CN107602709A - A kind of carboxymethyl nano cellulose material cleans preparation method - Google Patents
A kind of carboxymethyl nano cellulose material cleans preparation method Download PDFInfo
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Abstract
The present invention relates to carboxymethyl nano cellulose material to clean preparation method.By cellulosic material is preprocessed, drift oxygen slurrying, continous way oxygen bleaching, bleaching, the crushing of slurry and activation, etherificate, neutralization and purifying, nanosizing produce carboxymethyl nano cellulose material.The present invention prepares cellulose paste using a variety of stalks and plant waste as raw material cleaning pulping, then the preparation of CMC rice fiber is carried out again, expand the scope of nano-cellulose preparing raw material, technique is simply coherent, environmentally friendly low cost, a new approach for preparing nano-cellulose is opened, wide prospect is provided for the application of nano-cellulose.It is that functional nano cellulose fibre is directly prepared in raw material that can utilize cellulose by method proposed by the invention, obtained modified nanometer cellulose contains carboxyl and has good crystallinity, and obtained nano-cellulose crystal grain is small, this provides good basis for the application in product later stage.
Description
Technical field
The invention belongs to field of fine chemical, and in particular to a kind of carboxymethyl nano cellulose material cleans preparation side
Method.
Background technology
Nano cellulose material is by acidolysis, enzymolysis, alkalization catalysis or machine with the cellulose of the species such as cotton, wood, stalk
The size that the technologies such as tool shearing obtain is in nano level cellulose products.In the prior art, it is different according to preparation method, Nanowire
Dimension cellulosic 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 manufacture method reported both at home and abroad mainly includes：Chemical method, physical method, biological method and synthesis side
A variety of methods such as method.Wherein, biological enzyme digestion method is time-consuming, costly and difficulty is big, so external cellulose nano material at present
Preparation method is concentrated mainly on two kinds of Physical and chemical method.And chemical method is handled by strong acid, such as salt
Acid, sulfuric acid or phosphoric acid etc., these acid recovery difficults after cellulose acidolysis are big, cost is high, can only enter exercise in laboratory at present
With；Physical, such as directly using ultrasound, homogenize, mechanical crushing ball milling make cellulose reach nanoscale difficulty greatly,
Cause the nanoscale of product to be difficult to control, while the problems such as strength reason causes high energy consumption also be present, so being all introduced into application
Stage.
If in addition, first by cellulose nanosizing, then carrying out carboxy methylation or esterification, because nano-cellulose is in alkali, organic
It is difficult to control, collects the deficiencies of difficult in the presence of easily reuniting, disperseing difficult, derivatization process in solvent, especially nano-cellulose ether-ether
It is bigger to mix derived material preparation difficulty, it is achieved that the etherificate of nano-cellulose, first has to alkalize, and alkalizing greatly to destroy
The nanofeature of nano-cellulose, if after chemical reaction reaches etherificate again, then continue the nano shape of holding cellulose more
Difficulty, so being difficult to directly prepare the nano-cellulose with functional groups.
At present, the plant cellulose rule of origin such as wheat, corn, cotton stalk and bamboo, reed, straw slag enriches, and again
It is raw very competent, but it is still main utilization ways to take papermaking to be weaved with low side at present, or even still using the pollution ring such as burning
The means in border handle these products, bring the pollution of severe environments and the waste of cellulosic material, so, the reasonable profit of product
With by be this fibrid raw material developing direction.
The content of the invention
For in the prior art the defects of, the present invention provide it is a kind of it is quick, cost is low, reaction controllability is strong, Nanowire
Plain whisker yield height is tieed up, requires pretreatment of raw material degree simpler, the nanometer containing a small amount of ester group and carboxyl can be prepared simultaneously
The Cellulose nanocrystal of whisker and nanofiber must prepare modified nanometer cellulose and its preparation with the rapid cleaning of nanofiber
Method.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of carboxymethyl nano cellulose material provided by the invention cleans preparation method, including step：
A. pretreatment of raw material：Cellulosic material is added in prepreg solution and presoaks and crushes, is floated with without chlorine hydrogen peroxide system
The white chromophore removed in raw material；
B. oxygen pulping technique is floated：It is transported in blender and mixes after slurry after preimpregnation is concentrated, while adds bleaching medicine
Liquid I bleaches material；It is preferred that material is mixed using highly concentrated blender；
C. continous way oxygen bleaching technology：Slurry and bleaching decoction II are transported in continous way oxygen bleaching machine again by blender together
Bleaching；
D. the crushing and activation of slurry：Slurry is crushed with pulverizer, then fibre is made with organic solvent and alkali metal compound
Dimension element swelling；
E. it is etherified：The mixture of etherifying agent and organic solvent is added, is etherified at a temperature of 50-80 DEG C；
F. neutralize and purify：With the alkali in sour neutralization system；Product is centrifuged, after being washed with water, then centrifuged；It is preferred herein
Use deionized water；
G. nanosizing：Progress homogenization in high pressure homogenizer is imported after centrifugal material is diluted with water and obtains carboxymethyl fibre
Tie up plain nanofiber, i.e. CMNFs.
Further, above-mentioned carboxymethyl nano cellulose material is cleaned in preparation method, in the step A prepreg solution by
Following component forms by weight percentage：Alkali 2%, magnesium sulfate 0.4-0.5%, layer silicon 2-3%, sodium citrate 0.1%, methylene
Phosphonic acids 0.3-0.5%, bleeding agent 0.1%, surplus are water.Alkali can be the alkaline materials such as sodium hydroxide, potassium hydroxide, and layer silicon is
Laminated crystal of sodium disilicate, bleeding agent are AEO.
Further, above-mentioned carboxymethyl nano cellulose material is cleaned in preparation method, and cellulose is former in the step A
Expect for the one or more mixing in wheat stalk, maize straw, rice straw, cotton stalk, bamboo pulp, reed or bagasse, fiber
Plain raw material grinding particle size is no more than 60 mesh.
Further, above-mentioned carboxymethyl nano cellulose material is cleaned in preparation method, the temperature presoaked in the step A
Spend for 40-50 DEG C, the preimpregnation time is 40-60min.
Further, above-mentioned carboxymethyl nano cellulose material is cleaned in preparation method, the bleaching medicine in the step B
Liquid I is made up of following component：Hydrogen peroxide, alkali, Na2SiO3、MgSO4And NaBH4Composition.Hydrogen peroxide is H2O2, alkali can be hydrogen-oxygen
Change the inorganic bases such as sodium, potassium hydroxide.
Further, above-mentioned carboxymethyl nano cellulose material is cleaned in preparation method, the bleaching medicine in the step B
Liquid I is made up of following mass percent component：2-5% hydrogen peroxide, 3-5% alkali, 2% Na2SiO3、MgSO4And NaBH4
The bleaching agent of composition, surplus are water.
Further, above-mentioned carboxymethyl nano cellulose material is cleaned in preparation method, and decoction is bleached in the step C
II is made up of following parts by weight of component：Concentration is 27.5% 300 parts of hydrogen peroxide, 1 part of dicyandiamide catalyst, 60 parts of oxygen, phenanthrene
1 part of hello quinoline.
Further, above-mentioned carboxymethyl nano cellulose material is cleaned in preparation method, the etherifying agent in the step E
The chloroacetic organic solvent for being 40-60% for mass fraction, etherification time are 1-4 hours；Cellulose paste obtained by step D with
Chloroacetic mass ratio is 1：(0.20-0.50).
Further, above-mentioned carboxymethyl nano cellulose material is cleaned in preparation method, the cellulose in the step D
Mass ratio with alkali metal compound is 1：(0.18-0.45)；Cellulose swelling time is 0.5-3.0 hours, and swelling temperature is
5-35℃。
Further, above-mentioned carboxymethyl nano cellulose material is cleaned in preparation method, having in the step D and E
Solvent is one in isopropanol, ethanol, isopropanol/ethanol, acetone, toluene, ethanol/toluene, iso-propanol/toluene, isobutanol
Kind.
Further, above-mentioned carboxymethyl nano cellulose material is cleaned in preparation method, organic molten in the step F
The aqueous solution of agent is the ethanol/water solution that volume fraction is 70-90%.
Further, above-mentioned carboxymethyl nano cellulose material is cleaned in preparation method, at the homogeneous in the step G
The technological parameter of reason is：It is 2-5% that material to mass concentration, which is diluted with water, and the pressure of homogenizer processing is 20000-
45000psi, homogenization time are 40-80min.
The present invention has the advantages that：
1. pulping process does not pollute and obtained slurry quality is excellent, the pulping technique of three kinds of clean and effectives is employed：
The pre-preg technology of wooden material, the highly concentrated drift oxygen pulping technique of high energy mixing and continous way oxygen bleaching technology.Make using without chlorine system
For pre- preserved material, compared with the high pressure soda boiling technology of routine, reduce black liquid discharging, greatly reduce environmental pollution, high energy mixing
Mass transfer rate is accelerated, is advantageous to accelerate the speed of bleaching action process, improves the effect of bleaching, utilize hydrogen peroxide enriched with oxygen
Bleaching, substantially reduces hydrogen peroxide bleaching cost, while reaches the poly- purpose of drop, reduces the pressure to environment while ensures product matter
Amount.
2. pulping process is extremely strong for the applicability of raw material, the refined fiber products such as purified cotton, timber both can be used, also may be used
Using stalks such as wheat, corn, straw, cottons, the bamboo pulp of reed, bagasse and fast-growing etc. is used as pulping raw material, obtained product
The preparation requirement in later stage is satisfied by, the agricultural by product to be largely difficult by provides new utilization orientation.
3. adding etherifying agent by slurry process prepares carboxymethyl cellulose, drying is not then needed, after being directly diluted with water
Progress homogenization obtains nanoscale, fine with the controllable CMC rice of group content in importing high pressure homogenizer
Vc MNFs, no dry materials with moistening among the processing procedure that rises again, and process is simply coherent, easily operated, energy consumption is low, just
In industrialized production；
It is etherifying agent using monoxone, by controlling charging sequence, reaction temperature 4. the present invention uses cellulose as raw material
With the reaction time, it is determined that the optimum proportioning of other several compositions, process conditions, under safer reliable process conditions,
Carboxymethyl cellulose is prepared for, progress homogenization in high pressure homogenizer is imported after being then diluted with water and obtains carboxymethyl cellulose
Nanofiber CMNFs.The CMC rice fiber of preparation, its degree of substitution by carboxymethyl (i.e. DS) is 0.1-0.4, a diameter of
30-50nm, length are 0.1-10 μm.The product CMC rice fiber CMNFs for preparing gained has well hydrophilic
Property and material compatibility, have very wide application prospect.
To sum up, the present invention prepares cellulose paste using a variety of stalks and plant waste as raw material cleaning pulping, then enters again
Row CMC rice fiber CMNFs preparation, expands the scope of nano-cellulose preparing raw material, and technique simply connects
Pass through, environmental protection low cost, open a new approach for preparing nano-cellulose, for nano-cellulose application provide it is wide
Prospect.It is that functional nano cellulose is directly prepared in raw material that can utilize cellulose by method proposed by the invention
Fiber, obtained modified nanometer cellulose contains carboxyl and has good crystallinity, and obtained nano-cellulose crystal grain is small,
This provides good basis for the application in product later stage.
Brief description of the drawings
In order to illustrate more clearly of the technical scheme in the specific embodiment of the invention, embodiment will be retouched below
The required accompanying drawing used is briefly described in stating.
Fig. 1 is a kind of transmission electron microscope photo of CMC rice fiber prepared by embodiment 1 in the present invention；
Fig. 2 is the X ray diffracting spectrum of CMC rice fiber prepared by embodiment 2 in the present invention；
Fig. 3 is the infrared spectrogram of CMC rice fiber prepared by embodiment 2 in the present invention.
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
It is only the preferred embodiments of the present invention to apply example, is not intended to limit the invention, for those skilled in the art, this
Invention can have various modifications and variations.Within the spirit and principles of the invention, any modification for being made, equivalent substitution,
Improve etc., it should be included in the scope of the protection.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
It is mass percent, the component score is mass fraction if the percentage in example 1 to embodiment 5 is without specified otherwise.
Embodiment 1
By the wheat stalk powder 40g for being crushed to 60 mesh be added to containing sodium hydroxide 2%, magnesium sulfate 0.4%, layer silicon 2%,
Sodium citrate 0.1%, methylene phosphonic acid 0.3%, bleeding agent 0.1% the aqueous solution in, 60min, mistake are presoaked under the conditions of 40 DEG C
It is stand-by after filter.Wheat stalk powder after preimpregnation is transported in blender, added by hydrogen peroxide concentration 2%, sodium hydroxide is dense
Spend 3%, Na2SiO3、MgSO4And NaBH4The bleaching liquid I 2000g bleaching 1h of concentration 2%, are sent into continuous after bleaching liquid is filtered
Formula oxygen bleaching machine, add the drift of 300 parts of hydrogen peroxide, 1 part of dicyandiamide catalyst, 60 parts of oxygen, 1 part of ferrosin that concentration is 27.5%
White liquor II bleaches 1h again, then filters, dries.
Under agitation, 12g sodium hydroxides are added in the isopropanol/water solution that 600g mass concentrations are 85%,
Then the wheat stalk powder 40g for being crushed to 60 mesh is added, is reacted at 20 DEG C l.5 hour, 13.5g is added and contains 50% chloroethene
Monoxone/ethanol solution of acid, it is warming up to 50 DEG C and reacts 1 hour, then is warming up to 75 degree and reacts 0.5 hour.After reaction terminates, use
Glacial acetic acid/ethanol solution neutralizes, and is then washed, and centrifuges, material then is diluted with water into 2.5% concentration, equal with high pressure
Matter machine homogeneous 40min under 30000psi pressure conditions, it can obtain CMC rice fiber CMNFs.
Obtained CMC rice fiber CMNFs is dried in vacuo, is tested and marked according to GB1904-2005
Standard, it is 0.25 with grey alkaline process test degree of substitution by carboxymethyl；With transmission electron microscope observing CMC rice fiber CMNFs, its
A diameter of 40nm, length 800nm.
Embodiment 2
The cotton stalk powder 40g for being crushed to 60 mesh is added to containing sodium hydroxide 2%, magnesium sulfate 0.4%, layer silicon 3%, lemon
Lemon acid sodium 0.1%, methylene phosphonic acid 0.4%, bleeding agent 0.1% the aqueous solution in, 50min is presoaked under the conditions of 50 DEG C, filter
It is stand-by afterwards.Cotton stalk powder after preimpregnation is transported in blender, added by hydrogen peroxide concentration 3%, naoh concentration
4%, Na2SiO3、MgSO4And NaBH4The bleaching liquid I 2000g bleaching 1h of concentration 2%, continous way is sent into after bleaching liquid is filtered
Oxygen bleaching machine, add the bleaching of 300 parts of hydrogen peroxide, 1 part of dicyandiamide catalyst, 60 parts of oxygen, 1 part of ferrosin that concentration is 27.5%
Liquid II bleaches 1h again, then filters, dries.
Under agitation, 15g sodium hydroxides are added in the isopropanol/water solution that 600g mass concentrations are 85%,
Then the cotton stalk powder 40g for being crushed to 60 mesh is added, is reacted 2 hours at 20 DEG C, it is chloroacetic that addition 16.6g contains 50%
Monoxone/ethanol solution, it is warming up to 50 DEG C and reacts 1.5 hours, then is warming up to 75 degree and reacts 0.5 hour.After reaction terminates, ice is used
Acetic acid/ethanol solution neutralizes, and is then washed, and centrifuges, material then is diluted with water into 2.0% concentration, use is high-pressure homogeneous
Machine homogeneous 50min under 30000psi pressure conditions, it can obtain CMC rice fiber CMNFs.
Obtained CMC rice fiber CMNFs is dried in vacuo, is tested and marked according to GB1904-2005
Standard, it is 0.29 with grey alkaline process test degree of substitution by carboxymethyl；With transmission electron microscope observing CMC rice fiber CMNFs, its
A diameter of 45nm, length 900nm.
Embodiment 3
The reed pulp 40g for being crushed to 50 mesh is added to containing sodium hydroxide 2%, magnesium sulfate 0.4%, layer silicon 2%, citric acid
Sodium 0.1%, methylene phosphonic acid 0.5%, bleeding agent 0.1% the aqueous solution in, 40min is presoaked under the conditions of 50 DEG C, is treated after filtering
With.Cotton stalk powder after preimpregnation is transported in blender, added by hydrogen peroxide concentration 2%, naoh concentration 4%,
Na2SiO3、MgSO4And NaBH4The bleaching liquid I 2000g bleaching 1h of concentration 2%, are sent into continous way oxygen bleaching after bleaching liquid is filtered
Machine, add 300 parts of hydrogen peroxide, 1 part of dicyandiamide catalyst, 60 parts of oxygen, the bleaching liquid II of 1 part of ferrosin that concentration is 27.5%
1h is bleached again, is then filtered, is dried.
Under agitation, 12g sodium hydroxides are added in the isopropanol/water solution that 600g mass concentrations are 85%,
Then the reed pulp 40g for being crushed to 50 mesh is added, is reacted 2 hours at 20 DEG C, 13.0g is added and contains 50% chloroacetic chloroethene
Acid/ethanol solution, it is warming up to 50 DEG C and reacts 1.0 hours, then is warming up to 75 degree and reacts 0.5 hour.After reaction terminates, with ice vinegar
Acid/ethanol solution neutralizes, and is then washed, and centrifuges, material then is diluted with water into 2.5% concentration, uses high pressure homogenizer
The homogeneous 50min under 30000psi pressure conditions, it can obtain CMC rice fiber CMNFs.
Obtained CMC rice fiber CMNFs is dried in vacuo, is tested and marked according to GB1904-2005
Standard, it is 0.27 with grey alkaline process test degree of substitution by carboxymethyl；With transmission electron microscope observing CMC rice fiber CMNFs, its
A diameter of 38nm, length 750nm.
Embodiment 4
The reed for being crushed to 50 mesh and bagasse mixed slurry 40g are added to containing sodium hydroxide 2%, magnesium sulfate 0.5%, layer
Silicon 3%, sodium citrate 0.1%, methylene phosphonic acid 0.5%, bleeding agent 0.1% the aqueous solution in, presoaked under the conditions of 50 DEG C
40min, it is stand-by after filtering.Reed after preimpregnation and bagasse mixed slurry are transported in blender, added by hydrogen peroxide concentration
3%, naoh concentration 5%, Na2SiO3、MgSO4And NaBH4The bleaching liquid I 2000g bleaching 1h of concentration 2%, by bleaching liquid
Continous way oxygen bleaching machine is sent into after filtering, adds 300 parts of hydrogen peroxide, 1 part of dicyandiamide catalyst, oxygen 60 that concentration is 27.5%
Part, the bleaching liquid II of 1 part of ferrosin bleach 1h again, then filter, dry.
Under agitation, 11g sodium hydroxides are added in the isopropanol/water solution that 600g mass concentrations are 85%,
Then reed and the bagasse mixed slurry 40g for being crushed to 50 mesh are added, is reacted 2 hours at 20 DEG C, 12.0g is added and contains 50%
Chloroacetic monoxone/ethanol solution, it is warming up to 50 DEG C and reacts 1.0 hours, then is warming up to 75 degree and reacts 0.5 hour.Reaction knot
Shu Hou, neutralized with glacial acetic acid/ethanol solution, then washed, centrifuged, material is then diluted with water to 2.5% concentration, used
High pressure homogenizer homogeneous 50min under 25000psi pressure conditions, it can obtain CMC rice fiber CMNFs.
Obtained CMC rice fiber CMNFs is dried in vacuo, is tested and marked according to GB1904-2005
Standard, it is 0.24 with grey alkaline process test degree of substitution by carboxymethyl；With transmission electron microscope observing CMC rice fiber CMNFs, its
A diameter of 32nm, length 680nm.
Embodiment 5
The wheat stalk for being crushed to 40 mesh and maize straw mixed slurry 40g are added to containing sodium hydroxide 2%, magnesium sulfate
0.4%th, in the aqueous solution of layer silicon 2%, sodium citrate 0.1%, methylene phosphonic acid 0.5%, bleeding agent 0.1%, in 40 DEG C of conditions
Lower preimpregnation 40min, it is stand-by after filtering.Wheat stalk after preimpregnation and maize straw mixed slurry are transported in blender, added
Enter by hydrogen peroxide concentration 2%, naoh concentration 4%, Na2SiO3、MgSO4And NaBH4The bleaching liquid I 2000g drifts of concentration 2%
White 1h, continous way oxygen bleaching machine is sent into after bleaching liquid is filtered, adds 300 parts of hydrogen peroxide, dicyandiamide catalysis that concentration is 27.5%
1 part of agent, 60 parts of oxygen, the bleaching liquid II of 1 part of ferrosin bleach 1h again, then filter, dry.
Under agitation, 15g sodium hydroxides are added in the isopropanol/water solution that 600g mass concentrations are 85%,
Then the wheat stalk and maize straw mixed slurry 40g for being crushed to 40 mesh are added, is reacted 2 hours at 20 DEG C, adds 16.7g
Containing 50% chloroacetic monoxone/ethanol solution, it is warming up to 50 DEG C and reacts 1.5 hours, then to be warming up to 75 degree of reactions 0.5 small
When.After reaction terminates, neutralized with glacial acetic acid/ethanol solution, then washed, centrifuged, be then diluted with water to material
2.0% concentration, with high pressure homogenizer under 30000psi pressure conditions homogeneous 60min, can obtain CMC rice fibre
Vc MNFs.
Obtained CMC rice fiber CMNFs is dried in vacuo, is tested and marked according to GB1904-2005
Standard, it is 0.26 with grey alkaline process test degree of substitution by carboxymethyl；With transmission electron microscope observing CMC rice fiber CMNFs, its
A diameter of 49nm, length 1100nm.
Fig. 1 is CMC rice fiber CMNFs prepared by embodiment 1 transmission electron microscope picture (TEM), therefrom can be with
Nano-cellulose diameter can be clearly seen about between 10-50 nanometers, length is in nanometer to micron order, it was demonstrated that the inventive method
What is obtained is nano-cellulose fiber.
Fig. 2 is CMC rice fiber CMNFs prepared by embodiment 2 X ray diffracting spectrum (XRD), according to
Data in figure, the crystallinity that obtained CMC rice fiber CMNFs can be obtained by calculating is 45.3%, it was demonstrated that
The material has good crystallinity.
Fig. 3 is CMC rice fiber CMNFs prepared by embodiment 2 infrared spectrogram (IR), can from figure
To find out 1600cm in product-1There is COO- absorption vibration peak in place, it was demonstrated that contains carboxylic group in CMMFs.
Above-mentioned sign can prove, by method proposed by the invention can sharp straw be that raw material prepares straw base
CMC rice fiber CMNFs, obtained CMC rice fiber CMNFs contain carboxyl and with good
Crystallinity, this provides good basis for the application in product later stage.
Claims (10)
1. a kind of carboxymethyl nano cellulose material cleans preparation method, it is characterised in that including step：
A. pretreatment of raw material：Cellulosic material is added in prepreg solution and presoaks and crushes；
B. oxygen pulping technique is floated：It is transported in blender and mixes after slurry after preimpregnation is concentrated, while adds the I drifts of bleaching decoction
White material；
C. continous way oxygen bleaching technology：Slurry and bleaching decoction II are transported in continous way oxygen bleaching machine and floated again by blender together
In vain；
D. the crushing and activation of slurry：Slurry is crushed with pulverizer, then cellulose is made with organic solvent and alkali metal compound
Swelling；
E. it is etherified：The mixture of etherifying agent and organic solvent is added, is etherified at a temperature of 50-80 DEG C；
F. neutralize and purify：With the alkali in sour neutralization system；Product is centrifuged, after being washed with water, then centrifuged；
G. nanosizing：Progress homogenization in high pressure homogenizer is imported after centrifugal material is diluted with water and obtains carboxymethyl cellulose
Nanofiber.
2. carboxymethyl nano cellulose material according to claim 1 cleans preparation method, it is characterised in that
Prepreg solution is made up of by weight percentage following component in the step A：
Alkali 2%, magnesium sulfate 0.4-0.5%, layer silicon 2-3%, sodium citrate 0.1%, methylene phosphonic acid 0.3-0.5%, bleeding agent
0.1%th, surplus is water.
3. carboxymethyl nano cellulose material according to claim 1 cleans preparation method, it is characterised in that
Cellulosic material is wheat stalk, maize straw, rice straw, cotton stalk, bamboo pulp, reed or bagasse in the step A
In one or more mixing, cellulosic material grinding particle size is no more than 50 mesh.
4. carboxymethyl nano cellulose material according to claim 1 cleans preparation method, it is characterised in that
The temperature presoaked in the step A is 40-50 DEG C, and the preimpregnation time is 40-60min.
5. carboxymethyl nano cellulose material according to claim 1 cleans preparation method, it is characterised in that
Bleaching decoction I in the step B is made up of following component：
Hydrogen peroxide, alkali, Na2SiO3、MgSO4、NaBH4Formed with water.
6. carboxymethyl nano cellulose material according to claim 5 cleans preparation method, it is characterised in that
Bleaching decoction I in the step B is made up of following mass percent component：2-5% hydrogen peroxide, 3-5% alkali,
2% Na2SiO3、MgSO4And NaBH4The bleaching agent of composition, surplus are water.
7. carboxymethyl nano cellulose material according to claim 1 cleans preparation method, it is characterised in that
Decoction II is bleached in the step C to be made up of following parts by weight of component：
Concentration is 27.5% 300 parts of hydrogen peroxide, 1 part of dicyandiamide catalyst, 60 parts of oxygen, 1 part of ferrosin.
8. carboxymethyl nano cellulose material according to claim 1 cleans preparation method, it is characterised in that
Etherifying agent in the step E is the chloroacetic organic solvent that mass fraction is 40-60%, and etherification time is that 1-4 is small
When；Cellulose paste obtained by step D is 1 with chloroacetic mass ratio：(0.20-0.50)；
The mass ratio of cellulose and alkali metal compound in the step D is 1：(0.18-0.45)；Cellulose swelling time is
0.5-3.0 hours, swelling temperature are 5-35 DEG C.
9. carboxymethyl nano cellulose material according to claim 1 cleans preparation method, it is characterised in that
Organic solvent in the step D and E is isopropanol, ethanol, isopropanol/ethanol, acetone, toluene, ethanol/toluene, different
One kind in propyl alcohol/toluene, isobutanol；The aqueous solution of organic solvent in the step F is the second that volume fraction is 70-90%
Alcohol/the aqueous solution.
10. carboxymethyl nano cellulose material according to claim 1 cleans preparation method, it is characterised in that
The technological parameter of homogenization in the step G is：It is 2-5% that material to mass concentration, which is diluted with water, at homogenizer
The pressure of reason is 20000-45000psi, and the homogenization time is 40-80min.
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| CN110357973A (en) * | 2018-04-10 | 2019-10-22 | 上海长光企业发展有限公司 | A kind of sodium carboxymethylcellulose and its preparation method and application |
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| CN114790249A (en) * | 2022-04-15 | 2022-07-26 | 北京理工大学 | Straw-based cellulose derivative and preparation method and application thereof |
| CN115521382A (en) * | 2022-10-19 | 2022-12-27 | 向能新型材料科技(河北)有限公司 | Preparation method of sodium carboxymethylcellulose by high-purity bath slurry method |
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| CN108330558A (en) * | 2018-03-08 | 2018-07-27 | 唐卫兵 | A kind of preparation method of the hydrophobic fibre element chitosan nano fiber spinning solution of antibacterial functions |
| CN110357973A (en) * | 2018-04-10 | 2019-10-22 | 上海长光企业发展有限公司 | A kind of sodium carboxymethylcellulose and its preparation method and application |
| CN111019005A (en) * | 2019-12-13 | 2020-04-17 | 华南理工大学 | Method for preparing carboxylated nanocellulose by using citric acid hydrolysis and combining catalyst and ultrasonic-assisted two-step process |
| CN111019003A (en) * | 2019-12-18 | 2020-04-17 | 华南理工大学 | Waste fabric nanocellulose and preparation method thereof |
| CN114790249A (en) * | 2022-04-15 | 2022-07-26 | 北京理工大学 | Straw-based cellulose derivative and preparation method and application thereof |
| CN115521382A (en) * | 2022-10-19 | 2022-12-27 | 向能新型材料科技(河北)有限公司 | Preparation method of sodium carboxymethylcellulose by high-purity bath slurry method |
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