CN109942720A - A kind of nano cellulose material and its preparation method and application - Google Patents
A kind of nano cellulose material and its preparation method and application Download PDFInfo
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- CN109942720A CN109942720A CN201910252496.4A CN201910252496A CN109942720A CN 109942720 A CN109942720 A CN 109942720A CN 201910252496 A CN201910252496 A CN 201910252496A CN 109942720 A CN109942720 A CN 109942720A
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Abstract
The present invention provides a kind of nano cellulose material and its preparation method and application, the nano cellulose material is nanofiber cellulose aggregate；It wherein, is in terms of 100% by the summation of the intermolecular hydrogen bonding of the nano cellulose material and intramolecular hydrogen bond, the intensity of the intramolecular hydrogen bond of the nano cellulose material is 50% or more；The tensile strength of the nano cellulose material is 75MPa or more and flexural strength is 80MPa or more.Nano cellulose material provided by the invention is in the case where only including nano-cellulose, with excellent mechanical strength.
Description
Technical field
The invention belongs to technical field of nano material, it is related to a kind of nano cellulose material and its preparation method and application.
Background technique
Cellulose is reserves natural polymer the most abundant in the world, due to renewable, non-toxic, highly-safe
And the features such as environmental-friendly and obtain the extensive research of people.Nano-cellulose is cellulose by processing and defibering becomes and receives
The general name of the other fiber of meter level, according to the draw ratio and structure of fiber, nano-cellulose can be divided into it is cellulose nano-fibrous,
Cellulose nanocrystal and bacteria cellulose etc..Nano-cellulose have high mechanical strength, large specific surface area, high Young's modulus with
And it is easy to the features such as modifying, and it is widely used in macromolecule reinforcing agent, water-oil separating material, high-strength absorbing material and airsetting
The fields such as glue.
Currently, the preparation of nano-cellulose achieves more achievement, it, can be by nano-cellulose according to the difference of preparation method
Preparation be divided into physical method, chemical method；Wherein, physical method mainly includes high pressure homogenization method, polishing and ultrasonication method,
It is biggish cellulose nano-fibrous that high pressure homogenization method is typically prepared draw ratio, polishing prepare simultaneously it is cellulose nano-fibrous and
Cellulose nanocrystal, it is lesser cellulose nano-fibrous that ultrasonication method prepares draw ratio, it is however generally that, it is prepared by physical method
New group will not be introduced in cellulose surface during nano-cellulose, preparation efficiency is higher, but energy consumption is relative to other
It is excessive for method；Chemical method mainly includes TEMPO oxidizing process, sulphuric acid hydrolysis etc., uses TEMPO oxidizing process preparation surface richness
Containing carboxyl and draw ratio it is biggish cellulose nano-fibrous, use sulphuric acid hydrolysis preparation Cellulose nanocrystal etc., chemical legal system
Standby nano-cellulose greatly destroys the hydrogen bond between cellulosic molecule usually along with the modification to cellulose.
The hydrogen bond network of cellulose is by constituting between cellulosic molecule with intramolecular hydrogen bond.For not doing the fibre of modification
It is of substantially equal with the hydrogen bond relative intensity of intramolecular between cellulosic molecule for dimension element, it is received carrying out processing preparation to cellulose
During rice cellulose, along with the significantly destruction to hydrogen bond, especially to the drying process of nano-cellulose, often
Way is exactly to destroy its hydrogen bond, avoids its reunion, and then obtain nano-cellulose, and obtained nano-cellulose, which is often used as, to be changed
Property agent or functional additive use.
Such as CN105107390A discloses a kind of cellulose acetate/nano-cellulose blended ultrafiltration membrane；Alkali body is used first
Be that sodium hydroxide/urea aqueous solution pre-processes raw material filter paper, filter to it is neutral and after drying with sulfuric acid solution into
Row acidolysis processing obtains nano-cellulose after dilution, centrifugation, drying；Then use cellulose acetate and nano-cellulose for
Additive is added in membrane material, selects the mixed solvent of acetone and n,N-Dimethylformamide, carries out deaeration after mixing evenly, scrape
It is immersed after film in the gel pond of certain temperature and obtains blended ultrafiltration membrane.The ultrafiltration membrane porosity that the invention obtains is higher, and mechanical
Better performances.CN105671662A discloses a kind of cellulose nano-fibrous preparation method, includes the following steps: that (1) will be fine
It ties up plain raw material to smash, is dissolved with homogeneous solubilising reagent, produce cellulose solution；(2) cellulose made from step (1) is molten
Liquid injects in the nano aperture in foraminous die plate；(3) with the foraminous die plate for being marked with cellulose solution in solvent wash step (2),
After cellulose solvent in nano aperture in foraminous die plate is removed, the cellulose being fixed in nano aperture can be obtained and receive
Rice fiber；(4) foraminous die plate in step (3) is dissolved with solvent, the cellulose nano-fibrous of array structure can be obtained.This
Class material has the characteristics such as high-specific surface area, high intensity and elasticity.
In the art, the application for developing more nano-celluloses is the emphasis of research.
Summary of the invention
The purpose of the present invention is to provide a kind of nano cellulose materials and its preparation method and application.It is provided by the invention
Nano cellulose material has intensity high, the good advantage of bending resistance can be used as in the case where only including nano-cellulose
Engineering material.
In order to achieve that object of the invention, the invention adopts the following technical scheme:
In a first aspect, the nano cellulose material is nanofiber the present invention provides a kind of nano cellulose material
Cellulose aggregate.
Wherein, with the summation of the intensity of the intermolecular hydrogen bonding of the nano cellulose material and intramolecular hydrogen bond for 100%
Meter, the intensity of the intramolecular hydrogen bond of the nano cellulose material 50% or more, such as 56%, 58%, 60%, 62%,
65%, 68%, 70%, 80% etc..
The tensile strength of the nano cellulose material is 75-120MPa, such as 80MPa, 90MPa, 100MPa, 110MPa
Deng, and flexural strength be 80-180MPa, such as 90MPa, 100MPa, 110MPa, 120MPa, 130MPa, 140MPa,
150MPa, 160MPa, 170MPa etc..
In the present invention, the hydrogen bond network intensity of cellulose can be measured by FTIR spectrum.In wave number
3000-3700cm-1The relatively strong absworption peak occurred is hydrogen bond made of the hydroxyl of cellulose associates, we pass through Gauss curve fitting,
Can calculate between cellulosic molecule with the respective HYDROGEN BOND INTENSITY of intramolecular.
It is of substantially equal with the hydrogen bond relative intensity of intramolecular between cellulosic molecule for cellulose, and in cellulose
During preparing nano-cellulose, for chemical Treatment cellulose, since along with modification, hydrogen bond is had resulted in
The destruction of high degree simultaneously as being mainly exactly to destroy its hydrogen bond to the drying of the dispersion liquid of nano-cellulose avoids it
Reunite, therefore, the nano-cellulose finally obtained is generally floury structure.
The increase of intramolecular hydrogen bond intensity will increase nano-cellulose and form fibrous structure, and fibrous structure is for power
Performance is learned to be advantageous.The present invention provides a kind of nano cellulose materials, can only include the case where nano-cellulose
Under, there is excellent mechanical strength, wherein tensile strength may be up to 120MPa, and flexural strength may be up to 180MPa.
Preferably, the diameter of the nano-cellulose is 10-100nm, such as 10-20nm, 30-50nm, 20-40nm, 50-
100nm, 40-100nm, 10-70nm, 20-80nm, 90-100nm etc., draw ratio 100-1000, such as 100-200,100-
300,400-600,500-700,300-800,900-1000 etc..
Preferably, the intensity of the intramolecular hydrogen bond of the nano cellulose material 60% or more, such as 61%, 62%,
64%, 65%, 68% etc..
Preferably, the tensile strength of the nano cellulose material be 120MPa or more and flexural strength be 180MPa with
On.
Second aspect, the present invention provides a kind of preparation method of nano cellulose material according to first aspect,
The preparation method includes the following steps:
Nano-cellulose dispersion liquid is dry by natural drying and/or vacuum and far-infrared, obtain the nano-cellulose
Material.
Method of the present invention by spontaneously drying and/or vacuum and far-infrared is dry, can be such that the hydrogen bond network of cellulose sends out
It is raw to reset, nano-cellulose intramolecular hydrogen bond will not only reduced, the hydrogen bond that will increase nano-cellulose intramolecular instead is made
With, and then the compactness of nano cellulose material can be increased, making the nano cellulose material finally obtained is only including nanometer
There is excellent performance in the case where cellulose.
Preferably, the preparation method is that it is nano-cellulose is dry by vacuum and far-infrared, obtain the nanofiber
Cellulosic material.
The dry method of the preferred vacuum and far-infrared of the present invention, such method can be to avoid may under natural drying condition
Phenomena such as alice of appearance.
Preferably, the dry operation wavelength of the vacuum and far-infrared is 5.6-15 μm, for example, 6 μm, 8 μm, 10 μm, 12 μm,
14 μm etc..
Preferably, the temperature of the natural drying is 10-80 DEG C, such as 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C
Deng preferably 20-50 DEG C.
Preferably, the preparation method of the dispersion liquid of the nano-cellulose includes: cellulosic material dispersion liquid by mechanical
Processing obtains nano-cellulose dispersion liquid.
Preferably, the cellulosic material includes herbaceous plant, herbal derivative, xylophyta or xylophyta
Derivative in any one or at least two combination.
Preferably, in cellulosic material dispersion liquid, the mass ratio of the cellulosic material and dispersion solvent is 1:(10-
200), such as 1:20,1:40,1:50,1:60,1:80,1:100,1:120,1:150,1:180 etc., further preferred 1:(10-
100)。
Preferably, the dispersion solvent is water.
Preferably, the mechanical treatment includes ultrasonic treatment and/or mechanical lapping.
Preferably, the frequency of the ultrasonic treatment be 1-50kHz, such as 5kHz, 10kHz, 15kHz, 20kHz, 25kHz,
30kHz, 35kHz, 40kHz, 45kHz etc., further preferred 10-30kHz.
Preferably, the mechanical lapping uses rotary-type ball mill, oscillating mode ball mill, planet-shaped ball mill, collision type
Ball mill, mortar grinder instrument or mortar formula beveller are ground.
Preferably, the rate of the grinding be 100-1000rpm, such as 200rpm, 300rpm, 400rpm, 500rpm,
600rpm, 700rpm, 800rpm, 900rpm etc., the milling time be 1-100h, such as 10h, 20h, 30h, 40h, 50h,
60h, 70h, 80h, 90h etc., the rate further preferably ground are 200-500rpm, and the time of grinding is 2-50h.
As optimal technical scheme, the preparation method includes the following steps:
(1) cellulosic material dispersion liquid is obtained into nano-cellulose dispersion liquid by ultrasonic treatment and/or mechanical lapping；
(2) the nano-cellulose dispersion liquid for obtaining step (1) is dry by natural drying and/or vacuum and far-infrared, obtains
To the nano cellulose material.
Nano cellulose material preparation method provided by the invention is simple, low in cost, environmentally protective, it is easy to accomplish industry
Metaplasia produces.
The third aspect, the present invention provides the answering as engineering plastics of the nano cellulose material according to first aspect
With.
Preferably, the engineering material is used as household material, can substitute wood for furniture etc..
Nano cellulose material provided by the invention has intensity high, and the good feature of bending resistance can replace solid wood
Deng in household material.
Compared with the existing technology, the invention has the following advantages:
(1) nano cellulose material provided by the invention is in the case where only including nano-cellulose, with excellent
Mechanical strength, wherein tensile strength may be up to 120MPa, and flexural strength may be up to 180MPa.
(2) provided by the invention preparation method is simple, low in cost, environmentally protective, and is easily achieved scale metaplasia
It produces.
Detailed description of the invention
Fig. 1 is the electron scanning micrograph for the nano cellulose material that embodiment 1 provides.
Fig. 2 is the transmission electron microscope photo for the nano-cellulose dispersion liquid that embodiment 1 provides.
Fig. 3 is the infrared spectrogram of the raw material that embodiment 1 provides and the nano cellulose material finally obtained.
Fig. 4 is the optical photograph for the nano cellulose material that embodiment 1 is prepared.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
A kind of nano cellulose material, the preparation method is as follows:
(1) herbaceous plant cellulosic material is mixed with water according to the mass ratio of 1:25, is then carried out using mechanical stirring
Stirring 2h obtains cellulose aqueous dispersions；Processing 4h (ultrasound is carried out to cellulose aqueous dispersions using ultrasonic cell disruption instrument
Wave cell crushing instrument power 800W, frequency 20kHz are handled using ice bath in ultrasonic procedure), nano-cellulose dispersion can be obtained
Liquid.
(2) obtained nano-cellulose dispersion liquid is subjected at 25 DEG C natural drying 120h, nanofiber can be obtained
Cellulosic material.
Embodiment 2
Difference with embodiment 1 is only that in the present embodiment, step (2) uses the vacuum drying method of far infrared, work
Making wavelength is 10 μm.
Embodiment 3-4
Difference with embodiment 1 is only that, in the present embodiment, the drying temperature of step (2) is 80 DEG C (embodiment 3),
50 DEG C (embodiment 4), as long as drying time is dry by material.
Embodiment 5
A kind of nano cellulose material, the preparation method is as follows:
(1) cellulose is mixed with water according to the mass ratio of 1:20, is then stirred 2h using mechanical stirring and obtains fibre
Tie up plain aqueous dispersions.Processing 6h (ultrasonic cell disruption instrument is carried out to cellulose aqueous dispersions using ultrasonic cell disruption instrument
Power 900W, frequency 20kHz are handled using ice bath in ultrasonic procedure), nano-cellulose dispersion liquid can be obtained.
(2) obtained nano-cellulose dispersion liquid is placed in mold, natural drying 120h is carried out at 25 DEG C, can obtained
To nano cellulose material.
Embodiment 6
A kind of nano cellulose material, the preparation method is as follows:
(1) cellulose is mixed with water according to the mass ratio of 1:50, is then stirred 2h using mechanical stirring and obtains fibre
Tie up plain aqueous dispersions.Processing 4h (ultrasonic cell disruption instrument is carried out to cellulose aqueous dispersions using ultrasonic cell disruption instrument
Power 800W, frequency 20kHz are handled using ice bath in ultrasonic procedure), nano-cellulose dispersion liquid can be obtained.
(2) obtained nano-cellulose dispersion liquid is placed in mold, natural drying 100h is carried out at 35 DEG C, can obtained
To nano cellulose material.
Embodiment 7
A kind of nano cellulose material, the preparation method is as follows:
(1) cellulose is mixed with water according to the mass ratio of 1:25, is then stirred 2h using mechanical stirring and obtains fibre
Tie up plain aqueous dispersions.Ball milling 12h is carried out to cellulose aqueous dispersions using planetary ball mill, nano-cellulose point can be obtained
Dispersion liquid.
(2) obtained nano-cellulose dispersion liquid is placed in mold, natural drying 120h is carried out at 25 DEG C, can obtained
To nano cellulose material.
Embodiment 8
A kind of nano cellulose material, the preparation method is as follows:
(1) cellulose is mixed with water according to the mass ratio of 1:20, is then stirred 2h using mechanical stirring and obtains fibre
Tie up plain aqueous dispersions.Ball milling is carried out for 24 hours to cellulose aqueous dispersions using planetary ball mill, nano-cellulose point can be obtained
Dispersion liquid.
(2) obtained nano-cellulose dispersion liquid is placed in mold, natural drying 120h is carried out at 25 DEG C
Obtain nano cellulose material.
Embodiment 9
A kind of nano cellulose material, the preparation method is as follows:
(1) cellulose is mixed with water according to the mass ratio of 1:10, is then stirred 2h using mechanical stirring and obtains fibre
Tie up plain aqueous dispersions.Processing 8h (ultrasonic cell disruption instrument is carried out to cellulose aqueous dispersions using ultrasonic cell disruption instrument
Power 800W, frequency 20kHz are handled using ice bath in ultrasonic procedure), nano-cellulose dispersion liquid can be obtained.
(2) obtained nano-cellulose dispersion liquid is placed in mold, natural drying 120h is carried out at 25 DEG C
Obtain nano cellulose material.
Embodiment 10
A kind of nano cellulose material, the preparation method is as follows:
(1) cellulose is mixed with water according to the mass ratio of 1:30, is then stirred 2h using mechanical stirring and obtains fibre
Tie up plain aqueous dispersions.Processing 8h (ultrasonic cell disruption instrument is carried out to cellulose aqueous dispersions using ultrasonic cell disruption instrument
Power 900W, frequency 20kHz are handled using ice bath in ultrasonic procedure), nano-cellulose dispersion liquid can be obtained.
(2) obtained nano-cellulose dispersion liquid is placed in mold, natural drying 120h is carried out at 25 DEG C
Obtain nano cellulose material.
Comparative example 1
Difference with embodiment 1 is only that, in this comparative example, step (2) is dried using the technology of freeze-drying.
Comparative example 2
Difference with embodiment 1 is only that, in this comparative example, step (2) uses supercritical drying.
Performance test
The nano cellulose material provided embodiment and comparative example is tested for the property, the method is as follows:
(1) scanning electron microscope and transmission electron microscope observation its microscopic appearance microscopic appearance: are utilized；
Fig. 1 is the electron scanning micrograph for the nano cellulose material that embodiment 1 provides, and Fig. 2 is that embodiment 1 provides
Nano-cellulose dispersion liquid transmission electron microscope photo, as seen from the figure, nano-cellulose dispersion liquid prepared by the present invention
Diameter between 10-100nm, the nano cellulose material finally obtained shows mutually to be overlapped between nano-cellulose, structure
At the appearance of three-dimensional net structure entirety.
(2) it the relative intensity of intermolecular hydrogen bonding and intramolecular hydrogen bond: is measured by FTIR spectrum, passes through height
This fitting, calculate between cellulosic molecule with the respective HYDROGEN BOND INTENSITY of intramolecular.
Fig. 3 is the red of the raw material (herbaceous plant cellulose) provided of embodiment 1 and the nano cellulose material finally obtained
External spectrum figure, wherein a is raw material, and b is the nano cellulose material finally obtained.
(3) it tensile strength: is tested according to national standard GB/T 1040-92；
Fig. 4 is the optical photograph for the nano cellulose material that embodiment 1 is prepared.
(4) it flexural strength: is tested according to national standard GB/T 9341-2000.
Test result is shown in Table 1:
Table 1
By embodiment and performance test it is found that nano cellulose material provided by the invention is only including nano-cellulose
In the case of, with excellent mechanical strength, wherein tensile strength is in 75MPa or more and flexural strength is 80MPa or more,
And tensile strength may be up to 120MPa, and flexural strength may be up to 180MPa.
By the comparison of embodiment 1 and embodiment 2 it is found that the present invention prepares nanofiber material using vacuum and far-infrared drying
Material has better mechanical strength, by the comparison of embodiment 1 and embodiment 3-4 it is found that during the preparation process, natural drying
Temperature is 10-80 DEG C, preferably 20-50 DEG C, most preferably natural drying at room temperature.
By the comparison of embodiment 1 and comparative example 1-2 it is found that the nanofiber material that preparation method of the invention is prepared
Expect tensile strength with higher and flexural strength, can be applied directly as engineering plastics etc..
The Applicant declares that the present invention is explained by the above embodiments nano cellulose material and its preparation side of the invention
Method and application, but the invention is not limited to above-mentioned processing steps, that is, do not mean that the present invention must rely on above-mentioned processing step
It could implement.It should be clear to those skilled in the art, any improvement in the present invention, to raw material selected by the present invention
Equivalence replacement and addition, the selection of concrete mode of auxiliary element etc., all fall within protection scope of the present invention and the open scope
Within.
Claims (10)
1. a kind of nano cellulose material, which is characterized in that the nano cellulose material is nanofiber cellulose aggregate；
Wherein, described in terms of by the summation of the intermolecular hydrogen bonding of the nano cellulose material and intramolecular hydrogen bond intensity for 100%
The intensity of the intramolecular hydrogen bond of nano cellulose material is 50% or more；
Also, the tensile strength of the nano cellulose material is 75MPa or more and flexural strength is 80MPa or more.
2. nano cellulose material according to claim 1, which is characterized in that the diameter of the nano-cellulose is 10-
100nm, draw ratio 100-1000.
3. nano cellulose material according to claim 1 or 2, which is characterized in that point of the nano cellulose material
The intensity of hydrogen bond is 60% or more in son；
Preferably, the tensile strength of the nano cellulose material is 120MPa or more and flexural strength is 180MPa or more.
4. the preparation method of nano cellulose material described in any one of -3 according to claim 1, which is characterized in that described
Preparation method includes the following steps:
Nano-cellulose dispersion liquid is dry by natural drying and/or vacuum and far-infrared, obtain the nano cellulose material.
5. the preparation method according to claim 4, which is characterized in that the preparation method is that by nano-cellulose dispersion liquid
It is dry by vacuum and far-infrared, obtain the nano cellulose material.
6. preparation method according to claim 4 or 5, which is characterized in that the dry operation wavelength of the vacuum and far-infrared
It is 5.6-15 μm；
Preferably, the temperature of the natural drying is 10-80 DEG C, preferably 20-50 DEG C.
7. the preparation method according to any one of claim 4-6, which is characterized in that the dispersion of the nano-cellulose
The preparation method of liquid, which includes: cellulosic material dispersion liquid, obtains nano-cellulose dispersion liquid by mechanical treatment；
Preferably, the cellulosic material includes spreading out for herbaceous plant, herbal derivative, xylophyta or xylophyta
In biology any one or at least two combination；
Preferably, in cellulosic material dispersion liquid, the mass ratio of the cellulosic material and dispersion solvent is 1:(10-200),
Further preferred 1:(10-100)；
Preferably, the dispersion solvent is water.
8. preparation method according to claim 7, which is characterized in that the mechanical treatment includes ultrasonic treatment and/or machine
Tool grinding；
Preferably, the frequency of the ultrasonic treatment is 1-50kHz, further preferred 10-30kHz；
Preferably, the mechanical lapping uses rotary-type ball mill, oscillating mode ball mill, planet-shaped ball mill, collision type ball milling
Machine, mortar grinder instrument or mortar formula beveller are ground；
Preferably, the rate of the grinding is 100-1000rpm, and the milling time is 1-100h, is further preferably ground
Rate is 200-500rpm, and the time of grinding is 2-50h.
9. the preparation method according to any one of claim 4-8, which is characterized in that the preparation method includes as follows
Step:
(1) cellulosic material dispersion liquid is obtained into nano-cellulose dispersion liquid by ultrasonic treatment and/or mechanical lapping；
(2) the nano-cellulose dispersion liquid for obtaining step (1) is dry by natural drying and/or vacuum and far-infrared, obtains institute
State nano cellulose material.
10. application of the nano cellulose material described in any one of -3 as engineering plastics according to claim 1；
Preferably, the engineering plastics are used as household material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110495612A (en) * | 2019-09-17 | 2019-11-26 | 广东海洋大学 | A kind of production method of seawater rice chaff cellulose powder |
| CN113818272A (en) * | 2021-09-26 | 2021-12-21 | 上海爱普食品工业有限公司 | Preparation method of biomass nanocellulose |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105218841A (en) * | 2014-07-02 | 2016-01-06 | 中国科学院金属研究所 | A kind of by the simple method for preparing of graphite to composite graphite alkene paper |
| CN107915853A (en) * | 2017-10-27 | 2018-04-17 | 华南理工大学 | A kind of nano-cellulose/graphene composite and flexible film and preparation method and application |
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2019
- 2019-03-29 CN CN201910252496.4A patent/CN109942720A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105218841A (en) * | 2014-07-02 | 2016-01-06 | 中国科学院金属研究所 | A kind of by the simple method for preparing of graphite to composite graphite alkene paper |
| CN107915853A (en) * | 2017-10-27 | 2018-04-17 | 华南理工大学 | A kind of nano-cellulose/graphene composite and flexible film and preparation method and application |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110495612A (en) * | 2019-09-17 | 2019-11-26 | 广东海洋大学 | A kind of production method of seawater rice chaff cellulose powder |
| CN113818272A (en) * | 2021-09-26 | 2021-12-21 | 上海爱普食品工业有限公司 | Preparation method of biomass nanocellulose |
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Application publication date: 20190628 |