CN113802379A - Preparation method of durable and efficient antibacterial nylon 6 fiber and product thereof - Google Patents
Preparation method of durable and efficient antibacterial nylon 6 fiber and product thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a durable high-efficiency antibacterial nylon 6 fiber and a product thereof, wherein a modified monomer is added in a caprolactam polymerization process, the modified monomer is copolymerized into a molecular chain, a polar short chain is introduced into a molecular chain side chain, the modified nylon 6 fiber is obtained in a melt spinning mode, an antibacterial agent is added into an oil agent in the spinning process, the fiber is adsorbed with the antibacterial agent in an oiling stage, and then a heat treatment stage is carried out, so that the antibacterial agent and the polar short chain on the molecular chain form a strong combination form of an ionic bond or a chemical bond, and the durable high-efficiency antibacterial nylon 6 fiber is obtained. The antibacterial nylon 6 fiber has the characteristics of high efficiency, broad spectrum, safety and lasting antibiosis, the antibacterial rate of the antibacterial nylon 6 fiber reaches more than 95%, the antibacterial performance of the antibacterial nylon 6 fiber is not reduced after being washed for more than 50 times, the utilization efficiency of the antibacterial agent is high, the wearing safety of the nylon 6 fiber is obviously improved, and the antibacterial nylon 6 fiber can be widely applied to the fields of household and clothes textiles.
Description
Technical Field
The invention belongs to the technical field of polyamide preparation, and particularly relates to a preparation method of a durable high-efficiency antibacterial nylon 6 fiber and a product thereof.
Background
The nylon 6 fiber is made into the nylon 6 fiber with antibacterial performance by changing the components or molecular structure of the fiber by a physical or chemical modification method. The antibacterial nylon 6 fiber has good inhibition and killing effects on bacteria, fungi and other microorganisms, and can be applied to clothes, especially footwear, underwear and the like which are easy to breed bacteria. Along with the improvement of living standard of people, the nylon 6 fiber and the products thereof are endowed with health care function, and the development of the nylon 6 fiber with high efficiency, broad spectrum, safety and lasting antibiosis becomes an important research direction.
At present, the essence of endowing nylon 6 fiber with antibacterial performance is to introduce an antibacterial agent into the fiber in a mode of in-situ addition or surface coating, however, the in-situ addition of the antibacterial agent is distributed at various positions of the nylon 6 fiber, so that the utilization efficiency of the antibacterial agent is not high, meanwhile, the addition amount of the antibacterial agent cannot be too much, otherwise, spinning forming is affected, and as the nylon 6 fiber is usually processed by melt forming, the added antibacterial agent needs good thermal stability, so the types of the added antibacterial agent are limited, and the added antibacterial agent is usually an inorganic antibacterial agent, so the application of the antibacterial agent is further limited.
The nylon 6 fiber is endowed with antibacterial property by a surface coating method, and the antibacterial agent or the coating is mainly combined with the fiber by physical acting force, so that the defects of poor durability, poor washing resistance and the like exist; in addition, the surface grafting can be realized mainly by the irradiation grafting, but the irradiation resistance of nylon 6 is poor, the irradiation treatment can damage the structure of the nylon 6 fiber, the hand feeling and the mechanical property of the nylon 6 fiber are further influenced, and the long-term application of the nylon 6 fiber is influenced.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made keeping in mind the above and/or other problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a preparation method of a durable and efficient antibacterial nylon 6 fiber.
In order to solve the technical problems, the invention provides the following technical scheme: a method for preparing durable high-efficiency antibacterial nylon 6 fiber comprises,
dissolving a modified monomer and diamine in a solvent to prepare a 40-70 wt% solution, stirring at 55-85 ℃ for 40-110 min, cooling and standing the obtained mixed solution to separate out crystals, filtering, washing and drying the obtained crystals to obtain a modified salt, wherein the modified monomer comprises one or more of butane-1, 1, 4-tricarboxylic acid, butane-1, 1,4, 4-tetracarboxylic acid, hexane-1, 1,6, 6-tetracarboxylic acid, ornithine, 2-hydroxyadipic acid, 2-hydroxysuccinic acid and 2-aminoadipic acid;
uniformly mixing caprolactam, water and an antioxidant to prepare a ring-opening reaction raw material, and carrying out a ring-opening reaction to obtain a nylon 6 prepolymer; wherein the addition amount of water is 0.1-5 wt% relative to the mass of caprolactam;
preparing a 50-60 wt% aqueous solution of a modifier salt, mixing a nylon 6 prepolymer in the aqueous solution at a temperature of 200-230 ℃ and a pressure of 1.7-2.3 MPa, reacting for 1-3 h, then releasing the pressure to normal pressure, raising the temperature to 250-265 ℃ in the pressure release process, then reacting for 0.5-4 h under a pressure of-0.1-0 MPa and a temperature of 250-265 ℃, cooling and granulating the melt to obtain modified nylon 6 slices;
extracting modified nylon 6 slices with hot water, drying, melting by a screw, extruding, cooling, and oiling to obtain modified nylon 6 fibers, wherein the oiling agent is an antibacterial agent-added oil agent;
and carrying out heat treatment on the modified nylon 6 fiber to obtain the antibacterial nylon 6 fiber.
As a preferred scheme of the preparation method of the durable high-efficiency antibacterial nylon 6 fiber, the method comprises the following steps: the modified monomer accounts for 0.1-3 wt% of the total mass of the modified nylon 6 slice.
As a preferred scheme of the preparation method of the durable high-efficiency antibacterial nylon 6 fiber, the method comprises the following steps: the diamine comprises one or more of hexamethylene diamine, pentamethylene diamine and butanediamine.
As a preferred scheme of the preparation method of the durable high-efficiency antibacterial nylon 6 fiber, the method comprises the following steps: dissolving a modified monomer and diamine in a solvent, wherein the solvent is one of water, ethanol, methanol and acetonitrile, and the molar ratio of amino in the diamine to carboxyl in the modified monomer is 1-1.002: 1.
As a preferred scheme of the preparation method of the durable high-efficiency antibacterial nylon 6 fiber, the method comprises the following steps: cooling and standing to separate out crystals, wherein the cooling temperature is 2-15 ℃, and the standing time is 2-5 hours; and (3) releasing the pressure to normal pressure, wherein the pressure release duration is 0.5-2.5 h.
As a preferred scheme of the preparation method of the durable high-efficiency antibacterial nylon 6 fiber, the method comprises the following steps: the antioxidant comprises one or more of 4-amino-2, 2,6, 6-tetramethylpiperidine, bis (2,2,6, 6-tetramethyl-3-piperidinylamino) -isophthalamide, antioxidant 1010 and antioxidant 1098;
the antioxidant accounts for 0.001-0.5% of caprolactam.
As a preferred scheme of the preparation method of the durable high-efficiency antibacterial nylon 6 fiber, the method comprises the following steps: the ring-opening reaction temperature is 230-270 ℃, the pressure is 0-0.6 MPa, and the reaction time is 2-9 h;
the hot water extraction temperature is 100-120 ℃, and the hot water extraction time is 5-10 h.
As a preferred scheme of the preparation method of the durable high-efficiency antibacterial nylon 6 fiber, the method comprises the following steps: the content of the antibacterial agent in the oil solution is 5-15 wt%;
the antibacterial agent comprises one or more of quaternary ammonium salt antibacterial agent, chitosan antibacterial agent and guanidine salt antibacterial agent;
the content of the antibacterial agent in the modified nylon 6 fiber is 0.1-1 wt%.
As a preferred scheme of the preparation method of the durable high-efficiency antibacterial nylon 6 fiber, the method comprises the following steps: the antibacterial nylon 6 fiber comprises FDY, DTY and staple fiber; wherein the content of the first and second substances,
the spinning process of the FDY is 255-285 ℃, the spinning speed is 4500-6000 m/min, the cooling air temperature is 15-30 ℃, the air speed is 0.4-1.0 m/s, the relative humidity is 60-90%, the temperature of a first hot roller is 60-100 ℃, the temperature of a second hot roller is 140-180 ℃, and the multiple is 1.2-2.0 times, so that the FDY fiber is prepared;
spinning the DTY at 253-282 ℃ and elasticizing at 160-190 ℃ in a first hot box, 140-180 ℃ in a second hot box and 1.2-2.0 times in multiple to obtain DTY fibers;
the spinning temperature of the short fiber is 250-275 ℃, the spinning speed is 800-1500 m/min, the cooling air temperature is 15-20 ℃, the air speed is 0.2-0.6 m/s, the relative humidity is 60-80%, the heat treatment process comprises the steps of stretching at the temperature of 60-80 ℃, the pre-stretching ratio is 1.02-1.08, the primary stretching ratio is 2.50-3.50, the secondary stretching ratio is 1.02-1.13, and the heat setting temperature is 156-175 ℃, and then the short fiber is obtained by cutting.
The invention further aims to overcome the defects in the prior art and provide a product prepared by the preparation method of the durable and efficient antibacterial nylon 6 fiber, wherein the breaking strength of the product is 2.5-4.5 cN/dtex, the elongation at break of the product is 20-40%, the antibacterial rate on escherichia coli, staphylococcus aureus and candida albicans reaches more than 95%, and the performance is not reduced after 50 times of water washing.
The invention has the beneficial effects that:
(1) the invention provides a preparation method of a durable high-efficiency antibacterial nylon 6 fiber, which is characterized in that a polar short chain is introduced into a polyamide molecular chain side chain in a copolymerization mode, so that an antibacterial agent can be connected to the surface of the fiber in a strong combination mode of ionic bonds or chemical bonds, the antibacterial property of the fiber is greatly improved, the utilization efficiency of the antibacterial agent is improved, and the fiber is endowed with excellent comprehensive properties.
(2) The antibacterial agent used in the invention is an organic antibacterial agent, has the characteristics of safety and high efficiency, simultaneously optimizes the preparation process of the antibacterial nylon 6 fiber, avoids the defect that the organic antibacterial agent cannot resist high temperature, and simultaneously has simple production process and low cost.
(3) The preparation method of the antibacterial nylon 6 provided by the invention can enable the antibacterial agent to be enriched on the surface of the nylon 6 fiber, effectively improves the utilization efficiency of the antibacterial agent, reduces the usage amount of the antibacterial agent, improves the forming stability of the nylon 6 fiber, and greatly reduces the cost.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The raw materials of caprolactam, antioxidant, antibacterial agent, modified monomer and oil agent in the invention are all industrial grade common commercial products.
Example 1
The embodiment provides a preparation method of a durable high-efficiency antibacterial nylon 6 fiber, which comprises the following steps:
(1) dissolving butane-1, 1, 4-tricarboxylic acid and butanediamine in water to prepare a 50wt% solution, stirring at 70 ℃ for 70min, cooling and standing the obtained mixed solution to separate out crystals (the cooling temperature is 35 ℃, the standing time is 3 hours), filtering, washing and drying the obtained crystals to obtain a modified salt, wherein the molar ratio of amino groups to carboxyl groups is 1.001: 1;
(2) uniformly mixing caprolactam, water and 4-amino-2, 2,6, 6-tetramethylpiperidine to prepare a ring-opening reaction raw material, and carrying out a ring-opening reaction to obtain a nylon 6 prepolymer; wherein the addition amount of water is 0.5wt% relative to the mass of caprolactam; the addition amount of 4-amino-2, 2,6, 6-tetramethylpiperidine is 0.2 percent relative to the mass of caprolactam, the ring-opening reaction temperature is 250 ℃, the pressure is 0.3MPa, and the reaction time is 4 hours;
(3) preparing a 60wt% aqueous solution of a modifier salt, mixing a nylon 6 prepolymer in an environment with the temperature of 220 ℃ and the pressure of 2.0MPa, reacting for 1.5h, then releasing the pressure to normal pressure, wherein the pressure release duration is 1.0h, the temperature is raised to 255 ℃ in the pressure release process, then reacting for 3h under the conditions that the pressure is-0.09 MPa and the temperature is 255 ℃, cooling and granulating the melt to obtain modified nylon 6 slices, wherein a modified monomer in the modified nylon 6 slices accounts for 1.1% of the total mass of the modified nylon 6 slices;
(4) extracting modified nylon 6 slices with hot water (the hot water extraction temperature is 110 ℃, the hot water extraction time is 6 hours), drying, melting by a screw, extruding, cooling, and oiling to obtain modified nylon 6FDY fibers, wherein in the oil preparation process, a quaternary ammonium salt antibacterial agent is added into an oil solution (Kekai S6352C 3), the content of the antibacterial agent in the oil solution is 11.5wt%, the antibacterial agent is added into the oil solution in a blending manner, and the content of the quaternary ammonium salt antibacterial agent in the modified nylon 6 fibers is 0.81%;
the spinning process of the FDY is 259 ℃, the spinning speed is 5500m/min, the cooling air temperature is 18 ℃, the air speed is 0.7m/s, the relative humidity is 80%, the temperature of the first hot roll is 70 ℃, the temperature of the second hot roll is 170 ℃, and the multiple is 1.6 times;
the breaking strength of the product is 4.6cN/dtex, and the elongation at break is 40%.
Example 2
The embodiment provides a preparation method of a durable high-efficiency antibacterial nylon 6 fiber, which comprises the following steps:
(1) dissolving butane-1, 1,4, 4-tetracarboxylic acid and butanediamine in alcohol to prepare 65wt% solution, stirring at 60 deg.C for 100min, cooling the obtained mixed solution, standing for precipitating crystal (cooling temperature is 5 deg.C, standing time is 3 hr), filtering, washing the obtained crystal, and drying to obtain modified salt with molar ratio of amine group to carboxyl group of 1.0005: 1;
(2) uniformly mixing caprolactam, water and bis (2,2,6, 6-tetramethyl-3-piperidylamino) -isophthalamide to prepare a ring-opening reaction raw material, and carrying out a ring-opening reaction to obtain a nylon 6 prepolymer; wherein the addition amount of water is 2wt% relative to the mass of caprolactam; the addition amount of bis (2,2,6, 6-tetramethyl-3-piperidylamino) -isophthalamide is 0.4 percent relative to the mass of caprolactam, the ring-opening reaction temperature is 260 ℃, the pressure is 0.5MPa, and the reaction time is 2 hours;
(3) preparing a 60wt% aqueous solution of a modifier salt, mixing a nylon 6 prepolymer in an environment with the temperature of 200 ℃ and the pressure of 1.7MPa, reacting for 3 hours, then releasing the pressure to normal pressure, releasing the pressure for 2.5 hours, raising the temperature to 265 ℃ in the pressure releasing process, then reacting for 3.5 hours under the conditions of the pressure of-0.1 MPa and the temperature of 260 ℃, cooling and granulating a melt to obtain modified nylon 6 slices, wherein a modified monomer in the modified nylon 6 slices accounts for 1.5% of the total mass of the modified nylon 6 slices;
(4) extracting modified nylon 6 slices with hot water (the hot water extraction temperature is 120 ℃, the hot water extraction time is 7 hours), drying, melting by a screw, extruding, cooling, and oiling to obtain modified nylon 6 POY fibers, wherein the spinning temperature is 266 ℃, carboxymethyl chitosan (molecular weight 543) is added into an oiling agent solution (bamboo F-5178) in the oiling agent preparation process, the content of an antibacterial agent in the oiling agent solution is 7 wt%, the antibacterial agent is added into the oiling agent solution in a blending mode, and the content of the carboxymethyl chitosan in the modified nylon 6 POY fibers is 0.84%;
the POY fiber is subjected to elasticizing and heat setting to obtain nylon 6 DTY fiber, wherein the elasticizing and heat setting process comprises the steps that the temperature of a first hot box is 170 ℃, the temperature of a second hot box is 160 ℃, and the multiple is 1.5 times;
the breaking strength of the product is 4.3cN/dtex, and the elongation at break is 32%.
Example 3
The embodiment provides a preparation method of a durable high-efficiency antibacterial nylon 6 fiber, which comprises the following steps:
(1) dissolving 2-hydroxysuccinic acid and butanediamine in methanol to prepare a 70wt% solution, stirring at 55 ℃ for 100min, cooling and standing the obtained mixed solution to separate out crystals (the cooling temperature is 4 ℃ and the standing time is 5 hours), filtering, washing and drying the obtained crystals to obtain a modified salt, wherein the molar ratio of amino groups to carboxyl groups is 1.002: 1;
(2) uniformly mixing caprolactam, water and an antioxidant 1010 to prepare a ring-opening reaction raw material, and carrying out a ring-opening reaction to obtain a nylon 6 prepolymer; wherein the addition amount of water is 1wt% relative to the mass of caprolactam; the addition amount of the antioxidant 1010 is 0.3 percent relative to the mass of caprolactam, the ring-opening reaction temperature is 245 ℃, the pressure is 0.38MPa, and the reaction time is 4.5 h;
(3) preparing a 50wt% aqueous solution of a modifier salt, mixing a nylon 6 prepolymer in an environment with the temperature of 210 ℃ and the pressure of 1.85MPa, reacting for 2 hours, then releasing the pressure to normal pressure, releasing the pressure for 1.5 hours, raising the temperature to 263 ℃ in the pressure release process, then reacting for 1 hour under the conditions of the pressure of-0.08 MPa and the temperature of 261 ℃, cooling and granulating the melt to obtain modified nylon 6 slices, wherein the modified monomer in the modified nylon 6 slices accounts for 1.8% of the total mass of the modified nylon 6 slices;
(4) extracting modified nylon 6 slices with hot water (the hot water extraction temperature is 100 ℃, the hot water extraction time is 6 hours), drying, melting by a screw, extruding, cooling, oiling, drafting, heat setting, cutting and the like to obtain modified nylon 6 short fibers, wherein in the oil preparation process, amino chitosan (molecular weight 483) is added into an oil solution (bamboo F-582), the content of an antibacterial agent in the oil solution is 6wt%, the antibacterial agent is added into the oil solution in a blending mode, and the content of the amino chitosan in the modified nylon 6 short fibers is 0.75%;
the spinning temperature of the short fiber is 270 ℃, the spinning speed is 1300m/min, the cooling air temperature is 18 ℃, the air speed is 0.4m/s, and the relative humidity is 80%, the heat treatment process comprises the steps of stretching at 70 ℃, pre-stretching multiplying power is 1.03, primary stretching multiplying power is 3.10, secondary stretching multiplying power is 1.03, and heat setting temperature is 166 ℃, and then the short fiber is cut to obtain the antibacterial PA6 short fiber;
the product has a breaking strength of 5.1cN/dtex and an elongation at break of 31%.
Example 4
The embodiment provides a preparation method of a durable high-efficiency antibacterial nylon 6 fiber, which comprises the following steps:
(1) dissolving 2-aminoadipic acid and pentanediamine in water to prepare a 45wt% solution, stirring at 56 ℃ for 90min, cooling and standing the obtained mixed solution to separate out crystals (the cooling temperature is 2 ℃ and the standing time is 3 hours), filtering, washing and drying the obtained crystals to obtain a modified salt, wherein the molar ratio of amino groups to carboxyl groups is 1.002: 1;
(2) uniformly mixing caprolactam, water and an antioxidant 1098 to prepare a ring-opening reaction raw material, and carrying out a ring-opening reaction to obtain a nylon 6 prepolymer; wherein the addition amount of water is 2.5wt% relative to the mass of caprolactam; the addition amount of the antioxidant 1098 is 0.2 percent relative to the mass of caprolactam, the ring-opening reaction temperature is 365 ℃, the pressure is 0.3MPa, and the reaction time is 4 hours;
(3) preparing a 50wt% aqueous solution of a modifier salt, mixing a nylon 6 prepolymer in an environment with the temperature of 225 ℃ and the pressure of 2.2MPa, reacting for 1h, then releasing the pressure to normal pressure, releasing the pressure for 1.3h, raising the temperature to 265 ℃ in the pressure releasing process, then reacting for 1h under the conditions of the pressure of-0.1 MPa and the temperature of 265 ℃, cooling and granulating a melt to obtain modified nylon 6 slices, wherein a modified monomer in the modified nylon 6 slices accounts for 1.3% of the total mass of the modified nylon 6 slices;
(4) extracting modified nylon 6 slices with hot water (the hot water extraction temperature is 110 ℃, the hot water extraction time is 8 hours), drying, melting by a screw, extruding, cooling, and oiling to obtain modified nylon 6FDY fibers, wherein in the oil preparation process, a guanidinium antibacterial agent is added into an oil solution (Kekai S6352C 3), the content of the antibacterial agent in the oil solution is 13.5wt%, the antibacterial agent is added into the oil solution in a blending manner, and the content of the guanidinium antibacterial agent in the modified nylon 6FDY fibers is 0.83%;
the spinning process of the FDY is 275 ℃, the spinning speed is 5800 m/min, the cooling air temperature is 15 ℃, the air speed is 0.8m/s, the relative humidity is 90%, the temperature of the first hot roll is 90 ℃, the temperature of the second hot roll is 170 ℃, and the multiple is 1.3 times, so that the modified PA 6FDY fiber is prepared;
the breaking strength of the product is 4.8cN/dtex, and the elongation at break is 35%.
Comparative example 1
(1) Uniformly mixing caprolactam, water and 4-amino-2, 2,6, 6-tetramethylpiperidine to prepare a ring-opening reaction raw material, and carrying out a ring-opening reaction to obtain a nylon 6 prepolymer; wherein the addition amount of water is 0.5wt% relative to the mass of caprolactam; the addition amount of 4-amino-2, 2,6, 6-tetramethylpiperidine is 0.2 percent relative to the mass of caprolactam, the ring-opening reaction temperature is 250 ℃, the pressure is 0.3MPa, and the reaction time is 4 hours; then reacting for 3h under the conditions that the pressure is-0.09 MPa and the temperature is 255 ℃, and cooling and granulating the melt to obtain nylon 6 slices;
(2) extracting nylon 6 slices with hot water (the hot water extraction temperature is 110 ℃, the hot water extraction time is 6 hours), drying, melting by a screw, extruding, cooling, and oiling to obtain modified nylon 6FDY fiber, wherein in the oil preparation process, a quaternary ammonium salt antibacterial agent is added into an oil solution (Kekai S6352C 3), the content of the antibacterial agent in the oil solution is 11.5wt%, and the content of the quaternary ammonium salt antibacterial agent in the modified nylon 6 fiber is 0.81%;
the spinning process of the FDY is 259 ℃, the spinning speed is 5500m/min, the cooling air temperature is 18 ℃, the air speed is 0.7m/s, the relative humidity is 80%, the temperature of the first hot roll is 70 ℃, the temperature of the second hot roll is 170 ℃, and the multiple is 1.6 times;
the breaking strength of the product is 4.7cN/dtex, and the elongation at break is 39%.
Comparative example 2
The antibacterial agent is coated on the surface of the nylon 6 fabric in a surface finishing mode, and the finishing process flow is as follows:
cloth spreading and sewing head → singeing → desizing → mercerizing → (liquid ammonia → pH water washing) → soaking antibacterial and deodorant → no-ironing → baking → water washing → tentering → preshrinking;
the antibacterial fabric obtained had an antibacterial agent (guanidine salt type antibacterial agent) content of 0.83 wt%.
Comparative example 3
(1) Uniformly mixing nylon 6 and a quaternary ammonium salt antibacterial agent, conveying the mixture to a spinning assembly, and melting, extruding, cooling and oiling the mixture by a screw to obtain modified nylon 6FDY antibacterial fiber, wherein the content of the quaternary ammonium salt antibacterial agent in the modified nylon 6 fiber is 2.1%;
(2) the spinning process of the FDY is 259 ℃, the spinning speed is 5500m/min, the cooling air temperature is 18 ℃, the air speed is 0.7m/s, the relative humidity is 80%, the temperature of the first hot roll is 70 ℃, the temperature of the second hot roll is 170 ℃, and the multiple is 1.6 times.
In the invention, the antibacterial effect of the sample is detected according to the standard FZ/T730232006.
Data for examples and comparative examples are shown in table 1.
TABLE 1
According to the invention, the modified monomer is added in the nylon 6 polymerization process, so that the side chain of a molecular chain contains a strong polar functional group, the modified nylon 6 fiber is obtained through melt spinning, the antibacterial agent is adsorbed on the surface of the fiber in the oiling stage of the fiber, and the functional group on the antibacterial agent and the functional group on the surface of the fiber are interacted in the heat treatment stage, so that the antibacterial agent is grafted to the surface of the fiber in a strong combination mode of ionic bond or chemical bond combination, and the antibacterial component is enriched on the surface of the nylon 6 fiber as much as possible, thereby reducing the use of the functional component, and simultaneously not reducing the functional effect, namely improving the utilization efficiency of the antibacterial agent, so that the fiber has the characteristics of high efficiency, broad spectrum, safety and lasting antibacterial.
The monomer selected by the invention is used for enabling part of functional groups not to react and thus to be exposed on a molecular chain, so that the monomer with higher symmetry (containing a single functional group) is selected, after a certain functional group on one side reacts, the reactivity of the adjacent functional groups is reduced due to a reaction barrier, the molecular chain is more prone to form direct connection, the monomer containing two crown functional group modified monomers with different activities is selected, the purpose of selection is to enable the crown functional group with high activity to react, and the crown functional group with low activity is left, thereby providing beneficial help for coating the antibacterial agent. For the reaction monomers, the 2-aminoadipic acid modified monomer containing two crown energy groups with different activities has better effect. If a polyfunctional group-modified monomer having high symmetry is selected, a high polymer having a high degree of crosslinking is formed, which affects fiber formation.
In order to achieve the preset effect, the modified monomer is firstly salified and then added into a polymerization system, so that the problem of low molecular weight caused by adding a polyfunctional monomer into the reaction is solved.
The invention seeks for lasting and high-efficiency antibacterial efficiency, and the antibacterial agent is required to be on the surface of the fiber and has higher binding force, and in the binding force, ionic bonds and covalent bonds are two binding forces with the highest binding force, so that the antibacterial agent can be loaded on the surface of the fiber by the two binding forces, but because the polarity of polyamide molecular chains is low and sites cannot be provided, a polar short-chain branch is introduced to improve the polarity of the molecular chains in a polymerization modification mode, so that the efficient and lasting antibacterial modification is realized, similarly, the antibacterial agent is fixed on the surface of the fiber or fabric by means of polyurethane or siloxane coating only in a coating mode, but the antibacterial agent depends on intermolecular action, the acting force is weaker, and the lasting effect is not obvious.
In order to solve the problems of durability and antibacterial efficiency of the antibacterial fiber, the invention introduces polar short chains into the side chains of polyamide molecular chains in a copolymerization mode, so that the antibacterial agent can be connected to the surface of the fiber in a strong combination mode of ionic bonds or chemical bonds, the antibacterial property of the fiber is greatly improved, the utilization efficiency of the antibacterial agent is improved, and the fiber is endowed with excellent comprehensive performance. Compared with the surface coating mode, the method improves the durability of the antibacterial performance of the fiber, reduces the use of the finishing agent, and avoids the damage of irradiation grafting on the structure and the performance of the nylon 6 fiber compared with the irradiation grafting mode.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A preparation method of durable and efficient antibacterial nylon 6 fibers is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
dissolving a modified monomer and diamine in a solvent to prepare a 40-70 wt% solution, stirring at 55-85 ℃ for 40-110 min, cooling and standing the obtained mixed solution to separate out crystals, filtering, washing and drying the obtained crystals to obtain a modified salt, wherein the modified monomer comprises one or more of butane-1, 1, 4-tricarboxylic acid, butane-1, 1,4, 4-tetracarboxylic acid, hexane-1, 1,6, 6-tetracarboxylic acid, ornithine, 2-hydroxyadipic acid, 2-hydroxysuccinic acid and 2-aminoadipic acid;
uniformly mixing caprolactam, water and an antioxidant to prepare a ring-opening reaction raw material, and carrying out a ring-opening reaction to obtain a nylon 6 prepolymer; wherein the addition amount of water is 0.1-5 wt% relative to the mass of caprolactam;
preparing a 50-60 wt% aqueous solution of a modifier salt, mixing a nylon 6 prepolymer in the aqueous solution at a temperature of 200-230 ℃ and a pressure of 1.7-2.3 MPa, reacting for 1-3 h, then releasing the pressure to normal pressure, raising the temperature to 250-265 ℃ in the pressure release process, then reacting for 0.5-4 h under a pressure of-0.1-0 MPa and a temperature of 250-265 ℃, cooling and granulating the melt to obtain modified nylon 6 slices;
extracting modified nylon 6 slices with hot water, drying, melting by a screw, extruding, cooling, and oiling to obtain modified nylon 6 fibers, wherein the oiling agent is an antibacterial agent-added oil agent;
and carrying out heat treatment on the modified nylon 6 fiber to obtain the antibacterial nylon 6 fiber.
2. The method for preparing the durable high-efficiency antibacterial nylon 6 fiber according to claim 1, which is characterized by comprising the following steps: the modified monomer accounts for 0.1-3 wt% of the total mass of the modified nylon 6 slice.
3. The method for preparing the durable high-efficiency antibacterial nylon 6 fiber according to claim 1, which is characterized by comprising the following steps: the diamine comprises one or more of hexamethylene diamine, pentamethylene diamine and butanediamine.
4. A method for preparing the durable high-efficiency antibacterial nylon 6 fiber as claimed in claim 1 or 3, which is characterized in that: dissolving a modified monomer and diamine in a solvent, wherein the solvent is one of water, ethanol, methanol and acetonitrile, and the molar ratio of amino in the diamine to carboxyl in the modified monomer is 1-1.002: 1.
5. The method for preparing the durable highly effective antibacterial nylon 6 fiber according to claim 1 or 2, characterized in that: cooling and standing to separate out crystals, wherein the cooling temperature is 2-15 ℃, and the standing time is 2-5 hours; and (3) releasing the pressure to normal pressure, wherein the pressure release duration is 0.5-2.5 h.
6. The method for preparing the durable highly effective antibacterial nylon 6 fiber according to claim 1 or 2, characterized in that: the antioxidant comprises one or more of 4-amino-2, 2,6, 6-tetramethylpiperidine, bis (2,2,6, 6-tetramethyl-3-piperidinylamino) -isophthalamide, antioxidant 1010 and antioxidant 1098;
the antioxidant accounts for 0.001-0.5% of caprolactam.
7. The method for preparing the durable high-efficiency antibacterial nylon 6 fiber according to claim 1, which is characterized by comprising the following steps: the ring-opening reaction temperature is 230-270 ℃, the pressure is 0-0.6 MPa, and the reaction time is 2-9 h;
the hot water extraction temperature is 100-120 ℃, and the hot water extraction time is 5-10 h.
8. The method for preparing the durable high-efficiency antibacterial nylon 6 fiber according to claim 1, which is characterized by comprising the following steps:
the content of the antibacterial agent in the oil solution is 5-15 wt%;
the antibacterial agent comprises one or more of quaternary ammonium salt antibacterial agent, chitosan antibacterial agent and guanidine salt antibacterial agent;
the content of the antibacterial agent in the modified nylon 6 fiber is 0.1-1 wt%.
9. The method for preparing the durable high-efficiency antibacterial nylon 6 fiber according to claim 1, which is characterized by comprising the following steps: the antibacterial nylon 6 fiber comprises FDY, DTY and staple fiber; wherein the content of the first and second substances,
the spinning process of the FDY is 255-285 ℃, the spinning speed is 4500-6000 m/min, the cooling air temperature is 15-30 ℃, the air speed is 0.4-1.0 m/s, the relative humidity is 60-90%, the temperature of a first hot roller is 60-100 ℃, the temperature of a second hot roller is 140-180 ℃, and the multiple is 1.2-2.0 times, so that the FDY fiber is prepared;
spinning the DTY at 253-282 ℃ and elasticizing at 160-190 ℃ in a first hot box, 140-180 ℃ in a second hot box and 1.2-2.0 times in multiple to obtain DTY fibers;
the spinning temperature of the short fiber is 250-275 ℃, the spinning speed is 800-1500 m/min, the cooling air temperature is 15-20 ℃, the air speed is 0.2-0.6 m/s, the relative humidity is 60-80%, the heat treatment process comprises the steps of stretching at the temperature of 60-80 ℃, the pre-stretching ratio is 1.02-1.08, the primary stretching ratio is 2.50-3.50, the secondary stretching ratio is 1.02-1.13, and the heat setting temperature is 156-175 ℃, and then the short fiber is obtained by cutting.
10. The product prepared by the preparation method of the lasting high-efficiency antibacterial nylon 6 fiber in any one of claims 1 to 9 is characterized in that: the product has the breaking strength of 2.5-4.5 cN/dtex, the elongation at break of 20-40%, the bacteriostasis rate to escherichia coli, staphylococcus aureus and candida albicans of more than 95%, and the performance is not reduced after washing for 50 times.
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