CN101423614B - Luminescent fibre hydrogel and preparation method thereof - Google Patents
Luminescent fibre hydrogel and preparation method thereof Download PDFInfo
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- CN101423614B CN101423614B CN2008101976468A CN200810197646A CN101423614B CN 101423614 B CN101423614 B CN 101423614B CN 2008101976468 A CN2008101976468 A CN 2008101976468A CN 200810197646 A CN200810197646 A CN 200810197646A CN 101423614 B CN101423614 B CN 101423614B
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Abstract
The invention relates to a luminescent cellulose hydrogel and a preparation method thereof. The preparation method for the luminescent cellulose hydrogel is as follows: firstly, cellulose is dissolved in an aqueous solution of NaOH/urea to obtain a NaOH/urea combined aqueous solution which is dissolved with the cellulose, wherein the mass percent concentration of NaOH is between 6 and 10 percent,the mass percent concentration of urea is between 4 and 12, and the mass percent concentration of the cellulose in the combined aqueous solution is between 1 and 6 percent; secondly, CdSe/ZnS quantumdots the surfaces of which are provided with carboxyl groups are added into the combined aqueous solution, wherein a mol ratio of the cellulose to the quantum dots is between 10 to 1 and 1,000 to 1, the dimension of the CdSe/ZnS quantum dots is between 2 and 7 nanometers, and the concentration of the CdSe/ZnS quantum dots is between 0.1 and 200 mu M; and thirdly, a crosslinking agent - epichlorohydrin with required amount is added into the combined aqueous solution, and the combined aqueous solution is subjected to chemical crosslinking reaction and placed at a gel temperature until the luminescent cellulose hydrogel is formed. The luminescent cellulose hydrogel can be widely applied in the fields of optical elements, biomedicine, control and release of medicines, etc.
Description
Technical field
The present invention relates to a kind of luminescent fibre hydrogel and preparation method thereof, belong to polymeric material field.
Background technology
Plant cellulose is a renewable resources the abundantest on the earth, and cellulose materials can be belonged to environment-friendly material by microbiological degradation after discarded.Do not use also not produce objectionable impurities, utilizing renewable resources production environment friendly materials is field, forward position, the world today.Recently, the preparation and the application development of hydrogel are rapider, and plurality of advantages such as water-absorbent, environmental sensitivity, water-retentivity, biocompatibility etc. receive much concern it, particularly cause the extensive attention of researcher based on the preparation of the luminous hydrogel of quantum dot.But present luminous hydrogel only has report based on synthetic macromolecule, and still finds no any report based on cellulosic luminous hydrogel.But because the biological degradability of synthetic macromolecule hydrogel is bad, institute so that its production and application be greatly limited.
Summary of the invention
The purpose of this invention is to provide a kind of luminescent fibre hydrogel and preparation method thereof, simple because of the preparation method of this luminescent fibre hydrogel, fast, raw materials cost is low, and whole technological process is pollution-free, so products obtained therefrom has better biocompatibility and biodegradability.The luminous hydrogel of this biodegradable Mierocrystalline cellulose can be widely used in optics, bio-medical, fields such as controlled delivery of pharmaceutical agents release.
Realize that the technical scheme that the object of the invention adopted is that luminescent fibre hydrogel adopts following method preparation: is 6～10% with cellulose dissolution in the NaOH mass percent concentration, the urea quality percentage concentration is in the aqueous solution of 4～12% NaOH/ urea, obtain being dissolved with cellulosic NaOH/ urea combination solution, cellulosic mass percent concentration is 1～6% in the combination solution, be that the ratio of 10:1～1000:1 adds and is of a size of 2～7nm in the mol ratio of Mierocrystalline cellulose and quantum dot then, concentration is 0.1 μ M～200 μ M, and the surface has the CdSe/ZnS quantum dot of carboxyl, the linking agent epoxy chloropropane that adds requirement at last, through chemical crosslink reaction, place under the gelling temp until forming luminescent fibre hydrogel, used cellulosic viscosity-average molecular weight scope is 30,000 to 100,000.
Compared with the prior art, the present invention has following advantage:
The present invention is a raw material with the natural polymer Mierocrystalline cellulose, and dissolution process is for very simple and direct, quick, free of contamination process.With Mierocrystalline cellulose and quantum dot uniform mixing, crosslinking reaction is very rapid, and is not high to temperature requirement, helps suitability for industrialized production, the easy recycling use of waste liquid.The present invention is a raw material with sodium hydroxide, urea, water, and low price is simple to operation, environmentally safe.Than previous methods tangible technical progress is arranged.
Embodiment
Below in conjunction with concrete example technical scheme of the present invention is described further:
Embodiment 1
With 0.4 gram Mierocrystalline cellulose (viscosity-average molecular weight M η=3.5 * 10
4) be scattered in 9.6 grams and contain in the mixed aqueous solution of 6wt%NaOH and 4wt% urea, be chilled to-20～-10 ℃ in advance, thawing after 5～24 hours to stir obtains transparent cellulose solution, and cellulose solution concentration is 2wt%.With 100 μ l concentration is 17.9 μ M, the CdSe/ZnS quantum dot that the surface that is of a size of 3.4nm has carboxyl mixes with cellulose solution, epoxy chloropropane with 1ml is added drop-wise in the mixing solutions then, be warming up to 60 ℃ of gelling temps, obtain the cellulose aquagel of burn red under the ultraviolet lamp after 0.5 hour.The luminescent fibre hydrogel that forms is used distilled water flushing repeatedly, removed residual NaOH, urea and linking agent epoxy chloropropane.
Embodiment 2
With 0.3 gram Mierocrystalline cellulose (viscosity-average molecular weight M
η=3.5 * 10
4) be scattered in 9.7 grams and contain in the mixed aqueous solution of 8wt%NaOH and 10wt% urea, be chilled to-20～-10 ℃ in advance, thawing after 5～24 hours to stir obtains transparent cellulose solution, and cellulose solution concentration is 3wt%.With 100 μ l concentration is 10.8 μ M, the quantum dot and the cellulose solution that are of a size of 3nm mix, the epoxy chloropropane of 0.8ml is added drop-wise in the mixing solutions, is warming up to 50 ℃ of gelling temps, obtain the cellulose aquagel that ultraviolet lamp issues yellow-green light after 2 hours.The luminescent fibre hydrogel that forms is used distilled water flushing repeatedly, removed residual NaOH, urea and linking agent epoxy chloropropane.Wherein used CdSe/ZnS quantum dot is hud typed structure, and the surface is carboxylated, and presents negative charge.
Embodiment 3
With 0.2 gram Mierocrystalline cellulose (viscosity-average molecular weight M
η=3.5 * 10
4) be scattered in 9.8 grams and contain in the mixed aqueous solution of 6wt%NaOH and 4wt% urea, be chilled to-20～-10 ℃ in advance, thawing after 5～24 hours to stir obtains transparent cellulose solution, and cellulose solution concentration is 2wt%.With 100 μ l concentration is 29.12 μ M, and the quantum dot and the cellulose solution that are of a size of 3.1nm mix.The epoxy chloropropane of 0.5ml is added drop-wise in the mixing solutions, is warming up to 30 ℃, obtain the cellulose aquagel that ultraviolet lamp issues sodium yellow after 12 hours.The luminescent fibre hydrogel that forms is used distilled water flushing repeatedly, removed residual NaOH, urea and linking agent epoxy chloropropane.
Embodiment 4
With 0.3 gram Mierocrystalline cellulose (viscosity-average molecular weight M
η=3.5 * 10
4) be scattered in 9.7 grams and contain in the mixed aqueous solution of 8wt%NaOH and 10wt% urea, be chilled to-20～-10 ℃ in advance, thawing after 5～24 hours to stir obtains transparent cellulose solution, and cellulose solution concentration is 2wt%.With 100 μ l concentration is 136.93 μ M, and the quantum dot and the cellulose solution that are of a size of 2.8nm mix.The epoxy chloropropane of 0.5ml is added drop-wise in the mixing solutions, is warming up to 80 ℃, obtain the cellulose aquagel of glow green under the ultraviolet lamp after 0.5 hour.The luminescent fibre hydrogel that forms is used distilled water flushing repeatedly, removed residual NaOH, urea and linking agent epoxy chloropropane.
The luminescent fibre hydrogel of the present invention's preparation is not luminous under visible light, but the luminescent fibre hydrogel that different condition makes under ultraviolet lamp can send the light of various different colours respectively.
Claims (8)
1. luminescent fibre hydrogel, it is characterized in that adopting following method preparation: is 6～10% with cellulose dissolution in the NaOH mass percent concentration, the urea quality percentage concentration is in the aqueous solution of 4～12% NaOH/ urea, obtain being dissolved with cellulosic NaOH/ urea combination solution, cellulosic mass percent concentration is 1～6% in the combination solution, be that the ratio of 10:1～1000:1 adds and is of a size of 2～7nm in the mol ratio of Mierocrystalline cellulose and quantum dot then, concentration is 0.1 μ M～200 μ M, and the surface has the CdSe/ZnS quantum dot of carboxyl, the linking agent epoxy chloropropane that adds requirement at last, through chemical crosslink reaction, place under the gelling temp until forming luminescent fibre hydrogel, used cellulosic viscosity-average molecular weight scope is 30,000 to 100,000.
2. the preparation method of the described luminescent fibre hydrogel of claim 1, it is characterized in that concrete preparation process is: is 6～10% with cellulose dissolution in the NaOH mass percent concentration, the urea quality percentage concentration is in the aqueous solution of 4～12% NaOH/ urea, obtain being dissolved with cellulosic NaOH/ urea combination solution, cellulosic mass percent concentration is 1～6% in the combination solution, be that the ratio of 10:1～1000:1 adds and is of a size of 2～7nm in the mol ratio of Mierocrystalline cellulose and quantum dot then, concentration is 0.1 μ M～200 μ M, and the surface has the CdSe/ZnS quantum dot of carboxyl, the linking agent epoxy chloropropane that adds requirement at last, through chemical crosslink reaction, place under the gelling temp until forming luminescent fibre hydrogel.
3. the preparation method of luminescent fibre hydrogel according to claim 2, it is characterized in that: Mierocrystalline cellulose is joined stir in the combination solution of NaOH/ urea after,-10～-20 ℃ freezing 5～24 hours, the stirring of thawing again obtains being dissolved with cellulosic NaOH/ urea combination solution.
4. the preparation method of luminescent fibre hydrogel according to claim 2, it is characterized in that: used CdSe/ZnS quantum dot is hud typed structure, the surface is carboxylated, and presents negative charge.
5. the preparation method of luminescent fibre hydrogel according to claim 2 is characterized in that: the amount of used epoxy chloropropane is 0.1～1.5ml/10g with the ratio that adds the solution before the epoxy chloropropane, and epoxy chloropropane is added dropwise in the solution.
6. the preparation method of luminescent fibre hydrogel according to claim 2, it is characterized in that: gelling temp is 30～80 ℃.
7. the preparation method of luminescent fibre hydrogel according to claim 2, it is characterized in that: the reaction times is 0.5～12 hour.
8. the preparation method of luminescent fibre hydrogel according to claim 2 is characterized in that: the luminescent fibre hydrogel that forms is used distilled water flushing repeatedly, removed residual NaOH, urea and linking agent.
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| CN108277683A (en) * | 2018-01-23 | 2018-07-13 | 福州大学 | A kind of preparation method of the flexible fluorescent paper based on azelon or cell cellulose |
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| CN101716484B (en) * | 2009-12-14 | 2011-10-05 | 江南大学 | Preparation method of fluorescence quantum-dot coding polycaprolactone microballoon sphere |
| CN101857684A (en) * | 2010-06-10 | 2010-10-13 | 武汉大学 | Chitin hydrogel and preparation method and application thereof |
| CN104449738B (en) * | 2014-10-23 | 2016-08-24 | 吉林大学 | Cellulose and semi-conductor nano particles compound, preparation method and the application in LED encapsulates |
| CN108084460A (en) * | 2017-11-15 | 2018-05-29 | 深圳大学 | A kind of cellulose/black phosphorus quantum dot composite hydrogel and preparation method thereof |
| CN107936266B (en) * | 2017-11-15 | 2021-10-26 | 深圳大学 | Cellulose/black phosphorus nanosheet composite hydrogel and preparation method thereof |
| CN107915867B (en) * | 2017-11-24 | 2020-11-27 | 山东大学 | Straw cellulose hydrogel-CdS nano quantum dot composite and preparation method thereof |
| CN110137330A (en) * | 2019-04-04 | 2019-08-16 | 苏州星烁纳米科技有限公司 | Quantum dot LED light source and preparation method thereof |
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| CN1299888A (en) * | 2000-12-27 | 2001-06-20 | 天津南开戈德集团有限公司 | Ultraviolet fluorescent fiber making method |
| CN1577906A (en) * | 2003-06-27 | 2005-02-09 | 三星电子株式会社 | Method for producing quantum dot silicate thin film for light emitting device |
| CN1702100A (en) * | 2005-05-30 | 2005-11-30 | 武汉大学 | Microporous membrane and its preparing process and use thereof |
| CN101164676A (en) * | 2007-08-22 | 2008-04-23 | 武汉大学 | Method for preparing cellulose gel film |
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Patent Citations (4)
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| CN1299888A (en) * | 2000-12-27 | 2001-06-20 | 天津南开戈德集团有限公司 | Ultraviolet fluorescent fiber making method |
| CN1577906A (en) * | 2003-06-27 | 2005-02-09 | 三星电子株式会社 | Method for producing quantum dot silicate thin film for light emitting device |
| CN1702100A (en) * | 2005-05-30 | 2005-11-30 | 武汉大学 | Microporous membrane and its preparing process and use thereof |
| CN101164676A (en) * | 2007-08-22 | 2008-04-23 | 武汉大学 | Method for preparing cellulose gel film |
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| CN108277683A (en) * | 2018-01-23 | 2018-07-13 | 福州大学 | A kind of preparation method of the flexible fluorescent paper based on azelon or cell cellulose |
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