CN103820875B - The preparation method of ZnO quantum dot/wool keratin complex function nanofiber - Google Patents
The preparation method of ZnO quantum dot/wool keratin complex function nanofiber Download PDFInfo
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- CN103820875B CN103820875B CN201410072523.7A CN201410072523A CN103820875B CN 103820875 B CN103820875 B CN 103820875B CN 201410072523 A CN201410072523 A CN 201410072523A CN 103820875 B CN103820875 B CN 103820875B
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Abstract
The present invention relates to the preparation method of a kind of ZnO quantum dot/wool keratin multifunctional nano fiber, comprise: wool fibre is cleaned by (1), use the degreasing of ethanol-acetone mixed solvent again, then pulverize, then the wool fibre after pulverizing is joined in urea composite fluid, dissolving obtains keratin liquid solution, afterwards by centrifugal, saltout, frozen dried obtains wool keratin powder; By wool keratin powder dissolution in formic acid, add PEO stirring and dissolving after stirring and dissolving and obtain wool keratin formic acid solution; (2) heat the ethanolic solution of zinc acetate, then add LiOHH
2o forms ZnO quantum dot; (3) in the keratin formic acid solution of step (1) gained, add above-mentioned ZnO quantum dot, be uniformly mixed, finally carry out electrostatic spinning.The present invention is with low cost, simple to operate, and gained multifunctional nano fiber has the photoelectric properties such as high visible light transmissivity, high absorption of UV and low-resistivity.
Description
Technical field
The invention belongs to the preparation field of complex function nanofiber, the preparation method of particularly a kind of ZnO quantum dot/wool keratin complex function nanofiber.
Background technology
Wool keratin matter fiber is as one of human use's natural fiber material comparatively early, due to the restriction of wool quality and textile technology, there is a large amount of staple fibres every year, crude fibre goes out of use, make the research of the regeneration of this fibrid and method always by people are paid close attention to.Wool fibre main component is alpha-Keratin, the three-dimensional stability structure that keratin molecule is cross-linked by cystine linkage, hydrogen bond, sat linkage and other key effect height of formation, due to the complicated compactness of its structure, it does not under general condition dissolve, it is destroy the cystine linkage of protein molecule by reagent such as highly basic, strong acid, reductant or oxidants or peptide bond resolves into small peptide that tradition dissolves the method for wool protein, the waste of the unfriendly solvents of environment such as a large amount of inorganic acid of these method ubiquities, alkali, reductant or oxidant, causes serious impact to environment.
But the good technique made new advances by integration and development in traditional method carries out solvent to wool fibre, and in lower temperature and the dissolving completing wool fibre in the shorter time, ensure that the keratin molecule amount extracted is comparatively large, spinning properties is better, is probing into of being necessary.
Nano zine oxide (ZnO quantum dots), also known as Zinc oxide quantum dot, referred to as ZnO QDs, there are excellent photoelectric properties, tempting application prospect is demonstrated in fields such as bio-imaging, photovoltaic device and Light-Emitting Diodes, and widely ZnO quantum dot that people pay close attention to not only has significant quantum effect, also have the advantage of ZnO body phase material concurrently.Just based on these features above, ZnO quantum dot is with a wide range of applications in fields such as photochemical catalyst, piezo-resistance, sensor, piezo-electric device, solar cell, transparency electrode, biological detection as a kind of multifunctional material.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of a kind of ZnO quantum dot/wool keratin multifunctional nano fiber, the method with the fiber such as waste wool, cashmere for raw material, with low cost, simple to operate, be easy to realize suitability for industrialized production, obtained ZnO quantum dot/wool keratin multifunctional nano fiber has the photoelectric properties such as high visible light transmissivity, high absorption of UV and low-resistivity.
The preparation method of a kind of ZnO quantum dot of the present invention/wool keratin multifunctional nano fiber, comprising:
(1) wool fibre is cleaned, use ethanol-acetone mixed solvent degreasing 5-24 hour again, then pulverize, then the wool fibre after pulverizing is joined in urea composite fluid, be warming up to 60-90 DEG C, dissolve 0.5-24 hour under magnetic stirring, obtain keratin liquid solution, afterwards by centrifugal, saltout, frozen dried obtains wool keratin powder; Wool fibre after wherein pulverizing accounts for the 5-30% of the weight percentage of urea composite fluid;
By wool keratin powder dissolution in formic acid, after stirring and dissolving, adding PEO(polyethylene glycol oxide) stirring and dissolving obtains wool keratin formic acid solution; Wherein wool keratin powder accounts for the percentage by weight of formic acid be the weight ratio of 5-30%, PEO and wool keratin powder is 0.05:1-0.5:1;
(2) heat the ethanolic solution of zinc acetate, make ZnAc
22H
2o forms Zn after dissolving
2+compound, as presoma, wherein zinc ion concentration is 0.025-0.2M; According to Zn
2+: OH-=1:0.5-1:2 adds LiOHH
2o, make above-mentioned presoma generation poly-condensation and hydrolysis, reaction temperature is 0-50 DEG C, concentrated in Rotary Evaporators, forms ZnO quantum dot;
(3) in the keratin formic acid solution of step (1) gained, add above-mentioned ZnO quantum dot, wherein the addition of ZnO quantum dot is the 1-5% of wool keratin weight, is uniformly mixed 0.5-2 hour at normal temperatures, obtains ZnO quantum dot/wool keratin solution;
(4) adopt above-mentioned ZnO quantum dot/wool keratin solution to carry out electrostatic spinning, obtain ZnO quantum dot/wool keratin multifunctional nano fiber.
The process cleaned by wool fibre described in step (1) for first to wash with water, then uses detergent washing 20-40 minute, and the condition of wherein detergent washing is: detergent concentration is 3-6 grams per liter, temperature 40-70 DEG C, bath raio 10:1-50:1.
Above-mentioned detergent is the compound of one or more in detergent 209, cleanser 105, detergent 6501, detergent LS.
In ethanol-acetone mixed solvent described in step (1), the volume ratio of ethanol and acetone is 1:1-2:1.
The concrete operations of the pulverizing described in step (1) are by pulverizer process, and wool fibre is ground into the powder that diameter is micron level.
The diameter of the powder described in step (1) is 10-800 micron.
Urea composite fluid described in step (1) is sodium hydrogensulfite and/or SDS(dodecyl sodium sulfate) with the mixing material of urea, wherein, urea 100-300g/L, SDS5-10g/L, sodium hydrogensulfite 10-30g/L.。
The mean molecule quantity 200000-600000 of the polyethylene glycol oxide described in step (1).
The percentage by weight that the ZnO quantum dot added in step (3) accounts for keratin formic acid solution is 1-10%.
The condition of the electrostatic spinning described in step (4) is voltage 5-25kV, spinning distance 5-20cm, pump speed are 0.005-2 ml/hour, spinning time 0.5-24 hour.
The present invention dissolves the reducing process of wool fibre by improvement tradition, add the solvent of the keratin oxidation that can prevent from dissolving, and develop the method for the environment-friendly type solvent had, urea liquid molten is altogether with non-volatile, stable to water and air, therefore the natural macromolecular material such as silk-fibroin, wool keratin can be dissolved and regenerate and derivative reaction, solve a difficult problem for resource reclaim recycling simultaneously.
Beneficial effect:
1, of the present invention with low cost, simple to operate, be easy to realize suitability for industrialized production.
2, the present invention is with the fiber such as waste wool, cashmere for raw material, namely reduces costs, and economizes on resources, again protection of the environment.
3, the ZnO quantum dot obtained by the present invention/wool keratin nano functional fiber has the photoelectric properties such as high visible light transmissivity, high absorption of UV and low-resistivity, and textiles can be made to have the well performance such as antistatic and uvioresistant.
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
1) washed with water by wool, then use detergent 209 washing 30 minutes, then degreasing 5 hours in ethanol-acetone (mixed proportion is 1:1) mixed solvent, final powder is broken into powder (diameter is generally tens to hundreds of micron); Detergent LR-2093 grams per liter, temperature 40 DEG C, bath raio 50:1.Raw material after cleaning is joined in urea composite fluid (urea 100g/L, SDS5g/L, sodium hydrogensulfite 30g/L), its Raw is 10% of liquid weight percentage, at 90 DEG C, dissolve 4 hours under magnetic stirring, just can obtain the keratin liquid solution of respective concentration; Afterwards by centrifugal, saltout, frozen dried obtains wool keratin powder.By wool keratin powder dissolution in formic acid solution, make weight ratio be 5%, after stirring and dissolving, add PEO(polyethylene glycol oxide, mean molecule quantity 600,000), PEO: wool keratin=1:9, namely last stirring and dissolving obtains the formic acid solution of wool keratin.
2) heat the ethanolic solution of zinc acetate, in presoma, the amount of zinc ion is 0.1M.By adding LiOHH
2the test of this group of O is by changing LiOHH
2the consumption of O, i.e. Zn
2+: OH-=1:1, make above-mentioned precursor generation poly-condensation and hydrolysis, reaction temperature is chosen as 0 DEG C, finally forms ZnO quantum dot.
3) 1) add above-mentioned 1% Zinc oxide quantum dot in the keratin liquid solution of gained, stirring at normal temperature 0.5 hour, with Static Spinning equipment at voltage 15kV, spinning distance 15cm, pump speed is spinning 3 hours under 0.01 ml/hour of condition, obtains ZnO quantum dot/wool keratin multifunctional nano fiber.
Embodiment 2
1) washed with water by wool, then use detergent 209 washing 30 minutes, then degreasing 5 hours in ethanol-acetone (mixed proportion is 1:1) mixed solvent, final powder is broken into powder (diameter is generally tens to hundreds of micron); Detergent LR-2093 grams per liter, temperature 40 DEG C, bath raio 50:1.Raw material after cleaning is joined in urea composite fluid (urea 100g/L, SDS5g/L, sodium hydrogensulfite 30g/L), its Raw is 105% of liquid weight percentage, at 90 DEG C, dissolve 4 hours under magnetic stirring, just can obtain the keratin liquid solution of respective concentration; Afterwards by centrifugal, saltout, frozen dried obtains wool keratin powder.By wool keratin powder dissolution in formic acid solution, make weight ratio be 10%, after stirring and dissolving, add PEO(polyethylene glycol oxide, mean molecule quantity 600,000), PEO: wool keratin=1:8, namely last stirring and dissolving obtains the formic acid solution of wool keratin.
2) heat the ethanolic solution of zinc acetate, in presoma, the amount of zinc ion is 0.1M.By adding the test of this group of LiOHH2O by changing LiOHH
2the consumption of O, i.e. Zn
2+: OH-=1:2, make above-mentioned precursor generation poly-condensation and hydrolysis, reaction temperature is chosen as 25 DEG C, finally forms ZnO quantum dot.
3) 1) add above-mentioned 1% Zinc oxide quantum dot in the keratin liquid solution of gained, stirring at normal temperature 0.5 hour, with Static Spinning equipment at voltage 15kV, spinning distance 20cm, pump speed is spinning 3 hours under 0.02 ml/hour of condition, obtains ZnO quantum dot/wool keratin multifunctional nano fiber.
Embodiment 3
1) washed with water by wool, then use detergent 209 washing 30 minutes, then degreasing 5 hours in ethanol-acetone (mixed proportion is 1:1) mixed solvent, final powder is broken into powder (diameter is generally tens to hundreds of micron); Detergent LR-2093 grams per liter, temperature 40 DEG C, bath raio 50:1.Raw material after cleaning is joined in urea composite fluid (urea 100g/L, SDS5g/L, sodium hydrogensulfite 30g/L), its Raw is 10% of liquid weight percentage, at 90 DEG C, dissolve 4 hours under magnetic stirring, just can obtain the keratin liquid solution of respective concentration; Afterwards by centrifugal, saltout, frozen dried obtains wool keratin powder.By wool keratin powder dissolution in formic acid solution, make weight ratio be 15%, after stirring and dissolving, add PEO(polyethylene glycol oxide, mean molecule quantity 600,000), PEO: wool keratin=1:9, namely last stirring and dissolving obtains the formic acid solution of wool keratin.
2) heat the ethanolic solution of zinc acetate, in presoma, the amount of zinc ion is 0.05M.By adding LiOHH
2the test of this group of O is by changing LiOHH
2the consumption of O, i.e. Zn
2+: OH-=1:1, make above-mentioned precursor generation poly-condensation and hydrolysis, reaction temperature is chosen as 0 DEG C, finally forms ZnO quantum dot.
3) 1) add above-mentioned 1% Zinc oxide quantum dot in the keratin liquid solution of gained, stirring at normal temperature 0.5 hour, with Static Spinning equipment at voltage 20kV, spinning distance 15cm, pump speed is spinning 3 hours under 0.01 ml/hour of condition, obtains ZnO quantum dot/wool keratin multifunctional nano fiber.
Embodiment 4
1) washed with water by wool, then use detergent 209 washing 30 minutes, then degreasing 5 hours in ethanol-acetone (mixed proportion is 1:1) mixed solvent, final powder is broken into powder (diameter is generally tens to hundreds of micron); Detergent LR-2093 grams per liter, temperature 40 DEG C, bath raio 50:1.Raw material after cleaning is joined in urea composite fluid (urea 100g/L, SDS5g/L, sodium hydrogensulfite 30g/L), its Raw is 10% of liquid weight percentage, at 90 DEG C, dissolve 4 hours under magnetic stirring, just can obtain the keratin liquid solution of respective concentration; Afterwards by centrifugal, saltout, frozen dried obtains wool keratin powder.By wool keratin powder dissolution in formic acid solution, make weight ratio be 5%, after stirring and dissolving, add PEO(polyethylene glycol oxide, mean molecule quantity 600,000), PEO: wool keratin=1:9, namely last stirring and dissolving obtains the formic acid solution of wool keratin.
2) heat the ethanolic solution of zinc acetate, in presoma, the amount of zinc ion is 0.2M.By adding LiOHH
2the test of this group of O is by changing LiOHH
2the consumption of O, i.e. Zn
2+: OH-=1:0.5, make above-mentioned precursor generation poly-condensation and hydrolysis, reaction temperature is chosen as 50 DEG C, finally forms ZnO quantum dot.
3) 1) add above-mentioned 2% Zinc oxide quantum dot in the keratin liquid solution of gained, stirring at normal temperature 0.5 hour, with Static Spinning equipment at voltage 15kV, spinning distance 20cm, pump speed is spinning 3 hours under 0.01 ml/hour of condition, obtains ZnO quantum dot/wool keratin multifunctional nano fiber.
Claims (9)
1. a preparation method for ZnO quantum dot/wool keratin multifunctional nano fiber, comprising:
(1) wool fibre is cleaned, use ethanol-acetone mixed solvent degreasing 5-24 hour again, then pulverize, then the wool fibre after pulverizing is joined in urea composite fluid, be warming up to 60-90 DEG C, dissolve 0.5-24 hour under magnetic stirring, obtain keratin liquid solution, afterwards by centrifugal, saltout, frozen dried obtains wool keratin powder; Wool fibre after wherein pulverizing accounts for the 5-30% of the weight percentage of urea composite fluid; Wherein urea composite fluid is the mixing material of sodium hydrogensulfite and/or SDS and urea, wherein urea 100-300g/L, SDS 5-10g/L, sodium hydrogensulfite 10-30g/L;
By wool keratin powder dissolution in formic acid, add PEO stirring and dissolving after stirring and dissolving and obtain wool keratin formic acid solution; Wherein wool keratin powder accounts for the percentage by weight of formic acid be the weight ratio of 5-30%, PEO and wool keratin powder is 0.05:1-0.5:1;
(2) heat the ethanolic solution of zinc acetate, make ZnAc
22H
2o forms Zn after dissolving
2+compound, as presoma, wherein zinc ion concentration is 0.025-0.2M; According to Zn
2+: OH
-=1:0.5-1:2 adds LiOHH
2o, make above-mentioned presoma generation poly-condensation and hydrolysis, reaction temperature is 0-50 DEG C, concentrated in Rotary Evaporators, forms ZnO quantum dot;
(3) in the keratin formic acid solution of step (1) gained, above-mentioned ZnO quantum dot is added, wherein the addition of ZnO quantum dot is the 1-5% of wool keratin weight, be uniformly mixed 0.5-2 hour at normal temperatures, obtain ZnO quantum dot/wool keratin solution;
(4) adopt above-mentioned ZnO quantum dot/wool keratin solution to carry out electrostatic spinning, obtain ZnO quantum dot/wool keratin multifunctional nano fiber.
2. the preparation method of a kind of ZnO quantum dot according to claim 1/wool keratin multifunctional nano fiber, it is characterized in that: the process cleaned by wool fibre described in step (1) is for first to wash with water, use detergent washing 20-40 minute again, wherein the condition of detergent washing is: detergent concentration 3-6 grams per liter, temperature 40-70 DEG C, bath raio 10:1-50:1.
3. the preparation method of a kind of ZnO quantum dot according to claim 2/wool keratin multifunctional nano fiber, is characterized in that: described detergent is the compound of one or more in detergent 209, cleanser 105, detergent 6501, detergent LS.
4. the preparation method of a kind of ZnO quantum dot according to claim 1/wool keratin multifunctional nano fiber, is characterized in that: in the ethanol-acetone mixed solvent described in step (1), the volume ratio of ethanol and acetone is 1:1-2:1.
5. the preparation method of a kind of ZnO quantum dot according to claim 1/wool keratin multifunctional nano fiber, it is characterized in that: the concrete operations of the pulverizing described in step (1) are by pulverizer process, and wool fibre is ground into the powder that diameter is micron level.
6. the preparation method of a kind of ZnO quantum dot according to claim 1/wool keratin multifunctional nano fiber, is characterized in that: the diameter of the powder described in step (1) is 10-800 micron.
7. the preparation method of a kind of ZnO quantum dot according to claim 1/wool keratin multifunctional nano fiber, is characterized in that: the mean molecule quantity 200000-600000 of the polyethylene glycol oxide described in step (1).
8. the preparation method of a kind of ZnO quantum dot according to claim 1/wool keratin multifunctional nano fiber, is characterized in that: the percentage by weight that the ZnO quantum dot added in step (3) accounts for keratin formic acid solution is 1-10%.
9. the preparation method of a kind of ZnO quantum dot according to claim 1/wool keratin multifunctional nano fiber, is characterized in that: the condition of the electrostatic spinning described in step (4) is voltage 5-25kV, spinning distance 5-20cm, pump speed are 0.005-2 ml/hour, spinning time 0.5-24 hour.
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| CN104264369B (en) * | 2014-10-21 | 2016-08-17 | 天津工业大学 | The method of keratin/PEO biological nano fibrous membrane is prepared in two step crosslinkings |
| TWI553174B (en) * | 2015-04-20 | 2016-10-11 | Preparation of Quantum Dot Fiber | |
| CN106480538B (en) * | 2016-09-21 | 2019-07-02 | 上海咏姿时装有限公司 | A kind of quantum dot/regenerated silk fiber and preparation method thereof based on electrostatic spinning |
| CN107681047B (en) * | 2017-08-11 | 2020-03-27 | 河北大学 | Organic degradable resistance-variable nerve bionic device and preparation method and application thereof |
| CN108179547B (en) * | 2017-12-19 | 2020-08-11 | 东华大学 | Preparation method of fluorescent nanofiber membrane used as heavy metal antimony visual detector |
| CN108477942A (en) * | 2018-03-28 | 2018-09-04 | 南通滋梦纺纺织品有限公司 | A kind of quantum health quilt and preparation method thereof |
| CN108978213B (en) * | 2018-06-27 | 2020-11-06 | 上海兆妩品牌管理有限公司 | Modification method of flax fibers |
| CN108751257A (en) * | 2018-08-10 | 2018-11-06 | 厦门大学 | A kind of method of biocompatibility molybdenum disulfide liquid phase stripping |
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| CN1435516A (en) * | 2002-12-12 | 2003-08-13 | 内蒙古鄂尔多斯羊绒集团有限责任公司 | Technique for processing regenerated keratin functional fibre |
| CN101166560A (en) * | 2005-05-03 | 2008-04-23 | 宝洁公司 | Compositions comprising discrete particle aggregates and/or agglomerate for application to keratin fibers |
| CN102182061A (en) * | 2011-03-04 | 2011-09-14 | 东华大学 | Preparation method of ITO (indium tin oxide)/wool keratin solution compound functional finishing agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1435516A (en) * | 2002-12-12 | 2003-08-13 | 内蒙古鄂尔多斯羊绒集团有限责任公司 | Technique for processing regenerated keratin functional fibre |
| CN101166560A (en) * | 2005-05-03 | 2008-04-23 | 宝洁公司 | Compositions comprising discrete particle aggregates and/or agglomerate for application to keratin fibers |
| CN102182061A (en) * | 2011-03-04 | 2011-09-14 | 东华大学 | Preparation method of ITO (indium tin oxide)/wool keratin solution compound functional finishing agent |
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