CN101445609B - Hydroscopic cellulose hydrogel and preparation method thereof - Google Patents
Hydroscopic cellulose hydrogel and preparation method thereof Download PDFInfo
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- CN101445609B CN101445609B CN2008101976453A CN200810197645A CN101445609B CN 101445609 B CN101445609 B CN 101445609B CN 2008101976453 A CN2008101976453 A CN 2008101976453A CN 200810197645 A CN200810197645 A CN 200810197645A CN 101445609 B CN101445609 B CN 101445609B
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Abstract
The invention relates to a hydroscopic cellulose hydrogel and a preparation method thereof. The preparation method of the hydrogel is as follows: carboxymethyl cellulose and cellulose are respectively dissolved in the water solution of NaOH/urea in which the concentration of NaOH is 6-10wt%, and the concentration of the urea is 4-12wt%; the NaOH/urea mixed water solution of 1-5wt% of the carboxymethyl cellulose and the NaOH/urea mixed water solution of 1-5wt% of the cellulose are obtained; then the NaOH/urea mixed water solution of the carboxymethyl cellulose and the NaOH/urea mixed water solution of cellulose are mixed according to the weight ratio: 9:1-1:9 and stirred evenly, and the mixed solution is obtained; the mixed solution is also added with certain amount of cross linker epoxy chloropropane; after the chemical cross linking reaction, the mixed solution is placed at the gelatin temperature until the hydroscopic cellulose hydrogel is formed, wherein, the water absorbing capacity is 50-1,000g/g. The hydrogel has very good salt sensitivity and high hydroscopicity and is capable of being widely used in the fields of agriculture, health care and medicine.
Description
Technical field
The present invention relates to a kind of hydroscopic cellulose hydrogel and preparation method thereof, belong to polymeric material field.
Background technology
Plant cellulose is a renewable resources the abundantest on the earth, and carboxymethyl cellulose is cellulosic a kind of derivative, and is the same with Mierocrystalline cellulose, belongs to environment-friendly material.Make full use of Mierocrystalline cellulose and carboxymethyl cellulose and not only can protect environment, and can save limited petroleum resources.Recently, the preparation and the application development of hydrogel are rapider, and their plurality of advantages such as water-absorbent, environmental sensitivity, water-retentivity, biocompatibility etc. receive much concern it.What reported mainly is the synthetic macromolecule hydrogel, and they can not biological degradations and its production application is limited to.And the report of relevant cellulose aquagel all is to be raw material with the derivative after the cellulose-derivedization at present, can not get good intensity.Therefore limited further developing of this class material.
Summary of the invention
The purpose of this invention is to provide a kind of hydroscopic cellulose hydrogel and its production and use, because of the preparation method of this hydroscopic cellulose hydrogel simple, raw materials cost is low, whole technological process is pollution-free, products obtained therefrom water content height has brine sensitivity, good biocompatibility, biodegradable, and show more excellent performance.Particularly introduce carboxymethyl cellulose and make this hydrogel have very high swelling capacity, so this material is with a wide range of applications in agricultural and physiological hygiene field.
Realize that following method prepares for this hydroscopic cellulose hydrogel adopts for technical scheme that the object of the invention adopted: in the aqueous solution that carboxymethyl cellulose, Mierocrystalline cellulose are dissolved in respectively that the NaOH mass percent concentration is 6～10%, the urea quality percentage concentration is 4～12% NaOH/ urea, obtain mass percent concentration and be the NaOH/ urea combination solution of 1～5% carboxymethyl cellulose and mass percent concentration and be 1～5% cellulosic NaOH/ urea combination solution; Be to mix in 9: 1～1: 9 then by weight with the NaOH/ urea combination solution of carboxymethyl cellulose and cellulosic NaOH/ urea combination solution, stir mixing solutions, the linking agent epoxy chloropropane that adds requirement again, through chemical crosslink reaction, place under the gelling temp until forming hydroscopic cellulose hydrogel, its water-intake rate is 50～1000g/g, and used carboxymethyl cellulose, cellulosic viscosity-average molecular weight are 30,000～100,000
Compared with the prior art, the present invention has following advantage:
The present invention is a raw material with the abundantest natural polymer Mierocrystalline cellulose and the derivative thereof in source, and wherein, dissolution process is for very easy, quick, free of contamination process.This preparation method and the hydrogel that makes thereof have tangible technical progress than existent method.Wherein, crosslinking reaction is also 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.Particularly introducing carboxymethyl cellulose makes this hydrogel have very high swelling capacity.
Description of drawings
Accompanying drawing for the water-absorption fiber hydrogel of the present invention preparation at the photo under the various states: (a) be in hydrogel under the solvent swelling state after the suction; (b) xerogel; (c) hydrogel after the contraction in sodium chloride solution.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described further:
3 gram carboxymethyl celluloses are scattered in 97 grams contain in the mixed aqueous solution of 6wt%NaOH and 4wt% urea, at room temperature stir and dissolve until carboxymethyl cellulose.With 3 gram Mierocrystalline cellulose (viscosity-average molecular weight M
η=3.5 * 10
4) be scattered in 97 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.Get 90g cmc soln and 10g cellulose solution and mix, wherein carboxymethyl cellulose and cellulosic weight ratio are 9: 1, and carboxymethyl cellulose and Mierocrystalline cellulose close and account for 3% of solution.The epoxy chloropropane of 10ml is added drop-wise in the 100g mixing solutions, is warming up to 60 ℃, obtain carboxymethyl cellulose and cellulosic weight ratio after 2 hours and be 9: 1 water-absorption fiber hydrogel.Water-intake rate is 1000g/g.
Embodiment 2
3 gram carboxymethyl celluloses are scattered in 97 grams contain in the mixed aqueous solution of 8wt%NaOH and 10wt% urea, at room temperature stir and dissolve until carboxymethyl cellulose.With 3 gram Mierocrystalline cellulose (viscosity-average molecular weight M
η=3.5 * 10
4) be scattered in the mixed aqueous solution of 97 gram 8wt%NaOH and 10wt% urea, be chilled to-20～-10 ℃ in advance, thawing after 5～24 hours to stir obtains transparent cellulose solution.Get 80g cmc soln and 20g cellulose solution and mix, wherein carboxymethyl cellulose and cellulosic weight ratio are 8: 2, and carboxymethyl cellulose and Mierocrystalline cellulose close and account for 3% of solution.The epoxy chloropropane of 10ml is added drop-wise in the 100g mixing solutions, is warming up to 50 ℃, obtain carboxymethyl cellulose and cellulosic weight ratio after 6 hours and be 8: 2 water-absorption fiber hydrogel.Water-intake rate is 800g/g.
Embodiment 3
3 gram carboxymethyl celluloses are scattered in 97 grams contain in the mixed aqueous solution of 6wt%NaOH and 4wt% urea, at room temperature stir and dissolve until carboxymethyl cellulose.With 3 gram Mierocrystalline cellulose (viscosity-average molecular weight M
η=3.5 * 10
4) be scattered in 97 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.Get 70g cmc soln and 30g cellulose solution and mix, wherein carboxymethyl cellulose and cellulosic weight ratio are 7: 3, and carboxymethyl cellulose and Mierocrystalline cellulose close and account for 3% of solution.The epoxy chloropropane of 10ml is added drop-wise in the 100g mixing solutions, is warming up to 40 ℃, obtain carboxymethyl cellulose and cellulosic weight ratio after 10 hours and be 7: 3 water-absorption fiber hydrogel.Water-intake rate is 500g/g.
Embodiment 4
3 gram carboxymethyl celluloses are scattered in 97 grams contain in the mixed aqueous solution of 6～8wt%NaOH and 10～12wt% urea, at room temperature stir and dissolve until carboxymethyl cellulose.With 3 gram Mierocrystalline cellulose (viscosity-average molecular weight M
η=3.5 * 10
4) be scattered in 97 grams and contain in the mixed aqueous solution of 6～8wt%NaOH and 10～12wt% urea, be chilled to-20～-10 ℃ in advance, thawing after 5～24 hours to stir obtains transparent cellulose solution.Get 60g cmc soln and 40g cellulose solution and mix, wherein carboxymethyl cellulose and cellulosic weight ratio are 6: 4, and carboxymethyl cellulose and Mierocrystalline cellulose close and account for 3% of solution.The epoxy chloropropane of 10ml is added drop-wise in the 100g mixing solutions, is warming up to 30 ℃, obtain carboxymethyl cellulose and cellulosic weight ratio after 12 hours and be 6: 4 water-absorption fiber hydrogel.Water-intake rate is 400g/g.
Embodiment 5
3 gram carboxymethyl celluloses are scattered in 97 grams contain in the mixed aqueous solution of 8wt%NaOH and 10wt% urea, at room temperature stir and dissolve until carboxymethyl cellulose.With 3 gram Mierocrystalline cellulose (viscosity-average molecular weight M
η=3.5 * 10
4) be scattered in 97 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.Get 50g cmc soln and 50g cellulose solution and mix, wherein carboxymethyl cellulose and cellulosic weight ratio are 5: 5, and carboxymethyl cellulose and Mierocrystalline cellulose close and account for 3% of solution.The epoxy chloropropane of 10ml is added drop-wise in the 100g mixing solutions, is warming up to 60 ℃, obtain carboxymethyl cellulose and cellulosic weight ratio after 2 hours and be 5: 5 water-absorption fiber hydrogel.Water-intake rate is 200g/g.
The water-absorption fiber hydrogel that embodiment 5 makes is done water absorption test, the results are shown in accompanying drawing, a is for being in the hydrogel photo under the solvent swelling state among the figure after absorbing water; B is the xerogel photo; C is the hydrogel photo after shrinking in sodium chloride solution.
Embodiment 6
3 gram carboxymethyl celluloses are scattered in 97 grams contain in the mixed aqueous solution of 6wt%NaOH and 4wt% urea, at room temperature stir and dissolve until carboxymethyl cellulose.With 3 gram Mierocrystalline cellulose (viscosity-average molecular weight M
η=3.5 * 10
4) be scattered in 97 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.Get 90g cmc soln and 10g cellulose solution and mix, wherein carboxymethyl cellulose and cellulosic weight ratio are 1: 9, and carboxymethyl cellulose and Mierocrystalline cellulose close and account for 3% of solution.The epoxy chloropropane of 10ml is added drop-wise in the 100g mixing solutions, is warming up to 60 ℃, obtain carboxymethyl cellulose and cellulosic weight ratio after 2 hours and be 1: 9 water-absorption fiber hydrogel.Water-intake rate is 50g/g.
That raw cellulose is used in the foregoing description all is viscosity-average molecular weight M
η=3.5 * 10
4Mierocrystalline cellulose, in the reality, the raw cellulose viscosity-average molecular weight is can both satisfy the dissolved requirement at 30,000～100,000 o'clock, all can adopt.
Claims (7)
1. hydroscopic cellulose hydrogel, it is characterized in that adopting following method preparation: in the aqueous solution that carboxymethyl cellulose, Mierocrystalline cellulose are dissolved in respectively that the NaOH mass percent concentration is 6～10%, the urea quality percentage concentration is 4～12% NaOH/ urea, obtain mass percent concentration and be the NaOH/ urea combination solution of 1～5% carboxymethyl cellulose and mass percent concentration and be 1～5% cellulosic NaOH/ urea combination solution; Be to mix in 9: 1～1: 9 then by weight with the NaOH/ urea combination solution of carboxymethyl cellulose and cellulosic NaOH/ urea combination solution, stir mixing solutions, the linking agent epoxy chloropropane that adds requirement again, through chemical crosslink reaction, place under the gelling temp until forming hydroscopic cellulose hydrogel, its water-intake rate is 50～1000g/g, and used carboxymethyl cellulose, cellulosic viscosity-average molecular weight are 30,000～100,000.
2. the preparation method of the described hydroscopic cellulose hydrogel of claim 1, it is characterized in that concrete preparation process is: in the aqueous solution that carboxymethyl cellulose, Mierocrystalline cellulose are dissolved in respectively that the NaOH mass percent concentration is 6～10%, the urea quality percentage concentration is 4～12% NaOH/ urea, obtain mass percent concentration and be the NaOH/ urea combination solution of 1～5% carboxymethyl cellulose and mass percent concentration and be 1～5% cellulosic NaOH/ urea combination solution; Be to mix in 9: 1～1: 9 then by weight with the NaOH/ urea combination solution of carboxymethyl cellulose and cellulosic NaOH/ urea combination solution, stir mixing solutions, the linking agent epoxy chloropropane that adds requirement again, through chemical crosslink reaction, place under the gelling temp until forming hydroscopic cellulose hydrogel, used cellulosic viscosity-average molecular weight is 30,000～100,000.
3. the preparation method of hydroscopic cellulose hydrogel according to claim 2, it is characterized in that: stir in the NaOH/ aqueous solution of urea until the carboxymethyl cellulose dissolving adding under the carboxymethyl cellulose room temperature, obtain the NaOH/ urea combination solution of carboxymethyl cellulose.
4. the preparation method of hydroscopic cellulose hydrogel according to claim 2, it is characterized in that: with add under the Mierocrystalline cellulose room temperature stir in the NaOH/ aqueous solution of urea after,-20～-10 ℃ freezing 5～24 hours, the stirring of thawing obtains cellulosic NaOH/ urea combination solution.
5. the preparation method of hydroscopic cellulose hydrogel according to claim 2, it is characterized in that: the amount of the epoxy chloropropane of adding and the ratio of mixing solutions are 0.5～1.5ml/10g.
6. the preparation method of hydroscopic cellulose hydrogel according to claim 2, it is characterized in that: gelling temp is 30～60 ℃.
7. the preparation method of hydroscopic cellulose hydrogel according to claim 2, it is characterized in that: gel time is 2～12 hours.
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| CN101880410B (en) * | 2010-07-21 | 2014-08-13 | 武汉大学 | High-strength transparent cellulose material and preparation method thereof |
| WO2015097033A1 (en) * | 2013-12-23 | 2015-07-02 | Basf Se | Polysaccharide hydrogels |
| CN103788217B (en) * | 2013-12-26 | 2016-05-11 | 昆明理工大学 | A kind of cellulose gel glue material, Preparation method and use |
| CN104387609B (en) * | 2014-11-18 | 2018-06-01 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of cellulose porous adsorbing material |
| DE102015121383B4 (en) * | 2015-12-08 | 2017-10-12 | Technische Universität Berlin | Modified cellulose fibers, process for their preparation, their use, filter aids or filter plates and methods for the artificial clarification of turbid liquids |
| CN106084259B (en) * | 2016-07-29 | 2019-01-18 | 华南理工大学 | A kind of preparation method of cellulose aquagel |
| CN106492266B (en) * | 2016-10-14 | 2019-08-06 | 湖北大学 | A kind of surface has antibacterial nano-silver/zinc oxide composite hydrogel dressing preparation method |
| CN107200853B (en) * | 2017-05-27 | 2020-01-31 | 武汉理工大学 | dendrimer/carboxymethyl cellulose super-absorbent gel and preparation and application thereof |
| CN107254069A (en) * | 2017-06-26 | 2017-10-17 | 苏州凌科特新材料有限公司 | A kind of cellulose family high hydroscopic resin and preparation method thereof |
| CN108976481B (en) * | 2018-07-20 | 2020-11-20 | 广西大学 | Thiourea-modified cellulose-based hydrogel and preparation method thereof |
| CN109912830A (en) * | 2019-03-10 | 2019-06-21 | 深港产学研基地 | Dopamine/bacterial cellulose gel preparation method |
| CN112108016A (en) * | 2020-10-13 | 2020-12-22 | 天津工业大学 | Preparation method of spider-web-structure-imitated oil-water separation membrane |
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