CN107236049A - A kind of nano-cellulose and preparation method thereof - Google Patents
A kind of nano-cellulose and preparation method thereof Download PDFInfo
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- CN107236049A CN107236049A CN201710511863.9A CN201710511863A CN107236049A CN 107236049 A CN107236049 A CN 107236049A CN 201710511863 A CN201710511863 A CN 201710511863A CN 107236049 A CN107236049 A CN 107236049A
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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
- 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
- C08B15/04—Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
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Abstract
The invention provides a kind of in gel, microgranular, powdered or sheet nano-cellulose and preparation method thereof.Preparation method includes cellulosic raw material being added in reaction solution, under certain ph, continue stirring reaction 4.5~18.0 hours, use absolute ethyl alcohol terminating reaction, reaction product is through centrifugation, precipitating reagent precipitation, cleaning solution washing, filter membrane suction filtration, gel nano-cellulose can be made, if microgranular, powdered or sheet nano-cellulose can be made through vacuum freeze drying again.The reaction solution is the mixed liquor of NO free radical, periodate, sodium bromide and sodium hypochlorite.The method processing time that the present invention is provided is short, and technique is simple, is adapted to industrial-scale production.The nano-cellulose product that the present invention is provided, contain the functional group of high concentration on surface, there is good redispersibility in the dispersion liquids such as water, ethanol, had broad application prospects in fields such as nano composite material, medical macromolecular materials, functional dress ornament, 3D printing and photoelectricity.
Description
Technical field
The invention belongs to cellulose technology field, more particularly to a kind of nano-cellulose and preparation method thereof.
Background technology
Nano-cellulose is that the size of certain dimension in three dimensions is less than a kind of 100nm cellulosic material.Nanometer
Cellulose has small-size effect, surface-interface effect and macro quanta tunnel effect, shows light, electricity, magnetic and the change of uniqueness
Characteristic is learned, " 21 century most promising material " is described as, has caused the great attention of national governments and scientific circles, in new material
Had broad application prospects in research and new technical field.
Cellulose is the main component of plant cell wall, is also a kind of renewable organic resource most abundant on the earth.Profit
Clean energy resource can be not only produced with cellulose, moreover it is possible to produce high performance material and high valuable chemicals to replace fossil resource
The product of origin.Due to adjacent cellulose microfibril chemical crosslinking or physical entanglement together, efficient nano neutralizing is long and slender
Dimension element is always a difficult point of cellulose higher value application.The preparation method of nano-cellulose mainly has Physical, chemical method
And bioanalysis.Physical mainly has high pressure homogenization method, microjet method, mill and supercritical ultrasonics technology etc., and the major defect of Physical is
High energy consumption, can be up to 25kWh/kg sometimes.Chemical method handles cellulose using inorganic acid highly basic, and strong acid and strong base is rotten to equipment
Corrosion is big and is difficult to reclaim, and liquid waste processing is relatively difficult, pollutes environment.The enzyme of bioanalysis is expensive and severe reaction conditions,
The reaction efficiency relatively low reaction time is long.Also need to carry out mechanical treatment after organic acid system acidifying to fiber progress solution fibre
(CN105646721).2,2,6,6- tetramethyl piperidine nitrogen oxides (TEMPO) catalytic oxidations are one more than the comparison being reported
Preparation method is planted, but high-pressure homogeneous wait also is needed for after oxidation and carries out solution fibre (Japan Patent JP201440530；
CN101874043).Prepared to realize that nano-cellulose industrialized production must develop a kind of efficiently simple nano-cellulose
Method.
Powered anionic group is introduced on the surface of cellulose microfibril, electrostatic row is formed between adjacent microfibril
Hydrogen bond action between reprimand, destruction cellulosic molecule, can reduce energy expenditure during solution fibre.Although TEMPO catalytic oxidations can
To introduce carboxylic group on microfibril surface, but the concentration of carboxylic group maximum is no more than 1.8mmol/g celluloses.Need hair
A kind of bright method, it is as much as possible that powered group, the relatively low fine energy consumption of machinery solution, high-efficiency production of nano are introduced on microfibril surface
Cellulose.
It is well known that cellulose is the chain macromolecule chemical combination that D-Glucose (AGU) is combined with β-Isosorbide-5-Nitrae glycosidic bond
Altogether containing 3 hydroxyls on C2, C3 and C6 position in thing, each D-Glucose.Periodate (such as KIO4, NaIO4Deng) can select
Property oxidation C2 and C3 positions on hydroxyl, and NO free radical (such as 2,2,6,6- tetramethyl piperidine nitrogen oxides (TEMPO) and its spreads out
Biological or homologue and HP (NHPI) and its derivative or homologue) it is then selective oxidation C6
On hydroxyl one carboxyl of formation, introduce electronegative group on cellulose microfibril surface.Present invention firstly provides use nitrogen oxygen
Free radical and the periodate method that mixed oxidization substrate cellulose prepares nano-cellulose simultaneously.According to cellulose molecular structure
The characteristics of, utilize the complementation of C2 and C3 hydroxyls of periodate selective oxidation, C6 hydroxyls of NO free radical selective oxidation
Property, while the hydroxyl on selective oxidation C2, C3 and C6 positions respectively, the theory of carboxyl can be introduced by improving microfibril surface
Maximum, to improve the electrostatic repulsion forces between the ability for introducing charged group, increase microfibril, the fine energy consumption of reduction machinery solution
Either remove the fine process of machinery solution.
The content of the invention
Present invention solves the technical problem that be to provide a kind of nano-cellulose product with New function and feature and its
High efficiency preparation method.
The nano-cellulose product that the present invention is provided is gel, powdered, microgranular or sheet, is contained on surface highly concentrated
The functional group of degree, has good redispersibility in the dispersion liquids such as water, ethanol.
According to another aspect of the present invention there is provided a kind of preparation method of nano-cellulose, including cellulose is former
Material is added in reaction solution, under certain ph, is continued stirring reaction 4.5~18.0 hours, is used absolute ethyl alcohol terminating reaction,
Gel nano-cellulose can be made through centrifugation, precipitating reagent precipitation, cleaning solution washing, filter membrane suction filtration in reaction product, if again through true
Microgranular, powdered or sheet nano-cellulose can be made in vacuum freecing-dry.The reaction solution is NO free radical, periodic acid
The mixed liquor of salt, sodium bromide and sodium hypochlorite.
The method processing time that the present invention is provided is short, and technique is simple, is adapted to industrial-scale production.Gained nano-cellulose
Material has wide application in fields such as nano composite material, medical macromolecular materials, functional dress ornament, 3D printing and photoelectricity
Prospect.
The present invention provides a kind of nano-cellulose product and preparation method thereof, and detailed step includes：
Cellulosic raw material is added in reaction solution, under certain ph, continues stirring reaction 4.5~18.0 hours,
Absolute ethyl alcohol terminating reaction is used, gel can be made through centrifugation, precipitating reagent precipitation, cleaning solution washing, filter membrane suction filtration in reaction product
Nano-cellulose, if microgranular, powdered or sheet nano-cellulose can be made through vacuum freeze drying again.
The cellulosic raw material can be commercialization microcrystalline cellulose, and pulp inlet, wood pulp, cotton pulp and gunny products are made
Purifying cellulose, stalk or algae etc. extract the purifying cellulose for preparing；Consolidating for cellulosic raw material contains in reaction solution
Measure as 0.005~0.02g/mL.
The reaction solution is the mixed liquor of NO free radical, periodate, sodium bromide and sodium hypochlorite.
The NO free radical can be 2,2,6,6- tetramethyl piperidine nitrogen oxides (TEMPO), TEMPO derivative or
At least one of TEMPO homologues, HP (NHPI), NHPI derivative or NHPI homologues.
Described TEMPO, TEMPO derivative and the chemical structural formula of TEMPO homologues are shown in Fig. 1.Mainly have：(1) 2,2,
6,6- tetramethyl piperidine nitrogen oxides (or 2,2,6,6- tetramethyl piperidine -1- oxygen radicals；English name is 2,2,6,6-
Tetramethyl-1-piperidinyloxy, is abbreviated as TEMPO)；(2) 4- acetylaminohydroxyphenylarsonic acids 2,2,6,6- tetramethyl piperidine nitrogens
Oxide (English name is 4-acetamido-TEMPO)；(3) (English name is 4- methoxyl groups-tetramethyl piperidine oxygen radical
4-methoxy-TEMPO)；(4) 4- carboxyls -2,2, (English name is 4-carboxy- to 6,6- tetramethyl piperidine 1- oxygen radicals
TEMPO)；(5) 4- amino-2,2,6,6-tetramethylpiperidines oxygen radical (English name is 4-amino-TEMPO)；(6) 4- phosphines
Acyloxy -2,2,6,6- tetramethyl -1- piperidones (English name is 4-phosphonooxy-TEMPO)；(7) 4- hydroxy piperidines
Alcohol oxygen radical (English name is 4-hydroxy-TEMPO)；(8) 4- oxygen -2,2,6,6- tetramethyl piperidine -1- oxygen radicals
(English name is 4-oxo-TEMPO)；(9) 3- carboxyls -2,2,5,5- tetramethyl -1- pyrrolidinyl oxygen radical (English names
For 3-carboxy-PROXYL)；(10) 3- carboxyls -2,2, (English name is 3- to 5,5- tetramethyl nafoxidine NO free radicals
carbamoyl-PROXYL)；(11) 3- carbamyls -2,2, (English name is 3- to 5,5- tetramethyl -3- pyrrolin -1- epoxides
Carbamoyl-2,2,5,5-tetramethyl-3-pyrrolin-1-oxyl).It should be understood that TEMPO, TEMPO derivative and
The chemical structural formula of TEMPO homologues includes these chemical structural formulas in Fig. 1, but is not limited only to this 11 kinds, these chemistry knots
Structure formula is only illustrative of the invention and is not intended to limit the scope of the invention.
Described NHPI, NHPI derivative and the chemical structural formula of NHPI homologues are shown in Fig. 2.Mainly have：(1) N- hydroxyls are adjacent
BIDA (English name is N-Hydroxyphthalimide, is abbreviated as NHPI)；(2) I-hydroxybenzotriazole (English
Literary fame is referred to as N-hydroxybenzotriazole, is abbreviated as HBT)；(3) (English name is 5- oximinos barbituric acid
Violuric acid, are abbreviated as VA).It should be understood that NHPI, NHPI derivative and the chemical structural formula of NHPI homologues include
These chemical structural formulas in Fig. 2, but be not limited only to this 3 kinds, these chemical structural formulas be merely to illustrate the present invention rather than
Limit the scope of the present invention.
The periodate can be at least one of potassium metaperiodate, sodium metaperiodate, barium periodate etc..
The sodium hypochlorite also can be replaced sodium chlorite.
The amount ranges of NO free radical are preferably 0.25~1.00mmol/g celluloses in the reaction solution.
The amount ranges of the reaction solution meso-periodic acid salt are preferably 1~4mmol/g celluloses.
The amount ranges of sodium bromide are preferably 4~12mmol/g celluloses in the reaction solution.
The amount ranges of sodium hypochlorite or sodium chlorite are preferably 4~12mmol/g celluloses in the reaction solution.
The amount ratio of NO free radical and periodate is preferably 1: 2~1: 8 in the reaction solution
The certain ph scope is between pH9~pH11.
The cleaning solution is hydrochloric acid solution and absolute ethyl alcohol or ethanol water.
The concentration of the hydrochloric acid solution is preferably 0.4~0.6N.
The ratio of ethanol is preferably 100%~50% in the ethanol water.
Cleaning solution washing washing times be preferably hydrochloric acid solution and absolute ethyl alcohol or ethanol water wash 1 respectively~
4 times.
The filter membrane suction filtration preferably uses 22~80 micron membrane filters and carries out suction filtration.
The vacuum freeze drying is preferably to dry 1~48 hour.
Beneficial effect
The preparation method of nano-cellulose provided by the present invention, combines C2 and C3 hydroxyls of periodate selective oxidation
The characteristics of base, C6 hydroxyls of NO free radical selective oxidation, pretreatment conciliates the fine step of process one and completes to have prepared Nanowire
Dimension element, eliminates the fine step of machinery solution of high energy consumption, reduces energy consumption and production cost.Technique is simple to operation, it is not necessary to high
Expensive equipment, is suitable for industrial-scale production.
Nano-cellulose purity prepared by the present invention is high, even size distribution, can in gel, it is microgranular, powdered or
Sheet.Maximum carboxylated (carboxyl concentration is up to 3.0mmol/g celluloses) can be realized, and selective oxidation can be passed through
The consumption regulation and control carboxylated degree of agent.The nano-cellulose product that the present invention is provided, the functional group of high concentration is contained on surface,
There is good redispersibility in the dispersion liquids such as water, ethanol, in nano composite material, medical macromolecular materials, functional clothes
The fields such as decorations, 3D printing and photoelectricity have broad application prospects.
Brief description of the drawings
Fig. 1 TEMPO, TEMPO derivative and the chemical constitution of TEMPO homologues
Fig. 2 NHPI, NHPI derivative and the chemical constitution of NHPI homologues
Powdered nano-cellulose prepared by Fig. 3 embodiments
The transmission electron microscope picture of nano-cellulose prepared by Fig. 4 embodiments
Gel nano-cellulose prepared by Fig. 5 embodiments
Flake nano cellulose prepared by Fig. 6 embodiments
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
In the beaker that 500ml distilled water is added to 1L, by 2.5mmol TEMPO (2,2,6,6- tetramethyl piperidine nitrogen oxidations
Thing), 40mmol NaBr, 10mmolNaIO4Beaker is added, is stirred energetically with magnetic stirring apparatus 5 minutes.Held in magnetic stirring apparatus
Continuous stirring simultaneously, adds the microcrystalline cellulose of 5g commercializations in beaker.After stirring, 40mmol NaClO is slowly added to.
Continue stirring reaction 9 hours.Every 1.0 hours during reaction, a pH value is adjusted with 2M NaOH, the pH value of reaction solution is maintained
10.5 or so.After reaction 9 hours, 5mL absolute ethyl alcohol terminating reactions, 10 minutes reaction time are added.Whole experimental implementation is kept away
Light is carried out.By reaction solution low-speed centrifugal 2 minutes, to be precipitated supernatant with absolute ethyl alcohol, it is then centrifuged for.Precipitation is used into 0.5N hydrochloric acid
Respectively cleaned with ethanol twice, cross film water wash and vacuum filter after, then through after vacuum freeze drying 48 hours both powdered nanometer
Cellulose, as shown in Figure 3.After nano-cellulose powder in ethanol redisperse, transmission electron microscope observing picture as shown in figure 4,
Obtained powder has good redispersibility.
Embodiment 2
In the beaker that 500ml distilled water is added to 1L, by 2.5mmol TEMPO (2,2,6,6- tetramethyl piperidine nitrogen oxidations
Thing), 40mmol NaBr, 10mmolNaIO4Beaker is added, is stirred energetically with magnetic stirring apparatus 5 minutes.Held in magnetic stirring apparatus
Continuous stirring simultaneously, adds the microcrystalline cellulose of 5g commercializations in beaker.After stirring, 40mmol NaClO is slowly added to.
Continue stirring reaction 10 hours.Every 1.0 hours during reaction, a pH value is adjusted with 2M NaOH, the pH value of reaction solution is maintained
10.5 or so.After reaction 9 hours, 5mL absolute ethyl alcohol terminating reactions, 10 minutes reaction time are added.Whole experimental implementation is kept away
Light is carried out.By reaction solution low-speed centrifugal 2 minutes, supernatant is precipitated with absolute ethyl alcohol, is then centrifuged for.Will precipitation with 0.5N hydrochloric acid and
Ethanol respectively cleaning twice, cross film water wash and vacuum filter after both gel nano-cellulose, as shown in Figure 5.Transmission electron microscope is seen
Examine display fibre diameter and be respectively less than 100 nanometers.
Embodiment 3
In addition to vacuum drying time is 8 hours, remaining operating method be the same as Example 1, the sheet that can be made as shown in Figure 6 is received
Rice cellulose.
Embodiment 4
Except the reaction time is 4 hours, powdered nano-cellulose can be also made in remaining operating method be the same as Example 1.
Embodiment 5
Nano-cellulose is prepared using common wood pulp as raw material.First the hemicellulose and wood in wood pulp are removed with universal method
Quality.With glacial acetic acid and sodium chlorite removing lignin, hemicellulose is removed with potassium hydroxide, purifying cellulose is made, below
Operating method be the same as Example 1, you can nano-cellulose is made.
Embodiment 6
Nano-cellulose is prepared using Russian pulp inlet as raw material.Removing hemicellulose and lignin prepare cleaning cellulose
The method be the same as Example 5 of element, purifying cellulose prepares the operating method be the same as Example 1 of nano-cellulose, you can Nanowire is made
Dimension element.
Embodiment 7
By 500ml distilled water add 1L beaker in, by 2.5mmol NHPI (HP),
40mmol NaBr、10mmolNaIO4Beaker is added, is stirred energetically with magnetic stirring apparatus 5 minutes.Persistently stirred in magnetic stirring apparatus
Mix simultaneously, the microcrystalline cellulose of 5g commercializations is added in beaker.After stirring, 40mmol NaClO is slowly added to.Continue
Stirring reaction 10 hours.Every 1.0 hours during reaction, a pH value is adjusted with 2M NaOH, the pH value of reaction solution is maintained
10.5 or so.After reaction 9 hours, 5mL absolute ethyl alcohol terminating reactions, 10 minutes reaction time are added.Whole experimental implementation lucifuge
Carry out.By reaction solution low-speed centrifugal 2 minutes, supernatant is precipitated with absolute ethyl alcohol, is then centrifuged for.By precipitation 0.5N hydrochloric acid and second
Alcohol respectively cleaning twice, cross film water wash and vacuum filter after, then through vacuum freeze drying both nano-cellulose.
Claims (10)
1. a kind of nano-cellulose and preparation method thereof, it is characterised in that cellulosic raw material is added in reaction solution, in spy
Determine under pH value, continue stirring reaction 4.5~18.0 hours, use absolute ethyl alcohol terminating reaction, reaction product is sunk through centrifugation, precipitating reagent
Form sediment, cleaning solution is washed, filter membrane suction filtration, nano-cellulose is made after vacuum freeze drying.
2. a kind of nano-cellulose according to claim 1 and preparation method thereof, it is characterised in that the cellulose former material
Material can be commercialization microcrystalline cellulose, pulp inlet, wood pulp, cotton pulp and purifying cellulose made from gunny products, crops straw
Stalk or algae etc. extract the purifying cellulose prepared；In reaction solution the solid content of cellulosic raw material be 0.005~
0.02g/mL。
3. a kind of nano-cellulose according to claim 1 and preparation method thereof, it is characterised in that the reaction solution is nitrogen
Oxygen radical, periodate, the mixed liquor of sodium bromide and sodium hypochlorite.
4. NO free radical according to claim 3 is 2,2,6,6- tetramethyl piperidine nitrogen oxides (TEMPO), TEMPO
Derivative or the examination of at least one of homologue, HP (NHPI), NHPI derivatives or homologue
Agent.
5. periodate according to claim 3 is the examination of at least one of potassium metaperiodate, sodium metaperiodate, barium periodate etc.
Agent.
6. sodium hypochlorite according to claim 3 also can be replaced sodium chlorite.
7. a kind of nano-cellulose according to claim 1 and preparation method thereof, it is characterised in that the certain ph model
Enclose between pH9~pH11.
8. a kind of nano-cellulose according to claim 1 and preparation method thereof, it is characterised in that the drying means is
Vacuum freeze-drying method, drying time is 1~48 hour.
9. a kind of nano-cellulose according to claim 1 and preparation method thereof, it is characterised in that the nano-cellulose
Product is gel, powdered, microgranular or sheet.
10. a kind of nano-cellulose according to claim 1 and preparation method thereof, it is characterised in that the nano-cellulose
Functional group containing high concentration, the functional group is carboxyl or aldehyde radical.
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| CN115975457B (en) * | 2022-12-15 | 2024-05-03 | 广东省漆色彩新型材料有限公司 | Water-based paint composition and preparation method thereof |
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