CN106674586A - Method for preparing cellulose nanocrystalline sponge material - Google Patents
Method for preparing cellulose nanocrystalline sponge material Download PDFInfo
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- CN106674586A CN106674586A CN201611152564.2A CN201611152564A CN106674586A CN 106674586 A CN106674586 A CN 106674586A CN 201611152564 A CN201611152564 A CN 201611152564A CN 106674586 A CN106674586 A CN 106674586A
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- cellulose
- cellulose nanocrystal
- acid solution
- sponge material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
- C08L1/04—Oxycellulose; Hydrocellulose, e.g. microcrystalline cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/04—Oxycellulose; Hydrocellulose
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to a method for preparing a cellulose nanocrystalline sponge material. The method comprises the following steps: 1) mixing pretreated biomass cellulose with mixed acid, performing a reaction for 2-10 hours at 50-130 DEG C, after the reaction is completed, performing water washing and centrifugal treatment, and adjusting the pH value of the mixed liquid to be 7 so as to obtain a cellulose nanocrystalline suspension; and 2) pouring the obtained cellulose nanocrystalline suspension into plastic molds of different shapes, and performing freeze-drying, thereby obtaining the cellulose nanocrystalline sponge material of a designed shape. The material is simple and feasible and rapid and efficient in preparation process, is extracted from biomass cellulose, is capable of turning waste into wealth, is green, environmental-friendly and reproducible, and can be degraded in a multifunctional complete biological manner. The obtained cellulose nanocrystalline has the characteristics of an ultra-high length-diameter ratio, a shape of a long nanowire, molecular chain windable self-assembling molding, massive nanocrystalline surface modification groups, an efficient netting effect and the like.
Description
Technical field
The invention belongs to the preparation field of Cellulose nanocrystal, more particularly, to a kind of Cellulose nanocrystal sponge material
Preparation method.
Background technology
Face under the shortage of oil fossil energy, the background of ecological deterioration in the world today, people throw more attention
Enter among the research of recyclable materials or the energy.The composite of renewable biomass raw material is expected to substitute petrochemical-based polymers
Become most promising material.Cellulose is most abundant in nature and biodegradable natural polymer, exploitation
Reproducible cellulose resource will become a kind of trend.On the other hand, the annual a large amount of abandoneds of various natural biomass, burning,
Cause fearful environmental pollution and the wasting of resources.Cellulose is hydrolyzed under certain condition with acid, when cellulose sour water
When solving nano-scale, between 1-100nm, it is very big that specific surface area becomes particle diameter distribution, referred to as Cellulose nanocrystal
(Cellulose Nanocrystalline,CNC).Cellulose nanocrystal has lightweight, degradable, renewable, good biology
The compatibility and the characteristic of numerous nano-particle, so its application is more and more extensively (CN201610031569.3).But due to normal
CNC is generally bar-shaped or spherical, and draw ratio is relatively low, causes the enhancement effect that CNC is weak, the easy small deformation of material itself and send out
Raw destruction.Additionally, sample is powder, store and using extremely inconvenience, it is virtually impossible to reuse.Therefore, one kind is sought more
It is extremely urgent for tough, the more convenient CNC preparation methoies for using.
The content of the invention
In order to overcome the deficiencies in the prior art, a kind of preparation process green of present invention offer is simple, easy to operate, can design oneself
Molding and the preparation method of the Cellulose nanocrystal sponge material with superelevation draw ratio.
The technical solution adopted for the present invention to solve the technical problems is：A kind of preparation of Cellulose nanocrystal sponge material
Method, comprises the following steps：
1) pretreated biomass cellulose is mixed with nitration mixture, 2-10h, wherein biomass is reacted at 50-130 DEG C
Cellulose is 1 with the solid-to-liquid ratio of nitration mixture：30-120g/mL, reaction is washed after terminating, centrifugal treating is adjusted to the pH value of mixed liquor
7, obtain Cellulose nanocrystal suspension；
2) by step 1) in the Cellulose nanocrystal suspension for obtaining insert in mould, lyophilization 12-48h obtains final product sea
The Cellulose nanocrystal material of continuous shape.
In mould of different shapes, especially process without the need for other just can be obtained not Cellulose nanocrystal suspension with molding
The spongy fiber element nanocrystalline material of similar shape, resulting spongy fiber element nanocrystalline material is loose porous, and has
There is higher mechanical strength, programmable material shape can be obtained according to default mold shape.
Further, the step 1) in biomass cellulose be Rhizoma Zingiberis Recenss fiber, cotton fiber, flaxen fiber or coir.
Further, the step 2) in lyophilization temperature be -50 DEG C.
Further, the step 1) in nitration mixture be acid solution A and acid solution B mixed liquor；Acid solution A be formic acid, ascorbic acid,
One or two or more combination in citric acid, the concentration of acid solution A is 1-10mol/L；Acid solution B be hydrochloric acid, the concentration of acid solution B
For 1-10mol/L.
Further, the step 1) in acid solution A and acid solution B volume ratio be 5-9:1-5.
Further, the step 1) in acid solution A and acid solution B volume ratio be 9:1 or 8:2 or 7:3 or 6:4 or 5:5.
Further, the step 1) in the Cellulose nanocrystal that obtains in long wire, its a diameter of 5-50nm, length is
500-2000nm, draw ratio is 25-400.
Further, the step 1) in the surface group of Cellulose nanocrystal that obtains have ester group, hydroxyl and carboxyl.
The present invention carries out acidolysis and nano level cellulose product is obtained with natural biomass materials as raw material using common acid
Product, using reclaiming by centrifuge acid solution after the completion of reaction, are preferably minimized the wasting of resources and complete low value natural biological
The increase in value of matter, reduces to a certain extent environmental pollution.Obtained superelevation aspect fibers element is nanocrystalline with more
Surface group and more effective net catch effect, with high intensity and high tenacity, and can self-forming be sponge material, be easy to storage
Deposit and reuse, for further chemical modification and practical application such as sewage purification etc. has more probabilities.
Preparation process of the present invention is simple, quickness and high efficiency, extracts from biomass cellulose, turns waste into wealth, green ring
Protect renewable, and multi-functional complete biodegradable.Gained Cellulose nanocrystal there is the draw ratio of superelevation, in long nano wire
Shape, strand can wind self-assembled molding, nanocrystal surface can be the features such as modification group be abundant, efficient net catches effect.It is certainly
The spongy material of shaping has higher mechanical property, abundant pore space structure, porosity is high and shape recovery is good, in nanometer
The fields such as composite, sewage flocculation material, tissue stent material have potential application potentiality, and are adapted to industrially scalable life
Produce.
The invention has the beneficial effects as follows：(1) experimental implementation involved in the present invention is simple, can in normal experiment room
To carry out, instrument and equipment is simply common, takes short.Experiment raw materials derive from the reproducible natural biological of environmental protection
Matter, turns waste into wealth, sustainable development, and the mineral acid low cost used is recyclable, reduces the wasting of resources；(2) present invention is adopted
Prepared by nitration mixture, make Cellulose nanocrystal surface with ester group and carboxyl, and Cellulose nanocrystal prepared by the present invention is with super
High length-diameter ratio, single fiber element is nanocrystalline can to carry more groups, it is meant that single fiber element is nanocrystalline can to possess more
Electronegative carboxyl remove Liquidity limit, the adsorption of metal ions of such as sewage disposal has higher efficiency, long fibre element
Nanocrystalline net is caught effect and also can be greatly enhanced, for fields such as nano composite material, sewage flocculation material, tissue stent materials
Using with very extensive potential value.
Description of the drawings
Fig. 1 be the present invention superelevation draw ratio Cellulose nanocrystal field emission scanning electron microscope figure (FE-SEM) with
The digital photograph figure of the programmable Cellulose nanocrystal sponge package material from shaping.
Fig. 2 is the infrared spectrogram (FTIR) of the Cellulose nanocrystal of superelevation draw ratio.
Specific embodiment
In order that those skilled in the art are better understood from the present invention program, below in conjunction with the embodiment of the present invention
Accompanying drawing, to the technical scheme in inventive embodiments clear, complete description is carried out, it is clear that described embodiment is only this
A part of embodiment of invention, rather than the embodiment of whole.Based on the embodiment in the present invention, those of ordinary skill in the art
The every other embodiment obtained under the premise of creative work is not made, should all belong to the scope of protection of the invention.
Embodiment one
Mix for the hydrochloric acid of 6mol/L with the formic acid and concentration by concentration for 6mol/L after the cleaning of discarded Rhizoma Zingiberis Recenss fiber is shredded
The mixed acid solution for closing is 1 by solid-to-liquid ratio:100g/mL mixes, and wherein the volume ratio of formic acid and hydrochloric acid is 5:5, it is put into hydro-thermal
In kettle, 3h is reacted in 110 DEG C of baking oven, reaction terminates rear Deca ammonia and adjusts pH value to 7, and centrifugation washing 3 times is placed on plastics
- 50 DEG C of lyophilization 12h in mould, obtain spongy fiber element nanocrystalline material (a).The observation under scanning electron microscope obtains fiber
The length of plain nanometer rods is 500-1000nm, and a diameter of 5-40nm, draw ratio is 25-200.
Embodiment two
Mix for the hydrochloric acid of 6mol/L with the citric acid and concentration by concentration for 3mol/L after the cleaning of discarded cotton fiber is shredded
The mixed acid solution for closing is 1 by solid-to-liquid ratio:75g/mL mixes, and wherein the volume ratio of citric acid and hydrochloric acid is 7:3, it is put into hydro-thermal
In kettle, 4h is reacted in 120 DEG C of baking oven, reaction terminates rear Deca ammonia and adjusts pH value to 7, and centrifugation washing 4 times is placed on plastics
- 50 DEG C of lyophilization 24h in mould, obtain spongy fiber element nanocrystalline material (b).The observation under scanning electron microscope obtains fiber
The length of plain nanometer rods is 600-1200nm, and a diameter of 5-50nm, draw ratio is 25-240.
Embodiment three
Form for the mixed in hydrochloric acid of 6mol/L with the formic acid and concentration by concentration for 6mol/L after coir cleaning is shredded
Mixed acid solution by solid-to-liquid ratio be 1:50g/mL mixes, and wherein the volume ratio of formic acid and hydrochloric acid is 9:1, in being put into water heating kettle,
5h is reacted in 130 DEG C of baking oven, reaction terminates rear Deca ammonia and adjusts pH value to 7, and centrifugation is washed 3 times, be placed in mould of plastics-
50 DEG C of lyophilizations 48, obtain spongy fiber element nanocrystalline material (c).The observation under scanning electron microscope obtains cellulose nanometer rods
Length be 500-1500nm, a diameter of 5-40nm, draw ratio is 25-300.
Example IV
Mix for the hydrochloric acid of 6mol/L with the formic acid and concentration by concentration for 3mol/L after the cleaning of discarded Rhizoma Zingiberis Recenss fiber is shredded
The mixed acid solution for closing is 1 by solid-to-liquid ratio:100g/mL mixes, and wherein the volume ratio of formic acid and hydrochloric acid is 5:5, burn in round bottom
Solid-liquid is sufficiently mixed in bottle, the fresh-keeping film phonograph seal of bottleneck, and 7h is reacted in 60 DEG C of water-baths, and reaction terminates rear Deca ammonia and adjusts
To 7, centrifugation washing 5 times is placed on -50 DEG C of lyophilization 12h in mould of plastics to pH value, obtains spongy fiber element nanocrystalline material
(d).The length that observation obtains cellulose nanometer rods under scanning electron microscope is 500-1600nm, a diameter of 5-40nm, and draw ratio is
25-320。
Embodiment five
Form for the mixed in hydrochloric acid of 6mol/L with the formic acid and concentration by concentration for 3mol/L after flaxen fiber cleaning is shredded
Mixed acid solution by solid-to-liquid ratio be 1:75g/mL mixes, and wherein the volume ratio of formic acid and hydrochloric acid is 7:3, the solid-liquid in round-bottomed flask
It is sufficiently mixed, the fresh-keeping film phonograph seal of bottleneck, 7h is reacted in 70 DEG C of water-baths, reaction terminates rear Deca ammonia and adjusts pH value to 7,
Centrifugation washing 3 times, is placed on -50 DEG C of lyophilization 24h in mould of plastics, obtains spongy fiber element nanocrystalline material (e).Sweeping
The length for retouching electric Microscopic observation acquisition cellulose nanometer rods is 500-1500nm, and a diameter of 5-50nm, draw ratio is 30-300.
Embodiment six
By coir cleaning shred after with by concentration for 3mol/L citric acid and concentration for 6mol/L mixed in hydrochloric acid and
Into mixed acid solution by solid-to-liquid ratio be 1:50g/mL mixes, and wherein the volume ratio of citric acid and hydrochloric acid is 9:1, in round-bottomed flask
Solid-liquid is sufficiently mixed, the fresh-keeping film phonograph seal of bottleneck, and 7h is reacted in 80 DEG C of water-baths, and reaction terminates rear Deca ammonia and adjusts pH value
To 7, centrifugation washing 5 times is placed on -50 DEG C of lyophilization 48h in mould of plastics, obtains spongy fiber element nanocrystalline material (f).
The length that observation obtains cellulose nanometer rods under scanning electron microscope is 600-1800nm, and a diameter of 5-50nm, draw ratio is 25-
360。
Determine embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6 under scanning electron microscope (SEM) photograph to prepare
Cellulose nanocrystal sponge material microcosmic draw ratio, and contrast with other preparation methoies.
From data in table 1, the Cellulose nanocrystal sponge material obtained using preparation method of the present invention
A Cellulose nanocrystal that (), (b), (c), (d), (e), the draw ratio of (f) are significantly prepared higher than additive method.
Table 1
| Sample | Sulfuric acid process | (a) | (b) | (c) | (d) | (e) | (f) |
| Draw ratio | 10-40 | 25-200 | 30-240 | 25-300 | 25-320 | 30-300 | 25-360 |
Above-mentioned specific embodiment is used for illustrating the present invention, rather than limits the invention, the present invention's
In spirit and scope of the claims, any modifications and changes made to the present invention both fall within the protection model of the present invention
Enclose.
Claims (8)
1. a kind of preparation method of Cellulose nanocrystal sponge material, it is characterised in that comprise the following steps：
1) pretreated biomass cellulose is mixed with nitration mixture, 2-10h, wherein biomass fiber is reacted at 50-130 DEG C
Element is 1 with the solid-to-liquid ratio of nitration mixture：30-120g/mL, reaction is washed after terminating, the pH value of mixed liquor is adjusted to 7 by centrifugal treating, is obtained
To Cellulose nanocrystal suspension；
2) by step 1) in the Cellulose nanocrystal suspension for obtaining insert in mould, lyophilization 12-48h obtains final product spongy
Cellulose nanocrystal material.
2. the preparation method of Cellulose nanocrystal sponge material according to claim 1, it is characterised in that：The step 1)
In biomass cellulose be Rhizoma Zingiberis Recenss fiber, cotton fiber, flaxen fiber or coir.
3. the preparation method of Cellulose nanocrystal sponge material according to claim 1, it is characterised in that：The step 2)
Middle lyophilization temperature is -50 DEG C.
4. the preparation method of Cellulose nanocrystal sponge material according to claim 1, it is characterised in that：The step 1)
Middle nitration mixture is the mixed liquor of acid solution A and acid solution B；Acid solution A is the one or two or more in formic acid, ascorbic acid, citric acid
Combination, the concentration of acid solution A is 1-10mol/L；Acid solution B is hydrochloric acid, and the concentration of acid solution B is 1-10mol/L.
5. the preparation method of the Cellulose nanocrystal sponge material according to claim 1 or 3, it is characterised in that：The step
It is rapid 1) in acid solution A and acid solution B volume ratio be 5-9:1-5.
6. the preparation method of Cellulose nanocrystal sponge material according to claim 4, it is characterised in that：The step 1)
The volume ratio of middle acid solution A and acid solution B is 9:1 or 8:2 or 7:3 or 6:4 or 5:5.
7. the preparation method of Cellulose nanocrystal sponge material according to claim 1, it is characterised in that：The step 1)
In the Cellulose nanocrystal that obtains in long wire, its a diameter of 5-50nm, length is 500-2000nm, and draw ratio is 25-400.
8. the preparation method of Cellulose nanocrystal sponge material according to claim 1, it is characterised in that：The step 1)
In the surface group of Cellulose nanocrystal that obtains have ester group, hydroxyl and carboxyl.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108467509A (en) * | 2018-03-10 | 2018-08-31 | 浙江理工大学 | A kind of preparation method for the Cellulose nanocrystal/layer/polyaniline conductive flexibility aeroge having both capacitance and sensing function |
| CN110760009A (en) * | 2019-10-31 | 2020-02-07 | 华南农业大学 | Preparation method of nano-cellulose |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040663A (en) * | 2010-12-06 | 2011-05-04 | 东华大学 | Preparation method of narrow-distribution cellulose nanocrystalline |
| CN102311505A (en) * | 2011-07-18 | 2012-01-11 | 东华大学 | Method for preparing cellulose nanospheres based on waste dissolvable fibers |
| CN103382225A (en) * | 2013-07-22 | 2013-11-06 | 浙江理工大学 | Surface esterification modification method for cellulose nanocrystalline |
| CN105949519A (en) * | 2016-05-09 | 2016-09-21 | 郭舒洋 | Preparation method of nano-zinc oxide cellulose sponge material |
-
2016
- 2016-12-14 CN CN201611152564.2A patent/CN106674586A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040663A (en) * | 2010-12-06 | 2011-05-04 | 东华大学 | Preparation method of narrow-distribution cellulose nanocrystalline |
| CN102311505A (en) * | 2011-07-18 | 2012-01-11 | 东华大学 | Method for preparing cellulose nanospheres based on waste dissolvable fibers |
| CN103382225A (en) * | 2013-07-22 | 2013-11-06 | 浙江理工大学 | Surface esterification modification method for cellulose nanocrystalline |
| CN105949519A (en) * | 2016-05-09 | 2016-09-21 | 郭舒洋 | Preparation method of nano-zinc oxide cellulose sponge material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108467509A (en) * | 2018-03-10 | 2018-08-31 | 浙江理工大学 | A kind of preparation method for the Cellulose nanocrystal/layer/polyaniline conductive flexibility aeroge having both capacitance and sensing function |
| CN110760009A (en) * | 2019-10-31 | 2020-02-07 | 华南农业大学 | Preparation method of nano-cellulose |
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