CN102061000B - Method for dissolving bacterial cellulose with high polymerization degree - Google Patents
Method for dissolving bacterial cellulose with high polymerization degree Download PDFInfo
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- CN102061000B CN102061000B CN2010105984511A CN201010598451A CN102061000B CN 102061000 B CN102061000 B CN 102061000B CN 2010105984511 A CN2010105984511 A CN 2010105984511A CN 201010598451 A CN201010598451 A CN 201010598451A CN 102061000 B CN102061000 B CN 102061000B
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- aqueous solution
- polymerization degree
- bacterial cellulose
- bacteria cellulose
- zncl
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention relates to a method for dissolving bacterial cellulose with high polymerization degree, comprising the steps of: (1) boiling bacterial cellulose with the polymerization degree of 1500-6000 by using a NaOH aqueous solution, washing with distilled water to a neutral state, drying in vacuum, and grinding into powder for later use: and (2) preparing a ZnCl2 aqueous solution with the mass fraction of 65-80%, adding the bacterial cellulose obtained in the step (1) into the ZnCl2 aqueous solution, stirring for reaction till the bacterial cellulose is completely dissolved and obtaining a bacterial cellulose solution. The method provided by the invention has the advantages of simple dissolving process and easily controlled technology, can be used for directly dissolving the bacterial cellulose without activation, and can ensure that the bacterial cellulose is not subjected to derivatization and is kept with favorable property; and compared with other novel cellulose solvent systems of methyl morpholine oxide, ionic liquid and LiCl/DMAC (Dimethylacetylamide), the used ZnCl2 solvent system has the advantages of greenness, stability, low price, easiness of recovery and the like.
Description
Technical field
The invention belongs to the dissolving field of bacteria cellulose, particularly a kind of dissolving method of high-polymerization degree bacteria cellulose.
Background technology
Mierocrystalline cellulose extensively exists on the earth, is the abundantest natural polymer of occurring in nature.Except plant cellulose, with acetobacter xylinum (Acetobacter Xylinum) but be the also synthetic cellulose of certain micro-organisms of representative, be referred to as bacteria cellulose (BC).Bacteria cellulose is the fiber substance that micromolecular glucide forms through microbial fermentation.There are association products such as no xylogen, pectin and semicellulose in the hyperfine fibre network that it is made up of ultra-fine fibre with the form of pure cellulose.Compare with the traditional plant Mierocrystalline cellulose; Bacterial fibers have many premium propertiess; As purity is high, the polymerization degree is big, percent crystallinity is high, wetting ability is strong, Young's modulus is high, tensile strength is high, anti-tear ability is strong; And have than high-biocompatibility, biological fitness and favorable biological degradability,, under conditions such as acidity, mikrobe and cellulase catalysis, can be biodegradable into small-molecule substances such as monose at occurring in nature.Therefore, bacteria cellulose receives the extensive concern of scientific circles as a kind of new microbial synthetic materials, has obtained widespread use at aspects such as foodstuffs industry, biomedical material, photovaltaic material, strongtheners.
Bacteria cellulose itself be exactly a kind of width be that 30～100nm, thickness are the silk ribbon shape fiber of 3～8nm.It as fiber, is both saved soil (bacteria cellulose output of equal area soil production is cotton 100 times), do not received factor affecting such as weather again; Do not consume petroleum; Biodegradable behind production process cleaning, the product abandonment, therefore have the characteristic of ecological fiber.But the product of bacteria cellulose is three-dimensional manometer network film at present, and integral body can be used as nano material and uses, but fiber separation wherein is very difficult, is difficult to direct weaving, has therefore limited its application in fiber art.
Have a lot of hydroxyls in the bacteria cellulose macromole, intramolecularly, intermolecular ydrogen bonding effect are strong, and the Mierocrystalline cellulose aggregate percent crystallinity that forms is high, and the polymerization degree is big, and physicochemical property is stable, and second-order transition temperature is higher.Therefore before being heated to cellulosic melt temperature, Mierocrystalline cellulose decomposes, is difficult to melt-processed.And compare plant cellulose, bacteria cellulose has more complicated microtexture, makes bacteria cellulose than the more difficult processing of plant cellulose.Seeking the suitable solvent dissolution of bacteria cellulose, dissolve processing, is the main direction of studying of cellulose regenerated processing.
Summary of the invention
Technical problem to be solved by this invention provides a kind of dissolving method of high-polymerization degree bacteria cellulose; This method dissolution process is simple, and technology controlling and process is easy, and the direct dissolving of bacteria cellulose is not needed activation; Do not make it that derivatize take place, can keep the bacteria cellulose excellent characteristic; Employed ZnCl
2Solvent system is compared with other Mierocrystalline cellulose novel dissolvent systems such as oxidation methyl morpholine, ionic liquid and LiCl/DMAC, has green, stable, low price, is easy to advantage such as recovery.
The dissolving method of a kind of high-polymerization degree bacteria cellulose of the present invention comprises:
(1) with the polymerization degree be the bacteria cellulose of 1500-6000 with NaOH aqueous solution poach, be washed with distilled water to neutrality afterwards, vacuum-drying, grinding powder is subsequent use;
(2) the configuration quality mark is the ZnCl of 65%-80%
2The aqueous solution, the bacteria cellulose powder that step (1) is obtained is by ZnCl
2Aqueous solution massfraction 0.5%～10% joins ZnCl in 75～100 ℃
2Stirring reaction 1～2h in the aqueous solution is cooled to 50～75 ℃ of continuation stirring reaction 1～4h with solution then and dissolves fully to it, makes bacterial cellulose solution.
NaOH aqueous solution massfraction in the said step (1) is 1%, and the poach temperature is 80～100 ℃, and the poach time is 30～60min, and the vacuum-drying temperature is 60～90 ℃.
Said poach temperature is 80 ℃, and the poach time is 45min, and the vacuum-drying temperature is 75 ℃.
ZnCl in the said step (2)
2The massfraction proportioning of zinc chloride and water satisfies ZnCl in the aqueous solution
2.nH
2O, n=2～4.
Reaction in the said step (2) is carried out in a vacuum, and feeds protection of inert gas.
The bacterial cellulose solution transparency that makes in the said step (2) is high, is true solution.
Beneficial effect
(1) dissolution process of the present invention is simple, and technology controlling and process is easy, and the direct dissolving of bacteria cellulose is not needed activation, does not make it that derivatize take place, and can keep the bacteria cellulose excellent characteristic;
(2) ZnCl used in the present invention
2Solvent system is compared with other Mierocrystalline cellulose novel dissolvent systems such as oxidation methyl morpholine, ionic liquid and LiCl/DMAC, has green, stable, low price, is easy to advantage such as recovery.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
With the polymerization degree be 1756 bacteria cellulose with the 1wt%NaOH aqueous solution at 80 ℃ of following poach 45min, then use the zero(ppm) water thorough washing to neutral (pH=7.0), under 75 ℃, carry out vacuum-drying 12h, and grinding powder; The configuration quality mark is the ZnCl of 65wt%
2The aqueous solution is heated to zinc chloride and dissolves fully, and this solvent system satisfies ZnCl
2.4H
2O; With ZnCl
2The above-mentioned bacteria cellulose powder of aqueous solution 6wt% joins in the solvent that is disposed, and reactor drum is vacuumized, and charges into N
2Protect, stir down fast 45min, then, reduce system temperature to 60 ℃, continue to stir fast 1.5h, obtain consoluet bacterial cellulose solution at 80 ℃.The bacterial cellulose solution that present embodiment obtained is faint yellow, and transparency is higher, and system viscosity is less.
Embodiment 2
With the polymerization degree be 2836 bacteria cellulose with the 1wt%NaOH aqueous solution at 80 ℃ of following poach 30min, then use the zero(ppm) water thorough washing to neutral (pH=7.0), under 60 ℃, carry out vacuum-drying 12h, and grinding powder; The configuration quality mark is the ZnCl of 71.5wt%
2The aqueous solution is heated to zinc chloride and dissolves fully, and this solvent system satisfies ZnCl
2.3H
2O; With ZnCl
2The above-mentioned bacteria cellulose powder of aqueous solution 6wt% joins in the solvent of configuration, and reactor drum is vacuumized, and charges into N
2Protect, stir down fast 75min, then, reduce system temperature to 65 ℃, continue to stir fast 2.5h, obtain consoluet bacteria cellulose true solution at 80 ℃.The bacterial cellulose solution that present embodiment obtained is brown, and transparency is higher, and system viscosity is bigger, can be in order to preparation regenerated bacteria cellulosefilm and regenerated bacteria cellulosic fibre.
Embodiment 3
With the polymerization degree be 3520 bacteria cellulose with the 1wt%NaOH aqueous solution at 80 ℃ of following poach 60min, then use the zero(ppm) water thorough washing to neutral (pH=7.0), under 90 ℃, carry out vacuum-drying 12h, and grinding powder; The configuration quality mark is the ZnCl of 71.5wt%
2The aqueous solution is heated to zinc chloride and dissolves fully, and this solvent system satisfies ZnCl
2.3H
2O; With ZnCl
2The above-mentioned bacteria cellulose powder of aqueous solution 5wt% joins in the solvent of configuration, and reactor drum is vacuumized, and charges into N
2Protect, stir down fast 75min, then, reduce system temperature to 70 ℃, continue to stir fast 2.5h, obtain consoluet bacterial cellulose solution at 80 ℃.The bacterial cellulose solution that present embodiment obtained is dark-brown, translucency, and system viscosity is bigger, can be in order to preparation regenerated bacteria cellulosefilm and regenerated bacteria cellulosic fibre.
Embodiment 4
With the polymerization degree be 4283 bacteria cellulose with the 1wt%NaOH aqueous solution at 80 ℃ of following poach 45min, then use the zero(ppm) water thorough washing to neutral (pH=7.0), under 75 ℃, carry out vacuum-drying 12h, and grinding powder; The configuration quality mark is the ZnCl of 71.5wt%
2The aqueous solution is heated to zinc chloride and dissolves fully, and this solvent system satisfies ZnCl
2.3H
2O; With ZnCl
2The above-mentioned bacteria cellulose powder of aqueous solution 5wt% adds in the solvent of configuration, and reactor drum is vacuumized, and charges into N
2Protect, stir down fast 90min, then, reduce system temperature to 70 ℃, continue to stir fast 2h, obtain consoluet bacterial cellulose solution at 80 ℃.The bacterial cellulose solution that present embodiment obtained is dark-brown, translucency, and system viscosity is bigger, can be in order to preparation regenerated bacteria cellulosefilm and regenerated bacteria cellulosic fibre.
Embodiment 5
With the polymerization degree be 5120 bacteria cellulose with the 1wt%NaOH aqueous solution at 80 ℃ of following poach 45min, then use the zero(ppm) water thorough washing to neutral (pH=7.0), under 75 ℃, carry out vacuum-drying 12h, and grinding powder; The configuration quality mark is the ZnCl of 71.5wt%
2The aqueous solution is heated to zinc chloride and dissolves fully, and this solvent system satisfies ZnCl
2.3H
2O; With ZnCl
2The above-mentioned bacteria cellulose powder of aqueous solution 4wt% joins in the solvent of configuration, and reactor drum is vacuumized, and charges into N
2Protect, stir down fast 2h, then, reduce system temperature to 75 ℃, continue to stir fast 3h, obtain consoluet bacterial cellulose solution at 85 ℃.The bacterial cellulose solution that present embodiment obtained is dark-brown, translucency, and system viscosity is bigger, can be in order to preparation regenerated bacteria cellulosefilm and regenerated bacteria cellulosic fibre.
Claims (6)
1. the dissolving method of a high-polymerization degree bacteria cellulose comprises:
(1) with the polymerization degree be the bacteria cellulose of 1500-6000 with NaOH aqueous solution poach, be washed with distilled water to neutrality afterwards, vacuum-drying, grinding powder is subsequent use;
(2) the configuration quality mark is the ZnCl of 65%-80%
2The aqueous solution, the bacteria cellulose powder that step (1) is obtained is by ZnCl
2Aqueous solution massfraction 0.5%～10% joins ZnCl in 75～100 ℃
2Stirring reaction 1～2h in the aqueous solution is cooled to 50～75 ℃ of continuation stirring reaction 1～4h with solution then and dissolves fully to it, makes bacterial cellulose solution.
2. the dissolving method of a kind of high-polymerization degree bacteria cellulose according to claim 1; It is characterized in that: the NaOH aqueous solution massfraction in the said step (1) is 1%; The poach temperature is 80～100 ℃, and the poach time is 30～60min, and the vacuum-drying temperature is 60～90 ℃.
3. the dissolving method of a kind of high-polymerization degree bacteria cellulose according to claim 2 is characterized in that: said poach temperature is 80 ℃, and the poach time is 45min, and the vacuum-drying temperature is 75 ℃.
4. the dissolving method of a kind of high-polymerization degree bacteria cellulose according to claim 1 is characterized in that: the ZnCl in the said step (2)
2The massfraction proportioning of zinc chloride and water satisfies ZnCl in the aqueous solution
2.nH
2O, n=2～4.
5. the dissolving method of a kind of high-polymerization degree bacteria cellulose according to claim 1 is characterized in that: the reaction in the said step (2) is carried out in a vacuum, and feeds protection of inert gas.
6. the dissolving method of a kind of high-polymerization degree bacteria cellulose according to claim 1 is characterized in that: the bacterial cellulose solution transparency that makes in the said step (2) is high, is true solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105984511A CN102061000B (en) | 2010-12-21 | 2010-12-21 | Method for dissolving bacterial cellulose with high polymerization degree |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105984511A CN102061000B (en) | 2010-12-21 | 2010-12-21 | Method for dissolving bacterial cellulose with high polymerization degree |
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| Publication Number | Publication Date |
|---|---|
| CN102061000A CN102061000A (en) | 2011-05-18 |
| CN102061000B true CN102061000B (en) | 2012-07-25 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102816810B (en) * | 2012-09-10 | 2014-06-04 | 广东省微生物研究所 | Method for preparing bacterial cellulose microbes for controlling polymerization degrees of bacterial cellulose |
| CN108676099A (en) * | 2018-05-17 | 2018-10-19 | 天津科技大学 | A kind of preparation method of oxidizing bacteria cellulose solution |
| CN110041564A (en) * | 2019-03-29 | 2019-07-23 | 北京林业大学 | The in-situ preparation method of cellulose antibacterial film, the cellulose antibacterial film by this method preparation and its application |
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2010
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Non-Patent Citations (1)
| Title |
|---|
| 熊犍等.纤维素在ZnCl2水溶液中的溶解性能及再生结构.《华南理工大学学报（自然科学版）》.2010,第38卷(第2期),第23-27页. * |
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