CN105949330A - Method for hydrophobic modification of nanocrystalline cellulose - Google Patents
Method for hydrophobic modification of nanocrystalline cellulose Download PDFInfo
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Abstract
The invention discloses a method for hydrophobic modification of nanocrystalline cellulose and belongs to the technical field of functional nano materials. According to the method, nanocrystalline cellulose is dispersed in aqueous solution, dispersion liquid is treated with ferric chloride and tannin, centrifugal separation is conducted to obtain iron-tannin membrane modified nanocrystalline cellulose, then the iron-tannin membrane modified nanocrystalline cellulose is dispersed in an ethyl alcohol and water mixed solution containing low-surface-energy substance, centrifugal layering is conducted on mixed liquid obtained after reaction, and then freeze drying is conducted to obtain the nanocrystalline cellulose with a hydrophobization modified surface. The prepared hydrophobization modified nanocrystalline cellulose can be uniformly dispersed in various polar solvents, product diversity is high, preparing process is simple, environment pollution is avoided, and cost is low. The hydrophobization modified nanocrystalline cellulose is suitable for large-scale production and has broad application prospects in fields including nano-composite reinforcing materials and biomedical materials.
Description
Technical field
A kind of method that the present invention relates to nano micro crystal cellulose hydrophobic modification, belongs to function nano material technology
Field.
Background technology
Nano micro crystal cellulose is as a kind of natural biomaterial, because of the crystalline texture of its height, unique length
Footpath is proved to can be applicable to regenerative medicine than the specific surface area with super large, optical application, and automobile is applied, and synthesizes material
The fields such as material.Additionally nanofiber have the highest hot strength, high Young's modulus, is various synthetic materials
Well reinforce filler.While it is true, due to hydroxyl that nano-cellulose surface is numerous determines it can not be fine
Ground dissolves and is dispersed in weak polar solvent, non-aqueous media and polymeric media, thus the biggest limit it and fit
By scope, thus, it is necessary to by chemical method, nano-cellulose is modified, to expand its application model
Enclose.
In order to improve nano-cellulose peptizaiton in non-aqueous media, researchers have employed a lot of chemistry and change
Property technology, as connected Hydrophobic small molecules, graft polymers and oligomer, absorption hydrophobic compound to nanofiber
The hydroxyl on element surface is first-class.Such as, king etc. utilize acetylation, hydroxyethylation, hydroxypropylation to nano microcrystalline fibre
Dimension element carries out surface modification, thus improves the dispersibility of nano micro crystal cellulose, and research finds, changes after drying
The product of property can disperse through ultrasonic in suitable solvent, and the diameter of nano micro crystal cellulose particle does not has
Significantly change (Front Chem Eng China, 2007,1,228-232).Chinese patent CN105175637A is public
Exploitation by atom transfer radical polymerization (ATRP) modified Nano microcrystalline cellulose ferritic, improve its heat stability and
Its compatibility with organic material.First Jonoobi etc. carry out preparing acetic acid esterified modified to micron order fiber, then
Nano level acetic acid esterified cellulose has been obtained so that it is may be uniformly dispersed in acetone and ethanol by mechanical lapping
In (Cellulose, 2010,17,299-307).Lin etc. are solvent and catalyst with pyridine, fine to nano microcrystalline
Dimension element carries out preparing acetic acid esterified modified, has obtained uniformly.Modified product (the Carbohydrate being scattered in dichloromethane
Polymers,2011,83,1834-1842)。
In the research in past, all there is certain deficiency in these research methoies, and some needs carry out the change of complexity
Learn reaction response pre-treatment thus destroy the structure of fiber, and in the method for modifying of the biggest number, will be just organic
Carrying out in solvent, severe reaction conditions, reaction scheme is complicated, and industrialization cost is high.Explore environmental protection, height
Imitate the surface-hydrophobicized method of modifying of quick nano micro crystal cellulose, the range of application to extension nano-cellulose
And have great importance in the reinforced effects improving composite.
Recently, Caruso etc. develops a kind of simple, quick, safe, cheap coating material, and this coating is led to
Crossing step self assembly ferrum (III) and natural polyphenol compounds forms, polyphenol compound is widely present in plant
In, containing abundant pyrogallol in polyphenol, hydrogen bond, hydrophobic bond or covalent bond and various base material effects can be passed through,
Can adhere at nearly all substrate surface, form stable clad (Science 2013,341,154).Simultaneously
Containing abundant catechol group in polyphenol-metal carbonyl coat, it is possible to effectively tie with metal or inorganic non-metallic
Closing, additionally under physiological environment, these groups are easily oxidized into quinoid structure, thus with containing mercaptan
(SH), amino (NH2) or the organic molecule of imino group (NH) there is Michael's addition or schiff base reaction, thus
Effectively functional molecular is chemically bonded to material surface.Polyphenol method of modifying is simple to operate, economical and efficient,
Environmental protection, is the most successfully applied to the research fields such as biomaterial, oil-water separation, the energy.
While it is true, in disclosed Research Literature and patent, yet there are no this kind of method of use to nanometer
Microcrystalline Cellulose carries out surface-hydrophobicized modification, therefore according to utilizing the fast reaction of metal-polyphenol layer, strong more
Tack and the feature of secondary response activity, under temperate condition, the most quickly be bonded to hydrophobic compound to receive
Rice microcrystalline Cellulose surface, prepares the nano micro crystal cellulose of surface-hydrophobicized modification, thus greatly expands
Open up its range of application.This method can effectively reduce the hydrophilic of nano-cellulose, improves cellulose with poly-
Interface compatibility between compound, improves the nano micro crystal cellulose reinforced effects to material.The method operation letter
Single, environmental protection, production cost is low, is industrially with a wide range of applications.
Summary of the invention
For above-mentioned existing problems, it is an object of the invention to overcome drawbacks described above, it is provided that a kind of technique is simple,
Environmental protection, the hydrophobic modification method realizing nano micro crystal cellulose rapidly and efficiently, for meeting mesh of the present invention
Technical solution be: a kind of method of nano micro crystal cellulose hydrophobic modification, described preparation method is pressed
Following steps are carried out:
A, by 1 gram of nano micro crystal cellulose ultrasonic disperse in 100 grams of deionized waters, the frequency of ultrasound wave be 20～
50KHz, states then up in dispersion liquid and is sequentially added into 0.01～0.20 gram of FeCl3.6H2O and 0.04～0.80 gram of list
Thujic acid, under the conditions of 25 DEG C～40 DEG C, the speed with 500～1500r/min stirs reaction 0.01～1 hour,
By the NaOH solution of 0.1mol/L, above-mentioned reacted dispersion liquid being adjusted to pH value subsequently is 7.6-9.5,
Under the conditions of 25 DEG C～40 DEG C, continue stirring reaction 1 hour, reacted dispersion liquid is centrifuged layering, abandons
Go the supernatant, obtain the water-fast suspension of lower floor, respectively with after ethanol and deionized water wash suspension
Recentrifuge is layered, and repeats 3～5 times, the suspension after cleaning is carried out lyophilization and must arrive surface and be modified with ferrum
The nano micro crystal cellulose of-tannin sorrel layer, cryodesiccated temperature is-80 DEG C～-40 DEG C, pressure be 10～
80Pa, the time is 5～20 hours, and wherein, centrifuge speed is 7000～12000r/min；
B, the nano micro crystal cellulose ultrasonic disperse that the ferrum obtained through step A-tannin sorrel layer is modified is being contained
The concentration of low-surface energy substance is in the mixed solution of 100mL second alcohol and water of 0.01～0.1mol/L, ultrasound wave
Frequency be 20～50KHz, wherein the volume ratio of second alcohol and water is 7:3, is adjusted by above-mentioned dispersion liquid with triethylamine
Saving pH value is 8～10, under the conditions of 25～40 DEG C, after stirring is reacted 6～24 hours, obtains after reaction
Dispersion liquid be centrifuged layering, discard the supernatant, obtain the water-fast suspension of lower floor, and use respectively
After ethanol and deionized water wash lower floor suspension, recentrifuge layering, repeats 3～5 times, the suspension after cleaning
Obtaining the nano micro crystal cellulose of surface-hydrophobicized modification after liquid is freeze-dried, cryodesiccated temperature is-80
DEG C～-40 DEG C, pressure is 10～80Pa, and the time is 5～20 hours, wherein, centrifuge speed be 7000～
12000r/min。
Described nano micro crystal cellulose is to prepare using cotton fiber or bamboo fibre or flaxen fiber or wood pulp as raw material
One in nano micro crystal cellulose.
Described nano micro crystal cellulose is shaped as bar-shaped or ellipticity, a diameter of 10～100nm.
Described low-surface energy substance is n-dodecyl mercaptan or n-octadecane base mercaptan or n-dodecylamine or positive ten
One in eight amine.
Owing to have employed above technical scheme, the invention have the advantages that
The method that the present invention provides overcomes the deficiencies in the prior art, based on covalent layer-by-layer self assembly principle, tannin
Acid and iron ion quickly can be self-assembly of metal-polyphenol film layer at material surface by a step covalency can be
Nearly all substrate surface adheres to, and forms stable clad.Simultaneously containing abundant in polyphenol-metal carbonyl coat
Catechol group, it is possible to be effectively combined with metal or inorganic non-metallic, additionally under physiological environment, these
Group is easily oxidized into quinoid structure, thus with containing mercaptan (SH), amino (NH2) or imino group (NH)
Organic molecule there is Michael's addition or schiff base reaction, thus effectively by low-surface-energy molecule strong bonded
To material surface.The inventive method by various nano micro crystal cellulose ultrasonic disperse in deionized water, through chlorine
Change after ferrous solution and tannic acid process, be rapidly formed on nano micro crystal cellulose surface the polyphenol of strong bonded-
Metal carbonyl coat, this bionic coating has anti-deformation nature, stability, reactivity and the biology of excellence
The compatibility, can directly react with mercaptan or amino molecule and hydrophobic chain covalency is fixed on surface, and whole reaction
Process is carried out under the conditions of gentle alkalescence, it is not necessary to add extra adhesive agent or coupling agent.The inventive method changes
The nano micro crystal cellulose that property obtains has good hydrophobic performance, the agglomeration of nano micro crystal cellulose granule
Decline, DMF, N,N-dimethylacetamide, dimethyl sulfoxide and 1,3-can be uniformly dispersed in
In the various polarity solvents such as dimethyl-2-imidazolinone.The kind of nano micro crystal cellulose material is not had by the method
Restricted, the structure of nano-cellulose, product diversification will not be destroyed, be widely used, and preparation technology is simple,
Environment is not polluted, low cost, be suitable for large-scale production, at nano combined reinforcing material, bio-medical
The fields such as material have broad application prospects.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described.A kind of nano micro crystal cellulose hydrophobic
Changing method of modifying, described preparation method sequentially includes the following steps:
1. the hydrophobic modification method of a nano micro crystal cellulose, it is characterised in that described preparation method is pressed
Following steps are carried out:
A, by 1 gram of nano micro crystal cellulose ultrasonic disperse in 100 grams of deionized waters, the frequency of ultrasound wave be 20～
50KHz, states then up in dispersion liquid and is sequentially added into 0.01～0.20 gram of FeCl3.6H2O and 0.04～0.80 gram of list
Thujic acid, under the conditions of 25 DEG C～40 DEG C, the speed with 500～1500r/min stirs reaction 0.01～1 hour,
By the NaOH solution of 0.1mol/L, above-mentioned reacted dispersion liquid being adjusted to pH value subsequently is 7.6-9.5,
Under the conditions of 25 DEG C～40 DEG C, continue stirring reaction 1 hour, reacted dispersion liquid is centrifuged layering, abandons
Go the supernatant, obtain the water-fast suspension of lower floor, respectively with after ethanol and deionized water wash suspension
Recentrifuge is layered, and repeats 3～5 times, the suspension after cleaning is carried out lyophilization and must arrive surface and be modified with ferrum
The nano micro crystal cellulose of-tannin sorrel layer, cryodesiccated temperature is-80 DEG C～-40 DEG C, pressure be 10～
80Pa, the time is 5～20 hours, and wherein, centrifuge speed is 7000～12000r/min, described nanometer
Microcrystalline Cellulose is the nano microcrystalline fiber prepared as raw material using cotton fiber or bamboo fibre or flaxen fiber or wood pulp
One in element, described nano micro crystal cellulose is shaped as bar-shaped or ellipticity, a diameter of 10～100nm.
B, the nano micro crystal cellulose ultrasonic disperse that the ferrum obtained through step A-tannin sorrel layer is modified is being contained
The concentration of low-surface energy substance is in the mixed solution of 100mL second alcohol and water of 0.01～0.1mol/L, ultrasound wave
Frequency be 20～50KHz, wherein the volume ratio of second alcohol and water is 7:3, is adjusted by above-mentioned dispersion liquid with triethylamine
Saving pH value is 8～10, under the conditions of 25～40 DEG C, after stirring is reacted 6～24 hours, obtains after reaction
Dispersion liquid be centrifuged layering, discard the supernatant, obtain the water-fast suspension of lower floor, and use respectively
After ethanol and deionized water wash lower floor suspension, recentrifuge layering, repeats 3～5 times, the suspension after cleaning
Obtaining the nano micro crystal cellulose of surface-hydrophobicized modification after liquid is freeze-dried, cryodesiccated temperature is-80
DEG C～-40 DEG C, pressure is 10～80Pa, and the time is 5～20 hours, wherein, centrifuge speed be 7000～
12000r/min, described low-surface energy substance is n-dodecyl mercaptan or n-octadecane base mercaptan or n-dodecylamine
Or the one in octadecyl amine.
The inventive method by various nano micro crystal cellulose ultrasonic disperse in deionized water, obtains homodisperse
Suspension, by the dispersion liquid obtained after iron chloride and tannic acid solution process, iron ion is being received with polyphenol group
Rice microcrystalline Cellulose surface carries out a step self assembly effect, quickly forms the polyphenol-metal carbonyl coat of strong bonded,
This clad has anti-deformation nature, stability, reactivity and the biocompatibility of excellence, can be directly
React with mercaptan or amino molecule and hydrophobic chain covalency is fixed on nano micro crystal cellulose surface, thus dredged
The nano micro crystal cellulose that aquation is modified, whole processing procedure is without adding extra adhesive agent or coupling agent or urging
Agent, and the nano micro crystal cellulose used can be prepared easily by the method that document is reported.The present invention
The nano micro crystal cellulose that method modification obtains has good hydrophobic performance, and the reunion of nanofiber crude granule is made
With decline, can be uniformly dispersed in DMF, N,N-dimethylacetamide, dimethyl sulfoxide and
In the solution that the various polarity such as 1,3-dimethyl-2-imidazolinone are different.The method is to nano micro crystal cellulose material
The kind of material does not limit, and will not destroy the structure of nano-cellulose, product diversification, be widely used, and system
Standby technique is simple, does not pollutes environment, low cost, is suitable for large-scale production, at nano combined enhancing material
The fields such as material, bio-medical material have broad application prospects.
Specific embodiment
Embodiment 1
By the rod-like nano-crystalline cellulose ultrasonic disperse of 1 gram of a diameter of 10nm prepared for raw material with cotton fiber in
In 100 grams of deionized waters, the frequency of ultrasound wave is 20KHz, is then sequentially added into 0.01 gram of FeCl3.6H2O and
0.04 gram of tannic acid, at 25 DEG C, with 500r/min moral mixing speed stirring reaction 0.1 hour, uses subsequently
It is 7.6 that reacted dispersion liquid is adjusted to pH value by the NaOH solution of 0.1mol/L, at 25 DEG C, continues stirring
1 hour, reacted dispersion liquid is centrifuged layering, discards the supernatant, obtain lower floor water-fast
Suspension, and respectively with recentrifuge after ethanol and deionized water wash suspension, be repeated 3 times, will be deposited in
Pressure is at 10Pa ,-80 DEG C after lyophilization 5h, obtains the nano micro crystal cellulose that ferrum-tannin sorrel layer is modified；
The nano micro crystal cellulose ultrasonic disperse modified by ferrum obtained above-tannin sorrel layer is containing 0.202g positive ten
In the mixed solution of the 100mL second alcohol and water of dialkyl group mercaptan, the frequency of ultrasound wave is 20KHz, wherein ethanol
Being 7:3 with the volume ratio of water, be 8 with triethylamine regulation mixed solution pH value, under the conditions of 25 DEG C, stirring stirring is anti-
After answering 6 hours, the dispersion liquid obtained is centrifuged layering, discards the supernatant, obtain lower floor not after reaction
It is dissolved in the suspension of water, and respectively with recentrifuge layering, weight after ethanol and deionized water wash lower floor suspension
Multiple 3～5 times, wherein, centrifuge speed is 7000r/min, and the suspension after cleaning is 10Pa at pressure,
At-80 DEG C, after lyophilization 5h, obtain the nano micro crystal cellulose of surface-hydrophobicized modification.
Embodiment 2
By the ellipticity nano micro crystal cellulose ultrasonic disperse of 1 gram of a diameter of 50nm prepared for raw material with bamboo fibre
In 100 grams of deionized waters, the frequency of ultrasound wave is 50KHz, is then sequentially added into 0.04 gram of FeCl3.6H2O and
0.16 gram of tannic acid, at 40 DEG C, with 1000r/min moral mixing speed stirring reaction 1 hour, uses subsequently
It is 9.5 that reacted dispersion liquid is adjusted to pH value by the NaOH solution of 0.1mol/L, at 40 DEG C, continues stirring
1 hour, reacted dispersion liquid is centrifuged layering, discards the supernatant, obtain lower floor water-fast
Suspension, respectively with recentrifuge layering after ethanol and deionized water wash suspension, is repeated 3 times, will suspend
Liquid after lyophilization 20h, obtains the nano microcrystalline that ferrum-tannin sorrel layer is modified at pressure is 80Pa ,-40 DEG C
Cellulose；The nano micro crystal cellulose ultrasonic disperse modified by ferrum obtained above-tannin sorrel layer is containing 2.86
In the mixed solution of the 100mL second alcohol and water of g n-octadecane base mercaptan, the frequency of ultrasound wave is 50KHz, its
The volume ratio of middle second alcohol and water is 7:3, is 10 with triethylamine regulation mixed solution pH value, under the conditions of 40 DEG C,
After stirring reaction 24 hours, the dispersion liquid obtained is centrifuged layering, discards the supernatant, obtain after reaction
The water-fast suspension of lower floor, and divide with recentrifuge after ethanol and deionized water wash lower floor suspension respectively
Layer, repeats 3～5 times, and wherein, centrifuge speed is 12000r/min, and the suspension after cleaning at pressure is
80Pa, at-40 DEG C, lyophilization obtains the nano micro crystal cellulose of surface-hydrophobicized modification after 20 hours.
Embodiment 3
By ultrasonic point of the ellipticity nano micro crystal cellulose of 1 gram of a diameter of 100nm prepared for raw material with flaxen fiber
Dissipating in 100 grams of deionized waters, the frequency of ultrasound wave is 50KHz, is then sequentially added into 0.2 gram of FeCl3.6H2O
With 0.8 gram of tannic acid, at 30 DEG C, with 1500r/min moral mixing speed stirring reaction 1 hour, use subsequently
It is 9.5 that reacted dispersion liquid is adjusted to pH value by the NaOH solution of 0.1mol/L, at 30 DEG C, continues stirring
1 hour, reacted dispersion liquid is centrifuged layering, discards the supernatant, obtain lower floor water-fast
Suspension, respectively with recentrifuge layering after ethanol and deionized water wash suspension, is repeated 3 times, will suspend
Liquid after lyophilization 15h, obtains the nano microcrystalline that ferrum-tannin sorrel layer is modified at pressure is 60Pa ,-60 DEG C
Cellulose；The nano micro crystal cellulose ultrasonic disperse that ferrum obtained above-tannin sorrel layer is modified is being contained
In the mixed solution of the 100mL second alcohol and water of 0.269g octadecyl amine, the frequency of ultrasound wave is 40KHz, its
The volume ratio of middle second alcohol and water is 7:3, is 9 with triethylamine regulation mixed solution pH value, under the conditions of 30 DEG C,
After stirring reaction 12 hours, the dispersion liquid obtained is centrifuged layering, discards the supernatant, obtain after reaction
The water-fast suspension of lower floor, and divide with recentrifuge after ethanol and deionized water wash lower floor suspension respectively
Layer, repeats 3～5 times, and wherein, centrifuge speed is 10000r/min, and the suspension after cleaning at pressure is
60Pa, at-60 DEG C, lyophilization obtains the nano micro crystal cellulose of surface-hydrophobicized modification after 15 hours.
Embodiment 4
By the rod-like nano-crystalline cellulose ultrasonic disperse of 1 gram of a diameter of 80nm prepared for raw material with wood pulp in
In 100 grams of deionized waters, the frequency of ultrasound wave is 50KHz, is then sequentially added into 0.1 gram of FeCl3.6H2O and 0.4
Gram tannic acid, at 35 DEG C, with 1500r/min moral mixing speed stirring reaction 0.5 hour, uses 0.1mol/L subsequently
NaOH solution reacted dispersion liquid is adjusted to pH value is 8.5, at 35 DEG C, continue stirring 1 hour,
Reacted dispersion liquid is centrifuged layering, discards the supernatant, obtain the water-fast suspension of lower floor,
Respectively with recentrifuge layering after ethanol and deionized water wash suspension, it is repeated 3 times, by suspension at pressure
For 50Pa, at-50 DEG C after lyophilization 20h, obtain the nano micro crystal cellulose that ferrum-tannin sorrel layer is modified；
The nano micro crystal cellulose ultrasonic disperse modified by ferrum obtained above-tannin sorrel layer is containing 0.37g positive ten
In the mixed solution of the 100mL second alcohol and water of diamidogen, the frequency of ultrasound wave is 50KHz, wherein second alcohol and water
Volume ratio be 7:3, with triethylamine regulation mixed solution pH value be 9, under the conditions of 35 DEG C, stir reaction 24
After hour, the dispersion liquid obtained is centrifuged layering, discards the supernatant, obtain lower floor and do not dissolve in after reaction
The suspension of water, and respectively with recentrifuge layering after ethanol and deionized water wash lower floor suspension, repeat 3～
5 times, wherein, centrifuge speed is 10000r/min, and the suspension after cleaning is 50Pa at pressure ,-50 DEG C
Under, lyophilization obtains the nano micro crystal cellulose of surface-hydrophobicized modification after 20 hours.
Claims (4)
1. the hydrophobic modification method of a nano micro crystal cellulose, it is characterised in that described preparation method by with
Lower step is carried out:
A, by 1 gram of nano micro crystal cellulose ultrasonic disperse in 100 grams of deionized waters, the frequency of ultrasound wave is
20～50KHz, state then up in dispersion liquid and be sequentially added into 0.01～0.20 gram of FeCl3.6H2O and 0.04～0.80
Gram tannic acid, under the conditions of 25 DEG C～40 DEG C, it is little that the speed with 500～1500r/min stirs reaction 0.01～1
Time, by the NaOH solution of 0.1mol/L, above-mentioned reacted dispersion liquid being adjusted to pH value subsequently is 7.6-9.5,
Under the conditions of 25 DEG C～40 DEG C, continue stirring reaction 1 hour, reacted dispersion liquid be centrifuged layering,
Discard the supernatant, obtain the water-fast suspension of lower floor, respectively with ethanol and deionized water wash suspension
Rear recentrifuge is layered, and repeats 3～5 times, the suspension after cleaning is carried out lyophilization and must arrive surface and be modified with
The nano micro crystal cellulose of ferrum-tannin sorrel layer, cryodesiccated temperature is-80 DEG C～-40 DEG C, pressure be 10～
80Pa, the time is 5～20 hours, and wherein, centrifuge speed is 7000～12000r/min；
B, the nano micro crystal cellulose ultrasonic disperse that the ferrum obtained through step A-tannin sorrel layer is modified is being contained
The concentration of low-surface energy substance is in the mixed solution of 100mL second alcohol and water of 0.01～0.1mol/L, ultrasound wave
Frequency be 20～50KHz, wherein the volume ratio of second alcohol and water is 7:3, is adjusted by above-mentioned dispersion liquid with triethylamine
Saving pH value is 8～10, under the conditions of 25～40 DEG C, after stirring is reacted 6～24 hours, obtains after reaction
Dispersion liquid be centrifuged layering, discard the supernatant, obtain the water-fast suspension of lower floor, and use respectively
After ethanol and deionized water wash lower floor suspension, recentrifuge layering, repeats 3～5 times, the suspension after cleaning
Obtaining the nano micro crystal cellulose of surface-hydrophobicized modification after liquid is freeze-dried, cryodesiccated temperature is-80
DEG C～-40 DEG C, pressure is 10～80Pa, and the time is 5～20 hours, wherein, centrifuge speed be 7000～
12000r/min。
The hydrophobic modification method on a kind of nano micro crystal cellulose surface the most according to claim 1, it is special
Levy and be: described nano micro crystal cellulose is for preparing as raw material using cotton fiber or bamboo fibre or flaxen fiber or wood pulp
Nano micro crystal cellulose in one.
The hydrophobic modification method on a kind of nano micro crystal cellulose surface the most according to claim 1, it is special
Levy and be: described nano micro crystal cellulose is shaped as bar-shaped or ellipticity, a diameter of 10～100nm.
The hydrophobic modification method on a kind of nano micro crystal cellulose surface the most according to claim 1, it is special
Levy and be: described low-surface energy substance be n-dodecyl mercaptan or or n-octadecane base mercaptan or n-dodecylamine or
One in octadecyl amine.
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