CN103410001B - Preparation method of self-cleaning cotton fabric based on light-induced polymer free radicals for degrading pollutants - Google Patents
Preparation method of self-cleaning cotton fabric based on light-induced polymer free radicals for degrading pollutants Download PDFInfo
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- CN103410001B CN103410001B CN201310287742.2A CN201310287742A CN103410001B CN 103410001 B CN103410001 B CN 103410001B CN 201310287742 A CN201310287742 A CN 201310287742A CN 103410001 B CN103410001 B CN 103410001B
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Abstract
The invention discloses a manufacturing method of cotton fabric based on light-induced polymer free radicals for degrading pollutants, which belongs to the technical field of functional textiles. According to the manufacturing method, an appropriate H donor agent and a crosslinking agent are selected by utilizing the characteristic that sulfonated polyether ether ketone has high activities to H atoms in organic substances under light induction, so as to cross-link and form a film on the cotton fabric rich in hydroxyl to prepare the self-cleaning fabric which can generate the polymer free radicals by lighting and has an elimination effect on the pollutants. The manufacturing method mainly comprises the following steps: (1) preparing a composite finishing liquid of light-induced free-radical polymer, wherein the finishing liquid contains the sulfonated polyether ether ketone, H donor polymer, the crosslinking agent, HCL (hydrogen chloride) and the like; and (2) padding and baking the cotton fabric in the finishing liquid. The cotton fabric which is prepared by using the preparation method and has a function of degrading the pollutants by the light induction has the effects of antibiosis, pesticide degradation, pigment degradation and the like, can be used for common clothing, medical fabric, household fabric and the like, and has a wide application prospect.
Description
Technical field
The invention belongs to function textile field, specifically relate to a kind of automatically cleaning COTTON FABRIC preparation method based on photic high molecular free radical degradation of contaminant.
Background technology
The intelligent surface with automatic cleaning function has a very wide range of applications prospect in daily life and industry, and it can reduce clean brought environmental pollution and water power expends in the application in the fields such as glass, pottery, automobile and weaving.Therefore, in the current whole world under the abnormal prerequisite paid attention to of environment and energy problem, the research of self-cleaning surface becomes one of hot issue of people's concern.And at field of textiles, the self-cleaning fabrics with contaminant degradation function not only can alleviate the environment and energy problem that wash and bring, can also effectively shield and clear up as various environmental contaminants such as bacterium, virus, pesticide, spots, these pollutants are avoided to be damaged human body by skin or respiratory tract, so the COTTON FABRIC with contaminant degradation function can be widely used in the aspects such as townwear, biochemical protective clothes, health care, food processing, environment, farm, military affairs.
The self-cleaning fabrics with contaminant degradation function is mainly prepared from based on photocatalysis principle at present, as in function textile field, the Walid A. Daoud etc. of the great loyalty of Xin and Australian Meng Nashi university prepares anatase type nano TiO at dacron and surface of cotton fabric
2crystalline membrane, can improve the anti-microbial property of fabric, and the blue 2G dyestuff of the Neolan that can effectively degrade, has automatic cleaning action; Deakin University Hurren etc. has prepared TiO on wool fabric surface
2thin layer, result shows this wool fabric surface has catalytic degradation automatically cleaning effect to red wine stain; Domestic Wang Chaoxia etc. then have studied rare earth ion thulium (Tm) doped Ti O
2the self-cleaning performance of modified cotton fabric, result display light according to during 3h to the degradation rate of capsorubin dirt about 94%.2011, Walid A. Daoud etc. to people over nearly 5 years by nanometer technology (mainly nano-TiO
2) realize the self-cleaning research of macromolecular fibre and summarize, indicate some problems that the method exists, as inorganic TiO
2the fastness that particle is combined with fiber is not good, be easy to come off, fabric hand is bad and it is dispersed etc. at fiber surface to be difficult to.In addition, Donghua University king builds celebrating etc.
]think that the self-cleaning condition of this kind of photooxidant needs could eliminate under sunlight prolonged exposure, therefore this series products is applicable to outdoor occasion more, as exterior coating, cladding glass etc.Therefore, develop and be applicable to polymer fiber material and the self-cleaning surface of high performance, cost degradation also needs new thinking.
Summary of the invention
In order to solve the above-mentioned technical problem existed in prior art, the invention provides a kind of automatically cleaning COTTON FABRIC preparation method based on photic high molecular free radical degradation of contaminant, comprising the steps:
(1) photic free radical macromolecule composite finishing liquid is prepared:
Every L dressing liquid consists of the following composition: sulfonated polyether-ether-ketone 2.5 ~ 15g; H donor polymerization thing 5 ~ 17.5g; Crosslinking agent 1 ~ 10wt%; Add HCl and regulate pH to 2 ~ 5;
Preparation steps: by soluble in water for described sulfonated polyether-ether-ketone, is heated to 50 DEG C of dissolvings under ultrasound environments; Take appropriate H donor polymerization thing, soluble in water fully swelling after, be heated to 85 DEG C of dissolvings, under 70 DEG C of conditions, two kinds of solution be fully uniformly mixed, add appropriate HCl, after 5min, add appropriate crosslinking agent;
(2) COTTON FABRIC is padded and is baked:
Pad: COTTON FABRIC padding machine floods mangle after 30 ~ 50min in above-mentioned dressing liquid, a leaching one is rolled, pick-up rate 70 ~ 110%;
Bake: pad rear COTTON FABRIC 80 ~ 90 DEG C of preliminary drying 20 ~ 40 min in an oven, then bake 60 ~ 240 s at 130 ~ 160 DEG C.
Further, described sulfonated polyether-ether-ketone sulfonation degree is 70 ~ 90%.
Further, described H donor polymerization thing is polymine or polyvinyl alcohol.
Further, described crosslinking agent is epoxychloropropane or glutaraldehyde.
The present invention has following features:
(1) SPEEK that the present invention is used has excellent mechanical property, heat resistance and chemical proofing, usually the fields such as fuel cell, milipore filter, reverse osmosis membrane, bio-medical material are applied to, the laminated film that the softness that can be formed with polymer such as PVA and PEI, light transmission are good, so it is applicable to fabric face and prepares functional textile.
(2) the photic automatically cleaning polymer applications that proposes of the present invention is when COTTON FABRIC, can with-OH the base on the large molecule of cotton fiber by crosslinked or grafting strong bonded, thus its fastness is higher and do not affect the physical property such as feel, gloss of fibrous material; Overcome the fastness that inorganic photocatalyst granular is combined with fiber not good, be easy to come off, fabric hand is bad and be difficult in the problem such as fiber surface is dispersed.Therefore, with adopt inorganic nano-particle (as TiO at present
2) reach the self-cleaning method of fiber surface and compare and have certain characteristic and advantage.
(3) the living radical oxidisability that in the present invention, Polymer Systems produces is than nanometer Ti
2the hydroxyl radical free radical (OH) that O produces is weak, not only to human body safety, and can not cause excessive damage to polymer film and fiber, affect the persistence of film and the brute force of fiber
(4) what the present invention adopted is the green path of pollutant purification under a kind of temperate condition, therefore, by suitably improving the process that also may be used for waste gas and Pollutants in Wastewater.
(5) first by the textiles of sulfonated polyether-ether-ketone (SPEEK) for the preparation of contaminant degradation function, relative to inorganic photochemical catalyst, SPEEK, as a kind of organic polymer, is that the fabric of polymer has higher compatibility with same.
Detailed description of the invention
The invention will be further described below.
The self-cleaning fabrics preparation method clearing up pollutant based on photic high molecular reactive free radical of the present invention, first by the textiles of sulfonated polyether-ether-ketone (SPEEK) for the preparation of contaminant degradation function.This is because SPEEK contains BP group, it can form n under light-initiated, π * excited triplet state, higher activity is had to the hydrogen atom in other compounds, as it and polyvinyl alcohol (PVA) coexists time, PVA is as H atom donor, and can form two kinds of polymeric alcohol free radicals under light-initiated, course of reaction is shown below:
（1）
（2）
In formula (2), the Alpha-hydroxy free radical of PVA also can form new SPEEK free radical with second polyphenyl ketone radical reaction.Because coupled reaction between produced SPEEK free radical is comparatively slow, under room temperature condition this free radical to there is the life-span longer; Therefore, once form high molecular free radical after light-initiated, the effect of decomposing pollutant can just be played for a long time.If there is being O
2under the condition participated in, O
2the stronger active ultra-oxygen anion free radical O of oxidisability can be formed by one-electron reduction
2 -and protonated HO
2free radical:
(3)
HO
2·
H
++ ·O
2 - (4)
Therefore, above-mentioned product can carry out more effective oxidative degradation to the pollutant of material surface, plays better automatically cleaning effect; And their oxidisability is than nanometer Ti
2the hydroxyl radical free radical (OH) that O produces is weak, not only to human body safety, and can not cause excessive damage to polymer film and fiber, affect the persistence of film and the brute force of fiber.On the other hand, BP radical anion C (Φ)
2o
-oxidation-reduction potential be 2.0V, higher than the oxidation-reduction potential of SPEEK free radical, will be stronger with the reactivity of organic pollution; BP radical anion can at secondary amine (R
2nH) formed under existent condition:
（5）
Therefore, select suitable compound system (as with polymine PEI), can be formed active stronger containing BP group radical anion polymer at fiber surface:
[RR’C=O]
m+ [R
1NHR
2]
n+ hv →[RR’C·O
-]
m+ [R
1R
2NH
+]
n (6)
In sum, carry out decomposing pollutant thus prepare automatically cleaning fabric to be feasible by the organic polymer of photic generation active material.
Embodiment 1
Automatically cleaning COTTON FABRIC manufacture method based on photic high molecular free radical degradation of contaminant:
The preparation of organic pollutant COTTON FABRIC:
1) be, by 15g sulfonation degree that 70.3% sulfonated polyether-ether-ketone adds in 500mL deionized water, under ultrasound environments, be heated to 50 DEG C of dissolvings;
2), by 5g polyvinyl alcohol add in 500mL deionized water, first cold water swellable 2h, after be heated to 85 DEG C of stirring and dissolving;
3), by the sulfonated polyether-ether-ketone dissolved join in the polyvinyl alcohol dissolved, be heated to 70 DEG C, add the crosslinking agent glutaraldehyde adding 6wt% after HCl regulates pH to 2.3,5min, vigorous stirring 5min, is configured to 1L dressing liquid, and is cooled to room temperature;
4), impregnated in the dressing liquid cooled by one piece of foursquare cotton, control bath raio is 1:20, mangle after dipping 50min, and a leaching one is rolled, and pick-up rate 70%, 80 DEG C of preliminary drying 40min, 160 DEG C bake 120s, wash with water, 80 DEG C of oven dry.
The performance test of COTTON FABRIC
Contaminant degradation performance
The cotton processed being impregnated in concentration is in the simulating pollution thing methyl orange aqueous solution of 100mg/L, takes out and dry after 5min, adopts DatacolorSF600 type computer color measurement and color match instrument to record its K/S value; It is irradiated 1h under 365nm, 500W uviol lamp, then records its K/S value.Calculating K/S value rate of change R
Wash durability
COTTON FABRIC is placed in the soap lye of soap flakes 5g/L, bath raio 1:50, soap at 40 DEG C 30min, then cold wash 10min, dries, then survey its contaminant degradation performance.
The stiffness of fabric, smoothness, pliability test
The circular specimen of clip diameter 10cm, takes its quality, and records thickness, adopt Nucybertek Phabromet Fabric Style instrument, carry out the test of hardness, smoothness, pliability, 3 samples surveyed by often kind of sample, and the test result mean value of 3 samples is the test result of this sample.
The whiteness test of fabric
Testing sample is converted into 4 layers, the full-automatic whiteness instrument of WSD-3C type is measured, on one piece of fabric, coat side is respectively got 3 different points and is measured, and gets the whiteness value that the Hunter whiteness mean value measured for 3 times is sample.
Finished tensile strength test
Test according to standard GB/T 3923.1-1997 " textile fabric tensile property ".
Embodiment 2 ~ embodiment 5
Change the consumption of SPEEK, H donor in every 1L dressing liquid, the sulfonation degree of SPEEK, pH value, dosage of crosslinking agent, dip time, pick-up rate, preliminary drying temperature and time, baking temperature and time.
Table 1, each embodiment technical recipe
The performance test of the COTTON FABRIC after table 2, each embodiment process
Finally, it is also to be noted that what enumerate above is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (3)
1., based on the automatically cleaning COTTON FABRIC preparation method of photic high molecular free radical degradation of contaminant, comprise the steps:
(1) photic free radical macromolecule composite finishing liquid is prepared:
Often liter of dressing liquid consists of the following composition: sulfonated polyether-ether-ketone 2.5 ~ 15g; H donor polymerization thing 5 ~ 17.5g; Crosslinking agent 1 ~ 10wt%; Add HCl and regulate pH to 2 ~ 5, described sulfonated polyether-ether-ketone sulfonation degree is 70 ~ 90%;
Preparation steps: by soluble in water for described sulfonated polyether-ether-ketone, is heated to 50 DEG C of dissolvings under ultrasound environments; Take appropriate H donor polymerization thing, soluble in water fully swelling after, be heated to 85 DEG C of dissolvings, under 70 DEG C of conditions, two kinds of solution be fully uniformly mixed, add appropriate HCl, after 5min, add appropriate crosslinking agent;
(2) COTTON FABRIC is padded and is baked:
Pad: COTTON FABRIC padding machine floods mangle after 30 ~ 50min in above-mentioned dressing liquid, a leaching one is rolled, pick-up rate 70 ~ 110%;
Bake: pad rear COTTON FABRIC 80 ~ 90 DEG C of preliminary drying 20 ~ 40 min in an oven, then bake 60 ~ 240 s at 130 ~ 160 DEG C.
2. the automatically cleaning COTTON FABRIC preparation method based on photic high molecular free radical degradation of contaminant according to claim 1, is characterized in that: described H donor polymerization thing is polymine or polyvinyl alcohol.
3. the automatically cleaning COTTON FABRIC preparation method based on photic high molecular free radical degradation of contaminant according to claim 1, is characterized in that: described crosslinking agent is epoxychloropropane or glutaraldehyde.
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| CN105178021A (en) * | 2015-09-18 | 2015-12-23 | 浙江理工大学 | Preparation method of pure-cotton fabric easy to clean |
| CN105178020A (en) * | 2015-09-18 | 2015-12-23 | 浙江理工大学 | Production method of conductive pure-cotton fabric |
| CN105256539A (en) * | 2015-09-18 | 2016-01-20 | 浙江理工大学 | Preparation method of self-cleaning formaldehyde removing wall cloth |
| CN105177995A (en) * | 2015-09-18 | 2015-12-23 | 浙江理工大学 | Preparation method for anti-bacteria pure cotton fabric |
| CN108373560A (en) * | 2018-02-05 | 2018-08-07 | 高源� | A kind of degradable polymeric packaging material of the transparency and preparation method thereof |
| CN109825382B (en) * | 2019-03-25 | 2021-02-09 | 苏州衣然生物科技有限公司 | Preparation for degrading pesticide residues in natural fabric and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102071568A (en) * | 2009-11-19 | 2011-05-25 | 香港纺织及成衣研发中心 | Photocatalyst self-cleaning finishing agent and preparation and application method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102071568A (en) * | 2009-11-19 | 2011-05-25 | 香港纺织及成衣研发中心 | Photocatalyst self-cleaning finishing agent and preparation and application method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Radical-Induced Generation of Small Silver Particles in SPEEK/PVA Polymer Films and Solutions: UV-Vis, EPR, and FT-IR Studies;A.S.Korchev et.al.;《Langmuir》;20061231;第22卷(第1期);375-384 * |
| Self-cleaning fibers via nanotechnology: a virtual reality;Wing Sze Tung and Walid A. Daoud;《Journal of Materials Chemistry》;20111231;7858-7869 * |
| Sulfonated Poly(Ether Ether Ketone)/Poly(Vinyl Alcohol) Sensitizing System for Solution Photogeneration of Small Ag, Au,and Cu Crystallites;A.S.Korchev et.al.;《J.Phys.Chem》;20051231;第109卷(第16期);7733-7745 * |
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