CN113186614B - Antibacterial high-strength high-modulus polyethylene colored fiber and preparation method thereof - Google Patents

Antibacterial high-strength high-modulus polyethylene colored fiber and preparation method thereof Download PDF

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Publication number
CN113186614B
CN113186614B CN202110504958.4A CN202110504958A CN113186614B CN 113186614 B CN113186614 B CN 113186614B CN 202110504958 A CN202110504958 A CN 202110504958A CN 113186614 B CN113186614 B CN 113186614B
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antibacterial
dye
molecular weight
drafting
fiber
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CN113186614A (en
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王刚强
吕汪洋
张间芳
包建娜
王鑫宇
顾彩琴
俞凌晓
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Zhejiang Jinhao New Material Co ltd
Zhejiang Sci Tech University ZSTU
Shangyu Industrial Technology Research Institute of ZSTU
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Zhejiang Jinhao New Material Co ltd
Zhejiang Sci Tech University ZSTU
Shangyu Industrial Technology Research Institute of ZSTU
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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
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
    • D02J1/224—Selection or control of the temperature during stretching
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
    • D02J1/228—Stretching in two or more steps, with or without intermediate steps
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B13/00—Treatment of textile materials with liquids, gases or vapours with aid of vibration
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/14—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using phthalocyanine dyes without vatting
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/79—Polyolefins

Abstract

The invention relates to the technical field of special fiber preparation, and provides an antibacterial high-strength high-modulus polyethylene colored fiber and a preparation method thereof. The preparation method takes the phthalocyanine as the coloring dye, not only has coloring function, but also can combine with antibacterial particles to further increase the antibacterial activity of the fiber; the mass concentration of the dye bath solution is 1-10%, so that the dye is uniformly dispersed in the bath solution, is not easy to migrate in the subsequent super-stretching, and the coloring uniformity is ensured. Moreover, the ultrahigh molecular weight polyethylene is doped in the swelling process of the antibacterial particles, so that the adsorbability of the antibacterial particles is improved; the gel silk is dipped in dye bath solution formed by phthalocyanine after extraction and drying, thereby making up the reduction of bacteriostatic effect caused by the escape of part of bacteriostatic particles and ensuring the bacteriostatic property and color of fiber.

Description

Antibacterial high-strength high-modulus polyethylene colored fiber and preparation method thereof
Technical Field
The invention relates to the technical field of special fiber preparation, in particular to an antibacterial high-strength high-modulus polyethylene colored fiber and a preparation method thereof.
Background
The ultra-high molecular weight polyethylene (UHMWPE) fiber is one of three high-performance fibers, and has high strength, high modulus and low density (0.97 g/cm) 3 ) Excellent chemical stability and good wear resistance, and is widely applied in the fields of national defense and military, aerospace and the like. Besides playing an important role in the fields of military, national defense and the like, the UHMWPE fiber is widely applied to the civil fields of medical materials, sports equipment and the like. With the expansion of the application field of UHMWPE fiber, the demand of antibacterial UHMWPE colored fiber is more and more.
Chinese patent publication No. CN109868518A discloses a method for producing bacteriostatic ultrahigh molecular weight polyethylene fibers, which uses nano antibacterial metal oxide, Ag + salt and nano Ag as inorganic antibacterial agents, then feeds the inorganic antibacterial agents, UHMWPE master batches and other auxiliary agents into a twin-screw extruder, and obtains UHMWPE fibers by extrusion spinning, cooling, solidification, extraction, drying and super-drawing. Chinese patent publication No. CN109440211A discloses a method for producing antibacterial mother liquor of antibacterial ultrahigh molecular weight polyethylene fiber, which comprises the following raw materials by weight: 10-30 parts of an antibacterial polymer, 70-90 parts of a solvent, 0-3 parts of a surfactant, 0-1 part of a dispersant and 0.3-5 parts of a compatibilizer, wherein the antibacterial polymer is a polymer formed by copolymerizing one or more monomers and is used as a basic skeleton, and an antibacterial group is fixed on the basic skeleton in a coordination bond and covalent bond mode.
Chinese patent publication No. CN102586925A discloses a method for preparing colored fibers for ultra-high molecular weight polyethylene rope net, which comprises preparing colored master batch of ultra-high molecular weight polyethylene powder from ultra-high molecular weight polyethylene resin, HDPE polyethylene and colored pigment toner, swelling, cooling, extruding, spinning, solidifying in water bath, extracting, drying, and performing three-stage hot drawing to obtain colored ultra-high molecular weight polyethylene fibers. Chinese patent publication No. CN101230499A discloses a colored high-strength polyethylene fiber and a method for manufacturing the same, which is prepared by mixing an inorganic pigment additive into ultra-high molecular weight polyethylene, adding 0.5 to 3% of the ultra-high molecular weight polyethylene by weight, and then swelling, dissolving, spinning, extracting, drying, post-drawing, and winding.
The method adds the antibacterial particles or colored particles into the spinning solution to prepare the antibacterial UHMWPE fibers or UHMWPE colored fibers, has simple process flow and low production cost, but the obtained ultrahigh molecular weight polyethylene fibers have single functionality. In order to enable the fiber to have multiple properties, when multiple functional materials are added into a system, the particles are inorganic particles, so that the problem of poor mechanical properties of the multifunctional fiber is caused by uneven mixing.
Disclosure of Invention
In view of the above, the present invention aims to provide a bacteriostatic high-strength high-modulus polyethylene colored fiber and a preparation method thereof. The antibacterial high-strength high-modulus polyethylene colored fiber prepared by the invention has excellent mechanical property and antibacterial activity.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of bacteriostatic high-strength high-modulus polyethylene colored fiber, which comprises the following steps:
mixing the ultrahigh molecular weight polyethylene, the antibacterial particles and a spinning solvent, and swelling and dissolving to obtain a spinning solution;
extruding and coagulating the spinning solution to obtain gel filaments;
extracting and drying the gel silk to obtain a fiber precursor;
soaking the fiber precursor in dye bath, taking out, and performing super-stretching, heat setting and rolling to obtain the antibacterial high-strength high-modulus polyethylene colored fiber;
the dye bath solution is formed by mixing a dye and an organic solvent, wherein the dye comprises phthalocyanine; the organic solvent comprises one or more of tetrahydrofuran, N-dimethylformamide and hexafluoroisopropanol; the mass concentration of the dye bath liquid is 1-10%; the particle size of the dye is 100-600 nm.
Preferably, the dye bath is prepared by a process comprising the steps of:
mixing a dye and an organic solvent under the condition of stirring or ultrasound to obtain the dye bath solution; the stirring speed is 50-300 rpm, and the ultrasonic power is 500-800W.
Preferably, the weight average molecular weight of the ultra-high molecular weight polyethylene is 300 to 600 ten thousand; the particle size of the ultra-high molecular weight polyethylene is 50-200 mu m.
Preferably, the bacteriostatic particles are nano silver or nano copper; the particle size of the antibacterial particles is 50-200 nm.
Preferably, the mass ratio of the ultrahigh molecular weight polyethylene to the antibacterial particles is 100: (1-5); the total mass concentration of the ultrahigh molecular weight and the antibacterial particles in the spinning solution is 3-8%.
Preferably, the temperature of the extrusion is 260-280 ℃.
Preferably, the diameter of the jelly glue silk is 100-500 mu m.
Preferably, the dipping is carried out under the condition of ultrasonic oscillation, and the power of the ultrasonic oscillation is 500-800W; the dipping time is 15-60 min.
Preferably, the super-stretching comprises: sequentially carrying out primary drafting, secondary drafting and tertiary drafting; the temperature of the primary drafting is 130-145 ℃, and the multiple of the primary drafting is 4-6 times; the temperature of the secondary drafting is 140-150 ℃, and the multiple of the secondary drafting is 2-5 times; the temperature of the three-stage drafting is 140-150 ℃, and the multiple of the three-stage drafting is 1-3 times.
The invention also provides the bacteriostatic high-strength high-modulus polyethylene colored fiber obtained by the technical scheme, wherein the rupture strength of the bacteriostatic high-strength high-modulus polyethylene colored fiber is 29.4-33.5 cN/dtex, and the initial modulus is 1264-1484 cN/dtex.
The invention provides a preparation method of bacteriostatic high-strength high-modulus polyethylene colored fiber, which comprises the following steps: mixing the ultrahigh molecular weight polyethylene, the antibacterial particles and a spinning solvent, and swelling and dissolving to obtain a spinning solution; extruding the spinning solution and bundling by a coagulating bath to obtain gel filaments; extracting and drying the gel silk to obtain a fiber precursor; soaking the fiber precursor in dye bath, taking out, and sequentially carrying out super-stretching, heat setting and rolling to obtain the antibacterial high-strength high-modulus polyethylene colored fiber; the dye bath solution is formed by mixing a dye and an organic solvent, wherein the dye comprises phthalocyanine; the organic solvent comprises one or more of tetrahydrofuran, N-dimethylformamide and hexafluoroisopropanol; the mass concentration of the dye bath solution is 1-10%; the particle size of the dye is 100-600 nm.
The preparation method of the invention takes the phthalocyanine as the coloring dye, not only has coloring function, but also has bacteriostatic function, and can further increase the bacteriostatic property of the fiber; the mass concentration of the dye bath solution is 1-10%, so that the dye is uniformly dispersed in the bath solution, is not easy to migrate in the subsequent super-stretching, and the coloring uniformity is ensured. Moreover, the ultrahigh molecular weight polyethylene is doped in the antibacterial particles in the mixing process, so that the adsorbability of the antibacterial particles is improved; the gel silk is dipped in dye bath solution formed by phthalocyanine after extraction and drying, thereby making up for the reduction of bacteriostatic effect caused by the escape of bacteriostatic particles and ensuring the bacteriostatic property and color of the fiber. The data of the examples show that: the rupture strength of the antibacterial high-strength high-modulus polyethylene colored fiber is 29.4-33.5 cN/dtex, the initial modulus is 1264-1484 cN/dtex, the antibacterial rate to escherichia coli is greater than or equal to 95%, and the antibacterial rate to staphylococcus aureus is greater than or equal to 95%.
Detailed Description
The invention provides a preparation method of bacteriostatic high-strength high-modulus polyethylene colored fiber, which comprises the following steps:
mixing the ultrahigh molecular weight polyethylene, the antibacterial particles and a spinning solvent, and swelling and dissolving to obtain a spinning solution;
extruding and coagulating the spinning solution to obtain gel filaments;
extracting and drying the gel silk to obtain a fiber precursor;
and (3) soaking the fiber precursor in dye bath, taking out, and sequentially carrying out super-stretching, heat setting and rolling to obtain the antibacterial high-strength high-modulus polyethylene colored fiber.
In the present invention, the starting materials used in the present invention are preferably commercially available products unless otherwise specified.
The invention mixes the ultra-high molecular weight polyethylene, the antibacterial particles and the spinning solvent, and swells and dissolves the mixture to obtain the spinning solution.
In the present invention, the weight average molecular weight of the ultrahigh molecular weight polyethylene is preferably 300 to 600 ten thousand, and more preferably 400 to 500 ten thousand; the particle size of the ultra-high molecular weight polyethylene is preferably 50 to 200 μm, and more preferably 100 to 150 μm.
In the invention, the bacteriostatic particles are preferably nano silver or nano copper; the particle size of the antibacterial particles is preferably 50-200 nm.
In the present invention, the spinning solvent is preferably white oil.
In the invention, the mass ratio of the ultrahigh molecular weight polyethylene to the bacteriostatic particles is preferably 100: (1-5), more preferably 100: (2-3). In the invention, the total mass concentration of the ultrahigh molecular weight and bacteriostatic particles in the spinning solution is preferably 3-8%, more preferably 5-7%, and more preferably 6%.
In the present invention, the mixing is preferably performed under a stirring condition, and the rotation speed of the stirring is preferably 100 to 200rpm, and more preferably 150 rpm; the mixing time is preferably 15-30 min; the temperature of the mixing is preferably room temperature, i.e. neither additional heating nor additional cooling is required.
In the invention, the swelling temperature is preferably 120-145 ℃, and more preferably 125-140 ℃; the swelling time is preferably 30-60 min, and more preferably 35-40 min. In the invention, the dissolving temperature is preferably 160-250 ℃, and more preferably 200-240 ℃; the dissolving time is preferably 20 to 60min, and more preferably 30 to 50 min.
After the spinning solution is obtained, the invention performs extrusion and coagulation bath bundling on the spinning solution to obtain the gel silk.
In the invention, the extrusion temperature is preferably 260-280 ℃, and more preferably 270 ℃. In the present invention, the extrusion is preferably carried out on a spinneret of a twin-screw extruder.
In the present invention, the solvent of the coagulation bath bundle is preferably water; the water is preferably deionized water. In the invention, the diameter of the jelly silk is preferably 100-500 μm.
After the gel silk is obtained, the fiber precursor is obtained by extracting and drying the gel silk.
In the invention, the solvent for extraction preferably comprises one or more of xylene, hydrocarbon cleaning agent, gasoline, n-octane, n-heptane, acetone, dichloromethane, dichloroethane, carbon tetrachloride and trichlorotrifluoroethane, and is preferably dichloromethane or n-octane. In the invention, the bath ratio of the extraction is preferably (10-30): 1, more preferably (15 to 25): 1, more preferably 20: 1. in the invention, the drying temperature is preferably 60-80 ℃, and more preferably 60 ℃; the drying means is preferably hot air blowing.
After a fiber precursor is obtained, the fiber precursor is soaked in dye bath liquid, and after the fiber precursor is taken out, the fiber precursor is sequentially subjected to super-stretching, heat setting and rolling to obtain the antibacterial high-strength high-modulus polyethylene colored fiber.
In the invention, the dye bath solution is formed by mixing a dye and an organic solvent; the dye comprises a phthalocyanine; the phthalocyanine preferably comprises one or more of iron phthalocyanine, copper phthalocyanine, zinc phthalocyanine, cobalt phthalocyanine, manganese phthalocyanine, modified iron phthalocyanine, modified copper phthalocyanine, modified zinc phthalocyanine, modified cobalt phthalocyanine and modified manganese phthalocyanine, and further preferably comprises cobalt phthalocyanine, iron phthalocyanine, copper phthalocyanine or modified zinc phthalocyanine; the modified zinc phthalocyanine is preferably tetraaminozinc phthalocyanine. In the invention, the particle size of the dye is 100-600 nm, preferably 300-400 nm. In the present invention, the organic solvent preferably includes one or more of tetrahydrofuran, N-dimethylformamide and hexafluoroisopropanol, and more preferably N, N-dimethylformamide, tetrahydrofuran or hexafluoroisopropanol. In the present invention, the mass concentration of the dye bath solution is 1 to 10%, and more preferably 5 to 8%.
In the present invention, the dye bath is preferably prepared by a method comprising the steps of: and mixing the dye and the organic solvent under the condition of stirring or ultrasound to obtain the dye bath solution. In the present invention, the rotation speed of the stirring is preferably 50 to 300rpm, and more preferably 100 to 200 rpm. In the invention, the power of the ultrasonic wave is preferably 500-800W, and more preferably 600-700W. In the invention, the mixing time is preferably 30-40 min.
In the invention, the dipping is preferably carried out under the condition of ultrasonic oscillation, and the power of the ultrasonic oscillation is preferably 500-800W, and more preferably 600-700W; the dipping time is preferably 15-60 min, and more preferably 30-40 min.
In the present invention, the super-stretching preferably includes: and sequentially carrying out primary drafting, secondary drafting and tertiary drafting. In the invention, the temperature of the primary drafting is preferably 130-145 ℃, and further preferably 135-140 ℃; the primary drafting multiple is preferably 4-6 times, and more preferably 5 times. In the invention, the temperature of the secondary drawing is preferably 140-150 ℃, and more preferably 145 ℃; the secondary drafting multiple is preferably 2-5 times, and more preferably 3-4 times. In the invention, the temperature of the three-stage drafting is preferably 140-150 ℃, and further preferably 145 ℃; the multiple of the three-stage drafting is preferably 1 to 3 times, and more preferably 1.2 to 2 times.
In the present invention, the heat setting is preferably performed by tension heat setting.
The rolling parameters are not particularly limited in the invention, and the rolling process known to those skilled in the art can be adopted.
The invention also provides the antibacterial high-strength high-modulus polyethylene colored fiber prepared by the preparation method of the technical scheme. In the invention, the rupture strength of the bacteriostatic high-strength high-modulus polyethylene colored fiber is 29.4-33.5 cN/dtex, the initial modulus is 1264-1484 cN/dtex, the bacteriostatic rate on escherichia coli is more than or equal to 95%, and the bacteriostatic rate on staphylococcus aureus is more than or equal to 95%.
The antibacterial high-strength high-modulus polyethylene colored fiber provided by the invention has excellent mechanical properties and antibacterial activity.
The bacteriostatic high-strength high-modulus polyethylene colored fiber and the preparation method thereof provided by the invention are described in detail with reference to the following examples, but they should not be construed as limiting the scope of the invention.
Example 1
Mixing ultra-high molecular weight polyethylene (with the particle size of 100 mu m and the weight-average molecular weight of 400 ten thousand) and nano copper (with the particle size of 100nm) according to the mass ratio of 100: 3 adding into white oil, putting into a feeding tank for dissolving, stirring at room temperature at 150rpm for 15min, swelling at 120 ℃ for 30min, and dissolving at 200 ℃ for 60min to form the spinning solution with the total mass concentration of the ultra-high molecular weight polyethylene and the nano-copper of 5%.
Metering the spinning solution, feeding the spinning solution into a double-screw extruder, extruding the spinning solution at 270 ℃ through a spinneret plate, and bundling the spinning solution by a coagulating bath (the reagent of the coagulating bath is water, and the temperature is room temperature) to form gel silk, wherein the diameter of the gel silk is about 300 mu m.
And (3) extracting the gel silk in dichloromethane (bath ratio is 30: 1), and drying at 60 ℃ to obtain a fiber precursor.
Adding copper phthalocyanine (with particle size of 300nm) into tetrahydrofuran, and performing ultrasonic dispersion at 600W for 30min to obtain dyeing bath solution with concentration of 5%.
Placing the fiber precursor in the dyeing bath liquid, performing ultrasonic oscillation at 600W for 30min, taking out, and performing super-stretching, heat setting and rolling to obtain the antibacterial high-strength high-modulus polyethylene colored fiber, wherein the super-stretching comprises primary stretching, secondary stretching and tertiary stretching in sequence; the temperature of the primary drafting is 140 ℃, and the multiple of the primary drafting is 6 times; the temperature of the secondary drawing is 145 ℃, and the multiple of the secondary drawing is 5 times; the temperature of the three-stage drawing is 145 ℃, and the multiple of the three-stage drawing is 1.2 times.
The breaking strength of the antibacterial high-strength high-modulus polyethylene colored fiber is 31.2cN/dtex, and the initial modulus is 1385 cN/dtex.
According to the third part of GB/T20944.3-2008 evaluation of antibacterial performance of textiles: the procedure of the shaking method was used to perform the antibacterial activity test on the antibacterial UHMWPE colored fibers prepared in this example. The test result is as follows, the bacteriostasis rate of the antibacterial UHMWPE colored fiber provided by the embodiment to escherichia coli is more than or equal to 95%, and the bacteriostasis rate to staphylococcus aureus is more than or equal to 95%.
Example 2
Mixing ultra-high molecular weight polyethylene (with the particle size of 100 mu m and the weight-average molecular weight of 400 ten thousand) and nano silver (with the particle size of 100nm) according to the mass ratio of 100: 2 adding into white oil, putting into a feeding tank for dissolving, stirring at room temperature at 150rpm for 15min, swelling at 125 ℃ for 35min, and dissolving at 240 ℃ for 40min to form the spinning solution with the total mass concentration of the ultra-high molecular weight polyethylene and the nano silver of 7%.
Metering the spinning solution, feeding the spinning solution into a double-screw extruder, extruding the spinning solution at 270 ℃ through a spinneret plate, and bundling the spinning solution by a coagulating bath (the reagent of the coagulating bath is water, and the temperature is room temperature) to form gel silk, wherein the diameter of the gel silk is about 300 mu m.
And (3) extracting the gel silk in n-octane (bath ratio is 30: 1), and drying at 60 ℃ to obtain a fiber precursor.
Tetraaminozinc phthalocyanine (particle size 400nm) was added to N, N-dimethylformamide, and stirred and dispersed at 600rpm for 30min to obtain a dyeing bath solution having a concentration of 8%.
Placing the fiber precursor in the dyeing bath liquid, performing ultrasonic oscillation at 600W for 30min, taking out, and performing super-stretching, heat setting and rolling to obtain antibacterial high-strength high-modulus polyethylene colored fiber; the super-drawing comprises primary drawing, secondary drawing and tertiary drawing which are sequentially carried out; the temperature of the primary drafting is 135 ℃, and the multiple of the primary drafting is 5 times; the temperature of the secondary drawing is 145 ℃, and the multiple of the secondary drawing is 5 times; the temperature of the three-stage drawing is 145 ℃, and the multiple of the three-stage drawing is 2 times.
The rupture strength of the antibacterial high-strength high-modulus polyethylene colored fiber is 32.8N/dtex, and the modulus is 1484 cN/dtex.
The antibacterial UHMWPE colored fiber obtained in the embodiment is detected in the manner of the embodiment 1, and the detection structure shows that the antibacterial rate of the antibacterial UHMWPE colored fiber provided in the embodiment to Escherichia coli is greater than or equal to 95%, and the antibacterial rate to Staphylococcus aureus is greater than or equal to 95%.
Example 3
Mixing ultra-high molecular weight polyethylene (with the particle size of 150 mu m and the weight average molecular weight of 500 ten thousand) and nano copper (with the particle size of 200nm) according to the mass ratio of 100: 5 adding into white oil solution, putting into a feeding tank for dissolving, stirring at room temperature and 150rpm for 15min, swelling at 120 ℃ for 40min, and dissolving at 220 ℃ for 50min to form a spinning solution with the total mass concentration of high molecular weight polyethylene and nano-copper being 6%.
Metering the spinning solution, feeding the spinning solution into a double-screw extruder, extruding the spinning solution at 270 ℃ through a spinneret plate, and bundling the spinning solution by a coagulating bath (water, the temperature is room temperature) to form gel silk, wherein the diameter of the obtained gel silk is about 300 mu m.
And (3) extracting the gel silk in dichloromethane (bath ratio is 30: 1), and drying at 60 ℃ to obtain a fiber precursor.
Adding iron phthalocyanine (particle size of 300nm) into tetrahydrofuran, and ultrasonically dispersing at 600W for 40min to obtain 3% dyeing bath solution.
Placing the fiber precursor in the dyeing bath liquid, performing ultrasonic oscillation at 600W for 30min, taking out, performing super-stretching, heat setting and rolling to obtain antibacterial high-strength high-modulus polyethylene colored fiber; the super-stretch comprises: sequentially carrying out primary drafting, secondary drafting and tertiary drafting; the temperature of the primary drafting is 140 ℃, and the multiple of the primary drafting is 5 times; the temperature of the secondary drawing is 140 ℃, and the multiple of the secondary drawing is 4 times; the temperature of the three-stage drafting is 145 ℃, and the multiple of the three-stage drafting is 1.5 times.
The breaking strength of the antibacterial high-strength high-modulus polyethylene colored fiber is 29.4cN/dtex, and the modulus is 1264 cN/dtex.
The antibacterial UHMWPE colored fiber obtained in the embodiment is detected in the manner of the embodiment 1, and the detection structure shows that the antibacterial rate of the antibacterial UHMWPE colored fiber provided in the embodiment to Escherichia coli is greater than or equal to 95%, and the antibacterial rate to Staphylococcus aureus is greater than or equal to 95%.
Example 4
The weight ratio of ultra-high molecular weight polyethylene (with the grain diameter of 100 mu m and the weight average molecular weight of 500 ten thousand) to nano silver (with the grain diameter of 150nm) is 100: 3 adding the mixture into a white oil solution, putting the mixture into a feeding tank for dissolving, stirring the mixture at the room temperature of 200rpm for 20min, swelling the mixture at the temperature of 120 ℃ for 35min, and dissolving the mixture at the temperature of 250 ℃ for 35min to form a spinning solution with the total mass concentration of the ultra-high molecular weight polyethylene and the nano-silver of 5%.
The spinning solution is metered and fed into a twin-screw extruder and extruded through a spinneret at 270 ℃, and is bundled by a coagulating bath (water, the temperature is room temperature) to form gel filaments, and the diameter of the obtained gel filaments is about 300 mu m.
And (3) extracting the gel silk in dichloromethane (bath ratio is 30: 1), and drying at 60 ℃ to obtain a fiber precursor.
Adding cobalt phthalocyanine (with particle size of 400nm) into hexafluoroisopropanol, and ultrasonically stirring at 700W for 30min for dispersion to obtain a dyeing bath solution with concentration of 5%.
Placing the fiber precursor in the dyeing bath liquid, performing ultrasonic oscillation at 800W for 25min, taking out, and performing super-stretching, heat setting and rolling to obtain antibacterial high-strength high-modulus polyethylene colored fiber; the super-drawing comprises primary drawing, secondary drawing and tertiary drawing which are sequentially carried out; the temperature of the primary drafting is 138 ℃, and the multiple of the primary drafting is 4 times; the temperature of the secondary drawing is 145 ℃, and the multiple of the secondary drawing is 4 times; the temperature of the three-stage drawing is 145 ℃, and the multiple of the three-stage drawing is 3 times.
The rupture strength and the initial modulus of the obtained antibacterial high-strength high-modulus polyethylene colored fiber are tested by the method GB-T29554-2013, and the rupture strength and the initial modulus of the obtained antibacterial high-strength high-modulus polyethylene colored fiber are 33.5cN/dtex and 1464cN/dtex respectively.
The antibacterial UHMWPE colored fiber obtained in the embodiment is detected in the manner of the embodiment 1, and the detection structure shows that the antibacterial rate of the antibacterial UHMWPE colored fiber provided in the embodiment to Escherichia coli is greater than or equal to 95%, and the antibacterial rate to Staphylococcus aureus is greater than or equal to 95%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.

Claims (9)

1. A preparation method of antibacterial high-strength high-modulus polyethylene colored fibers is characterized by comprising the following steps:
mixing the ultrahigh molecular weight polyethylene, the antibacterial particles and a spinning solvent, and swelling and dissolving to obtain a spinning solution;
extruding the spinning solution and bundling by a coagulating bath to obtain gel filaments;
extracting and drying the gel silk to obtain a fiber precursor;
soaking the fiber precursor in dye bath, taking out, and sequentially carrying out super-stretching, heat setting and rolling to obtain the antibacterial high-strength high-modulus polyethylene colored fiber;
the dye bath solution is formed by mixing a dye and an organic solvent, wherein the dye comprises phthalocyanine; the organic solvent comprises one or more of tetrahydrofuran, N-dimethylformamide and hexafluoroisopropanol; the mass concentration of the dye bath solution is 1-10%; the particle size of the dye is 100-600 nm;
the super-stretching comprises: sequentially carrying out primary drafting, secondary drafting and tertiary drafting; the temperature of the primary drafting is 130-145 ℃, and the multiple of the primary drafting is 4-6 times; the temperature of the secondary drafting is 140-150 ℃, and the multiple of the secondary drafting is 2-5 times; the temperature of the three-stage drafting is 140-150 ℃, and the multiple of the three-stage drafting is 1-3 times.
2. The method of claim 1, wherein the dye bath is prepared by a method comprising the steps of:
mixing a dye and an organic solvent under the condition of stirring or ultrasound to obtain the dye bath solution; the stirring speed is 50-300 rpm, and the ultrasonic power is 500-800W.
3. The production method according to claim 1, wherein the ultra-high molecular weight polyethylene has a weight average molecular weight of 300 to 600 ten thousand; the particle size of the ultra-high molecular weight polyethylene is 50-200 mu m.
4. The preparation method of claim 1, wherein the bacteriostatic particles are nano silver or nano copper; the particle size of the antibacterial particles is 50-200 nm.
5. The preparation method according to claim 1, 3 or 4, wherein the mass ratio of the ultrahigh molecular weight polyethylene to the bacteriostatic particles is 100: (1-5); the total mass concentration of the ultrahigh molecular weight and the antibacterial particles in the spinning solution is 3-8%.
6. The method of claim 1, wherein the temperature of the extrusion is 260 to 280 ℃.
7. The method according to claim 1 or 6, wherein the diameter of the jelly wire is 100 to 500 μm.
8. The preparation method according to claim 1, wherein the dipping is performed under the condition of ultrasonic oscillation, and the power of the ultrasonic oscillation is 500-800W; the dipping time is 15-60 min.
9. The antibacterial high-strength high-modulus polyethylene colored fiber obtained by the preparation method of any one of claims 1 to 8, wherein the breaking strength of the antibacterial high-strength high-modulus polyethylene colored fiber is 29.4 to 33.5cN/dtex, and the initial modulus is 1264 to 1484 cN/dtex.
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