CN106866827A - Modified nanometer cellulose containing various functional groups and preparation method thereof - Google Patents
Modified nanometer cellulose containing various functional groups and preparation method thereof Download PDFInfo
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- CN106866827A CN106866827A CN201710119752.3A CN201710119752A CN106866827A CN 106866827 A CN106866827 A CN 106866827A CN 201710119752 A CN201710119752 A CN 201710119752A CN 106866827 A CN106866827 A CN 106866827A
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- C08B13/00—Preparation of cellulose ether-esters
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
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Abstract
The present invention relates to a kind of modified nanometer cellulose containing various functional groups and preparation method thereof.After the present invention mixes weak diacid with water, carboxymethylcellulose calcium powder is added, mixed liquor centrifugation obtains standing centrifugation with rear during solid mixture adds water and alkali；Solid add water washing, solid product is centrifuged to obtain, stratification in solid product water, upper suspension goes to remove water the modified nanometer cellulose whisker that must contain various functional groups, and homogenization obtains the modified cellulose nanofiber containing various functional groups after lower floor's solids of sedimentation dilute with water.The present invention prepares nano-cellulose CMNW and CMNFs by raw material of carboxymethylcellulose calcium, expand the scope of nano-cellulose preparing raw material, hydrolyzed by weak acid and homogenizer homogeneous prepares nano-cellulose, process acid can be reclaimed all, environmentally friendly low cost, it is a new approach for preparing nano-cellulose, and can directly prepares the nano-cellulose new material with mixing carboxyl, for the application of nano-cellulose provides wide prospect.
Description
Technical field
The invention belongs to field of fine chemical, and in particular to a kind of modified nanometer cellulose containing various functional groups and its
Preparation method.
Background technology
Nano cellulose material is by technologies such as acidolysis, enzymolysis, alkalization catalysis or mechanical shearings with cotton, wood pulp fiber element
The size for obtaining is in nano level cellulose products.Nano-cellulose has crystallinity high, degradable, high intensity, extremely low heat
The advantages such as the coefficient of expansion, can be widely used in biomedicine, automobile making, Aero-Space, 3D printing, building, the special material of military project
The fields such as material, electronic product, cosmetics, coating, paint, food, papermaking, composite and enhancing by polymer.
In the prior art, different according to preparation method, nano cellulose material is broadly divided into nano cellulose crystal
(Cellulose Nanowhiskers, abridge CNWs), nano-cellulose (Cellulose Nanofibrils, abridge CNFs)
Two major classes, in the different each own performance advantages of oneself in application scenario.The nano cellulose material manufacturer for reporting both at home and abroad
Method mainly includes：Chemical method, physical method, biological method and synthetic method etc. are various.Wherein, biological enzyme digestion method it is time-consuming,
Costly and difficulty is big, so foreign countries' cellulose nano material preparation method is concentrated mainly on Physical and chemical method two at present
Kind.But, chemical method is processed by strong acid, such as hydrochloric acid, sulfuric acid or phosphoric acid etc., and these acid are after cellulose acidolysis
Recovery difficult is big, high cost, can only be used in laboratory at present；Physical, such as directly using ultrasound, homogenize, machinery
Crushing ball milling etc. makes cellulose reach the difficult very big of nanoscale, causes the nanoscale of product to be difficult to control to, while also depositing
The problems such as reason causes high energy consumption in strength, so being all introduced into the application stage.
If additionally, first by cellulose nanosizing, then carrying out carboxy methylation or esterification, because nano-cellulose is in alkali, organic
There is the characteristics of dispersion is difficult, derivatization process is difficult to control in solvent, especially prepared by nano-cellulose ether-ether mixing derived material
Difficulty is bigger, it is achieved that the etherificate of nano-cellulose, first has to alkalization, and alkalizing can greatly destroy the nanometer of nano-cellulose
Feature, if after chemical reaction reaches etherificate, esterification again, then continues to keep the nano shape of cellulose more difficult, so difficult
Directly to prepare the nano-cellulose with functional groups.
The content of the invention
For defect of the prior art, a kind of energy reduces cost of present invention offer, reaction controllability are strong, and carboxylic is contained simultaneously
Carboxylic modified nanometer cellulose of base and ester group and preparation method thereof.
To achieve the above object, the technical solution adopted by the present invention is：
The preparation method of the modified nanometer cellulose containing various functional groups that the present invention is provided comprises the following steps：
A. weak diacid and water are first mixed to form stabilization acid solution, are then added carboxymethylcellulose calcium powder described steady
Determine to form mixed liquor in acid solution；Described weak diacid is binary organic monoacid, and dissociation constant Ka is less than at such as 25 DEG C
0.0001 dicarboxylic acids.
B. mixed liquor centrifugation is obtained into solid mixture and adds water and alkali, regulation pH value to 6.8-7.2 stands centrifugation；
C. gained solid repeats add water washing, centrifugation step 2-3 times after centrifugation will be stood, and obtains solid product, solid product
Thing stratification in water obtains upper suspension and lower floor's solids of sedimentation；
D. upper suspension goes moisture removal to obtain final product the modified nanometer cellulose whisker CMNW containing various functional groups, and lower floor is solid
Being imported after body precipitation dilute with water carries out homogenization and obtains the modified cellulose containing various functional groups receiving in high pressure homogenizer
Rice fiber CMNFs.
Gained liquid carries out centrifugation except liquid under 100 DEG C of high temperature after mixed liquor centrifugation in the step B, contains a large amount of mistakes
The liquid of journey acid enters recrystallization groove, the recrystallization of implementation process acid under the conditions of not forced cooling, such that it is able to implementation process
The recovery of acid.
The present invention is esterified using carboxymethylcellulose calcium under the acid condition of binary acid, is obtained with carboxylic group and binary
The mixed derivative of perester radical：Modified nanometer cellulose whisker CMNW and modified cellulose nanofiber CMNFs, both belong to two
The cellulose of parent's property derives nano material.Prepared CMNW and CMNFs are in biological medicine, papermaking, 3D printing, food and life
Life scientific domain can be as chelating agent, couplant, the agent of guarantor's type, reinforcing agent, solubilizer, thickener and excipient etc., with huge
Big application potential.
Because the modified nanometer cellulose product obtained by preparation directly contains binary acid after carboxymethyl group and esterification
The carboxylic group having, increased the range of application and effect of nano-cellulose, be to carry out chemical modification to nano-cellulose to be
One effective way.
Further, in the preparation method of the above-mentioned modified nanometer cellulose containing various functional groups, institute in the step A
Weak diacid is stated for malonic acid and/or ethanedioic acid.
Further, in the preparation method of the above-mentioned modified nanometer cellulose containing various functional groups, carboxylic in the step A
Methylcellulose powder is added in the stabilization acid solution in temperature as 75-100 DEG C carries out acidification 2-8h and obtain mixed liquor.
Further, in the preparation method of the above-mentioned modified nanometer cellulose containing various functional groups, the step B and step
The temperature of centrifugal treating is 100 DEG C in rapid C.
It is further preferred that in the preparation method of the above-mentioned modified nanometer cellulose containing various functional groups, the step A
Described in carboxymethylcellulose calcium substitution value be 0.15-0.75.
The inventive method carries out weak acid acidizing pretreatment to low substituted carboxymethylcellulose calcium, then is homogenized, not only
Process acid-utilising recrystallization technology is reclaimed, and the energy consumption that homogenizes is substantially reduced, under specification process conditions, the mixing ether-ether for obtaining
Nano-cellulose yardstick it is controllable.The manufacturing cost of the modified nanometer cellulose containing various functional groups can be reduced, realized without dirt
Green colouring is manufactured, and realizes that product yardstick controllability is strong.
Further, it is steady in the step A in the preparation method of the above-mentioned modified nanometer cellulose containing various functional groups
Determining acid solution compound method is：
Weak diacid and water are hybridly prepared into acid aqueous dispersion under normal temperature, are stirred and the formation that gradually heats up is uniform steady
Determine acid solution；
Before the carboxymethylcellulose calcium powder adds the stabilization acid solution, the stabilization acid solution temperature control is in 10-
40℃。
Further, in the preparation method of the above-mentioned modified nanometer cellulose containing various functional groups, institute in the step A
The mass fraction for stating stabilization acid solution is 30-60%, and the carboxymethylcellulose calcium powder and the mass ratio for stablizing acid solution are 1：
(20-30)。
Further, in the preparation method of the above-mentioned modified nanometer cellulose containing various functional groups, add in the step B
The quality for entering water is 20-30 times of the solid mixture, and the alkali of neutralization is that the NaOH that mass fraction is 15-25% is water-soluble
Liquid.
Further, in the preparation method of the above-mentioned modified nanometer cellulose containing various functional groups, in the step D under
Solids of sedimentation concentration after layer solids of sedimentation dilute with water is mass fraction 2-5%, and the pressure of homogenizer treatment is 20000-
45000psi, the homogenization time is 40-80min.
Still more preferably, in the centrifugal process of above steps, the rotating speed of centrifuge is not less than 2000r/min, from
The heart time is no less than 3min.Can so cause that various products are separated more thoroughly, save preparation time, more be produced
Thing.
Being prepared according to preparation method as described above can simultaneously obtain two kinds of modified nanometer cellulose products：It is modified and receives
Rice cellulose whiskers CMNW and modified cellulose nanofiber CMNFs, both of which contains carboxylic group and ester group；It is described to change
Property a diameter of 5-30nm of nano-cellulose whisker CMNW, length be 20-150nm；The modified cellulose nanofiber CMNFs
A diameter of 30-50nm, length be 0.1-10 μm.
Either CMNW or CMNFs have good hydrophily and material compatibility to product obtained by preparation, have
Very wide application prospect.
It should be noted that, CMNW is the english abbreviation title of product modified nanometer cellulose whisker of the present invention, and CMNFs is this
The english abbreviation title of invention product modified cellulose nanofiber, both sizes are different but are modified nanometer cellulose product
Product, described " nano-cellulose whisker CMNW " and " modified cellulose nanofiber CMNFs " is for preferably in the present invention
Two kinds of products are distinguished, rather than the repetition of name of product is repeated.
In sum, the present invention prepares modified nanometer cellulose CMNW, CMNFs by raw material of carboxymethylcellulose calcium, expands
The scope of nano-cellulose preparing raw material, is hydrolyzed by weak acid and homogenizer homogeneous prepares modified nanometer cellulose, process acid
All reclaim, environmental protection low cost opens a new approach for preparing nano-cellulose, and the modified Nano directly prepared is fine
Dimension element has the new material of mixing carboxyl, for the application of nano-cellulose provides wide prospect.By proposed by the invention
Method can be that raw material directly prepares functional nano cellulose fibre using carboxymethylcellulose calcium, obtained being modified is received
Rice cellulose contains carboxyl and has good crystallinity, and obtained nano-cellulose crystal grain is small, and this should for the product later stage
With there is provided good basis.
Brief description of the drawings
In order to illustrate more clearly of the technical scheme in the specific embodiment of the invention, specific embodiment will be retouched below
The accompanying drawing to be used needed for stating is briefly described.
Fig. 1 is the saturating of the modified cellulose nanofiber CMNFs containing various functional groups of the preparation of embodiment 1 in the present invention
Penetrate electromicroscopic photograph；
Fig. 2 is the saturating of the modified nanometer cellulose whisker CMNW containing various functional groups of the preparation of embodiment 1 in the present invention
Penetrate electromicroscopic photograph；
Fig. 3 is the modified nanometer cellulose whisker CMNW and carboxylic containing various functional groups of the preparation of embodiment 2 in the present invention
The infrared spectrum comparison diagram of methylcellulose；
Fig. 4 is modified nanometer cellulose whisker CMNW containing various functional groups and carboxylic first prepared by the embodiment of the present invention 2
The X-ray diffraction contrast collection of illustrative plates of base cellulose.
Specific embodiment
With reference to specific embodiment, the present invention will be further described.It should be noted that the reality described in the present invention
Example only the preferred embodiments of the present invention are applied, is not intended to limit the invention, for a person skilled in the art, this
Invention can have various modifications and variations.All any modifications within the spirit and principles in the present invention, made, equivalent,
Improve etc., should be included within the scope of the present invention.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, belongs to the scope of protection of the invention.Implement
If the percentage in example 1 to embodiment 5 is mass percent without specified otherwise.
The embodiment preparation parameter of table 1
Embodiment 1 to embodiment 5 is prepared by the following method according to listed parameter in table 1：
1. weak diacid is scattered in the water of acidolysis groove, prepares 100 parts of malonic acid or ethanedioic acid of mass fraction 50%
Deng weak diacid aqueous dispersion, the acid solution of uniform stabilization is formed, weigh 5 parts of carboxymethylcellulose calciums slow under agitation
Add in acid solution, then heat to reaction certain hour after 75-100 DEG C and form dispersed mixed liquor.
2. mixed liquor is poured into terminating reaction in 200 parts of deionized waters, then with 20%, 19%, 22%, 25%, 25%
NaOH solution is neutralized to weakly acidic pH, is repeatedly centrifuged after standing, until upper liquid is rendered as stable white suspension, collects upper strata and hangs
Turbid liquid and lower sediment thing, suspension individually deposits CMNW in suspension, and sediment then carries out homogenizing step into homogenizer.
3. the concentration deionized water of sediment is diluted to 2%, 2%, 3%, 4%, 4%, uses high pressure homogenizer inlet wire
The homogeneous 60min under 20000,25000,30000,30000,30000psi pressure conditions, can be containing functional group it is modified
Cellulose nano-fibrous CMNFs.
Embodiment 1 is as shown in table 1 to the design parameter of the preparation of embodiment 5：
Fig. 1 is the transmission electron microscope picture of the modified cellulose nanofiber CMNFs containing various functional groups prepared by embodiment 1
(TEM) diameter of modified cellulose nanofiber CMNFs, is therefrom can clearly be seen that about between 20-50nm, and length is in
Micron order, it was demonstrated that what the inventive method was obtained is cellulose nano-fibrous.Fig. 2 is the preparation of embodiment 1 containing various functional groups
Modified nanometer cellulose whisker CMNW transmission electron microscope picture (TEM), it can be seen that the size of whisker is more uniform, and its is a diameter of
5-30nm, length are 20-150nm.
Fig. 3 is modified nanometer cellulose whisker CMNW and carboxymethyl cellulose containing various functional groups prepared by embodiment 2
Infrared spectrum (IR) comparison diagram of element, top is the infrared spectrum curve of carboxymethylcellulose calcium, preparing for embodiment 2 on the lower
The modified nanometer cellulose whisker CMNW containing various functional groups infrared spectrum curve.It can be seen that prepare containing carboxyl
Modified nanometer cellulose whisker CMNW in 1700cm-1And 1600cm-1Place occurs in that the C=O's of the ester group and COO- of carboxylate radical
Absorb vibration peak, it was demonstrated that contain carboxylic group in the modified nanometer cellulose whisker CMNW obtained by preparation.
Fig. 4 is modified nanometer cellulose whisker CMNW and carboxymethyl cellulose containing various functional groups prepared by embodiment 2
The X-ray diffraction of element contrasts collection of illustrative plates (XRD), top for the X-ray of carboxymethylcellulose calcium is spread out curve, on the lower be embodiment 2
The X-ray of the modified nanometer cellulose whisker CMNW containing various functional groups for preparing is spread out curve.As can be seen from the figure implement
Modified nanometer cellulose whisker CMNW of the preparation gained containing various functional groups of example 2 is more sharp than the peak of carboxymethylcellulose calcium, half height
It is wide small, it was demonstrated that the crystal grain of obtained modified nanometer cellulose whisker CMNW is small, advantages of good crystallization.
Above-mentioned sign may certify that, can be that raw material is direct using carboxymethylcellulose calcium by method proposed by the invention
Two kinds of functional nano celluloses are prepared, obtained modified cellulose nanofiber CMNFs and modified nanometer cellulose are brilliant
Palpus CMNW containing carboxyl and has good crystallinity, and this provides good basis for the application in product later stage.
Claims (10)
1. the preparation method of the modified nanometer cellulose of various functional groups is contained, it is characterised in that：Comprise the following steps：
A. weak diacid and water are first mixed to form stabilization acid solution, carboxymethylcellulose calcium powder is then added into the stabilization acid
Mixed liquor is formed in solution；
B. mixed liquor centrifugation is obtained into solid mixture and adds water and alkali, regulation pH value to 6.8-7.2 stands centrifugation；
C. gained solid repeats add water washing, centrifugation step 2-3 times after centrifugation will be stood, and obtains solid product, and solid product exists
Stratification obtains upper suspension and lower floor's solids of sedimentation in water；
D. upper suspension goes moisture removal to obtain final product the modified nanometer cellulose whisker CMNW containing various functional groups, and lower floor's solid sinks
Being imported after the dilute with water of shallow lake carries out the modified cellulose Nanowire that homogenization obtains containing various functional groups in high pressure homogenizer
Vc MNFs.
2. the preparation method of the modified nanometer cellulose containing various functional groups according to claim 5, it is characterised in that：
Weak diacid described in the step A is malonic acid and/or ethanedioic acid.
3. the preparation method of the modified nanometer cellulose containing various functional groups according to claim 5, it is characterised in that：
Carboxymethylcellulose calcium powder carries out acidification 2- for 75-100 DEG C in adding the stabilization acid solution in temperature in the step A
8h obtains mixed liquor.
4. the preparation method of the modified nanometer cellulose containing various functional groups according to claim 1, it is characterised in that：
The temperature of centrifugal treating is 100 DEG C in the step B and step C.
5. the preparation method of the modified nanometer cellulose containing various functional groups according to claim 1, it is characterised in that：
The substitution value of carboxymethylcellulose calcium described in the step A is 0.15-0.75.
6. the preparation method of the modified nanometer cellulose containing various functional groups according to claim 1, it is characterised in that：
Stabilization acid solution compound method is in the step A：
Weak diacid and water are hybridly prepared into acid aqueous dispersion under normal temperature, are stirred and the uniform stabilization acid of the formation that gradually heats up
Solution；
Before the carboxymethylcellulose calcium powder adds the stabilization acid solution, the stabilization acid solution temperature control is at 10-40 DEG C.
7. the preparation method of the modified nanometer cellulose containing various functional groups according to claim 1, it is characterised in that：
The mass fraction of stabilization acid solution described in the step A is 30-60%, the carboxymethylcellulose calcium powder and stablizes acid solution
Mass ratio be 1：(20-30).
8. the preparation method of the modified nanometer cellulose containing various functional groups according to claim 1, it is characterised in that：
The quality that water is added in the step B is 20-30 times of the solid mixture, and the alkali of neutralization is that mass fraction is 15-
The 25% NaOH aqueous solution.
9. the preparation method of the modified nanometer cellulose containing various functional groups according to claim 1, it is characterised in that：
Solids of sedimentation concentration in the step D after lower floor's solids of sedimentation dilute with water is mass fraction 2-5%, the pressure of homogenizer treatment
Power is 20000-45000psi, and the homogenization time is 40-80min.
10. preparation method as in one of claimed in any of claims 1 to 9 prepare obtained by being received containing the modified of various functional groups
Rice cellulose, it is characterised in that：Obtain two kinds of modified nanometer cellulose products simultaneously：Modified nanometer cellulose whisker CMNW and change
The cellulose nano-fibrous CMNFs of property, both of which contains carboxylic group and ester group；The modified nanometer cellulose whisker CMNW
A diameter of 5-30nm, length be 20-150nm；A diameter of 30-50nm, the length of the modified cellulose nanofiber CMNFs
It is 0.1-10 μm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107602711A (en) * | 2017-09-14 | 2018-01-19 | 北京理工大学 | A kind of modified cellulose nano whisker, fiber and preparation method thereof |
| CN111395031A (en) * | 2020-03-23 | 2020-07-10 | 华南理工大学 | Method for synchronously preparing cellulose nanowhiskers and cellulose nanofibrils |
| CN111465620A (en) * | 2017-12-07 | 2020-07-28 | 日本制纸株式会社 | Carboxymethylated cellulose nanofibers |
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| CN105646721A (en) * | 2016-01-21 | 2016-06-08 | 中国科学院青岛生物能源与过程研究所 | Preparation method of nanocellulose fibrils |
| CN105713099A (en) * | 2016-01-21 | 2016-06-29 | 中国科学院青岛生物能源与过程研究所 | Method combining formic acid preprocessing and high-pressure homogenization to prepare nano-crystalline cellulose fibrils |
| CN106084070A (en) * | 2016-06-03 | 2016-11-09 | 华南理工大学 | A kind of high-performance nano cellulose and environment-friendly preparation method thereof thereof and application |
| CN106084071A (en) * | 2016-08-11 | 2016-11-09 | 中国科学院青岛生物能源与过程研究所 | A kind of method preparing nano-cellulose sustainably |
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2017
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105646721A (en) * | 2016-01-21 | 2016-06-08 | 中国科学院青岛生物能源与过程研究所 | Preparation method of nanocellulose fibrils |
| CN105713099A (en) * | 2016-01-21 | 2016-06-29 | 中国科学院青岛生物能源与过程研究所 | Method combining formic acid preprocessing and high-pressure homogenization to prepare nano-crystalline cellulose fibrils |
| CN106084070A (en) * | 2016-06-03 | 2016-11-09 | 华南理工大学 | A kind of high-performance nano cellulose and environment-friendly preparation method thereof thereof and application |
| CN106084071A (en) * | 2016-08-11 | 2016-11-09 | 中国科学院青岛生物能源与过程研究所 | A kind of method preparing nano-cellulose sustainably |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107602711A (en) * | 2017-09-14 | 2018-01-19 | 北京理工大学 | A kind of modified cellulose nano whisker, fiber and preparation method thereof |
| CN111465620A (en) * | 2017-12-07 | 2020-07-28 | 日本制纸株式会社 | Carboxymethylated cellulose nanofibers |
| CN111395031A (en) * | 2020-03-23 | 2020-07-10 | 华南理工大学 | Method for synchronously preparing cellulose nanowhiskers and cellulose nanofibrils |
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Application publication date: 20170620 |