CN1272480C - Nano-antibacterial material, its preparation method and use - Google Patents
Nano-antibacterial material, its preparation method and use Download PDFInfo
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- CN1272480C CN1272480C CN 200510023301 CN200510023301A CN1272480C CN 1272480 C CN1272480 C CN 1272480C CN 200510023301 CN200510023301 CN 200510023301 CN 200510023301 A CN200510023301 A CN 200510023301A CN 1272480 C CN1272480 C CN 1272480C
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- biotic material
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Abstract
The present invention provides a nano antibiotic material and a preparation method and the application thereof. The nano antibiotic material is formed by two procedures of monomer insertion and in-situ polymerization of acrylonitrile, copolymerisable quaternaryammonium salt compounds, organized montmorillonite, sodium lauryl sulfate and potassium persulfate. The present invention also provides an antibiotic polyacrylonitrile fiber which is prepared by that a nano antibiotic material is added in acrylon fibers according to a weight ratio of 0.1 to 10%. The antibiotic material has the advantages of no toxic side effect and long antibacterial action and can be uniformly dispersed in the acrylon fibers, so the prepared acrylon fibers have wide market functions and can be used for processing underclothes, gym suits, socks, etc.
Description
Technical field
The present invention relates to a kind of nano anti-biotic material and its production and use, relate in particular to a kind of polymer nanocomposite anti-biotic material and preparation method thereof, and with the antibacterial acrylic fibre fiber of its preparation.
Background technology
The current bactericide that uses divides from the mechanism of action can be divided into oxidizing bactericide and non-oxidizable bactericide two big classes.Oxidizing bactericide mainly contains Cl
2, NaClO, potassium permanganate, Br
2, O
3, H
2O
2Deng; Non-oxidizable bactericide has presses (gathering) season such as salt, (gathering) quaternary alkylphosphonium salt, silver ion, titanium dioxide, phenols etc.Can be divided into mineral-type, small organic molecule and macromolecule bactericide etc. from the structure of bactericide.But generally there are the problem of excess residual in mineral-type and micromolecule inorganic matter bactericide, can cause the secondary pollution of water.
Compare with traditional low molecule bactericide, that the macromolecule bactericide has is non-volatile, chemically stable good, generally can not infiltrate advantages such as human or animal's skin, toxicity is little, thereby has good application prospects.Because fiber has very big specific area, be filled into easily in the various bactericidal units simultaneously and go, fiber product is one of most important kind of macromolecule sterilization material.Sterilization fibre can or adopt the method for surface graft modification to obtain by bactericide and polyblend spinning.
Be the technology for preparing anti-bacterial fibre in the graft modification mode in the prior art:
(1) United States Patent (USP) U.S.5561167 selects ion-exchange fibre (containing cation exchange group and anion exchange groups such as primary amine, secondary amine, tertiary amine and quaternary ammonium salt such as carboxyl or sulfonic group) for use; By ion-exchange reactions, make partial cation cation exchange groups (being less than 50%) connect antibacterial metal ions (as silver ion, copper ion, zinc ion etc.), make anti-bacterial fibre.Patent is also used it and activated carbon fiber with, makes water purifier, and has inquired into fiber alignment density (general 0.13g/cm
3) with the relation of water flow velocity, find that in a large amount of tests antibacterial metal ions will be subjected to the influence of water temperature, PH as silver salt disinfectant, silver resin, also will be subjected to organic influence in the water; Relatively poor by the metal ion stability that ion-exchange grafts on the fiber, be difficult to the lasting stability antibacterial effect.(2) Chinese patent ZL02130694.X relates to a kind of preparation method of macromolecular sterilization fibre of grafted antibacterial monomer on its surface, select the macromolecular sterilization fibre of quaternary ammonium salt, halogenated amine and the preparation of macromolecular fibre graft reaction for use, be a kind of portable, do not need the polymeric treating agent specific operation condition, cheap.Processing target mainly concentrates on the removal to pathogenetic bacteria.
(3) Chinese patent ZL01129949.5 adopts the method for graft polypropylene nitrilation modification to prepare the method for New-type wide-spectrum anti-bacterial fibre.This method comprises the grafting of polyacrylonitrile on synthetic fiber, reaches further processes such as the dipping in hydrazine hydrate liquid, amidrazone structuring, basic hydrolysis.By the condition of control graft reaction, concentration, dip time and the liquid pricking rate of hydrazine hydrate maceration extract, regulate the intensity of structurized temperature and time of amidrazoneization and basic hydrolysis etc., make prepared novel antibacterial fiber have certain intensity and graft polypropylene nitrile amount, the chemical functional group of variety classes and content is contained on the surface simultaneously, performance with broad-spectrum antiseptic, and can be efficiently, kill bacteria or suppress the growth of bacterium enduringly.
All to have be to be connected in advance fine fiber surface in the grafting mode to antiseptic in the above technology, and in the grafting process, the post-processing difficulty that the use of a large amount of auxiliary agents has not only increased fiber has also increased product cost simultaneously greatly.Some grafting processes greatly reduce the performance of fiber, and the original performance of fiber is descended greatly, have antibacterial ability and have but lost the original functional characteristics of fiber, and practicality descends greatly, have also reduced this value of technology simultaneously.
Be the technology for preparing anti-bacterial fibre with blending method in the prior art:
(1) Chinese patent ZL02110160.4 is antibiotic bactericide with the nano particle, prepares a kind of method of anti-bacterial fibre with the solvent spinning method.With nano particle in certain proportion (1～7%wt) and special process join and prepare spinning solution in the polymer, then to spinning solution deaeration, filtration, carry out spinning with different solvent spinning methods, obtain containing acrylic fiber, viscose, polyvinyl chloride fibre fiber of nano particle etc.Method of the present invention makes antibacterial dacron, polypropylene fibre and polyamide fibre applicable to the high polymer (polyester, polypropylene, nylon 6 etc.) of melt spinning equally).Nano particle is uniformly dispersed in the fiber that is made by this method, and fibrous mechanical property is good, and has antibacterial functions, can be used as textile material and is used for industries such as clothes, drapery, carpet, medical treatment.
(2) Chinese patent ZL 00107688.4 adopts double-deck core skin structure, and its center core layer is that polypropylene material, cortex are polythene material, contains 3%～10% nanometer-level silver source power in the cortex gross dry weight in said cortex polythene material.The product of this invention can broad-spectrum antiseptic, and it is long-lasting, washability, stability, security, product having enhanced antibacterial action, and has taken into account the pull resistance and the resilience of product.
(3) Chinese patent ZL 00100160.4 adopts the method for dosing chitin and derivative thereof in fiber to prepare the method for anti-bacterial fibre, the product of this invention has strong inhibitory or killing effect to bacterial classifications such as Escherichia coli, and it is nontoxic, non-stimulated, biocompatibility, comfortableness, good permeability are a kind of desirable functional health products.
In the above technology, (1), (2) antiseptic is nano level inorganic matter, the toxicity that these inorganic nano materials have itself also is cumbersome thing, and fiber and contact skin also may cause the skin discomfort simultaneously, are chitin and derivative thereof in (3), the anti-transfer ability of antiseptic in (3) is better than independent inorganic mineral by contrast, toxic and side effect is little, but since its particle diameter bigger, the distribution in fiber with become fine relative difficult.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of polymer nanocomposite anti-biotic material and preparation method thereof, and with antibacterial acrylic fibre fiber of this anti-biotic material preparation and preparation method thereof, to solve shortcoming of the prior art.
One of purpose of the present invention is to provide a kind of nano anti-biotic material of polymer, and this anti-biotic material comprises following components in part by weight:
Acrylonitrile 100
But quaternary ammonium copolymer compound 10-20
Organic montmorillonite 10
Lauryl sodium sulfate 1-5
Potassium peroxydisulfate 0.1-5
Wherein said acrylonitrile is a polymer grade, the ion exchange capacity of described organic montmorillonite is 120mml/100g, but described quaternary ammonium copolymer compound is a vinyl benzyl dimethyl n octyl group ammonium salt, vinyl benzyl dimethyl n decyl ammonium salt, vinyl benzyl dimethyl n dodecyl ammonium salt, vinyl benzyl dimethyl n cetyl ammonium salt, 2-acryloxy hexyl leptodactyline, 2-methacryloxyethyl leptodactyline, acrylamidopropyl trimethyl ammonium salt, methacrylic acid aminopropyl leptodactyline, in propylene acyloxy Fixanol or the methacryloxy Fixanol one or more; Described lauryl sodium sulfate is an emulsifying agent; Described potassium peroxydisulfate is an initator.
Another object of the present invention is to provide the preparation method of this nano anti-biotic material, comprised the steps:
(1) insertion of monomer
But the 10g organic montmorillonite is added in the mixture of 100g acrylonitrile and 10-20g copolymerization quaternary ammonium compound, sonic oscillation 5-20min, standby.
(2) in-situ polymerization
In the three-necked bottle that agitator, reflux condenser and thermometer are housed, add the 90ml deionized water, add 1-5gSDS, stir, add the organic montmorillonite that sonicated crosses and the mixed liquor of monomer then while stirring, warming-in-water is dissolved in the potassium peroxydisulfate of 0.1-5g in the deionized water of 10ml, treats that water-bath rises to 60-80 ℃, add persulfate aqueous solution, reaction got the compound emulsion in 0.5-4 hour, used the saturated aqueous common salt breakdown of emulsion, washing, suction filtration is 60-80 ℃ of drying.
The present invention also provides the acrylic fiber that has added above-mentioned nano anti-biotic material, and the percentage by weight of nano anti-biotic material is 0.1-10% in this acrylic fiber, and fibre strength is 1.2-4.5CN/dtex, and elongation at break is 5-40%.
This antibacterial acrylic fibre fiber preparation method comprises the steps:
(1) with nano anti-biotic material and acrylic fiber spinning slurry according to 1: the part by weight of 20-40 mixes;
(2) (1) gained mixture is mixed with auxiliary agent, wherein the weight ratio of nano anti-biotic material and auxiliary agent is 5-20: 100;
(3) carry out spinning, be spun to fibrid and be: the long 0.5-2.5 rice of spinning dipping bath, 10-15 ℃, the spinning head hole count is the 3000-20000 hole, aperture 0.08-0.1mm, spinning speed be 5-40 rice/minute, behind the solidification forming, draw and stretch bath, drawing and stretching multiple is 5-10 times, bathes warm 92-95 ℃, fiber go out last draw stretch bath after, wash in 60-80 ℃ of hot water, last heat setting promptly makes the acrylic fiber that contains nano anti-biotic material.
Wherein said auxiliary agent is 30% sodium sulfocyanate (NaSCN).
This antibacterial acrylic fibre fiber can be through being processed into underwear, sportswear or socks etc.
In the resulting polymer nanocomposite anti-biotic material of the present invention because contain quaternary ammonium salt functional group, quaternary ammonium salt is because the effect of positive charge, the bacterium of adsoption band negative electrical charge and killing bacteria are realized antibacterial action rapidly, have the fast and fast advantage of sterilization of absorption simultaneously, reach good bactericidal effect.This anti-biotic material is nontoxic and non-stimulated to skin simultaneously, especially is suitable as underwear material.
And make anti-bacterial fibre by blending method, and it is carried out substance improve, specifically by dosing a kind of polymer nanocomposite anti-biotic material, improve the anti-microbial property persistence while of anti-bacterial fibre, the polymer nanocomposite antiseptic that use has no side effect, keep the fiber self performance, make it possess more wide application prospect.
(1) anti-microbial property is lasting: the fiber bactericide antiseptic that co-blended spinning obtains is uniformly distributed in the fiber, the anti-microbial property lasting stability, and Acceptable life is longer.
(2) antiseptic is connected with covalent bond with base material, and antibacterial components can not break away from stable performance with base material.
(3) different monomers is selected in the polyblend spinning, can select the different structure of different monolithic design for use according to application requirements.
(4) antiseptic is a nanometer polymer, and its main component is consistent with base material simultaneously, and there is not the antiseptic migration problem in the compatibility excellence.
(5) antiseptic is that polymer and mechanical mechanics property are close with base material with processing characteristics, to being spun to the fine influence of not having, has farthest kept original mechanical mechanics property of fiber.
Obviously, it is better that blending method prepares the anti-bacterial fibre anti-microbial property, and stability is more reliable.
But, adopt nontoxic and more reasonable to the non-stimulated polymer antiseptic of human body for the uncomfortable consequence that may produce skin of the toxicity that overcomes antiseptic itself.
The specific embodiment
Embodiment 1
(1) insertion of monomer
1gOMMT is added in the mixture of 10g acrylonitrile and 1 gram vinyl benzyl lauryl amine, sonic oscillation 10min, standby.
(2) in-situ polymerization
Add the 90ml deionized water in the 250ml three-necked bottle that agitator, reflux condenser and thermometer are housed, add 0.2gSDS, stir, add the OMMT that (1) sonicated crosses and the mixed liquor of monomer then while stirring, warming-in-water is with 0.1gK
2S
2O
8Be dissolved in the deionized water of 10ml, treat that water-bath rises to design temperature, add K
2S
2O
8The aqueous solution, reacted 2 hours the compound emulsion, use the saturated aqueous common salt breakdown of emulsion, wash, suction filtration is 70 ℃ of dryings.
(3) with (2) resulting polymers nano anti-biotic material in 1: 20 ratio (weight ratio) mix, make it evenly to disperse and do not precipitate special using through stirring.
(4) (3) gained mixture is mixed with 30% sodium sulfocyanate, wherein the weight ratio of nano anti-biotic material and 30% sodium sulfocyanate is 15: 100;
(5) being spun to fibrid is: long 2 meters of spinning dipping bath, bathing temperature is 12 ℃, the spinning head hole count is 10000 holes, and aperture 0.1mm, spinning speed are 30 meters/minute, behind the solidification forming, once draw with steam and to stretch or carry out secondary with boiling water and draw and stretch, drawing and stretching multiple is 8 times, bathes 94 ℃ of temperature, fiber go out last draw stretch bath after, in 75 ℃ of hot water, wash.Last heat setting promptly makes the antibacterial acrylic fibre fiber that contains the polymer nanocomposite anti-biotic material, and fiber can be through being processed into underwear, sportswear, socks etc.
Claims (6)
1. nano anti-biotic material is characterized in that this anti-biotic material comprises following components in part by weight:
Acrylonitrile 100
But quaternary ammonium copolymer compound 10-20
Organic montmorillonite 10
Lauryl sodium sulfate 1-5
Potassium peroxydisulfate 0.1-5.
2. nano anti-biotic material according to claim 1, it is characterized in that described acrylonitrile is a polymer grade, the ion exchange capacity of described organic montmorillonite is 120mml/100g, but described quaternary ammonium copolymer compound is a vinyl benzyl dimethyl n octyl group ammonium salt, vinyl benzyl dimethyl n decyl ammonium salt, vinyl benzyl dimethyl n dodecyl ammonium salt, vinyl benzyl dimethyl n cetyl ammonium salt, 2-acryloxy hexyl leptodactyline, 2-methacryloxyethyl leptodactyline, acrylamidopropyl trimethyl ammonium salt, methacrylic acid aminopropyl leptodactyline, in propylene acyloxy Fixanol or the methacryloxy Fixanol one or more.
3. the preparation method as claim 1 or 2 each described anti-biotic materials is characterized in that comprising the steps:
(1) insertion of monomer
But the 10g organic montmorillonite is added in the mixture of 100g acrylonitrile and 10-20g copolymerization quaternary ammonium compound, sonic oscillation 5-20min, standby.
(2) in-situ polymerization
In the three-necked bottle that agitator, reflux condenser and thermometer are housed, add the 90ml deionized water, add 1-5gSDS, stir, add the organic montmorillonite that sonicated crosses and the mixed liquor of monomer then while stirring, warming-in-water is dissolved in the potassium peroxydisulfate of 0.1-5g in the deionized water of 10ml, treats that water-bath rises to 60-80 ℃, add persulfate aqueous solution, reaction got the compound emulsion in 0.5-4 hour, used the saturated aqueous common salt breakdown of emulsion, washing, suction filtration is 60-80 ℃ of drying.
4. acrylic fiber that comprises claim 1 or 2 each described nano anti-biotic materials, the percentage by weight that it is characterized in that nano anti-biotic material in this acrylic fiber is 0.1-10%.
5. the preparation method of an acrylic fiber as claimed in claim 4 is characterized in that comprising the steps:
(1) with nano anti-biotic material and acrylic fiber spinning slurry according to 1: the part by weight of 20-40 mixes;
(2) (1) gained mixture is mixed with auxiliary agent, wherein the weight ratio of nano anti-biotic material and auxiliary agent is 5-20: 100;
(3) carry out spinning, be spun to fibrid and be: the long 0.5-2.5 rice of spinning dipping bath, 10-15 ℃, the spinning head hole count is the 3000-20000 hole, aperture 0.08-0.1mm, spinning speed be 5-40 rice/minute, behind the solidification forming, draw and stretch bath, drawing and stretching multiple is 5-10 times, bathes warm 92-95 ℃, fiber go out last draw stretch bath after, wash in 60-80 ℃ of hot water, last heat setting promptly makes the acrylic fiber that contains nano anti-biotic material;
Wherein said auxiliary agent is 30% sodium sulfocyanate.
6. the application of acrylic fiber as claimed in claim 4 in processing underwear, sportswear or socks.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510023301 CN1272480C (en) | 2005-01-13 | 2005-01-13 | Nano-antibacterial material, its preparation method and use |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510023301 CN1272480C (en) | 2005-01-13 | 2005-01-13 | Nano-antibacterial material, its preparation method and use |
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| CN1651617A CN1651617A (en) | 2005-08-10 |
| CN1272480C true CN1272480C (en) | 2006-08-30 |
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| CN 200510023301 Expired - Fee Related CN1272480C (en) | 2005-01-13 | 2005-01-13 | Nano-antibacterial material, its preparation method and use |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100413924C (en) * | 2006-11-07 | 2008-08-27 | 南京师范大学 | Polymer/montmorillonite-gallicin nano-antibacterial composite material and its preparation method |
| CN105442308A (en) * | 2014-09-02 | 2016-03-30 | 允友成(宿迁)复合新材料有限公司 | Antibiotic polylactic acid fiber and preparation method thereof |
| CN115161795B (en) * | 2022-07-11 | 2023-07-04 | 宁波奉化帆盛嘉业服饰有限公司 | Antibacterial fabric and preparation process thereof |
| CN116905241B (en) * | 2023-06-21 | 2024-04-12 | 深圳万旗服饰有限公司 | Cold-proof thermal fabric with self-heating effect and preparation method thereof |
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Granted publication date: 20060830 Termination date: 20100113 |