CN118087073A - Flame-retardant, antibacterial and antiviral PET (polyethylene terephthalate) fiber and preparation method thereof - Google Patents
Flame-retardant, antibacterial and antiviral PET (polyethylene terephthalate) fiber and preparation method thereof Download PDFInfo
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- CN118087073A CN118087073A CN202211500507.4A CN202211500507A CN118087073A CN 118087073 A CN118087073 A CN 118087073A CN 202211500507 A CN202211500507 A CN 202211500507A CN 118087073 A CN118087073 A CN 118087073A
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- antibacterial
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- retardant
- phosphorus
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- 230000000840 anti-viral effect Effects 0.000 title claims abstract description 102
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000003063 flame retardant Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
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- 239000008367 deionised water Substances 0.000 claims description 20
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- MORLYCDUFHDZKO-UHFFFAOYSA-N 3-[hydroxy(phenyl)phosphoryl]propanoic acid Chemical compound OC(=O)CCP(O)(=O)C1=CC=CC=C1 MORLYCDUFHDZKO-UHFFFAOYSA-N 0.000 claims description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910001431 copper ion Inorganic materials 0.000 claims description 6
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 6
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- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 238000005886 esterification reaction Methods 0.000 description 15
- 238000006068 polycondensation reaction Methods 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
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- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
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- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 3
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- MQUQNUAYKLCRME-INIZCTEOSA-N N-tosyl-L-phenylalanyl chloromethyl ketone Chemical compound C1=CC(C)=CC=C1S(=O)(=O)N[C@H](C(=O)CCl)CC1=CC=CC=C1 MQUQNUAYKLCRME-INIZCTEOSA-N 0.000 description 1
- 108010019160 Pancreatin Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- D01F6/92—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 polyesters
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to a flame-retardant, antibacterial and antiviral PET fiber and a preparation method thereof, wherein the fiber mainly comprises a PET matrix and self-assembled micro-nano structure Cu 2 O particles dispersed in the PET matrix; the self-assembled micro-nano structure Cu 2 O particles are micron-sized spheres formed by assembling a plurality of nano-sized Cu 2 O particles, wherein the assembling utilizes physical and/or chemical acting forces among phosphorus-nitrogen hyperbranched polymers wrapped on the surfaces of the nano-sized Cu 2 O particles; the preparation method comprises the following steps: and uniformly mixing the polyester melt and the liquid functional additive, performing tackifying treatment, and spinning the mixture after the tackifying treatment to obtain the flame-retardant, antibacterial and antiviral PET fiber. The product of the invention has excellent effects of flame retardance, antibiosis and antivirus, and has good spinnability and mechanical property.
Description
Technical Field
The invention belongs to the technical field of multifunctional PET fibers, and relates to a flame-retardant, antibacterial and antiviral PET fiber and a preparation method thereof.
Background
PET fibers are the most widely used and most consumed synthetic fibers in daily life and textile fields. PET fiber products are widely applied to the fields of textile, packaging, medical appliances and the like, but the functions of pure PET fibers are relatively single, and the molecular structure of PET lacks polar groups and chemical active functional groups, so that modification of PET molecules is relatively difficult. The PET fiber is generally subjected to blending modification by adopting a method of adding functional components in the processing process of the PET fiber, so that the PET fiber is endowed with more functionality.
Wherein the flame retardant function and the antibacterial function are hot spots for functional fiber research. The flame-retardant fiber can reduce the problems of inflammability, long flame-retardant time and the like of the traditional textile, reduce the possibility of fire occurrence and expansion, and has higher value and significance for improving public safety.
The antibacterial fiber can effectively resist the breeding of bacteria and reduce the possibility of infection, and the antiviral fiber can further resist the invasion of viruses and has an important effect on relieving diseases of human beings infected by bacteria or viruses.
At present, the single-function fiber has more researches, but the success cases of the fiber with three functional composite functions are less, and the technical difficulties are that a plurality of different modifiers are added for melt blending spinning, so that the modifiers are easy to interfere and conflict with each other, the functionality of the fiber is weakened or even vanished, the modifiers are easy to react with each other, the agglomeration of modified powder is enhanced, the complexity of a melt structure and a form is improved, the spinning difficulty is greatly improved, the spinnability is reduced, and the problems of broken ends, reduced product strength, poor dyeing uniformity and the like are easy to occur.
Therefore, research on a flame-retardant, antibacterial and antiviral PET fiber and a preparation method thereof is of great significance in order to solve the problems existing in the prior art.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a flame-retardant, antibacterial and antiviral PET fiber and a preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a flame-retardant, antibacterial and antiviral PET fiber mainly comprises a PET matrix and self-assembled micro-nano structure Cu 2 O particles dispersed in the PET matrix;
The self-assembled micro-nano structure Cu 2 O particles are micron-sized spheres formed by assembling a plurality of nano-sized Cu 2 O particles, wherein the assembling utilizes physical and/or chemical acting forces among phosphorus-nitrogen hyperbranched polymers wrapped on the surfaces of the nano-sized Cu 2 O particles;
the structural formula of the phosphorus-nitrogen hyperbranched polymer is as follows:
Wherein the wavy line represents a phosphorus-nitrogen hyperbranched polymer that can be further reacted to form more branching units; r has the structure of
The LOI of the fabric made of flame-retardant, antibacterial and antiviral PET fibers is not lower than 32.0%, the damage length is not more than 15.0cm, the burning time is not more than 15s, and the peak value of the heat release rate is not more than 200kw/m 2;
The antibacterial rate of the flame-retardant, antibacterial and antiviral PET fiber to escherichia coli is more than 99.99 percent, the antibacterial rate to staphylococcus aureus is more than 99.99 percent, and the antibacterial rate to candida albicans is more than or equal to 78 percent;
the antiviral activity value of the flame-retardant, antibacterial and antiviral PET fiber is more than or equal to 3.49, and the antiviral activity rate is more than or equal to 99.97%.
As a preferable technical scheme:
The content of the self-assembled micro-nano structure Cu 2 O particles in the flame-retardant, antibacterial and antiviral PET fiber is 0.4-1.2 wt%.
The flame-retardant, antibacterial and antiviral PET fiber has the average particle size of nano Cu 2 O particle of 6-8 nm and the average particle size of micron sphere of 1-1.4 microns.
The flame-retardant, antibacterial and antiviral PET fiber has branching degree DB of the phosphorus-nitrogen hyperbranched polymer of 0.45-0.55 and number average molecular weight Mn of 35000-55000 g/mol.
The flame-retardant, antibacterial and antiviral PET fiber has the specific surface area of the self-assembled micro-nano structure Cu 2 O particles of 50-80 m 2·g-1, and the content of the phosphorus-nitrogen hyperbranched polymer in the self-assembled micro-nano structure Cu 2 O particles of 22.8-24.0wt%.
The invention also provides a preparation method of the flame-retardant, antibacterial and antiviral PET fiber, which comprises the steps of uniformly mixing polyester melt and liquid functional additives, performing tackifying treatment, and spinning the mixture after the tackifying treatment to obtain the flame-retardant, antibacterial and antiviral PET fiber;
the preparation process of the liquid functional additive comprises the following steps: firstly, synthesizing a phosphorus-nitrogen hyperbranched polymer by using 2-carboxyethyl phenyl phosphinic acid and tris (hydroxyethyl) isocyanurate as raw materials through an A 2+B3 method, then adding the phosphorus-nitrogen hyperbranched polymer into a polyether amine aqueous solution to form a uniform and transparent reaction system, then dropwise adding a copper salt solution into the reaction system under the stirring condition, continuing stirring, and finally dropwise adding an ascorbic acid aqueous solution into the reaction system under the stirring condition, and continuing stirring to obtain the liquid functional additive.
As a preferable technical scheme:
the preparation method of the flame-retardant, antibacterial and antiviral PET fiber comprises the following steps of:
(1) Synthesizing a phosphorus-nitrogen hyperbranched polymer;
Firstly, mixing 2-carboxyethyl phenyl phosphinic acid, trishydroxyethyl isocyanurate and H 2 O according to the ratio of 0.1-0.2 mol to 0.1-0.15 mol to 100mL, heating to 120-150 ℃, preserving heat for a period of time until more than 80% of H 2 O is steamed out, vacuumizing to 0.098MPa, heating to 145-165 ℃ at the same time, and preserving heat and pressure for 2-2.5H to obtain the phosphorus-nitrogen hyperbranched polymer;
(2) Preparing a polyether amine aqueous solution;
Adding polyether amine into deionized water, magnetically stirring at 20-30 ℃ and fully dissolving to form polyether amine aqueous solution;
(3) The stirring speed is kept unchanged, the temperature is kept unchanged, and the phosphorus-nitrogen hyperbranched polymer is added into the polyether amine aqueous solution to form a uniform and transparent reaction system;
(4) Dropwise adding copper salt solution into the reaction system through a constant pressure dropping funnel under the stirring condition, and continuously stirring for 1h;
(5) And (3) dropwise adding the ascorbic acid aqueous solution into the reaction system through a constant pressure dropping funnel under the stirring condition, and continuing stirring for 2-3 h to obtain the liquid functional additive.
The preparation method of the flame-retardant, antibacterial and antiviral PET fiber comprises the following steps that in the step (2), polyether amine is polyether amine M-600; the mass ratio of the polyetheramine to the deionized water is 1:4-6; the stirring speed is 300-400 r/min;
In the step (3), the mass ratio of the phosphorus-nitrogen hyperbranched polymer to the polyetheramine is 1:15-20;
In the step (4), the stirring speed is 300-400 r/min; the concentration of the copper salt solution is 0.15-0.175M, and the copper salt solution consists of cupric acetate monohydrate and deionized water; the dropping speed is 3-4 mL/min; the mass ratio of the copper salt solution to the phosphorus-nitrogen hyperbranched polymer is 1:2-3;
in the step (5), the stirring speed is 300-400 r/min; the concentration of the ascorbic acid aqueous solution is 0.7-0.875M; the molar ratio of the ascorbic acid to the copper ions in the reaction system is 1:2; the dropping rate is 3-4 mL/min.
According to the preparation method of the flame-retardant, antibacterial and antiviral PET fiber, the intrinsic viscosity of the mixture after tackifying treatment is 0.60-0.70 dL/g; the spinning process is as follows: filtering the mixture after tackifying treatment by a melt filter, conveying the mixture to a melt cooler by a melt booster pump, cooling to 277-280 ℃, conveying the mixture to a spinning box by a multistage static mixer, metering and filtering the mixture, extruding the mixture by a spinneret plate, cooling, oiling, stretching and shaping the mixture, and winding the mixture to obtain the flame-retardant, antibacterial and antiviral PET fiber.
According to the preparation method of the flame-retardant, antibacterial and antiviral PET fiber, the feeding amount of a metering pump in a spinning box body is 55-60 g/min, the pressure of a spinning component is 180-200 bar, the temperature of the spinning box body is 275-295 ℃, the spinneret plate is 36-hole spinneret plates, and the hole specification is 0.3 multiplied by 0.75mm; the cooling adopts a spinning side air blowing device with the air speed of 0.4-0.5 m/s for blowing and cooling; the temperature of the first hot roller is 70-90 ℃ during stretching and shaping, the temperature of the second hot roller is 130-180 ℃, and the stretching multiple is 3.0-4.0.
The preparation method of the flame-retardant, antibacterial and antiviral PET fiber comprises the following steps of:
(1) Esterification reaction;
Preparing ethylene glycol and refined terephthalic acid with a molar ratio of 1.3-1.8:1 into slurry, feeding the mixed slurry into an esterification kettle by adopting a metering pump, and esterifying to form an oligomer, wherein the esterification reaction temperature is 250-267 ℃, the pressure is 0.27-0.35 MPa, and the time is 2-3 h;
(2) Performing polycondensation reaction;
Adding the oligomer and a catalyst into a polycondensation reaction kettle, and carrying out polycondensation reaction under the negative pressure condition with the absolute pressure of below 80Pa, wherein the reaction temperature is 275-285 ℃, the reaction time is 1.5-2 h, and the polyester is obtained, wherein the catalyst is any one of antimony trioxide, ethylene glycol antimony or antimony acetate, and the addition amount is 250-300 ppm of the mass of the oligomer.
The principle of the invention is as follows:
The hyperbranched polymer added in the process of synthesizing the liquid functional additive can be used as a template agent in the process of synthesizing Cu 2 O to promote the formation of a micro-nano structure, and in addition, the hyperbranched polymer reserved on the surface of Cu 2 O after the preparation is finished can be used as an organic matter to enhance the compatibility between the liquid functional additive and a polyester matrix. In the spinning process, a melt direct spinning method is adopted, and the liquid functional additive is added into the spinning melt to facilitate uniform mixing between the liquid functional additive and the spinning melt. Meanwhile, the micro-nano structure Cu 2 O functional particles in the liquid functional additive have excellent antibacterial and antiviral properties, compared with single nano-size or single micro-size Cu 2 O, the micro-nano structure Cu 2 O functional particles avoid the problem of nano-size aggregation, and meanwhile, the disadvantage of insufficient specific surface area of the pure micro-size is overcome, so that the liquid functional additive has more excellent antibacterial and antiviral properties, the phosphorus-containing hyperbranched polymer on the surface of the particles has excellent flame retardant property, the effect of adding various single functional additives can be achieved by adding the single liquid functional additive, the mutual interference and collision of the modifiers can be avoided, further, the functional weakening of fibers is avoided, and the problems that the modified powder aggregation is enhanced, the melt structure and the form complexity are improved, the spinning difficulty is greatly improved, the spinnability is reduced, the breakage is easy to occur, the product strength is reduced, the dyeing uniformity is poor and the like due to the fact that the modifiers are easy to react with each other are avoided.
The beneficial effects are that:
the product of the invention has excellent flame-retardant, antibacterial and antiviral effects; the method has simple process.
Drawings
FIG. 1 is a schematic diagram of the composition and structure of micro-nano structure Cu 2 O;
fig. 2 is an antibacterial dot pattern of the PET fiber of comparative example 1 and examples 1 to 3 and a blank sample.
Detailed Description
The application is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
The test methods involved in the following examples and comparative examples are as follows:
Test method of LOI value of fabric: the method comprises the steps of weaving fibers into a sock leg (fabric) by adopting a sock weaving machine, adopting a JF-3 type oxygen index instrument, referring to a test standard GB/T5454-1997 of oxygen index method for testing the combustion performance of textiles, and taking the fabric with the size of 150 multiplied by 58mm as a test sample; during testing, the test sample to be tested is placed in a mixed air flow of nitrogen and oxygen, and the minimum oxygen concentration for maintaining flame burning of the fabric is recorded.
The test method for the continuous burning time, the damage length and the molten drop condition of the fabric comprises the following steps: the method comprises the steps of weaving fibers into a sock leg (fabric) by adopting a sock weaving machine, performing a vertical combustion test by referring to a test standard GB/T5454-1997 vertical method for testing the combustion performance of textiles, and taking the fabric with the size of 300 multiplied by 80mm as a test sample; the test process is to fix the sample on the U-shaped clamp, the height of flame is 4cm when the igniter ignites under the sample, and the continuous burning time, damage length and molten drop condition of the fabric in the test process are recorded.
Cone calorimetric test: the tackified mixture (melt) was prepared into test plaques of dimensions 100X 3mm using a vertical injection molding machine, and then tested according to ISO 5660 using a cone calorimeter model FTT 007.
The antibacterial performance test method comprises the following steps: the antibacterial property of the fiber is tested according to GB/T20944.3-2008 by adopting an oscillation method, and the antibacterial property is specifically as follows: washing the oiling agent on the surface of the fiber by absolute ethyl alcohol, drying the surface ethanol and shearing the surface ethanol; weighing 750mg of fiber sample, and sterilizing in an autoclave at 121 ℃ for 30min for later use; shake culturing Escherichia coli and Staphylococcus aureus in appropriate nutrient broth at 37deg.C for 18 hr, and shake culturing Candida albicans in appropriate nutrient broth at 28deg.C for 24 hr; 7.5mg of chopped fibers were dispersed in 100mL of a nutrient solution containing 10 4～9.9×106 CFU/mL of Escherichia coli, staphylococcus aureus or Candida albicans, and after shaking culture at 37℃for 18 hours (Candida albicans 28 ℃) 1.0mL of the strain suspension was removed from the test flask, and 5-stage gradient dilution was performed by 10-fold dilution to ensure that the cultured colonies could be easily and correctly counted; the diluted solution was spotted uniformly on a broth agar plate, the diluted solution of each concentration was spotted in parallel 4 times (i.e., 4 colony spots in parallel), incubated at 37℃for 18 hours (Candida albicans was incubated at 28℃for 48 hours), photographed and the number of bacterial Colony Forming Units (CFU) at the most clear concentration of the colonies on the plate was calculated, and the antibacterial rate of the material was calculated by the following formula:
Wherein R is the antibacterial rate of the material; CFUctrl is the average colony count after 18h of contact between the control group (i.e. blank sample) and the test bacteria; CFUexpt is the average colony count after 18h of contact with the test bacteria.
The test method of antiviral performance comprises the following steps:
The TCID 50 method is adopted according to the textile antiviral standard ISO 18184:2014, testing the antiviral property of the fiber, specifically: washing the oiling agent on the surface of the fiber with absolute ethyl alcohol, drying the surface ethanol, then washing the test fiber in deionized water at 60 ℃ for 10 times, drying for later use, weighing 0.40g of fiber sample dried for later use, shearing the fiber sample into a 20mm long sample, and placing the sample into an autoclave at 121 ℃ for 15 minutes under 103kPa for later use; influenza A H1N1 (A/PR/8/34) virus is used as a virus strain, and MDCK cells (dog kidney transformed cells) are used as host cells; culturing MDCK cells in 10mL of DMEM culture solution (DMEM culture solution diluted with deionized water to 10wt% concentration) with the concentration of 10wt% in CO 2 atmosphere at 37 ℃ for 24 hours at constant temperature to form MDCK cell mixed solution; transferring 0.1mL of MDCK cell mixed solution, dripping the mixed solution into 96 pore plates to ensure that 2-3X 10 4 cells are arranged in each pore plate, and culturing for 12 hours to form a single-layer cell membrane;
Dispersing the prepared fiber sample after sterilization in 100mL of mixed solution containing about 10 7 CFU/mL of H1N1 virus A, culturing at 37 ℃ for 18 hours, and taking out 1.0mL of the H1N1 virus A from a test bottle; the method for diluting the A type H1N1 virus liquid by 10 times comprises the following specific steps: continuously diluting the virus solution 10 times by using serum-free DMEM containing 1.0 mug/mL of TPCK pancreatin as a diluent, wherein the virus concentration is diluted from 10 6 CFU/mL to 10 1 CFU/mL;
Inoculating diluted virus liquid onto single-layer cell membrane of 96-well plate, inoculating one longitudinal row (8-well) of each dilution, inoculating 100 μl of each well, and culturing blank cells as control; placing in an incubator at 37 ℃ under CO 2 atmosphere for 2 hours; using an inverted microscope to view the condition of cytopathy in the plate; calculating TCID 50 by Behrens-Karber method;
Antiviral activity value: Wherein: m v is an antiviral activity value; lg (Va) is the common logarithmic average of 3 infectious titer values immediately after control inoculation; lg (V c) is the usual logarithmic average of 3 infectious titer values after 2h exposure to antiviral fabric specimens;
The antiviral activity rate Mr is calculated by the following steps:
example 1
A preparation method of flame-retardant, antibacterial and antiviral PET fibers comprises the following specific steps:
(1) Preparing raw materials;
preparation of liquid functional additives:
(I) Synthesizing a phosphorus-nitrogen hyperbranched polymer;
Firstly, mixing 2-carboxyethyl phenyl phosphinic acid, trihydroxyethyl isocyanuric acid ester and H 2 O according to the ratio of 0.15mol:0.1mol:100mL, heating to 135 ℃, preserving heat for a period of time until 82% of H 2 O is distilled out, vacuumizing to 0.098MPa, heating to 160 ℃, preserving heat and preserving pressure for 2 hours to obtain a phosphorus-nitrogen hyperbranched polymer;
the structural formula of the prepared phosphorus-nitrogen hyperbranched polymer is as follows: Wherein the wavy line represents a phosphorus-nitrogen hyperbranched polymer that can be further reacted to form more branching units; r has the structure of The branching degree DB of the phosphorus-nitrogen hyperbranched polymer is 0.48, and the number average molecular weight Mn is 42000g/mol;
(II) preparing an aqueous solution of polyetheramine M-600;
Adding polyether amine M-600 into deionized water, magnetically stirring at a stirring speed of 400r/min at a temperature of 25 ℃, and fully dissolving to form polyether amine M-600 water solution; wherein the mass ratio of the polyether amine M-600 to the deionized water is 1:5;
(III) adding the phosphorus-nitrogen hyperbranched polymer into a polyether amine M-600 aqueous solution to form a uniform and transparent reaction system while keeping the stirring speed and the temperature unchanged; wherein the mass ratio of the phosphorus-nitrogen hyperbranched polymer to the polyetheramine M-600 is 1:20;
(IV) under the stirring condition of the stirring speed of 400r/min, dropwise adding a copper salt solution with the concentration of 0.17M and composed of cupric acetate monohydrate and deionized water into a reaction system through a constant-pressure dropping funnel at the dropwise adding rate of 4mL/min and the dropwise adding volume of 0.5mL, and continuously stirring for 1h; wherein the mass ratio of the copper salt solution to the phosphorus-nitrogen hyperbranched polymer is 1:3;
(V) under the stirring condition that the stirring speed is 400r/min, dropwise adding an ascorbic acid aqueous solution with the concentration of 0.815M into a reaction system through a constant pressure dropping funnel at the dropwise adding rate of 4mL/min and the volume of each drop of 0.5mL, and continuing stirring for 2.5h to obtain a liquid functional additive; wherein the molar ratio of the ascorbic acid to the copper ions in the reaction system is 1:2;
Preparation of polyester melt:
(i) Esterification reaction;
preparing ethylene glycol and refined terephthalic acid with a molar ratio of 1.6:1 into slurry, and feeding the mixed slurry into an esterification kettle by adopting a metering pump, wherein the esterification reaction temperature is 265 ℃, the pressure is 0.3MPa, and the time is 3 hours;
(ii) Performing polycondensation reaction;
Adding the oligomer and a catalyst into a polycondensation reaction kettle, and carrying out polycondensation reaction under the negative pressure condition of 78Pa absolute pressure, wherein the reaction temperature is 280 ℃ and the reaction time is 2 hours, thus obtaining polyester, wherein the catalyst is ethylene glycol antimony, and the addition amount is 300ppm of the mass of the oligomer;
(2) Uniformly mixing the polyester melt and the liquid functional additive in the step (1), and then performing tackifying treatment to obtain a mixture;
After the tackifying treatment, the intrinsic viscosity of the mixture obtained was 0.7dL/g;
(3) Filtering the mixture subjected to tackifying treatment prepared in the step (2) through a melt filter, conveying the mixture to a melt cooler through a melt booster pump, cooling to 280 ℃, conveying the mixture to a spinning box through a multistage static mixer, metering and filtering the mixture, extruding the mixture through a spinneret plate, cooling, oiling, stretching and shaping and winding the mixture to obtain flame-retardant, antibacterial and antiviral PET fibers;
Wherein, the feeding amount of a metering pump in a spinning box body is 58g/min, the pressure of a spinning component is 200bar, the temperature of the spinning box body is 280 ℃, a spinneret plate is 36-hole spinneret plate, and the hole specification is 0.3 multiplied by 0.75mm; the cooling adopts a spinning side air blowing device with the air speed of 0.5m/s for blowing and cooling; the temperature of the first hot roller is 85 ℃, the temperature of the second hot roller is 160 ℃ and the stretching multiple is 3 during stretching and shaping.
The prepared flame-retardant, antibacterial and antiviral PET fiber consists of a PET matrix and self-assembled micro-nano structure Cu 2 O particles with the average specific surface area of 60m 2·g-1 dispersed in the PET matrix, wherein the composition and structure of the micro-nano structure Cu 2 O are shown in figure 1; the content of the self-assembled micro-nano structure Cu 2 O particles in the flame-retardant, antibacterial and antiviral PET fiber is 0.4wt%; the self-assembled micro-nano structure Cu 2 O particles are micron-sized spheres with the average particle diameter of 1.2 mu m formed by assembling a plurality of Cu 2 O particles with the average particle diameter of 6.8 nm; wherein the assembly utilizes physical and/or chemical forces between the phosphorus-nitrogen hyperbranched polymers encapsulated on the surfaces of the nanoscale Cu 2 O particles.
Comparative example 1
A process for producing PET fibers was substantially the same as in example 1 except that the step (1) in comparative example 1 was not prepared with a liquid functional additive, and that the step (2) was conducted with a tackifying treatment only on the polyester melt to obtain a product.
Example 2
A preparation method of flame-retardant, antibacterial and antiviral PET fibers is basically the same as that of example 1, except that the mass ratio of polyester melt to liquid functional additive is different, so that the content of self-assembled micro-nano structure Cu 2 O particles in the prepared flame-retardant, antibacterial and antiviral PET fibers is 0.8wt%.
Example 3
A preparation method of flame-retardant, antibacterial and antiviral PET fibers is basically the same as that of example 1, except that the mass ratio of polyester melt to liquid functional additive is different, so that the content of self-assembled micro-nano structure Cu 2 O particles in the prepared flame-retardant, antibacterial and antiviral PET fibers is 1.2wt%.
The burning properties of the fabrics of example 1, comparative example 1, example 2, example 3 are shown in table 1;
TABLE 1
As can be seen from Table 1, the PET fiber fabric produced in comparative example 1 had an LOI of only 21.0, was easily burned when it was exposed to fire, and the flame rapidly spread on the fabric, and a large number of flame droplets were produced. After Cu 2 O is added, the LOI value of the fiber fabric is stably improved, the continuous burning time and the damage length are also reduced, and the molten drop phenomenon is also obviously improved.
In the cone calorimetric test, the peak heat release rate of the tackified mixture sample plate obtained in comparative example 1 was 416.1kw/m 2, the peak heat release rate of the tackified mixture sample plate obtained in example 1 was 190kw/m 2, the peak heat release rate of the tackified mixture sample plate obtained in example 2 was 188.3kw/m 2, and the peak heat release rate of the tackified mixture sample plate obtained in example 3 was 159.1kw/m 2. The result shows that the introduction of Cu 2 O reduces the peak value of the heat release rate of the PET fiber and improves the flame retardant property.
The antibacterial properties of the fibers of example 1, comparative example 1, example 2, example 3 are shown in table 2:
TABLE 2
As is clear from Table 2, the PET fiber of comparative example 1 had an antibacterial activity against Escherichia coli of 9.68% and an antibacterial activity against Staphylococcus aureus of 14.71%, and had no antibacterial effect against Candida albicans. Compared with comparative example 1, the antibacterial performance of the fibers of examples 1 to 3 is obviously improved, the antibacterial rate of the fibers of example 1 against escherichia coli is >99.99%, the antibacterial rate of staphylococcus aureus is >99.99%, the antibacterial rate of candida albicans is 78.16%, the antibacterial rate of the fibers of examples 2 and 3 against candida albicans is improved along with the improvement of the content of Cu 2 O, and specific spot plate data are shown in fig. 2, so that the introduction of the self-assembled micro-nano structure Cu 2 O imparts a good antibacterial effect to the fibers, and the antibacterial effect is better along with the addition of the content of Cu 2 O.
The antiviral properties of the fibers of example 1 and comparative example 1 are shown in table 3:
TABLE 3 Table 3
Note that: the antiviral activity value of comparative example 1 was 0.17, and the antiviral activity rate was 32.4; the antiviral activity value of example 1 was 3.49, and the antiviral activity rate was 99.97.
Analysis of results: the standard prescribes that the antiviral activity value of the textile is lower than 3.0, namely the antiviral activity rate is lower than 99.9 percent, so that the antiviral effect of the sample is small; the antiviral activity value of the PET fiber of comparative example 1 was 0.17, the antiviral activity rate was 32.40%, and the antiviral activity value of the fiber of example 1 was 3.49, the antiviral activity rate was 99.97%. The result proves that the fiber added with the self-assembled micro-nano structure Cu 2 O has excellent antiviral property.
In order to demonstrate that the mechanical properties of the fibers of the present application are not affected even when liquid functional additives are added during the preparation process, the mechanical properties of comparative example 1 and example 3 were tested.
The testing method comprises the following steps: with reference to GB/T14344-2008 "method for testing tensile Property of chemical fiber filaments", test is performed, and the test conditions are set as follows: the initial clamping distance of the two clamping devices is 250mm, the stretching speed is 500mm/min, the tension coefficient is 0.5, the stretching multiple is 4.5, each sample is subjected to 10 parallel tests, and when the standard deviation is below 10%, the average value of test data is taken as a result.
The breaking strength of comparative example 1 was 6.1cN/dtex, the elongation at break was 33.3%, the breaking strength of example 3 was 6.5cN/dtex, and the elongation at break was 33.2%.
In addition, the fiber of example 3 was continuously processed for 30min without filament breakage, hairiness and drift, and the nose pressure was stable and spinnability was good, so that it was found that the fiber of the application, with the addition of the liquid functional additive during the preparation, did not affect its spinnability.
Example 4
A preparation method of flame-retardant, antibacterial and antiviral PET fibers comprises the following specific steps:
(1) Preparing raw materials;
preparation of liquid functional additives:
(I) Synthesizing a phosphorus-nitrogen hyperbranched polymer;
Firstly, mixing 2-carboxyethyl phenyl phosphinic acid, trihydroxyethyl isocyanuric acid ester and H 2 O according to the ratio of 0.1mol to 100mL, heating to 120 ℃, preserving heat for a period of time until 85% of H 2 O is steamed out, vacuumizing to 0.098MPa, heating to 145 ℃, preserving heat and preserving pressure for 2.5 hours to obtain a phosphorus-nitrogen hyperbranched polymer;
the structural formula of the prepared phosphorus-nitrogen hyperbranched polymer is as follows: Wherein the wavy line represents a phosphorus-nitrogen hyperbranched polymer that can be further reacted to form more branching units; r has the structure of/> The branching degree DB of the phosphorus-nitrogen hyperbranched polymer is 0.45, and the number average molecular weight Mn is 35000g/mol;
(II) preparing an aqueous solution of polyetheramine M-600;
Adding polyether amine M-600 into deionized water, magnetically stirring at a stirring speed of 400r/min at a temperature of 20 ℃, and fully dissolving to form polyether amine M-600 water solution; wherein the mass ratio of the polyether amine M-600 to the deionized water is 1:4;
(III) adding the phosphorus-nitrogen hyperbranched polymer into a polyether amine M-600 aqueous solution to form a uniform and transparent reaction system while keeping the stirring speed and the temperature unchanged; wherein the mass ratio of the phosphorus-nitrogen hyperbranched polymer to the polyetheramine M-600 is 1:15;
(IV) under the stirring condition of the stirring speed of 300r/min, dropwise adding a copper salt solution with the concentration of 0.15M and composed of cupric acetate monohydrate and deionized water into a reaction system through a constant-pressure dropping funnel at a dropwise adding rate of 3mL/min and the dropwise adding volume of 0.5mL, and continuing stirring for 1h; wherein the mass ratio of the copper salt solution to the phosphorus-nitrogen hyperbranched polymer is 1:2;
(V) under the stirring condition that the stirring speed is 300r/min, dropwise adding an ascorbic acid aqueous solution with the concentration of 0.7M into a reaction system through a constant pressure dropping funnel at a dropwise adding rate of 3mL/min and the volume of each drop of 0.5mL, and continuing stirring for 2h to obtain a liquid functional additive; wherein the molar ratio of the ascorbic acid to the copper ions in the reaction system is 1:2;
Preparation of polyester melt:
(i) Esterification reaction;
Preparing ethylene glycol and refined terephthalic acid with a molar ratio of 1.3:1 into slurry, and feeding the mixed slurry into an esterification kettle by adopting a metering pump, wherein the esterification reaction temperature is 250 ℃, the pressure is 0.35MPa, and the time is 2 hours;
(ii) Performing polycondensation reaction;
Adding the oligomer and a catalyst into a polycondensation reaction kettle, and carrying out polycondensation reaction under the condition of negative pressure of 79Pa absolute pressure, wherein the reaction temperature is 275 ℃, the reaction time is 2 hours, and the polyester is obtained, wherein the catalyst is ethylene glycol antimony, and the addition amount is 250ppm of the mass of the oligomer;
(2) Uniformly mixing the polyester melt and the liquid functional additive in the step (1), and then performing tackifying treatment to obtain a mixture;
After the tackifying treatment, the intrinsic viscosity of the mixture obtained was 0.65dL/g;
(3) Filtering the mixture after the tackifying treatment prepared in the step (2) through a melt filter, transporting the mixture to a melt cooler through a melt booster pump, cooling to 277 ℃, transporting the mixture to a spinning box through a multistage static mixer, metering and filtering the mixture, extruding the mixture through a spinneret plate, cooling, oiling, stretching and shaping the mixture, and winding the mixture to obtain flame-retardant, antibacterial and antiviral PET fibers;
Wherein, the feeding amount of a metering pump in a spinning box body is 55g/min, the pressure of a spinning component is 180bar, the box body temperature of the spinning component is 275 ℃, a spinneret plate is 36-hole spinneret plates, and the hole specification is 0.3 multiplied by 0.75mm; the cooling adopts a spinning side air blowing device with the air speed of 0.4m/s for blowing and cooling; the temperature of the first hot roller is 70 ℃, the temperature of the second hot roller is 130 ℃ and the stretching multiple is 3 during stretching and shaping.
The prepared flame-retardant, antibacterial and antiviral PET fiber consists of a PET matrix and self-assembled micro-nano structure Cu 2 O particles with the average specific surface area of 50m 2·g-1 dispersed in the PET matrix; the content of the self-assembled micro-nano structure Cu 2 O particles in the flame-retardant, antibacterial and antiviral PET fiber is 0.6wt%; the self-assembled micro-nano structure Cu 2 O particles are micron-sized spheres with the average particle diameter of 1 mu m formed by assembling a plurality of Cu 2 O particles with the average particle diameter of 6 nm; wherein, the assembly utilizes the physical and/or chemical acting force between the phosphorus-nitrogen hyperbranched polymers coated on the surfaces of the nano Cu 2 O particles;
The LOI of the fabric made of the flame-retardant, antibacterial and antiviral PET fiber is 32.0%, the damage length is 13.2cm, and the burning time is 13s; according to the cone calorimetric test method, the peak value of the heat release rate of the obtained tackified mixture sample plate is 200kw/m 2; the antibacterial rate of the flame-retardant, antibacterial and antiviral PET fiber to escherichia coli is more than 99.99 percent, the antibacterial rate to staphylococcus aureus is more than 99.99 percent, and the antibacterial rate to candida albicans is 80 percent; the flame-retardant, antibacterial and antiviral PET fiber has an antiviral (influenza A H1N1 (A/PR/8/34)) activity value of 3.51 and an antiviral (influenza A H1N1 (A/PR/8/34)) activity rate of 99.97%.
Example 5
A preparation method of flame-retardant, antibacterial and antiviral PET fibers comprises the following specific steps:
(1) Preparing raw materials;
preparation of liquid functional additives:
(I) Synthesizing a phosphorus-nitrogen hyperbranched polymer;
Firstly, mixing 2-carboxyethyl phenyl phosphinic acid, trihydroxyethyl isocyanuric acid ester and H 2 O according to the ratio of 0.18mol to 0.12mol to 100mL, heating to 125 ℃, preserving heat for a period of time until 83% of H 2 O is distilled out, vacuumizing to 0.098MPa, heating to 155 ℃, preserving heat and preserving pressure for 2.3 hours to obtain a phosphorus-nitrogen hyperbranched polymer;
the structural formula of the prepared phosphorus-nitrogen hyperbranched polymer is as follows: Wherein the wavy line represents a phosphorus-nitrogen hyperbranched polymer that can be further reacted to form more branching units; r has the structure of/> The branching degree DB of the phosphorus-nitrogen hyperbranched polymer is 0.55, and the number average molecular weight Mn is 50000g/mol;
(II) preparing an aqueous solution of polyetheramine M-600;
adding polyether amine M-600 into deionized water, magnetically stirring at a stirring speed of 350r/min at 25 ℃, and fully dissolving to form polyether amine M-600 water solution; wherein the mass ratio of the polyether amine M-600 to the deionized water is 1:5;
(III) adding the phosphorus-nitrogen hyperbranched polymer into a polyether amine M-600 aqueous solution to form a uniform and transparent reaction system while keeping the stirring speed and the temperature unchanged; wherein the mass ratio of the phosphorus-nitrogen hyperbranched polymer to the polyetheramine M-600 is 1:17;
(IV) under the stirring condition of the stirring speed of 350r/min, dropwise adding a copper salt solution with the concentration of 0.16M and composed of cupric acetate monohydrate and deionized water into a reaction system through a constant-pressure dropping funnel at the dropwise adding rate of 4mL/min and the dropwise adding volume of 0.5mL, and continuing stirring for 1h; wherein the mass ratio of the copper salt solution to the phosphorus-nitrogen hyperbranched polymer is 1:2;
(V) under the stirring condition that the stirring speed is 350r/min, dropwise adding an ascorbic acid aqueous solution with the concentration of 0.8M into a reaction system through a constant pressure dropping funnel at the dropwise adding rate of 4mL/min and the volume of each drop of 0.5mL, and continuing stirring for 3h to obtain a liquid functional additive; wherein the molar ratio of the ascorbic acid to the copper ions in the reaction system is 1:2;
Preparation of polyester melt:
(i) Esterification reaction;
Preparing ethylene glycol and refined terephthalic acid with a molar ratio of 1.5:1 into slurry, and feeding the mixed slurry into an esterification kettle by adopting a metering pump, wherein the esterification reaction temperature is 257 ℃, the pressure is 0.33MPa, and the time is 2 hours;
(ii) Performing polycondensation reaction;
Adding the oligomer and a catalyst into a polycondensation reaction kettle, and performing polycondensation reaction under the negative pressure condition of 78Pa absolute pressure, wherein the reaction temperature is 280 ℃, the reaction time is 1.8h, and the polyester is obtained, wherein the catalyst is antimony trioxide, and the addition amount is 276ppm of the mass of the oligomer;
(2) Uniformly mixing the polyester melt and the liquid functional additive in the step (1), and then performing tackifying treatment to obtain a mixture;
after the tackifying treatment, the intrinsic viscosity of the mixture obtained was 0.68dL/g;
(3) Filtering the mixture subjected to tackifying treatment prepared in the step (2) through a melt filter, conveying the mixture to a melt cooler through a melt booster pump, cooling the mixture to 278 ℃, conveying the mixture to a spinning box through a multistage static mixer, metering and filtering the mixture, extruding the mixture through a spinneret plate, cooling, oiling, stretching and shaping the mixture, and winding the mixture to obtain flame-retardant, antibacterial and antiviral PET fibers;
wherein, the feeding amount of the metering pump in the spinning box body is 57g/min, the pressure of the spinning component is 190bar, the temperature of the spinning box body is 285 ℃, the spinneret plate is 36-hole spinneret plate, and the hole specification is 0.3 multiplied by 0.75mm; the cooling adopts a spinning side air blowing device with the air speed of 0.4m/s for blowing and cooling; the temperature of the first hot roller is 80 ℃, the temperature of the second hot roller is 150 ℃ and the stretching multiple is 3.5 during stretching and shaping.
The prepared flame-retardant, antibacterial and antiviral PET fiber consists of a PET matrix and self-assembled micro-nano structure Cu 2 O particles with the average specific surface area of 80m 2·g-1 dispersed in the PET matrix; the content of the self-assembled micro-nano structure Cu 2 O particles in the flame-retardant, antibacterial and antiviral PET fiber is 0.9wt%; the self-assembled micro-nano structure Cu 2 O particles are micron-sized spheres with the average particle diameter of 1.4 mu m formed by assembling a plurality of Cu 2 O particles with the average particle diameter of 8 nm; wherein, the assembly utilizes the physical and/or chemical acting force between the phosphorus-nitrogen hyperbranched polymers coated on the surfaces of the nano Cu 2 O particles;
The LOI of the fabric made of the flame-retardant, antibacterial and antiviral PET fiber is 34.4%, the damage length is 9.4cm, and the burning time is 8s; according to the cone calorimeter test method, the peak heat release rate of the obtained tackified mixture sample plate is 147.6kw/m 2; the antibacterial rate of the flame-retardant, antibacterial and antiviral PET fiber to escherichia coli is more than 99.99 percent, the antibacterial rate to staphylococcus aureus is more than 99.99 percent, and the antibacterial rate to candida albicans is 82 percent; the flame-retardant, antibacterial and antiviral PET fiber has an antiviral (influenza A H1N1 (A/PR/8/34)) activity value of 3.6 and an antiviral (influenza A H1N1 (A/PR/8/34)) activity rate of 99.98%.
Example 6
A preparation method of flame-retardant, antibacterial and antiviral PET fibers comprises the following specific steps:
(1) Preparing raw materials;
preparation of liquid functional additives:
(I) Synthesizing a phosphorus-nitrogen hyperbranched polymer;
Firstly, mixing 2-carboxyethyl phenyl phosphinic acid, trihydroxyethyl isocyanuric acid ester and H 2 O according to the ratio of 0.2mol to 0.15mol to 100mL, heating to 150 ℃, preserving heat for a period of time until 85% of H 2 O is steamed out, vacuumizing to 0.098MPa, heating to 165 ℃, preserving heat and preserving pressure for 2 hours to obtain a phosphorus-nitrogen hyperbranched polymer;
the structural formula of the prepared phosphorus-nitrogen hyperbranched polymer is as follows: Wherein the wavy line represents a phosphorus-nitrogen hyperbranched polymer that can be further reacted to form more branching units; r has the structure of/> The branching degree DB of the phosphorus-nitrogen hyperbranched polymer is 0.5, and the number average molecular weight Mn is 55000g/mol;
(II) preparing an aqueous solution of polyetheramine M-600;
Adding polyether amine M-600 into deionized water, magnetically stirring at a stirring speed of 300r/min at a temperature of 30 ℃, and fully dissolving to form polyether amine M-600 water solution; wherein the mass ratio of the polyether amine M-600 to the deionized water is 1:6;
(III) adding the phosphorus-nitrogen hyperbranched polymer into a polyether amine M-600 aqueous solution to form a uniform and transparent reaction system while keeping the stirring speed and the temperature unchanged; wherein the mass ratio of the phosphorus-nitrogen hyperbranched polymer to the polyetheramine M-600 is 1:20;
(IV) under the stirring condition of the stirring speed of 400r/min, dropwise adding a copper salt solution with the concentration of 0.175M and composed of cupric acetate monohydrate and deionized water into a reaction system through a constant-pressure dropping funnel at the dropwise adding rate of 4mL/min and the dropwise adding volume of 0.5mL, and continuing stirring for 1h; wherein the mass ratio of the copper salt solution to the phosphorus-nitrogen hyperbranched polymer is 1:3;
(V) under the stirring condition that the stirring speed is 400r/min, dropwise adding an ascorbic acid aqueous solution with the concentration of 0.875M into a reaction system through a constant pressure dropping funnel at the dropwise adding rate of 4mL/min and the volume of each drop of 0.5mL, and continuing stirring for 3h to obtain a liquid functional additive; wherein the molar ratio of the ascorbic acid to the copper ions in the reaction system is 1:2;
Preparation of polyester melt:
(i) Esterification reaction;
Preparing ethylene glycol and refined terephthalic acid with a molar ratio of 1.8:1 into slurry, and feeding the mixed slurry into an esterification kettle by adopting a metering pump, wherein the esterification reaction temperature is 267 ℃, the pressure is 0.27MPa, and the time is 3 hours;
(ii) Performing polycondensation reaction;
adding the oligomer and a catalyst into a polycondensation reaction kettle, and performing polycondensation reaction under the negative pressure condition of 75Pa absolute pressure, wherein the reaction temperature is 285 ℃, the reaction time is 1.5h, and the polyester is obtained, wherein the catalyst is antimony acetate, and the addition amount is 300ppm of the mass of the oligomer;
(2) Uniformly mixing the polyester melt and the liquid functional additive in the step (1), and then performing tackifying treatment to obtain a mixture;
After the tackifying treatment, the intrinsic viscosity of the mixture obtained was 0.7dL/g;
(3) Filtering the mixture subjected to tackifying treatment prepared in the step (2) through a melt filter, conveying the mixture to a melt cooler through a melt booster pump, cooling to 280 ℃, conveying the mixture to a spinning box through a multistage static mixer, metering and filtering the mixture, extruding the mixture through a spinneret plate, cooling, oiling, stretching and shaping and winding the mixture to obtain flame-retardant, antibacterial and antiviral PET fibers;
wherein, the feeding amount of a metering pump in a spinning box body is 60g/min, the pressure of a spinning component is 200bar, the temperature of the spinning box body is 295 ℃, a spinneret plate is 36-hole spinneret plates, and the hole specification is 0.3 multiplied by 0.75mm; the cooling adopts a spinning side air blowing device with the air speed of 0.5m/s for blowing and cooling; the temperature of the first hot roller is 90 ℃, the temperature of the second hot roller is 180 ℃ and the stretching multiple is 4 during stretching and shaping.
The prepared flame-retardant, antibacterial and antiviral PET fiber consists of a PET matrix and self-assembled micro-nano structure Cu 2 O particles with the average specific surface area of 70m 2·g-1 dispersed in the PET matrix; the content of the self-assembled micro-nano structure Cu 2 O particles in the flame-retardant, antibacterial and antiviral PET fiber is 1.1wt%; the self-assembled micro-nano structure Cu 2 O particles are micron-sized spheres with the average particle diameter of 1.3 mu m formed by assembling a plurality of Cu 2 O particles with the average particle diameter of 7.2 nm; wherein, the assembly utilizes the physical and/or chemical acting force between the phosphorus-nitrogen hyperbranched polymers coated on the surfaces of the nano Cu 2 O particles;
The LOI of the fabric made of the flame-retardant, antibacterial and antiviral PET fiber is 35%, the damage length is 7.8cm, and the burning time is 5s; according to the cone calorimeter test method, the peak value of the heat release rate of the obtained tackified mixture sample plate is 126.7kw/m 2; the antibacterial rate of the flame-retardant, antibacterial and antiviral PET fiber to escherichia coli is more than 99.99 percent, the antibacterial rate to staphylococcus aureus is more than 99.99 percent, and the antibacterial rate to candida albicans is 85 percent; the flame-retardant, antibacterial and antiviral PET fiber has an antiviral (influenza A H1N1 (A/PR/8/34)) activity value of 3.66 and an antiviral (influenza A H1N1 (A/PR/8/34)) activity rate of 99.97%.
Claims (10)
1. The flame-retardant, antibacterial and antiviral PET fiber is characterized by mainly comprising a PET matrix and self-assembled micro-nano structure Cu 2 O particles dispersed in the PET matrix;
The self-assembled micro-nano structure Cu 2 O particles are micron-sized spheres formed by assembling a plurality of nano-sized Cu 2 O particles, wherein the assembling utilizes physical and/or chemical acting forces among phosphorus-nitrogen hyperbranched polymers wrapped on the surfaces of the nano-sized Cu 2 O particles;
the structural formula of the phosphorus-nitrogen hyperbranched polymer is as follows:
Wherein the wavy line represents a phosphorus-nitrogen hyperbranched polymer that can be further reacted to form more branching units; r has the structure of
The LOI of the fabric made of flame-retardant, antibacterial and antiviral PET fibers is not lower than 32.0%, the damage length is not more than 15.0cm, the burning time is not more than 15s, and the peak value of the heat release rate is not more than 200kw/m 2;
The antibacterial rate of the flame-retardant, antibacterial and antiviral PET fiber to escherichia coli is more than 99.99 percent, the antibacterial rate to staphylococcus aureus is more than 99.99 percent, and the antibacterial rate to candida albicans is more than or equal to 78 percent;
the antiviral activity value of the flame-retardant, antibacterial and antiviral PET fiber is more than or equal to 3.49, and the antiviral activity rate is more than or equal to 99.97%.
2. The flame-retardant, antibacterial and antiviral PET fiber according to claim 1, wherein the content of the self-assembled micro-nano structure Cu 2 O particles in the flame-retardant, antibacterial and antiviral PET fiber is 0.4-1.2 wt%.
3. The flame retardant, antibacterial and antiviral PET fiber according to claim 1, wherein the average particle size of nano-sized Cu 2 O particles is 6 to 8nm and the average particle size of micro-sized spheres is 1 to 1.4 μm.
4. The flame-retardant, antibacterial and antiviral PET fiber according to claim 1, wherein the branching degree DB of the phosphorus-nitrogen hyperbranched polymer is 0.45-0.55, and the number average molecular weight Mn is 35000-55000 g/mol.
5. The flame-retardant, antibacterial and antiviral PET fiber according to claim 1, wherein the specific surface area of the self-assembled micro-nano structure Cu 2 O particles is 50-80 m 2·g-1, and the content of the phosphorus-nitrogen hyperbranched polymer in the self-assembled micro-nano structure Cu 2 O particles is 22.8-24.0wt%.
6. A preparation method of flame-retardant, antibacterial and antiviral PET fibers is characterized in that polyester melt and liquid functional additives are uniformly mixed and then subjected to tackifying treatment, and the mixture after the tackifying treatment is spun to prepare the flame-retardant, antibacterial and antiviral PET fibers;
the preparation process of the liquid functional additive comprises the following steps: firstly, synthesizing a phosphorus-nitrogen hyperbranched polymer by using 2-carboxyethyl phenyl phosphinic acid and tris (hydroxyethyl) isocyanurate as raw materials through an A 2+B3 method, then adding the phosphorus-nitrogen hyperbranched polymer into a polyether amine aqueous solution to form a uniform and transparent reaction system, then dropwise adding a copper salt solution into the reaction system under the stirring condition, continuing stirring, and finally dropwise adding an ascorbic acid aqueous solution into the reaction system under the stirring condition, and continuing stirring to obtain the liquid functional additive.
7. The method for preparing the flame-retardant, antibacterial and antiviral PET fiber according to claim 6, wherein the preparation steps of the liquid functional additive are as follows:
(1) Synthesizing a phosphorus-nitrogen hyperbranched polymer;
Firstly, mixing 2-carboxyethyl phenyl phosphinic acid, trishydroxyethyl isocyanurate and H 2 O according to the ratio of 0.1-0.2 mol to 0.1-0.15 mol to 100mL, heating to 120-150 ℃, preserving heat for a period of time until more than 80% of H 2 O is steamed out, vacuumizing to 0.098MPa, heating to 145-165 ℃ at the same time, and preserving heat and pressure for 2-2.5H to obtain the phosphorus-nitrogen hyperbranched polymer;
(2) Preparing a polyether amine aqueous solution;
Adding polyether amine into deionized water, magnetically stirring at 20-30 ℃ and fully dissolving to form polyether amine aqueous solution;
(3) The stirring speed is kept unchanged, the temperature is kept unchanged, and the phosphorus-nitrogen hyperbranched polymer is added into the polyether amine aqueous solution to form a uniform and transparent reaction system;
(4) Dropwise adding copper salt solution into the reaction system through a constant pressure dropping funnel under the stirring condition, and continuously stirring for 1h;
(5) And (3) dropwise adding the ascorbic acid aqueous solution into the reaction system through a constant pressure dropping funnel under the stirring condition, and continuing stirring for 2-3 h to obtain the liquid functional additive.
8. The method for preparing flame-retardant, antibacterial and antiviral PET fibers according to claim 7, wherein in the step (2), the polyetheramine is polyetheramine M-600; the mass ratio of the polyetheramine to the deionized water is 1:4-6; the stirring speed is 300-400 r/min;
In the step (3), the mass ratio of the phosphorus-nitrogen hyperbranched polymer to the polyetheramine is 1:15-20;
In the step (4), the stirring speed is 300-400 r/min; the concentration of the copper salt solution is 0.15-0.175M, and the copper salt solution consists of cupric acetate monohydrate and deionized water; the dropping speed is 3-4 mL/min; the mass ratio of the copper salt solution to the phosphorus-nitrogen hyperbranched polymer is 1:2-3;
in the step (5), the stirring speed is 300-400 r/min; the concentration of the ascorbic acid aqueous solution is 0.7-0.875M; the molar ratio of the ascorbic acid to the copper ions in the reaction system is 1:2; the dropping rate is 3-4 mL/min.
9. The method for producing a flame retardant, antibacterial and antiviral PET fiber according to claim 6, wherein the intrinsic viscosity of the mixture after the tackifying treatment is 0.60 to 0.70dL/g; the spinning process is as follows: filtering the mixture after tackifying treatment by a melt filter, conveying the mixture to a melt cooler by a melt booster pump, cooling to 277-280 ℃, conveying the mixture to a spinning box by a multistage static mixer, metering and filtering the mixture, extruding the mixture by a spinneret plate, cooling, oiling, stretching and shaping the mixture, and winding the mixture to obtain the flame-retardant, antibacterial and antiviral PET fiber.
10. The method for preparing the flame-retardant, antibacterial and antiviral PET fiber according to claim 9, wherein the feeding amount of a metering pump in a spinning box is 55-60 g/min, the pressure of a spinning assembly is 180-200 bar, the temperature of the spinning box is 275-295 ℃, a spinneret plate is 36-hole spinneret plates, and the hole specification is 0.3 multiplied by 0.75mm; the cooling adopts a spinning side air blowing device with the air speed of 0.4-0.5 m/s for blowing and cooling; the temperature of the first hot roller is 70-90 ℃ during stretching and shaping, the temperature of the second hot roller is 130-180 ℃, and the stretching multiple is 3.0-4.0.
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