CN118685876B - A rare earth functional material for antibacterial spinning and rare earth antibacterial fabric - Google Patents

Abstract

The present invention provides a rare earth functional material for antibacterial spinning and a rare earth antibacterial fabric, wherein the rare earth functional material comprises a rare earth composite material CMO and a polymer quantum dot powder P.CDs in a mass ratio of (3-5):(1-2). The present invention introduces highly antibacterial rare earth functional materials and polymer quantum dot powder P.CDs into the spun fibers, thereby increasing the loading rate of the antibacterial material and verifying the washability and duration of the antibacterial defense of the highly antibacterial material.

Description

Rare earth functional material for antibacterial spinning and rare earth antibacterial fabric

Technical Field

The invention belongs to the field of textiles, and particularly relates to a rare earth functional material for antibacterial spinning and a rare earth antibacterial fabric.

Background

In warm and humid environments, where the clothing may be contaminated with microorganisms, this environment is most suitable for the growth of bacteria, which can produce unpleasant odors. During human activity, textile fabrics can affect perspiration and odor formation, perspiration secretion, bacterial count and moist environment are three major factors in skin odor generation. Since textile materials are organic materials, they are favorable substrates for microbial growth, sweat produced by human skin provides nutrients for bacteria. Under extreme conditions, microorganisms can cause serious problems such as fabric decay, unpleasant odors, and health problems of infectious diseases. Spinning is one of the raw materials of clothing, and can be in direct contact with sweat, because 99% of the sweat is water, once people sweat, an excellent culture environment is provided for bacterial growth, and body odor is generated. The development of textile fabrics with antimicrobial components is increasingly of interest to researchers.

Different types of substances, such as oxidizing agents, coagulants, metals or quaternary ammonium compounds are used for the antibiotic additives, but most of the antibiotic agents are harmful and toxic. Current research focuses on the high activity of silver against viruses, fungi and bacteria, and its application in wound dressings, creams, surgical prostheses, dental implants, medical paints, etc. has been widely developed.

The silver solution with different concentrations is subjected to electroless plating on the nylon fiber, but the defects of the coating are increasingly obvious, and the silver is stripped from the fiber by washing, so that the antibacterial efficiency of the product is reduced. Nano-silver particles and colloidal silver have been used to enhance the antimicrobial properties of polymer fibers, but they may migrate into the body or leach out, and have the limitation of being costly.

Disclosure of Invention

In view of the above, the invention aims to overcome the defects in the prior art, and provides a rare earth functional material for antibacterial spinning and a rare earth antibacterial fabric, according to the invention, the rare earth functional material with high antibacterial property is introduced into the fiber of antibacterial spinning, so that the loading rate of the antibacterial material is improved, and the washing fastness and the duration of antibacterial defense of the high antibacterial material are verified.

In order to achieve the above purpose, the technical scheme of the invention is realized as follows:

In a first aspect, the invention provides a rare earth functional material for antibacterial spinning, comprising the following components in percentage by mass (3-5): the rare earth composite material CMO and the polymer quantum dot powder P.CDs of the (1-2);

The preparation method of the rare earth composite material CMO comprises the following steps: adding cerium salt and manganese sulfate into water, heating and stirring, adding acetic acid, dropwise adding NaOH solution, separating out precipitate, centrifuging to remove supernatant, washing the precipitate, drying and concentrating, and calcining to obtain rare earth composite material CMO;

the preparation method of the polymer quantum dot powder P.CDs comprises the following steps:

dissolving and diluting the polymer raw material with water, stirring uniformly, heating, naturally cooling to room temperature after heating, finally dialyzing the solution to remove impurities, and freeze-drying the dialyzed product to obtain polymer quantum dot powder P.

Preferably, the mass ratio of the cerium salt to the manganese sulfate is (20-60): (0.1-5).

Preferably, the cerium salt is one or more of cerium nitrate, cerium sulfate and cerium chloride.

Preferably, the mass ratio of the acetic acid to the cerium salt is (1-10): (20-60).

Preferably, the concentration of the NaOH solution is 0.1-0.3 g/mL.

Preferably, the heating temperature in the preparation method of the rare earth composite material CMO is 80-160 ℃, and the stirring time is 21-24h.

Preferably, the calcination temperature is 300-800 ℃ and the calcination time is 1-6 h.

Preferably, the mass to water ratio of the polymer raw material is: 1 to 10 g of the polymer raw material is added to 1 to 30 mL of water.

Preferably, the polymer raw material is Polyethylenimine (PEI) and/or Polyethylene (PE).

Preferably, the heating temperature is 160-180 ℃ and the heating time is 10-12h in the preparation method of the polymer quantum dot powder P.CDs.

Preferably, the dialysis is performed by using a cut-off bag of 10 kDa, changing the solution every 4-12 hours, and the dialysis duration is 10-60 h.

In a second aspect, the invention also provides a preparation method of the rare earth functional material, which comprises the following steps:

Adding water and a water-based dispersing agent into the rare earth composite material CMO, then sanding, wherein the particle size of the rare earth composite material CMO after sanding is 600-700nm, and uniformly mixing and stirring the sanded rare earth composite material CMO and polymer quantum dot powder P and CDs to obtain the rare earth functional material.

In a third aspect, the invention also provides an application of the rare earth functional material in preparing rare earth antibacterial fabrics.

Preferably, the rare earth functional material in the rare earth antibacterial fabric is added in the mass percentage of 1-2.5 per mill. The percentage is the optimized addition, when the addition of rare earth functional materials in the rare earth antibacterial fabric is less than 1 per mill, the antibacterial effect is drastically reduced, and when the addition of rare earth functional materials in the rare earth antibacterial fabric is more than 2.5 per mill, the yarn surface is rough and cannot be woven into yarns, and meanwhile, the loading rate, the washing fastness and the duration of antibacterial defense of the antibacterial materials are drastically reduced.

Compared with the prior art, the invention has the following advantages:

(1) The rare earth composite material CMO has a strong active oxygen catalysis effect due to the unique charge structure and infrared radiation, and can cause microorganisms to generate oxidative stress so as to cause the death of the microorganisms. The antibacterial rate of the rare earth functional material for escherichia coli and staphylococcus aureus is more than or equal to 98 percent, and the antibacterial rate for candida albicans is more than or equal to 95 percent.

(2) Since the polymer quantum dot size in the present invention is much smaller than the diameter of the fiber, a uniformly distributed nanostructure can be formed inside the fiber. Such nanostructures can effectively disperse stresses. And the polymer quantum dots and the fibers have stronger interface interaction, and the interaction can improve the binding force in the fibers, so that the relative sliding among the parts is reduced when the fibers are subjected to external force, and the tensile property of the fibers is improved.

(3) The polymer quantum dots in the invention can be subjected to crosslinking reaction with the fiber and the rare earth material in a chemical bond or physical adsorption mode to form a three-dimensional network structure. The network structure can effectively limit the movement of molecular chains in the fiber, so that the relative sliding among the molecular chains is reduced when the fiber is acted by external force, and the tensile property of the fiber is improved. Meanwhile, after the polymer quantum dots are introduced and crosslinked, the yarns and the rare earth materials can be firmly locked together. Thereby improving the loading rate, the washing fastness and the duration of the antibacterial defense of the antibacterial yarn.

Drawings

FIG. 1 is a scanning electron microscope image of a rare earth functional material formulation;

FIG. 2 is a graph showing the inhibiting effect of rare earth functional materials on E.coli;

FIG. 3 is a graph showing the inhibitory effect of yarn on E.coli;

FIG. 4 is a rare earth functional material loading detection result of a yarn;

FIG. 5 is a graph showing the effect of the yarn on inhibiting E.coli (E.coli) after water washing.

Detailed Description

Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. All chemicals were used without further treatment as the test reagents used in the following examples, and distilled water (ρ=18.2M Ω·cm, 25 ℃) was obtained from the Millipore milli-Q water purification system. Coli (e.coli) was from beijing four-ring biopharmaceutical limited. If not specified, the biochemical reagents are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.

The present invention will be described in detail with reference to examples.

Example 1

(1) Preparation of rare earth composite material CMO

Adding 20g of cerium nitrate and 0.1g of manganese sulfate into 50ml of water, stirring at 80 ℃ for 21h, adding 10 ml of AcOH as a blocking agent for blocking, then dropwise adding 10g/100 ml of NaOH solution to separate out precipitate, centrifuging at 8000rpm for 60 min to remove supernatant, washing the precipitate with water and ethanol, drying and concentrating, and calcining at 800 ℃ for 1h to obtain the rare earth composite material CMO.

(2) Preparation of polymer quantum dot powder P.CDs

5G of Polyethylenimine (PEI) was diluted in 9.5 mL distilled water and the above mixed solution was transferred to a stainless steel autoclave lined with polytetrafluoroethylene. After heating at 160℃for 10 hours, the autoclave was taken out and naturally cooled to room temperature. Finally, the distilled water is dialyzed for more than 48h with a 10 kDa cut-off bag, and the solution is changed every 8h to remove all impurities. And finally, freeze-drying the product to obtain the polymer quantum dot powder P.CDs.

(3) Preparation of rare earth functional material

Adding 450mL of water and 5g of aqueous 2800 dispersing agent into 50g of rare earth composite material CMO, uniformly stirring, placing into a sand mill, performing sand milling for 6 hours, wherein the particle size of the rare earth composite material CMO after sand milling is 600-700nm, and mixing the rare earth composite material CMO and polymer quantum dot powder P.CDs after sand milling according to a mass ratio of 3:1, and uniformly stirring. Particle size distribution of the rare earth functional material formulation is monitored by a particle sizer, and as can be seen from fig. 1, the particle size after formulation matching is stabilized near 678 nm.

Example 2

(1) Preparation of rare earth composite material CMO

Adding 40g of cerium nitrate and 3g of manganese sulfate into 200ml of water, stirring for 24 hours at 100 ℃, adding 1 ml of AcOH as a blocking agent for blocking, then dripping 30g/100 ml of NaOH solution to separate out precipitate, centrifuging at 30000rpm for 60 min to remove supernatant, washing the precipitate with water and ethanol, drying and concentrating, and calcining at 600 ℃ for 3 hours to obtain the rare earth composite material CMO.

(2) Preparation of polymer quantum dot powder P.CDs

1G of Polyethylene (PE) was diluted in 20mL of distilled water, and the above mixed solution was transferred to a stainless steel autoclave lined with polytetrafluoroethylene. After heating at 160℃for 12 hours, the autoclave was taken out and naturally cooled to room temperature. Finally, the distilled water is dialyzed for more than 48 h with a 10 kDa cut-off bag, and the solution is changed every 8h to remove all impurities. And finally, freeze-drying the product to obtain the polymer quantum dot powder P.CDs.

(3) Preparation of rare earth functional material

Adding 450mL of water and 5g of aqueous 2800 dispersing agent into 50g of rare earth composite material CMO, uniformly stirring, placing into a sand mill, performing sand milling for 6 hours, wherein the particle size of the rare earth composite material CMO after sand milling is 600-700nm, and mixing the rare earth composite material CMO and polymer quantum dot powder P.CDs after sand milling according to a mass ratio of 3:2, mixing the materials in proportion and stirring the materials uniformly.

Example 3

(1) Preparation of rare earth composite material CMO

Adding 60g of cerium nitrate and 5g of manganese sulfate into 500ml of water, stirring for 24 hours at 100 ℃, adding 8ml of AcOH as a blocking agent for blocking, then dripping 20g/100 ml of NaOH solution to separate out precipitate, centrifuging at 30000rpm for 60min to remove supernatant, washing the precipitate with water and ethanol, drying and concentrating, and calcining at 300 ℃ for 6 hours to obtain the rare earth composite material CMO.

(2) Preparation of polymer quantum dot powder P.CDs

5G of Polyethylenimine (PEI) and 5g of Polyethylene (PE) were diluted in 30mL of distilled water, and the above mixed solution was transferred to a stainless steel autoclave lined with polytetrafluoroethylene. After heating at 180℃for 10 hours, the autoclave was taken out and naturally cooled to room temperature. Finally, the distilled water is dialyzed for more than 48h with a 10 kDa cut-off bag, and the solution is changed every 8h to remove all impurities. And finally, freeze-drying the product to obtain the polymer quantum dot powder P.CDs.

(3) Preparation of rare earth functional material

Adding 450mL of water and 5g of aqueous 2800 dispersing agent into 50g of rare earth composite material CMO, uniformly stirring, placing into a sand mill, performing sand milling for 6 hours, wherein the particle size of the rare earth composite material CMO after sand milling is 600-700nm, and mixing the rare earth composite material CMO and polymer quantum dot powder P.CDs after sand milling according to a mass ratio of 5:2, mixing the materials in proportion and stirring the materials uniformly.

Comparative example 1

The difference between this comparative example and example 1 is that: the rare earth composite material CMO and polymer quantum dot powder P.CDs are prepared according to the mass ratio of 6:1.

Comparative example 2

The difference between this comparative example and example 1 is that: the rare earth composite material CMO and polymer quantum dot powder P.CDs are prepared according to the mass ratio of 1:1.

Comparative example 3

The difference between this comparative example and example 1 is that: the rare earth compound used in the step (1) is lanthanum chloride.

Comparative example 4

The difference between this comparative example and example 1 is that: the mass of cerium nitrate in the step (1) was 65g and the mass of manganese sulfate was 0.1g.

Comparative example 5

The difference between this comparative example and example 1 is that: the mass of cerium nitrate in the step (1) was 20g and the mass of manganese sulfate was 6g.

Comparative example 6

The difference between this comparative example and example 1 is that: the mass of Polyethylenimine (PEI) in step (2) was 0.5g.

Comparative example 7

The difference between this comparative example and example 1 is that: the mass of Polyethylenimine (PEI) in step (2) was 11g.

Comparative example 8

The difference between this comparative example and example 1 is that: and (3) not adding polymer quantum dot powder P.CDs in the step (3).

Test example 1 rare earth composite CMO powder bacteriostasis test

Firstly, weighing 10mg of rare earth composite material CMO powder prepared in examples 1-3 and comparative examples 3-5, adding 1mL of PBS buffer solution, using ultrasound to assist dispersion, wherein the concentration of the rare earth composite material CMO is 10 g/L, then sucking 100uL of prepared rare earth composite material CMO solution in an ultra-clean workbench, mixing with 800uL of PBS buffer solution, simultaneously sucking 900uL of PBS buffer solution directly by a control group, and standing at room temperature for standby.

Then, the escherichia coli subjected to secondary activation is diluted 10 ⁴ times by PBS according to a 10-time dilution gradient in an ultra-clean workbench, the concentration of the strain is controlled to be 1 multiplied by 10 ⁵-1×10⁶ cfu/mL, 100uL of diluted escherichia coli bacteria liquid is respectively added into 900uL of PBS (control group) and 900uL of rare earth composite material CMO solution (experimental group, CMO with the final concentration of 1 g/L) prepared in examples 1-3 and 3-5, the mixture is placed in a constant temperature shaking table, incubated at 37 ℃ for 18 hours and then coated on an LB plate, the coated LB plate is placed in a constant temperature incubator for overnight culture, and experimental results are observed after bacterial colonies grow on the plate.

As shown in FIG. 2, examples 1-3 and comparative example 3 have very good inhibitory effect on E.coli, with inhibitory effect between 99-100%. While comparative examples 4 and 5 did not show a good antibacterial effect, the antibacterial effect was only 20-40%. Similarly, our bacteriostasis tests on staphylococcus aureus (s. Aureus) and candida albicans (c. Albicans) of examples 1-3 showed that the bacteriostasis rate of staphylococcus aureus was greater than 98% and the bacteriostasis rate of candida albicans was greater than 95%.

Application example antibacterial spinning thread forming method

2000 G polyethylene terephthalate (PET) is respectively taken, 2g of rare earth functional materials prepared in the example 1 and the comparative examples 1, 2, 6, 7 and 8 are respectively introduced, the rare earth functional materials are cut into pieces, crushed and dissolved, after the temperature is raised to 120 ℃, melt is extruded into air by a spinneret plate under the action of a screw rod, naturally cooled and drafted to form fibers, and the prepared fibers are woven into yarns by adopting a method conventional in the art and are sequentially named as Y1, Y2, Y3, Y4, Y5 and Y6.

Test example 2 antibacterial property detection of textiles

The fiber prepared in the application example is woven into yarn by a method conventional in the art for antibacterial detection, and the detection method refers to GB/T20944.3-2008 section 3 of evaluation of antibacterial Properties of textiles published by the country 2008-04-29: the experiment was performed by the oscillation method. The specific process comprises the following steps: 3-4g of yarns Y1, Y2, Y3, Y4, Y5 and Y6 to be tested and control yarns (GB/T20944.3-2008 standard control samples purchased by a mechanism) are respectively taken into a 250mL beaker, 250mL of phosphorus-free standard detergent containing 0.2% is added into the beaker, and after uniform mixing, the mixture is placed into a magnetic stirrer for stirring, and stirring conditions are as follows: 600 revolutions, 49 ℃, stirring for 45min, taking out a sample, washing with pure water for 2 times each for 1min, wherein the washing cycle is carried out for 5 times. Finally, in order to eliminate the interference of the detergent, the yarn is fully cleaned by clean water and placed in a sterile plate for sun drying. Cutting a sample to be detected and a control sample into small fragments after sun drying, respectively placing the small fragments in clean 250mL conical flasks, sealing the mouths, sterilizing the conical flasks in a high-pressure steam sterilizing pot at 121 ℃ for 20min, taking out the sterilized sample after sterilization, cooling the sample at room temperature, adding the sterilized sample into 70mL of PBS under a sterile condition, and placing the sample at room temperature for standby.

Taking out the escherichia coli subjected to secondary activation culture, respectively diluting the escherichia coli 10000 times by using sterile PBS, adding 5mL of escherichia coli after dilution into an conical flask containing 70mLPBS of yarn to be tested and a control sample, uniformly mixing, placing each yarn group to be tested and each control sample group into a constant-temperature shaking table, and vibrating at 24 ℃ and 150rpm for 18 hours. After shaking for 18h in each experimental group, 1mL of shaking contact liquid is absorbed for 10-time gradient dilution, and 100 mu L of shaking contact liquid is taken to a sterile LB plate for plate coating after the shaking contact liquid is respectively diluted to 0, 10, 100 and 1000 times. Each sample, each dilution gradient was set up in 3 sets of parallelism. After being coated, the mixture is placed in a constant temperature incubator for culturing at 37 ℃. Finally, selecting a flat plate with proper colony number for observation, and judging the antibacterial capability of the textile according to the colony number.

As shown in FIG. 3, the antibacterial effect of the yarn Y1 on the Escherichia coli reaches 99.2%, while the antibacterial effect of the yarns Y2, Y3, Y4, Y5 and Y6 on the Escherichia coli is between 40 and 70%. The CMO powder of the antibacterial rare earth functional material can provide a strong antibacterial effect, and the polymer quantum dot powder P.CDs can enable the CMO powder to be better attached to the surface of the yarn, so that when the CMO powder and the CMO powder are mixed in a proper proportion and then added into the spinning process of the yarn, the produced yarn product can show a very good antibacterial effect, and when the proportion is improper or the synthetic proportion of the polymer quantum dot powder P.CDs is not proper, the polymer quantum dot powder P.CDs cannot provide the most effective crosslinking effect, and further the antibacterial property of the yarn product is poor.

Test example 3 rare earth functional material load detection of textiles

Scanning and irradiating the yarns Y1, Y2, Y3, Y4, Y5 and Y6 by using an electron microscope, observing the inlay quantity of the rare earth functional material on the surface of the yarns within the length range of 200 mu m, and judging the loading capacity of the rare earth functional material on the yarns according to the quantity.

As shown in fig. 4, the number of rare earth materials loaded on the yarn Y1 is about 226, and the number of rare earth materials of other yarns of Y1, Y2, Y3, Y4, Y5 and Y6 is obviously smaller than Y1 in the same visual field, which indicates that the yarn Y1 can more effectively bear the rare earth materials, so that the rare earth materials are more tightly combined with the yarn, and further the washing resistance and the antibacterial capability of the yarn are enhanced.

Test example 4 tensile force detection of textiles

The yarns Y1, Y2, Y3, Y4, Y5 and Y6 are respectively placed in clamps on a universal mechanical testing machine, and the positions and angles of the clamps are adjusted so that the sample is in the correct position and state in the testing process. After confirming that the sample is clamped and positioned correctly, starting the machine, detecting the breaking tensile force intensity, and recording the strength of the yarn when the yarn is broken.

As shown in Table 1, the diameter of the yarn Y1 is slightly thicker than that of other yarn products, but the breaking strength is far higher than that of other yarns, the breaking strength/diameter is taken as a comprehensive judgment standard of the tensile strength, the yarn Y1 is 218, the other yarns are 130-150, and the tensile property of the yarn Y1 is obviously improved.

TABLE 1 tensile force testing of yarn products

Test example 5 detection of Water washing resistance of textiles

The method comprises the steps of adding 4g of phosphorus-free washing powder into each liter of water to prepare a washing solution, adding 400mL of the washing solution into a 500mL beaker, adding 5g of yarns Y1, Y2, Y3, Y4, Y5 and Y6 into the washing solution, adding 10 steel balls with the diameter of 6mm into the washing solution, adding friction force, finally stirring by using a stirring paddle, wherein the stirring speed is 120rpm, washing for 30min for one time, drying all samples after washing for 50 times, detecting the antibacterial effect of the yarns again, and detecting the water-fast washing degree of the textiles through the antibacterial effect.

As shown in FIG. 5, after 50 times of washing, the antibacterial effect of the yarn Y1 is 95.5%, only 2% is reduced, but the yarns Y2, Y3, Y4, Y5 and Y6 are greatly reduced by 30-40% respectively, and the reduction degree cannot meet the washing requirement in daily life.

The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (6)

1. A rare earth functional material for antibacterial spinning is characterized in that: the rare earth functional material comprises the following components in percentage by mass (3-5): the rare earth composite material CMO and the polymer quantum dot powder P.CDs of the (1-2);

The preparation method of the rare earth composite material CMO comprises the following steps: adding cerium salt and manganese sulfate into water, heating and stirring, adding acetic acid, dropwise adding NaOH solution, separating out precipitate, centrifuging to remove supernatant, washing the precipitate, drying and concentrating, and calcining to obtain rare earth composite material CMO;

the preparation method of the polymer quantum dot powder P.CDs comprises the following steps:

dissolving and diluting a polymer raw material with water, uniformly stirring, heating, naturally cooling to room temperature after heating, finally dialyzing the solution to remove impurities, and freeze-drying the dialyzed product to obtain polymer quantum dot powder P, CDs;

the mass ratio of the cerium salt to the manganese sulfate is (20-60): (0.1-5);

The cerium salt is one or more of cerium nitrate, cerium sulfate and cerium chloride;

The mass to water ratio of the polymer raw materials is as follows: adding 1-10 g of polymer raw material into 1-30 mL of water;

the polymer raw material is polyethyleneimine.

2. The rare earth functional material for antibacterial spinning according to claim 1, characterized in that: the mass ratio of the acetic acid to the cerium salt is (1-10): (20-60); the concentration of the NaOH solution is 0.1-0.3 g/mL.

3. The rare earth functional material for antibacterial spinning according to claim 1, characterized in that: the heating temperature in the preparation method of the rare earth composite material CMO is 80-160 ℃, and the stirring time is 21-24 hours; the calcination temperature is 300-800 ℃, and the calcination time is 1-6 h.

4. The rare earth functional material for antibacterial spinning according to claim 1, characterized in that: the heating temperature is 160-180 ℃ and the heating time is 10-12 hours in the preparation method of the polymer quantum dot powder P.CDs; the dialysis is performed by using a cut-off bag of 10 kDa, and the solution is changed every 4-12 hours, and the dialysis duration is 10-60 h.

5. A method for preparing the rare earth functional material according to any one of claims 1 to 4, characterized in that: the method comprises the following steps:

Adding water and a water-based dispersing agent into the rare earth composite material CMO, then sanding, wherein the particle size of the rare earth composite material CMO after sanding is 600-700nm, and uniformly mixing and stirring the sanded rare earth composite material CMO and polymer quantum dot powder P and CDs to obtain the rare earth functional material.

6. Use of the rare earth functional material according to any one of claims 1-4 for preparing rare earth antibacterial fabrics, characterized in that: the rare earth functional material in the fiber of the rare earth antibacterial fabric accounts for 1-2.5 per mill.