CN112695407A - Glass silver-loaded antibacterial polyester fiber and preparation method thereof - Google Patents
Glass silver-loaded antibacterial polyester fiber and preparation method thereof Download PDFInfo
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- CN112695407A CN112695407A CN202011579238.6A CN202011579238A CN112695407A CN 112695407 A CN112695407 A CN 112695407A CN 202011579238 A CN202011579238 A CN 202011579238A CN 112695407 A CN112695407 A CN 112695407A
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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
- D01F6/92—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
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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
- 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
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Abstract
The invention discloses a glass silver-carrying antibacterial polyester fiber: 5-10% of glass silver-loaded antibacterial master batch and 90-95% of polyester chips; the glass silver-loaded antibacterial master batch is prepared from the following components in percentage by weight: 10-20% of modified porous glass silver-loaded powder and 80-90% of polyester powder; the modified porous glass silver-loaded powder is prepared from porous glass silver-loaded powder and 3-glycidyl ether oxypropyl trimethoxy silane coupling agent powder accounting for 0.1-1 wt% of the porous glass silver-loaded powder; the porous glass silver-carrying powder is obtained by dissolving porous glass in a silver nitrate solution to prepare a solution with the concentration of 0.05-0.2 g/ml and then calcining the solution; the porous glass is obtained by preparing glass powder from the following components in percentage by weight and then acidifying the glass powder: 60-63% of silicon dioxide, 27-30% of boron oxide, 8.5-9.0% of sodium oxide and 1-1.5% of aluminum oxide. The fiber has the characteristics of no yellowing and antibiosis.
Description
Technical Field
The invention belongs to the technical field of synthetic fiber preparation, and particularly relates to a glass silver-loaded antibacterial polyester fiber and a preparation method thereof.
Background
With the development of social economy and the improvement of the living standard of people, the protection consciousness of people on health and the requirement on the environmental quality are also improved. In order to effectively reduce the invasion of pathogenic microorganisms such as bacteria to human bodies, antibacterial textile materials are attracting more and more attention and are gradually becoming demands and choices of people. Therefore, the development and production of various antibacterial polyester fibers has been one of the development directions of functional polyester fibers. At present, the domestic and foreign antibacterial polyester fibers are mainly prepared by a blending method, namely, when polyester is spun, the antibacterial fibers are prepared by adding an inorganic antibacterial agent, mainly a metal ion type antibacterial agent, and blending and melting the polyester.
Compared with organic antibacterial agents, the metal ion antibacterial agent has the characteristics of strong and durable antibacterial capability and good thermal stability, particularly, pathogenic microorganisms such as bacteria and the like are not easy to generate antibacterial mutation on the metal ion antibacterial agent, but Hg2+, Cd2+, Pb2+ and Cr3+ have large residual toxicity on human bodies, so the inorganic antibacterial agent widely used at present is a silver, copper and zinc ion antibacterial agent, and the antibacterial effect of the silver ion antibacterial agent is most obvious under the condition of the same addition amount. The present antibacterial mother particles for polyester spinning are prepared by loading silver ion antibacterial agent on porous material, then blending the antibacterial mother particles and polyester chips, melting and spinning, and further endowing polyester fiber with antibacterial property. Because the inner surfaces of the pores have a large amount of Si-OH, the porous glass can be subjected to surface modification and modification, so that the porous glass is gradually developed into a novel carrier material with multifunctional purposes and is applied to the aspects of chromatographic analysis, optical fiber communication, seawater desalination and the like at present.
Although there are many reports on glass-supported antibacterial agents, related researches mainly focus on soluble glass, silver ions in the glass release silver ions existing in the glass through integral dissolution of the glass so as to achieve an antibacterial effect, but secondary environmental pollution caused by rich phosphorus is easily caused, and different porous glass antibacterial materials have the characteristics of high temperature resistance, corrosion resistance, microbial pollution resistance and the like, and the pore diameter of the porous glass can be regulated and controlled according to requirements by adjusting preparation parameters, and the slow release speed of antibacterial components can be regulated by changing the heat treatment temperature of the glass. The porous glass needs no polycondensation or re-sintering physical pore-forming process, and is prepared through separating some glass components into two mutually communicated phases in certain temperature range, treating one phase with inorganic acid to dissolve out and maintaining the other phase structure unchanged to leave porous three-dimensional communicated structure with silica skeleton as main component. Besides the characteristics of inorganic materials, the porous inorganic material also has the advantages of large specific surface area, high porosity and the like, particularly, the pore diameter of the porous inorganic material is not changed by the temperature, the type and the acidity of the solution, and the porous inorganic material does not swell in the solution.
In view of the above, there is a need to develop an antibacterial polyester fiber based on porous glass.
Disclosure of Invention
The invention aims to provide the glass silver-loaded antibacterial polyester fiber which has the characteristic of low yellowing tendency, the silver-loaded amount of the glass is adjustable, the production process flow is simple, and the batch production is convenient.
The invention also aims to provide a preparation method of the glass silver-loaded antibacterial polyester fiber.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a glass silver-loaded antibacterial polyester fiber, which is prepared from the following components in percentage by weight: 5-10% of glass silver-loaded antibacterial master batch and 90-95% of polyester chips;
the glass silver-loaded antibacterial master batch is prepared from the following components in percentage by weight: 10-20% of modified porous glass silver-loaded powder and 80-90% of polyester powder;
the modified porous glass silver-loaded powder is prepared from the following components in percentage by weight: the silver-carrying porous glass powder and 3-glycidoxypropyltrimethoxysilane coupling agent powder accounting for 0.1-1 wt% of the silver-carrying porous glass powder;
the porous glass silver-carrying powder is obtained by dissolving porous glass in a silver nitrate solution to prepare a solution with the concentration of 0.05-0.2 g/ml and then calcining the solution;
the porous glass is obtained by preparing glass powder from the following components in percentage by weight and then acidifying the glass powder: 60-63% of silicon dioxide, 27-30% of boron oxide, 8.5-9.0% of sodium oxide and 1-1.5% of aluminum oxide.
Preferably, the glass silver-loaded antibacterial polyester fiber is prepared from the following components in percentage by weight: 6 percent of glass silver-carrying antibacterial master batch and 94 percent of polyester chip.
Preferably, the glass silver-loaded antibacterial master batch is prepared from the following components in percentage by weight: 15% of modified porous glass silver-carrying powder and 85% of polyester powder.
Preferably, the modified porous glass silver-loaded powder is prepared from the following components in percentage by weight: the porous glass silver-carrying powder and 3-glycidoxypropyltrimethoxysilane coupling agent powder accounting for 0.5 percent of the weight of the porous glass silver-carrying powder.
Preferably, the porous glass silver-loaded powder is obtained by dissolving porous glass in a silver nitrate solution to prepare a solution with the concentration of 0.1g/ml and then calcining the solution.
Preferably, the porous glass is obtained by preparing glass powder from the following components in percentage by weight and then acidifying the glass powder: 60% of silicon dioxide, 30% of boron oxide, 8.5% of sodium oxide and 1.5% of aluminum oxide.
The cross section of the glass silver-loaded antibacterial polyester fiber can be a circular, single-hollow, multi-hollow, cross-shaped and other cross sections; the nominal linear density of the fiber is 0.89dtex to 6.67 dtex.
In a second aspect of the invention, a preparation method of the glass silver-loaded antibacterial polyester fiber is provided, which comprises the following steps:
firstly, the preparation method of the porous glass silver-loaded powder comprises the following steps:
grinding and uniformly mixing silicon dioxide, boron oxide, sodium oxide and aluminum oxide, melting at high temperature, stirring and cooling with water, filtering, drying, crushing and ball-milling until the particle size is 0.5-0.6 um to obtain glass powder;
carrying out phase-splitting heat treatment on the glass powder, and acidifying to obtain porous glass;
dissolving porous glass in silver nitrate solution, adjusting pH value to 9.0, processing in a dark and constant temperature water bath (temperature is 40 ℃ for 20 minutes), filtering, washing until pH value is 7.0, drying (70 ℃) and calcining (temperature is 380-420 ℃, preferably 400 ℃, time is 20-40 min) to obtain porous glass silver-loaded powder;
secondly, the preparation method of the modified porous glass silver-carrying powder comprises the following steps:
mixing the porous glass silver-loaded powder prepared in the first step with 3-glycidyl ether oxypropyl trimethoxy silane coupling agent powder, and performing ball milling and sieving to obtain surface-modified porous glass silver-loaded powder with the particle size of 0.3-0.4 um;
thirdly, the preparation method of the glass silver-carrying antibacterial master batch comprises the following steps:
blending the modified porous glass silver-carrying powder prepared in the second step with polyester powder, drying (drying for 10 hours at 120 ℃), extruding and melting by a screw, extruding, cooling by water, drawing strips, granulating and drying to prepare glass silver-carrying antibacterial master batches;
fourthly, the preparation method of the glass silver-loaded antibacterial polyester fiber comprises the following steps:
and (2) independently metering the dried glass silver-loaded antibacterial master batch and the dried polyester chips by using an injection machine, blending, performing melt spinning, winding and barrel dropping to obtain precursor fibers, and performing post-spinning drafting and tension heat setting on the precursor fibers to obtain the glass silver-loaded antibacterial polyester fibers.
The temperature of the high-temperature melting in the first step is 1450-1500 ℃, and the time is 0.5-1.5 hours; preferably at 1450 ℃ for 1 hour.
The temperature of the phase separation heat treatment in the first step is 550-580 ℃ (580 ℃ is preferred), and the heat treatment time is 12-24 hours (12 hours is preferred).
In the first step, the aperture of the porous glass is 3.0-5.5 nm, and the specific surface area is 75-110 m2The weight loss rate is 36.8-38.2 percent.
The specific steps of obtaining the porous glass after acidification in the first step are as follows:
and (2) dissolving the glass powder in hydrochloric acid, wherein the concentration is 0.1g/ml, the molar concentration of the hydrochloric acid is 0.05mol/L, the temperature is 90-95 ℃ (preferably 95 ℃), keeping the temperature for 24-30 h, carrying out suction filtration and pure water washing until the pH value is 7.0, and drying at the temperature of 100-110 ℃ to prepare the porous glass.
The concentration of the silver nitrate solution in the first step is 0.05 mol/L.
In the third step, the particle size of the polyester powder is 0.3-0.4 um.
And the melting temperature of the screw in the third step is 272-282 ℃.
And in the fourth step, the drying temperature of the glass silver-loaded antibacterial master batch is 120 ℃, and the drying time is 8-12 hours.
And in the fourth step, the drying temperature of the polyester chip is 120 ℃, and the drying time is 8-12 hours.
In the fourth step, the spinning temperature is 275-285 ℃, the spinning speed is 1000-1100 m/min, the drafting multiple is 3.4-4.5 times, and the heat setting temperature is 170 +/-2 ℃.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the invention provides a glass silver-carrying antibacterial polyester fiber, which is prepared by mixing SiO2-B2O3-Na2O-Al2O3After high-temperature melting to prepare glass, phase-splitting heat treatment and inorganic acid treatment are carried out on the glass at proper temperature to dissolve out a sodium-boron phase, thus preparing the porous glass with the nanometer aperture and the porous three-dimensional communicated structure taking a silicon dioxide framework as a main part, the porous glass can contain more silver ions after being treated by silver nitrate solution, the porous glass is calcined and ball-milled to prepare glass silver-loaded antibacterial master batches, and the master batches and polyester chips are blended, melt-spun, drawn and heat-set to prepare the glass silver-loaded antibacterial polyester fiber, so that the lasting capacity of antibacterial of the antibacterial agent is obviously enhanced.
In the glass silver-loaded antibacterial polyester fiber provided by the invention, the aperture and the silver loading amount of the porous glass can be regulated and controlled according to needs. The fiber sample is placed under a standard light source box and is irradiated by an ultraviolet lamp for 30 days, and no yellowing phenomenon is found. The fiber sample is placed under natural light for 3 months, no yellowing phenomenon is found, and the glass silver-loaded antibacterial polyester fiber has better weather resistance.
The pore diameter and the silver carrying amount of the porous glass are regulated and controlled as follows: in a glass system prepared by mixing silicon dioxide, boron oxide, sodium oxide and aluminum oxide according to a certain proportion and melting at a high temperature (a small amount of aluminum oxide is added to mainly play a role in increasing the chemical stability of the glass and contributing to the phase-splitting heat treatment of the glass), an immiscible region is latent, when the prepared glass is subjected to the phase-splitting heat treatment under a proper temperature condition, the prepared glass is separated into two mutually communicated phases with different structural properties, wherein one phase is a silicon dioxide continuous phase, and the other phase is a communicated phase formed by boron oxide and sodium oxide. And then the characteristic that the boron oxide-sodium oxide phase is soluble in hydrochloric acid and the silicon dioxide phase is insoluble in hydrochloric acid is utilized, so that a large number of communicated pore channels are generated after the boron oxide-sodium oxide communicated phase is dissolved out, and the nano-pore porous glass mainly comprising a silicon dioxide framework is prepared. The aperture of the porous glass can be controlled by regulating and controlling the composition ratio of the glass, the temperature and time of the phase-splitting heat treatment of the glass, the concentration of the acidification treatment of the glass, and the treatment temperature and time. The more thorough the phase separation heat treatment, the more the boron oxide-sodium oxide phase dissolves out, and the larger the pore diameter of the prepared porous glass. The three are in a system, and one of them is not necessary. The silver loading of the porous glass is prepared by adopting an adsorption method, and the silver loading of the porous glass is further controlled by controlling the solid-to-liquid ratio of the porous glass to a silver nitrate solution, the concentration of silver nitrate, the pH value of the solution, the temperature of water bath and the time.
The invention has simple production process flow and convenient batch production, and provides a selection of a novel antibacterial polyester fiber raw material for manufacturing antibacterial textile materials for customers.
The invention mainly solves the defects that the pore diameter and pore canal of the silver antibacterial agent carrier material used by the existing polyester fiber, such as zirconium phosphate, sodium zirconium phosphate and other porous materials, are difficult to adjust, the silver-carrying amount is difficult to adjust, and the silver antibacterial polyester fiber is easy to yellow. The pore diameter, pore canal and silver-carrying capacity of the porous glass can be regulated and controlled as required by selecting proper glass composition proportion, high-temperature melting, phase separation treatment, acidification treatment and silver-carrying adsorption treatment. In addition, the raw materials for preparing the porous glass are easily available, and the method is convenient for industrial production in the future.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The fiber bacteriostasis rate test in the embodiment of the invention adopts GB/T20944.3-2008 < evaluation of textile antibacterial performance part 3 >: oscillation method (Vital energy); the specific surface area, pore size distribution and the like of the porous glass are tested by a nitrogen adsorption capacity method. The weight loss ratio of the porous glass refers to the weight difference of the glass after heat treatment and phase separation before and after acid dipping treatment in the weight before treatment. The silver loading of the porous glass was determined by the Fourard method.
Example 1
The preparation method of the glass silver-loaded antibacterial polyester fiber comprises the following steps:
firstly, the preparation method of the porous glass silver-loaded powder comprises the following steps:
according to the weight percentage of 60 percent to 30 percent to 8.5 percent to 1.5 percent, 18g of chemically pure silicon dioxide, 9g of boron oxide, 2.55g of sodium oxide and 0.45g of alumina are put into a mortar for grinding, mixed evenly and put into a silicon carbide crucible, the crucible is put into a silicon-molybdenum rod resistance furnace heated to 1450 ℃, the temperature is kept for 1 hour under the condition of continuous stirring, the clear molten liquid is poured into a stainless steel container filled with pure water, stirring is carried out while pouring, transparent glass is prepared, and the glass is filtered, dried, crushed and ball-milled until the grain diameter is 0.5-0.6 um, thus obtaining the glass powder.
And putting the glass powder into a crucible, putting the crucible into a resistance furnace at 580 ℃ for heat treatment for 12 hours, and taking out the crucible, wherein the glass powder in the crucible is milky white.
Preparing milky white glass powder into a solution according to the solid-to-liquid ratio of 1g to 10ml of hydrochloric acid to each gram of glass powder, wherein the concentration of the hydrochloric acid is 0.05 mol/L. Placing the flask containing the solution in a constant-temperature water bath at 95 ℃ for 24 hours at constant temperature, carrying out suction filtration, washing the glass with pure water until the pH value is 7.0, and placing the glass in a 105 ℃ oven to be dried to constant weight to obtain the porous glass. The weight loss rate of the glass after acid treatment is 38.2 percent, the aperture of the porous glass is 5.0nm, and the specific surface area is 80m2/g。
Preparing porous glass-silver nitrate solution according to the solid-to-liquid ratio of 1 g/g porous glass to 10ml silver nitrate solution, wherein the concentration of the silver nitrate solution is 0.05 mol/L. Adjusting the pH value of the solution to 9.0 by using ammonia water, sealing a beaker filled with the solution by using plastic paper, placing the beaker in a constant-temperature water bath tank at 40 ℃, carrying out light-shielding treatment for 20 minutes, carrying out suction filtration and washing until the pH value is 7.0, placing the beaker in a 70 ℃ oven for drying, placing the dried porous glass silver-loaded powder in a 400 ℃ oven for calcining treatment for 30 minutes, taking out the porous glass silver-loaded powder, and cooling the porous glass silver-loaded powder to room temperature to obtain the porous glass silver-loaded powder. The silver loading of the porous glass was measured to be 35.62mg/g by the Folder method.
Secondly, the preparation method of the modified porous glass silver-carrying powder comprises the following steps:
and (2) putting the porous glass silver-loaded powder prepared in the first step into a grinding tank, adding 3-glycidyl ether oxypropyl trimethoxy silane coupling agent powder accounting for 0.5 percent of the weight of the porous glass silver-loaded powder, and performing ball milling and sieving to obtain the surface-modified porous glass silver-loaded powder with the particle size of 0.3-0.4 um.
Thirdly, the preparation method of the glass silver-carrying antibacterial master batch comprises the following steps:
and (2) blending 15g of the modified porous glass silver-loaded powder prepared in the second step with 85% of polyester powder according to the weight percentage of 15%, drying for 10 hours at 120 ℃, extruding and melting by a screw, extruding, water cooling, drawing, granulating and drying to prepare the glass silver-loaded antibacterial master batch, wherein the melting temperature of the screw is 272-282 ℃.
After dehydrating the polyester chips, ball-milling the polyester chips until the particle size of the polyester powder is 0.3-0.4 um.
Fourthly, the preparation method of the glass silver-loaded antibacterial polyester fiber with the nominal linear density of 1.56dtex comprises the following steps:
independently drying the glass silver-loaded antibacterial master batch prepared in the third step and polyester chips, wherein the drying temperature of the glass silver-loaded antibacterial master batch is 120 ℃, and the drying time is 8 hours; the drying temperature of the polyester chip is 120 ℃, and the drying time is 12 hours. 6g of dried glass silver-loaded antibacterial master batch and 94g of polyester chips are separately metered by an injection machine according to the weight percentage of 6 percent to 94 percent, melt spinning, winding and barrel falling are carried out after blending to prepare protofilaments, the protofilaments are subjected to post-spinning drafting, tension heat setting and other processes to prepare the glass silver-loaded antibacterial polyester fiber, the cross section is circular, the spinning temperature is 275-285 ℃, the winding speed is 1050m/min, the drafting multiple is 3.80 times, and the tension heat setting temperature is 170 +/-2 ℃. The measured linear density of the fiber is 1.58dtex, the breaking strength is 4.62cN/dtex, and the bacteriostasis rate of the fiber to staphylococcus aureus and escherichia coli is more than 99%. The fiber sample is placed under a standard light source box and is irradiated by an ultraviolet lamp for 30 days, and no yellowing phenomenon is found. The fiber sample is placed under natural light for 3 months, and no yellowing phenomenon is found.
Example 2
The preparation method of the glass silver-loaded antibacterial polyester fiber with the nominal linear density of 3.33dtex and single hollow cross section comprises the following steps:
independently drying the glass silver-loaded antibacterial master batch prepared in the third step of the embodiment 1 and polyester chips, wherein the drying temperature of the master batch is 120 ℃, and the drying time is 8 hours; the polyester chip is dried at 120 ℃ for 12 hours. 6g of dried glass silver-loaded antibacterial master batch and 94g of polyester chips are separately measured according to the weight percentage of 6 percent to 94 percent by an injection machine, melt spinning, winding and barrel dropping are carried out after blending to prepare protofilaments, the protofilaments are subjected to post-spinning drafting, tension heat setting and other processes to prepare the glass silver-loaded antibacterial polyester fiber, the spinning temperature is 275-282 ℃, the winding speed is 1000m/min, the drafting multiple is 4.15 times, and the tension heat setting temperature is 170 +/-2 ℃. The measured linear density of the fiber is 3.34dtex, the breaking strength is 4.41cN/dtex, and the bacteriostasis rate of the fiber to staphylococcus aureus and escherichia coli is more than 99%.
Example 3
The fourth step in example 1 was modified to: the dried glass silver-loaded antibacterial master batch and the dried polyester chip are separately measured by an injection machine according to the weight percentage of 5 percent to 95 percent, other method steps are the same as the embodiment 1, the glass silver-loaded antibacterial polyester fiber is obtained, the cross section is circular, the actually measured fiber linear density is 1.58dtex, the breaking strength is 4.61cN/dtex, and the bacteriostasis rate of the fiber to staphylococcus aureus and escherichia coli is more than 99 percent. The fiber sample is placed under a standard light source box and is irradiated by an ultraviolet lamp for 30 days, and no yellowing phenomenon is found. The fiber sample is placed under natural light for 3 months, and no yellowing phenomenon is found.
Example 4
The fourth step in example 1 was modified to: the dried glass silver-loaded antibacterial master batch and the polyester chip are separately measured by an injection machine according to the weight percentage of 8 percent to 92 percent, other method steps are the same as the embodiment 1, the glass silver-loaded antibacterial polyester fiber is obtained, the cross section is circular, the actually measured fiber linear density is 1.58dtex, the breaking strength is 4.60cN/dtex, and the bacteriostasis rate of the fiber to staphylococcus aureus and escherichia coli is more than 99 percent. The fiber sample is placed under a standard light source box and is irradiated by an ultraviolet lamp for 30 days, and no yellowing phenomenon is found. The fiber sample is placed under natural light for 3 months, and no yellowing phenomenon is found.
Example 5
The temperature for the phase separation heat treatment of the glass powder in example 1 was adjusted as follows:
phase splittingThe heat treatment temperature is 550 ℃, the time is 12 hours, when other processes are not changed, the weight loss rate of the glass after acid treatment is 36.8 percent, the average pore diameter of the porous glass is 3.0nm, and the specific surface area is 110m2/g。
Or, when the temperature of the phase separation heat treatment is 570 ℃, the time is 12 hours, and other processes are not changed, the weight loss rate of the glass after acid treatment is 37.8 percent, the average pore diameter of the porous glass is 4.2nm, and the specific surface area is 98m2/g。
Comparative example 1
Preparation of silver-loaded glass antibacterial polyester fiber with nominal linear density of 1.56dtex (changing calcination temperature of porous glass silver-loaded)
The calcining temperature of the porous glass silver-carrying powder in the first step of the example 1 is changed from 400 ℃ in the example 1 to 500 ℃, the same as the rest of the example 1, the color of the calcined and cooled porous glass silver-carrying powder turns yellow, the linear density of the prepared fiber is measured to be 1.58dtex, the breaking strength is 4.61cN/dtex, and the bacteriostasis rate of the fiber to staphylococcus aureus and escherichia coli is only 75%. The fiber sample is placed under a standard light source box and is irradiated by an ultraviolet lamp for 5 days, and the fiber has yellowing phenomenon. The result shows that when the calcining treatment temperature of the porous glass silver-loaded powder is 500 ℃, part of silver ions are converted into atoms due to high temperature, the color of the porous glass silver-loaded powder turns yellow, and the antibacterial effect of the corresponding fiber is also obviously reduced.
Comparative example 2
Preparation of glass silver-carrying antibacterial polyester fiber (surface modification of porous glass silver-carrying is not carried out)
The second step in example 1 was deleted, and the rest of the example 1 found: when the prepared fiber is spun, the pressure of the component is increased, the component is frequently replaced, and the fiber can not be spun seriously, which indicates that the porous glass silver-loaded powder without surface modification is easy to agglomerate and block a filter screen of the component.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The glass silver-loaded antibacterial polyester fiber is characterized by being prepared from the following components in percentage by weight: 5-10% of glass silver-loaded antibacterial master batch and 90-95% of polyester chips;
the glass silver-loaded antibacterial master batch is prepared from the following components in percentage by weight: 10-20% of modified porous glass silver-loaded powder and 80-90% of polyester powder;
the modified porous glass silver-loaded powder is prepared from the following components in percentage by weight: the silver-carrying porous glass powder and 3-glycidoxypropyltrimethoxysilane coupling agent powder accounting for 0.1-1 wt% of the silver-carrying porous glass powder;
the porous glass silver-carrying powder is obtained by dissolving porous glass in a silver nitrate solution to prepare a solution with the concentration of 0.05-0.2 g/ml and then calcining the solution;
the porous glass is obtained by preparing glass powder from the following components in percentage by weight and then acidifying the glass powder: 60-63% of silicon dioxide, 27-30% of boron oxide, 8.5-9.0% of sodium oxide and 1-1.5% of aluminum oxide.
2. The glass-loaded silver antibacterial polyester fiber according to claim 1, characterized in that the glass-loaded silver antibacterial polyester fiber is prepared from the following components in percentage by weight: 6 percent of glass silver-carrying antibacterial master batch and 94 percent of polyester chip.
3. The glass silver-loaded antibacterial polyester fiber according to claim 1, wherein the glass silver-loaded antibacterial master batch is prepared from the following components in percentage by weight: 15% of modified porous glass silver-carrying powder and 85% of polyester powder.
4. The glass silver-loaded antibacterial polyester fiber according to claim 1, wherein the modified porous glass silver-loaded powder is prepared from the following components in percentage by weight: the porous glass silver-carrying powder and 3-glycidoxypropyltrimethoxysilane coupling agent powder accounting for 0.5 percent of the weight of the porous glass silver-carrying powder.
5. The glass silver-loaded antibacterial polyester fiber according to claim 1, wherein the porous glass is obtained by preparing glass powder from the following components in percentage by weight and then acidifying the glass powder: 60% of silicon dioxide, 30% of boron oxide, 8.5% of sodium oxide and 1.5% of aluminum oxide;
the cross section of the glass silver-loaded antibacterial polyester fiber can be circular, single hollow, multiple hollow and cross-shaped; the nominal linear density of the fiber is 0.89dtex to 6.67 dtex.
6. A method for preparing the glass-supported silver antibacterial polyester fiber according to any one of claims 1 to 5, which is characterized by comprising the following steps:
firstly, the preparation method of the porous glass silver-loaded powder comprises the following steps:
grinding and uniformly mixing silicon dioxide, boron oxide, sodium oxide and aluminum oxide, melting at high temperature, stirring and cooling with water, filtering, drying, crushing and ball-milling until the particle size is 0.5-0.6 um to obtain glass powder;
carrying out phase-splitting heat treatment on the glass powder, and acidifying to obtain porous glass;
dissolving porous glass in silver nitrate solution, adjusting pH value to 9.0, processing in a dark and constant-temperature water bath, performing suction filtration and washing until pH value reaches 7.0, and drying and calcining to obtain porous glass silver-loaded powder;
secondly, the preparation method of the modified porous glass silver-carrying powder comprises the following steps:
mixing the porous glass silver-loaded powder prepared in the first step with 3-glycidyl ether oxypropyl trimethoxy silane coupling agent powder, and performing ball milling and sieving to obtain surface-modified porous glass silver-loaded powder with the particle size of 0.3-0.4 um;
thirdly, the preparation method of the glass silver-carrying antibacterial master batch comprises the following steps:
blending the modified porous glass silver-carrying powder prepared in the second step with polyester powder, drying, extruding and melting by a screw, extruding, cooling by water, drawing strips, granulating and drying to prepare glass silver-carrying antibacterial master batches;
fourthly, the preparation method of the glass silver-loaded antibacterial polyester fiber comprises the following steps:
and (2) independently metering the dried glass silver-loaded antibacterial master batch and the dried polyester chips by using an injection machine, blending, performing melt spinning, winding and barrel dropping to obtain precursor fibers, and performing post-spinning drafting and tension heat setting on the precursor fibers to obtain the glass silver-loaded antibacterial polyester fibers.
7. The preparation method of the glass silver-loaded antibacterial polyester fiber according to claim 6, wherein the high-temperature melting temperature in the first step is 1450-1500 ℃, and the time is 0.5-1.5 hours;
the temperature of the phase separation heat treatment in the first step is 550-580 ℃, and the heat treatment time is 12-24 hours;
in the first step, the aperture of the porous glass is 3.0-5.5 nm, and the specific surface area is 75-110 m2The weight loss rate is 36.8-38.2 percent.
8. The method for preparing the silver-loaded glass antibacterial polyester fiber according to claim 6, wherein the specific steps of obtaining the porous glass after acidification in the first step are as follows:
dissolving the glass powder in hydrochloric acid, wherein the concentration is 0.1g/ml, the molar concentration of the hydrochloric acid is 0.05mol/L, the temperature is 90-95 ℃, the constant temperature is kept for 24-30 hours, and the porous glass is prepared by carrying out suction filtration and pure water washing until the pH value is 7.0 and drying at the temperature of 100-110 ℃;
the concentration of the silver nitrate solution in the first step is 0.05 mol/L.
9. The preparation method of the glass silver-loaded antibacterial polyester fiber according to claim 6, wherein the particle size of the polyester powder in the third step is 0.3-0.4 um;
and the melting temperature of the screw in the third step is 272-282 ℃.
10. The method for preparing the glass-supported silver antibacterial polyester fiber according to claim 6, wherein in the fourth step, the drying temperature of the glass-supported silver antibacterial master batch is 120 ℃, and the drying time is 8-12 hours;
in the fourth step, the drying temperature of the polyester chip is 120 ℃, and the drying time is 8-12 hours;
in the fourth step, the spinning temperature is 275-285 ℃, the spinning speed is 1000-1100 m/min, the drafting multiple is 3.4-4.5 times, and the heat setting temperature is 170 +/-2 ℃.
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