CN113201939A - Bacteriostatic agent and application thereof, ultrahigh molecular weight polyethylene bacteriostatic fiber and preparation method thereof - Google Patents

Bacteriostatic agent and application thereof, ultrahigh molecular weight polyethylene bacteriostatic fiber and preparation method thereof Download PDF

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CN113201939A
CN113201939A CN202110504142.1A CN202110504142A CN113201939A CN 113201939 A CN113201939 A CN 113201939A CN 202110504142 A CN202110504142 A CN 202110504142A CN 113201939 A CN113201939 A CN 113201939A
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bacteriostatic
molecular weight
water
fiber
weight polyethylene
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吕汪洋
王刚强
包建娜
陈淑君
单兴刚
王鑫宇
俞凌晓
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Zhejiang University of Technology ZJUT
Zhejiang Sci Tech University ZSTU
Zhejiang University of Science and Technology ZUST
Shangyu Industrial Technology Research Institute of ZSTU
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Zhejiang University of Technology ZJUT
Shangyu Industrial Technology Research Institute of ZSTU
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Abstract

The invention provides a bacteriostatic agent and application thereof, and ultrahigh molecular weight polyethylene bacteriostatic fiber and a preparation method thereof, and belongs to the technical field of bacteriostatic ultrahigh molecular weight polyethylene. The bacteriostatic agent provided by the invention comprises a first impregnation solution and a second impregnation solution which are separately packaged; the first impregnation solution comprises Tris (hydroxymethyl) aminomethane (Tris), an inorganic acid, dopamine hydrochloride, polyethyleneimine and water; the second impregnation solution includes a water-soluble transition metal salt and water. The bacteriostatic agent provided by the invention has a good bacteriostatic effect, is firmly combined with the ultrahigh molecular weight polyethylene fibers, does not have the problem of rapid loss of the bacteriostatic agent, does not basically influence the mechanical properties of the ultrahigh molecular weight polyethylene fibers, and can also improve the hydrophilicity of the ultrahigh molecular weight polyethylene fibers.

Description

Bacteriostatic agent and application thereof, ultrahigh molecular weight polyethylene bacteriostatic fiber and preparation method thereof
Technical Field
The invention relates to the technical field of bacteriostatic ultrahigh molecular weight polyethylene, and particularly relates to a bacteriostatic agent and application thereof, and ultrahigh molecular weight polyethylene bacteriostatic fibers and a preparation method thereof.
Background
The ultra-high molecular weight polyethylene (UHMWPE) fiber has unique comprehensive performance and is one of three high-performance fibers in the world. The UHMWPE fiber prepared by the gel spinning method has the advantages of high specific energy absorption, low dielectric constant, low friction coefficient, excellent bending property, impact resistance, cutting resistance, ultraviolet resistance, chemical corrosion resistance and the like, and is widely applied to the fields of military and national defense, aerospace, protective equipment and the like. In recent years, with the increasing application requirements of UHMWPE fibers in the fields of civil fabrics, medical devices and the like, the enrichment of the antibacterial activity of the UHMWPE fibers is important.
However, it is difficult to effectively bind the above inorganic and organic bacteriostats because UHMWPE fibers have low surface energy and surface tension, high crystallinity, and an extremely smooth surface. UHMWPE fiber is combined with bacteriostatic agent after surface modification by methods such as chemical reagent oxidation, plasma surface treatment, corona discharge surface treatment and the like, although the method can increase the binding force between the fiber and the bacteriostatic agent, the mechanical property of the fiber can be influenced; moreover, the production of UHMWPE fiber needs to go through the processes of high-temperature dissolution, spinning, high-temperature hot drawing and the like, many bacteriostats are easy to generate chemical reaction at high temperature to cause failure, and meanwhile, the subsequent drawing process can also cause the micromolecule bacteriostats to migrate to the surface of the fiber and be rapidly lost.
For example, chinese patent CN109868518A discloses a bacteriostatic UHMWPE fiber, which adopts an inorganic bacteriostatic agent of anatase type nano TiO2And/or nano ZnO; although the bacteriostatic effect of the bacteriostatic agent is good, the mechanical property of the UHMWPE fiber material can be obviously weakened by adding the bacteriostatic agent. Chinese patent CN109440211A discloses an antibacterial mother liquor for producing bacteriostatic UHMWPE fibers, which comprises the following components 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 one or more than two of a polyvinyl quaternary ammonium salt antibacterial polymer, a polyvinyl quaternary phosphonium salt antibacterial polymer, a polyvinyl guanidinium salt antibacterial polymer and a polyvinyl pyridinium salt antibacterial polymer; although the bacteriostatic agent has excellent and long-lasting antibacterial effect, the bacteriostatic agent can adversely affect the mechanical properties of the UHMWPE fibers. Chinese patent CN107151403A discloses an antibacterial water supply pipeline, wherein the adopted inorganic antibacterial agent is a nano silver ion antibacterial agent; however, the bacteriostatic rate of the bacteriostatic agent is not ideal, and nano silver ions are easy to lose from the material, so that the bacteriostatic rate of the material is further reduced.
Disclosure of Invention
In view of the above, the present invention aims to provide a bacteriostatic agent and an application thereof, an ultrahigh molecular weight polyethylene bacteriostatic fiber and a preparation method thereof, and the bacteriostatic agent provided by the present invention has a good bacteriostatic effect, is not easy to run off in the process of preparing the bacteriostatic ultrahigh molecular weight polyethylene fiber, and basically does not affect the mechanical properties of the bacteriostatic ultra-high molecular weight polyethylene fiber.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a bacteriostatic agent, which comprises a first impregnation solution and a second impregnation solution which are separately packaged;
the first dipping solution comprises trihydroxymethyl aminomethane, inorganic acid, dopamine hydrochloride, polyethyleneimine and water;
the second impregnation solution includes a water-soluble transition metal salt and water.
Preferably, the concentration of the tris (hydroxymethyl) aminomethane in the first dipping solution is 1-10 g/L;
the concentration of the dopamine hydrochloride is 1-4 g/L;
the concentration of the polyethyleneimine is 2-8 g/L.
Preferably, the pH value of the dipping solution is 8-10.
Preferably, the water-soluble transition metal salt comprises one or more of water-soluble copper salt, water-soluble silver salt and water-soluble zinc salt.
Preferably, the concentration of the water-soluble transition metal salt in the second dipping solution is 10-100 mmol/L.
The invention provides application of the bacteriostatic agent in the technical scheme in preparation of ultra-high molecular weight polyethylene bacteriostatic fibers.
The invention provides a preparation method of an ultrahigh molecular weight polyethylene antibacterial fiber, which comprises the following steps:
carrying out first treatment on the ultrahigh molecular weight polyethylene fibers by using a first dipping solution in a bacteriostatic agent to obtain pre-bacteriostatic fibers;
and carrying out second treatment on the pre-bacteriostatic fibers by adopting a second impregnation liquid in the bacteriostatic agent to obtain the ultrahigh molecular weight polyethylene bacteriostatic fibers.
Preferably, the first treatment mode is soaking or coating; the temperature of the first treatment is room temperature, and the time is 0.5-24 h.
Preferably, the second treatment mode is soaking or coating; the temperature of the second treatment is room temperature, and the time is 0.1-6 h.
The invention provides the ultrahigh molecular weight polyethylene antibacterial fiber obtained by the preparation method in the technical scheme.
The invention provides a bacteriostatic agent, which comprises a first impregnation solution and a second impregnation solution which are separately packaged; the first impregnation solution comprises Tris (hydroxymethyl) aminomethane (Tris), an inorganic acid, dopamine hydrochloride, polyethyleneimine and water; the second impregnation solution includes a water-soluble transition metal salt and water. The bacteriostatic agent provided by the invention has good bacteriostatic effect, is firmly combined with the ultrahigh molecular weight polyethylene fiber through coordination bonds, and cannot be easily released, so that the problem that the bacteriostatic agent can be quickly lost does not exist, the mechanical property of the ultrahigh molecular weight polyethylene fiber cannot be basically influenced, and the hydrophilicity of the ultrahigh molecular weight polyethylene fiber can be improved. As shown in the results of the examples, the antibacterial rate of the prepared antibacterial fiber on escherichia coli is 98.2-99.9%, the antibacterial rate on staphylococcus aureus is 98.7-99.9%, and the antibacterial effect is excellent; the breaking strength of the UHMWPE fiber is 40.8cN/dtex, the initial Young's modulus is 1688cN/dtex, the breaking strength of the UHMWPE bacteriostatic fiber prepared by the invention is 39.6-40.2 cN/dtex, the initial Young's modulus is 1602-1726 cN/dtex, the breaking strength is reduced by 1.5-3.9% relative to the UHMWPE fiber, and the change amount of the initial Young's modulus relative to the UHMWPE fiber is-5.1-2.2%.
The invention provides application of the bacteriostatic agent in the technical scheme in preparation of ultra-high molecular weight polyethylene bacteriostatic fibers.
The invention provides a preparation method of an ultrahigh molecular weight polyethylene antibacterial fiber, which comprises the following steps: carrying out first treatment on the ultrahigh molecular weight polyethylene fibers by using a first dipping solution in a bacteriostatic agent to obtain pre-bacteriostatic fibers; and carrying out second treatment on the pre-bacteriostatic fibers by adopting a second impregnation liquid in the bacteriostatic agent to obtain the ultrahigh molecular weight polyethylene bacteriostatic fibers. According to the preparation method provided by the invention, the prepared ultrahigh molecular weight polyethylene antibacterial fiber has excellent antibacterial effect, mechanical property and hydrophilicity; moreover, the preparation method provided by the invention is mild in condition, simple to operate and suitable for industrial production.
The invention also provides the ultrahigh molecular weight polyethylene antibacterial fiber obtained by the preparation method in the technical scheme, and the ultrahigh molecular weight polyethylene antibacterial fiber provided by the invention has excellent antibacterial effect, mechanical property and hydrophilicity.
Drawings
Fig. 1 is an antibacterial circle test chart of the UHMWPE bacteriostatic fiber prepared in example 1 and the UHMWPE fiber of comparative example 1, wherein a is comparative example 1 and b is example 1;
fig. 2 is a graph of the results of hydrophilicity tests on the UHMWPE bacteriostatic fibers prepared in example 1 and the UHMWPE fibers of comparative example 1, where a is comparative example 1 and b is example 1.
Detailed Description
The invention provides a bacteriostatic agent, which comprises a first impregnation solution and a second impregnation solution which are separately packaged;
the first dipping solution comprises trihydroxymethyl aminomethane, inorganic acid, dopamine hydrochloride, polyethyleneimine and water;
the second impregnation solution includes a water-soluble transition metal salt and water.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
In the present invention, the first dipping solution includes tris (hydroxymethyl) aminomethane, an inorganic acid, dopamine hydrochloride, polyethyleneimine, and water. In the invention, the concentration of the tris (hydroxymethyl) aminomethane in the first dipping solution is preferably 1-10 g/L, more preferably 2-8 g/L, and most preferably 5-6 g/L; the concentration of the dopamine hydrochloride is preferably 1-4 g/L, more preferably 1.5-3.5 g/L, and most preferably 2-3 g/L; the concentration of the polyethyleneimine is preferably 2-8 g/L, more preferably 3-7 g/L, and most preferably 5-6 g/L. In the invention, the mass ratio of the polyethyleneimine to the dopamine hydrochloride is preferably (1-3): 1, more preferably (1.5 to 2.5): 1, most preferably 2: 1. In the present invention, the water is preferably deionized water. In the invention, the inorganic acid is preferably a hydrochloric acid solution or a sulfuric acid solution, and the concentration of the hydrochloric acid solution or the sulfuric acid solution is independently preferably 1-2 mol/L, and more preferably 1.5 mol/L; the amount of the inorganic acid used is not particularly limited, and the first impregnation solution may have a pH of 8 to 10, and the pH is more preferably 8 to 9, and even more preferably 8.5. The number average molecular weight of the polyethyleneimine is not particularly limited in the present invention, and the molecular weight known to those skilled in the art may be used; in the embodiment of the present invention, the number average molecular weight of the polyethyleneimine is preferably 600.
In the present invention, the second impregnation solution includes a water-soluble transition metal salt and water. In the present invention, the water-soluble transition metal salt preferably includes one or more of a water-soluble copper salt, a water-soluble silver salt and a water-soluble zinc salt; the water-soluble copper salt preferably comprises one or more of copper sulfate, copper chloride and copper nitrate; the water soluble silver salt preferably comprises silver nitrate; the water-soluble zinc salt preferably comprises one or more of zinc acetate, zinc nitrate and zinc sulfate. In the present invention, the water is preferably deionized water. In the present invention, the concentration of the water-soluble transition metal salt in the second dipping solution is preferably 10 to 100mmol/L, more preferably 20 to 90mmol/L, and most preferably 20mmol, 30mmol, 40mmol, 50mmol, 60mmol, 70mmol, 80mmol or 90 mmol.
In the present invention, the preparation method of the bacteriostatic agent preferably comprises the following steps:
(1) mixing trihydroxymethyl aminomethane, inorganic acid, dopamine hydrochloride, polyethyleneimine and water to obtain a first impregnation solution;
(2) dissolving a water-soluble transition metal salt in water to obtain a second impregnation solution;
(3) independently subpackaging the first impregnation solution and the second impregnation solution to obtain the bacteriostatic agent;
the step (1) and the step (2) have no time sequence.
The method comprises the steps of mixing trihydroxymethyl aminomethane, inorganic acid, dopamine hydrochloride and polyethyleneimine to obtain a first impregnation solution. In the present invention, the mixing order is preferably to first mix Tris and water to obtain a Tris solution; adding inorganic acid into the Tris solution for second mixing to obtain an alkaline Tris solution; and adding dopamine hydrochloride and polyethyleneimine into the alkaline Tris solution for third mixing to obtain a first impregnation solution. In the present invention, the first mixing, the second mixing, and the third mixing are preferably agitation mixing; the temperature of the stirring and mixing is preferably room temperature; the stirring and mixing speed is not particularly limited in the invention, and the stirring speed known to those skilled in the art can be adopted; the time for the first mixing is not particularly limited, and tris (hydroxymethyl) aminomethane can be dissolved in water; the time for the second mixing is not particularly limited, and the raw materials can be uniformly mixed; in the present invention, the time for the third mixing is not particularly limited, and dopamine hydrochloride and polyethyleneimine may be dissolved in an alkaline Tris solution.
According to the invention, a water-soluble transition metal salt is dissolved in water to obtain a second impregnation solution. In the present invention, the temperature of the dissolution is preferably room temperature.
The first dipping solution and the second dipping solution are independently packaged to obtain the bacteriostatic agent. The independent dispensing manner is not particularly limited in the present invention, and a dispensing manner known to those skilled in the art may be adopted.
The invention provides application of the bacteriostatic agent in the technical scheme in preparation of ultra-high molecular weight polyethylene bacteriostatic fibers. The bacteriostatic agent provided by the invention cannot lose efficacy due to easy chemical reaction at high temperature, cannot migrate to the surface of the fiber and quickly run off, and basically cannot influence the mechanical property of the ultrahigh molecular weight polyethylene fiber.
The invention provides a preparation method of an ultrahigh molecular weight polyethylene antibacterial fiber, which comprises the following steps:
carrying out first treatment on the ultrahigh molecular weight polyethylene fibers by using a first dipping solution in a bacteriostatic agent to obtain pre-bacteriostatic fibers;
and carrying out second treatment on the pre-bacteriostatic fibers by adopting a second impregnation liquid in the bacteriostatic agent to obtain the ultrahigh molecular weight polyethylene bacteriostatic fibers.
The invention adopts a first dipping solution in a bacteriostatic agent to carry out first treatment on the ultra-high molecular weight polyethylene fiber to obtain the pre-bacteriostatic fiber.
In the present invention, the weight average molecular weight of the ultra-high molecular weight polyethylene fiber is preferably 300 to 600 ten thousand, and more preferably 400 to 500 ten thousand. In the invention, the ultra-high molecular weight polyethylene bacteriostatic fiber is preferably placed in an alcohol solvent for ultrasonic treatment and then dried before use; the alcohol solvent is preferably ethanol, the using amount of the alcohol solvent is not particularly limited, and the UHMWPE fibers can be immersed; the power of ultrasonic treatment is preferably 500-1200W, and more preferably 600-800W; the time of ultrasonic treatment is preferably 20-40 min, and more preferably 30 min; the purpose of the ultrasonic treatment is to remove impurities on the surface of the fiber; the drying temperature is preferably 50-80 ℃, and more preferably 55-65 ℃; the drying time is preferably 1-6 h, and more preferably 1-2 h.
The amount of the first impregnation solution is not particularly limited, and the ultra-high molecular weight polyethylene fibers can be immersed. In the present invention, the temperature of the first treatment is preferably room temperature; the first treatment time is preferably 0.5-24 h, more preferably 5-20 h, and most preferably 10-15 h; the first treatment is preferably carried out by soaking or coating; the soaking is preferably carried out under the condition of stirring, and the stirring speed is preferably 50-1000 rpm, more preferably 200-500 rpm; the coating is preferably carried out under shaking conditions; the frequency of the oscillation is preferably 50 to 500rpm, more preferably 100 to 200 rpm.
In the present invention, in the first treatment process, dopamine and polyethyleneimine form a cross-linked structure, so as to form a coating on the surface of the fiber, and the reaction is as shown in formula (1):
Figure BDA0003057649860000071
wherein, the two polymerized structural formulas are both basic structural units of the obtained cross-linked polymer, and the wavy line represents the connection basic structural unit.
After the first treatment, the method preferably further comprises the step of washing the ultra-high molecular weight polyethylene fiber after the first treatment with water and then drying to obtain the pre-antibacterial fiber. The washing times are not specially limited, and the washing liquid is washed until the washing liquid is neutral; the drying temperature is preferably 50-80 ℃, and more preferably 55-65 ℃; the drying time is preferably 1-6 h, and more preferably 1-2 h.
After obtaining the pre-bacteriostatic fiber, the invention adopts a second impregnation liquid in the bacteriostatic agent to carry out second treatment on the pre-bacteriostatic fiber to obtain the ultra-high molecular weight polyethylene bacteriostatic fiber
The dosage of the second impregnation solution is not particularly limited, and the pre-antibacterial fiber can be immersed. In the present invention, the temperature of the second treatment is preferably room temperature; the second treatment time is preferably 0.1-6 h, more preferably 0.5-4 h, and most preferably 1-3 h; the second treatment mode is preferably soaking; the soaking is preferably carried out under the condition of stirring or shaking, and the stirring speed is preferably 50-1000 rpm, more preferably 200-500 rpm; the frequency of the oscillation is preferably 50 to 500rpm, more preferably 100 to 200 rpm.
In the invention, the coordination reaction occurs in the second treatment process, and metal ions can be fixed on the surface of the fiber, so that the fiber has antibacterial performance, and meanwhile, the mechanical property of the fiber is hardly influenced, and the generated reaction is shown as a formula (2):
Figure BDA0003057649860000081
wherein the wavy line represents the crosslinked polymer formed during the first treatment, and M is Cu, Ag or Zn.
After the second treatment, the method preferably further comprises the step of washing the ultra-high molecular weight polyethylene fiber after the second treatment with water and then drying to obtain the pre-antibacterial fiber. In the present invention, the number of times of the water washing is not particularly limited, and the unreacted second impregnation liquid washing solution may be removed; the drying temperature is preferably 50-80 ℃, and more preferably 55-65 ℃; the drying time is preferably 1-6 h, and more preferably 1-2 h.
The invention also provides the ultrahigh molecular weight polyethylene antibacterial fiber obtained by the preparation method of the technical scheme. In the invention, the breaking strength of the ultra-high molecular weight polyethylene bacteriostatic fiber is preferably 39.5-41 cN/dtex, and more preferably 39.6-40.4 cN/dtex; the initial Young modulus of the ultra-high molecular weight polyethylene bacteriostatic fiber is preferably 1600-1750 cN/dtex, and more preferably 1602-1726 cN/dtex; the ultrahigh molecular weight polyethylene bacteriostatic fiber has good hydrophilic performance; the antibacterial rate of the ultra-high molecular weight polyethylene antibacterial fiber is preferably more than 98%. The ultrahigh molecular weight polyethylene antibacterial fiber provided by the invention has excellent antibacterial effect, mechanical property and hydrophilicity.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The bacteriostatic agent comprises the following components:
first impregnation solution: 6.057g of Tris (hydroxymethyl) aminomethane (Tris), 1mol/L hydrochloric acid solution, 2g of dopamine hydrochloride, 2g of polyethyleneimine and 1L of deionized water; the pH value is 8.5;
second impregnation solution: 12.5g copper sulfate pentahydrate and 1L deionized water.
Putting UHMWPE fibers with the weight-average molecular weight of 400 ten thousand into absolute ethyl alcohol, carrying out ultrasonic treatment for 30min under the condition of 600W, taking out, washing with water, and drying for 1h under the condition of 60 ℃ to obtain pretreated UHMWPE fibers;
6.057g of Tris is dissolved in 1L of deionized water to obtain a Tris solution; adding 1mol/L hydrochloric acid solution into the obtained Tris solution to adjust the pH value to 8.5 to obtain alkaline Tris solution; dissolving 2g of dopamine hydrochloride and 2g of polyethyleneimine in the alkaline Tris solution to obtain a first impregnation solution; immersing the pretreated UHMWPE fiber into a first impregnation solution, stirring and coating for 12h, taking out the fiber, washing with water, and drying at 60 ℃ for 1h to obtain a pre-antibacterial fiber;
dissolving 12.5g of blue vitriod in 1L of deionized water to obtain a second dipping solution; and (3) placing the pre-antibacterial fiber in a second dipping solution, stirring for 0.5h at room temperature, washing with water, and drying for 1h at the temperature of 60 ℃ to obtain the UHMWPE antibacterial fiber.
Example 2
The bacteriostatic agent comprises the following components:
first impregnation solution: 6.057g of Tris (hydroxymethyl) aminomethane (Tris), 1mol/L hydrochloric acid solution, 1g of dopamine hydrochloride, 2g of polyethyleneimine and 1L of deionized water, wherein the pH value is 8.5;
second impregnation solution: 8.49g silver nitrate and 1L deionized water.
Putting UHMWPE fibers with the weight-average molecular weight of 450 ten thousand into absolute ethyl alcohol, carrying out ultrasonic treatment for 30min under the condition of 700W, taking out, washing with water, and drying for 1h under the condition of 60 ℃ to obtain pretreated UHMWPE fibers;
6.057g of Tris is dissolved in 1L of deionized water to obtain a Tris solution; adding 1mol/L hydrochloric acid solution into the obtained Tris solution to adjust the pH value to 8.5 to obtain alkaline Tris solution; dissolving 1g of dopamine hydrochloride and 2g of polyethyleneimine in the alkaline Tris solution to obtain a first impregnation solution; immersing the pretreated UHMWPE fiber into a first impregnation solution, stirring and coating for 10 hours, taking out the fiber, washing with water, and drying at 60 ℃ for 1 hour to obtain a pre-antibacterial fiber;
dissolving 8.49g of silver nitrate in 1L of deionized water to obtain a second impregnation solution; and (3) placing the pre-antibacterial fiber in a second dipping solution, stirring for 1h at room temperature, taking out, washing with water, and drying for 1h at the temperature of 60 ℃ to obtain the UHMWPE antibacterial fiber.
Example 3
The bacteriostatic agent comprises the following components:
first impregnation solution: 6.057g of Tris (hydroxymethyl) aminomethane (Tris), 1mol/L hydrochloric acid solution, 3g of dopamine hydrochloride, 6g of polyethyleneimine and 1L of deionized water; the pH value is 8.5;
second impregnation solution: 17.5g copper sulfate pentahydrate and 1L deionized water.
Putting UHMWPE fibers with the weight-average molecular weight of 450 ten thousand into absolute ethyl alcohol, carrying out ultrasonic treatment for 30min under the condition of 600W, taking out, washing with water, and drying for 1h under the condition of 60 ℃ to obtain pretreated UHMWPE fibers;
6.057g of Tris is dissolved in 1L of deionized water to obtain a Tris solution; adding 1mol/L hydrochloric acid solution into the obtained Tris solution to adjust the pH value to 8.5 to obtain alkaline Tris solution; dissolving 3g of dopamine hydrochloride and 6g of polyethyleneimine in the alkaline Tris solution to obtain a first impregnation solution; immersing the pretreated UHMWPE fiber into a first impregnation solution, stirring and coating for 8 hours, taking out the fiber, washing with water, and drying at 60 ℃ for 1 hour to obtain a pre-antibacterial fiber;
dissolving 17.5g of blue vitriod in 1L of deionized water to obtain a second dipping solution; and (3) placing the pre-antibacterial fiber in a second dipping solution, stirring for 2h at room temperature, taking out, washing with water, and drying for 1h at 60 ℃ to obtain the UHMWPE antibacterial fiber.
Example 4
The bacteriostatic agent comprises the following components:
first impregnation solution: 6.057g of Tris (hydroxymethyl) aminomethane (Tris), 1mol/L hydrochloric acid solution, 2g of dopamine hydrochloride, 4g of polyethyleneimine and 1L of deionized water; the pH value is 8.5;
second impregnation solution: 11.9g of copper chloride dihydrate and 1L of deionized water.
Putting UHMWPE fibers with the weight-average molecular weight of 450 ten thousand into absolute ethyl alcohol, carrying out ultrasonic treatment for 30min under the condition of 800W, taking out, washing with water, and drying for 1h under the condition of 65 ℃ to obtain pretreated UHMWPE fibers;
6.057g of Tris is dissolved in 1L of deionized water to obtain a Tris solution; adding 1mol/L hydrochloric acid solution into the obtained Tris solution to adjust the pH value to 8.5 to obtain alkaline Tris solution; dissolving 2g of dopamine hydrochloride and 4g of polyethyleneimine in the alkaline Tris solution to obtain a first impregnation solution; immersing the pretreated UHMWPE fiber into a first impregnation solution, stirring and coating for 12h, taking out the fiber, washing with water, and drying at 60 ℃ for 1h to obtain a pre-antibacterial fiber;
dissolving 11.9g of copper chloride dihydrate in 1L of deionized water to obtain a second impregnation solution; and (3) placing the pre-antibacterial fiber in a second dipping solution, stirring for 0.2h at room temperature, taking out, washing with water, and drying for 1h at 60 ℃ to obtain the UHMWPE antibacterial fiber.
Example 5
The bacteriostatic agent comprises the following components:
first impregnation solution: 6.057g of Tris (hydroxymethyl) aminomethane (Tris), 1mol/L hydrochloric acid solution, 2.5g of dopamine hydrochloride, 5g of polyethyleneimine and 1L of deionized water; the pH value is 8.5;
second impregnation solution: 13.3g silver nitrate and 1L deionized water.
Putting UHMWPE fibers with the weight-average molecular weight of 450 ten thousand into absolute ethyl alcohol, carrying out ultrasonic treatment for 30min under the condition of 600W, taking out, washing with water, and drying for 1h under the condition of 60 ℃ to obtain pretreated UHMWPE fibers;
6.057g of Tris is dissolved in 1L of deionized water to obtain a Tris solution; adding 1mol/L hydrochloric acid solution into the obtained Tris solution to adjust the pH value to 8.5 to obtain alkaline Tris solution; dissolving 2.5g of dopamine hydrochloride and 5g of polyethyleneimine in the alkaline Tris solution to obtain a first impregnation solution; immersing the pretreated UHMWPE fiber into a first impregnation solution, stirring and coating for 12h, taking out the fiber, washing with water, and drying at 60 ℃ for 1h to obtain a pre-antibacterial fiber;
dissolving 13.3g of silver nitrate in 1L of deionized water to obtain a second impregnation solution; and (3) placing the pre-antibacterial fiber in a second dipping solution, stirring for 0.4h at room temperature, taking out, washing with water, and drying for 1h at the temperature of 60 ℃ to obtain the UHMWPE antibacterial fiber.
Comparative example 1
Untreated UHMWPE fibers having a weight average molecular weight of 450 ten thousand.
Test example
(1) Antibacterial property and mechanical property tests are carried out on the UHMWPE antibacterial fibers prepared in the embodiments 1-5 and the UHMWPE fibers prepared in the comparative example 1, and the test results are shown in Table 1.
Wherein the test method of the breaking strength and the initial Young modulus is GB-T29554-2013.
The antibacterial property test method is WS/T650-2019: an Antibacterial and bacteriostatic effect evaluation Method (evaluating Method for Efficacy of Antibacterial and bacteriosis). The formula for calculating the antibacterial rate is as follows: x ═ A0-A1)/A0X100%, wherein, X is the antibacterial rate and the unit is; a. the0Is the inoculum size of the untreated UHMWPE fibers; a. the1The test chart of the antibacterial zone for the recovery bacterial quantity of the UHMWPE bacteriostatic fiber is shown in figure 1, wherein a is a comparative example 1, and b is an example 1. As can be seen from fig. 1, the UHMWPE antimicrobial fiber produced according to the present invention is a non-leaching antimicrobial fiber.
Table 1 results of performance tests of UHMWPE bacteriostatic fibers prepared in examples 1-5 and UHMWPE fibers of comparative example 1
Figure BDA0003057649860000121
As can be seen from the table 1, the antibacterial rate of the prepared antibacterial fiber on escherichia coli is 98.2-99.9%, the antibacterial rate on staphylococcus aureus is 98.7-99.9%, and the antibacterial effect is excellent; the breaking strength of the UHMWPE fiber is 40.8cN/dtex, the initial Young's modulus is 1688cN/dtex, the breaking strength of the UHMWPE bacteriostatic fiber prepared by the invention is 39.6-40.2 cN/dtex, the initial Young's modulus is 1602-1726 cN/dtex, the breaking strength is reduced by 1.5-3.9% relative to the UHMWPE fiber, and the change amount of the initial Young's modulus relative to the UHMWPE fiber is-5.1-2.2%.
The contact angle of the UHMWPE bacteriostatic fibers prepared in example 1 was 0 ° and the contact angle of the UHMWP fibers of comparative example 1 was 112 °, the contact angle results are shown in fig. 2, where a is comparative example 1 and b is example 2. As can be seen from fig. 2, the UHMWPE bacteriostatic fibers prepared by the present invention have excellent hydrophilicity.
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 decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A bacteriostatic agent is characterized by comprising a first impregnation solution and a second impregnation solution which are separately dispensed;
the first dipping solution comprises trihydroxymethyl aminomethane, inorganic acid, dopamine hydrochloride, polyethyleneimine and water;
the second impregnation solution includes a water-soluble transition metal salt and water.
2. The bacteriostatic agent according to claim 1, wherein the concentration of tris in the first impregnation solution is 1-10 g/L;
the concentration of the dopamine hydrochloride is 1-4 g/L;
the concentration of the polyethyleneimine is 2-8 g/L.
3. The bacteriostatic agent according to claim 1 or 2, wherein the pH value of the dipping solution is 8-10.
4. The bacteriostatic agent according to claim 1, wherein the water-soluble transition metal salt comprises one or more of water-soluble copper salt, water-soluble silver salt and water-soluble zinc salt.
5. The bacteriostatic agent according to claim 1 or 4, wherein the concentration of the water-soluble transition metal salt in the second impregnation solution is 10 to 100 mmol/L.
6. Use of the bacteriostatic agent according to any one of claims 1 to 5 in the preparation of ultra-high molecular weight polyethylene bacteriostatic fiber.
7. A preparation method of an ultrahigh molecular weight polyethylene antibacterial fiber is characterized by comprising the following steps:
carrying out first treatment on the ultrahigh molecular weight polyethylene fibers by using a first dipping solution in a bacteriostatic agent to obtain pre-bacteriostatic fibers;
and carrying out second treatment on the pre-bacteriostatic fibers by adopting a second impregnation liquid in the bacteriostatic agent to obtain the ultrahigh molecular weight polyethylene bacteriostatic fibers.
8. The method for preparing the composite material according to claim 7, wherein the first treatment is soaking or coating; the temperature of the first treatment is room temperature, and the time is 0.5-24 h.
9. The method according to claim 7, wherein the second treatment is a dipping or coating; the temperature of the second treatment is room temperature, and the time is 0.1-6 h.
10. The ultra-high molecular weight polyethylene bacteriostatic fiber obtained by the preparation method of any one of claims 7 to 9.
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