CN104072787B - A kind of method of preparing highly concentrated nano cellulose colloid - Google Patents
A kind of method of preparing highly concentrated nano cellulose colloid Download PDFInfo
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Abstract
The invention discloses a kind of method of preparing highly concentrated nano cellulose colloid. Prepare nano-cellulose by Mechanical Method, chemical method, bioanalysis or force chemistry, gained nano-cellulose, by centrifugal or micropore filter-cloth filtering, is separated itself and reaction precipitation thing, makes nano-cellulose colloid; Nano-cellulose colloid cryogenic freezing is frozen, make to form and assemble and tangle between nano-cellulose; Freezing icing nano-cellulose colloid is placed on to 0 DEG C and thaws above, the nano-cellulose of assembling and tangling is precipitated; By sediment, by filtration, press filtration and carrying out washing treatment, products therefrom is scattered in solvent under mechanical shearing effect, makes highly concentrated nano cellulose colloid. The inventive method can reach the effect of Simultaneous purification and concentrated nano-cellulose colloid, and the step that simplifies the operation reduces production cycle and the cost of nano-cellulose greatly, is easy to apply.
Description
Technical field
The invention belongs to field of nano material preparation, particularly a kind of method of preparing highly concentrated nano cellulose colloid.
Background technology
In order to alleviate and to solve world today's greenhouse gases, the energy and resource exhaustion, the significant problem such as environmental pollution is serious, develop renewable circulation, environmental protection, degradable material has become much-talked-about topic, expects that it can replace the use taking fossil energy as basic material in some aspects.
Nano-cellulose is that natural plant fibre passes through Mechanical Method [A.N.Nakagaito, etal.Appl.Phys.A78, 547-552 (2004)], chemical method [RobertJ.Moon, etal.Chem.Soc.Rev., 2011, 40, 3941-3994], force chemistry [YongHuang, ChemSusChem2012, 5, 2319-2322] etc. means obtain there is high length-diameter ratio, high-specific surface area, high strength (Young's modulus is about 110 ~ 220Gpa), have the Young's modulus higher than kevlar fiber and the thermal coefficient of expansion lower than general pottery nano material [Wang Shiwen etc. Science Bulletin, 2013, 24:2385-2392.], have bio-compatible concurrently simultaneously, sustainable, degradable, the advantages such as environmental protection.
By acid-hydrolysis method [Q.Q.Wangetal.Cellulose (2012) 19:2033-2047], TEMPO is oxidized [AkiraIsogai, etal.Biomacromolecules, 2006, 7 (6): 1687-1691], grafting chloroactic acid method [LarsW gberg, etal.Langmuir2008, 24, 784-795], periodate oxidation method [HenrikkiLiimatainen, etal.Cellulose (2013) 20:741-749] etc. in the nano-cellulose colloid last handling process prepared of method because needs are separated from reactant by the method such as centrifugal, again through purification process such as dialysis deionizations, the solid content that obtains the nano-cellulose colloid that neutral impurity content is few is lower. nano-cellulose, after conventional method is dry, due to effects such as intermolecular easy formation hydrogen bond and entanglement, is scattered in it in water so just very difficult, so can only preserve with the form of colloid at present again. but the cost that will certainly increase nano-cellulose compared with the nano-cellulose of low-solid content in long-range transport and delivery process, limits its application. Chinese invention patent application [application number 201310236188.5] discloses a kind of preparation method of highly concentrated nano cellulose colloid, it passes through to control rotary evaporation process conditions by the nano-cellulose colloid of low concentration, temperature (30-50 DEG C), rotating speed (2-6rpm) concentrates the nano-cellulose colloid of preparation high concentration (mass fraction 40% and above concentration). but before the method is concentrated, nano-cellulose colloid must fall the ion dialyses in solution, just can concentrate. dialysis procedure length consuming time, the production cost of increase nano-cellulose.
Summary of the invention
The object of the invention is to overcome the deficiency of existing nano-cellulose concentration technique, a kind of method of preparing highly concentrated nano cellulose colloid is provided.
Concrete steps are:
(1) prepare nano-cellulose by Mechanical Method, chemical method, bioanalysis or force chemistry, gained nano-cellulose, by centrifugal or micropore filter-cloth filtering, is separated itself and sediment, makes nano-cellulose colloid.
(2) nano-cellulose colloid cryogenic freezing step (1) being made is frozen, and makes in freezing freezing process, to form and assemble and tangle between nano-cellulose; Then, freezing icing nano-cellulose colloid is placed on to 0 DEG C and thaws above, the nano-cellulose of assembling and tangling is precipitated; Then, by sediment, by filtration, press filtration and carrying out washing treatment, products therefrom is scattered in solvent under mechanical shearing effect, makes highly concentrated nano cellulose colloid.
The aperture of described micropore filter cloth is 0.001 ~ 1 micron.
Described mechanical shearing effect comprises high speed machine paddling process, high pressure homogenizer homogenizing method, ball-milling method, mill method and ultrasonic dispersion.
Described solvent is the one in water, dimethyl formamide, dimethyl sulfoxide (DMSO), acetone, acetonitrile, oxolane, methacrylic acid, dioxane and aniline.
The present invention compared with prior art, has the following advantages and beneficial effect:
(1) the inventive method can reach the effect of Simultaneous purification and concentrated nano-cellulose colloid, and do not need to remove with dialysis the acid, alkali or other chemical reagent that in nano-cellulose colloid preparation process, produce, the step that simplifies the operation, reduces production cycle and the cost of nano-cellulose greatly.
(2) preparation method's variation of the required nano-cellulose colloid of the inventive method, is easy to apply.
Brief description of the drawings
Fig. 1 is the freeze concentration process photo that the embodiment of the present invention 1 makes nano-cellulose colloid, wherein: a is the nano-cellulose dispersion liquid (before freezing) after centrifugation; B is the nano-cellulose precipitation (after freezing) after freeze-thaw; C is the nano-cellulose colloid (mass fraction 2.13wt%) after freeze concentration; D is the nano-cellulose colloid (mass fraction 3.77wt%) after freeze concentration.
Fig. 2 is the freeze concentration process photo that the invention process 2 makes nano-cellulose colloid, and wherein A is the nano-cellulose dispersion liquid (before freezing) after centrifugation; B is the nano-cellulose precipitation (after freezing) after freeze-thaw; C is the nano-cellulose colloid (mass fraction 0.49wt%) after freeze concentration.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further, but the present invention is not limited to following instance.
Embodiment 1:
(1) prepare nano-cellulose by sulfuric acid process (one in chemical method): first, the paper pulp fiber of over dry is mixed with certain density sulfuric acid solution, the liquor ratio of controlling paper pulp fiber and sulfuric acid solution is 1:9, controlling the mass concentration of sulfuric acid after mixing is 58%, then at room temperature infiltrate 30 minutes, transferred to again in reactor, controlling temperature is 55 DEG C, react 10 hours, after reaction finishes, add water wherein and stop reaction, filter to obtain fiber, then fiber is dissociated into nano-cellulose under high-speed stirred, then centrifugal itself and the sediment of making is separated, the nano-cellulose colloid that makes low acidity (is shown in Fig. 1 a).
(2) the nano-cellulose colloid of low acidity step (1) being made freezes by refrigerator cryogenic freezing, makes in freezing freezing process, to form and assemble and tangle between nano-cellulose; Then, freezing icing nano-cellulose colloid is placed at 25 DEG C and is thawed, the nano-cellulose that makes to assemble and tangle precipitates and (sees in Fig. 1 b), sediment is again by filtration, press filtration and carrying out washing treatment, products therefrom is distributed in water by high speed machine paddling process, and the neutral nano-cellulose colloid that makes mass fraction and be 2.13wt% (is shown in Fig. 1 c). In the time that mass fraction is concentrated to 3.77wt%, nano-cellulose colloid is gel (to be seen in Fig. 1 d).
Embodiment 2:
(1) prepare nano-cellulose by sodium chloroacetate method (one in chemical method): first, the paper pulp fiber of over dry is mixed with certain density NaOH solution, the liquor ratio of controlling paper pulp fiber and NaOH solution is 1:8, controlling the mass concentration of NaOH after mixing is 12%, then at room temperature infiltrate 30 minutes, transferred in reactor, adding mass fraction is 95% industrial alcohol, reaction is warming up to 75 DEG C, add sodium chloroacetate (with the mass ratio of paper pulp fiber be 1:1.5), react 3 hours, after having reacted, with distilled water by product washes clean, then, it is mixed with water, regulating pH is alkalescence, under stirring, high speed machine makes nano-cellulose again, then be the micropore filter-cloth filtering of 0.5 micron with aperture, itself and sediment are separated, make nano-cellulose colloid (seeing A in Fig. 2).
(2) nano-cellulose colloid step (1) being made freezes by refrigerator-freezer cryogenic freezing, makes in freezing freezing process, to form and assemble and tangle between nano-cellulose; Then, freezing icing nano-cellulose colloid is placed at 25 DEG C and is thawed, make the nano-cellulose precipitate (seeing B in Fig. 2) of assembling and tangling, sediment is again by filtration, press filtration and carrying out washing treatment, products therefrom is distributed in water by ball-milling method, making mass fraction is the neutral nano-cellulose colloid of 0.49wt%, is gel (seeing C in Fig. 2).
Embodiment 3:
(1) prepare nano-cellulose by sodium periodate method (one in chemical method): preparation method is with reference to HenrikkiLiimatainenetal.Cellulose (2013) 20:741-749, made product is the micropore filter-cloth filtering of 0.8 micron with aperture, itself and sediment are separated, make the nano-cellulose colloid of low acidity.
(2) the nano-cellulose colloid of low acidity step (1) being made freezes by refrigerator cryogenic freezing, makes in freezing freezing process, to form and assemble and tangle between nano-cellulose; Then, freezing icing nano-cellulose colloid is placed at 25 DEG C and is thawed, the nano-cellulose of assembling and tangling is precipitated, sediment is again by filtration, press filtration and carrying out washing treatment, products therefrom is distributed in water by high pressure homogenizer homogenizing method, makes highly concentrated nano cellulose colloid.
Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention. For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description. Here cannot give exhaustive to all embodiments. Everyly belong to apparent variation or the still row in protection scope of the present invention of variation that technical scheme of the present invention extends out.
Claims (1)
1. prepare a method for highly concentrated nano cellulose colloid, it is characterized in that concrete steps are:
(1) prepare nano-cellulose by Mechanical Method, chemical method, bioanalysis or force chemistry, gained nano-cellulose, by centrifugal or micropore filter-cloth filtering, is separated itself and reaction precipitation thing, makes nano-cellulose colloid;
(2) nano-cellulose colloid cryogenic freezing step (1) being made is frozen, and makes in freezing freezing process, to form and assemble and tangle between nano-cellulose; Then, freezing icing nano-cellulose colloid is placed on to 0 DEG C and thaws above, the nano-cellulose of assembling and tangling is precipitated; Then, by sediment, by filtration, press filtration and carrying out washing treatment, products therefrom is scattered in solvent under mechanical shearing effect, makes highly concentrated nano cellulose colloid;
The aperture of described micropore filter cloth is 0.001 ~ 1 micron;
Described mechanical shearing effect comprises high speed machine paddling process, high pressure homogenizer homogenizing method, ball-milling method, mill method and ultrasonic dispersion;
Described solvent is the one in water, dimethyl formamide, dimethyl sulfoxide (DMSO), acetone, acetonitrile, oxolane, methacrylic acid, dioxane and aniline.
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| CN104761648B (en) * | 2015-04-15 | 2016-11-30 | 桂林理工大学 | A kind of low energy consumption preparation method of nano-cellulose |
| CN107460759B (en) * | 2017-08-18 | 2020-12-22 | 华南理工大学 | Rapid purification method of nano-cellulose suspension |
| CN111172805A (en) * | 2020-01-10 | 2020-05-19 | 中国制浆造纸研究院有限公司 | Preparation method of biomass-based barrier coating |
| CN113150309B (en) * | 2021-03-26 | 2022-10-25 | 湖北福力德鞋业有限责任公司 | Method for modifying anionic waterborne polyurethane emulsion by carboxyl nanocellulose |
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| CN102899950A (en) * | 2012-10-25 | 2013-01-30 | 福建农林大学 | Method for preparing nano cellulose by simultaneous assistance of ultrasonic waves and microwaves |
| CN102977393A (en) * | 2012-11-30 | 2013-03-20 | 中南林业科技大学 | Preparation method of transparent waterproof plant nanometer fiber composite material |
| CN103304824A (en) * | 2013-06-15 | 2013-09-18 | 浙江理工大学 | Preparation method of high-concentration nano microcrystalline cellulose gel |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102899950A (en) * | 2012-10-25 | 2013-01-30 | 福建农林大学 | Method for preparing nano cellulose by simultaneous assistance of ultrasonic waves and microwaves |
| CN102977393A (en) * | 2012-11-30 | 2013-03-20 | 中南林业科技大学 | Preparation method of transparent waterproof plant nanometer fiber composite material |
| CN103304824A (en) * | 2013-06-15 | 2013-09-18 | 浙江理工大学 | Preparation method of high-concentration nano microcrystalline cellulose gel |
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