CN117107388B - Antibacterial flame-retardant polyamide fiber material and preparation method thereof - Google Patents

Antibacterial flame-retardant polyamide fiber material and preparation method thereof Download PDF

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CN117107388B
CN117107388B CN202311256311.XA CN202311256311A CN117107388B CN 117107388 B CN117107388 B CN 117107388B CN 202311256311 A CN202311256311 A CN 202311256311A CN 117107388 B CN117107388 B CN 117107388B
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CN117107388A (en
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樊文斌
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Dongguan Xinhong Engineering Plastics Co ltd
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms

Abstract

The invention provides an antibacterial flame-retardant polyamide fiber material and a preparation method thereof, belonging to the technical field of new materials. Preparing carboxylated carbon nano tube, loading Cu and Ag, and then mixing the carboxylated carbon nano tube with phosphorus-nitrogen flame retardant modified TiO 2 /SiO 2 The nano particles are compounded, added into caprolactam for in-situ polymerization, composite slices are prepared, dried, and the antibacterial flame-retardant polyamide fiber material is prepared through melt spinning. The antibacterial flame-retardant polyamide fiber material prepared by the invention has good wear resistance, good antibacterial, ultraviolet aging resistance and flame retardant properties, obviously improved elongation at break, tensile strength, thermal stability and the like, and good washability and flexibility, thereby greatly widening the application range and having wide application prospect.

Description

Antibacterial flame-retardant polyamide fiber material and preparation method thereof
Technical Field
The invention relates to the technical field of new materials, in particular to an antibacterial flame-retardant polyamide fiber material and a preparation method thereof.
Background
In recent years, new technologies and new materials are continuously emerging, so that the variety of functional textiles is increased, the functional textiles are developed into an important high-tech industry, and more functional textiles are developed into an important high-tech industry. More and more textile enterprises are beginning to pay attention to high added value functional textiles. With the progress of science and technology and the improvement of the living standard of people, more and higher requirements on the functionality of textiles in production and living are put forward, such as comfort, aesthetic property and health of products, whether the products are green and environment-friendly, whether the requirements of special industries can be met, and the like.
Polyamide 66 is a species having the greatest yield and consumption of polyamide, and accounts for about 50% of the total amount of polyamide. The polyamide 66 has a plurality of excellent performances such as high strength, wear resistance and the like, and is widely applied to the fields of construction, textile, chemical industry, military and the like. However, polyamide fibers have the disadvantages of poor flame retardance, poor light resistance and easiness in generating bacteria, and therefore wider application of the polyamide fibers is affected.
The addition of the effective flame retardant and the related synergistic flame retardant can make the polyamide 66 material have flame retardance, which is a common method in the prior flame retardant technology, and the two methods of blending and copolymerization are generally adopted from the technical point of view. Most of the researches at present focus on blending granulation of polyamide 66, blended flame retardant and related synergistic flame retardant, and the blending mode exposes various defects such as large addition amount of flame retardant, poor dispersibility, limited performance of polyamide 66 and the like, so that the application range of the blended flame retardant polyamide 66 is narrowed. The copolymerization of reactive flame retardant and polyamide 66 monomer is adopted, and flame retardant units are introduced into the macromolecular chain of polyamide 66, so that the permanent flame retardance of polyamide 66 is realized, and the important point of research on flame retardant polyamide 66 in recent years. At present, a large number of patent reports on copolymerized flame retardant polyamide 66 are emerging.
Chinese patent No. CN104211954B discloses a preparation method of halogen-free flame retardant nylon 66 polymer, which adopts a reactive flame retardant DOPO derivative to be copolymerized with dibasic acid or diamine to generate salt, and then is copolymerized with nylon 66 salt to obtain halogen-free flame retardant nylon 66. Chinese patent No. CN105155018B discloses a method for preparing a copolymerized flame-retardant polyamide 66 fiber, which comprises preparing a block flame-retardant polyamide 66 copolymer from a phosphorus-containing reactive flame retardant through polymerization, granulating the polyamide 66 copolymer, drying, and melt spinning to prepare the flame-retardant polyamide 66 fiber. The Chinese patent No. CN1266445C adopts the reactive flame retardant CEPPA to copolymerize with the monomer of nylon 66 to obtain the flame retardant nylon 66 polymer, and the flame retardant molecule is keyed into the polymer molecule chain, so that the flame retardant property of the product is long-term effective. The flame-retardant polyamide 66 polymer obtained by copolymerizing the reactive flame retardant or flame-retardant prepolymer and the polyamide 66 monomer is a scheme for effectively improving the flame retardant property of the polyamide 66 product, but in the copolymerization flame-retardant polyamide 66, a large amount of steric hindrance effect is formed due to the introduction of the flame retardant, so that the viscosity of the copolymerization flame-retardant polyamide 66 is lower, a re-tackifying process is required, the problems of yellowing or mismatching of terminal amino groups and the like are easily caused, and the subsequent processing or spinning is troublesome.
The Chinese patent No. 103774265B discloses a preparation method of antibacterial fibers, which comprises the steps of adding antibacterial agent zinc oxide particles into a polymer, and spinning by a melt electrostatic spinning technology to obtain the antibacterial fibers.
The Chinese patent No. 101705614B discloses a preparation method of nickel-plated silver-plated aromatic polyamide conductive fibers, which comprises the following steps: after washing and degreasing and removing impurities on the surface of the fiber, a catalyst active layer is plated on the surface of the fiber by sensitization and activation, and a soaking method is adopted to carry out nickel plating and silver plating respectively.
Chinese patent No. 102877287B discloses a preparation method of halogen-containing amine antibacterial cellulose fabric, wherein fabric is immersed in periodate solution for selective oxidation, aldehyde groups are generated on the surface of the fabric, an antibacterial agent is added by a grafting method, the grafting cost of the surface of the fabric is relatively high, and the mechanical property of the fabric is damaged due to the addition of peroxide initiator in the grafting process.
Disclosure of Invention
The invention aims to provide an antibacterial flame-retardant polyamide fiber material and a preparation method thereof, which not only have good wear resistance, but also have good antibacterial, ultraviolet aging resistance and flame retardant properties, and the elongation at break, tensile strength, thermal stability and the like of the material are obviously improved, so that the material has good washability and good flexibility, thereby greatly widening the application range of the material and having wide application prospect.
The technical scheme of the invention is realized as follows:
the invention provides an antibacterial flame-retardant polyamide fiber materialThe preparation method of the material comprises the steps of preparing carboxylated carbon nano tubes, loading Cu and Ag, and then mixing the carboxylated carbon nano tubes with phosphorus-nitrogen flame retardant modified TiO 2 /SiO 2 The nano particles are compounded, added into caprolactam for in-situ polymerization, composite slices are prepared, dried, and the antibacterial flame-retardant polyamide fiber material is prepared through melt spinning.
As a further improvement of the invention, the method comprises the following steps:
s1, preparing carboxylated carbon nanotubes: uniformly mixing the multiwall carbon nanotube and the mixed acid, performing ultrasonic heating and stirring reaction, adding water for dilution, centrifuging, washing and drying to obtain the carboxylated carbon nanotube;
s2, preparing Cu-loaded carboxylated carbon nanotubes: adding the carboxylated carbon nanotube prepared in the step S1 into water, adding soluble copper salt, dropwise adding a reducing agent, heating and stirring for reaction, centrifuging, washing and drying to prepare the Cu-loaded carboxylated carbon nanotube;
S3, preparing the Cu/Ag loaded carboxylated carbon nanotube: adding the Cu-loaded carboxylated carbon nanotube prepared in the step S2 into water, adding silver nitrate, stirring and mixing uniformly, adding glucose, heating and stirring for reaction, centrifuging, washing and drying to prepare the Cu/Ag-loaded carboxylated carbon nanotube;
s4, modified TiO 2 /SiO 2 Preparation of nanoparticle-Cu/Ag loaded carboxylated carbon nanotubes: dissolving titanium alkoxide and alkyl orthosilicate in ethanol to obtain a mixed solution A; adding a phosphorus-nitrogen flame retardant, glucose and acetic acid into an ethanol water solution to obtain a mixed solution B; adding the mixed solution A into the mixed solution B, adding the Cu/Ag loaded carboxylated carbon nano tube prepared in the step S3, stirring and mixing uniformly, heating and stirring for reaction, centrifuging and drying to obtain modified TiO 2 /SiO 2 nanoparticle-Cu/Ag loaded carboxylated carbon nanotubes;
the structural formula of the phosphorus-nitrogen flame retardant is shown as formula I:
wherein r=c1-C4 straight alkyl chain;
s5, preparing an antibacterial flame-retardant polyamide fiber material: the modified TiO prepared in the step S4 2 /SiO 2 Adding nano particles-Cu/Ag loaded carboxylated carbon nano tubes and caprolactam into a polyamide reactor for in-situ polymerization, preparing composite slices, drying, and preparing the antibacterial flame-retardant polyamide fiber material through melt spinning.
As a further improvement of the invention, the mixed acid in the step S1 is a mixture of concentrated sulfuric acid and concentrated hydrochloric acid, the volume ratio is 4-5:1, and the mass fraction of the concentrated sulfuric acid is more than 98%; the mass fraction of the concentrated hydrochloric acid is more than 37.5%, and the mass ratio of the multiwall carbon nanotubes to the mixed acid is 1:80-100, wherein the heating temperature is 45-50 ℃, the ultrasonic power is 700-1000W, and the time is 3-5h.
As a further improvement of the present invention, the mass ratio of the carboxylated carbon nanotubes, the soluble copper salt and the reducing agent in the step S2 is 1:0.2-0.4:5-7, wherein the soluble copper salt is selected from at least one of copper chloride, copper nitrate and copper sulfate, the reducing agent is selected from at least one of ascorbic acid and sodium ascorbate, and the temperature of the heating and stirring reaction is 75-85 ℃ and the time is 7-10h.
As a further improvement of the invention, in the step S3, the mass ratio of the Cu-loaded carboxylated carbon nano tube to the silver nitrate to the glucose is 1:0.1-0.2:3-5, the temperature of the heating and stirring reaction is 95-100 ℃, and the time is 0.5-1h.
As a further improvement of the present invention, the titanium alkoxide in step S4 is selected from at least one of tetraethyl titanate, tetrabutyl titanate, tetraisopropyl titanate, titanium tetrachloride and titanium trichloride; the alkyl orthosilicate is methyl orthosilicate or ethyl orthosilicate, and the mass ratio of the titanium alkoxide, the alkyl orthosilicate, the phosphorus-nitrogen flame retardant, glucose, acetic acid and the carboxylated carbon nano tube loaded with Cu/Ag is 10-12:5-7:7-10:0.3-0.5:7-10:7-10; the temperature of the heating and stirring reaction is 170-200 ℃, the time is 3-5h, and the concentration of the ethanol water solution is 55-65wt%.
As a further improvement of the invention, the preparation method of the phosphorus-nitrogen flame retardant comprises the following steps: and (3) reacting hexachlorocyclotriphosphazene with an alkali compound to obtain the phosphorus-nitrogen flame retardant.
As a further improvement of the invention, the mole ratio of hexachlorocyclotriphosphazene and alkali compound is 1:3-5:6-6.1, wherein the reaction temperature is 35-45 ℃ and the reaction time is 3-5h.
As a further improvement of the present invention, the modified TiO in step S5 2 /SiO 2 The mass ratio of the nano particle-Cu/Ag loaded carboxylated carbon nano tube to caprolactam is 2-4:90-110, wherein the in-situ polymerization condition is that ring opening is carried out for 2-3 hours at the temperature of 220-240 ℃ and the pressure of 0.3-0.5MPa, polycondensation is carried out for 2-4 hours at the temperature of 270-280 ℃, and the temperature of melt spinning is 255-275 ℃.
The invention further protects the antibacterial flame-retardant polyamide fiber material prepared by the preparation method.
The invention has the following beneficial effects:
the multiwall carbon nanotube is relatively active, a large number of carboxyl groups are formed on the surface after being treated by mixed acid, on one hand, cu ions and Ag ions are convenient to complex, simple substance Cu and Ag can be formed by reduction and loading under the action of reducing agent ascorbic acid and glucose respectively, the dispersibility is good, the agglomeration of simple substance Cu and Ag is not easy to occur, the phenomenon that ions are greatly overflowed due to the fact that the direct addition of simple substance Cu and Ag has large surface area and unstable energy and is easy to agglomerate and oxidize is avoided, the threat to human health is caused, meanwhile, the addition of two metals has antibacterial synergistic effect, the sterilizing effect on gram-positive bacteria and gram-negative bacteria is greatly improved, and the antibacterial and antifungal capabilities are good; on the other hand, the carboxyl of the carboxyl modified multiwall carbon nanotube can react with the terminal amino group in the polyamide molecule in a condensation manner, and is grafted to a molecular chain, so that the dispersibility of the carboxyl modified multiwall carbon nanotube is improved, and the interfacial interaction of the composite fiber material is enhanced, so that the elongation at break, the tensile strength and the thermal stability of the composite fiber are obviously improved.
The phosphorus-nitrogen flame retardant prepared by the invention contains multiple active groups, has good flame retardant property, and can be used for preparing nano SiO in the later period 2 Si-O, si-C can be formed during combustionThe protective layer realizes the ternary synergistic flame retardant effect, solves the defects of single flame retardant element and unobvious effect of the halogen-free flame retardant, has high stability and can be used as a bridge to connect the modified TiO 2 /SiO 2 The nano particles and the carboxylated carbon nano tubes loaded with Cu/Ag are connected to the polyamide material through reaction, so that the dispersibility of the inorganic material is improved, and a good improvement effect is achieved.
Nanometer TiO 2 The energy gap of 3.2eV is provided, and the ultraviolet absorption effect is strong; nano SiO 2 The ultraviolet light can be almost scattered, the ultraviolet light shielding property is excellent, meanwhile, the thermal stability of the two inorganic nano materials is good, and the inorganic nano materials are fixedly assembled on the surface of the polyamide fiber, so that a compact ultraviolet aging resistant coating can be formed, the ultraviolet damage of the fiber is weakened, the ultraviolet aging resistant capability of the fiber is improved, and meanwhile, the nano TiO 2 Also has good photocatalysis antibacterial capability and plays a good synergistic antibacterial role. However, in general, the inorganic nano material has small particle size and large specific surface area, is extremely easy to agglomerate, is not easy to disperse uniformly during direct polymerization, is easy to cause blockage of a spinneret plate, affects continuous production, reduces the performance of fibers, and reduces the mechanical properties of the fibers.
The phosphorus-nitrogen flame retardant prepared by the invention has rich amino structure, and when titanium alkoxide and alkyl orthosilicate form sol, a part of amino can react or be grafted through hydrogen bonds to prepare TiO 2 /SiO 2 On the nano particles, modified particles are formed, and the other part of amino groups can react with carboxylated carbon nano tubes loaded with Cu/Ag or graft through hydrogen bonds, so as to prepare modified TiO 2 /SiO 2 The nano particle-Cu/Ag loaded carboxylated carbon nanotube and caprolactam are polymerized in situ to prepare the antibacterial flame-retardant polyamide fiber material, which has good antibacterial, ultraviolet aging resistant, flame retardant, mechanical property improving and other effects.
The antibacterial flame-retardant polyamide fiber material prepared by the invention has good wear resistance, good antibacterial, ultraviolet aging resistance and flame retardant properties, obviously improved elongation at break, tensile strength, thermal stability and the like, and good washability and flexibility, thereby greatly widening the application range and having wide application prospect.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The multi-wall carbon nanotubes are of industrial grade and are purchased from the scientific and technological company of carbon-rich graphene, suzhou.
Preparation example 1 preparation of phosphorus-nitrogen flame retardant
The synthetic route is as follows:
the method comprises the following steps: adding 0.06mol of ethylenediamine and 0.03mol of NaOH into 200mL of tetrahydrofuran at the temperature of 0 ℃, adding 0.01mol of hexachlorocyclotriphosphazene, stirring at the temperature of 0 ℃ for reaction for 1h, heating to 35 ℃, continuously stirring for reaction for 3h, filtering, washing and drying the product, and thus obtaining the phosphorus-nitrogen flame retardant. ESI-MS calculated: c (C) 12 H 43 N 15 P 3 (m+h) +490.30, found: 490.3, the yield thereof was found to be 92.2%.
Nuclear magnetic results: 1 H NMR(300MHz，CDCl 3 )δ2.92(m，24H)，2.0(br，18H)。
preparation example 2 preparation of phosphorus-nitrogen flame retardant
The method comprises the following steps: adding 0.061mol of 1, 3-propylene diamine and 0.05mol of NaOH into 200mL of tetrahydrofuran at the temperature of 0 ℃, adding 0.01mol of hexachlorocyclotriphosphazene, stirring at the temperature of 0 ℃ for reaction for 1h, heating to 45 ℃, continuously stirring for reaction for 5h, filtering, washing and drying the product, and thus obtaining the phosphorus-nitrogen flame retardant. ESI-MS calculated: c (C) 18 H 55 N 15 P 3 (m+h) +574.39, found: 574.4, yield 90.7％。
Nuclear magnetic results: 1 H NMR(300MHz，CDCl 3 )δ2.65(m，24H)，2.0(br，18H)，1.82(m，12H)。
preparation example 3 preparation of phosphorus-nitrogen flame retardant
The method comprises the following steps: adding 0.0605mol of 1, 3-propylene diamine and 0.04mol of KOH into 200mL of tetrahydrofuran at the temperature of 0 ℃, adding 0.01mol of hexachlorocyclotriphosphazene, stirring and reacting for 1h at the temperature of 0 ℃, heating to 40 ℃, continuously stirring and reacting for 4h, filtering, washing and drying the product to obtain the phosphorus-nitrogen flame retardant with the yield of 91.4%.
Example 1
The embodiment provides a preparation method of an antibacterial flame-retardant polyamide fiber material, which comprises the following steps:
s1, preparing carboxylated carbon nanotubes: uniformly mixing 1 part by weight of multi-wall carbon nano tube and 80 parts by weight of mixed acid, performing ultrasonic treatment at 700W, heating to 45 ℃, stirring and reacting for 3 hours, adding 500 parts by weight of water for dilution, centrifuging, washing and drying to obtain carboxylated carbon nano tube;
the mixed acid is a mixture of concentrated sulfuric acid and concentrated hydrochloric acid, the volume ratio is 4:1, and the mass fraction of the concentrated sulfuric acid is more than 98%; the mass fraction of the concentrated hydrochloric acid is more than 37.5%;
s2, preparing Cu-loaded carboxylated carbon nanotubes: adding 1 part by weight of the carboxylated carbon nanotube prepared in the step S1 into 100 parts by weight of water, adding 0.2 part by weight of copper chloride, dropwise adding 5 parts by weight of ascorbic acid, heating to 75 ℃, stirring for reacting for 7 hours, centrifuging, washing, and drying to prepare the Cu-loaded carboxylated carbon nanotube;
s3, preparing the Cu/Ag loaded carboxylated carbon nanotube: adding 1 part by weight of the Cu-loaded carboxylated carbon nanotube prepared in the step S2 into 100 parts by weight of water, adding 0.1 part by weight of silver nitrate, stirring and mixing for 10min, adding 3 parts by weight of glucose, heating to 95 ℃, stirring and reacting for 0.5h, centrifuging, washing and drying to prepare the Cu/Ag-loaded carboxylated carbon nanotube;
S4, modified TiO 2 /SiO 2 Preparation of nanoparticle-Cu/Ag loaded carboxylated carbon nanotubes: 10 parts by weight of tetraethyl titanate and 5 parts by weight ofDissolving methyl orthosilicate in 200 parts by weight of ethanol to obtain a mixed solution A; 7 parts by weight of the phosphorus-nitrogen flame retardant prepared in preparation example 1, 0.3 part by weight of glucose and 7 parts by weight of acetic acid are added into 200 parts by weight of 55wt% ethanol aqueous solution to obtain a mixed solution B; adding the mixed solution A into the mixed solution B, adding 7 parts by weight of the Cu/Ag loaded carboxylated carbon nanotubes prepared in the step S3, stirring and mixing for 15min, performing hydrothermal reaction in a reaction kettle, heating the reactor to 170 ℃, stirring and reacting for 3h, centrifuging, and drying to obtain modified TiO 2 /SiO 2 nanoparticle-Cu/Ag loaded carboxylated carbon nanotubes;
s5, preparing an antibacterial flame-retardant polyamide fiber material: 2 parts by weight of the modified TiO prepared in the step S4 2 /SiO 2 Adding the nano particle-Cu/Ag loaded carboxylated carbon nano tube and 90 parts by weight of caprolactam into a polyamide reactor for in-situ polymerization, wherein the in-situ polymerization condition is that the temperature is 220 ℃, the ring opening is carried out for 2 hours under the pressure of 0.3MPa, the polycondensation is carried out for 2 hours under the temperature of 270 ℃, the composite slice is prepared, and the composite slice is dried and is subjected to melt spinning at the temperature of 255 ℃ to obtain the antibacterial flame-retardant polyamide fiber material.
Example 2
The embodiment provides a preparation method of an antibacterial flame-retardant polyamide fiber material, which comprises the following steps:
s1, preparing carboxylated carbon nanotubes: uniformly mixing 1 part by weight of multi-wall carbon nano tube and 100 parts by weight of mixed acid, performing 1000W ultrasonic treatment, heating to 50 ℃, stirring and reacting for 5 hours, adding 500 parts by weight of water for dilution, centrifuging, washing and drying to obtain carboxylated carbon nano tube;
the mixed acid is a mixture of concentrated sulfuric acid and concentrated hydrochloric acid, the volume ratio is 5:1, and the mass fraction of the concentrated sulfuric acid is more than 98%; the mass fraction of the concentrated hydrochloric acid is more than 37.5%;
s2, preparing Cu-loaded carboxylated carbon nanotubes: adding 1 part by weight of the carboxylated carbon nanotube prepared in the step S1 into 100 parts by weight of water, adding 0.4 part by weight of copper sulfate, dropwise adding 7 parts by weight of ascorbic acid, heating to 85 ℃, stirring and reacting for 10 hours, centrifuging, washing and drying to prepare the Cu-loaded carboxylated carbon nanotube;
s3, preparing the Cu/Ag loaded carboxylated carbon nanotube: adding 1 part by weight of the Cu-loaded carboxylated carbon nanotube prepared in the step S2 into 100 parts by weight of water, adding 0.2 part by weight of silver nitrate, stirring and mixing for 10min, adding 5 parts by weight of glucose, heating to 100 ℃, stirring and reacting for 1h, centrifuging, washing and drying to prepare the Cu/Ag-loaded carboxylated carbon nanotube;
S4, modified TiO 2 /SiO 2 Preparation of nanoparticle-Cu/Ag loaded carboxylated carbon nanotubes: dissolving 12 parts by weight of tetrabutyl titanate and 7 parts by weight of tetraethoxysilane in 200 parts by weight of ethanol to obtain a mixed solution A; 10 parts by weight of the phosphorus-nitrogen flame retardant prepared in preparation example 2, 0.5 part by weight of glucose and 10 parts by weight of acetic acid are added into 200 parts by weight of 65wt% ethanol aqueous solution to obtain a mixed solution B; adding the mixed solution A into the mixed solution B, adding 10 parts by weight of the Cu/Ag loaded carboxylated carbon nanotubes prepared in the step S3, stirring and mixing for 15min, performing hydrothermal reaction in a reaction kettle, heating the reactor to 200 ℃, stirring and reacting for 5h, centrifuging, and drying to obtain modified TiO 2 /SiO 2 nanoparticle-Cu/Ag loaded carboxylated carbon nanotubes;
s5, preparing an antibacterial flame-retardant polyamide fiber material: 4 parts by weight of the modified TiO prepared in the step S4 2 /SiO 2 Adding the nano particle-Cu/Ag loaded carboxylated carbon nano tube and 110 parts by weight of caprolactam into a polyamide reactor for in-situ polymerization, wherein the in-situ polymerization condition is that ring opening is carried out for 3 hours at the temperature of 240 ℃ and the pressure of 0.5MPa, polycondensation is carried out for 4 hours at the temperature of 280 ℃, composite slices are prepared, and the composite slices are dried and melt-spun at the temperature of 275 ℃ to obtain the antibacterial flame-retardant polyamide fiber material.
Example 3
The embodiment provides a preparation method of an antibacterial flame-retardant polyamide fiber material, which comprises the following steps:
s1, preparing carboxylated carbon nanotubes: uniformly mixing 1 part by weight of multi-wall carbon nano tube and 90 parts by weight of mixed acid, carrying out ultrasonic treatment at 850W, heating to 47 ℃, stirring and reacting for 4 hours, diluting with 500 parts by weight of water, centrifuging, washing and drying to obtain carboxylated carbon nano tube;
the mixed acid is a mixture of concentrated sulfuric acid and concentrated hydrochloric acid, the volume ratio is 4.5:1, and the mass fraction of the concentrated sulfuric acid is more than 98%; the mass fraction of the concentrated hydrochloric acid is more than 37.5%;
s2, preparing Cu-loaded carboxylated carbon nanotubes: adding 1 part by weight of the carboxylated carbon nanotube prepared in the step S1 into 100 parts by weight of water, adding 0.3 part by weight of copper chloride, dropwise adding 6 parts by weight of ascorbic acid, heating to 80 ℃, stirring and reacting for 8.5 hours, centrifuging, washing and drying to prepare the Cu-loaded carboxylated carbon nanotube;
s3, preparing the Cu/Ag loaded carboxylated carbon nanotube: adding 1 part by weight of the Cu-loaded carboxylated carbon nanotube prepared in the step S2 into 100 parts by weight of water, adding 0.15 part by weight of silver nitrate, stirring and mixing for 10min, adding 4 parts by weight of glucose, heating to 98 ℃, stirring and reacting for 1h, centrifuging, washing and drying to prepare the Cu/Ag-loaded carboxylated carbon nanotube;
S4, modified TiO 2 /SiO 2 Preparation of nanoparticle-Cu/Ag loaded carboxylated carbon nanotubes: dissolving 11 parts by weight of tetrabutyl titanate and 6 parts by weight of tetraethoxysilane in 200 parts by weight of ethanol to obtain a mixed solution A; adding 8.5 parts by weight of the phosphorus-nitrogen flame retardant prepared in preparation example 3, 0.4 part by weight of glucose and 8.5 parts by weight of acetic acid into 200 parts by weight of 60wt% ethanol aqueous solution to obtain a mixed solution B; adding the mixed solution A into the mixed solution B, adding 8.5 parts by weight of the Cu/Ag loaded carboxylated carbon nanotubes prepared in the step S3, stirring and mixing for 15min, performing hydrothermal reaction in a reaction kettle, heating the reactor to 185 ℃, stirring and reacting for 4h, centrifuging, and drying to obtain modified TiO 2 /SiO 2 nanoparticle-Cu/Ag loaded carboxylated carbon nanotubes;
s5, preparing an antibacterial flame-retardant polyamide fiber material: 3 parts by weight of the modified TiO prepared in the step S4 2 /SiO 2 Adding the nano particle-Cu/Ag loaded carboxylated carbon nano tube and 100 parts by weight of caprolactam into a polyamide reactor for in-situ polymerization, wherein the in-situ polymerization condition is that the temperature is 230 ℃, the ring opening is 2.5 hours under the pressure of 0.5MPa, the polycondensation reaction is carried out for 3 hours under the temperature of 275 ℃, the composite slice is prepared, and the antibacterial flame-retardant polyamide fiber material is prepared by drying and melt spinning at the temperature of 265 ℃.
Comparative example 1
In comparison with example 3, the difference is that step S1 is not performed.
The method comprises the following steps:
s1, preparing a Cu-loaded carboxylated carbon nanotube: adding 1 part by weight of multi-wall carbon nano tube into 100 parts by weight of water, adding 0.3 part by weight of copper chloride, dropwise adding 6 parts by weight of ascorbic acid, heating to 80 ℃, stirring and reacting for 8.5 hours, centrifuging, washing and drying to obtain Cu-loaded carbon nano tube;
s2, preparing Cu/Ag-loaded carbon nanotubes: adding 1 part by weight of the Cu-loaded nanotube prepared in the step S1 into 100 parts by weight of water, adding 0.15 part by weight of silver nitrate, stirring and mixing for 10min, adding 4 parts by weight of glucose, heating to 98 ℃, stirring and reacting for 1h, centrifuging, washing and drying to prepare the Cu/Ag-loaded carbon nanotube;
s3, modified TiO 2 /SiO 2 Preparation of nanoparticle-Cu/Ag loaded carbon nanotubes: dissolving 11 parts by weight of tetrabutyl titanate and 6 parts by weight of tetraethoxysilane in 200 parts by weight of ethanol to obtain a mixed solution A; adding 8.5 parts by weight of the phosphorus-nitrogen flame retardant prepared in preparation example 3, 0.4 part by weight of glucose and 8.5 parts by weight of acetic acid into 200 parts by weight of 60wt% ethanol aqueous solution to obtain a mixed solution B; adding the mixed solution A into the mixed solution B, adding 8.5 parts by weight of the Cu/Ag loaded carboxylated carbon nanotubes prepared in the step S2, stirring and mixing for 15min, performing hydrothermal reaction in a reaction kettle, heating the reactor to 185 ℃, stirring and reacting for 4h, centrifuging, and drying to obtain modified TiO 2 /SiO 2 nanoparticle-Cu/Ag loaded carbon nanotubes;
s4, preparing an antibacterial flame-retardant polyamide fiber material: 3 parts by weight of the modified TiO prepared in the step S3 2 /SiO 2 Adding nano particles, cu/Ag-loaded carbon nano tubes and 100 parts by weight of caprolactam into a polyamide reactor for in-situ polymerization, wherein the in-situ polymerization condition is that ring opening is carried out for 2.5 hours at the temperature of 230 ℃ and the pressure of 0.5MPa, polycondensation is carried out for 3 hours at the temperature of 275 ℃, composite slices are prepared, and the composite slices are dried and melt-spun at the temperature of 265 ℃ to obtain the antibacterial flame-retardant polyamide fiber material.
Comparative example 2
In comparison with example 3, the difference is that step S2 is not performed.
The method comprises the following steps:
s1, preparing carboxylated carbon nanotubes: uniformly mixing 1 part by weight of multi-wall carbon nano tube and 90 parts by weight of mixed acid, carrying out ultrasonic treatment at 850W, heating to 47 ℃, stirring and reacting for 4 hours, diluting with 500 parts by weight of water, centrifuging, washing and drying to obtain carboxylated carbon nano tube;
the mixed acid is a mixture of concentrated sulfuric acid and concentrated hydrochloric acid, the volume ratio is 4.5:1, and the mass fraction of the concentrated sulfuric acid is more than 98%; the mass fraction of the concentrated hydrochloric acid is more than 37.5%;
s3, preparing the Ag-loaded carboxylated carbon nanotubes: adding 1 part by weight of the carboxylated carbon nanotube prepared in the step S1 into 100 parts by weight of water, adding 0.15 part by weight of silver nitrate, stirring and mixing for 10min, adding 4 parts by weight of glucose, heating to 98 ℃, stirring and reacting for 1h, centrifuging, washing and drying to prepare the Ag-loaded carboxylated carbon nanotube;
S3, modified TiO 2 /SiO 2 Preparation of nanoparticle-Ag-loaded carboxylated carbon nanotubes: dissolving 11 parts by weight of tetrabutyl titanate and 6 parts by weight of tetraethoxysilane in 200 parts by weight of ethanol to obtain a mixed solution A; adding 8.5 parts by weight of the phosphorus-nitrogen flame retardant prepared in preparation example 3, 0.4 part by weight of glucose and 8.5 parts by weight of acetic acid into 200 parts by weight of 60wt% ethanol aqueous solution to obtain a mixed solution B; adding the mixed solution A into the mixed solution B, adding 8.5 parts by weight of the Ag-loaded carboxylated carbon nanotubes prepared in the step S2, stirring and mixing for 15min, performing hydrothermal reaction in a reaction kettle, heating the reaction kettle to 185 ℃, stirring and reacting for 4h, centrifuging, and drying to obtain modified TiO 2 /SiO 2 nanoparticle-Ag-loaded carboxylated carbon nanotubes;
s4, preparing an antibacterial flame-retardant polyamide fiber material: 3 parts by weight of the modified TiO prepared in the step S3 2 /SiO 2 Adding nano particles-Ag-loaded carboxylated carbon nano tubes and 100 parts by weight of caprolactam into a polyamide reactor for in-situ polymerization, wherein the in-situ polymerization condition is that ring opening is carried out for 2.5 hours at the temperature of 230 ℃ and the pressure of 0.5MPa, polycondensation is carried out for 3 hours at the temperature of 275 ℃, composite slices are prepared, and the composite slices are dried and melt-spun at the temperature of 265 ℃ to obtain the antibacterial flame-retardant polyamide fiber material.
Comparative example 3
In comparison with example 3, the difference is that step S3 is not performed.
The method comprises the following steps:
s1, preparing carboxylated carbon nanotubes: uniformly mixing 1 part by weight of multi-wall carbon nano tube and 90 parts by weight of mixed acid, carrying out ultrasonic treatment at 850W, heating to 47 ℃, stirring and reacting for 4 hours, diluting with 500 parts by weight of water, centrifuging, washing and drying to obtain carboxylated carbon nano tube;
the mixed acid is a mixture of concentrated sulfuric acid and concentrated hydrochloric acid, the volume ratio is 4.5:1, and the mass fraction of the concentrated sulfuric acid is more than 98%; the mass fraction of the concentrated hydrochloric acid is more than 37.5%;
s2, preparing Cu-loaded carboxylated carbon nanotubes: adding 1 part by weight of the carboxylated carbon nanotube prepared in the step S1 into 100 parts by weight of water, adding 0.3 part by weight of copper chloride, dropwise adding 6 parts by weight of ascorbic acid, heating to 80 ℃, stirring and reacting for 8.5 hours, centrifuging, washing and drying to prepare the Cu-loaded carboxylated carbon nanotube;
s3, modified TiO 2 /SiO 2 Preparation of nanoparticle-Cu-loaded carboxylated carbon nanotubes: dissolving 11 parts by weight of tetrabutyl titanate and 6 parts by weight of tetraethoxysilane in 200 parts by weight of ethanol to obtain a mixed solution A; adding 8.5 parts by weight of the phosphorus-nitrogen flame retardant prepared in preparation example 3, 0.4 part by weight of glucose and 8.5 parts by weight of acetic acid into 200 parts by weight of 60wt% ethanol aqueous solution to obtain a mixed solution B; adding the mixed solution A into the mixed solution B, adding 8.5 parts by weight of the Cu-loaded carboxylated carbon nanotubes prepared in the step S2, stirring and mixing for 15min, performing hydrothermal reaction in a reaction kettle, heating the reactor to 185 ℃, stirring and reacting for 4h, centrifuging, and drying to obtain modified TiO 2 /SiO 2 nanoparticle-Cu-loaded carboxylated carbon nanotubes;
s4, preparing an antibacterial flame-retardant polyamide fiber material: 3 parts by weight of the modified TiO prepared in the step S3 2 /SiO 2 Adding nano particle-Cu loaded carboxylated carbon nano tube and 100 parts by weight of caprolactam into a polyamide reactor for in-situ polymerization, wherein the in-situ polymerization condition is that ring opening is carried out for 2.5 hours at the temperature of 230 ℃ and the pressure of 0.5MPa, polycondensation is carried out for 3 hours at the temperature of 275 ℃, composite slices are prepared, and then drying and melting are carried out at the temperature of 265 DEG CAnd preparing the antibacterial flame-retardant polyamide fiber material by melt spinning.
Comparative example 4
In comparison with example 3, the difference is that tetraethyl titanate is not added in step S4.
The method comprises the following steps:
s4, modified SiO 2 Preparation of nanoparticle-Cu/Ag loaded carboxylated carbon nanotubes: 17 parts by weight of ethyl orthosilicate is dissolved in 200 parts by weight of ethanol to obtain a mixed solution A; adding 8.5 parts by weight of the phosphorus-nitrogen flame retardant prepared in preparation example 3, 0.4 part by weight of glucose and 8.5 parts by weight of acetic acid into 200 parts by weight of 60wt% ethanol aqueous solution to obtain a mixed solution B; adding the mixed solution A into the mixed solution B, adding 8.5 parts by weight of the Cu/Ag loaded carboxylated carbon nanotubes prepared in the step S3, stirring and mixing for 15min, performing hydrothermal reaction in a reaction kettle, heating the reactor to 185 ℃, stirring and reacting for 4h, centrifuging, and drying to obtain modified SiO 2 nanoparticle-Cu/Ag loaded carboxylated carbon nanotubes.
Comparative example 5
In comparison with example 3, the difference is that no ethyl orthosilicate was added in step S4.
The method comprises the following steps:
s4, modified TiO 2 Preparation of nanoparticle-Cu/Ag loaded carboxylated carbon nanotubes: 17 parts by weight of tetrabutyl titanate is dissolved in 200 parts by weight of ethanol to obtain a mixed solution A; adding 8.5 parts by weight of the phosphorus-nitrogen flame retardant prepared in preparation example 3, 0.4 part by weight of glucose and 8.5 parts by weight of acetic acid into 200 parts by weight of 60wt% ethanol aqueous solution to obtain a mixed solution B; adding the mixed solution A into the mixed solution B, adding 8.5 parts by weight of the Cu/Ag loaded carboxylated carbon nanotubes prepared in the step S3, stirring and mixing for 15min, performing hydrothermal reaction in a reaction kettle, heating the reactor to 185 ℃, stirring and reacting for 4h, centrifuging, and drying to obtain modified TiO 2 nanoparticle-Cu/Ag loaded carboxylated carbon nanotubes.
Comparative example 6
In comparison with example 3, the difference is that in step S4, tetraethyl orthosilicate and tetraethyl titanate are not added.
The method comprises the following steps:
s4, preparing the modified Cu/Ag loaded carboxylated carbon nanotube: adding 8.5 parts by weight of the phosphorus-nitrogen flame retardant prepared in the preparation example 3, 0.4 part by weight of glucose and 8.5 parts by weight of acetic acid into 200 parts by weight of 60wt% ethanol water solution, adding 8.5 parts by weight of the Cu/Ag loaded carboxylated carbon nanotubes prepared in the step S3, stirring and mixing for 15min, performing hydrothermal reaction in a reaction kettle, heating the reactor to 185 ℃, stirring and reacting for 4h, centrifuging, and drying to obtain the modified Cu/Ag loaded carboxylated carbon nanotubes.
Comparative example 7
The difference from example 3 is that the phosphorus-nitrogen flame retardant was not added in step S4.
The method comprises the following steps:
s4, modified TiO 2 /SiO 2 Preparation of nanoparticle-Cu/Ag loaded carboxylated carbon nanotubes: dissolving 11 parts by weight of tetrabutyl titanate and 6 parts by weight of tetraethoxysilane in 200 parts by weight of ethanol to obtain a mixed solution A; adding 0.4 weight part of glucose and 8.5 weight parts of acetic acid into 200 weight parts of 60 weight percent ethanol water solution to obtain a mixed solution B; adding the mixed solution A into the mixed solution B, adding 8.5 parts by weight of the Cu/Ag loaded carboxylated carbon nanotubes prepared in the step S3, stirring and mixing for 15min, performing hydrothermal reaction in a reaction kettle, heating the reactor to 185 ℃, stirring and reacting for 4h, centrifuging, and drying to obtain modified TiO 2 /SiO 2 nanoparticle-Cu/Ag loaded carboxylated carbon nanotubes.
Comparative example 8
The difference compared with example 3 is that the phosphorus-nitrogen based flame retardant in step S4 is replaced with 1, 3-propanediamine.
The method comprises the following steps:
s4, modified TiO 2 /SiO 2 Preparation of nanoparticle-Cu/Ag loaded carboxylated carbon nanotubes: dissolving 11 parts by weight of tetrabutyl titanate and 6 parts by weight of tetraethoxysilane in 200 parts by weight of ethanol to obtain a mixed solution A; adding 8.5 parts by weight of 1, 3-propylene diamine, 0.4 part by weight of glucose and 8.5 parts by weight of acetic acid into 200 parts by weight of 60wt% ethanol aqueous solution to obtain a mixed solution B; adding the mixed solution A into the mixed solution B, and adding 8.5 parts by weight of the Cu/Ag loaded carboxyl prepared in the step S3 Dissolving carbon nano tube, stirring and mixing for 15min, performing hydrothermal reaction in a reaction kettle, heating the reactor to 185 ℃, stirring and reacting for 4h, centrifuging, and drying to obtain modified TiO 2 /SiO 2 nanoparticle-Cu/Ag loaded carboxylated carbon nanotubes.
Comparative example 9
The difference compared with example 3 is that the carboxylated carbon nanotubes loaded with Cu/Ag are not added in step S4.
The method comprises the following steps:
s4, modified TiO 2 /SiO 2 Preparation of nanoparticle-Cu/Ag loaded carboxylated carbon nanotubes: dissolving 11 parts by weight of tetrabutyl titanate and 6 parts by weight of tetraethoxysilane in 200 parts by weight of ethanol to obtain a mixed solution A; adding 8.5 parts by weight of the phosphorus-nitrogen flame retardant prepared in preparation example 3, 0.4 part by weight of glucose and 8.5 parts by weight of acetic acid into 200 parts by weight of 60wt% ethanol aqueous solution to obtain a mixed solution B; adding the mixed solution A into the mixed solution B, stirring and mixing for 15min, performing hydrothermal reaction in a reaction kettle, heating the reactor to 185 ℃, stirring and reacting for 4h, centrifuging, and drying to obtain the modified TiO 2 /SiO 2 And (3) nanoparticles.
Comparative example 10
The difference compared with example 3 is that the TiO is modified in step S5 2 /SiO 2 The nanoparticle-Cu/Ag loaded carboxylated carbon nanotubes are replaced by an equivalent amount of Cu/Ag loaded carboxylated carbon nanotubes.
The method comprises the following steps:
s5, preparing an antibacterial flame-retardant polyamide fiber material: adding 3 parts by weight of the Cu/Ag loaded carboxylated carbon nano tube prepared in the step S3 and 100 parts by weight of caprolactam into a polyamide reactor for in-situ polymerization, wherein the in-situ polymerization condition is that the temperature is 230 ℃, the ring opening is 2.5 hours under the condition of 0.5MPa, the polycondensation is carried out for 3 hours at the temperature of 275 ℃, the composite slice is prepared, and the composite slice is dried and melt-spun at the temperature of 265 ℃ to prepare the antibacterial flame-retardant polyamide fiber material.
Test example 1
Antibacterial property tests were performed on the antibacterial flame-retardant polyamide fiber materials prepared in examples 1 to 3 and comparative examples 1 to 10 of the present invention. The results are shown in Table 1.
The oscillation method and the colony counting method are adopted: reference to evaluation of antimicrobial Properties of textiles section 3: the test for antibacterial activity was carried out by the shaking method (GB/T20944.3-2008).
And (3) bacteriostasis circle experiment: pressing the obtained antibacterial flame-retardant polyamide fiber material into round shape with diameter of 1cm, sterilizing with ultraviolet lamp for 30min, and diluting bacterial solutions of Escherichia coli (ATCC 25922) and Staphylococcus aureus (ATCC 25923) to 10 respectively 8 cfu/mL, taking 100 mu L of the solid culture substrate, uniformly spreading bacterial liquid by using a spreader, placing round fibers in the center of a culture dish, finally placing the fibers in a constant temperature incubator at 37 ℃ for culturing for 12 hours, taking out the fibers, and testing the diameter (mm) of a bacteriostasis zone.
TABLE 1
As can be seen from the above table, the antibacterial flame-retardant polyamide fiber material prepared in examples 1 to 3 of the present invention has excellent antibacterial properties.
Test example 2 cytotoxicity
Cytotoxicity test was performed on the antibacterial flame retardant polyamide fiber materials prepared in examples 1 to 3 and comparative examples 1 to 10 of the present invention. Mouse embryo fibroblast (3T 3 cell) is used as experimental cell, and the cell is cultured to reach the cell concentration of 5×10 after cell plating 4 10mg of the antibacterial flame-retardant polyamide fiber material was added to an orifice plate (blank group: 3T3 cells and DMEM medium) after sterilization, and 100. Mu.L of DMEM (dulbecco's modified eagle medium) medium was added to each sample group, and after culturing for 24 hours in an incubator, the medium was taken out, dried by suction, washed, 100. Mu.L of DMEM medium was added, and then 0.02mL of MTT (thiazole blue) stain was added under a dark condition, and after culturing for 4 hours in the incubator, all the liquid was aspirated, 150mL of dimethyl sulfoxide was added, and shaking reaction was performed for 10 minutes, absorbance at 490nm and 570nm was measured, to calculate cell activity (%). The results are shown in Table 2.
TABLE 2
As can be seen from the above table, the antibacterial flame-retardant polyamide fiber materials prepared in examples 1 to 3 of the present invention have lower cytotoxicity.
Test example 3
The antibacterial flame-retardant polyamide fiber materials prepared in examples 1 to 3 and comparative examples 1 to 10 of the present invention were subjected to a comprehensive performance test. The results are shown in Table 3.
Mechanical property test: the samples were dried and injection molded into standard bars and tested for mechanical properties using a universal material tester according to ISO 527-1-2012.
Limiting Oxygen Index (LOI): tested according to GB/T2406-1993 standard.
Vertical combustion experiments were carried out according to GB 4096-1984.
TABLE 3 Table 3
Group of Tensile Strength (MPa) Elongation at break (%) LOI value (%) Flame retardant rating
Example 1 93.9 106.7 33.5 V-0
Example 2 94.5 103.2 33.9 V-0
Example 3 95.1 107.5 34.2 V-0
Comparative example 1 90.1 102.7 32.7 V-0
Comparative example 2 92.3 103.4 32.9 V-0
Comparative example 3 91.7 102.8 32.5 V-0
Comparative example 4 90.8 100.5 32.3 V-0
Comparative example 5 89.4 98.3 29.8 V-1
Comparative example 6 88.2 95.7 28.5 V-1
Comparative example 7 87.6 92.4 25.7 V-2
Comparative example 8 88.4 95.8 26.1 V-2
Comparative example 9 85.1 89.1 32.3 V-0
Comparative example 10 86.6 91.2 24.5 V-2
As can be seen from the above table, the antibacterial flame-retardant polyamide fiber material prepared in the embodiments 1-3 of the invention has better flame retardant property and mechanical property.
Test example 4
The antibacterial flame-retardant polyamide fiber materials prepared in examples 1 to 3 and comparative examples 1 to 10 of the present invention were subjected to a water washing resistance test, and after washing the prepared materials 50 times, the tensile strength and the LOI value were measured. The results are shown in Table 4.
TABLE 4 Table 4
Group of Tensile Strength (MPa) LOI value (%)
Example 1 92.3 32.7
Example 2 93.0 33.0
Example 3 94.1 33.7
Comparative example 1 86.7 28.8
Comparative example 2 90.4 30.2
Comparative example 3 89.5 29.9
Comparative example 4 87.8 29.4
Comparative example 5 86.5 26.8
Comparative example 6 85.1 24.5
Comparative example 7 83.9 23.2
Comparative example 8 84.5 24.5
Comparative example 9 84.1 29.2
Comparative example 10 81.0 21.1
As shown in the table above, the antibacterial flame-retardant polyamide fiber material prepared in the examples 1-3 of the invention has better water-washing resistance.
Comparative example 1 compared to example 3, step S1 was not performed. The mechanical property is reduced, the washing resistance is reduced, the antibacterial property is reduced, and the cytotoxicity is improved. The multiwall carbon nanotube is relatively active, and after the mixed acid treatment, a large number of carboxyl groups are formed on the surface, so that on one hand, cu ions and Ag ions are conveniently complexed, and the capabilities of resisting viruses, fungi and the like are improved; on the other hand, the carboxyl of the carboxyl modified multiwall carbon nanotube can react with the terminal amino group in the polyamide molecule in a condensation manner, and is grafted to a molecular chain, so that the dispersibility of the carboxyl modified multiwall carbon nanotube is improved, and the interfacial interaction of the composite fiber material is enhanced, so that the elastic modulus, tensile strength and thermal stability of the composite fiber are obviously improved.
Comparative example 2 compared to example 3, step S2 was not performed. Comparative example 3 in comparison with example 3, step S3 was not performed. Comparative example 9 compared with example 3, the Cu/Ag-loaded carboxylated carbon nanotubes were not added in step S4. The antibacterial property is lowered. According to the invention, the multiwall carbon nanotube is complexed with Cu ions and Ag ions, and the multiwall carbon nanotube can be reduced and loaded to form simple substance Cu and Ag respectively under the action of reducing agent ascorbic acid and glucose, so that the multiwall carbon nanotube has good dispersibility, is not easy to agglomerate simple substance Cu and Ag, avoids the situation that ions are greatly overflowed due to the fact that the direct addition of simple substance Cu and Ag has large surface area and unstable energy and is easy to agglomerate and oxidize, and threatens the health of a human body, and meanwhile, the addition of two metals has antibacterial synergistic effect, so that the sterilizing effect on gram-positive bacteria and gram-negative bacteria is greatly improved, and the antibacterial and antifungal capabilities are good.
In comparative examples 4 and 5, in comparison with example 3, tetraethyl titanate or tetraethyl orthosilicate was not added in step S4. Comparative example 6 in comparison with example 3, no tetraethyl orthosilicate and no tetraethyl titanate were added in step S4. Comparative example 10 compared with example 3, the TiO was modified in step S5 2 /SiO 2 The nanoparticle-Cu/Ag loaded carboxylated carbon nanotubes are replaced by an equivalent amount of Cu/Ag loaded carboxylated carbon nanotubes. Reduced mechanical properties, reduced water-washing resistance and reduced antibacterial propertiesAnd the flame retardance is lowered. Nanometer TiO 2 The energy gap of 3.2eV is provided, and the ultraviolet absorption effect is strong; nano SiO 2 The ultraviolet light can be almost scattered, the ultraviolet light shielding property is excellent, meanwhile, the thermal stability of the two inorganic nano materials is good, and the inorganic nano materials are fixedly assembled on the surface of the polyamide fiber, so that a compact ultraviolet aging resistant coating can be formed, the ultraviolet damage of the fiber is weakened, the ultraviolet aging resistant capability of the fiber is improved, and meanwhile, the nano TiO 2 Also has good photocatalysis antibacterial capability and plays a good synergistic antibacterial role. However, in general, the inorganic nano material has small particle size and large specific surface area, is extremely easy to agglomerate, is not easy to disperse uniformly during direct polymerization, is easy to cause blockage of a spinneret plate, affects continuous production, reduces the performance of fibers, and reduces the mechanical properties of the fibers.
In comparative example 7, in comparison with example 3, no phosphorus-nitrogen flame retardant was added in step S4. Comparative example 8 in comparison with example 3, the phosphorus-nitrogen based flame retardant in step S4 was replaced with 1, 3-propanediamine. The mechanical property is reduced, the water washing resistance is reduced, the antibacterial property is reduced, the cytotoxicity is improved, and the flame retardance is reduced. The phosphorus-nitrogen flame retardant prepared by the invention contains multiple active groups, has good flame retardant property, and can be used for preparing nano SiO in the later period 2 The Si-O, si-C protective layer can be formed in the combustion process, thereby realizing the ternary synergistic flame retardant effect, solving the defects of single flame retardant element and unobvious effect of the halogen-free flame retardant, along with high stability, and being capable of being used as a bridge to connect modified TiO 2 /SiO 2 The nano particles and the carboxylated carbon nano tubes loaded with Cu/Ag are connected to the polyamide material through reaction, so that the dispersibility of the inorganic material is improved, and a good improvement effect is achieved.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (10)

1. Antibacterial flame-retardant polyamideA process for preparing fibrous material includes such steps as preparing carboxylated carbon nanotubes, loading Cu and Ag, and mixing it with TiO modified by P-N flame-retarding agent 2 /SiO 2 Compounding the nano particles, adding the nano particles into caprolactam for in-situ polymerization to prepare a composite slice, drying, and preparing the antibacterial flame-retardant polyamide fiber material through a melt spinning method;
the structural formula of the phosphorus-nitrogen flame retardant is shown as formula I:
a formula I;
wherein r=c1-C4 is a linear alkyl chain.
2. The method of manufacturing according to claim 1, comprising the steps of:
s1, preparing carboxylated carbon nanotubes: uniformly mixing the multiwall carbon nanotube and the mixed acid, performing ultrasonic heating and stirring reaction, adding water for dilution, centrifuging, washing and drying to obtain the carboxylated carbon nanotube;
s2, preparing Cu-loaded carboxylated carbon nanotubes: adding the carboxylated carbon nanotube prepared in the step S1 into water, adding soluble copper salt, dropwise adding a reducing agent, heating and stirring for reaction, centrifuging, washing and drying to prepare the Cu-loaded carboxylated carbon nanotube;
s3, preparing the Cu/Ag loaded carboxylated carbon nanotube: adding the Cu-loaded carboxylated carbon nanotube prepared in the step S2 into water, adding silver nitrate, stirring and mixing uniformly, adding glucose, heating and stirring for reaction, centrifuging, washing and drying to prepare the Cu/Ag-loaded carboxylated carbon nanotube;
S4, modified TiO 2 /SiO 2 Preparation of nanoparticle-Cu/Ag loaded carboxylated carbon nanotubes: dissolving titanium alkoxide and alkyl orthosilicate in ethanol to obtain a mixed solution A; adding a phosphorus-nitrogen flame retardant, glucose and acetic acid into an ethanol water solution to obtain a mixed solution B; adding the mixed solution A into the mixed solution B, and adding the Cu/Ag loaded carboxylated carbon nano-particles prepared in the step S3Tube, stirring and mixing uniformly, heating and stirring to react, centrifuging and drying to obtain modified TiO 2 /SiO 2 nanoparticle-Cu/Ag loaded carboxylated carbon nanotubes;
s5, preparing an antibacterial flame-retardant polyamide fiber material: the modified TiO prepared in the step S4 2 /SiO 2 Adding nano particles-Cu/Ag loaded carboxylated carbon nano tubes and caprolactam into a polyamide reactor for in-situ polymerization, preparing composite slices, drying, and preparing the antibacterial flame-retardant polyamide fiber material through melt spinning.
3. The preparation method according to claim 2, wherein in the step S1, the mixed acid is a mixture of concentrated sulfuric acid and concentrated hydrochloric acid, the volume ratio is 4-5:1, and the mass fraction of the concentrated sulfuric acid is >98%; the mass fraction of the concentrated hydrochloric acid is more than 37.5%, and the mass ratio of the multiwall carbon nanotubes to the mixed acid is 1:80-100, wherein the heating temperature is 45-50 ℃, the ultrasonic power is 700-1000W, and the time is 3-5h.
4. The preparation method according to claim 2, wherein the mass ratio of the carboxylated carbon nanotubes, the soluble copper salt and the reducing agent in the step S2 is 1:0.2-0.4:5-7, wherein the soluble copper salt is selected from at least one of copper chloride, copper nitrate and copper sulfate, the reducing agent is selected from at least one of ascorbic acid and sodium ascorbate, and the temperature of the heating and stirring reaction is 75-85 ℃ and the time is 7-10h.
5. The preparation method according to claim 2, wherein in the step S3, the mass ratio of the carboxylated carbon nanotubes loaded with Cu, silver nitrate and glucose is 1:0.1-0.2:3-5, the temperature of the heating and stirring reaction is 95-100 ℃, and the time is 0.5-1h.
6. The method according to claim 2, wherein the titanium alkoxide in step S4 is at least one selected from the group consisting of tetraethyl titanate, tetrabutyl titanate, tetraisopropyl titanate, titanium tetrachloride and titanium trichloride; the alkyl orthosilicate is methyl orthosilicate or ethyl orthosilicate, and the mass ratio of the titanium alkoxide, the alkyl orthosilicate, the phosphorus-nitrogen flame retardant, glucose, acetic acid and the carboxylated carbon nano tube loaded with Cu/Ag is 10-12:5-7:7-10:0.3-0.5:7-10:7-10; the temperature of the heating and stirring reaction is 170-200 ℃, the time is 3-5h, and the concentration of the ethanol water solution is 55-65wt%.
7. The method of claim 6, wherein the phosphorus-nitrogen flame retardant is prepared by the following steps: and (3) reacting hexachlorocyclotriphosphazene, alkali and diamine compound to obtain the phosphorus-nitrogen flame retardant.
8. The method of claim 7, wherein the mole ratio of hexachlorocyclotriphosphazene, base and diamine compound is 1:3-5:6-6.1, wherein the reaction temperature is 35-45 ℃ and the reaction time is 3-5h.
9. The method according to claim 2, wherein the modified TiO in step S5 2 /SiO 2 The mass ratio of the nano particle-Cu/Ag loaded carboxylated carbon nano tube to caprolactam is 2-4:90-110, wherein the in-situ polymerization condition is that ring opening is carried out for 2-3 hours at the temperature of 220-240 ℃ and the pressure of 0.3-0.5MPa, polycondensation is carried out for 2-4 hours at the temperature of 270-280 ℃, and the temperature of melt spinning is 255-275 ℃.
10. An antibacterial flame retardant polyamide fiber material produced by the production method according to any one of claims 1 to 9.
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