CN111793851A

CN111793851A - Radiation-proof fiber based on nano material and preparation method thereof

Info

Publication number: CN111793851A
Application number: CN202010463148.4A
Authority: CN
Inventors: 不公告发明人
Original assignee: Jiaxing Juetuo Technology Co ltd
Current assignee: Jiaxing Juetuo Technology Co ltd
Priority date: 2020-05-27
Filing date: 2020-05-27
Publication date: 2020-10-20

Abstract

The invention relates to the technical field of radiation-proof textile materials, in particular to radiation-proof fiber based on nano materials and a preparation method thereof, wherein the radiation-proof cellulose comprises the following components in percentage by weight: 3.5-48.5% of activated carbon resin loaded with nano zinc oxide; 0.1-1.5% of yttrium-doped zinc ferrite; the rest of polyester chips; the nano zinc oxide is prepared by taking dihydromyricetin as a template, and the weight ratio of the nano zinc oxide to the yttrium-doped zinc ferrite is 1: 25-30. The fiber has excellent mechanical strength, radiation resistance, ultraviolet light transmittance resistance and virus and germ inhibition effects, is excellent in water washing resistance and light aging resistance, and prolongs the service life of fiber products while improving the quality of the fiber products.

Description

Radiation-proof fiber based on nano material and preparation method thereof

Technical Field

The invention relates to the technical field of radiation-proof textile materials, in particular to radiation-proof fibers based on a nanometer material and a preparation method thereof.

Background

With the rapid development of modern technology, invisible and untouchable pollution sources are increasingly concerned by various circles, namely electromagnetic radiation called 'invisible killer'. For a good conductor, the human body, electromagnetic waves inevitably constitute a certain degree of harm. Generally, radar systems, television and radio transmission systems, radio frequency and microwave medical equipment, communication transmission stations, ultrahigh voltage power lines, most household appliances and the like can generate electromagnetic radiation sources with various forms, different frequencies and different intensities. Nowadays, electromagnetic radiation pollution is recognized as an important pollution source which endangers the ecological environment. The united nations environmental conference also ranks the pollution control objects as important pollution control objects. The widespread use of electromagnetic technology has also brought people to notice the pollution problem that it brings while enjoying the benefits that it brings. The problem of preventing and controlling electromagnetic radiation pollution also becomes an important difficult point and a hot point problem in the field of environmental laws.

The clothes are basic necessities of life, and besides the effect of beauty, the heat preservation is an important effect of the clothes in the global temperate zone and cold regions. Cotton, animal hair, chemical fibers and the like are widely applied to manufacturing of warm clothes. Most commonly, the temperature of the human body is maintained by increasing the number of pieces of the worn clothes, and the proper temperature of the human body is maintained only by increasing the thickness of the fabric, so that the requirement of people on the consumption of clothing products cannot be met, and the produced clothes which are only used for increasing the thickness of the fabric to maintain the proper temperature of the human body are troublesome, inconvenient and not beautiful. In addition, radiation protection, especially against ultraviolet radiation, is a problem that people begin to think about when wearing clothes. Traditional clothes rarely have an ultraviolet-proof function, and the function is added only to special sun-proof clothes. Professional sun-blocking clothes can play the effect of ultraviolet protection, radiation protection, but usually the price is high, is not suitable for general crowd. The sun-proof clothes with low price has poor ultraviolet effect, and even the sun-proof function is not much different from that of common clothes.

Radiation-proof fibers in the prior art are disclosed, for example, in a Chinese patent with an authorization publication number of CN106381684B, a preparation method of multilayer radiation-proof fibers based on ferrite and nano materials is disclosed, and the preparation method comprises the following steps: adding ultrahigh molecular weight polyethylene into a solvent, stirring until the ultrahigh molecular weight polyethylene is completely dissolved, adding nano silicon carbide powder and an amphoteric surfactant, uniformly mixing, slowly evaporating to be viscous, mechanically drawing wires, and thermally drying to form inner-layer fibers; soaking the inner layer fiber in polypyrrole liquid, oscillating, taking out, and airing to obtain a middle layer fiber; adding the gel containing the ferrite into the fibroin aqueous solution, adding the cationic surfactant, stirring and concentrating to form viscous liquid, coating the viscous liquid on the surface of the middle-layer fiber, drying, re-coating and drying to form a product, wherein the high ferrite content of the gel inevitably affects the smoothness of the fiber, and the ferrite adheres to the surface of the fiber in the modes of coating, drying, re-coating and re-drying, so that the fastness of the ferrite is insufficient, the fastness to washing is inevitably poor, and the radiation protection performance of the fiber in the later stage of multi-washing is reduced.

The above background disclosure is only for the purpose of assisting understanding of the inventive concept and technical solutions of the present invention, and does not necessarily belong to the prior art of the present patent application, and should not be used for evaluating the novelty and inventive step of the present application in the case that there is no clear evidence that the above content is disclosed at the filing date of the present patent application.

Disclosure of Invention

In view of the above, the present invention aims to provide a radiation protection fiber based on a nano material and a preparation method thereof, wherein the fiber has excellent mechanical strength, radiation protection performance, ultraviolet light transmittance resistance and virus and germ inhibition effect, and is excellent in water washing resistance and light aging resistance, and the service life of the fiber product is prolonged while the quality of the fiber product is improved.

In order to achieve the above object, the present invention provides several aspects of technical solutions as follows.

In a first aspect, the invention provides a radiation-proof fiber based on a nano material, wherein the radiation-proof cellulose comprises the following components in percentage by weight:

3.5-48.5% of activated carbon resin loaded with nano zinc oxide;

0.1-1.5% of yttrium-doped zinc ferrite;

the rest of polyester chips;

wherein the nano zinc oxide is prepared by taking dihydromyricetin as a template, and

the weight ratio of the nano zinc oxide to the yttrium-doped zinc ferrite is 1: 25-30.

The radiation-proof fiber provided by the invention contains nano zinc oxide and yttrium-doped zinc ferrite which are prepared by taking dihydromyricetin nano emulsion as a template in a special weight ratio, and can not only achieve 98-99.99% inhibition rate on staphylococcus aureus, escherichia coli, mould, candida albicans and the like, but also achieve more than 98% inhibition rate on influenza virus, adenovirus and the like; in addition, the active carbon and yttrium doped zinc ferrite loaded with the nano zinc oxide are dispersed in the polyester as spherical mobile phases, and a continuous functional dispersion phase is formed through melt spinning, so that the nano zinc oxide-loaded active carbon and yttrium doped zinc ferrite has an excellent effect of shielding radiation penetration.

In some preferred embodiments, the aforementioned nano-zinc oxide supported activated carbon resin is obtained by blending and granulating nano-zinc oxide supported activated carbon and resin.

In some preferred embodiments, the preparation method of the nano-zinc oxide supported activated carbon resin specifically comprises:

1) uniformly mixing coffee grounds with nano titanium dioxide and silver ions (the content of the silver ions in silver nitrate in the application is the mass fraction or mass ratio of the mass of the silver in the silver nitrate relative to the total amount), then adding a silane coupling agent with the total solid content of 1.5-2.0 wt%, fully grinding for at least 30min, placing the mixture in a vacuum furnace with the vacuum degree of at least 0.02MPa, heating the vacuum furnace to 430-445 ℃, preserving the heat for at least 30min, and naturally cooling to the room temperature to obtain the modified coffee carbon activated carbon;

2) under nitrogen purging, adding pyrrole monomer solution into the activated carbon obtained in the step 1), carrying out constant-temperature oscillation reaction for at least 18h, filtering and washing for at least 3-5 times, drying for at least 24h in a vacuum drying oven at the temperature of not higher than 60 ℃ and not higher than 0.02MPa, taking out, grinding until the activated carbon passes through at least 200 meshes of sieve to obtain the activated carbon;

3) and 2) dispersing the activated carbon into sufficient deionized water, adding nano zinc oxide, stirring at a low speed of 120-240 r/min for at least 3h, removing the deionized water by low-temperature rotary evaporation, and performing blending granulation on the activated carbon loaded with the nano zinc oxide and resin to obtain the activated carbon resin loaded with the nano zinc oxide.

In other preferred embodiments, in the step 1) of preparing the nano zinc oxide-loaded activated carbon resin, the coffee grounds are at least one of coffee grounds waste in the process of preparing coffee, roasted coffee grounds, microencapsulated roasted coffee grounds or microencapsulated coffee essential oil.

In other preferred embodiments, in the step 1) of preparing the activated carbon resin loaded with nano zinc oxide, the weight ratio of the coffee grounds to the nano titanium dioxide and the silver ions is 1000: 3-10: 0.5-0.8.

In other preferred embodiments, in the step 1) of preparing the nano zinc oxide-loaded activated carbon resin, the silane coupling agent is vinyltriethoxysilane or vinyltrimethoxysilane.

In other preferable embodiments, in the step 1) of preparing the activated carbon resin loaded with nano zinc oxide, the temperature rise rate of the vacuum furnace is 3-5 ℃/min.

In other preferred embodiments, in the step 2) of preparing the activated carbon resin loaded with nano zinc oxide, the weight ratio of the activated carbon to the pyrrole monomer is 1: 1.7-1.9.

In other preferred embodiments, in the step 2) of preparing the activated carbon resin loaded with nano zinc oxide, the constant temperature reaction temperature is 42-45 ℃ and the oscillation frequency is 120-240 r/min.

In other preferred embodiments, in the step 3) of preparing the activated carbon resin loaded with nano zinc oxide, the activated carbon resin loaded with nano zinc oxide contains 6.5 to 10.0 wt% of activated carbon and 0.15 to 0.30 wt% of nano zinc oxide.

In other preferred embodiments, in the step 3) of preparing the nano zinc oxide-loaded activated carbon resin, the resin is at least one of polypropylene, polyethylene terephthalate, polytrimethylene terephthalate, or polybutylene terephthalate resin.

The organic residues in the coffee grounds can be further removed by high-temperature roasting, the coffee grounds are carbonized and modified by a silane coupling agent, the particle size of the coffee grounds is reduced, surface wrinkles and ridge-shaped structures are increased, nano titanium dioxide particles and silver ions can be attached to the wrinkles and ridge-shaped structures, more excellent antibacterial performance is given to the coffee carbon activated carbon, the resin can be given excellent water washing resistance and light aging resistance after the coffee grounds are loaded with nano zinc oxide and blended and granulated with the resin, the radiation protection durability and the antiviral and antibacterial durability of the final radiation protection fibers are remarkably enhanced, and the service life of the fiber products is prolonged while the quality of the fiber products is improved.

In other preferred embodiments, in the step 3) of preparing the nano zinc oxide-loaded activated carbon resin, the nano zinc oxide is prepared by the following method: according to the mass ratio of 2-2.5: 1, dihydromyricetin and ZnSO are added₄·7H₂Dissolving O in sufficient deionized water, adjusting the pH value of the mixed solution to 6.5-6.8 by using 0.05-0.08 mol/L sodium hydroxide solution, stirring for at least 1h at 120-180 r/min, calcining the reaction solution for at least 2h at 380-395 ℃, cooling to room temperature, alternately washing for at least 3 times by using deionized water and absolute ethyl alcohol respectively, and drying to obtain the catalyst. According to the method, the nano zinc oxide is prepared by taking dihydromyricetin as a template, the dihydrooxidase and zinc ions form a compound, then the compound is cracked in the calcining process, organic fragments can serve as a stabilizer in the nano zinc oxide forming process and are difficult to clean, compared with pure zinc oxide, the nano zinc oxide prepared by the method can bring excellent washing resistance to a final product, namely the radiation-proof fiber, the radiation-proof efficiency and the antibacterial effect are not obviously attenuated after 100 times of washing, the radiation-proof duration of the fiber is remarkably prolonged, and the application value is improved.

In some preferred embodiments, the aforementioned yttrium-doped zinc ferrite is prepared by a method comprising the steps of:

1) dissolving analytically pure yttrium nitrate, zinc nitrate and ferric nitrate in a proper amount of deionized water, then adding malic acid solution according to the mass ratio of nitrate to malic acid of 1: 1.3-1.5, adjusting the pH of the mixed solution to be neutral by ammonia water, heating to 75-80 ℃, and stirring until wet gel is formed;

2) and (2) drying the wet gel in a forced air drying oven at 110 ℃ for at least 3h, taking out, igniting the wet gel to obtain a gray brown powder, grinding the powder for at least 1h, heating to 955-980 ℃, and roasting for at least 2.5h to obtain the yttrium-doped zinc ferrite. The process for preparing the yttrium-doped zinc ferrite by the method is easy to control, the obtained ferrite has high doping degree, the radiation resistance of the fiber can be obviously improved after the ferrite is mixed with polyester for melt spinning, the protection coefficient is high, the ultraviolet transmittance is low, in addition, the ferrite also has good light aging resistance, and the fracture strength of more than 93 percent can still be kept after 120h illumination accelerated aging test.

In other preferred embodiments, in step 1) of preparing the yttrium-doped zinc ferrite, the ratio of the amounts of the yttrium nitrate, the zinc nitrate and the ferric nitrate is 0.02-0.025: 0.3-0.4: 1.

In other preferred embodiments, in the step 1) of preparing the yttrium-doped zinc ferrite, the temperature rise rate is 3-5 ℃/min.

In other preferred embodiments, in the step 1) of preparing the yttrium-doped zinc ferrite, the stirring speed is 180 to 240 r/min.

In other preferred embodiments, in the step 2) of preparing the yttrium-doped zinc ferrite, the temperature rise rate is 5-10 ℃/min.

In some preferred embodiments, the polyester chip is at least one of polyethylene terephthalate, polytrimethylene terephthalate, or polybutylene terephthalate resin.

The application firstly loads the nano zinc oxide into the coffee carbon activated carbon, and then the coffee carbon activated carbon and the resin are mixed and granulated to prepare the activated carbon resin loaded with the nano zinc oxide, then the active carbon resin loaded with the nano zinc oxide and yttrium-doped zinc ferrite are doped into a polyester chip to form a continuous functional dispersion phase through melt spinning, and finally preparing the radiation-proof fiber based on the nano material, wherein the radiation-proof fiber has excellent mechanical strength and stronger inhibition effect on viruses and germs, and the fiber product has the performances of shielding radiation penetration, ultraviolet transmission and light aging resistance, can still keep more than 93 percent of breaking strength after 120h illumination accelerated aging test, has excellent washing fastness, obviously improves the radiation protection durability and the antiviral and antibacterial durability, and prolongs the service life of the fiber product while improving the quality of the fiber product.

In a second aspect, the invention further provides a preparation method of the radiation-proof fiber based on the nanomaterial in the first aspect, and specifically, the radiation-proof fiber based on the nanomaterial is obtained by mixing the activated carbon resin loaded with the nano zinc oxide, the yttrium-doped zinc ferrite and the polyester chip, and then carrying out melt spinning.

In some preferred embodiments, the melt spinning process conditions may be in accordance with the prior art, such as, but not limited to: the spinning temperature is 275-300 ℃, the spinning speed is 600-2000 m/min, the blowing temperature is 25-30 ℃, the relative humidity of air supply is 60-90%, and the air speed is 0.3-0.5 m/s.

In a third aspect, the present application also provides applications of the radiation protective fibers of the first or second aspects, including but not limited to:

1) the pregnant woman is dressed; and/or

2) Infant children's garments; and/or

3) A smelting site; and/or

4) A fire-fighting clothing lining; and/or

5) Outdoor protective clothing.

The invention has the beneficial effects that:

1) compared with pure zinc oxide, after the nano zinc oxide prepared by taking dihydromyricetin as a template is blended and granulated with resin, the resin can be endowed with excellent water washing resistance and light aging resistance, and the radiation resistance durability and the antiviral and antibacterial durability of the final radiation-proof fiber are obviously enhanced;

2) the process for preparing the yttrium-doped zinc ferrite by the method is easy to control, the doping degree of the obtained ferrite is high, the radiation resistance of the fiber can be obviously improved after the ferrite is mixed with polyester for melt spinning, the protection coefficient is high, the ultraviolet transmittance is low, in addition, the ferrite has good light aging resistance, and the fracture strength of more than 93 percent can still be kept after 120h illumination accelerated aging test;

3) the radiation-proof fiber based on the nano material is prepared by doping the activated carbon resin loaded with the nano zinc oxide and the yttrium-doped zinc ferrite into a polyester chip, forming a continuous functional dispersion phase through melt spinning, and finally obtaining the radiation-proof fiber based on the nano material.

The invention adopts the technical scheme for achieving the purpose, makes up the defects of the prior art, and has reasonable design and convenient operation.

Drawings

The foregoing and/or other objects, features, advantages and embodiments of the invention will be more readily understood from the following description taken in conjunction with the accompanying drawings in which:

FIG. 1 is a schematic diagram of the preparation process of nano zinc oxide of the present invention;

FIG. 2 is a schematic diagram of the detection of the anti-photoaging property of the fiber of the present invention.

Detailed Description

Those skilled in the art can appropriately substitute and/or modify the process parameters to implement the present disclosure, but it is specifically noted that all similar substitutes and/or modifications will be apparent to those skilled in the art and are deemed to be included in the present invention. While the products and methods of making described herein have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the products and methods of making described herein may be made and utilized without departing from the spirit and scope of the invention.

Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The present invention uses the methods and materials described herein; other suitable methods and materials known in the art may be used. The materials, methods, and examples described herein are illustrative only and are not intended to be limiting. All publications, patent applications, patents, provisional applications, database entries, and other references mentioned herein, and the like, are incorporated by reference herein in their entirety. In case of conflict, the present specification, including definitions, will control.

All percentages, parts, ratios, etc., are by weight unless otherwise indicated; additional instructions include, but are not limited to, "wt%" means weight percent, "mol%" means mole percent, "vol%" means volume percent.

When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5(1 to 5)" is described, the described range is understood to include ranges of "1 to 4(1 to 4)", "1 to 3(1 to 3)", "1 to 2(1 to 2) and 4 to 5(4 to 5)", "1 to 3(1 to 3) and 5", and the like. Where numerical ranges are described herein, unless otherwise stated, the ranges are intended to include the endpoints of the ranges, and all integers and fractions within the ranges.

When the term "about" is used to describe a numerical value or an end point value of a range, the disclosure should be understood to include the specific value or end point referred to.

Furthermore, "or" means "or" unless expressly indicated to the contrary, rather than "or" exclusively. For example, condition a "or" B "applies to any of the following conditions: a is true (or present) and B is false (or not present), a is false (or not present) and B is true (or present), and both a and B are true (or present).

In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are intended to mean no limitation on the number of occurrences (i.e., occurrences) of the element or component. Thus, "a" or "an" should be understood to include one or at least one and the singular forms of an element or component also include the plural unless the singular is explicitly stated.

It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation. The use of the phrase "comprising one of the elements does not exclude the presence of other like elements in the process, method, article, or apparatus that comprises the element.

The materials, methods, and examples described herein are illustrative only and not intended to be limiting unless otherwise specified. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.

The present invention is described in detail below.

Example 1: a radiation protection fiber based on nano materials:

the embodiment provides a radiation-proof fiber based on a nano material, and the radiation-proof cellulose comprises the following components in percentage by weight:

25.0 percent of activated carbon resin loaded with nano zinc oxide;

1.0% of yttrium-doped zinc ferrite;

74.0% of polyester chips;

the weight ratio of the nano zinc oxide to the yttrium-doped zinc ferrite is 1: 25.

The radiation protection fiber based on the nano material is prepared by the following steps:

1) preparing the activated carbon resin loaded with the nano zinc oxide:

1.1) uniformly mixing the coffee grounds waste with nano titanium dioxide and silver ions according to the weight ratio of 100:5:0.5, then adding vinyl trimethoxy silane with the total solid content of 1.8 wt%, fully grinding for 30min, placing in a vacuum furnace with the vacuum degree of 0.02MPa, heating the vacuum furnace to 440 ℃ at the speed of 5 ℃/min, preserving heat for 30min, and naturally cooling to room temperature to obtain the modified coffee carbon activated carbon;

1.2) under nitrogen purging, adding 1.8 weight times of pyrrole monomer solution into the activated carbon in the step 1.1), carrying out constant-temperature oscillation reaction at 45 ℃ and 180r/min for 24h, filtering and washing for at least 5 times, drying for 24h in a vacuum drying oven at 60 ℃ and 0.02MPa, taking out, grinding until the dried product is sieved by a 240-mesh sieve to obtain the activated carbon;

1.3) mixing dihydromyricetin and ZnSO according to the mass ratio of 2:1₄·7H₂Dissolving O in sufficient deionized water, adjusting the pH value of the mixed solution to 6.5 by using 0.05mol/L sodium hydroxide solution, stirring for 1h at 180r/min, calcining the reaction solution at 392 ℃ for 2h, cooling to room temperature, alternately washing with deionized water and absolute ethyl alcohol for 4 times, and drying to obtain the nano zinc oxide;

1.4) dispersing the activated carbon obtained in the step 1.2) into sufficient deionized water, adding the nano zinc oxide obtained in the step 1.3), stirring at a low speed of 180r/min for 3h, removing the deionized water by low-temperature rotary evaporation, and performing blending granulation on the activated carbon loaded with the nano zinc oxide and polytrimethylene terephthalate to obtain the activated carbon resin loaded with the nano zinc oxide, wherein the weight content of the activated carbon is 8.4%, and the weight content of the nano zinc oxide is 0.16%;

2) preparing yttrium-doped zinc ferrite:

2.1) dissolving analytically pure yttrium nitrate, zinc nitrate and ferric nitrate into a proper amount of deionized water according to the mass ratio of 0.023:0.035:1, then adding malic acid solution according to the mass ratio of nitrate to malic acid of 1:1.5, adjusting the pH of the mixed solution to be neutral by ammonia water, heating to 78 ℃ at the speed of 8 ℃/min, and stirring until wet gel is formed;

2.2) drying the wet gel obtained in the step 2.1) in a forced air drying oven at 110 ℃ for 3h, taking out and igniting the wet gel to obtain a gray brown powder, grinding the powder for 1h, heating to 960 ℃ and roasting for 2.5h to obtain the finished product;

3) preparing radiation protection fiber based on nano material:

mixing the activated carbon resin loaded with nano zinc oxide, yttrium-doped zinc ferrite and polyethylene glycol terephthalate slices, and then carrying out melt spinning to obtain the radiation-proof fiber based on the nano material; the melt spinning process conditions are as follows: the spinning temperature is 290 ℃, the spinning speed is 1200m/min, the blowing temperature is 25 ℃, the relative humidity of air supply is 75 percent, and the air speed is 0.5 m/s.

Example 2: another radiation protection fiber based on nano materials:

this example provides another radiation protective fiber based on nano material, the components, the proportion and the preparation method of the radiation protective fiber are basically the same as those of example 1, except that in this example, the components of the radiation protective fiber are not added with the activated carbon resin loaded with nano zinc oxide, and the deficiency is complemented by polyester chips.

Example 3: another radiation protection fiber based on nano materials:

this example provides another radiation protective fiber based on nano material, the composition, ratio and preparation method of the radiation protective fiber are basically the same as example 1, except that in this example, the activated carbon resin is not loaded with any nano zinc oxide or zinc oxide, i.e. the activated carbon resin is melt-spun with yttrium doped zinc ferrite and polyester chips.

Example 4: another radiation protection fiber based on nano materials:

this example provides another radiation protective fiber based on nano material, the components, the ratio and the preparation method of the radiation protective fiber are basically the same as those of example 1, except that in this example, activated carbon resin loaded with nano zinc oxide is prepared by using commercially available activated carbon powder instead of coffee carbon activated carbon, the commercially available activated carbon powder is prepared from coconut shell, fruit shell, wood chips and anthracite, the particle size is 200 meshes, and the water content is 10%.

Example 5: another radiation protection fiber based on nano materials:

this example provides another radiation protective fiber based on nano-materials, which has basically the same components, formulation and preparation method as example 1, except that in this example, the nano-titanium dioxide is not added in the preparation of the modified coffee carbon activated carbon.

Example 6: another radiation protection fiber based on nano materials:

this example provides another radiation protective fiber based on nanomaterials, which has substantially the same composition, formulation and preparation method as example 1, except that in this example, modified coffee carbon activated carbon was prepared without the addition of anions.

Example 7: another radiation protection fiber based on nano materials:

this example provides another radiation protective fiber based on nanomaterials, which has substantially the same composition, formulation and preparation method as example 1, except that in this example, the activated carbon has not reacted with the pyrrole monomer solution when preparing the modified coffee carbon activated carbon.

Example 8: another radiation protection fiber based on nano materials:

this example provides another radiation protective fiber based on nano material, the composition, ratio and preparation method of the radiation protective fiber are basically the same as those of example 1, except that in this example, ordinary zinc oxide is used to replace nano zinc oxide.

Example 9: another radiation protection fiber based on nano materials:

this example provides another radiation protective fiber based on nano material, the composition, ratio and preparation method of the radiation protective fiber are substantially the same as those of example 1, except that in this example, gelatin is used to replace dihydromyricetin when preparing nano zinc oxide.

Example 10: another radiation protection fiber based on nano materials:

this example provides another radiation protective fiber based on nano material, the composition, ratio and preparation method of the radiation protective fiber are substantially the same as those of example 1, except that in this example, yttrium nitrate is not added when yttrium-doped zinc ferrite is prepared.

Example 11: another radiation protection fiber based on nano materials:

this example provides another radiation protective fiber based on nano material, the composition, ratio and preparation method of the radiation protective fiber are substantially the same as those of example 1, except that in this example, citric acid is used to replace malic acid when yttrium doped zinc ferrite is prepared.

Example 12: another radiation protection fiber based on nano materials:

this example provides another radiation-proof fiber based on nano-materials, the components, the ratio and the preparation method of the radiation-proof fiber are substantially the same as those of example 1, except that in this example, yttrium-doped zinc ferrite is not added to the components of the radiation-proof fiber, and the deficiency is made up of polyester chips

Example 13: another radiation protection fiber based on nano materials:

this example provides another radiation protective fiber based on nano material, the composition, ratio and preparation method of the radiation protective fiber are substantially the same as those of example 1, except that in this example, the weight ratio of nano zinc oxide to yttrium-doped zinc ferrite is 1:50, which can be specifically realized by adjusting the weight content of nano zinc oxide to 0.08% when preparing the activated carbon resin loaded with nano zinc oxide.

Example 14: another radiation protection fiber based on nano materials:

this example provides another radiation protective fiber based on nano material, the composition, ratio and preparation method of the radiation protective fiber are substantially the same as those of example 1, except that in this example, the weight ratio of nano zinc oxide to yttrium-doped zinc ferrite is 1:30, which can be specifically realized by adjusting the weight content of nano zinc oxide to 0.13% when preparing the activated carbon resin loaded with nano zinc oxide.

Example 15: another radiation protection fiber based on nano materials:

this example provides another radiation protective fiber based on nano material, the composition, ratio and preparation method of the radiation protective fiber are substantially the same as those of example 1, except that in this example, the weight ratio of nano zinc oxide to yttrium-doped zinc ferrite is 1:20, which can be specifically realized by adjusting the weight content of nano zinc oxide to 0.2% when preparing the activated carbon resin loaded with nano zinc oxide.

Experimental example 1: bacteriostasis:

the composite polyester fiber fabric is obtained by knitting the fibers in the embodiments 1-15, and the bacteriostatic action of the composite fibers in the embodiments 1-15 is detected by a vibration bottle method according to the evaluation part 3 of GB/T20944.3-2008 fabric antibacterial performance, and the statistical result is shown in Table 1.

TABLE 1 bacteriostatic action

As can be seen from table 1, the radiation protection fiber based on the nanomaterial in the preferred embodiment 1 of the present application has an inhibition rate of more than 98% against influenza virus, adenovirus, staphylococcus, escherichia coli, mold, candida albicans, and the like, and it can be seen that the inhibition rate of the radiation protection fiber against the above viruses and germs is significantly reduced after the active carbon resin component loaded with nano zinc oxide is changed.

Experimental example 2: radiation protection detection:

the fabric in the experimental example 1 is respectively made into ready-made clothes, the ultraviolet resistance performance of the ready-made clothes is detected by referring to the evaluation of ultraviolet resistance performance of textile products of GB/T18830 + 2009, the electromagnetic shielding performance of the ready-made clothes is detected by referring to the evaluation of ultraviolet resistance performance of textile products of GB/T22583-2009, and the detection results are shown in Table 2.

TABLE 2 radiation protection

As can be seen from table 2, the radiation protection fiber in preferred embodiment 1 of the present application has a protection coefficient of over 1000 against ultraviolet rays, and the ultraviolet transmittance can be maintained at about 0.5%, and it has a shielding effectiveness of over 50dB against 5.2GHz electromagnetic waves, and has excellent characteristics of preventing ultraviolet rays from transmitting and electromagnetic shielding effectiveness, and it can also be seen that, when any one of the activated carbon resin or yttrium-doped zinc ferrite which lacks nano zinc oxide loading affects the radiation protection performance of the radiation protection fiber, especially, the weight ratio of the nano zinc oxide to the ferrite is adjusted to reduce the ultraviolet protection capability and the electromagnetic shielding effectiveness, and it can also be seen that the yttrium-doped ferrite has an obvious positive effect of improving the radiation protection performance of the fiber.

Experimental example 3: detecting the radiation protection and washing resistance:

the ready-made clothes prepared based on the radiation-proof fibers of the examples in experimental example 2 were washed, and the radiation-proof data after 100 times of washing were respectively detected, and the statistical results are shown in table 3.

TABLE 3 radiation protection

First, as can be seen from table 3, the radiation protection performance in the preferred embodiment 1 of the present application is still excellent after 50 times or even 100 times of water washing, and it can be seen that, in the case of not adding or preparing the activated carbon resin loaded with nano zinc oxide according to the present application and not preparing yttrium-doped zinc ferrite according to the present application, the radiation protection and washing resistance of the obtained fiber are greatly reduced, and the blocking effect on ultraviolet rays and the shielding effect on electromagnetic radiation are both significantly reduced.

Experimental example 4: and (3) detecting the anti-light aging performance:

the fabric strength retention rate of the fabric in the experimental example 1 was measured by 120h light accelerated aging test, and the statistical results are shown in fig. 2. As can be seen from fig. 2, after 120h of light-irradiation accelerated aging, the radiation-proof fiber in the preferred embodiment 1 of the present application has excellent breaking strength retention rate, and the comparison shows that ferrite prepared without yttrium doping or citric acid instead of malic acid, and zinc ferrite without yttrium doping, etc. all cause significant damage to the light-irradiation aging resistance of the fiber.

Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.

In view of the numerous embodiments of the present invention, the experimental data of each embodiment is huge and is not suitable for being listed and explained herein one by one, but the contents to be verified and the final conclusions obtained by each embodiment are close. Therefore, the contents of the verification of the respective examples are not described herein, and the excellent points of the present invention will be described only by representative examples 1 to 15 and experimental examples 1 to 4.

The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

While the above detailed description has shown, described, and pointed out novel features as applied to various embodiments, it will be understood that various omissions, substitutions, and changes in the form and details of the device or method illustrated may be made without departing from the spirit of the disclosure. In addition, the various features and methods described above may be used independently of one another, or may be combined in various ways. All possible combinations and sub-combinations are intended to fall within the scope of the present disclosure. Many of the embodiments described above include similar components, and thus, these similar components are interchangeable in different embodiments. While the invention has been disclosed in the context of certain embodiments and examples, it will be understood by those skilled in the art that the invention extends beyond the specifically disclosed embodiments to other alternative embodiments and/or uses and obvious modifications and equivalents thereof. Accordingly, the invention is not intended to be limited by the specific disclosure of preferred embodiments herein.

Claims

1. A radiation protection fiber based on nanometer materials is characterized in that the radiation protection cellulose comprises the following components in percentage by weight:

3.5-48.5% of activated carbon resin loaded with nano zinc oxide;

0.1-1.5% of yttrium-doped zinc ferrite;

the rest of polyester chips;

2. The radiation protective fiber of claim 1 wherein: the activated carbon resin loaded with the nano zinc oxide is obtained by blending and granulating the activated carbon loaded with the nano zinc oxide and the resin.

3. The radiation protective fiber of claim 1 or 2, wherein: the preparation method of the activated carbon resin loaded with the nano zinc oxide specifically comprises the following steps:

1) uniformly mixing coffee grounds, nano titanium dioxide and silver ions, adding a silane coupling agent with the total solid content of 1.5-2.0 wt%, fully grinding for at least 30min, placing in a vacuum furnace with the vacuum degree of at least 0.02MPa, heating to 430-445 ℃ in the vacuum furnace, preserving heat for at least 30min, and naturally cooling to room temperature to obtain modified coffee carbon activated carbon;

4. The radiation protective fiber of claim 3 wherein: the weight ratio of the coffee grounds to the nano titanium dioxide and silver ions is 1000: 3-10: 0.5-0.8.

5. The radiation protective fiber of claim 3 or 4, wherein: the weight ratio of the activated carbon to the pyrrole monomer is 1: 1.7-1.9.

6. The radiation protective fiber according to any one of claims 1 to 5, characterized in that: in the activated carbon resin loaded with the nano zinc oxide, the weight content of the activated carbon is 6.5-10.0%, and the weight content of the nano zinc oxide is 0.15-0.30%.

7. The radiation protective fiber according to any one of claims 1 to 6, characterized in that: the nano zinc oxide is prepared by the following method: according to the mass ratio of 2-2.5: 1, dihydromyricetin and ZnSO are added₄·7H₂Dissolving O in sufficient deionized water, adjusting the pH of the mixed solution to 6.5-6.8 by using 0.05-0.08 mol/L sodium hydroxide solution, stirring for at least 1h at 120-180 r/min, calcining the reaction solution for at least 2h at the temperature of 380-395 ℃, cooling to room temperature, alternately washing for at least 3 times by using deionized water and absolute ethyl alcohol respectively, and drying to obtain the catalyst。

8. The radiation protective fiber according to any one of claims 1 to 7, wherein: the yttrium-doped zinc ferrite is prepared by a method comprising the following steps:

2) and (2) drying the wet gel in a forced air drying oven at 110 ℃ for at least 3h, taking out, igniting the wet gel to obtain a gray brown powder, grinding the powder for at least 1h, heating to 955-980 ℃, and roasting for at least 2.5h to obtain the yttrium-doped zinc ferrite.

9. The preparation method of the radiation-proof fiber based on the nano material as claimed in any one of claims 1 to 8, which is characterized in that the radiation-proof fiber based on the nano material is obtained by mixing the activated carbon resin loaded with nano zinc oxide, yttrium-doped zinc ferrite and polyester chips and then carrying out melt spinning.

10. Use of the radiation protective fiber of any of claims 1 to 9, characterized in that said use comprises:

1) the pregnant woman is dressed; and/or

2) Infant children's garments; and/or

3) A smelting site; and/or

4) A fire-fighting clothing lining; and/or

5) Outdoor protective clothing.