CN114540984B - High-strength coated yarn and production method thereof - Google Patents
High-strength coated yarn and production method thereof Download PDFInfo
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- CN114540984B CN114540984B CN202210367855.2A CN202210367855A CN114540984B CN 114540984 B CN114540984 B CN 114540984B CN 202210367855 A CN202210367855 A CN 202210367855A CN 114540984 B CN114540984 B CN 114540984B
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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
- D01F8/14—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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- 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
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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- 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
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The application relates to the technical field of coated yarn production, and particularly discloses a high-strength coated yarn and a production method thereof. The application relates to a high-strength coated yarn, which comprises a core yarn composed of polyester filaments, wherein the outside of the core yarn is coated with a coating layer, and the coating layer is mainly prepared from the following raw materials: polyvinyl chloride, a dispersing agent, a heat stabilizer, a plasticizer, an antioxidant, a pigment, an antibacterial agent and a reinforcing agent; the production method comprises the following steps: (1) preparation of color master batch: uniformly mixing the raw materials of each component of the coating layer, and cooling, extruding and granulating to obtain color master batch; (2) preparation of coated yarn: putting the core wire into a filament frame, and penetrating into a die through a tension positioning device; adding the color master batch obtained in the step (1) into a hopper, extruding, plasticizing and melting, and then feeding into a die; drawing the polyester filaments to pass through a die head for coating; and cooling the coated yarn after coating, and winding to obtain the coated yarn. The high-strength coated yarn has better antibacterial performance and tensile performance.
Description
Technical Field
The application relates to the technical field of coated yarn production, in particular to a high-strength coated yarn and a production method thereof.
Background
The coated yarn is a yarn with a novel structure, and is formed by taking filaments or short fibers as yarn cores and wrapping the filaments or short fiber yarns with another kind of yarn strips. The core yarn is coated by the covering yarn in a spiral mode, and the prepared yarn is uniform in evenness, fluffy and plump and smooth.
At present, common cladding yarn takes continuous spandex filaments as core filaments, and an outer layer is wound on the outer side of the core filaments in a spiral mode by chemical fiber filaments to form elastic cladding yarn. The coated yarn obtained by taking the chemical fiber filaments as raw materials has the problems of low strength and easy core exposure.
Disclosure of Invention
In order to improve the tensile strength of the coated yarn, the application provides a high-strength coated yarn and a production method thereof.
In a first aspect, the present application provides a high-strength covered yarn, which adopts the following technical scheme:
the high-strength coated yarn comprises a core yarn composed of polyester filaments, wherein the outside of the core yarn is coated with a coating layer, and the coating layer is mainly prepared from the following raw materials in parts by weight: 50-90 parts of polyvinyl chloride, 2-5 parts of dispersing agent, 1-2 parts of heat stabilizer, 25-30 parts of plasticizer, 2-5 parts of antioxidant, 2-5 parts of pigment, 5-10 parts of antibacterial agent and 5-10 parts of reinforcing agent, wherein the antibacterial agent is at least two of mesoporous zirconium phosphate, nano titanium dioxide and chitosan; the reinforcing agent consists of poly (1, 4-cyclohexanedimethylene terephthalate) resin, an acrylonitrile-butadiene-styrene copolymer, a maleic anhydride grafted SEBS compatilizer and modified POE (polyolefin elastomer) according to the mass ratio of (1-2) (3-4), and the preparation method of the modified POE comprises the following steps: and uniformly mixing polyethylene, POE elastomer, tri (2, 4-di-tert-butyl) phosphite ester, zinc stearate and calcium carbonate subjected to surface treatment of a coupling agent.
Preferably, the heat stabilizer is a calcium-zinc stabilizer.
Preferably, the plasticizer is epoxidized soybean oil.
By adopting the technical scheme, the antibacterial agent and the reinforcing agent are added into the coated wire, and the antibacterial agent is used for improving the antibacterial property of the coated wire, so that the influence of microorganisms such as bacteria on the mechanical property of the coated wire is reduced, the tensile strength of the coated wire is further improved, and the reinforcing agent and the antibacterial agent are mutually matched, so that the tensile strength of the coated wire is improved; the reinforcing agent is prepared by compounding a plurality of components, the poly-1, 4-cyclohexanedimethylene terephthalate resin has good cohesiveness and tensile property, the folding endurance is better, the acrylonitrile-butadiene-styrene copolymer is distributed in the poly-1, 4-cyclohexanedimethylene terephthalate resin in a particle form, the acrylonitrile-butadiene-styrene copolymer has high stretching viscosity, so that the cohesiveness between the poly-1, 4-cyclohexanedimethylene terephthalate resin and the polyvinyl chloride is conveniently improved, the tensile strength of a coating layer is further improved, the coating strength of the coating layer on a core wire is further improved, the tensile strength of a coated wire is also improved, the maleic anhydride grafting SEBS compatilizer is used as a compatilizer, the carboxyl group is higher, the reactivity is higher, the compatibility between the reinforcing agent and the polyvinyl chloride is further improved, the impact strength and the elongation at break of the coating layer are also improved, the tensile strength of the coating layer is conveniently improved, the molecular chain end of the coupling agent distributed on the surface of calcium carbonate generates good intermolecular effect on the polyethylene part in the POE elastomer, the tensile strength of the POE elastomer is further improved, the compatibility between the POE and the POE elastomer is better, the POE carrier is further improved, and the tensile strength of the POE elastomer is more compatible.
Preferably, the antibacterial agent and the reinforcing agent are formed by the mass ratio of (6-8) to (6-9).
Through adopting above-mentioned technical scheme, carry out further optimization to the proportion of reinforcing agent and antibacterial agent to make the ratio of reinforcing agent, antibacterial agent reach the best, antibacterial agent evenly distributed is in the cladding of cladding silk, thereby forms one deck protective layer, and then reduces the condition that the cladding silk appears going moldy, simultaneously under the effect of reinforcing agent, further improves the tensile strength of cladding silk.
Preferably, the antibacterial agent consists of mesoporous zirconium phosphate, nano titanium dioxide and chitosan according to the mass ratio of (1-2) (3-4).
By adopting the technical scheme, the antibacterial agent is prepared by mutually compounding three components of mesoporous zirconium phosphate, nano titanium dioxide and chitosan, and the proportion of the three components of the antibacterial agent is optimized, so that the proportion of the three components of the antibacterial agent is optimal, the integrity of a cell membrane is destroyed after the mesoporous zirconium phosphate contacts the cell membrane, and the content in a bacterial cell is leaked, so that microorganisms die; nano titanium dioxide passes through the cell membrane of bacteria and enters the bacteria to react with organic matters in the bacteria to generate carbon dioxide and water, so that the bacteria are decomposed; the chitosan is adsorbed on the surface of bacteria to form a layer of polymer film, so that nutrient substances are prevented from being transported into cells, metabolism of the bacteria is destroyed, and the antibacterial effect is achieved; mesoporous zirconium phosphate, nano titanium dioxide and chitosan are matched with each other, so that metabolism of bacteria is destroyed, antibacterial performance of the coated wire is improved, and tensile strength of the coated wire is improved.
Preferably, the nano titanium dioxide is modified nano titanium dioxide, and the modification method of the modified nano titanium dioxide comprises the following steps:
A. and (3) preparing a material: uniformly mixing nano titanium dioxide, a coupling agent and dimethylbenzene, heating for reaction, centrifuging the solution to obtain slurry, washing with absolute ethyl alcohol, centrifuging and drying to obtain a material I;
B. and (3) a material II: mixing and stirring the material I obtained in the step A, tetrahydrofuran and triethylamine, dropwise adding 2-bromoisobutyryl bromide solution, reacting, stopping stirring, reacting for 23-24 hours, washing with absolute ethyl alcohol, centrifuging and drying to obtain a material II;
C. and (3) a material III: mixing the material II obtained in the step B, methacrylic acid-dimethylaminoethyl ester, N, N, N ', N, ' N ' -pentamethyldiethylenetriamine and absolute methanol, cooling with liquid nitrogen, performing vacuum-thawing cycle for 2-3 times, adding CuBr, cooling with liquid nitrogen, performing vacuum-thawing cycle for 2-3 times, reacting, diluting with tetrahydrofuran, centrifuging, purifying, washing and drying to obtain a material III;
D. preparation of modified nano titanium dioxide: and C, uniformly mixing the material III, the bromo-n-hexane and the tetrahydrofuran obtained in the step C, centrifuging, purifying and drying to obtain the material III.
By adopting the technical scheme, the surface treatment is carried out on the nano titanium dioxide, then the acrylic polymer is grafted, so that the dispersibility of the nano titanium dioxide in the coating layer is improved, the agglomeration of nano particles is reduced, the sterilization performance of the nano titanium dioxide is improved, the antibacterial property of the coating layer is improved, and the antibacterial property of the coated wire is further improved.
Preferably, the nano titanium dioxide is anatase, and the particle size of the nano titanium dioxide is 30-50nm.
By adopting the technical scheme, the particle size of the nano titanium dioxide is smaller, so that the nano titanium dioxide is convenient to uniformly disperse in the raw material of the coating layer, the antibacterial property of the coating layer is further improved, and the anatase nano titanium dioxide has strong photochemical capacity and is convenient to react with various bacteria.
Preferably, the dispersing agent consists of polyethylene wax and oleamide according to the mass ratio of (1-3) to (2-4).
By adopting the technical scheme, the polyethylene wax has good compatibility with the toner, is convenient for wetting the pigment, and then permeates into the pores inside the pigment aggregate, weakens cohesive force, so that the pigment aggregate is easier to break under the action of external shearing force, and then is convenient to disperse in the coating layer; the addition of the oleamide is convenient for improving the processability of the coating layer, improving the fluidity of the melt, further improving the compatibility among the components, and the polyethylene wax and the oleamide are mutually matched, so that the compatibility of each group in the coating layer is convenient to be further improved, the antibacterial and reinforcing effects of the antibacterial agent and the reinforcing agent in the coating layer are further improved, and the antibacterial performance and the tensile strength of the coated wire are further improved.
Preferably, the antioxidant consists of antioxidant 264 and trisnonylphenyl phosphite according to the mass ratio of (1-2) to (2-3).
By adopting the technical scheme, the trisnonylphenyl phosphite ester is an effective stabilizer in the raw materials of the coating layer, has the functions of preventing discoloration and mechanical strength loss, is easy to disperse uniformly with other raw materials in the coating layer, has good oxidation resistance, does not increase the preparation cost of the coated wire after being compounded with the antioxidant 264, and simultaneously delays the oxidation speed of the coating layer and prolongs the oxidation induction period of the coating layer, thereby further improving the oxidation resistance of the coating layer.
Preferably, the thickness of the coating layer is 7-8 μm.
Through adopting above-mentioned technical scheme, when the thickness of coating is too thick, the cladding silk weight that thereby makes is great, and thickness is great, is unfavorable for later use, simultaneously, extravagant more coating's raw materials, and then improve the cost of preparation of cladding silk, when the thickness of coating is thinner, be inconvenient for cladding the core silk, simultaneously, the cladding silk performance of making is not good, tensile strength and antibacterial property are not good, when the thickness is in 7-8 mu m, be convenient for cladding the core silk on the one hand, improve the tensile property and the antibacterial property of cladding silk, on the other hand, reduce the waste of cladding layer material.
Preferably, the fineness of the polyester filaments is 35-40tex, the strength is 970-1000cN, and the elongation is 18-20%.
Through adopting above-mentioned technical scheme, polyester filament's fineness is less, is convenient for reduce the used raw materials of coating, and polyester filament powerful is higher, and the elongation is great, and the cladding of the coating of being convenient for, simultaneously, based on high powerful polyester filament, the tensile strength of the coated yarn of preparation is higher, is convenient for improve the tensile strength of coated yarn.
Preferably, the chitosan is modified chitosan, and the preparation method of the modified chitosan comprises the following steps:
s1, grafting chitosan: mixing and heating chitosan, acetic acid and 1-hydroxymethyl-5, 5-dimethyl hydantoin, reacting for 23-24h, cooling, and distilling under reduced pressure to obtain a viscous product; adding the sticky product into an acetone solution, stirring and mixing, removing floccules, and carrying out suction filtration, washing and drying to obtain grafted chitosan;
s2, modifying chitosan: dissolving grafted chitosan in acetic acid solution, regulating the concentration of the grafted chitosan to 3.5-4.0mg/mL, filtering, and regulating the pH value of the solution to be 6 to obtain grafted chitosan solution; dissolving sodium tripolyphosphate in ultrapure water, and dripping into the grafted chitosan solution to obtain the product.
In a second aspect, the application provides a method for producing a high-strength coated yarn, which adopts the following technical scheme:
a method for producing high-strength coated yarn comprises the following steps,
(1) Preparing color master batches: uniformly mixing the raw materials of each component of the coating layer, and cooling, extruding and granulating to obtain color master batch;
(2) Preparation of coated yarn: putting the core wire into a filament frame, and penetrating into a die through a tension positioning device; adding the color master batch obtained in the step (1) into a hopper, extruding, plasticizing and melting, and then feeding into a die; drawing the polyester filaments to pass through a die head for coating; and cooling the coated yarn after coating, and winding to obtain the coated yarn.
By adopting the technical scheme, the antibacterial agent and the reinforcing agent are added into the raw material of the coating layer of the coated wire, the antibacterial agent is used for destroying the metabolism system of bacteria, and then destroying the proliferation capacity of the bacteria, and further improving the antibacterial performance of the coated wire, the reinforcing agent is used for improving the tensile performance of the coated wire, and the reinforcing agent and the antibacterial agent are mutually matched, so that the tensile performance of the coated wire is conveniently improved together.
In summary, the application has the following beneficial effects:
1. according to the high-strength coated yarn, the antibacterial agent and the reinforcing agent are matched, and the antibacterial agent is used for improving the antibacterial performance of the coated yarn, so that the influence of microorganisms such as bacteria on the mechanical performance of the coated yarn is reduced, the reinforcing agent is convenient for improving the tensile performance of the coated yarn, and the antibacterial agent and the reinforcing agent are added together, so that the tensile performance of the coated yarn is convenient to improve.
2. The antibacterial agent in the high-strength coated wire disclosed by the application is compounded by multiple components, so that a metabolism system of microorganisms such as bacteria and the like is further damaged, the survival rate of the microorganisms such as bacteria and the like is further reduced, the antibacterial performance of the coated wire is further improved, and the influence of the microorganisms such as bacteria and the like on the performance of the coated wire is further reduced.
Detailed Description
The present application will be described in further detail with reference to examples.
Optionally, the manufacturer of the maleic anhydride grafted SEBS compatilizer is catalpa plastic source manufacturer.
Optionally, the mesoporous zirconium phosphate has a particle size of 200-500nm.
Alternatively, the manufacturer of the acrylonitrile-butadiene-styrene copolymer is Shanghai Fuchen plastic raw materials limited company.
Alternatively, the POE elastomer manufacturer is su state plastic materials, inc.
Alternatively, the manufacturer of 2-bromoisobutyryl bromide is Shanghai Ala Biochemical technology Co., ltd, and the purity is 98%.
Alternatively, the manufacturer of methacrylic acid-dimethylaminoethyl ester is Shanghai Ala Biochemical technologies Co., ltd.
Alternatively, the manufacturer of N, N, N ', N, ' N ' -pentamethyldiethylenetriamine is Sigma-Aldrich chemistry.
Alternatively, the manufacturer of 1-hydroxymethyl-5, 5-dimethylhydantoin is Tokyo kernel Chemicals.
Alternatively, the chitosan has a weight average molecular weight of 50000 and a degree of deacetylation of 90%.
Examples
Example 1
The high-strength coated yarn of the embodiment comprises a core yarn composed of polyester filaments, wherein a coating layer is coated outside the core yarn, and the coating layer is prepared from the following raw materials in weight: 50kg of polyvinyl chloride, 2kg of dispersing agent, 1kg of heat stabilizer, 25kg of plasticizer, 2kg of antioxidant, 2kg of pigment, 5kg of antibacterial agent and 5kg of reinforcing agent, wherein the dispersing agent is polyethylene wax, the heat stabilizer is calcium-zinc stabilizer, the plasticizer is epoxy soybean oil, the antioxidant is antioxidant 264, the pigment is titanium white, the antibacterial agent consists of mesoporous zirconium phosphate and nano titanium dioxide according to the mass ratio of 1:1, the reinforcing agent consists of poly (1, 4-cyclohexanedimethylene) resin, acrylonitrile-butadiene-styrene copolymer, maleic anhydride grafted SEBS compatilizer and modified POE according to the mass ratio of 1:1:2:2, and the preparation method of the modified POE comprises the following steps: I. surface treatment of calcium carbonate: firstly, drying light calcium carbonate at 110 ℃ for 2 hours, and then adding the light calcium carbonate into a high-speed mixer for stirring; diluting the metered titanate coupling agent with liquid paraffin, uniformly spraying wine onto calcium carbonate at 30 ℃, and stirring until the reaction is complete, thus obtaining the surface-treated calcium carbonate; II, preparation of modified POE: introducing surface-treated calcium carbonate and POE elastomer based on polyethylene as a carrier, simultaneously adding tri (2, 4-di-tert-butyl) phosphite ester and zinc stearate, mixing by a high-speed mixer, and extruding and granulating in a screw extruder; the thickness of the coating layer is 7 mu m, the fineness of the polyester filament is 35-40tex, the strength is 970-1000cN, and the elongation is 18-20%.
The production method of the high-strength coated yarn of the embodiment comprises the following steps:
(1) Preparing color master batches:
a. weighing the following raw materials in parts by mass: polyvinyl chloride, a dispersing agent, a heat stabilizer, a plasticizer, an antioxidant, a pigment, an antibacterial agent and a reinforcing agent;
b. mixing the components, and then putting the mixed components into a high-speed mixer for high-speed mixing;
c. stirring and cooling, transferring to a charging hopper, and conveying the charging hopper into a double-screw host machine through a conveying device;
d. cutting into particles by a granulator to form color master batches;
(2) Preparation of coated yarn:
a. forming polyester filament bundles by a plurality of polyester filaments 2, placing the polyester filament bundles into a filament frame, and penetrating into a die through a tension positioning device;
b. adding the color master batch into a hopper, heating, plasticizing and melting by a screw extruder, and then feeding into a die;
c. the traction disc drives the polyester filament bundles to pass through the die head for coating;
d. and cooling the coated wire after coating by circulating cooling water, and winding after entering an automatic wire diameter detector.
Examples 2 to 5
Examples 2 to 5 are coating layers of high-strength coated wires with different raw material composition ratios, and the raw material ratio of the coating layer of the high-strength coated wire corresponding to each example is shown in table 1, and the raw material ratio unit is kg.
Table 1 raw material ratio of coating layer of high-strength coated yarn of examples 1 to 5
Examples 2-5 differ from example 1 in that: the proportions of the components of the coating layer were different from those of example 1, and the other components were exactly the same as those of example 1.
The production method of the high strength coated yarn of examples 2 to 5 is exactly the same as that of example 1.
Example 6
This embodiment differs from embodiment 4 in that: the reinforcing agent consists of polyester resin, acrylonitrile-butadiene-styrene copolymer, maleic anhydride grafted SEBS compatilizer and modified POE according to the mass ratio of 2:2:4:4, the dispersing agent consists of polyethylene wax and oleamide according to the mass ratio of 1:4, the antioxidant consists of antioxidant 264 and trisnonylphenyl phosphite according to the mass ratio of 1:3, and the other components are exactly the same as in the example 4.
The production method of the high-strength covered yarn of this example was exactly the same as that of example 4.
Example 7
This embodiment differs from embodiment 6 in that: the antibacterial agent consists of mesoporous zirconium phosphate, nano titanium dioxide and chitosan according to the mass ratio of 1:1:3, and the other components are completely the same as in the example 6.
The production method of the high-strength covered yarn of this example was exactly the same as that of example 6.
Example 8
This embodiment differs from embodiment 6 in that: the antibacterial agent consists of mesoporous zirconium phosphate, nano titanium dioxide and chitosan according to the mass ratio of 2:2:4, and the other components are completely the same as in the example 6.
The production method of the high-strength covered yarn of this example was exactly the same as that of example 6.
Example 9
This embodiment differs from embodiment 8 in that: the nano titanium dioxide is modified nano titanium dioxide, and the modification method of the modified nano titanium dioxide comprises the following steps: A. material one: taking 0.5g of nano TiO 2 Adding the mixture into a three-mouth bottle filled with 9mL of KH550 and 50mL of dimethylbenzene, magnetically stirring, protecting by nitrogen, heating in an oil bath at 60 ℃ for reaction for 24 hours, centrifuging the solution to obtain slurry, washing with absolute ethyl alcohol, centrifuging for 5 times, drying in a vacuum oven at 60 ℃ for 24 hours, and grinding to obtain a material I;
B. and (3) a material II: adding 1.5g of the dry material I prepared in the step A into a flask, adding 50mL of tetrahydrofuran and 0.5mL of triethylamine, then placing into an ice bath at 20 ℃ for stirring, dropwise adding 2-bromoisobutyryl bromide solution, reacting for 1h, stopping stirring, reacting for 24h at 25 ℃, washing with absolute ethyl alcohol, centrifuging for 5 times, and drying in a vacuum oven at 60 ℃ for 24h to obtain a material II;
C. and (3) a material III: adding 0.3058g of a dried material II, 2.6726g of methacrylic acid-dimethylaminoethyl ester, 0.0180mL of N, N ', N, N' -pentamethyldiethylenetriamine and 1.0g of absolute methanol into a 10mL dry reaction bottle, cooling with liquid nitrogen, vacuum-thawing for 2 times, adding 0.0128g of CuBr under the protection of nitrogen in a frozen state, cooling with liquid nitrogen, vacuum-thawing for 2 times, stirring at 60 ℃ for 48 hours, exposing a sample to air for terminating the reaction, diluting with tetrahydrofuran, centrifuging for purification, repeatedly washing for 3 times, and drying the product in a vacuum oven at 60 ℃ for 12 hours to obtain a material III;
D. preparation of modified nano titanium dioxide: into a three 100mL flask of 0.5g of the material was charged 1.5mL of bromohexane and 35mL of tetrahydrofuran, and the mixture was stirred at room temperature for 24 hours, followed by dilution with tetrahydrofuran, followed by centrifugal purification, and repeated washing 3 times. And drying the product in a vacuum oven at 60 ℃ for 12 hours to obtain the product. The other is exactly the same as in example 8.
The production method of the high-strength covered yarn of this example was exactly the same as that of example 8.
Example 10
This embodiment differs from embodiment 9 in that: the chitosan is modified chitosan, and the modification method of the modified chitosan comprises the following steps: s1, grafting chitosan: weighing 3.22g (0.02 mol) of chitosan, putting the chitosan into a single-neck flask, adding 300m of acetic acid with the volume fraction of 1% to dissolve the chitosan, then adding 3.16g (0.02 mol) of 1-hydroxymethyl-5, 5-dimethylhydantoin, placing the single-neck flask into an oil bath environment at the temperature of 100 ℃ to react, stirring, condensing and refluxing, reacting for 24 hours, after the reaction is finished, slightly cooling the solution, decompressing and distilling to remove the solvent, obtaining a viscous product, dropwise adding the product into an acetone solution by using a dropper, stirring until the solution is milky, after removing the flocculent product, replacing the acetone solution, repeating the operation until the product is completely dripped, filtering and washing the obtained solid substance for 3-5 times by using acetone and ethanol on a suction filtration device, and vacuum drying the final product at the temperature of 45 ℃ for 48 hours; s2, modifying chitosan: dissolving grafted chitosan in acetic acid solution with volume fraction of 1%, regulating the concentration of the grafted chitosan to 4.0mg/mL, filtering, and regulating the pH=6 of the solution by using 1mol/L NaOH to obtain grafted chitosan solution; dissolving sodium tripolyphosphate in ultrapure water to obtain a solution with the concentration of 2.0 mg/mL; dropwise adding sodium tripolyphosphate into the grafted chitosan solution under continuous magnetic stirring, wherein the dropwise adding speed is 2mL/min, and observing the properties of a reaction product; obtaining the product. The other is exactly the same as in example 9.
The production method of the coated yarn with high-strength antibacterial function of this example is exactly the same as that of example 9.
Comparative example
Comparative example 1
This comparative example differs from example 1 in that: the coating layer was not added with an antibacterial agent, and the amount of the reinforcing agent added was 10kg, and the same as in example 1 was repeated.
The production method of the high-strength covered yarn of this comparative example is different from that of example 1 in that: (1) preparation of color master batch: a. weighing the following raw materials in parts by mass: polyvinyl chloride, a dispersing agent, a heat stabilizer, a plasticizer, an antioxidant, a pigment and a reinforcing agent; the other is exactly the same as in example 1.
Comparative example 2
This comparative example differs from example 1 in that: no reinforcing agent was added to the coating layer, and the amount of the antibacterial agent added was 10kg, and the same as in example 1 was repeated.
The production method of the high-strength covered yarn of this comparative example is different from that of example 1 in that: (1) preparation of color master batch: a. weighing the following raw materials in parts by mass: polyvinyl chloride, a dispersing agent, a heat stabilizer, a plasticizer, an antioxidant, a pigment and an antibacterial agent; the other is exactly the same as in example 1.
Comparative example 3
This comparative example differs from example 1 in that: the antibacterial agent was mesoporous zirconium phosphate, and the other was exactly the same as in example 1.
The production method of the high-strength covered yarn of this comparative example was exactly the same as in example 1.
Comparative example 4
This comparative example differs from example 1 in that: the reinforcing agent was a poly-1, 4-cyclohexanedimethylene terephthalate resin, and the other was exactly the same as in example 1.
The production method of the high-strength covered yarn of this comparative example was exactly the same as in example 1.
Comparative example 5
This comparative example differs from example 1 in that: the reinforcing agent consists of poly (1, 4-cyclohexanedimethylene terephthalate) resin and an acrylonitrile-butadiene-styrene copolymer according to a mass ratio of 2:3, and the other components are exactly the same as in example 1.
The production method of the high-strength covered yarn of this comparative example was exactly the same as in example 1.
Comparative example 6
This comparative example differs from example 1 in that: the reinforcing agent consists of poly-1, 4-cyclohexanedimethylene terephthalate resin, acrylonitrile-butadiene-styrene copolymer and maleic anhydride grafted SEBS compatilizer according to the mass ratio of 2:3:1, and the other components are exactly the same as in the example 1.
The production method of the high-strength covered yarn of this comparative example was exactly the same as in example 1.
Comparative example 7
This comparative example differs from example 1 in that: 45kg of polyvinyl chloride, 2kg of a dispersing agent, 1kg of a heat stabilizer, 15kg of a plasticizer, 2kg of an antioxidant, 2kg of a pigment, 3kg of a nano titanium dioxide and 3kg of a reinforcing agent, and the other steps are exactly the same as in example 1.
The production method of the high-strength covered yarn of this comparative example was exactly the same as in example 1.
Performance test
Antibacterial property detection: the high Jiang Baofu filaments obtained in examples 1 to 10 and comparative examples 1 to 7 were taken according to GB/T20944.3-2008, evaluation of antibacterial Properties of textiles section 3: the detection method in the oscillation method adopts escherichia coli and staphylococcus aureus as detection bacteria, and the antibacterial performance of the high-strength coated wire is detected, and the detection results are shown in table 2.
High-strength performance detection: the high Jiang Baofu filaments prepared in examples 1 to 10 and comparative examples 1 to 7 were used for tensile strength test of high-strength coated filaments according to the test method in GB/T3916-2013 test for breaking Strength and elongation at break (CRE method) of individual yarns of textile package yarns, and the test results are shown in Table 2.
TABLE 2 high strength coated yarn properties for examples 1-10 and comparative examples 1-7
In example 1, the antibacterial agent and the reinforcing agent are added to the raw material of the coating layer, and the antibacterial agent interacts with the reinforcing agent to improve the antibacterial property of the coating layer, so that the influence of bacteria on the tensile strength of the coating layer is reduced, and the reinforcing agent enhances the tensile strength of the coating layer, thereby improving the tensile strength and antibacterial property of the obtained coated wire, as compared with comparative examples 1 to 2, as can be seen from the combination of example 1 and comparative examples 1 to 2.
In combination with examples 1 and comparative examples 4 to 6 and with Table 2, it can be seen that, compared with comparative examples 4 to 7, the reinforcing agent in example 1 is obtained by compounding four components of a polyester resin, an acrylonitrile-butadiene-styrene copolymer, a maleic anhydride grafted SEBS (styrene-ethylene-butylene-styrene) compatibilizer and a modified POE, and the four components interact with each other, so that the tensile strength of the coated yarn is improved.
As can be seen from the combination of examples 1 to 6 and comparative example 7 and the combination of Table 2, examples 1 to 6, in which the proportions of the components of the coating layer were adjusted, give coated filaments having a large variation in antibacterial properties and tensile strength, and comparative example 8, in which the proportions outside the range of the present application were adopted, gave coated filaments
By combining examples 7-8 and comparative example 3 and combining Table 2, it can be seen that the antibacterial agent is composed of three components of mesoporous zirconium phosphate, nano titanium dioxide and chitosan, and the three components of the antibacterial agent influence the proliferation capacity of bacteria by changing the metabolism system of bacteria, thereby enhancing the antibacterial performance of the coated wire and simultaneously improving the stretching length of the coated wire.
By combining examples 9-10 and combining Table 2, it can be seen that the modification of the nano titanium dioxide and chitosan is convenient to further improve the antibacterial effect of the antibacterial agent, thereby reducing the influence of bacteria on the strength of the coated wire and further improving the tensile strength of the coated wire.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (7)
1. The utility model provides a high strength cladding silk, includes the core silk that comprises polyester filament, has the cladding at the outside cladding of core silk, its characterized in that: the coating layer is mainly prepared from the following raw materials in parts by weight: 50-90 parts of polyvinyl chloride, 2-5 parts of dispersing agent, 1-2 parts of heat stabilizer, 25-30 parts of plasticizer, 2-5 parts of antioxidant, 2-5 parts of pigment, 5-10 parts of antibacterial agent and 5-10 parts of reinforcing agent, wherein the reinforcing agent consists of poly (1, 4-cyclohexanedimethylene terephthalate) resin, acrylonitrile-butadiene-styrene copolymer, maleic anhydride grafted SEBS compatilizer and modified POE according to the mass ratio of (1-2): (1-2): (3-4): (3-4), and the preparation method of the modified POE comprises the following steps: uniformly mixing polyethylene, POE elastomer, tri (2, 4-di-tert-butyl) phosphite ester, zinc stearate and calcium carbonate subjected to surface treatment of a coupling agent to obtain the modified polyethylene/POE composite material; the antibacterial agent consists of mesoporous zirconium phosphate, nano titanium dioxide and chitosan according to the mass ratio of (1-2) (3-4); the nano titanium dioxide is anatase, and the particle size of the nano titanium dioxide is 30-50nm; s1, grafting chitosan, namely mixing and heating chitosan, acetic acid and 1-hydroxymethyl-5, 5-dimethyl hydantoin, reacting for 23-24 hours, cooling, and distilling under reduced pressure to obtain a viscous product; adding the sticky product into an acetone solution, stirring and mixing, removing floccules, and carrying out suction filtration, washing and drying to obtain grafted chitosan;
s2, modifying chitosan, namely dissolving grafted chitosan in acetic acid solution, adjusting the concentration of the grafted chitosan to 3.5-4.0mg/mL, filtering, adjusting the pH value of the solution to be 6 to obtain grafted chitosan solution, dissolving sodium tripolyphosphate in ultrapure water, and dripping the sodium tripolyphosphate into the grafted chitosan solution to obtain the modified chitosan; the nano titanium dioxide is modified nano titanium dioxide, and the modification method of the modified nano titanium dioxide comprises the following steps:
A. and (3) preparing a material: uniformly mixing nano titanium dioxide, a coupling agent and dimethylbenzene, heating for reaction, centrifuging the solution to obtain slurry, washing with absolute ethyl alcohol, centrifuging and drying to obtain a material I;
B. and (3) a material II: mixing and stirring the material I obtained in the step A, tetrahydrofuran and triethylamine, dropwise adding 2-bromoisobutyryl bromide solution, reacting, stopping stirring, reacting for 23-24 hours, washing with absolute ethyl alcohol, centrifuging and drying to obtain a material II;
C. and (3) a material III: mixing the material II obtained in the step B, methacrylic acid-dimethylaminoethyl ester, N, N, N ', N, ' N ' -pentamethyldiethylenetriamine and absolute methanol, cooling with liquid nitrogen, performing vacuum-thawing cycle for 2-3 times, adding CuBr, cooling with liquid nitrogen, performing vacuum-thawing cycle for 2-3 times, reacting, diluting with tetrahydrofuran, centrifuging, purifying, washing and drying to obtain a material III;
D. preparation of modified nano titanium dioxide: and C, uniformly mixing the material III, the bromo-n-hexane and the tetrahydrofuran obtained in the step C, centrifuging, purifying and drying to obtain the material III.
2. The method for producing a high-strength covered wire according to claim 1, wherein: the antibacterial agent and the reinforcing agent are formed by the following components in parts by mass (6-8) and (6-9).
3. The method for producing a high-strength covered wire according to claim 1, wherein: the dispersing agent consists of polyethylene wax and oleamide according to the mass ratio of (1-3) to (2-4).
4. The method for producing a high-strength covered wire according to claim 1, wherein: the antioxidant consists of antioxidant 264 and trisnonylphenyl phosphite according to the mass ratio of (1-2) to (2-3).
5. The method for producing a high-strength covered wire according to claim 1, wherein: the thickness of the coating layer is 7-8 mu m.
6. The method for producing a high-strength covered wire according to claim 1, wherein: the fineness of the polyester filament is 35-40tex, the strength is 970-1000cN, and the elongation is 18-20%.
7. A method of producing the high-strength covered wire according to any one of claims 1 to 6, characterized in that: the preparation method comprises the following steps of (1) preparing color master batch: uniformly mixing the raw materials of each component of the coating layer, and cooling, extruding and granulating to obtain color master batch;
(2) Preparation of coated yarn: putting the core wire into a filament frame, and penetrating into a die through a tension positioning device; adding the color master batch obtained in the step (1) into a hopper, extruding, plasticizing and melting, and then feeding into a die; drawing the polyester filaments to pass through a die head for coating; and cooling the coated yarn after coating, and winding to obtain the coated yarn.
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