CN103613790A - Preparation method of cellulose-based composite material - Google Patents
Preparation method of cellulose-based composite material Download PDFInfo
- Publication number
- CN103613790A CN103613790A CN201310587210.0A CN201310587210A CN103613790A CN 103613790 A CN103613790 A CN 103613790A CN 201310587210 A CN201310587210 A CN 201310587210A CN 103613790 A CN103613790 A CN 103613790A
- Authority
- CN
- China
- Prior art keywords
- magnesium silicate
- cellulose
- lithium magnesium
- sodium hydroxide
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Cosmetics (AREA)
Abstract
The invention relates to a preparation method of a cellulose-based composite material. The method comprises the following steps: preparing a cellulose solution and a lithium magnesium silicate solution; mixing the cellulose solution with the lithium magnesium silicate solution; coagulating and regenerating in a coagulating bath; washing and drying to obtain the cellulose-based composite material. According to the preparation method, lithium magnesium silicate can form a stable nanometer flake structure in a water system, so that ultra-fine dispersion of lithium magnesium silicate nano particles in the cellulose solution is realized, and the cellulose-based composite material, which is compact and even in structure, and is significantly improved in the tensile property, is prepared; dispersing is carried out in absence of any surfactant. Therefore, the preparation method is simple in steps, and has good practical application value.
Description
Technical field
The present invention relates to a kind of preparation method of cellulose base matrix material, be specifically related to utilize lithium magnesium silicate can in Mierocrystalline cellulose network structure, form the object that ultra-fine dispersion reaches improvement and fortifying fibre cellulosic material, belong to macromolecule material preparation area.
Background technology
Needs based on environment protection and Sustainable Development, it is the key content of current polymer research that the bio-based materials that Mierocrystalline cellulose is representative is take in development.As the abundantest natural polymer of occurring in nature, Mierocrystalline cellulose is with low cost, environmental friendliness, particularly there is higher biocompatibility and biodegradability, at numerous areas such as daily life, food, medicine, materials, be all expected to replace petrochemicals.On the one hand, Mierocrystalline cellulose can generate derivatived cellulose by chemical modification, common as carboxymethyl cellulose, Natvosol, hydroxypropylcellulose etc. be all common cellulose-derived product; On the other hand, Mierocrystalline cellulose can directly be used for preparing cellulose-based material without derivatize.But, the cellulose-based material if prepare with superior performance (high strength, high-clarity, high evenness), as cellulosefilm, fiber, aerogel etc., the best way is first Mierocrystalline cellulose to be carried out to non-derivative dissolving, cellulose dissolution system is regenerated in specific precipitation bath putting before this, could obtain the comparatively cellulose materials of even compact; About cellulosic dissolution system, there is N,N-dimethylacetamide/lithium chloride (DMAc/LiCl) system at present, 4-methylmorpholine-N-oxide compound/water (NMMO/ water) system, ion liquid system etc.
Although adopting the method that Mierocrystalline cellulose dissolves in advance can prepare structure cellulose materials comparatively uniformly, still there is the shortcomings such as structure is comparatively loose, mechanical strength is lower, Practical Performance is poor in prepared Single Fiber cellulosic material.The approach of effective raising Mierocrystalline cellulose performance is to add wherein nano particle to prepare a Mierocrystalline cellulose nano composite material, such as polynite, carbon nanotube, graphene oxide etc.Be characterized in that Mierocrystalline cellulose relies on hydrogen bond action to form to a certain degree crosslinked with being scattered in nano particle wherein, makes cellulosic structure finer and close evenly, thereby improves cellulosic mechanical property.The nano material such as carbon nanotube, Graphene, because having higher specific surface or length-to-diameter ratio, is good matrix material functional additive.In document, have been reported and utilize ion liquid dissolving Mierocrystalline cellulose, and good dispersiveness in ionic liquid is prepared Mierocrystalline cellulose/carbon nanotube (Graphene) nano composite material by carbon nanotube or Graphene.But carbon nanotube and Graphene have strong nonpolar and higher surface energy, thereby are difficult to be scattered in equably aqueous systems, so seldom see the report that utilizes aqueous systems to prepare Mierocrystalline cellulose/carbon nanotube (Graphene) nano composite material in document.Equally, such as subparticles such as polynites, need to carry out organically-modifiedly, could well peel off and obtain flake nano structure, otherwise as easy as rolling off a log precipitation and can not being dispersed in solvent system.And organic modification montmonrillonite is also only confined to could disperse preferably in organic medium (as ionic liquid), obtains montmorillonite particle good dispersion in cellulose materials prepare Mierocrystalline cellulose/Nano composite material of montmorillonite with this.Thus, in aqueous systems, all there is easy coagulation, difficult disperse or difficulty such as peels off at the factor in the nano particles such as carbon nanotube, Graphene, polynite, thereby restricted and utilize cellulosic water dissolution system to carry out the preparation of Mierocrystalline cellulose nano composite material, be difficult to obtain the Mierocrystalline cellulose nano composite material of compact and uniform structure, thereby effectively improve the mechanical property of cellulose-based material.
Chinese patent literature CN1869114A(application number: 200610043043.3) disclose a kind of straw fiber/Nanometer Composite Material Of Montmorillonite And Its Preparation Method.This matrix material is that Mierocrystalline cellulose is evenly inserted in montmorillonite layer, makes polynite and Mierocrystalline cellulose combine closely and be dispersed in Mierocrystalline cellulose and obtain with nanoscale; Combine the advantage of Mierocrystalline cellulose and polynite, have advantages of that traditional material is incomparable; Elasticity and thermotolerance have improved the workability of matrix material greatly, in fields such as space flight, physical culture and environmental protection, are with a wide range of applications.But the method need to be carried out modification to polynite, and montmorillonite-based nano particle easy coagulation in aqueous systems, straw fiber/Nano composite material of montmorillonite performance of preparation is not good.
Summary of the invention
For ultra-fine grain in prior art, easily occur to assemble and precipitation, be difficult to stable dispersion in cellulosic aqueous systems, be difficult to obtain structure homogeneous, the deficiency of the cellulose composite material of satisfactory mechanical property, the invention provides a kind of preparation method of cellulose base matrix material, a kind of preparation method of Mierocrystalline cellulose/lithium magnesium silicate matrix material is especially provided, utilize lithium magnesium silicate in aqueous systems, easily to form uniform and stable nanometer disperse system, obtain the ultra-fine dispersion system of lithium magnesium silicate nano-sheet particle in cellulose solution, improve structure and the mechanical property of cellulose base matrix material.
Technical scheme of the present invention is as follows:
A preparation method for cellulose base matrix material, step is as follows:
(1) sodium hydroxide/aqueous solution of urea being refrigerated to-12～-16 ℃, is that 1～5wt% adds Mierocrystalline cellulose by cellulose concentration, is stirred to Mierocrystalline cellulose and dissolves completely, obtains cellulosic sodium hydroxide/aqueous solution of urea; In described sodium hydroxide/aqueous solution of urea, the concentration of sodium hydroxide is 6～10wt%, and the concentration of urea is 10～15wt%; Described Mierocrystalline cellulose is linters or dissolving pulp;
(2) by lithium magnesium silicate concentration, be that 0.02～1wt% is scattered in lithium magnesium silicate in water, by naoh concentration, be that 6～8wt% adds sodium hydroxide, or the concentration that is 6～8wt%, urea by the concentration of sodium hydroxide is the mixture that 10～15wt% adds sodium hydroxide and urea; Be uniformly dispersed, obtain lithium magnesium silicate dispersion liquid;
(3) the lithium magnesium silicate dispersion liquid that cellulosic sodium hydroxide/aqueous solution of urea step (1) being obtained and step (2) obtain is (1～5) by weight: 1 mixes, and obtains the composite dispersion liquid of Mierocrystalline cellulose/lithium magnesium silicate;
(4) composite dispersion liquid of Mierocrystalline cellulose/lithium magnesium silicate is put into precipitation bath and soak, make the composite dispersion liquid of Mierocrystalline cellulose/lithium magnesium silicate solidify regeneration, through washing, dry, obtain cellulose base matrix material.
According to the present invention, preferred, in the described sodium hydroxide/aqueous solution of urea of step (1), the concentration of sodium hydroxide is 7～8wt%, and the concentration of urea is 12～14wt%; Described linters or the polymerization degree of dissolving pulp are 100～600.Described linters or dissolving pulp are conventional commercial product.
According to the present invention, preferred, in step (2), by lithium magnesium silicate concentration, be that 0.1～0.3wt% is scattered in lithium magnesium silicate in water; Described lithium magnesium silicate is nanometer lithium magnesium silicate powder, transmittance >=99%, commercial product.
According to the present invention, preferred, the precipitation bath described in step (4) is that volume ratio is 1/9～9/1 acetone/water mixing solutions, or, containing the mixing solutions of 5wt% sulfuric acid and 5wt% sodium sulfate; The temperature of described precipitation bath is 5～50 ℃, more preferably 10～30 ℃;
Described soak time is 5～30min, and the mode of described washing is for being soaked in water 20～60min or with water wash 20～60min, the described water content≤15wt% that is dried to.
According to the present invention, a preferred embodiment is as follows:
A preparation method for cellulose base matrix material, step is as follows:
(1) sodium hydroxide/aqueous solution of urea being refrigerated to-14 ℃, is that 3wt% adds Mierocrystalline cellulose by cellulose concentration, is stirred to Mierocrystalline cellulose and dissolves completely, obtains cellulosic sodium hydroxide/aqueous solution of urea; In described sodium hydroxide/aqueous solution of urea, the concentration of sodium hydroxide is 7wt%, and the concentration of urea is 12wt%; Described Mierocrystalline cellulose is that the polymerization degree is 525 dissolving pulp;
(2) by lithium magnesium silicate concentration, being that 0.3wt% is scattered in lithium magnesium silicate in water, is that 7wt% adds sodium hydroxide by naoh concentration, is uniformly dispersed, and obtains lithium magnesium silicate dispersion liquid;
(3) the lithium magnesium silicate dispersion liquid that cellulosic sodium hydroxide/aqueous solution of urea step (1) being obtained and step (2) obtain mixes by weight 2:1, obtains the composite dispersion liquid of Mierocrystalline cellulose/lithium magnesium silicate;
(4) composite dispersion liquid of Mierocrystalline cellulose/lithium magnesium silicate is put into precipitation bath and soak 20min, make the composite dispersion liquid of Mierocrystalline cellulose/lithium magnesium silicate solidify regeneration, through distilled water immersion 20min, wash, be dried to water content≤15wt%, obtain cellulose base matrix material; Described precipitation bath is that volume ratio is the acetone/water mixing solutions of 2:1, and the temperature of precipitation bath is 20 ℃.
The present invention utilizes lithium magnesium silicate as additive, and its advantage is can effectively overcome other conventional additives in water, to be difficult for the shortcoming of disperseing; And lithium magnesium silicate is tasteless, nontoxic, nonirritant, has high security, usually for fields such as makeup, medicine, coating.Lithium magnesium silicate is water insoluble, without adding any polymer or surfactant, just can in water, be exceedingly fast to moisten and rises, peels off, disperses to form nano-sheet structure, finally forms homogeneous, stable nanometer disperse system.And abundant hydroxyl is contained on lithium magnesium silicate surface, lithium magnesium silicate nano particle can form very strong hydrogen bond action with Mierocrystalline cellulose; The lithium magnesium silicate that the distinctive sheet structure of aqueous dispersions mesosilicic acid magnesium lithium has determined to be scattered in Mierocrystalline cellulose can play absorption and the cellulosic effect of building bridge effectively, cellulosic molecule is cross-linked to the firm three-dimensional net structure of formation, thereby improve the structure of cellulose-based material, improve its evenness, compactness and mechanical property.In a word, based on the lithium magnesium silicate characteristic that fast and stable disperses in aqueous systems, lithium magnesium silicate superfine nano platy shaped particle is dispersed in Mierocrystalline cellulose aqueous systems, prepare the compound nano dispersion fluid of Mierocrystalline cellulose and lithium magnesium silicate, and then obtain Mierocrystalline cellulose/lithium magnesium silicate nano composite material, with this, improved the performance of cellulose materials.
Compare with the existing method of preparing cellulose composite material, characteristics and advantages of the present invention is:
1, the present invention has utilized lithium magnesium silicate in aqueous systems, can form highly stable nano-sheet structure, obtain the ultra-fine dispersion of lithium magnesium silicate nano particle in cellulose solution, prepare the cellulose base matrix material that compact and uniform structure and tensile property significantly improve.
2, the present invention is without disperseing by any tensio-active agent, thereby step is simple, has good actual application value.
Accompanying drawing explanation
Fig. 1 is the tensile strength curve of the pure cellulose material prepared of the cellulose base matrix material prepared of embodiment of the present invention 1-4 and comparative example.
Fig. 2 is the stereoscan photograph of the pure cellulose material prepared of comparative example of the present invention.
Fig. 3 is the stereoscan photograph of the cellulose base matrix material of the embodiment of the present invention 1 preparation.
Fig. 4 is the stereoscan photograph of the cellulose base matrix material of the embodiment of the present invention 3 preparations.
Embodiment
Below by specific embodiment, the present invention will be further described, but be not limited to this.
Raw materials used conventional reagent, the commercial product of being in embodiment; Wherein: lithium magnesium silicate, Sihong County Hui Zhi Fine Chemical Co., Ltd is on sale; Embodiment 1-9 and comparative example Mierocrystalline cellulose used is dissolving pulp, and polymerization degree Wei525， Shandong YINYING Chemical Fiber Co., Ltd is on sale.
A preparation method for cellulose base matrix material, step is as follows:
(1) sodium hydroxide/aqueous solution of urea being refrigerated to-14 ℃, is that 3wt% adds Mierocrystalline cellulose by cellulose concentration, is stirred to Mierocrystalline cellulose and dissolves completely, obtains cellulosic sodium hydroxide/aqueous solution of urea; In described sodium hydroxide/aqueous solution of urea, the concentration of sodium hydroxide is 7wt%, and the concentration of urea is 12wt%;
(2) by lithium magnesium silicate concentration, being that 0.1wt% is scattered in lithium magnesium silicate in water, is that 7wt% adds sodium hydroxide by naoh concentration, is uniformly dispersed, and obtains lithium magnesium silicate dispersion liquid;
(3) the lithium magnesium silicate dispersion liquid that cellulosic sodium hydroxide/aqueous solution of urea step (1) being obtained and step (2) obtain mixes by weight 2:1, obtains the composite dispersion liquid of Mierocrystalline cellulose/lithium magnesium silicate;
(4) composite dispersion liquid of Mierocrystalline cellulose/lithium magnesium silicate is put into precipitation bath and soak 20min, make the composite dispersion liquid of Mierocrystalline cellulose/lithium magnesium silicate solidify regeneration, through distilled water immersion 20min, wash, be dried to water content≤15wt%, obtain cellulose base matrix material; Described precipitation bath is that volume ratio is the acetone/water mixing solutions of 2:1, and the temperature of precipitation bath is 20 ℃.
A preparation method for cellulose base matrix material, step is with embodiment 1, different:
In step (2), by lithium magnesium silicate concentration, be that 0.2wt% is scattered in lithium magnesium silicate in water.
Embodiment 3
A preparation method for cellulose base matrix material, step is with embodiment 1, different:
In step (2), by lithium magnesium silicate concentration, be that 0.3wt% is scattered in lithium magnesium silicate in water.
A preparation method for cellulose base matrix material, step is with embodiment 1, different:
In step (2), by lithium magnesium silicate concentration, be that 0.4wt% is scattered in lithium magnesium silicate in water.
A preparation method for cellulose base matrix material, step is as follows:
(1) sodium hydroxide/aqueous solution of urea being refrigerated to-12 ℃, is that 3wt% adds Mierocrystalline cellulose by cellulose concentration, is stirred to Mierocrystalline cellulose and dissolves completely, obtains cellulosic sodium hydroxide/aqueous solution of urea; In described sodium hydroxide/aqueous solution of urea, the concentration of sodium hydroxide is 7wt%, and the concentration of urea is 12wt%;
(2) by lithium magnesium silicate concentration, being that 0.1wt% is scattered in lithium magnesium silicate in water, is that 7wt% adds sodium hydroxide by naoh concentration, is uniformly dispersed, and obtains lithium magnesium silicate dispersion liquid;
(3) the lithium magnesium silicate dispersion liquid that cellulosic sodium hydroxide/aqueous solution of urea step (1) being obtained and step (2) obtain mixes by weight 2:1, obtains the composite dispersion liquid of Mierocrystalline cellulose/lithium magnesium silicate;
(4) composite dispersion liquid of Mierocrystalline cellulose/lithium magnesium silicate is put into precipitation bath and soak 20min, make the composite dispersion liquid of Mierocrystalline cellulose/lithium magnesium silicate solidify regeneration, through distilled water immersion 20min, wash, be dried to water content≤15wt%, obtain cellulose base matrix material; Described precipitation bath is the mixing solutions containing 5wt% sulfuric acid and 5wt% sodium sulfate.
Embodiment 6
A preparation method for cellulose base matrix material, step is as follows:
(1) sodium hydroxide/aqueous solution of urea being refrigerated to-16 ℃, is that 2wt% adds Mierocrystalline cellulose by cellulose concentration, is stirred to Mierocrystalline cellulose and dissolves completely, obtains cellulosic sodium hydroxide/aqueous solution of urea; In described sodium hydroxide/aqueous solution of urea, the concentration of sodium hydroxide is 6wt%, and the concentration of urea is 10wt%;
(2) by lithium magnesium silicate concentration, be that 0.4wt% is scattered in lithium magnesium silicate in water, the concentration that is 6wt%, urea by the concentration of sodium hydroxide is the mixture that 10wt% adds sodium hydroxide and urea, is uniformly dispersed, and obtains lithium magnesium silicate dispersion liquid;
(3) the lithium magnesium silicate dispersion liquid that cellulosic sodium hydroxide/aqueous solution of urea step (1) being obtained and step (2) obtain mixes by weight 4:1, obtains the composite dispersion liquid of Mierocrystalline cellulose/lithium magnesium silicate;
(4) composite dispersion liquid of Mierocrystalline cellulose/lithium magnesium silicate is put into precipitation bath and soak 30min, make the composite dispersion liquid of Mierocrystalline cellulose/lithium magnesium silicate solidify regeneration, through distilled water immersion 30min, wash, be dried to water content≤15wt%, obtain cellulose base matrix material; Described precipitation bath is the mixing solutions containing 5wt% sulfuric acid and 5wt% sodium sulfate.
Embodiment 7
A preparation method for cellulose base matrix material, step is with embodiment 6, different:
In step (1), by cellulose concentration, be that 5wt% adds Mierocrystalline cellulose;
In step (2), by lithium magnesium silicate concentration, be that 0.2wt% is scattered in lithium magnesium silicate in water;
In step (4), solidify regeneration after with distilled water drip washing 30min, be dried to water content≤15wt%, obtain cellulose base matrix material.
Embodiment 8
A preparation method for cellulose base matrix material, step is as follows:
(1) sodium hydroxide/aqueous solution of urea being refrigerated to-16 ℃, is that 4wt% adds Mierocrystalline cellulose by cellulose concentration, is stirred to Mierocrystalline cellulose and dissolves completely, obtains cellulosic sodium hydroxide/aqueous solution of urea; In described sodium hydroxide/aqueous solution of urea, the concentration of sodium hydroxide is 9wt%, and the concentration of urea is 14wt%;
(2) by lithium magnesium silicate concentration, be that 0.3wt% is scattered in lithium magnesium silicate in water, the concentration that is 9wt%, urea by the concentration of sodium hydroxide is the mixture that 14wt% adds sodium hydroxide and urea, is uniformly dispersed, and obtains lithium magnesium silicate dispersion liquid;
(3) the lithium magnesium silicate dispersion liquid that cellulosic sodium hydroxide/aqueous solution of urea step (1) being obtained and step (2) obtain mixes by weight 2:1, obtains the composite dispersion liquid of Mierocrystalline cellulose/lithium magnesium silicate;
(4) composite dispersion liquid of Mierocrystalline cellulose/lithium magnesium silicate is put into precipitation bath and soak 20min, make the composite dispersion liquid of Mierocrystalline cellulose/lithium magnesium silicate solidify regeneration, through distilled water immersion 40min, wash, be dried to water content≤15wt%, obtain cellulose base matrix material; Described precipitation bath is that volume ratio is the acetone/water mixing solutions of 5:1, and the temperature of precipitation bath is 10 ℃.
Embodiment 9
A preparation method for cellulose base matrix material, step is with embodiment 8, different:
In step (1), by cellulose concentration, be that 5wt% adds Mierocrystalline cellulose; In described sodium hydroxide/aqueous solution of urea, the concentration of sodium hydroxide is 10wt%, and the concentration of urea is 15wt%;
In step (2), by lithium magnesium silicate concentration, be that 0.4wt% is scattered in lithium magnesium silicate in water;
In step (4), solidify regeneration after with distilled water drip washing 30min, be dried to water content≤15wt%, obtain cellulose base matrix material; Described precipitation bath is that volume ratio is the acetone/water mixing solutions of 5:1, and the temperature of precipitation bath is 30 ℃.
Comparative example
The not preparation of the pure cellulose material of magnesium silicate lithium, step is as follows:
(1) sodium hydroxide/aqueous solution of urea being refrigerated to-14 ℃, is that 3wt% adds Mierocrystalline cellulose by cellulose concentration, is stirred to Mierocrystalline cellulose and dissolves completely, obtains cellulosic sodium hydroxide/aqueous solution of urea; In described sodium hydroxide/aqueous solution of urea, the concentration of sodium hydroxide is 7wt%, and the concentration of urea is 12wt%;
(2) in the mixing solutions of the acetone/water that is 2:1 by the cellulosic sodium hydroxide/aqueous solution of urea in step (1) in volume ratio, soak 20min, make Mierocrystalline cellulose solidify regeneration, through distilled water immersion 40min, wash, be dried to water content≤15wt%, obtain pure cellulose material.
Experimental example
Cellulose base matrix material containing different lithium magnesium silicate particles prepared by embodiment 1-4 and pure cellulose testing of materials tensile strength properties prepared by comparative example, test result is as shown in Figure 1; As shown in Figure 1, the cellulose base matrix material tensile strength that prepared by embodiment 1-4 obviously raises.
Fig. 2 is the stereoscan photograph of the pure cellulose material cross-section prepared of comparative example, Fig. 3 is the stereoscan photograph of cellulose base composite cross-sections of the magnesium silicate lithium particle of embodiment 1 preparation, Fig. 4 is the stereoscan photograph of cellulose base composite cross-sections of the magnesium silicate lithium particle of embodiment 3 preparation, from Fig. 2,3,4, pure cellulose material prepared by comparative example is coarse, loose uneven; The cellulose base matrix material of the magnesium silicate lithium particle of embodiment 1,3 preparations is more fine and close evenly.
Claims (7)
1. a preparation method for cellulose base matrix material, step is as follows:
(1) sodium hydroxide/aqueous solution of urea being refrigerated to-12～-16 ℃, is that 1～5wt% adds Mierocrystalline cellulose by cellulose concentration, is stirred to Mierocrystalline cellulose and dissolves completely, obtains cellulosic sodium hydroxide/aqueous solution of urea; In described sodium hydroxide/aqueous solution of urea, the concentration of sodium hydroxide is 6～10wt%, and the concentration of urea is 10～15wt%; Described Mierocrystalline cellulose is linters or dissolving pulp;
(2) by lithium magnesium silicate concentration, be that 0.02～1wt% is scattered in lithium magnesium silicate in water, by naoh concentration, be that 6～8wt% adds sodium hydroxide, or the concentration that is 6～8wt%, urea by the concentration of sodium hydroxide is the mixture that 10～15wt% adds sodium hydroxide and urea; Be uniformly dispersed, obtain lithium magnesium silicate dispersion liquid;
(3) the lithium magnesium silicate dispersion liquid that cellulosic sodium hydroxide/aqueous solution of urea step (1) being obtained and step (2) obtain is (1～5) by weight: 1 mixes, and obtains the composite dispersion liquid of Mierocrystalline cellulose/lithium magnesium silicate;
(4) composite dispersion liquid of Mierocrystalline cellulose/lithium magnesium silicate is put into precipitation bath and soak, make the composite dispersion liquid of Mierocrystalline cellulose/lithium magnesium silicate solidify regeneration, through washing, dry, obtain cellulose base matrix material.
2. the preparation method of cellulose base matrix material according to claim 1, is characterized in that, in the described sodium hydroxide/aqueous solution of urea of step (1), the concentration of sodium hydroxide is 7～8wt%, and the concentration of urea is 12～14wt%.
3. the preparation method of cellulose base matrix material according to claim 1, is characterized in that, the linters that step (1) is described or the polymerization degree of dissolving pulp are 100～600.
4. the preparation method of cellulose base matrix material according to claim 1, is characterized in that, in step (2), by lithium magnesium silicate concentration, is that 0.02～1wt% is scattered in lithium magnesium silicate in water.
5. the preparation method of cellulose base matrix material according to claim 1, is characterized in that, the precipitation bath described in step (4) is that volume ratio is 1/9～9/1 acetone/water mixing solutions, or, containing the mixing solutions of 5wt% sulfuric acid and 5wt% sodium sulfate; The temperature of described precipitation bath is 5～50 ℃.
6. the preparation method of cellulose base matrix material according to claim 1, it is characterized in that, soak time described in step (4) is 5～30min, and the mode of described washing is for being soaked in water 20～60min or with water wash 20～60min, the described water content≤15wt% that is dried to.
7. a preparation method for cellulose base matrix material, step is as follows:
(1) sodium hydroxide/aqueous solution of urea being refrigerated to-14 ℃, is that 3wt% adds Mierocrystalline cellulose by cellulose concentration, is stirred to Mierocrystalline cellulose and dissolves completely, obtains cellulosic sodium hydroxide/aqueous solution of urea; In described sodium hydroxide/aqueous solution of urea, the concentration of sodium hydroxide is 7wt%, and the concentration of urea is 12wt%; Described Mierocrystalline cellulose is that the polymerization degree is 525 dissolving pulp;
(2) by lithium magnesium silicate concentration, being that 0.3wt% is scattered in lithium magnesium silicate in water, is that 7wt% adds sodium hydroxide by naoh concentration, is uniformly dispersed, and obtains lithium magnesium silicate dispersion liquid;
(3) the lithium magnesium silicate dispersion liquid that cellulosic sodium hydroxide/aqueous solution of urea step (1) being obtained and step (2) obtain mixes by weight 2:1, obtains the composite dispersion liquid of Mierocrystalline cellulose/lithium magnesium silicate;
(4) composite dispersion liquid of Mierocrystalline cellulose/lithium magnesium silicate is put into precipitation bath and soak 20min, make the composite dispersion liquid of Mierocrystalline cellulose/lithium magnesium silicate solidify regeneration, through distilled water immersion 20min, wash, be dried to water content≤15wt%, obtain cellulose base matrix material; Described precipitation bath is that volume ratio is the acetone/water mixing solutions of 2:1, and the temperature of precipitation bath is 20 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310587210.0A CN103613790B (en) | 2013-11-19 | 2013-11-19 | A kind of preparation method of cellulose base matrix material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310587210.0A CN103613790B (en) | 2013-11-19 | 2013-11-19 | A kind of preparation method of cellulose base matrix material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103613790A true CN103613790A (en) | 2014-03-05 |
| CN103613790B CN103613790B (en) | 2016-04-13 |
Family
ID=50164512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310587210.0A Expired - Fee Related CN103613790B (en) | 2013-11-19 | 2013-11-19 | A kind of preparation method of cellulose base matrix material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103613790B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103896992A (en) * | 2014-04-17 | 2014-07-02 | 齐鲁工业大学 | Method for preparing oligosaccharides from lignocellulosic hydrolyzate |
| CN106694040A (en) * | 2016-11-30 | 2017-05-24 | 华南理工大学 | Preparation method of quantum dot cellulose-based photocatalytic composite material |
| CN106758500A (en) * | 2016-12-20 | 2017-05-31 | 齐鲁工业大学 | A kind of method of the modified papermaking filler of utilization cationic cellulose derivative |
| CN107973920A (en) * | 2017-11-15 | 2018-05-01 | 深圳大学 | A kind of cellulose/two-dimensional layer Material cladding hydrogel and preparation method thereof |
| CN108723390A (en) * | 2018-05-28 | 2018-11-02 | 广东省微生物研究所（广东省微生物分析检测中心） | A kind of short-cut method preparing nano silver composite antibacterial agent |
| CN109082119A (en) * | 2018-07-02 | 2018-12-25 | 东营欣邦电子科技有限公司 | A kind of cellulose modified polyimides corona-resistant film and preparation method thereof |
| CN110564007A (en) * | 2019-09-16 | 2019-12-13 | 香港理工大学 | Cellulose composite waterproof film and preparation method thereof |
| CN110684216A (en) * | 2019-10-20 | 2020-01-14 | 南京理工大学 | Highly filled regenerated cellulose-based functional composite material and preparation method thereof |
| CN114479165A (en) * | 2022-02-28 | 2022-05-13 | 苏州大学 | Method for preparing composite aerogel from montmorillonite microspheres and regenerated cellulose |
| CN116253972A (en) * | 2023-02-24 | 2023-06-13 | 苏州辰鹏电子新材料有限公司 | Preparation method of reinforced PBT composite material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4729795A (en) * | 1985-08-01 | 1988-03-08 | Betz Laboratories, Inc. | Stable slurries comprising powdered activated carbon |
| US20050051054A1 (en) * | 2003-09-08 | 2005-03-10 | White Leslie A. | Nanocomposites of cellulose and clay |
| CN1869114A (en) * | 2006-06-24 | 2006-11-29 | 西北师范大学 | Cellulose/montmorillonite nanometer composite material and its preparation method |
| CN101248224A (en) * | 2005-08-26 | 2008-08-20 | 连津格股份公司 | Cellulosic moulded body, method for manufacturing it and use thereof |
| CN102504299A (en) * | 2011-09-30 | 2012-06-20 | 江南大学 | Preparation method for regenerated cellulose/epoxy resin composite film |
-
2013
- 2013-11-19 CN CN201310587210.0A patent/CN103613790B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4729795A (en) * | 1985-08-01 | 1988-03-08 | Betz Laboratories, Inc. | Stable slurries comprising powdered activated carbon |
| US20050051054A1 (en) * | 2003-09-08 | 2005-03-10 | White Leslie A. | Nanocomposites of cellulose and clay |
| CN101248224A (en) * | 2005-08-26 | 2008-08-20 | 连津格股份公司 | Cellulosic moulded body, method for manufacturing it and use thereof |
| CN1869114A (en) * | 2006-06-24 | 2006-11-29 | 西北师范大学 | Cellulose/montmorillonite nanometer composite material and its preparation method |
| CN102504299A (en) * | 2011-09-30 | 2012-06-20 | 江南大学 | Preparation method for regenerated cellulose/epoxy resin composite film |
Non-Patent Citations (1)
| Title |
|---|
| 耿红娟等: "纤维素的溶解及纤维素功能性材料的制备", 《华东纸业》, vol. 44, no. 5, 15 October 2013 (2013-10-15), pages 4 - 9 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103896992B (en) * | 2014-04-17 | 2016-05-25 | 齐鲁工业大学 | A kind of method of producing compound sugar from ligno-cellulose hydrolysate |
| CN103896992A (en) * | 2014-04-17 | 2014-07-02 | 齐鲁工业大学 | Method for preparing oligosaccharides from lignocellulosic hydrolyzate |
| CN106694040A (en) * | 2016-11-30 | 2017-05-24 | 华南理工大学 | Preparation method of quantum dot cellulose-based photocatalytic composite material |
| CN106758500A (en) * | 2016-12-20 | 2017-05-31 | 齐鲁工业大学 | A kind of method of the modified papermaking filler of utilization cationic cellulose derivative |
| CN107973920A (en) * | 2017-11-15 | 2018-05-01 | 深圳大学 | A kind of cellulose/two-dimensional layer Material cladding hydrogel and preparation method thereof |
| CN108723390B (en) * | 2018-05-28 | 2021-04-06 | 广东省微生物研究所（广东省微生物分析检测中心） | Simple method for preparing nano-silver composite antibacterial agent |
| CN108723390A (en) * | 2018-05-28 | 2018-11-02 | 广东省微生物研究所（广东省微生物分析检测中心） | A kind of short-cut method preparing nano silver composite antibacterial agent |
| CN109082119A (en) * | 2018-07-02 | 2018-12-25 | 东营欣邦电子科技有限公司 | A kind of cellulose modified polyimides corona-resistant film and preparation method thereof |
| CN109082119B (en) * | 2018-07-02 | 2021-04-02 | 东营欣邦电子科技有限公司 | Cellulose modified polyimide corona-resistant film and preparation method thereof |
| CN110564007A (en) * | 2019-09-16 | 2019-12-13 | 香港理工大学 | Cellulose composite waterproof film and preparation method thereof |
| CN110564007B (en) * | 2019-09-16 | 2021-08-31 | 香港理工大学 | Cellulose composite waterproof film and preparation method thereof |
| CN110684216A (en) * | 2019-10-20 | 2020-01-14 | 南京理工大学 | Highly filled regenerated cellulose-based functional composite material and preparation method thereof |
| CN114479165A (en) * | 2022-02-28 | 2022-05-13 | 苏州大学 | Method for preparing composite aerogel from montmorillonite microspheres and regenerated cellulose |
| CN114479165B (en) * | 2022-02-28 | 2023-10-24 | 苏州大学 | Method for preparing composite aerogel from montmorillonite microspheres and regenerated cellulose |
| CN116253972A (en) * | 2023-02-24 | 2023-06-13 | 苏州辰鹏电子新材料有限公司 | Preparation method of reinforced PBT composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103613790B (en) | 2016-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103613790B (en) | A kind of preparation method of cellulose base matrix material | |
| HPS et al. | A review on chitosan-cellulose blends and nanocellulose reinforced chitosan biocomposites: Properties and their applications | |
| CN101381906B (en) | Alginate nano Ag antibacterial fiber and method for making same | |
| CN106283268B (en) | A kind of preparation method of cellulose/calcium alginate blended fiber | |
| JP5072846B2 (en) | Use of aqueous sodium hydroxide / thiourea solution in the manufacture of cellulose products on a pilot scale | |
| CN103059319B (en) | Preparation method of chitin nano fiber | |
| CN103933949B (en) | A kind of Carbon Nanotubes/Chitosan mesoporous sphere composite and preparation method thereof | |
| CN107955984B (en) | Graphene grafted polysaccharide Lyocell fiber and preparation method thereof | |
| CN105153438A (en) | Preparation method of high-strength high-swelling nanocellulose and polyving akohol composite hydrogel | |
| CN103993380A (en) | Method for preparing high-strength chitosan fiber | |
| CN108948377A (en) | A kind of quick dissolution method of chitosan and its application | |
| Mao et al. | Progress in nanocellulose preparation and application | |
| CN103173892A (en) | Preparation method of nano bamboo fiber composite material | |
| Lin et al. | Dissolution of cellulose in the mixed solvent of [bmim] Cl–DMAc and its application | |
| CN103469542B (en) | Bacterial cellulose fiber containing nano-silver chloride particles and preparation method of fiber | |
| CN102432892B (en) | Method for dissolving cellulose and method for preparing regenerated fiber | |
| CN109208112A (en) | Fiber and preparation method thereof containing polyelectrolyte | |
| CN103541034A (en) | Flame-retardant Lyocell fiber and preparation method thereof | |
| CN115304935B (en) | High-dispersion carbon nano tube/carbon black composite carbon material and preparation method thereof | |
| CN103556255B (en) | A kind of bamboo charcoal cellulose fiber and preparation method thereof | |
| CN1252163C (en) | Lithium hydrate and carbamide composition solvent for dissolving cellulous fiber and its use | |
| Lv et al. | Tuning the properties of pineapple peel cellulose nanofibrils by TEMPO-mediated oxidation and ball milling | |
| CN108866665B (en) | Antibacterial cellulose composite fiber and preparation method thereof | |
| CN105218837A (en) | A kind of method preparing unformed cellulose grain under aqueous phase solvent system | |
| CN103147144B (en) | Method for dissolving cellulose and method for preparing regenerated fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160413 Termination date: 20161119 |