CN113529206A - Antibacterial and deodorant ES fiber and preparation method thereof - Google Patents
Antibacterial and deodorant ES fiber and preparation method thereof Download PDFInfo
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- CN113529206A CN113529206A CN202010323146.5A CN202010323146A CN113529206A CN 113529206 A CN113529206 A CN 113529206A CN 202010323146 A CN202010323146 A CN 202010323146A CN 113529206 A CN113529206 A CN 113529206A
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- 238000002360 preparation method Methods 0.000 title abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 88
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- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 61
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 230000001877 deodorizing effect Effects 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 230000004048 modification Effects 0.000 claims abstract description 14
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 60
- 229910052799 carbon Inorganic materials 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 29
- 229920002873 Polyethylenimine Polymers 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
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- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 9
- 239000007822 coupling agent Substances 0.000 claims description 8
- 239000010410 layer Substances 0.000 claims description 6
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
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- 238000009987 spinning Methods 0.000 claims description 5
- 229940014800 succinic anhydride Drugs 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 22
- 238000004332 deodorization Methods 0.000 abstract description 10
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- 241000191967 Staphylococcus aureus Species 0.000 abstract description 8
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- 230000002195 synergetic effect Effects 0.000 abstract description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 8
- 239000003463 adsorbent Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
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- 238000011161 development Methods 0.000 description 2
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- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
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- 239000003575 carbonaceous material Substances 0.000 description 1
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- 230000007246 mechanism Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
-
- 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
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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- 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)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses an antibacterial deodorizing ES fiber and a preparation method thereof, wherein the antibacterial deodorizing ES fiber comprises the following raw material components in parts by weight: 95.5-99.1 parts of HDPE, 100-150 parts of PET, 0-1.5 parts of modified nano ZnO and 0-1.5 parts of modified nano TiO20-1.5 parts of novel activated carbon, wherein the novel activated carbon is a polycarboxylic activated carbon obtained by surface oxidation modification and grafting modification, and the preparation method of the antibacterial deodorizing ES fiber is provided, the composite antibacterial adsorption system provided by the invention is used for synergistic antibacterial deodorization, the antibacterial rate of the composite antibacterial adsorption system on escherichia coli and staphylococcus aureus reaches more than 99.9%, and the antibacterial adsorption performance is good; the mechanical property is good, and the application range is wide; the process is simple and the forming effect is good.
Description
Technical Field
The invention relates to an ES fiber and a preparation method thereof, in particular to an antibacterial deodorizing ES fiber and a preparation method thereof, belonging to the technical field of preparation of antibacterial deodorizing fibers.
Background
ES fiber, the earliest low-melting bicomponent composite fiber, was a polyolefin composite fiber developed by japan wisdom corporation and was commercialized in 1977. After the fiber is subjected to heat treatment, part of the surface layer is melted and bonded, the rest part of the surface layer is kept in a fiber state, meanwhile, the heat shrinkage rate is small, and the non-woven fabric can be directly formed without an adhesive. The ES fiber has the advantages of soft hand feeling, low processing temperature, no toxicity, no stimulation and light weight, can be in close contact with the skin of a human body, so the ES fiber is applied to disposable sanitary products in the largest field, such as baby diapers and sanitary napkins for high-grade women, which have higher requirements on the antibacterial performance, and the preparation and research of the ES fiber for antibacterial and deodorization increasingly become research hotspots. The ES fibers can be used in all major nonwoven processing methods. Different heat treatment methods are selected, including hot rolling, hot air and the like, so as to obtain non-woven fabrics with different effects.
In the prior art, the application range of the non-woven fabric is wider and wider, and the requirements on the air permeability, the adsorption and the antibacterial performance of the non-woven fabric are higher and higher. However, the antibacterial property, air permeability and adsorptivity of the ES fiber in the prior art are all to be improved.
Disclosure of Invention
The purpose of the invention is as follows: the first purpose of the invention is to provide the antibacterial and deodorant ES fiber with good antibacterial and deodorant properties, good mechanical properties and good forming effect, and the second purpose of the invention is to provide the preparation method of the antibacterial and deodorant ES fiber.
The technical scheme is as follows: the invention relates to an antibacterial deodorizing ES fiber which is prepared from the following raw materials in parts by weight: 95.5-99.1 parts of HDPE, 100-150 parts of PET, 0-1.5 parts of modified nano ZnO and 0-1.5 parts of modified nano TiO2And 0-1.5 parts of novel activated carbon, wherein the novel activated carbon is polycarboxyl activated carbon obtained by surface oxidation modification and grafting modification.
The PE has the advantages of good chemical stability, light weight, wide processing temperature range, good hydrophobicity, good moisture conductivity and the like, particularly, the HDPE has a lower melting point, and can be used as a fiber skin layer to be subjected to hot air bonding or hot rolling bonding at a lower temperature to form a non-woven fabric, so that a bonding agent is not required, the PE is ecological and environment-friendly, and the environment is not polluted. But poor adhesion and compatibility with other polymers. Polyester is the most used of the current synthetic fiber products, has the best combination property and relatively low cost, and is deeply concerned by various large manufacturers.
Therefore, based on the respective advantages of the two raw materials, the two polymers are compounded to prepare the bi-component sheath-core composite fiber with stable sheath-core structure and small dry-heat shrinkage rate, and the HDPE/PET sheath-core composite fiber for the high-grade sanitary material is developed, so that the great market demand can be met, the quality of domestic products can be improved to a certain extent, considerable economic benefits are generated, the development of the non-woven industry in China is promoted, the current situation of industrial textiles in China is rapidly changed, and the method has great significance for the development of high-grade sanitary materials in China.
As shown in fig. 3, the preparation method of the novel activated carbon of antibacterial and deodorant ES fiber of the present invention comprises the following steps:
(1) adding 125-250mL concentrated HNO with the mass fraction of 65 wt% into 5-10g of activated carbon AC3Stirring at 50-80 deg.C, condensing and refluxing for 14-20h, filtering, washing, and drying to obtain oxidation product AC-COOH;
(2) adding 25-50mL of thionyl chloride solution into 4-8g of AC-COOH, heating to 40-70 ℃ under the condition of stirring, carrying out condensation reflux reaction for 20-24h, respectively washing with anhydrous dichloromethane and tetrahydrofuran solution, and drying to obtain a chlorination product AC-COCl;
(3) under the anhydrous environment, the weight ratio of (3-4): 1, weighing the AC-COCl and the polyethyleneimine PEI, adding anhydrous dichloromethane, stirring for 10-15h, filtering, respectively washing with anhydrous dichloromethane and tetrahydrofuran solution, and drying to obtain a polyethyleneimine product AC-PEI;
(4) weighing AC-PEI and succinic anhydride SAA according to the mass ratio of 1-1.5: 1, adding anhydrous dichloromethane, reacting for 20-24h at the temperature of 30-50 ℃ under the stirring condition, filtering, washing and drying to obtain the novel active carbon AC-PEI-SAA.
The preparation method of the antibacterial deodorizing ES fiber comprises the following steps:
(1) slicing HDPE, modifying nano ZnO and modifying nano TiO2Or two or three of the novel active carbon are melted and blended to prepare the antibacterial deodorizing HDPE slices, the melting temperature is 190-230 ℃, the pressure is 500-1500Mpa, and the rotating speed of the screw is 40-80 r/min;
(2) heating the antibacterial and deodorant HDPE slices from room temperature to 50-80 ℃ for 0.5-2 hours, and preserving heat for 10-12 hours; cooling to 50-60 ℃ after 0.5-2 hours to obtain dried antibacterial and deodorant HDPE slices, and preserving heat for later use;
(3) raising the temperature of PET from room temperature to 50-80 ℃ for 0.5-3 hours, and preserving the heat for 1-2 hours; heating to 90-110 ℃ after 0.5-1 hour, and preserving heat for 8-12 hours; heating to 120-140 ℃ after 0.5-1 hour, and preserving heat for 8-15 hours; cooling to 50-60 ℃ after 1-4 hours to obtain dried PET, and preserving heat for later use;
(4) and carrying out composite melt spinning and drafting winding on the dried antibacterial and deodorant HDPE slices and the dried PET slices to obtain the antibacterial and deodorant ES fiber.
Further, step (2) and step (3) are carried out in a vacuum drum oven.
Preferably, 97 to 97.9 parts of HDPE, 0.9 to 1.2 parts of modified nano ZnO and 0.9 to 1.2 parts of modified nano TiO20.3-0.6 part of novel active carbon is melted and blended to prepare the antibacterial and deodorant HDPE slice, and the antibacterial and deodorant HDPE slice is melted and blendedThe melting temperature was 190 ℃.
Besides HDPE-4, other HDPE can form fibers with good forming effect with PET.
The particle size control range of the antibacterial agent is as follows: modified nano ZnO and modified nano TiO2: d98 is less than or equal to 100 nm; novel activated carbon: d98 is less than or equal to 3000 nm; heating the antibacterial and deodorant HDPE slices in a vacuum stranding oven from room temperature to 80 ℃ for 2 hours, and preserving heat for 10 hours; cooling to 60 ℃ after 2 hours, and keeping the temperature for later use; heating 150 parts of PET in a vacuum strand-rotating oven for 1 hour from room temperature to 80 ℃, and preserving heat for 2 hours; heating to 110 ℃ after 1 hour, and keeping the temperature for 12 hours; heating to 140 ℃ after 1 hour, and keeping the temperature for 14 hours; cooling to 60 ℃ after 2 hours, and keeping the temperature for later use; the melt spinning temperatures of the antibacterial and deodorant HDPE slices and the PET slices are 180-290 ℃ and 260-290 ℃ respectively, and the winding speed is 300-1200 m/min; carrying out composite melt spinning and drafting winding on the dried antibacterial and deodorant HDPE slices and PET to obtain antibacterial and deodorant ES fibers; the prepared antibacterial and deodorant ES fiber has a skin-core ratio of 40:60, and has high strength and elongation at break and low dry heat shrinkage rate, and the dry heat shrinkage rate is obviously reduced along with the increase of the heat setting temperature; when the antibacterial agent content of the prepared antibacterial deodorizing ES fiber reaches 1.5 mass percent, the antibacterial rate of the prepared antibacterial deodorizing ES fiber to escherichia coli and staphylococcus aureus reaches more than 99.9 percent, and all sterilization is basically realized; through methyl mercaptan air adsorption experiments, continuous experiments are carried out for 1200 minutes, and the filtered air still has no peculiar smell and has excellent adsorption and deodorization performance.
The invention mechanism is as follows: the antibacterial and deodorant ES fiber prepared by the invention achieves more efficient antibacterial and deodorant effects through the synergistic antibacterial adsorption effect of the composite antibacterial adsorbent: ZnO and TiO2Stable chemical property, safety, non-toxicity, modified nano ZnO and TiO2The surface is connected with a coupling agent with terminal hydroxyl, so that the agglomeration phenomenon can be reduced, and the compatibility with a base material is improved; the novel active carbon is an active carbon adsorption material with multi-carboxyl, and the carboxyl grafted on the surface of the novel active carbon can react with the terminal hydroxyl on the surface of the modified nano oxide, so that the nano antibacterial agent is chemically loaded; ZnO and TiO2The photocatalyst is compounded with active carbon, the porosity of the active carbon is utilized to form local high concentration in a fine range, and the problems of continuous use and secondary pollution can be solved through photocatalytic degradation desorption, the service time of the photocatalyst can be further prolonged, the service efficiency can be improved, and the nano ZnO and TiO can be improved2The novel active carbon material has high-efficiency adsorption performance while having antibacterial efficiency, so that the fiber has excellent adsorption and deodorization functions; meanwhile, the activated carbon particles with the ZnO connected on the surface are mutually repelled because the ZnO has positive charges, thereby reducing the agglomeration of the activated carbon particles and further improving the ZnO and TiO2The antibacterial and deodorant efficiency of the composite system with the active carbon can be improved at the same time, and the spinnability of the composite system in the fiber forming process can be improved.
0.3-4.5 parts of antibacterial adsorbent is added into the antibacterial deodorizing ES fiber according to the mass parts of the cortex. The skin-core compounding ratio of the antibacterial deodorizing ES fiber is 40/60 and 50/50.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: the composite antibacterial adsorption system is cooperated with antibacterial deodorization, the antibacterial rate to escherichia coli and staphylococcus aureus reaches more than 99.9%, and the antibacterial adsorption performance is good; the mechanical property is good, and the application range is wide; the process is simple and the forming effect is good.
Drawings
FIGS. 1(a) - (b) are cross-sectional profiles of fibers with different sheath-core composite ratios, FIG. 1(a) is a cross-sectional profile of HDPE/PET (50/50) fiber, and FIG. 1(b) is a cross-sectional profile of HDPE/PET (40/60) fiber;
FIGS. 2(a) - (b) show the results of the antibacterial test, FIG. 2(a) shows the results of the Escherichia coli test, and FIG. 2(b) shows the results of the Staphylococcus aureus test;
fig. 3 is a schematic diagram of a preparation process of the novel activated carbon.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
Example 1
The antibacterial and deodorant ES fiber is prepared from the following raw materials in parts by weight: 95.5 parts of HDPE, 100 parts of PET, 0.3 part of modified nano ZnO and 0.3 part of novel activityThe novel active carbon is a polycarboxyl active carbon obtained through surface oxidation modification and grafting modification, the antibacterial and deodorant ES fiber takes HDPE added with modified nano ZnO and the novel active carbon as a skin layer, the antibacterial and deodorant ES fiber takes PET as a core layer, and the antibacterial and deodorant ES fiber is prepared through melt composite spinning. Modified nano ZnO and modified nano TiO2The modifier is titanate coupling agent. The particle size of the modified nano ZnO is controlled to be D98-99 nm, and the particle size of the novel active carbon is controlled to be D98-2998 nm.
The preparation method of the novel antibacterial and deodorant ES fiber activated carbon comprises the following steps:
(1) adding 125mL of concentrated HNO with the mass fraction of 65 wt% into 5g of activated carbon AC3Stirring at a constant temperature of 60 ℃, condensing and refluxing for 14h, filtering, washing and drying for 48h to obtain an oxidation product AC-COOH;
(2) adding 25mL of thionyl chloride solution into 4g of AC-COOH, heating to 50 ℃ under the condition of stirring, carrying out condensation reflux reaction for 20h, respectively washing with anhydrous dichloromethane and tetrahydrofuran solution, and drying for 24h to obtain a chlorination product AC-COCl;
(3) under the anhydrous environment, according to the mass ratio of 3: 1, weighing AC-COCl and polyethyleneimine PEI, adding anhydrous dichloromethane, stirring for 10h, filtering, respectively cleaning with anhydrous dichloromethane and tetrahydrofuran solution, and drying for 24h to obtain a polyethyleneimine product AC-PEI;
(4) weighing AC-PEI and succinic anhydride SAA according to the mass ratio of 1:1, adding anhydrous dichloromethane, reacting for 20 hours at the temperature of 35 ℃ under the condition of stirring, filtering, washing and drying for 24 hours to obtain the novel active carbon AC-PEI-SAA.
The preparation method of the antibacterial and deodorant ES fiber is characterized by comprising the following steps:
(1) slicing HDPE, melting and blending modified nano ZnO and novel active carbon to obtain antibacterial deodorizing HDPE slices, wherein the melting temperature is 190 ℃, the pressure is 500Mpa, and the screw rotating speed is 40 r/min;
(2) in a vacuum drum oven, the antibacterial and deodorant HDPE slices are heated from room temperature to 50 ℃ for 0.5 hour, and then are kept warm for 10 hours; cooling to 50 ℃ after 0.5 hour to obtain dried antibacterial deodorizing HDPE slices, and keeping the temperature for later use;
(3) in a vacuum drum oven, PET is heated from room temperature to 50 ℃ for 0.5 hour, and the temperature is kept for 1 hour; heating to 90 ℃ after 0.5 hour, and keeping the temperature for 8 hours; heating to 120 ℃ after 0.5 hour, and keeping the temperature for 8 hours; cooling to 50 ℃ for 1 hour to obtain dried PET, and keeping the temperature for later use;
(4) and carrying out composite melt spinning and drafting winding on the dried antibacterial and deodorant HDPE slices and the dried PET slices, wherein the melt spinning temperature of the dried antibacterial and deodorant HDPE slices is 180 ℃, the melt spinning temperature of the dried PET slices is 260 ℃, and the winding speed is 300m/min, so that the antibacterial and deodorant ES fiber is obtained.
The antibacterial and deodorant ES fiber prepared by the embodiment has the antibacterial adsorbent content reaching 0.6 mass percent, and within 24 hours, the antibacterial rate to escherichia coli and staphylococcus aureus reaches more than 90 percent, so that the antibacterial and bacteriostatic requirements in daily life are basically met.
The antibacterial and deodorant ES fiber prepared by the embodiment is continuously tested for 1200 minutes through a methyl mercaptan air adsorption test, and the filtered air still has no peculiar smell and has excellent adsorption and deodorization performance.
Example 2
The antibacterial and deodorant ES fiber is prepared from the following raw materials in parts by weight: 99.1 parts of HDPE, 150 parts of PET, 1.5 parts of modified nano ZnO and 1.5 parts of modified nano TiO21.5 parts of novel active carbon, wherein the novel active carbon is polycarboxyl active carbon obtained by surface oxidation modification and graft modification, and the antibacterial and deodorant ES fiber is added with modified nano ZnO and modified nano TiO2HDPE of the novel active carbon is used as a skin layer, PET is used as a core layer of the antibacterial deodorizing ES fiber, and the antibacterial deodorizing ES fiber is prepared by melt composite spinning. Modified nano ZnO and modified nano TiO2The modifier is a borate coupling agent. Modified nano ZnO and modified nano TiO2The particle size of the novel active carbon is controlled to be D98-99 nm, and the particle size of the novel active carbon is controlled to be D98-2998 nm.
The preparation method of the novel antibacterial and deodorant ES fiber activated carbon comprises the following steps:
(1) adding 250mL of concentrated HNO with the mass fraction of 65 wt% into 10g of activated carbon AC3Stirring at a constant temperature of 60 ℃, condensing and refluxing for 20 hours, filtering, washing and drying for 60 hours to obtain an oxidation product AC-COOH;
(2) adding 50mL of thionyl chloride solution into 8g of AC-COOH, heating to 40 ℃ under the condition of stirring, carrying out condensation reflux reaction for 24 hours, respectively washing with anhydrous dichloromethane and tetrahydrofuran solution, and drying for 32 hours to obtain a chlorination product AC-COCl;
(3) under the anhydrous environment, according to the mass ratio of 4: 1, weighing AC-COCl and polyethyleneimine PEI, adding anhydrous dichloromethane, stirring for 15h, filtering, respectively cleaning with anhydrous dichloromethane and tetrahydrofuran solution, and drying for 32h to obtain a polyethyleneimine product AC-PEI;
(4) weighing AC-PEI and succinic anhydride SAA according to the mass ratio of 1.5:1, adding anhydrous dichloromethane, reacting for 24 hours at the temperature of 30 ℃ under the condition of stirring, filtering, washing and drying for 30 hours to obtain the novel active carbon AC-PEI-SAA.
The preparation method of the antibacterial and deodorant ES fiber is characterized by comprising the following steps:
(1) slicing HDPE, modifying nano ZnO and modifying nano TiO2Melting and blending with novel active carbon to obtain antibacterial deodorizing HDPE slices, wherein the melting temperature is 230 ℃, the pressure is 1500Mpa, and the screw rotation speed is 80 r/min;
(2) in a vacuum drum oven, heating the antibacterial and deodorant HDPE slices from room temperature to 80 ℃ for 2 hours, and preserving heat for 12 hours; cooling to 60 ℃ after 2 hours to obtain dried antibacterial deodorizing HDPE slices, and preserving heat for later use;
(3) in a vacuum drum oven, PET is heated from room temperature to 80 ℃ for 3 hours, and the temperature is kept for 2 hours; heating to 110 ℃ after 1 hour, and keeping the temperature for 12 hours; heating to 140 ℃ after 1 hour, and keeping the temperature for 15 hours; cooling to 60 ℃ for 4 hours to obtain dried PET, and preserving heat for later use;
(4) and carrying out composite melt spinning and drafting winding on the dried antibacterial and deodorant HDPE slices and the dried PET slices, wherein the melt spinning temperature of the dried antibacterial and deodorant HDPE slices is 290 ℃, the melt spinning temperature of the dried PET slices is 290 ℃, and the winding speed is 1200m/min, so that the antibacterial and deodorant ES fiber is obtained.
The antibacterial and deodorant ES fiber prepared by the embodiment has the antibacterial adsorbent content reaching 4.5% by mass, and within 24h, the antibacterial rate of Escherichia coli and Staphylococcus aureus reaches more than 99.9%, and all sterilization is basically realized.
The antibacterial and deodorant ES fiber prepared by the embodiment is continuously tested for 1200 minutes through a methyl mercaptan air adsorption test, and the filtered air still has no peculiar smell and has excellent adsorption and deodorization performance.
Example 3
The antibacterial and deodorant ES fiber is prepared from the following raw materials in parts by weight: 98 parts of HDPE, 120 parts of PET and 0.3 part of modified nano TiO20.3 part of novel active carbon, wherein the novel active carbon is polycarboxyl active carbon obtained by surface oxidation modification and graft modification, and the antibacterial and deodorant ES fiber is nano TiO modified2HDPE of the novel active carbon is used as a skin layer, PET is used as a core layer of the antibacterial deodorizing ES fiber, and the antibacterial deodorizing ES fiber is prepared by melt composite spinning. Modified nano TiO2The modifier is an aluminate coupling agent. Modified nano TiO2The particle size of the novel active carbon is controlled to be D98-99 nm, and the particle size of the novel active carbon is controlled to be D98-2998 nm.
The preparation method of the novel antibacterial and deodorant ES fiber activated carbon comprises the following steps:
(1) adding 125mL of concentrated HNO with the mass fraction of 65 wt% into 5g of activated carbon AC3Stirring at a constant temperature of 60 ℃, condensing and refluxing for 14h, filtering, washing and drying for 48h to obtain an oxidation product AC-COOH;
(2) adding 25mL of thionyl chloride solution into 4g of AC-COOH, heating to 70 ℃ under the condition of stirring, carrying out condensation reflux reaction for 20h, respectively washing with anhydrous dichloromethane and tetrahydrofuran solution, and drying for 24h to obtain a chlorination product AC-COCl;
(3) under the anhydrous environment, the weight ratio of 3.5: 1, weighing AC-COCl and polyethyleneimine PEI, adding anhydrous dichloromethane, stirring for 12h, filtering, respectively cleaning with anhydrous dichloromethane and tetrahydrofuran solution, and drying for 28h to obtain a polyethyleneimine product AC-PEI;
(4) weighing AC-PEI and succinic anhydride SAA according to the mass ratio of 1.2:1, adding anhydrous dichloromethane, reacting for 22h under the condition of stirring at 50 ℃, filtering, washing and drying for 26h to obtain the novel active carbon AC-PEI-SAA.
The preparation method of the antibacterial and deodorant ES fiber is characterized by comprising the following steps:
(1) slicing HDPE, modifying nano TiO2Melting and blending with novel active carbon to obtain antibacterial deodorizing HDPE slices, wherein the melting temperature is 200 ℃, the pressure is 1200Mpa, and the screw rotation speed is 60 r/min;
(2) in a vacuum drum oven, heating the antibacterial and deodorant HDPE slices from room temperature to 60 ℃ for 1 hour, and preserving heat for 11 hours; cooling to 55 ℃ after 1 hour to obtain dried antibacterial deodorizing HDPE slices, and keeping the temperature for later use;
(3) in a vacuum drum oven, heating PET from room temperature to 60 ℃ for 2 hours, and preserving heat for 1.5 hours; heating to 100 ℃ after 0.8 hour, and preserving heat for 10 hours; heating to 130 ℃ after 0.8 hour, and preserving heat for 10 hours; cooling to 55 ℃ after 3 hours to obtain dried PET, and preserving heat for later use;
(4) and carrying out composite melt spinning and drafting winding on the dried antibacterial and deodorant HDPE slices and the dried PET slices, wherein the melt spinning temperature of the dried antibacterial and deodorant HDPE slices is 220 ℃, the melt spinning temperature of the dried PET slices is 275 ℃, and the winding speed is 1000m/min, so as to obtain the antibacterial and deodorant ES fiber.
The antibacterial and deodorant ES fiber prepared by the embodiment has the antibacterial adsorbent content reaching 0.6 mass percent, and within 24 hours, the antibacterial rate to escherichia coli and staphylococcus aureus reaches more than 90 percent, so that the antibacterial and bacteriostatic requirements in daily life are basically met.
The antibacterial and deodorant ES fiber prepared by the embodiment is continuously tested for 1200 minutes through a methyl mercaptan air adsorption test, and the filtered air still has no peculiar smell and has excellent adsorption and deodorization performance.
Example 4
The antibacterial and deodorant ES fiber is prepared from the following raw materials in parts by weight: 99.1 parts of HDPE, 150 parts of PET, 1.5 parts of modified nano ZnO and 1.5 parts of modified nano TiO2Wherein the novel active carbon is a polycarboxyl active carbon obtained by surface oxidation modification and graft modification, and the antibacterial and deodorant ES fiber is prepared by adding modified nano ZnO and modified nano TiO2The HDPE is used as a skin layer, the antibacterial and deodorant ES fiber takes PET as a core layer, and the antibacterial and deodorant ES fiber is prepared by melt composite spinning. Modified nano ZnO and modified nano TiO2The modifier is a borate coupling agent. Modified nano ZnO and modified nano TiO2The particle size of (D98) is controlled to 99 nm.
The preparation method of the antibacterial and deodorant ES fiber is characterized by comprising the following steps:
(1) slicing HDPE, modifying nano ZnO and modifying nano TiO2Melting and blending to obtain antibacterial deodorant HDPE slices, wherein the melting temperature is 230 ℃, the pressure is 1500Mpa, and the screw rotating speed is 80 r/min;
(2) in a vacuum drum oven, heating the antibacterial and deodorant HDPE slices from room temperature to 80 ℃ for 2 hours, and preserving heat for 12 hours; cooling to 60 ℃ after 2 hours to obtain dried antibacterial deodorizing HDPE slices, and preserving heat for later use;
(3) in a vacuum drum oven, PET is heated from room temperature to 80 ℃ for 3 hours, and the temperature is kept for 2 hours; heating to 110 ℃ after 1 hour, and keeping the temperature for 12 hours; heating to 140 ℃ after 1 hour, and keeping the temperature for 15 hours; cooling to 60 ℃ for 4 hours to obtain dried PET, and preserving heat for later use;
(4) and carrying out composite melt spinning and drafting winding on the dried antibacterial and deodorant HDPE slices and the dried PET slices, wherein the melt spinning temperature of the dried antibacterial and deodorant HDPE slices is 290 ℃, the melt spinning temperature of the dried PET slices is 290 ℃, and the winding speed is 1200m/min, so that the antibacterial and deodorant ES fiber is obtained.
The antibacterial and deodorant ES fiber prepared by the embodiment has the antibacterial adsorbent content reaching 3.0% by mass, and within 24h, the antibacterial rate of Escherichia coli and Staphylococcus aureus reaches more than 99.9%, and all sterilization is basically realized.
The antibacterial and deodorant ES fiber prepared by the embodiment is continuously tested for 1200 minutes through a methyl mercaptan air adsorption test, and the filtered air still has no peculiar smell and has excellent adsorption and deodorization performance.
The HDPE is prepared from fiber-grade HDPE provided by six different manufacturers, and the advantages and disadvantages of different HDPE are compared through rheological property and viscosity matching research of PET, non-isothermal crystallization performance research and skin-core composite fiber preparation performance research. Different fiber grades of HDPE are shown in table 1.
TABLE 1 different fiber grades of HDPE
When the content of the antibacterial adsorbent of the prepared antibacterial deodorizing ES fiber reaches 1.5 percent of the mass fraction, the antibacterial rate reaches more than 99.9 percent, and the complete sterilization is basically realized.
The prepared antibacterial deodorizing ES fiber is continuously tested for 1200 minutes through a methyl mercaptan air adsorption test, and the filtered air still has no peculiar smell and has excellent adsorption and deodorization performances.
As shown in fig. 1(a) - (b), the scale bar is 1: 2000, it can be seen that the fiber has good forming effect, regular distribution of the sheath-core structure, long operation period of the spinneret plate for the component, stable pressure inside the component, almost within 8-10MPa, and good spinnability in practical application.
As shown in fig. 2(a) - (b), within 24h, when the content of the antibacterial agent reaches 0.9% of the mass fraction, the antibacterial rate reaches over 90%, the requirements of daily life on antibiosis and bacteriostasis are basically met, and when the content of the antibacterial agent reaches 1.5% of the mass fraction, the antibacterial rate reaches over 99.9%, and all sterilization is basically realized.
Claims (10)
1. The antibacterial and deodorant ES fiber is characterized by comprising the following raw material components in parts by weight: 95.5-99.1 parts of HDPE, 100-150 parts of PET, 0-1.5 parts of modified nano ZnO, 0-E1.5 parts of modified nano TiO2And 0-1.5 parts of novel activated carbon, wherein the novel activated carbon is polycarboxyl activated carbon obtained by surface oxidation modification and grafting modification.
2. The antibacterial and deodorant ES fiber according to claim 1, wherein: the antibacterial deodorizing ES fiber is added with modified nano ZnO and modified nano TiO2Or two or three kinds of HDPE in the novel active carbon are used as skin layers, the antibacterial and deodorant ES fiber takes PET as a core layer, and the antibacterial and deodorant ES fiber is prepared by melt composite spinning.
3. The antibacterial and deodorant ES fiber according to claim 1, wherein: the modified nano ZnO and the modified nano TiO2The modifier is one of titanate coupling agent, borate coupling agent or aluminate coupling agent.
4. The antibacterial and deodorant ES fiber according to claim 1, wherein: the modified nano ZnO and the modified nano TiO2The particle size of the novel active carbon is controlled to be less than or equal to D98 and less than or equal to 100nm, and the particle size of the novel active carbon is controlled to be less than or equal to D98 and less than or equal to 3000 nm.
5. A method for preparing novel activated carbon of antibacterial deodorizing ES fiber according to claim 1, comprising the steps of:
(1) adding 125-250mL of concentrated HNO with the mass fraction of 65 wt% into 5-10g of activated carbon AC3Stirring at 50-80 deg.C, condensing and refluxing for 14-20h, filtering, washing, and drying to obtain oxidation product AC-COOH;
(2) adding 25-50mL of thionyl chloride solution into 4-8g of AC-COOH, heating to 40-70 ℃ under the condition of stirring, carrying out condensation reflux reaction for 20-24h, respectively washing with anhydrous dichloromethane and tetrahydrofuran solution, and drying to obtain a chlorination product AC-COCl;
(3) under the anhydrous environment, the weight ratio of (3-4): 1, weighing the AC-COCl and the polyethyleneimine PEI, adding anhydrous dichloromethane, stirring for 10-15h, filtering, respectively washing with anhydrous dichloromethane and tetrahydrofuran solution, and drying to obtain a polyethyleneimine product AC-PEI;
(4) weighing AC-PEI and succinic anhydride SAA according to the mass ratio of 1-1.5: 1, adding anhydrous dichloromethane, reacting for 20-24h at the temperature of 30-50 ℃ under the stirring condition, filtering, washing and drying to obtain the novel active carbon AC-PEI-SAA.
6. The method for preparing a novel antibacterial and deodorant ES fiber activated carbon according to claim 5, characterized in that: in the step (1), the drying time is 48-60 h; in the step (2), the drying time is 24-32 h.
7. The method for preparing a novel antibacterial and deodorant ES fiber activated carbon according to claim 5, characterized in that: in the step (3), the drying time is 24-32 h; in the step (4), the drying time is 24-30 h.
8. A method for preparing the antibacterial deodorizing ES fiber according to claim 1, comprising the steps of:
(1) slicing HDPE, modifying nano ZnO and modifying nano TiO2Or two or three of the novel active carbon are melted and blended to prepare the antibacterial deodorizing HDPE slices, the melting temperature is 190-230 ℃, the pressure is 500-1500Mpa, and the rotating speed of the screw is 40-80 r/min;
(2) heating the antibacterial and deodorant HDPE slices from room temperature to 50-80 ℃ for 0.5-2 hours, and preserving heat for 10-12 hours; cooling to 50-60 ℃ after 0.5-2 hours to obtain dried antibacterial and deodorant HDPE slices, and preserving heat for later use;
(3) raising the temperature of PET from room temperature to 50-80 ℃ for 0.5-3 hours, and preserving the heat for 1-2 hours; heating to 90-110 ℃ after 0.5-1 hour, and preserving heat for 8-12 hours; heating to 120-140 ℃ after 0.5-1 hour, and preserving heat for 8-15 hours; cooling to 50-60 ℃ after 1-4 hours to obtain dried PET, and preserving heat for later use;
(4) and carrying out composite melt spinning and drafting winding on the dried antibacterial and deodorant HDPE slices and the dried PET slices to obtain the antibacterial and deodorant ES fiber.
9. The method for preparing antibacterial and deodorant ES fibers according to claim 8, characterized in that: and (3) performing the step (2) and the step (3) in a vacuum drum oven.
10. The method for preparing antibacterial and deodorant ES fibers according to claim 8, characterized in that: the melt spinning temperature of the dried antibacterial and deodorant HDPE slices in the step (4) is 180-290 ℃, the melt spinning temperature of the dried PET slices is 260-290 ℃, and the winding speed is 300-1200 m/min.
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