CN117188143A - Preparation method of antiviral and antiallergic acrylonitrile polymer fabric - Google Patents
Preparation method of antiviral and antiallergic acrylonitrile polymer fabric Download PDFInfo
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- CN117188143A CN117188143A CN202311218754.XA CN202311218754A CN117188143A CN 117188143 A CN117188143 A CN 117188143A CN 202311218754 A CN202311218754 A CN 202311218754A CN 117188143 A CN117188143 A CN 117188143A
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- antiallergic
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- 239000004744 fabric Substances 0.000 title claims abstract description 59
- 230000000840 anti-viral effect Effects 0.000 title claims abstract description 55
- 230000003266 anti-allergic effect Effects 0.000 title claims abstract description 43
- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 claims abstract description 29
- 239000010949 copper Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 24
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 24
- 239000000835 fiber Substances 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 12
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 11
- 239000002585 base Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 29
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 36
- 238000001035 drying Methods 0.000 description 26
- 238000001914 filtration Methods 0.000 description 26
- 230000007935 neutral effect Effects 0.000 description 26
- 238000005406 washing Methods 0.000 description 26
- 229920002972 Acrylic fiber Polymers 0.000 description 23
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 22
- 229910000365 copper sulfate Inorganic materials 0.000 description 21
- 239000013067 intermediate product Substances 0.000 description 18
- 239000013566 allergen Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 14
- 239000002775 capsule Substances 0.000 description 13
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Chemical compound Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 10
- 241000700605 Viruses Species 0.000 description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 8
- 229910052794 bromium Inorganic materials 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 238000007654 immersion Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 239000003094 microcapsule Substances 0.000 description 8
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- 229920000858 Cyclodextrin Polymers 0.000 description 2
- 239000001116 FEMA 4028 Substances 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000002155 anti-virotic effect Effects 0.000 description 2
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 2
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 2
- 229960004853 betadex Drugs 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229940099898 chlorophyllin Drugs 0.000 description 2
- 235000019805 chlorophyllin Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical class NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 2
- 238000011081 inoculation Methods 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000004627 regenerated cellulose Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000011053 TCID50 method Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- JHYFCXGDBIHJER-UHFFFAOYSA-L disodium bromide hydroxide Chemical compound [OH-].[Na+].[Na+].[Br-] JHYFCXGDBIHJER-UHFFFAOYSA-L 0.000 description 1
- BJVWCKXHSNBHGB-UHFFFAOYSA-L disodium;chloride;hydroxide Chemical compound [OH-].[Na+].[Na+].[Cl-] BJVWCKXHSNBHGB-UHFFFAOYSA-L 0.000 description 1
- XGZRAKBCYZIBKP-UHFFFAOYSA-L disodium;dihydroxide Chemical compound [OH-].[OH-].[Na+].[Na+] XGZRAKBCYZIBKP-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- AWOORJZBKBDNCP-UHFFFAOYSA-N molybdenum;oxotungsten Chemical compound [Mo].[W]=O AWOORJZBKBDNCP-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000013641 positive control Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- ORQYPOUSZINNCB-UHFFFAOYSA-N potassium;hypobromite Chemical compound [K+].Br[O-] ORQYPOUSZINNCB-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
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- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention relates to a preparation method of an antiviral and antiallergic acrylonitrile polymer fabric, which mainly solves the problems of complex process, high operation cost, poor antiviral and antiallergic performances and the like in the prior art for preparing the antiviral and antiallergic acrylonitrile polymer fabric, and comprises the following steps: the technical scheme that the acrylonitrile polymer raw material fabric is treated by the cross-linking agent and the strong alkaline water solution and then is immersed in the bivalent copper solution better solves the technical problems and can be used in the production of the antiviral and antiallergic acrylonitrile polymer fabric.
Description
Technical Field
The invention relates to a preparation method of an antiviral and antiallergic acrylonitrile polymer fabric and application of the antiviral and antiallergic acrylonitrile polymer fabric obtained by the method in the antiviral and antiallergic fabric.
Background
With the improvement of the life quality of people, the demand of polyacrylonitrile fabrics for resisting virus and allergen is on the rise, and therefore, the polyacrylonitrile fabrics are also the research and development hot spot in the field.
CN113718519a discloses that the fabric is finished with a molybdenum and/or tungsten-containing compound or a finishing agent which is a tungsten-molybdenum-oxygen salt to obtain an antiviral fabric, the antiviral activity rate is greater than 99%, but the molybdenum element and tungsten element in the adopted finishing agent are expensive, and the efficacy of whether the finished fabric is allergen-resistant is not mentioned.
CN 112176451A discloses an antibacterial and antiviral regenerated cellulose fiber and a preparation method thereof. The antibacterial and antiviral regenerated cellulose fiber comprises viscose fiber, single-layer capsule wall composite microcapsule and double-layer capsule wall composite microcapsule; the capsule cores in the single-layer capsule wall composite microcapsule and the double-layer capsule wall composite microcapsule independently comprise plant antibacterial and antiviral extracts and vitamins; the capsule wall component of the single-layer capsule wall composite microcapsule comprises beta-cyclodextrin, the capsule wall of the double-layer capsule wall composite microcapsule comprises an inner layer capsule wall and an outer layer capsule wall, the component of the inner layer capsule wall comprises beta-cyclodextrin, and the component of the outer layer capsule wall comprises porous starch; the wall of the single-layer wall composite microcapsule is grafted and crosslinked with the bonding fiber, and the wall of the double-layer wall composite microcapsule is grafted and crosslinked with the viscose fiber. However, this technique is too complex and costly.
CN 105377031A reports that adding copper-containing compounds to fiber-forming resins, such as polyesters, melt-spinning to obtain copper-containing fibers and further processing to obtain other forms of fabrics, gives products having antimicrobial and antiviral activity, but polyacrylonitrile polymer fibers cannot be prepared by this method to obtain copper-containing polyacrylonitrile fibers (also called acrylons) because the acrylonitrile polymer is decomposed in the molten state.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the technology of the anti-virus and anti-allergic polyacrylonitrile fabric in the prior art is complex, the operation cost is high, the anti-virus and anti-allergic performances are poor, and the like.
In order to solve one of the technical problems, the technical scheme of the invention is as follows:
a method for preparing an antiviral antiallergic acrylonitrile polymer fabric, comprising:
(1) The acrylonitrile polymer raw material fabric is treated by an intermolecular cross-linking agent solution to obtain an intermediate cross-linked fabric 1;
(2) The intermediate crosslinked fabric is treated by an aqueous solution containing strong alkali to obtain an intermediate fabric 2;
(3) The intermediate fabric 2 is impregnated with a cupric solution.
The method has simple process and low operation cost, and the obtained product has good antiviral and antiallergic properties. The use of the intermolecular crosslinking agent in the step (1) can improve the mechanical properties of the antiviral and antiallergic fabrics and also can improve the antiviral and antiallergic properties. And (2) the treatment of the strong alkaline aqueous solution improves the antiviral and antiallergic properties of the fabric.
In the case of treatment with both a crosslinking agent and a strong base, the above-mentioned crosslinking agent treatment-treatment with a strong base aqueous solution-impregnation of cupric salt gives a product which is significantly higher in antiviral, especially antiallergic, than the treatment with a strong base aqueous solution-treatment with a crosslinking agent hydrazine hydrate-impregnation of cupric salt, and also significantly higher than the treatment with a strong base mixture-impregnation of cupric salt.
For the product obtained according to the method, the person skilled in the art can further process further as desired, for example the product in the form of fibres can also be oiled, spun into yarns, further woven into cloths, etc. If the product obtained by the method of the invention is in the form of cloth, the fabric can be further processed into various products such as clothes, insoles, socks, gloves, bedclothes and the like.
In the above technical solution, the fabric may be a fiber, yarn or cloth. Those skilled in the art will recognize that the chemical mechanism of the acrylonitrile polymer raw fabric, whether fibers, yarns or cloth, is the same as that of the product obtained by performing the steps of the present invention, except that the raw fabric is in the form of the same product obtained by performing the steps of the present invention, and that the raw fabric is in the form of fibers only by taking the acrylonitrile polymer fibers (also called acrylic fibers) as examples and comparative examples in the specific embodiments of the present invention.
Of course, those skilled in the art will recognize that although the embodiments of the present invention are illustrated in the form of fibers, the resulting products are also in the form of fibers, the products in the form of fibers of the present invention may be further spun into yarns, and may be further woven into cloth.
In the above-mentioned embodiments, the crosslinking agent preferably has 2 or more amino groups in the molecule, and the amino groups are primary amino groups or secondary amino groups. For example, but not limited to, hydrazine and compositions may be represented as H 2 N-(-CH 2 CH 2 NH-) n Vinylamine compounds of-H, wherein n is, for example, but not limited to, 1 to 10. As non-limiting examples of vinylamine compounds, there are exemplified, but not limited to, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethylene polyamines, and the like.
In the above technical scheme, preferably, the strong base in the strong alkali-containing aqueous solution in the step (2) is alkali metal hydroxide.
In the above technical solution, preferably, the crosslinking agent is hydrazine hydrate.
In the above technical scheme, the concentration of hydrazine hydrate in the hydrazine hydrate solution is preferably 10-85% by weight in the step (1), for example, but not limited to, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% and the like. In the specific embodiment of the invention, the hydrazine hydrate aqueous solution with the weight concentration of 15% is adopted by the same ratio.
In the above technical solution, the preferred steps are as follows(1) The hydrazine hydrate solution is prepared by hydrazine hydrate (N) 2 H 4 ·H 2 O) to the raw fabric is 0.1 to 10, for example, but not limited to, 0.2, 0.3, 0.4, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, etc., more preferably 0.4 to 4, most preferably 0.5 to 3.
In the above technical scheme, the treatment temperature of the hydrazine hydrate solution in the step (1) is preferably 50-150 ℃. For example, but not limited to, step (1) treatment with hydrazine hydrate solution at a temperature of 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃,80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, and the like. More preferably 60 to 130 ℃. By way of comparison only, the embodiments of the present invention generally employ 80 ℃.
In the above technical scheme, the treatment time of the step (1) with the hydrazine hydrate solution is preferably 0.5-10 hours. For example, but not limited to, step (1) is treated with the hydrazine hydrate solution for 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, etc.
In the above technical scheme, the concentration of the alkali metal hydroxide solution in the strong alkali aqueous solution is preferably 1-50% by weight in the step (2). Such as, but not limited to, alkali metal hydroxide concentrations of 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 35%, 40%, 45%, etc.
In the above technical scheme, preferably, the alkali metal hydroxide in the step (2) is potassium hydroxide or sodium hydroxide.
In the above-described embodiment, the intermediate product 1 of step (2) is preferably calculated as the starting material web required for preparing it in step (1), and the alkali metal hydroxide is preferably calculated as sodium hydroxide providing an equivalent amount of hydroxide, the weight ratio of the alkali metal hydroxide of step (2) to the intermediate product 1 being from 0.1 to 4. Such as, but not limited to, the weight ratio of step (2) alkali metal hydroxide to intermediate 1 is 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, etc., more preferably 0.2 to 3.
In the technical scheme, the treatment temperature of the step (2) is preferably 50-150 ℃. Such as, but not limited to, step (2) processing temperatures of 55 ℃, 60 ℃, 65, 70 ℃, 75 ℃,80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, and the like. Only in the same way, 80 ℃ is generally adopted in the specific embodiment.
In the above technical scheme, the treatment time in the step (2) is preferably 0.5 to 5 hours. Such as, but not limited to, step (2) treatment time of 1 hour, 1.5 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, etc.
In the above-mentioned embodiment, it is preferable that the alkali aqueous alkali solution containing a strong alkali in the step (2) contains a bromine-containing compound in addition to the strong alkali. In the step (2), no strong alkali is adopted, only the bromine-containing compound has no obvious influence on the antiviral and antiallergic properties of the fabric, but when the step (2) is adopted to treat the fabric by adopting the aqueous solution containing the strong alkali and the bromine-containing compound, the bromine-containing compound has promotion effect on the strong alkali in terms of improving the antiviral and antiallergic properties of the fabric. To exert this promoting effect, the weight ratio of the strong base to the bromine-containing compound is not particularly limited, but by way of non-limiting example only, the weight ratio of the strong base to the bromine-containing compound is 0.1 to 10, more particularly, the weight ratio is 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, and the like.
In the above technical solution, preferably, the bromine-containing compound is bromide or hypobromite. The bromide is preferably sodium bromide or potassium bromide. The hypobromite is preferably sodium hypobromite or potassium hypobromite.
In the above technical scheme, preferably, the weight ratio of the cupric salt in the step (3) to the intermediate fabric 2 is independently 0.001-0.1 based on the raw fabric required for preparing the intermediate fabric in the step (1) in the step (3). Such as, but not limited to, a step (3) cupric solution to middle fabric 1 weight ratio and a step (3) cupric to middle fabric 2 weight ratio of 0.002, 0.003, 0.004, 0.005, 0.008, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, etc.
In the above technical scheme, the copper-containing weight concentration of the cupric solution in the step (3) is preferably 0.1-10%. For example, but not limited to, the copper-containing weight concentration of the cupric solution of step (3) is 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.5%, 3%, 3.5%, 4%, 5%, 6%, 7%, 8%, 9%, etc. Merely by way of comparison, the copper-containing concentration of the cupric solution in the specific embodiment is 0.5% by weight.
The solvent in the cupric solution is preferably water.
The source of the cupric ions in the cupric ion solution of step (3) is not particularly limited as long as it is a cupric ion compound such as, but not limited to, cupric nitrate, cupric sulfate, cupric chloride, cupric acetate, cupric sodium chlorophyllin, cupric potassium chlorophyllin, etc., which is dissolved in an aqueous medium. Copper sulfate is commonly used in the examples and comparative examples, which are merely comparable.
In the above technical scheme, the dipping temperature in the step (3) is preferably 40-120 ℃. Such as, but not limited to, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃,80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, and the like. If more than 50 and less than 100℃are suitable in order to avoid easy evaporation of water and operation under pressure. Only in the same way, 80 ℃ is generally adopted in the specific embodiment.
In the above technical scheme, the dipping time in the step (3) is preferably 0.2 to 5 hours. For example, but not limited to, step (3) dipping times are 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, 60 minutes, 65 minutes, 70 minutes, 75 minutes, 80 minutes, 85 minutes, 90 minutes, 95 minutes, 100 minutes, 110 minutes, 120 minutes, 130 minutes, 140 minutes, 150 minutes, 160 minutes, 170 minutes, 180 minutes, 200 minutes, 220 minutes, 240 minutes, 260 minutes, 280 minutes, and the like. More preferably 15 to 120 minutes.
In the above technical solution, it is more preferable that the bromine-containing compound in the step (2) includes both bromide and hypobromite, and the bromide and hypobromite have synergistic effect in enhancing the antiviral and antiallergic properties of the fabric. To provide this synergistic effect, the weight ratio of bromide to hypobromite is not particularly limited, for example, but not limited to, 0.1 to 10, more particularly, but not limited to, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, and the like. More preferably 0.2 to 2.
The second technical problem to be solved by the present invention is to provide a product obtained by the preparation method according to any one of the technical solutions of the above technical problems.
In order to solve the second technical problem, the technical scheme of the invention is as follows:
a product obtainable by the process according to any one of the above technical solutions.
The invention provides an application of a product in antiviral and/or antiallergic fabrics.
In order to solve the third technical problem, the technical scheme of the invention is as follows:
use of a product as described in the second of the above technical problems or a product obtained by a preparation method according to any one of the above technical problems in an antiviral and/or antiallergic fabric.
The antiviral properties of the fibers were evaluated using ISO 18184-2019. The sample form is short fiber with the diameter of 1.5D being 38mm, and the sampling amount is 0.40 g+/-0.05 g;
raw material acrylic fiber without antiviral and antiallergic treatment is used as a control sample, fiber with antiviral and antiallergic treatment is used as a test sample, test virus is H1N1 (ATCC VR 1469), virus counting is carried out by adopting a TCID50 method, and the antiviral activity rate is calculated according to the following formula:
R virus (virus) (％)＝((B-C)/B)×100％
In the formula (i),
R virus (virus) (%) is the antiviral activity rate (%);
b is the average titer value recovered after 2 hours of inoculation of 3 control samples, and the unit is TCID 50/bottle;
c is the average titer recovered 2 hours after inoculation of 3 antiviral samples in TCID 50/bottle.
R Virus (virus) Higher indicates better antiviral performance.
The antiallergic performance of the fibers was carried out according to the test method described in the standard annex D of the light industry Standard QB/T5365-2019 for air purifier, but the sample in the test was not a round coupon with a diameter of 50mm, but a short fiber with a 1.5 D.38 mm diameter was used, and the sampling amount of the short fiber was 0.4 g.+ -. 0.05 g. According to the standard, the anti-allergen ratio R Allergen and method for producing the same Is defined by the following formula:
R allergen and method for producing the same ＝(1-C B /C A )×100％
In the method, in the process of the invention,
R allergen and method for producing the same Is an anti-allergen ratio;
C B residual allergen concentration in nanograms per milliliter for the test group;
C A residual allergen concentration in nanograms per milliliter was used as a positive control.
R Allergen and method for producing the same The higher the antiallergic performance is, the better the antiallergic performance is.
The present invention will be described in detail with reference to the following specific embodiments.
Detailed Description
The raw material acrylic fiber adopted in the specific embodiment mode is acrylic short fiber with the diameter of 1.5 D.times.38 mm.
[ example 1 ]
1 part by weight of raw acrylic fiber was impregnated with 10 parts by weight of an aqueous copper sulfate solution (the weight concentration of copper in the aqueous copper sulfate solution is 0.5% in terms of copper) for 1 hour at 80 ℃. And then washing with water until the eluate is neutral, filtering, and drying at 80 ℃ to obtain an antiviral and antiallergic acrylic fiber product.
The antiviral activity rate of the product is 24.54% and the anti-allergen rate is 23.24% through test.
[ example 2 ]
1 part by weight of raw material acrylic fiber is immersed for 1 hour by 10 parts by weight of hydrazine hydrate aqueous solution with the weight concentration of 15 percent, and the immersion temperature is 80 ℃. Then, washing with water until the eluate is neutral, filtering, and drying at 80 ℃ to obtain an intermediate product 1.
Intermediate 1 was impregnated with 10 parts by weight of an aqueous copper sulfate solution (the weight concentration of copper in the aqueous copper sulfate solution was 0.5% based on copper) for 1 hour at 80 ℃. And then washing with water until the eluate is neutral, filtering, and drying at 80 ℃ to obtain an antiviral and antiallergic acrylic fiber product.
The antiviral activity rate of the product is 43.10% and the allergen rate is 40.81% through test.
[ example 3 ]
1 part by weight of raw material acrylic fiber is immersed in 10 parts by weight of 15% sodium hydroxide aqueous solution for 1 hour at 80 ℃. Then, washing with water until the eluate is neutral, filtering, and drying at 80 ℃ to obtain an intermediate product 1.
Intermediate 1 was impregnated with 10 parts by weight of an aqueous copper sulfate solution (the weight concentration of copper in the aqueous copper sulfate solution was 0.5% based on copper) for 1 hour at 80 ℃. And then washing with water until the eluate is neutral, filtering, and drying at 80 ℃ to obtain an antiviral and antiallergic acrylic fiber product.
The test shows that the product has antiviral activity rate of 55.96% and antiallergic rate of 54.66%.
[ example 4 ]
1 part by weight of raw material acrylic fiber is immersed for 1 hour by 10 parts by weight of hydrazine hydrate aqueous solution with the weight concentration of 15 percent, and the immersion temperature is 80 ℃. Then, washing with water until the eluate is neutral, filtering, and drying at 80 ℃ to obtain an intermediate product 1.
Intermediate 1 was impregnated with 10 parts by weight of 15% strength by weight aqueous sodium hydroxide solution for 1 hour at 80 ℃. Then, washing with water until the eluate is neutral, filtering, and drying at 80 ℃ to obtain an intermediate product 2.
Intermediate 2 was impregnated with 10 parts by weight of an aqueous copper sulfate solution (the weight concentration of copper in the aqueous copper sulfate solution was 0.5% based on copper) for 1 hour at 80 ℃. And then washing with water until the eluate is neutral, filtering, and drying at 80 ℃ to obtain an antiviral and antiallergic acrylic fiber product.
The antiviral activity rate of the product is 72.48% and the anti-allergen rate is 67.29% through testing.
[ example 5 ]
1 part by weight of raw material acrylic fiber is immersed for 1 hour by 10 parts by weight of hydrazine hydrate aqueous solution with the weight concentration of 15 percent, and the immersion temperature is 80 ℃. Then, washing with water until the eluate is neutral, filtering, and drying at 80 ℃ to obtain an intermediate product 1.
Intermediate 1 was immersed in 10 parts by weight of an aqueous sodium hydroxide-sodium bromide solution (wherein the sodium hydroxide concentration by weight was 5% and the sodium bromide concentration by weight was 10%) for 1 hour at 80 ℃. Then, washing with water until the eluate is neutral, filtering, and drying at 80 ℃ to obtain an intermediate product 2.
Intermediate 2 was impregnated with 10 parts by weight of an aqueous copper sulfate solution (the weight concentration of copper in the aqueous copper sulfate solution was 0.5% based on copper) for 1 hour at 80 ℃. And then washing with water until the eluate is neutral, filtering, and drying at 80 ℃ to obtain an antiviral and antiallergic acrylic fiber product.
The antiviral activity rate of the product is 79.85% and the anti-allergen rate is 72.74% through testing.
[ example 6 ]
1 part by weight of raw material acrylic fiber is immersed for 1 hour by 10 parts by weight of hydrazine hydrate aqueous solution with the weight concentration of 15 percent, and the immersion temperature is 80 ℃. Then, washing with water until the eluate is neutral, filtering, and drying at 80 ℃ to obtain an intermediate product 1.
Intermediate 1 was immersed in 10 parts by weight of an aqueous sodium hydroxide-sodium chloride solution (wherein the sodium hydroxide concentration by weight was 5% and the sodium chloride concentration by weight was 10%) for 1 hour at 80 ℃. Then, washing with water until the eluate is neutral, filtering, and drying at 80 ℃ to obtain an intermediate product 2.
Intermediate 2 was impregnated with 10 parts by weight of an aqueous copper sulfate solution (the weight concentration of copper in the aqueous copper sulfate solution was 0.5% based on copper) for 1 hour at 80 ℃. And then washing with water until the eluate is neutral, filtering, and drying at 80 ℃ to obtain an antiviral and antiallergic acrylic fiber product.
The antiviral activity rate of the product is 67.63% and the anti-allergen rate is 61.23% through testing.
[ example 7 ]
1 part by weight of raw material acrylic fiber is immersed for 1 hour by 10 parts by weight of hydrazine hydrate aqueous solution with the weight concentration of 15 percent, and the immersion temperature is 80 ℃. Then, washing with water until the eluate is neutral, filtering, and drying at 80 ℃ to obtain an intermediate product 1.
Intermediate 1 was impregnated with 10 parts by weight of an aqueous sodium bromide solution (wherein the sodium bromide concentration by weight was 15%) for 1 hour at 80 ℃. Then, washing with water until the eluate is neutral, filtering, and drying at 80 ℃ to obtain an intermediate product 2.
Intermediate 2 was impregnated with 10 parts by weight of an aqueous copper sulfate solution (the weight concentration of copper in the aqueous copper sulfate solution was 0.5% based on copper) for 1 hour at 80 ℃. And then washing with water until the eluate is neutral, filtering, and drying at 80 ℃ to obtain an antiviral and antiallergic acrylic fiber product.
The test shows that the product has antiviral activity rate of 41.39% and antiallergic rate of 39.23%.
[ example 8 ]
The only difference from example 5 is that sodium bromide is replaced by equal weights of sodium hypobromite, in particular:
1 part by weight of raw material acrylic fiber is immersed for 1 hour by 10 parts by weight of hydrazine hydrate aqueous solution with the weight concentration of 15 percent, and the immersion temperature is 80 ℃. Then, washing with water until the eluate is neutral, filtering, and drying at 80 ℃ to obtain an intermediate product 1.
Intermediate 1 was immersed in 10 parts by weight of an aqueous sodium hydroxide-sodium hypobromide solution (wherein the sodium hydroxide concentration by weight was 5% and the sodium hypobromide concentration by weight was 15%) for 1 hour at 80 ℃. Then, washing with water until the eluate is neutral, filtering, and drying at 80 ℃ to obtain an intermediate product 2.
Intermediate 2 was impregnated with 10 parts by weight of an aqueous copper sulfate solution (the weight concentration of copper in the aqueous copper sulfate solution was 0.5% based on copper) for 1 hour at 80 ℃. And then washing with water until the eluate is neutral, filtering, and drying at 80 ℃ to obtain an antiviral and antiallergic acrylic fiber product.
The antiviral activity rate of the product is 84.02% and the anti-allergen rate is 79.57% through test.
[ example 9 ]
1 part by weight of raw material acrylic fiber is immersed for 1 hour by 10 parts by weight of hydrazine hydrate aqueous solution with the weight concentration of 15 percent, and the immersion temperature is 80 ℃. Then, washing with water until the eluate is neutral, filtering, and drying at 80 ℃ to obtain an intermediate product 1.
Intermediate 1 was impregnated with 10 parts by weight of an aqueous sodium hypobromide solution (wherein the sodium hypobromide concentration by weight was 15%) for 1 hour at 80 ℃. Then, washing with water until the eluate is neutral, filtering, and drying at 80 ℃ to obtain an intermediate product 2.
Intermediate 2 was impregnated with 10 parts by weight of an aqueous copper sulfate solution (the weight concentration of copper in the aqueous copper sulfate solution was 0.5% based on copper) for 1 hour at 80 ℃. And then washing with water until the eluate is neutral, filtering, and drying at 80 ℃ to obtain an antiviral and antiallergic acrylic fiber product.
The test shows that the product has antiviral activity rate of 47.81% and antiallergic rate of 43.15%.
[ example 10 ]
1 part by weight of raw material acrylic fiber is immersed for 1 hour by 10 parts by weight of hydrazine hydrate aqueous solution with the weight concentration of 15 percent, and the immersion temperature is 80 ℃. Then, washing with water until the eluate is neutral, filtering, and drying at 80 ℃ to obtain an intermediate product 1.
Intermediate 1 was immersed in 10 parts by weight of an aqueous sodium hydroxide-sodium bromide-sodium hypobromide solution (wherein the sodium hydroxide concentration by weight was 5%, the sodium bromide concentration by weight was 6%, and the sodium hypobromide concentration by weight was 4%) for 1 hour at 80 ℃. Then, washing with water until the eluate is neutral, filtering, and drying at 80 ℃ to obtain an intermediate product 2.
Intermediate 2 was impregnated with 10 parts by weight of an aqueous copper sulfate solution (the weight concentration of copper in the aqueous copper sulfate solution was 0.5% based on copper) for 1 hour at 80 ℃. And then washing with water until the eluate is neutral, filtering, and drying at 80 ℃ to obtain an antiviral and antiallergic acrylic fiber product.
The test shows that the product has antiviral activity rate of 99.15% and antiallergic activity rate of 92.56%.
Claims (10)
1. A method for preparing an antiviral antiallergic acrylonitrile polymer fabric, comprising:
(1) The acrylonitrile polymer raw material fabric is treated by an intermolecular cross-linking agent solution to obtain an intermediate cross-linked fabric 1;
(2) The intermediate crosslinked fabric is treated by an aqueous solution containing strong alkali to obtain an intermediate fabric 2;
(3) The intermediate fabric 2 is impregnated with a cupric solution.
2. The method of claim 1, wherein the fabric is a fiber, yarn or cloth.
3. The method according to claim 1, wherein the crosslinking agent has at least 2 amino groups in the molecule, and the amino groups are primary amino groups or secondary amino groups.
4. The process according to claim 1, wherein the strong base in the aqueous alkali solution in step (2) is an alkali metal hydroxide.
5. The method of claim 3, wherein the cross-linking agent is hydrazine hydrate.
6. The process according to claim 5, wherein the concentration of hydrazine hydrate in the hydrazine hydrate solution is 10 to 85% by weight in step (1). And/or the weight ratio of the hydrazine hydrate solution to the raw fabric is 0.1 to 10, more preferably 0.4 to 4, in terms of n2h4.h2o. And/or the treatment temperature of step (1) with the hydrazine hydrate solution is 50 to 150 ℃, more preferably 70 to 130 ℃. And/or the treatment time with the hydrazine hydrate solution is 0.5 to 10 hours.
7. The process according to claim 4, wherein the alkali metal hydroxide concentration in the aqueous solution of step (2) is preferably 1 to 50% by weight. And/or preferably the alkali metal hydroxide of step (2) is potassium hydroxide or sodium hydroxide. And/or preferably the weight ratio of alkali metal hydroxide of step (2) to intermediate 1 is from 0.1 to 4, more preferably from 0.2 to 3, based on the weight of the starting fabric from which it is prepared in step (1). And/or preferably the treatment temperature in step (2) is 50 to 150 ℃. And/or preferably the treatment time in step (2) is from 0.5 to 5 hours.
8. The process according to claim 1, wherein the intermediate fabric 2 in the step (3) is prepared by the raw fabric required in the step (1) in a weight ratio of the divalent copper in the step (3) to the intermediate fabric 2 of 0.001 to 0.1. And/or preferably the cupric salt solution of step (3) contains copper in a concentration of 0.1 to 10% by weight. And/or preferably the impregnation temperature of step (3) is from 40 to 120 ℃, more preferably greater than 50 ℃ and less than 100 ℃. And/or preferably the impregnation time in step (3) is from 0.2 to 5 hours, more preferably from 15 to 120 minutes.
9. A product obtainable by the process according to any one of claims 1 to 8.
10. Use of a product according to claim 9 or obtained according to the method of preparation of any one of claims 1 to 8 in antiviral and/or antiallergic fabrics.
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