CN101164676A - Method for preparing cellulose gel film - Google Patents
Method for preparing cellulose gel film Download PDFInfo
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- CN101164676A CN101164676A CNA2007100530120A CN200710053012A CN101164676A CN 101164676 A CN101164676 A CN 101164676A CN A2007100530120 A CNA2007100530120 A CN A2007100530120A CN 200710053012 A CN200710053012 A CN 200710053012A CN 101164676 A CN101164676 A CN 101164676A
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Abstract
The present invention discloses a preparation method of cellulose hydrogel membrane. Said preparation method includes the following steps: (1), dissolving the cellulose in sodium hydroxide and urea mixed solution or sodium hydroxide and sulfourea mixed solution with-15deg.C- -5deg.C to make precooling treatment to obtain cellulose solution whose cellulose content is 0.01wt%-10wt%; (2), making the cellulose solution undergo the process of centrifugal defoaming treatment, then placing the cellutose solution in a mould and sealing, under the condition of that its pregelatification temperature is -20-40deg.C making pregelatification treatment of solution so as to obtain cellulose physical gel; (3), making the cellulose physical gel be soaked in deionized water until the solvent component sodium hydroxide, sulfourea or urea are removed from said gel to obtain cellulose gel membrane; and (4), placing the cellulose gel membrane into a swelling agent and removing water content so as to obtain the invented high-strength cellulose gel membrane.
Description
Technical field
The present invention relates to a kind of preparation method of cellulose gel film, both belonged to the natural polymer field, also belong to chemistry, health, agricultural, environmental project and material engineering field.
Background technology
Because biomembrane material is in bio-separation, fields such as organizational project and food processing have broad application prospects, so get more and more people's extensive concerning.Then owing to good chemical stability, recyclability and biocompatibility make it become one of membrane material that is most widely used, and are bringing into play enormous function in fields such as dialysis, ultrafiltration, counter-infiltrations for regenerated cellulose film and derivative thereof.Regenerated cellulose film mainly adopts viscose process and organic solvent method of reproduction to be prepared, but has caused serious environmental to pollute thus, has hindered the sustainable development of human society.At present, successfully developed a series ofly with NaOH, urea or thiocarbamide, water are the novel solvent system of component.These solvents are cellulosic direct solvent, adopt K cryogenic treatment, rapidly dissolving cellulos.Utilize the novel solvent system, adopt spin processes successfully to prepare cellulose fibre with high tensile, but because the quick random gathering of cellulose chain in the process of setting, in the novel solvent system, adopt cellulose gel film general intensity under hygrometric state of casting filming therapy preparation lower, thereby be difficult to be competent at application in fields such as organizational projects, and utilize that though the dual network technology can prepare some have the powerful cellulose composite aquogel of learning performance such as cellulose/gelatin double-network hydrogel etc., it is loaded down with trivial details but to have process, is unfavorable for the shortcoming of large-scale production.
Summary of the invention
The high pollution, the wet strength that exist in the prior art are low, process is loaded down with trivial details in order to overcome, be unfavorable for the problem of large-scale production, the invention provides a kind of method for preparing cellulose gel film, this method not only can solve the environmental problem of being brought in the cellulose membrane preparation process, and can enhance product performance, reduce production costs, be suitable for suitability for industrialized production.
For achieving the above object, the technical solution adopted in the present invention is as follows:
A kind of preparation method of cellulose gel film, adopt following concrete steps:
(1) cellulose is scattered in the mixed solvent of ℃ cooling processing in advance-15～-5, be made into the cellulose solution that content of cellulose is 0.01wt%～10wt%, mixed solvent is that sodium hydrate content is 4～12wt%, urea content is the mixed aqueous solution of 8～20wt%, or sodium hydrate content is 1～10wt%, and thiocarbamide content is the mixed aqueous solution of 4～15wt%;
(2) the cellulose solution evacuation and centrifugal degassing is handled to be placed in the mould seal, under-20～40 ℃ pregel temperature, carry out the solution gel processing and obtain cellulose physics gel;
(3) cellulose physics gel is soaked in the deionized water obtains the fiber water gel mould behind solvent composition NaOH, urea or the thiocarbamide in removing gel.
(4) gained fiber water gel mould is placed sweller fully soak the back of anhydrating and obtain the plain gel mould of high strength fibre.
Described mould is the mould that glass, stainless steel or various engineering plastics are made.
Described sweller is the mixed solution of mixed solution, polyethylene glycol and glycerine of water, polyethylene glycol, glycerine, water and polyethylene glycol mixed solution, water and glycerine or polyethylene glycol and water and glycerine three's mixed solution.
Compared with prior art, innovation of the present invention is as follows:
(1) the solvent for use system is NaOH/urea or NaOH/thiocarbamide dicyandiamide solution, both are cellulosic direct solvent system, fast the solvent polymerization degree is up to 800 various native celluloses, its concentration of ordinary dissolution can reach 10wt%, regenerated cellulose film by this system preparation has high porosity (＞80%), high strength advantages such as (hot strength can reach 100MPa during dry state), and the pattern of film and mechanical property can be regulated according to cellulose solution concentration and curing condition.
(2) according to cellulose solution Research on The Rheology achievement, the present invention has introduced the quiescent solution gel conversion first and has handled in preparation cellulose gel membrane process.Because cellulose chain activity under the physical gel attitude reduces, thereby effectively avoid the quick random accumulation of regenerative process medium chain, help forming structure closely and the gel mould of homogeneous.
(3) compare with other industrial processes such as Lyocell technology, technology of the present invention is simple, helps saving production cost, and the moulding of film is very convenient; Compare with the method for preparing high-strength gel such as nanometer composite technology, topological crosslinking technological and the dual network technology of nearest exploitation, this invention preparation method is simple, has avoided chemical crosslinking loaded down with trivial details in the preparation process, processing such as the introducing of dual network.
(4) the gel mould mechanical property of the present invention preparation is better than the cellulose membrane that is equipped with by traditional curtain coating legal system far away, and structure and performance can be by the controls of pregel temperature.
(5) this invention preparation process environmental protection is pollution-free, is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is the comparison diagram of mechanical property with the mechanical property of the cellulose gel film that adopts technical scheme provided by the invention to produce of the cellulose membrane of employing casting filming therapy preparation.
Fig. 2 is for the cellulose aquagel film that adopts the inventive method preparation and by the stress-strain diagram of the cellulose gel film of different molecular weight polyethylene glycol swelling.
Curve a, b and c correspond respectively to the (NH with 5.0wt% among Fig. 1
4)
2SO
4Solution and deionized water are coagulating agent by the stress-strain diagram of two kinds of cellulose gel films of The tape casting preparation and with the stress-strain diagram of the cellulose gel film of technology preparation of the present invention.
Curve a is the stress-strain diagram of the cellulose aquagel film of embodiment 1 preparation among Fig. 2, and stress-strain diagram b, c, d, e are respectively the stress-strain diagram of the cellulose gel film of embodiment 4,5,6 and 7 preparations.
The specific embodiment
Embodiment 1
5g cotton linters cellulose slurry is scattered in 100g and is chilled in advance in-5 ℃ the 4.5wt%NaOH/9.5wt% thiocarbamide mixed aqueous solution, stirred 10 minutes, obtain transparent cellulose solution.Cellulose solution after handling 10 minutes, evacuation and centrifugal degassing under the 8000rpm/min is injected special glass frame and sealing with ultracentrifuge.The instrument bezel that cellulose solution is housed was carried out solution gel down in freezing 12 hours at-20 ℃ to be handled, under 5 ℃, thaw then cellulose physics gel, then gained cellulose physics gel is taken out from mould and be placed on NaOH and the thiocarbamide of removing in the deionized water in the gel, deionized water upgraded once every about 5 hours, promptly obtained the cellulose aquagel film after cleaning about three times repeatedly.Its stress-strain diagram is seen a among Fig. 2.
7g cotton linters cellulose slurry is scattered in 100g and is chilled in advance in-10 ℃ the 7.0wt%NaOH/10.5wt% urea mixed aqueous solution, stirred 10 minutes, obtain transparent cellulose solution.Solution after handling 10 minutes, evacuation and centrifugal degassing under the 8000rpm/min is injected special glass frame and sealing with ultracentrifuge.With instrument bezel that cellulose solution is housed 5 ℃ preserve carried out in three weeks solution gel handle cellulose physics gel, gained cellulose physics gel takes out from mould and is placed on NaOH and the urea of removing in the deionized water in the gel then, deionized water upgraded once every about 5 hours, promptly obtained the cellulose aquagel film after cleaning three times repeatedly.
Embodiment 3
4g cotton linters cellulose slurry is scattered in 100g and is chilled in advance in-5 ℃ the 6.0wt%NaOH/9.5wt% urea mixed aqueous solution, stirred 10 minutes, obtain transparent cellulose solution.Cellulose solution after handling 10 minutes, evacuation and centrifugal degassing under the 8000rpm/min is injected special glass frame and sealing with ultracentrifuge.The instrument bezel that cellulose solution is housed was carried out getting cellulose physics gel after solution gel is handled 25 ℃ of preservations in one week, then gained cellulose physics gel is taken out from mould and be placed on NaOH and the urea of removing in the deionized water in the gel, deionized water upgraded once every about 5 hours, promptly obtained the cellulose aquagel film after cleaning three times repeatedly.
Embodiment 4
5g cotton linters cellulose slurry is scattered in 100g and is chilled in advance in-5 ℃ the 4.5wt%NaOH/9.5wt% thiocarbamide mixed aqueous solution, stirred 10 minutes, obtain transparent cellulose solution.Cellulose solution after handling 10min, evacuation and centrifugal degassing under the 8000rpm/min is injected special glass frame and sealing with ultracentrifuge.The instrument bezel that cellulose solution is housed was carried out solution gel down in freezing 12 hours at-20 ℃ handle, under 5 ℃, thaw then.Then gained cellulose physics gel is taken out from mould and be placed on NaOH and the thiocarbamide of removing in the deionized water in the gel, deionized water every renewal in about 5 hours once promptly obtains the cellulose aquagel film after cleaning three times repeatedly.At last gained cellulose aquagel film being placed at normal temperatures molecular weight is that 200 polyethylene glycol soaks, and fully removes the water in the cellulose aquagel film, obtains the cellulose gel film by the polyethylene glycol swelling, and its stress-strain diagram is seen the b among Fig. 2.
Embodiment 5
5g cotton linters cellulose slurry is scattered in 100g and is chilled in advance in-5 ℃ the 4.5wt%NaOH/9.5wt% thiocarbamide mixed aqueous solution, stirred 10 minutes, obtain transparent cellulose solution.Cellulose solution after handling 10min, evacuation and centrifugal degassing under the 8000rpm/min is injected special glass frame and sealing with ultracentrifuge.The instrument bezel that cellulose solution is housed was carried out solution gel down in freezing 12 hours at-20 ℃ handle, under 5 ℃, thaw then.Then gained cellulose physics gel is taken out from mould and be placed on NaOH and the thiocarbamide of removing in the deionized water in the gel, deionized water every renewal in about 5 hours once promptly obtains the cellulose aquagel film after cleaning about three times repeatedly.At last gained cellulose aquagel film being placed at normal temperatures molecular weight is that 400 polyethylene glycol soaks, and fully removes the water in the cellulose aquagel film, obtains the cellulose gel film by the polyethylene glycol swelling, and its stress-strain diagram is seen the c among Fig. 2.
5g cotton linters cellulose slurry is scattered in 100g and is chilled in advance in-5 ℃ the 4.5wt%NaOH/9.5wt% thiocarbamide mixed aqueous solution, stirred 10 minutes, obtain transparent cellulose solution.Cellulose solution after handling 10min, evacuation and centrifugal degassing under the 8000rpm/min is injected special glass frame and sealing with ultracentrifuge.The instrument bezel that cellulose solution is housed was carried out solution gel down in freezing 12 hours at-20 ℃ handle, under 5 ℃, thaw then.Then gained cellulose physics gel is taken out from mould and be placed on NaOH and the thiocarbamide of removing in the deionized water in the gel, deionized water every renewal in about 5 hours once promptly obtains the cellulose aquagel film after cleaning about three times repeatedly.At last gained cellulose aquagel film being placed at normal temperatures molecular weight is that 600 polyethylene glycol soaks, and fully removes the water in the cellulose aquagel film, obtains the cellulose gel film by the polyethylene glycol swelling, and its stress-strain diagram is seen the d among Fig. 2.
Embodiment 7
5g cotton linters cellulose slurry is scattered in 100g and is chilled in advance in-5 ℃ the 4.5wt%NaOH/9.5wt% thiocarbamide mixed aqueous solution, stirred 10 minutes, obtain transparent cellulose solution.Cellulose solution after handling 10 minutes, evacuation and centrifugal degassing under the 8000rpm/min is injected special glass frame and sealing with ultracentrifuge.The instrument bezel that cellulose solution is housed was carried out solution gel down in freezing 12 hours at-20 ℃ handle, under 5 ℃, thaw then.Then gained cellulose physics gel is taken out from mould and be placed on NaOH and the thiocarbamide of removing in the deionized water in the gel, deionized water every renewal in about 5 hours once promptly obtains the cellulose aquagel film after cleaning about three times repeatedly.It is that 400 polyethylene glycol soaks that gained cellulose aquagel film places molecular weight at normal temperatures, fully removes the water in the cellulose aquagel film, obtains the cellulose gel film by the polyethylene glycol swelling, and its stress-strain diagram is seen the e among Fig. 2.
Stress-strain diagram c among Fig. 1 and stress-strain diagram a and b are compared, can draw the cellulose gel film that the cellulose gel film produced by scheme provided by the invention prepares than additive method and have more good mechanical performance; The molecular weight polyethylene glycol that can draw as sweller according to Fig. 2 is directly proportional with the mechanical strength of the cellulose gel film of preparation.
Claims (3)
1. the preparation method of a cellulose gel film is characterized in that adopting following concrete steps:
(1) cellulose is scattered in the mixed solvent of ℃ cooling processing in advance-15～-5, be made into the cellulose solution that content of cellulose is 0.01 wt%～10wt%, mixed solvent is that sodium hydrate content is 4～12wt%, urea content is the mixed aqueous solution of 8～20wt%, or sodium hydrate content is 1～10wt%, and thiocarbamide content is the mixed aqueous solution of 4～15wt%;
(2) cellulose solution is obtained clear solution after evacuation and centrifugal degassing is handled, place mould to seal clear solution, under-20～40 ℃ pregel temperature, carry out the solution gel processing and obtain cellulose physics gel;
(3) cellulose physics gel is soaked in the deionized water obtains the cellulose aquagel film behind solvent composition NaOH, urea or the thiocarbamide in removing gel;
(4) gained cellulose aquagel film is placed sweller fully soak the back of anhydrating and obtain the plain gel mould of high strength fibre.
2. the preparation method of cellulose gel film according to claim 1, it is characterized in that: mould is the mould that glass, stainless steel or engineering plastics are made.
3. the preparation method of cellulose gel film according to claim 1 is characterized in that: sweller is the mixed solution of mixed solution, polyethylene glycol and glycerine of mixed solution, water and glycerine of water, polyethylene glycol, glycerine, water and polyethylene glycol or polyethylene glycol and water and glycerine three's mixed solution.
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| CN101880410A (en) * | 2010-07-21 | 2010-11-10 | 武汉大学 | High-strength transparent cellulose material and preparation method thereof |
| CN101423614B (en) * | 2008-11-14 | 2011-04-20 | 武汉大学 | Luminescent fibre hydrogel and preparation method thereof |
| CN102492163A (en) * | 2011-12-27 | 2012-06-13 | 武汉大学 | Preparation method of high-hydrophobicity cellulose membrane |
| CN102585255A (en) * | 2011-01-06 | 2012-07-18 | 华中农业大学 | Pectin/cellulose hydrogel material and preparation method thereof |
| CN102926015A (en) * | 2012-11-20 | 2013-02-13 | 东华大学 | Method for preparing hydroxyethyl cellulose fibers by adopting pre-gel method |
| CN103060937A (en) * | 2013-01-29 | 2013-04-24 | 武汉大学 | Preparation method of cellulose nanofiber |
| CN104892970A (en) * | 2015-06-26 | 2015-09-09 | 中国热带农业科学院农产品加工研究所 | Method for directly preparing membrane through wood fiber |
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| DD127967A1 (en) * | 1976-08-19 | 1977-10-26 | Guenter Knabe | METHOD OF SUBSTRATING PHOTOGRAPHIC FILM DOCUMENTS FROM CELLULOSETRIACETATE |
| CN1125845C (en) * | 2000-04-17 | 2003-10-29 | 武汉大学 | Solvent composition and its use |
| US20020019447A1 (en) * | 2000-07-03 | 2002-02-14 | Renn Donald Walter | Physical forms of clarified hydrocolloids of undiminished properties and method of producing same |
| US6929884B2 (en) * | 2001-04-19 | 2005-08-16 | Zinc Matrix Power, Inc. | Method for manufacture of films containing insoluble solids embedded in cellulose-based films |
| CN1235669C (en) * | 2002-09-04 | 2006-01-11 | 中国科学院大连化学物理研究所 | Separation membrane made from cellulose and its preparing method |
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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 |
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| CN102585255A (en) * | 2011-01-06 | 2012-07-18 | 华中农业大学 | Pectin/cellulose hydrogel material and preparation method thereof |
| CN102492163A (en) * | 2011-12-27 | 2012-06-13 | 武汉大学 | Preparation method of high-hydrophobicity cellulose membrane |
| CN102926015A (en) * | 2012-11-20 | 2013-02-13 | 东华大学 | Method for preparing hydroxyethyl cellulose fibers by adopting pre-gel method |
| CN102926015B (en) * | 2012-11-20 | 2015-04-08 | 东华大学 | Method for preparing hydroxyethyl cellulose fibers by adopting pre-gel method |
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| CN108063279A (en) * | 2016-11-07 | 2018-05-22 | 中国科学院化学研究所 | A kind of cellulose base gel polymer electrolyte and preparation method thereof and the lithium ion battery containing the electrolyte |
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| CN107619482A (en) * | 2017-09-25 | 2018-01-23 | 武汉大学 | A kind of preparation method of anisotropy double cross connection cellulose aquagel and membrane material |
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