CN111549392B - A kind of preparation method of antibacterial polyphenylene sulfide fiber - Google Patents
A kind of preparation method of antibacterial polyphenylene sulfide fiber Download PDFInfo
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- CN111549392B CN111549392B CN202010334543.2A CN202010334543A CN111549392B CN 111549392 B CN111549392 B CN 111549392B CN 202010334543 A CN202010334543 A CN 202010334543A CN 111549392 B CN111549392 B CN 111549392B
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 219
- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 155
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 155
- 239000000835 fiber Substances 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 239000000843 powder Substances 0.000 claims abstract description 79
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 68
- 239000011858 nanopowder Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 27
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 239000002270 dispersing agent Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000009987 spinning Methods 0.000 claims abstract description 10
- 229910020197 CePO4 Inorganic materials 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000725 suspension Substances 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 12
- 238000002074 melt spinning Methods 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 239000007822 coupling agent Substances 0.000 claims description 8
- 238000004381 surface treatment Methods 0.000 claims description 8
- 150000004645 aluminates Chemical class 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000004804 winding Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- ATGFTMUSEPZNJD-UHFFFAOYSA-N 2,6-diphenylphenol Chemical compound OC1=C(C=2C=CC=CC=2)C=CC=C1C1=CC=CC=C1 ATGFTMUSEPZNJD-UHFFFAOYSA-N 0.000 claims description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 3
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- JKBYAWVSVVSRIX-UHFFFAOYSA-N octadecyl 2-(1-octadecoxy-1-oxopropan-2-yl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)SC(C)C(=O)OCCCCCCCCCCCCCCCCCC JKBYAWVSVVSRIX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- -1 polyphenylene Polymers 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 229920000265 Polyparaphenylene Polymers 0.000 claims 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 239000004744 fabric Substances 0.000 abstract description 24
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 230000003385 bacteriostatic effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 41
- 238000012360 testing method Methods 0.000 description 15
- 238000011056 performance test Methods 0.000 description 10
- 239000003242 anti bacterial agent Substances 0.000 description 9
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000004753 textile Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZAAQJFLUOUQAOG-UHFFFAOYSA-N 4-benzyl-2,6-ditert-butylphenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=CC=CC=2)=C1 ZAAQJFLUOUQAOG-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- DKYDUFWOIUKRGU-UHFFFAOYSA-N [Ag+].[O-2].[Ce+3].[O-2] Chemical compound [Ag+].[O-2].[Ce+3].[O-2] DKYDUFWOIUKRGU-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 210000004962 mammalian cell Anatomy 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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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
- D01F6/94—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 other polycondensation products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/02—Polythioethers; Polythioether-ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2481/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2481/02—Polythioethers; Polythioether-ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
- C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Artificial Filaments (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明提供了一种抗菌聚苯硫醚纤维的制备方法，该方法采用聚苯硫醚抗菌母粒来制备抗菌聚苯硫醚纤维，所述的聚苯硫醚抗菌母粒，以重量百分数计，由以下原料组成：抗菌粉体为20%～30%，抗氧剂为0.2%～0.3%，分散剂为4%～7%，聚苯硫醚粉体为62.7%～75.8%，原料的重量百分数之和为100%；所述的抗菌粉体，以重量百分数计，由以下原料组成：聚合物包封的CePO4纳米粉体80%，Ce(OH)4纳米粉体为20%。采用本发明制备的抗菌聚苯硫醚母粒进行纺丝，所纺的抗菌聚苯硫醚纤维力学性能优良，具有优异的抗菌性能。按一定比例与普通聚苯硫醚纤维混纺制备的抗菌织物便具有较高的抑菌率，可以大幅度降低抗菌织物的生产成本。The invention provides a preparation method of antibacterial polyphenylene sulfide fiber. The method adopts polyphenylene sulfide antibacterial master batch to prepare antibacterial polyphenylene sulfide fiber, and the polyphenylene sulfide antibacterial master batch is calculated in weight percentage. , consists of the following raw materials: 20% to 30% of antibacterial powder, 0.2% to 0.3% of antioxidant, 4% to 7% of dispersant, 62.7% to 75.8% of polyphenylene sulfide powder, The sum of the percentages by weight is 100%; the antibacterial powder, in percentage by weight, is composed of the following raw materials: 80% of the polymer-encapsulated CePO 4 nano-powder, and 20% of the Ce(OH) 4 nano-powder. The antibacterial polyphenylene sulfide masterbatch prepared by the invention is used for spinning, and the spun antibacterial polyphenylene sulfide fiber has excellent mechanical properties and excellent antibacterial properties. The antibacterial fabric prepared by blending with ordinary polyphenylene sulfide fiber in a certain proportion has a high bacteriostatic rate, which can greatly reduce the production cost of the antibacterial fabric.
Description
Technical Field
The invention belongs to the field of fiber antibacterial modification, relates to polyphenylene sulfide fibers, and particularly relates to a preparation method of antibacterial polyphenylene sulfide fibers.
Background
In recent years, polyphenylene sulfide fibers have been widely used in textile industry due to their excellent flame retardancy, chemical resistance, high temperature resistance and physical and mechanical properties. However, as people's health awareness increases, the hygiene of textiles is receiving more and more attention. The widespread existence and spread of microorganisms such as bacteria has been an important threat to human health since the human society. The porous structure of the textile is easier to become a hotbed for breeding bacteria and fungi, and further the health of people is influenced. Therefore, the research and development of the antibacterial textiles have practical significance.
The technology for manufacturing the antibacterial functional fiber comprises a master batch method blending modification technology, an in-situ polymerization method, a post-finishing coating method and the like. The antibacterial fiber is prepared by adopting a post-finishing coating method, although the mass production is easy, a large amount of waste water is generated, the environment is polluted, the handfeel of the prepared fabric is hard, and the antibacterial durability is poor; the process for preparing the antibacterial fiber by the in-situ polymerization method is complex, the control difficulty is high, and the production cost is high; the master batch method blending modification technology is that before spinning, antibacterial powder and resin are mixed, and an antibacterial master batch is prepared by a double-screw extruder and then is used for preparing antibacterial fiber by melt spinning. The antibacterial fiber prepared by the master batch method blending technology has short process flow, simple and easy operation method and excellent antibacterial durability and washability. When the antibacterial polyphenylene sulfide fiber is prepared, the requirement on the stability of antibacterial powder is high due to the high spinning temperature.
The prior art discloses a polymer-based cerium-doped nano-zinc oxide composite antibacterial agent for fabrics and a preparation method thereof (application publication number: CN 105648745A). the method prepares the polymer-based cerium-doped nano-zinc oxide composite antibacterial agent by an in-situ method, and cerium ions are doped, so that the photocatalytic antibacterial performance of zinc oxide is effectively improved. However, the antibacterial agent is still influenced by the illumination condition, is suitable for the after-finishing coating of the fabric, and the prepared antibacterial fabric has poor antibacterial durability.
The prior art discloses a nano-mesoporous cerium oxide silver-loaded antibacterial agent and a preparation method thereof (application publication number: CN 101138342A). the antibacterial agent takes nano-mesoporous cerium oxide as a carrier and silver as an active center, and activates the antibacterial property of silver through the nano-mesoporous cerium oxide, and meanwhile, the antibacterial agent can resist high temperature and obtain better antibacterial effect. The antibacterial agent can be widely applied to the fields of ceramics, plastics, textiles and the like, but the antibacterial agent loads noble metal silver, so that the process is complex and the cost is high.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of an antibacterial polyphenylene sulfide fiber, which solves the technical problems of insufficient antibacterial and mechanical properties and high cost of the antibacterial polyphenylene sulfide fiber in the prior art.
In order to solve the technical problem, the application adopts the following technical scheme:
the preparation method of the antibacterial polyphenylene sulfide fiber is characterized in that the antibacterial polyphenylene sulfide master batch is adopted to prepare the antibacterial polyphenylene sulfide fiber, and the antibacterial polyphenylene sulfide master batch comprises the following raw materials in percentage by weight: 10 to 30 percent of antibacterial powder, 0.1 to 0.3 percent of antioxidant, 2 to 7 percent of dispersant, 69.7 to 87.9 percent of polyphenylene sulfide powder, and the sum of the weight percentages of the raw materials is 100 percent;
the antibacterial powder comprises the following raw materials in percentage by weight: polymer encapsulated CePO470% -85% of nano powder, Ce (OH)415 to 30 percent of nano powder, and the sum of the weight percentages of the raw materials is 100 percent.
The invention also has the following technical characteristics:
preferably, the polyphenylene sulfide antibacterial master batch comprises the following raw materials in percentage by weight: 20 to 30 percent of antibacterial powder, 0.2 to 0.3 percent of antioxidant, 4 to 7 percent of dispersant, 62.7 to 75.8 percent of polyphenylene sulfide powder, and the sum of the weight percentages of the raw materials is 100 percent;
the antibacterial powder comprises the following raw materials in percentage by weight: polymer encapsulated CePO480% of nano-powder, Ce (OH)4The content of the nano powder is 20 percent.
The antioxidant comprises the following raw materials in percentage by weight: 70% of 1, 3, 5-trimethyl-2, 4, 6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene and 30% of dioctadecyl thiodipropionate.
Specifically, the method specifically comprises the following steps:
respectively carrying out vacuum drying on the polyphenylene sulfide powder in a vacuum drying oven for 3h at 120 ℃ and then drying for 5h at 140 ℃ by using the antibacterial polyphenylene sulfide master batch and the polyphenylene sulfide slice, wherein the vacuum degree is always kept at 0.05-1.0 MPa, and the water content in the dried antibacterial polyphenylene sulfide master batch and the dried polyphenylene sulfide slice is lower than 0.003%;
secondly, adding the antibacterial polyphenylene sulfide master batch into a melt spinning machine for spinning according to the proportion that the total weight of the antibacterial powder in the antibacterial polyphenylene sulfide master batch accounts for 2-3% of the total weight of the antibacterial polyphenylene sulfide fiber of the final product;
and thirdly, air cooling and solidifying the fiber yarns extruded from the spinning machine, oiling the fiber yarns to integrate fiber bundles, guiding the fiber bundles to a drafting machine, drafting and shaping the fiber bundles, and then winding the fiber bundles on a pipe barrel to obtain the antibacterial polyphenylene sulfide fibers with the specification of 72D/36 f.
The melt spinning process conditions are as follows: the melt spinning temperature is 255 ℃, 320 ℃, 325 ℃ and 330 ℃ respectively from one zone to four zones, the hot plate temperature of the drawing zone is 60 ℃, 105 ℃ and 120 ℃ respectively, and the winding speed is 1000 m/min.
Preferably, the preparation process of the antibacterial powder comprises the following steps: firstly, CePO is mixed4The nanometer powder is processed to prepare polymer encapsulated CePO by surface treatment4Nano powder; second, polymer encapsulated CePO4Nano powder and Ce (OH)4Mixing the nanometer powder to obtain the antibacterial powder.
Preferably, the surface treatment process comprises: using an aluminate coupling agent to CePO4And (4) pretreating the nano powder. Weighing 10-15 g CePO4The nano powder is dispersed in 200ml deionized water to prepare suspension. 180mg of the aluminate coupling agent was weighed out and dissolved in n-butanol and added dropwise to the suspension. During the dropwise addition, the suspension should be placed in a 60 ℃ water bath and stirred at 60 rpm. After the completion of the dropwise addition, the temperature and the stirring speed were kept for 2 hours. Then washing the solid product with absolute ethyl alcohol to neutrality and drying to obtain the pretreated CePO4Nano powder;
weighing 50-100 mg of 2, 6-diphenylphenol, dissolving in 100ml of ethanol solution, adding 2-6 g of pretreated CePO4Forming a suspension of the nano powder, placing the suspension in a water bath kettle at 50 ℃, stirring at the speed of 120rpm, simultaneously adding 1-2 mg of cuprous bromide/2, 2' -bipyridyl complex, introducing oxygen, reacting for 5 hours, centrifugally separating the suspension, and adding a catalyst containing copperWashing the separated solid with 30% ethanol solution of sulfuric acid, washing with water, and drying to obtain polymer-encapsulated CePO4And (3) nano powder.
Preferably, the preparation process of the polyphenylene sulfide antibacterial master batch comprises the following steps:
firstly, performing vacuum drying on polyphenylene sulfide powder and antibacterial powder in a vacuum drying oven, drying for 2 hours at 120 ℃, then drying for 4 hours at 140 ℃, wherein the vacuum degree is always kept at 0.05-1.0 MPa, and the moisture in the dried polyphenylene sulfide powder is lower than 0.003%;
and secondly, uniformly mixing the antibacterial powder, the dispersing agent and the antioxidant with the dried polyphenylene sulfide powder, and then blending, extruding, water cooling and granulating by using a double-screw extruder to prepare the polyphenylene sulfide antibacterial master batch. The processing conditions of the double-screw extruder are as follows: the screw temperatures were 220 deg.C, 297 deg.C, 302 deg.C, 307 deg.C for the head and 210rpm for the screw from zone one to zone four.
Compared with the prior art, the invention has the beneficial technical effects that:
the invention relates to a rare earth compound CePO subjected to surface treatment4The nano powder is antibacterial powder. Inorganic antibacterial agents commonly used, such as TiO2ZnO, CuO and the like have single antibacterial action, and precious metal ions, simple substances and other antibacterial active substances are loaded to ensure the antibacterial effect, so that the production process is complex and the cost is high. CePO4The nano powder has low toxicity to mammalian cells and a unique antibacterial mechanism, can trigger the generation of active oxygen clusters to kill bacteria and can induce the physical damage of bacterial cells, so that the nano powder can show excellent antibacterial performance without loading other antibacterial substances.
(II) the invention adopts a two-step method to carry out surface treatment on the nano powder, and uses the polymer to carry out CePO4The nano powder is encapsulated, so that the agglomeration of the nano powder is reduced, the compatibility with a polyphenylene sulfide matrix is improved, and the adverse effect on the mechanical property of a fiber product is reduced.
(III) selecting a hyperdispersant in the preparation process of the master batch. One end of the hyperdispersant contains an anchoring groupImmobilization by electrochemical bonding to CePO4The other end of the nano powder is provided with a polymer chain segment to reduce CePO in the processing process through steric hindrance4The aggregation of the nano powder can obviously improve the problem of serious aggregation of the inorganic nano powder in the antibacterial master batch.
(IV) the antibacterial polyphenylene sulfide master batch prepared by the invention is used for spinning, and the spun antibacterial polyphenylene sulfide fiber has excellent mechanical property and excellent antibacterial property. The antibacterial fabric prepared by blending with the common polyphenylene sulfide fiber according to a certain proportion has higher bacteriostasis rate, and can greatly reduce the production cost of the antibacterial fabric.
The present invention is explained in further detail with reference to examples below.
Detailed Description
The weight average molecular weight of the polyphenylene sulfide powder is 35000-55000.
The weight average molecular weight of the polyphenylene sulfide slice is 35000-55000.
CePO in the invention4The grain diameter of the nano powder is 350 nm-450 nm.
Ce (OH) in the present invention4The grain diameter of the nano powder is 300nm to 425 nm.
The coupling agent in the invention is an aluminate coupling agent with the mark of DL-414.
The dispersant used in the present invention is either a hyper-dispersant having a designation DP330 or a hyper-dispersant having a designation DP 340.
The present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention fall within the protection scope of the present invention. The present invention will be described in further detail with reference to examples.
Example 1:
the embodiment provides a preparation method of antibacterial polyphenylene sulfide fiber, which is characterized in that the antibacterial polyphenylene sulfide fiber is prepared from polyphenylene sulfide antibacterial master batch, wherein the polyphenylene sulfide antibacterial master batch comprises the following raw materials in percentage by weight: 20 percent of antibacterial powder, 0.2 percent of antioxidant, 4 percent of dispersant and 75.8 percent of polyphenylene sulfide powder.
The preparation process of the polyphenylene sulfide antibacterial master batch comprises the following steps:
firstly, performing vacuum drying on polyphenylene sulfide powder and antibacterial powder in a vacuum drying oven, drying for 2 hours at 120 ℃, then drying for 4 hours at 140 ℃, wherein the vacuum degree is always kept at 0.05-1.0 MPa, and the moisture in the dried polyphenylene sulfide powder is lower than 0.003%;
and secondly, uniformly mixing the antibacterial powder, the dispersing agent and the antioxidant with the dried polyphenylene sulfide powder, and then blending, extruding, water cooling and granulating by using a double-screw extruder to prepare the polyphenylene sulfide antibacterial master batch. The processing conditions of the double-screw extruder are as follows: the screw temperatures were 220 deg.C, 297 deg.C, 302 deg.C, 307 deg.C for the head and 210rpm for the screw from zone one to zone four.
Specifically, the method specifically comprises the following steps:
respectively carrying out vacuum drying on the polyphenylene sulfide powder in a vacuum drying oven for 3h at 120 ℃ and then drying for 5h at 140 ℃ by using the antibacterial polyphenylene sulfide master batch and the polyphenylene sulfide slice, wherein the vacuum degree is always kept at 0.05-1.0 MPa, and the water content in the dried antibacterial polyphenylene sulfide master batch and the dried polyphenylene sulfide slice is lower than 0.003%;
secondly, adding the antibacterial polyphenylene sulfide master batch into a melt spinning machine for spinning according to the proportion that the total weight of the antibacterial powder in the antibacterial polyphenylene sulfide master batch accounts for 2% of the total weight of the antibacterial polyphenylene sulfide fiber of the final product;
the melt spinning process conditions are as follows: the melt spinning temperature is 255 ℃, 320 ℃, 325 ℃ and 330 ℃ respectively from one zone to four zones, the hot plate temperature of the drawing zone is 60 ℃, 105 ℃ and 120 ℃ respectively, and the winding speed is 1000 m/min.
And thirdly, air cooling and solidifying the fiber yarns extruded from the spinning machine, oiling the fiber yarns to integrate fiber bundles, guiding the fiber bundles to a drafting machine, drafting and shaping the fiber bundles, and then winding the fiber bundles on a pipe barrel to obtain the antibacterial polyphenylene sulfide fibers with the specification of 72D/36 f.
Specifically, the antibacterial powder comprises the following components in percentage by weightThe composition comprises the following raw materials: polymer encapsulated CePO480% of nano-powder, Ce (OH)4The content of the nano powder is 20 percent.
The preparation process of the antibacterial powder comprises the following steps: firstly, CePO is mixed4The nanometer powder is processed to prepare polymer encapsulated CePO by surface treatment4Nano powder; second, polymer encapsulated CePO4Nano powder and Ce (OH)4Mixing the nanometer powder to obtain the antibacterial powder.
The surface treatment process comprises the following steps: using an aluminate coupling agent to CePO4And (4) pretreating the nano powder. Weighing 10-15 g CePO4The nano powder is dispersed in 200ml deionized water to prepare suspension. 180mg of the aluminate coupling agent was weighed out and dissolved in n-butanol and added dropwise to the suspension. During the dropwise addition, the suspension should be placed in a 60 ℃ water bath and stirred at 60 rpm. After the completion of the dropwise addition, the temperature and the stirring speed were kept for 2 hours. Then washing the solid product with absolute ethyl alcohol to neutrality and drying to obtain the pretreated CePO4Nano powder;
weighing 50-100 mg of 2, 6-diphenylphenol, dissolving in 100ml of ethanol solution, adding 2-6 g of pretreated CePO4Forming a suspension by the nanometer powder, placing the suspension in a water bath kettle at 50 ℃, stirring at the speed of 120rpm, simultaneously adding 1-2 mg of cuprous bromide/2, 2' -bipyridyl complex, introducing oxygen, reacting for 5 hours, centrifugally separating the suspension, washing the separated solid with 30% ethanol solution containing sulfuric acid, washing with water, and drying to obtain the polymer encapsulated CePO4And (3) nano powder.
Specifically, the antioxidant comprises the following raw materials in parts by weight: 70% of 1, 3, 5-trimethyl-2, 4, 6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene and 30% of dioctadecyl thiodipropionate.
And (3) testing antibacterial performance: the fiber is processed into a thin plain weave fabric, and an antibacterial performance test is carried out according to the method GB/T20944.3-2008, and the test result is shown in table 1.
Example 2:
the embodiment provides a preparation method of antibacterial polyphenylene sulfide fiber, which is characterized in that the antibacterial polyphenylene sulfide fiber is prepared from polyphenylene sulfide antibacterial master batch, wherein the polyphenylene sulfide antibacterial master batch comprises the following raw materials in percentage by weight: 30% of antibacterial powder, 0.3% of antioxidant, 7% of dispersant and 62.7% of polyphenylene sulfide powder.
The preparation process of the polyphenylene sulfide antibacterial master batch is the same as that of the example 1.
The specific steps of the preparation method of the antibacterial polyphenylene sulfide fiber of the embodiment are basically the same as those of the embodiment 1, and the difference is only that the addition amount of the master batch is different. In this embodiment, the antibacterial polyphenylene sulfide master batch is added into the melt spinning machine to spin according to a ratio that the total weight of the antibacterial powder in the antibacterial polyphenylene sulfide master batch accounts for 3% of the total weight of the antibacterial polyphenylene sulfide fiber of the final product.
The antibacterial powder of this example was the same as the antibacterial powder of example 1.
The process for preparing the antibacterial powder of this example was the same as that of example 1.
The antioxidant of this example was the same as the antioxidant of example 1.
And (3) testing antibacterial performance: the fiber is processed into a thin plain weave fabric, and an antibacterial performance test is carried out according to the method GB/T20944.3-2008, and the test result is shown in table 1.
Example 3:
this embodiment provides a method for preparing an antibacterial polyphenylene sulfide fiber, in which the antibacterial polyphenylene sulfide master batch is used to prepare the antibacterial polyphenylene sulfide fiber, and the antibacterial polyphenylene sulfide master batch is the same as the antibacterial polyphenylene sulfide master batch of embodiment 2.
The preparation process of the polyphenylene sulfide antibacterial masterbatch is the same as that of the example 2.
The specific steps of the preparation method of the antibacterial polyphenylene sulfide fiber of the present example are the same as those of example 2.
The antibacterial powder of this example was the same as the antibacterial powder of example 2.
The process for preparing the antibacterial powder of this example was the same as that of example 2.
The antioxidant of this example was the same as the antioxidant of example 1.
Except for the antibacterial performance test of this example: the antibacterial polyphenylene sulfide fiber prepared in the embodiment and common polyphenylene sulfide fiber which is not subjected to antibacterial modification are blended and processed into a thin plain weave fabric, and the thin plain weave fabric comprises the following raw materials in parts by weight: 90% of antibacterial polyphenylene sulfide fiber and 10% of common polyphenylene sulfide fiber. And antibacterial performance test is carried out according to the method of GB/T20944.3-2008, and the test results are shown in Table 1.
Comparative example 1:
the comparative example provides a preparation method of antibacterial polyphenylene sulfide fiber, the method adopts polyphenylene sulfide antibacterial master batch to prepare the antibacterial polyphenylene sulfide fiber, and the difference between the polyphenylene sulfide antibacterial master batch of the comparative example and the polyphenylene sulfide antibacterial master batch of the example 1 is that antibacterial powder is not added in the comparative example, and the same amount of polyphenylene sulfide powder is used for the antibacterial powder in the formula.
The preparation process of the polyphenylene sulfide antibacterial masterbatch of the comparative example is basically the same as that of the example 1.
The preparation method of the antibacterial polyphenylene sulfide fiber of the present comparative example is substantially the same as that of example 1.
The antioxidant of this comparative example was the same as the antioxidant of example 1.
And (3) testing antibacterial performance: the fiber is processed into a thin plain weave fabric, and an antibacterial performance test is carried out according to the method GB/T20944.3-2008, and the test result is shown in table 1.
Comparative example 2:
the comparative example provides a preparation method of antibacterial polyphenylene sulfide fiber, the method adopts polyphenylene sulfide antibacterial master batch to prepare the antibacterial polyphenylene sulfide fiber, the polyphenylene sulfide antibacterial master batch of the comparative example is basically the same as the polyphenylene sulfide antibacterial master batch of the example 1, the difference is that the preparation steps of the antibacterial powder in the comparative example are different, and the comparative example does not adopt CePO powder4And (4) carrying out polymer encapsulation treatment on the nano powder.
The preparation process of the polyphenylene sulfide antibacterial masterbatch of the comparative example is basically the same as that of the example 1.
The preparation method of the antibacterial polyphenylene sulfide fiber of the present comparative example is substantially the same as that of example 1.
The antioxidant of this comparative example was the same as the antioxidant of example 1.
And (3) testing antibacterial performance: the fiber is processed into a thin plain weave fabric, and an antibacterial performance test is carried out according to the method GB/T20944.3-2008, and the test result is shown in table 1.
Comparative example 3:
the comparative example provides a preparation method of antibacterial polyphenylene sulfide fiber, the method adopts polyphenylene sulfide antibacterial master batch to prepare the antibacterial polyphenylene sulfide fiber, and the difference between the polyphenylene sulfide antibacterial master batch of the comparative example and the polyphenylene sulfide antibacterial master batch of the example 1 is that no dispersing agent is added in the comparative example, and the dispersing agent in the formula is replaced by equivalent polyphenylene sulfide powder.
The preparation process of the polyphenylene sulfide antibacterial masterbatch of the comparative example is basically the same as that of the example 1.
The preparation method of the antibacterial polyphenylene sulfide fiber of the present comparative example is substantially the same as that of example 1.
The antibacterial powder of this comparative example was the same as that of example 2.
The preparation process of the antibacterial powder of this comparative example was the same as that of the antibacterial powder of example 2.
The antioxidant of this comparative example was the same as the antioxidant of example 1.
And (3) testing antibacterial performance: the fiber is processed into a thin plain weave fabric, and an antibacterial performance test is carried out according to the method GB/T20944.3-2008, and the test result is shown in table 1.
Comparative example 4:
the comparative example provides a preparation method of antibacterial polyphenylene sulfide fiber, the method adopts polyphenylene sulfide antibacterial master batch to prepare the antibacterial polyphenylene sulfide fiber, the difference between the polyphenylene sulfide antibacterial master batch of the comparative example and the polyphenylene sulfide antibacterial master batch of the example 1 is that the antibacterial powder in the comparative example is different, and the antibacterial powder in the comparative example is CePO encapsulated by equal amount of polymer4And (3) nano powder.
The preparation process of the polyphenylene sulfide antibacterial masterbatch of the comparative example is basically the same as that of the example 1.
The preparation method of the antibacterial polyphenylene sulfide fiber of the present comparative example is substantially the same as that of example 1.
The antioxidant of this comparative example was the same as the antioxidant of example 1.
And (3) testing antibacterial performance: the fiber is processed into a thin plain weave fabric, and an antibacterial performance test is carried out according to the method GB/T20944.3-2008, and the test result is shown in table 1.
Comparative example 5:
the comparative example provides a preparation method of antibacterial polyphenylene sulfide fiber, the method adopts polyphenylene sulfide antibacterial master batch to prepare the antibacterial polyphenylene sulfide fiber, and the polyphenylene sulfide antibacterial master batch of the comparative example is the same as the polyphenylene sulfide antibacterial master batch of the example 2.
The preparation process of the polyphenylene sulfide antibacterial masterbatch of the comparative example is basically the same as that of the example 2.
The preparation method of the antibacterial polyphenylene sulfide fiber of the comparative example is substantially the same as that of example 2.
The antibacterial powder of this comparative example was the same as that of example 2.
The preparation process of the antibacterial powder of this comparative example was the same as that of the antibacterial powder of example 2.
The antioxidant of this comparative example was the same as the antioxidant of example 2.
The difference lies in the antibacterial performance test of the comparative example: the antibacterial polyphenylene sulfide fiber prepared in the embodiment and common polyphenylene sulfide fiber which is not subjected to antibacterial modification are blended and processed into a thin plain weave fabric, and the thin plain weave fabric comprises the following raw materials in parts by weight: 70% of antibacterial polyphenylene sulfide fiber and 30% of common polyphenylene sulfide fiber. And antibacterial performance test is carried out according to the method of GB/T20944.3-2008, and the test results are shown in Table 1.
Table 1 results of performance testing
As can be seen from Table 1, the polymer encapsulated CePO of the present invention4Nano powder and polyphenylene sulfide matrixThe compatibility between the fibers is obviously improved, the tensile strength and the elongation at break of the spun fiber are greatly improved, and the fiber has good elasticity, wearability and hand feeling.
As can be seen from table 1, the antibacterial polyphenylene sulfide fiber prepared by using the antibacterial powder of the present invention has excellent antibacterial performance, and when used for preparing fabrics, can be blended with common polyphenylene sulfide fibers which are not subjected to antibacterial modification to reduce production cost. When the mixing proportion of the common fiber is 30%, the bacteriostasis rate of the fabric is still higher than the minimum bacteriostasis rate standard value of the antibacterial fabric specified in GB/T20944.3-2008. In addition, the prepared fabric has excellent water washing resistance, and the bacteriostasis rate of the fabric to three types of bacteria is not reduced by more than 5 percent after the fabric is washed for 50 times.
As can be seen from table 1, the hyperdispersant of the present invention plays a key role in dispersing the antibacterial powder in the polyphenylene sulfide matrix. The mechanical property and the antibacterial property of the antibacterial polyphenylene sulfide master batch spun fiber added with the dispersing agent are both superior to those of the antibacterial master batch spun fiber not added with the hyper-dispersing agent.
Claims (8)
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