machine to obtain blended yarn, and the blended yarn is post-treated with chloroplatinic acid to obtain fire-retardant spinning yarn.

[0030] Firstly, benzyl benzoate was used as the core material, chitosan as the wall material, and glutaraldehyde as the cross-linking agent to prepare anti-mite microcapsules, and carbon-carbon double bonds were introduced on the surface of the anti-mite microcapsules; benzyl benzoate is a colorless oily liquid at room temperature, and has been widely proven to have excellent anti-mite effects. The anti-mite mechanism of benzyl benzoate is that it has contact toxicity to mites at low concentrations. Benzyl benzoate that contacts the mite epidermis can dissolve epidermal lipids, thereby increasing the water loss of mites and causing their dehydration and death; when mites ingest benzyl benzoate through their mouthparts, the substance It will decompose into benzoic acid in the digestive system, thus becoming toxic; in addition, the bitter almond smell of benzyl benzoate can also act on the nervous system of mites, and has a strong mite repellent effect; encapsulating benzyl benzoate in chitosan can achieve long-term sustained release of benzyl benzoate, giving the fire-retardant yarn excellent anti-mite properties; the carbon-carbon double bonds introduced on the surface of the anti-mite microcapsules can undergo silylation with the Si-H bonds introduced on the polyester fiber molecular chain under the catalysis of chloroplatinic acid, forming a cross-linked network, thereby improving the mechanical properties of the fire-retardant yarn.

[0031] Secondly, tetramethylcyclotetrasiloxane is ring-opened polymerized and terminated with 1,3-bis(3-hydroxypropyl)tetramethyldisiloxane to obtain a terminal hydroxyl siloxane oligomer; the secondary amine on diethanolamine reacts with the PH bond on 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to obtain functionalized DOPO; ethylene glycol, terminal hydroxyl siloxane oligomer, functionalized DOPO and dimethyl terephthalate are condensed to obtain functionalized polyester, and Si-O bonds, DOPO structures and Si-H bonds are introduced into the functionalized polyester molecular chain; the DOPO structure contains biphenyl rings and phenanthrene ring structures in the molecular structure, especially the side phosphorus groups in the form of cyclic O=PO bonds. The introduction of Si-O bonds has higher thermal and chemical stability than general, non-annulated organic phosphates, and better flame retardant properties, giving fire-retardant and flame-retardant spun yarns excellent flame retardant properties; the bond energy of Si-O bonds is greater than that of CC bonds, so compared with CC bonds, Si-O bonds need to absorb more heat and their own vibration energy to resolve the energy of thermal decomposition of polymer materials. The introduction of Si-O bonds can further improve the flame retardant properties of fire-retardant and flame-retardant spun yarns; the Si-H bonds introduced on the functionalized polyester molecular chains react with the carbon-carbon double bonds introduced on the anti-mite microcapsules and modified cotton fibers under the catalysis of chloroplatinic acid to undergo a silicon-hydrogen addition reaction to form a cross-linked network, thereby improving the mechanical properties of fire-retardant and flame-retardant spun yarns.

[0032] Finally, cotton fiber and maleic anhydride are reacted to obtain pre-modified cotton fiber, and carbon-carbon double bonds and carboxyl groups are introduced into the pre-modified cotton fiber; the carboxyl groups on the pre-modified cotton fiber are reacted with o-phenylenediamine to obtain modified cotton fiber; a benzimidazole structure is generated on the modified cotton fiber, and a carbon-carbon double bond is introduced; the benzimidazole structure generated on the modified cotton fiber has antibacterial and mite-killing effects, and can achieve insecticidal effects by inhibiting the activity of microtubule proteins in mite cells and inhibiting the digestion and nutrient absorption of the insect body, thereby further improving the anti-mite performance of the fire-retardant yarn; the carbon-carbon double bonds introduced on the modified cotton fiber can undergo silylation with the Si-H bonds introduced on the polyester fiber molecular chain under the catalysis of chloroplatinic acid to form a cross-linked network, thereby improving the mechanical properties of the fire-retardant yarn. DETAILED DESCRIPTION

[0033] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0034] Embodiment 1:

[0035] A method for preparing a fire-retardant spun yarn, the method comprising the following preparation steps:

[0036] (1) chitosan and 4% acetic acid aqueous solution are mixed at a mass ratio of 1:20 to prepare chitosan acetic acid solution; benzyl benzoate, Tween 80 and anhydrous ethanol are mixed at a mass ratio of 1:0.3:3 to prepare benzyl benzoate solution; under the stirring conditions of 10°C and 300 r / min, 0.4 times the mass of the chitosan acetic acid solution of benzyl benzoate solution is uniformly added dropwise to the chitosan acetic acid solution within 10 minutes, and then 0.1 times the mass of glutaraldehyde of the chitosan acetic acid solution is added, and the reaction is continued with stirring for 5 hours, centrifuged, washed with anhydrous ethanol for 3 times, and dried at -40°C for 36 hours to prepare anti-mite microcapsules;

[0037] (2) Tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide and dimethyl sulfoxide were mixed in a mass ratio of 1:0.01:0.01, stirred at 65°C and 300 r / min for 22 min, 1,3-bis(3-hydroxypropyl)tetramethyldisiloxane (0.2 times the mass of tetramethylcyclotetrasiloxane) was added, the stirring reaction was continued for 10 min, the temperature was cooled to room temperature, and the mixture was washed with an equal volume of deionized water and toluene, allowed to stand for stratification, the aqueous phase was removed, and the washing was repeated 3 times. The organic phase was placed in a drying oven and dried at 50°C for 10 h under vacuum conditions to obtain a terminal hydroxyl siloxane oligomer; diethanolamine and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide were added in a molar ratio of 1:1 to 1 mass of diethanolamine. 0 times of tetrahydrofuran, then add triethylamine (0.03 times of the mass of diethanolamine), stir and react at 300r / min, 50°C for 4h, and dry at 50°C for 10h under vacuum to obtain functionalized DOPO; ethylene glycol, terminal hydroxyl siloxane oligomer, functionalized DOPO, antimony trioxide, and trimethyl phosphate are evenly mixed at a mass ratio of 1:0.3:0.3:0.02:0.05, and dimethyl terephthalate (3 times of the molar amount of ethylene glycol) is added, placed in a condensation reaction kettle, stirred and reacted at 270°C, 300r / min for 2h, the pressure is reduced to 50Pa, and the stirring reaction is continued for 2h, and the material is discharged after cooling to room temperature, washed with deionized water 3 times, and dried at 60°C for 7h under vacuum to obtain functionalized polyester;

[0038] (3) The functionalized polyester, anti-mite microcapsules and dichloromethane were mixed uniformly in a mass ratio of 1:0.04:6, and stirred at 10°C and 300 r / min for 30 min to prepare a spinning solution; the spinning solution was loaded into a micro pump, and an aluminum foil covered on an ice plate was used as a receiving device. The receiving distance was adjusted to 16 cm. During the spinning process, the voltage was 23 kV, the propulsion rate was 0.6 mL / h, the ambient temperature was 10°C, and the spinning humidity was 50%. Electrospinning was performed in an electrospinning device to obtain polyester fibers;

[0039] (4) Maleic anhydride, benzoquinone, and N,N-dimethylformamide were mixed in a mass ratio of 1:0.03:16 to prepare a maleic anhydride solution; cotton fibers were immersed in the maleic anhydride solution, ultrasonically oscillated at 70°C for 6 hours, taken out, and dried at 50°C for 10 hours under vacuum conditions to obtain pre-modified cotton fibers; o-phenylenediamine and a hydrochloric acid aqueous solution with a molar concentration of 4 mol / L were mixed in a mass ratio of 1:14 to prepare an o-phenylenediamine solution; the pre-modified cotton fibers were immersed in the o-phenylenediamine solution, ultrasonically oscillated at 80°C for 14 hours, taken out, washed three times with a hydrochloric acid aqueous solution with a molar concentration of 2 mol / L, and dried at 50°C for 10 hours under vacuum conditions to obtain modified cotton fibers;

[0040] (5) The polyester fiber and the modified cotton fiber were spun in a spinning machine at a blending ratio of 3:2 to obtain a blended yarn; chloroplatinic acid and N,N-dimethylformamide were mixed evenly at a mass ratio of 1:40 to prepare a catalyst solution; the blended yarn was immersed in the catalyst solution, ultrasonically oscillated at 70°C for 6 hours, taken out, and dried at 50°C for 10 hours under vacuum conditions to obtain a fire-retardant spun yarn.

[0041] Embodiment 2:

[0042] A method for preparing a fire-retardant spun yarn, the method comprising the following preparation steps:

[0043] (1) chitosan and 5% acetic acid aqueous solution are mixed in a mass ratio of 1:25 to prepare chitosan acetic acid solution; benzyl benzoate, Tween 80 and anhydrous ethanol are mixed in a mass ratio of 1:0.4:3.5 to prepare benzyl benzoate solution; under stirring conditions of 20°C and 400 r / min, 0.45 times the mass of the chitosan acetic acid solution of benzyl benzoate solution is uniformly added dropwise to the chitosan acetic acid solution within 10 minutes, and then 0.15 times the mass of glutaraldehyde of the chitosan acetic acid solution is added, and the reaction is continued with stirring for 4.5 hours, centrifuged, washed with anhydrous ethanol for 4 times, and dried at -35°C for 38 hours to prepare anti-mite microcapsules;

[0044] (2) Tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide and dimethyl sulfoxide were mixed in a mass ratio of 1:0.02:0.02, stirred at 70°C and 400 r / min for 21 min, 1,3-bis(3-hydroxypropyl)tetramethyldisiloxane (0.25 times the mass of tetramethylcyclotetrasiloxane) was added, the stirring reaction was continued for 9 min, the temperature was cooled to room temperature, and the mixture was washed with an equal volume of deionized water and toluene, allowed to stand for stratification, the aqueous phase was removed, and the washing was repeated 4 times. The organic phase was placed in a drying oven and dried at 55°C for 9 h under vacuum conditions to obtain a terminal hydroxyl siloxane oligomer; diethanolamine and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide were added in a molar ratio of 1:1 to tetrahydrofuran (11 times the mass of diethanolamine) In the molten silica, add triethylamine (0.04 times the mass of diethanolamine), stir and react at 400r / min, 55°C for 3.5h, and dry at 55°C for 9h under vacuum to obtain functionalized DOPO; ethylene glycol, terminal hydroxyl siloxane oligomer, functionalized DOPO, antimony trioxide, and trimethyl phosphate are mixed evenly at a mass ratio of 1:0.35:0.35:0.03:0.06, add dimethyl terephthalate (3.5 times the molar amount of ethylene glycol), place in a polycondensation reactor, stir and react at 275°C, 400r / min for 1.5h, reduce the pressure to 75Pa, continue to stir and react for 1.5h, cool to room temperature, discharge, wash 4 times with deionized water, and dry at 55°C for 7.5h under vacuum to obtain functionalized polyester;

[0045] (3) The functionalized polyester, anti-mite microcapsules and dichloromethane were mixed uniformly in a mass ratio of 1:0.05:6.5, stirred at 20°C and 400 r / min for 25 min to prepare a spinning solution; the spinning solution was loaded into a micro pump, an ice plate covered with aluminum foil was used as a receiving device, the receiving distance was adjusted to 17 cm, the voltage during the spinning process was 24 kV, the propulsion rate was 0.65 mL / h, the ambient temperature was 20°C, the spinning humidity was 55%, and electrospinning was performed in an electrospinning device to obtain polyester fibers;

[0046] (4) Maleic anhydride, benzoquinone, and N,N-dimethylformamide were mixed in a mass ratio of 1:0.04:18 to prepare a maleic anhydride solution; cotton fiber was immersed in the maleic anhydride solution, ultrasonically oscillated at 75°C for 5.5 hours, taken out, and dried at 55°C for 9 hours under vacuum conditions to obtain pre-modified cotton fiber; o-phenylenediamine and a hydrochloric acid aqueous solution with a molar concentration of 4 mol / L were mixed in a mass ratio of 1:15 to prepare an o-phenylenediamine solution; the pre-modified cotton fiber was immersed in the o-phenylenediamine solution, ultrasonically oscillated at 85°C for 13 hours, taken out, washed 4 times with a hydrochloric acid aqueous solution with a molar concentration of 2 mol / L, and dried at 55°C for 9 hours under vacuum conditions to obtain modified cotton fiber;

[0047] (5) Spinning polyester fiber and modified cotton fiber in a spinning machine at a blending ratio of 3:2 to obtain blended yarn; mixing chloroplatinic acid and N,N-dimethylformamide in a mass ratio of 1:45 to prepare a catalyst solution; immersing the blended yarn in the catalyst solution, ultrasonically oscillating at 75°C for 5.5 hours, taking it out, and drying it at 55°C for 9 hours under vacuum conditions to obtain fire-retardant spun yarn.

[0048] Embodiment 3:

[0049] A method for preparing a fire-retardant spun yarn, the method comprising the following preparation steps:

[0050] (1) chitosan and 6% acetic acid aqueous solution are mixed at a mass ratio of 1:30 to prepare chitosan acetic acid solution; benzyl benzoate, Tween 80 and anhydrous ethanol are mixed at a mass ratio of 1:0.5:4 to prepare benzyl benzoate solution; under stirring conditions of 30°C and 500 r / min, 0.5 times the mass of the chitosan acetic acid solution of benzyl benzoate solution is uniformly added dropwise to the chitosan acetic acid solution within 10 minutes, and then 0.2 times the mass of glutaraldehyde of the chitosan acetic acid solution is added, and the reaction is continued with stirring for 4 hours, centrifuged, washed with anhydrous ethanol for 5 times, and dried at -30°C for 40 hours to prepare anti-mite microcapsules;

[0051] (2) Tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide and dimethyl sulfoxide were mixed uniformly in a mass ratio of 1:0.03:0.03, stirred at 75°C and 500 r / min for 20 min, 1,3-bis(3-hydroxypropyl)tetramethyldisiloxane (0.3 times the mass of tetramethylcyclotetrasiloxane) was added, the stirring reaction was continued for 8 min, the temperature was cooled to room temperature, and the mixture was washed with an equal volume of deionized water and toluene, allowed to stand for stratification, the aqueous phase was removed, the washing was repeated 5 times, the organic phase was placed in a drying oven, and dried at 60°C for 8 h under vacuum conditions to obtain a terminal hydroxyl siloxane oligomer; diethanolamine and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide were added in a molar ratio of 1:1 to 12 times the mass of diethanolamine. times of tetrahydrofuran, then add triethylamine (0.05 times of the mass of diethanolamine), stir and react at 500r / min, 60°C for 3h, and dry at 60°C for 8h under vacuum conditions to obtain functionalized DOPO; ethylene glycol, terminal hydroxyl siloxane oligomer, functionalized DOPO, antimony trioxide, and trimethyl phosphate are evenly mixed at a mass ratio of 1:0.4:0.4:0.04:0.07, and dimethyl terephthalate (4 times of the molar amount of ethylene glycol) is added, placed in a condensation reaction kettle, stirred and reacted at 280°C, 500r / min for 1h, the pressure is reduced to 100Pa, and the stirring reaction is continued for 1h, and the material is discharged after cooling to room temperature, washed with deionized water 5 times, and dried at 60°C for 7h under vacuum conditions to obtain functionalized polyester;

[0052] (3) The functionalized polyester, anti-mite microcapsules and dichloromethane were mixed uniformly in a mass ratio of 1:0.06:7, stirred at 30°C and 500 r / min for 20 min to prepare a spinning solution; the spinning solution was loaded into a micro pump, an ice plate covered with aluminum foil was used as a receiving device, the receiving distance was adjusted to 18 cm, the voltage during the spinning process was 25 kV, the propulsion rate was 0.7 mL / h, the ambient temperature was 30°C, the spinning humidity was 60%, and electrospinning was performed in an electrospinning device to obtain polyester fibers;

[0053] (4) Maleic anhydride, benzoquinone, and N,N-dimethylformamide were mixed in a mass ratio of 1:0.05:20 to prepare a maleic anhydride solution; cotton fiber was immersed in the maleic anhydride solution, ultrasonically oscillated at 80°C for 5 hours, taken out, and dried at 60°C for 8 hours under vacuum conditions to obtain pre-modified cotton fiber; o-phenylenediamine and a hydrochloric acid aqueous solution with a molar concentration of 4 mol / L were mixed in a mass ratio of 1:16 to prepare an o-phenylenediamine solution; the pre-modified cotton fiber was immersed in the o-phenylenediamine solution, ultrasonically oscillated at 90°C for 12 hours, taken out, washed 5 times with a hydrochloric acid aqueous solution with a molar concentration of 2 mol / L, and dried at 60°C for 8 hours under vacuum conditions to obtain modified cotton fiber;

[0054] (5) The polyester fiber and the modified cotton fiber are spun in a spinning machine at a blending ratio of 3:2 to obtain a blended yarn; chloroplatinic acid and N,N-dimethylformamide are mixed evenly at a mass ratio of 1:50 to prepare a catalyst solution; the blended yarn is immersed in the catalyst solution, ultrasonically oscillated at 80°C for 5 hours, taken out, and dried at 60°C for 8 hours under vacuum conditions to obtain a fire-retardant spun yarn.

[0055] Comparative Example 1:

[0056] The difference between the preparation method of the fire-retardant spun yarn of Comparative Example 1 and Example 2 is that step (1) is not performed, and step (3) is modified as follows: functionalized polyester and dichloromethane are mixed uniformly at a mass ratio of 1:6.5, stirred at 20°C and 400r / min for 25min to prepare a spinning solution; the spinning solution is loaded into a micro pump, an aluminum foil is covered on an ice plate as a receiving device, the receiving distance is adjusted to 17cm, the voltage during the spinning process is 24kV, the propulsion rate is 0.65mL / h, the ambient temperature is 20°C, the spinning humidity is 55%, and electrostatic spinning is performed in an electrostatic spinning device to obtain polyester fiber. The remaining steps are the same as in Example 2.

[0057] Comparative Example 2:

[0058] The difference between the preparation method of the fire-retardant spun yarn of Comparative Example 2 and that of Example 2 is that step (2) is different. Step (2) is modified as follows: tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide, and dimethyl sulfoxide are mixed uniformly in a mass ratio of 1:0.02:0.02, stirred and reacted at 70°C and 400r / min for 21min, 1,3-bis(3-hydroxypropyl)tetramethyldisiloxane with a mass of 0.25 times that of tetramethylcyclotetrasiloxane is added, and the stirring reaction is continued for 9min, cooled to room temperature, washed with an equal volume of deionized water and toluene, allowed to stand for stratification, the aqueous phase is removed, and the washing is repeated 4 times, and the organic phase is taken. The phases were placed in a drying oven and dried at 55°C for 9 hours under vacuum conditions to obtain a terminal hydroxyl siloxane oligomer; ethylene glycol, terminal hydroxyl siloxane oligomer, antimony trioxide, and trimethyl phosphate were mixed uniformly at a mass ratio of 1:0.35:0.03:0.06, and dimethyl terephthalate with a molar amount of 3.5 times that of ethylene glycol was added, and the mixture was placed in a polycondensation reactor, stirred at 275°C and 400r / min for 1.5 hours, the pressure was reduced to 75Pa, and the stirring reaction was continued for 1.5 hours, and the material was discharged after cooling to room temperature, washed with deionized water 4 times, and dried at 55°C for 7.5 hours under vacuum conditions to obtain a functionalized polyester. The remaining steps are the same as those in Example 2.

[0059] Comparative Example 3:

[0060] The preparation method of the fire-retardant spun yarn of Comparative Example 3 is different from that of Example 2 only in step (2). Step (2) is modified as follows: diethanolamine and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are added in a molar ratio of 1:1 to tetrahydrofuran (11 times the mass of diethanolamine), and then triethylamine (0.04 times the mass of diethanolamine) is added, and the reaction is stirred at 400 r / min and 55° C. for 3.5 h, and dried at 55° C. for 9 h under vacuum conditions to obtain functionalized DOPO ; Ethylene glycol, functionalized DOPO, antimony trioxide, and trimethyl phosphate were mixed uniformly in a mass ratio of 1:0.35:0.03:0.06, and dimethyl terephthalate was added in an amount 3.5 times the molar amount of ethylene glycol, and the mixture was placed in a polycondensation reactor, stirred at 275°C and 400r / min for 1.5h, the pressure was reduced to 75Pa, and the stirring reaction was continued for 1.5h, and the mixture was discharged after cooling to room temperature, washed with deionized water 4 times, and dried at 55°C for 7.5h under vacuum conditions to obtain functionalized polyester. The remaining steps were the same as those in Example 2.

[0061] Comparative Example 4:

[0062] The preparation method of the fire-retardant spun yarn of Comparative Example 4 is different from that of Example 2 in that step (4) is not performed, and step (5) is modified as follows: spinning polyester fiber and cotton fiber in a spinning machine at a blending ratio of 3:2 to obtain a blended yarn; mixing chloroplatinic acid and N,N-dimethylformamide in a mass ratio of 1:45 to prepare a catalyst solution; immersing the blended yarn in the catalyst solution, ultrasonically oscillating at 75°C for 5.5 hours, taking it out, and drying it at 55°C under vacuum for 9 hours to obtain the fire-retardant spun yarn. The remaining steps are the same as those of Example 2.

[0063] Test Example 1

[0064] Flame retardant performance test

[0065] Test method: According to GB / T5454 "Textile Combustion Performance Test Oxygen Index Method", the limiting oxygen index of the embodiment and the comparative example was tested using an oxygen index instrument. The results are shown in Table 1.

[0066] Table 1

[0067]

[0068]

[0069] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 4 in Table 1, it can be found that the fire-retardant spun yarn prepared by the present invention has good flame retardant properties.

[0070] By comparison, the limiting oxygen index of Examples 1 to 3 is greater than that of Comparative Example 2, indicating that the secondary amine on diethanolamine reacts with the PH bond on 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to obtain functionalized DOPO; ethylene glycol, terminal hydroxyl siloxane oligomer, functionalized DOPO and dimethyl terephthalate are polycondensed to obtain functionalized polyester, and a DOPO structure is introduced into the functionalized polyester molecular chain; the DOPO structure contains biphenyl ring and phenanthrene ring structures in the molecular structure, especially the side phosphorus group is introduced in the form of a cyclic O=PO bond, so it has higher thermal stability and chemical stability than general, non-annulated organic phosphates, better flame retardant properties, and imparts excellent flame retardant properties to fire-retardant and flame-retardant spun yarns.

[0071] By comparison, the limiting oxygen index of Examples 1 to 3 is greater than that of Comparative Example 3, indicating that tetramethylcyclotetrasiloxane is ring-opened polymerized and end-capped with 1,3-bis(3-hydroxypropyl)tetramethyldisiloxane to obtain terminal hydroxyl siloxane oligomers; ethylene glycol, terminal hydroxyl siloxane oligomers, functionalized DOPO and dimethyl terephthalate are polycondensed to obtain functionalized polyester, and Si-O bonds are introduced into the functionalized polyester molecular chain; the bond energy of the Si-O bond is greater than that of the CC bond, so compared with the CC bond, the Si-O bond needs to absorb more heat and its own vibration energy to resolve the energy of thermal decomposition of the polymer material, and the introduction of the Si-O bond can further improve the flame retardant properties of the fire-retardant spinning yarn.

[0072] Test Example 2

[0073] Anti-mite performance test

[0074] Test method: Referring to GB / T24253-2009, the anti-mite performance of the embodiment and the comparative example was tested by the avoidance method. The embodiment and the comparative example were cut into 30 mm short fibers, and 0.4 g of the short fibers were weighed as a sample. Three parallel samples were set for each group. The results are shown in Table 2.

[0075] Table 2

[0076] Mite avoidance rate (%) Mite avoidance rate (%) Example 1 90.47 Comparative Example 1 68.95 Example 2 91.86 Comparative Example 2 89.87 Example 3 90.73 Comparative Example 3 90.04 Comparative Example 4 71.58

[0077] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 4 in Table 2, it can be found that the fire-retardant spun yarn prepared by the present invention has good anti-mite performance.

[0078] By comparison, the mite avoidance rates of Examples 1 to 3 are greater than that of Comparative Example 1, indicating that the anti-mite microcapsules are prepared with benzyl benzoate as the core material, chitosan as the wall material, and glutaraldehyde as the cross-linking agent; benzyl benzoate is a colorless oily liquid at room temperature, and has been widely proven to have excellent anti-mite effects. The anti-mite mechanism of benzyl benzoate is that it has contact toxicity to mites at low concentrations. Benzyl benzoate that contacts the mite epidermis can dissolve epidermal lipids, thereby increasing the water loss of the mite and causing its dehydration and death; when mites ingest benzyl benzoate through their mouthparts, the substance will decompose into benzoic acid in their digestive system, thereby producing toxicity; in addition, the bitter almond smell of benzyl benzoate can also act on the nervous system of mites, and has a strong mite repellent effect; coating benzyl benzoate in chitosan can achieve long-term sustained release of benzyl benzoate, giving the fire-retardant spinning yarn excellent anti-mite performance.

[0079] By comparison, the mite avoidance rate of Examples 1 to 3 is greater than that of Comparative Example 4, indicating that pre-modified cotton fibers are obtained by reacting cotton fibers and maleic anhydride, and carboxyl groups are introduced into the pre-modified cotton fibers; the carboxyl groups on the pre-modified cotton fibers are reacted with o-phenylenediamine to obtain modified cotton fibers; a benzimidazole structure is generated on the modified cotton fibers; the benzimidazole structure generated on the modified cotton fibers has antibacterial and mite-killing effects, and can achieve insecticidal effects by inhibiting the activity of microtubule proteins in mite cells and inhibiting the digestion and nutrient absorption of the insect body, thereby further improving the anti-mite performance of the fire-retardant yarn.

[0080] Test Example 3

[0081] Mechanical properties testing

[0082] Test method: Referring to GB / T3916-2013, the breaking strength of the examples and comparative examples was tested using a YG061F electronic single yarn strength tester. The results are shown in Table 3.

[0083] Table 3

[0084] Breaking strength (cN / tex) Breaking strength (cN / tex) Example 1 22.68 Comparative Example 1 19.21 Example 2 23.51 Comparative Example 2 22.43 Example 3 22.37 Comparative Example 3 16.35 Comparative Example 4 18.72

[0085] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 4 in Table 3, it can be found that the fire-retardant spun yarn prepared by the present invention has good mechanical properties.

[0086] By comparison, the breaking strength of Examples 1 to 3 is greater than that of Comparative Example 1, indicating that the anti-mite microcapsules are prepared with benzyl benzoate as the core material, chitosan as the wall material, and glutaraldehyde as the cross-linking agent, and carbon-carbon double bonds are introduced on the surface of the anti-mite microcapsules; the carbon-carbon double bonds introduced on the surface of the anti-mite microcapsules can undergo silyl hydroaddition with the Si-H bonds introduced on the polyester fiber molecular chain under the catalysis of chloroplatinic acid to form a cross-linked network, thereby improving the mechanical properties of the fire-retardant spun yarn.

[0087] By comparison, the breaking strength of Examples 1 to 3 is greater than that of Comparative Example 3, indicating that tetramethylcyclotetrasiloxane is ring-opening polymerized and end-capped with 1,3-bis(3-hydroxypropyl)tetramethyldisiloxane to obtain terminal hydroxyl siloxane oligomers; ethylene glycol, terminal hydroxyl siloxane oligomers, functionalized DOPO and dimethyl terephthalate are polycondensed to obtain functionalized polyester, and Si-H bonds are introduced into the functionalized polyester molecular chain; the Si-H bonds introduced into the functionalized polyester molecular chain react with the carbon-carbon double bonds introduced into the anti-mite microcapsules and modified cotton fibers under the catalysis of chloroplatinic acid to undergo a silylation reaction to form a cross-linked network, thereby improving the mechanical properties of the fire-retardant spun yarn.

[0088] By comparison, the breaking strength of Examples 1 to 3 is greater than that of Comparative Example 4, indicating that the cotton fiber is reacted with maleic anhydride and o-phenylenediamine in sequence to obtain the modified cotton fiber; a carbon-carbon double bond is introduced into the modified cotton fiber; the carbon-carbon double bond introduced into the modified cotton fiber can undergo silylation with the Si-H bond introduced into the polyester fiber molecular chain under the catalysis of chloroplatinic acid to form a cross-linked network, thereby improving the mechanical properties of the fire-retardant spun yarn.

[0089] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A fire-retardant spun yarn, characterized in that: The fire-retardant spun yarn is prepared by using benzyl benzoate as core material, chitosan as wall material, and glutaraldehyde as cross-linking agent to prepare anti-mite microcapsules; ethylene glycol, terminal hydroxyl siloxane oligomer, functionalized DOPO and dimethyl terephthalate are polycondensed to prepare functionalized polyester; the functionalized polyester and anti-mite microcapsules are prepared into spinning solution, and the polyester fiber is prepared by electrostatic spinning; the polyester fiber and modified cotton fiber are blended in a spinning machine to prepare blended yarn, and the blended yarn is post-treated with chloroplatinic acid to prepare the fire-retardant spun yarn; The terminal hydroxyl siloxane oligomer is prepared by ring-opening polymerization of tetramethylcyclotetrasiloxane and end-capping with 1,3-bis(3-hydroxypropyl)tetramethyldisiloxane; The functionalized DOPO is prepared by reacting diethanolamine and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide; The modified cotton fiber is prepared by reacting pre-modified cotton fiber and o-phenylenediamine; The pre-modified cotton fiber is prepared by reacting cotton fiber and maleic anhydride.

2. A method for preparing a fire-retardant spun yarn, characterized in that: The method for preparing the fire-retardant spun yarn comprises the following preparation steps: (1) chitosan and 4% to 6% acetic acid aqueous solution are mixed uniformly in a mass ratio of 1:(20 to 30) to prepare a chitosan acetic acid solution; under the conditions of 10 to 30° C. and 300 to 500 r / min stirring, 0.4 to 0.5 times the mass of the chitosan acetic acid solution of benzyl benzoate solution is uniformly added dropwise to the chitosan acetic acid solution within 10 minutes, and then 0.1 to 0.2 times the mass of the chitosan acetic acid solution of glutaraldehyde is added, and the reaction is continued with stirring for 4 to 5 hours, centrifuged, washed with anhydrous ethanol for 3 to 5 times, and dried at -40 to -30° C. for 36 to 40 hours to prepare anti-mite microcapsules; (2) adding diethanolamine and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in a molar ratio of 1:1 to tetrahydrofuran (10 to 12 times the mass of diethanolamine), then adding triethylamine (0.03 to 0.05 times the mass of diethanolamine), stirring at 300 to 500 r / min and 50 to 60° C. for 3 to 4 hours, and drying at 50 to 60° C. for 8 to 10 hours under vacuum conditions to obtain functionalized DOPO; adding ethylene glycol, terminal hydroxyl siloxane oligomer, functionalized DOPO, antimony trioxide, and trimethyl phosphate in a mass ratio of 1:

1. The mixture is uniformly mixed with 1:(0.3-0.4):(0.3-0.4):(0.02-0.04):(0.05-0.07), and dimethyl terephthalate with a molar amount of 3-4 times of ethylene glycol is added, and the mixture is placed in a polycondensation reactor, and stirred at 270-280°C and 300-500r / min for 1-2h, and the pressure is reduced to 50-100Pa, and the stirring reaction is continued for 1-2h. After cooling to room temperature, the mixture is discharged, washed with deionized water for 3-5 times, and dried at 50-60°C for 7-8h under vacuum conditions to obtain a functional polyester. (3) mixing the functionalized polyester, anti-mite microcapsules and dichloromethane in a mass ratio of 1:(0.04-0.06):(6-7), stirring at 10-30° C. and 300-500 r / min for 20-30 min to prepare a spinning solution; loading the spinning solution into a micro pump, using an ice plate covered with aluminum foil as a receiving device, and performing electrospinning in an electrospinning device to obtain polyester fibers; (4) immersing the cotton fiber in a maleic anhydride solution, ultrasonically oscillating at 70-80° C. for 5-6 hours, taking it out, and drying it at 50-60° C. for 8-10 hours under vacuum conditions to obtain pre-modified cotton fiber; immersing the pre-modified cotton fiber in an o-phenylenediamine solution, ultrasonically oscillating at 80-90° C. for 12-14 hours, taking it out, washing it 3-5 times with a hydrochloric acid aqueous solution with a molar concentration of 2 mol / L, and drying it at 50-60° C. for 8-10 hours under vacuum conditions to obtain modified cotton fiber; (5) Spinning polyester fiber and modified cotton fiber in a spinning machine at a blending ratio of 3:2 to obtain a blended yarn; immersing the blended yarn in a catalyst solution, ultrasonically oscillating at 70-80° C. for 5-6 hours, taking it out, and drying it at 50-60° C. for 8-10 hours under vacuum conditions to obtain a fire-retardant spun yarn.

3. The method for preparing a fire-retardant spun yarn according to claim 2, characterized in that: The chitosan in step (1) has a deacetylation degree of 93% and a weight average molecular weight of 85 kDa.

4. The method for preparing a fire-retardant spun yarn according to claim 2, characterized in that: The preparation method of the benzyl benzoate solution in step (1) is as follows: benzyl benzoate, Tween 80 and anhydrous ethanol are uniformly mixed in a mass ratio of 1:(0.3-0.5):(3-4) to prepare a benzyl benzoate solution.

5. The method for preparing a fire-retardant spun yarn according to claim 2, characterized in that: The preparation method of the terminal hydroxyl siloxane oligomer in step (2) is as follows: tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide and dimethyl sulfoxide are uniformly mixed in a mass ratio of 1:(0.01-0.03):(0.01-0.03), stirred and reacted at 65-75°C and 300-500r / min for 20-22min, 1,3-bis(3-hydroxypropyl)tetramethyldisiloxane in an amount of 0.2-0.3 times the mass of tetramethylcyclotetrasiloxane is added, the stirring reaction is continued for 8-10min, the temperature is cooled to room temperature, and the terminal hydroxyl siloxane is washed with a mixture of equal volumes of deionized water and toluene, the mixture is allowed to stand for stratification, the aqueous phase is removed, the washing is repeated 3-5 times, the organic phase is placed in a drying oven, and dried at 50-60°C for 8-10h under vacuum conditions to obtain the terminal hydroxyl siloxane oligomer.

6. The method for preparing a fire-retardant spun yarn according to claim 2, characterized in that: The process parameters of the electrospinning in step (3) are as follows: adjusting the receiving distance to 16-18 cm, the voltage during spinning to 23-25 ​​kV, the propulsion rate to 0.6-0.7 mL / h, the ambient temperature to 10-30° C., and the spinning humidity to 50%-60%.

7. The method for preparing a fire-retardant spun yarn according to claim 2, characterized in that: The preparation method of the maleic anhydride solution in step (4) is as follows: maleic anhydride, p-benzoquinone, and N,N-dimethylformamide are uniformly mixed in a mass ratio of 1:(0.03-0.05):(16-20) to prepare a maleic anhydride solution.

8. The method for preparing a fire-retardant spun yarn according to claim 2, characterized in that: The preparation method of the o-phenylenediamine solution in step (4) is as follows: o-phenylenediamine and a hydrochloric acid aqueous solution with a molar concentration of 4 mol / L are uniformly mixed in a mass ratio of 1:(14-16) to prepare an o-phenylenediamine solution.

9. The method for preparing a fire-retardant spun yarn according to claim 2, characterized in that: The cotton fiber in step (4) is specifically kapok fiber, with a length of 28 to 36 mm and a linear density of 1.6 to 2.2 dtex.

10. The method for preparing a fire-retardant spun yarn according to claim 2, characterized in that: The preparation method of the catalyst solution in step (5) is as follows: chloroplatinic acid and N,N-dimethylformamide are uniformly mixed in a mass ratio of 1:(40-50) to prepare a catalyst solution.

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