CN105949330B - A kind of hydrophobic modification method of nano micro crystal cellulose - Google Patents
A kind of hydrophobic modification method of nano micro crystal cellulose Download PDFInfo
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Abstract
The present invention discloses a kind of hydrophobic modification method of nano micro crystal cellulose, belongs to function nano field of material technology.This method is used nano micro crystal cellulose dispersion in aqueous solution, after iron chloride and tannic acid processing dispersion liquid, it is centrifugally separating to obtain the nano micro crystal cellulose of iron tannic acid film layer modification, then it is dispersed in the mixed solution of the second alcohol and water containing low-surface energy substance, the mixed liquor obtained after reaction carries out centrifugation layering, and freeze-drying obtains the nano micro crystal cellulose of surface-hydrophobicized modification.The nano micro crystal cellulose of hydrophobic modification prepared by this method can be uniformly dispersed in various polarity solvent, product diversification, and preparation process is simple, environment is not polluted, it is at low cost, it is suitble to large-scale production, has broad application prospects in fields such as nano combined reinforcing material, bio-medical materials.
Description
Technical field
The present invention relates to a kind of methods of nano micro crystal cellulose hydrophobic modification, belong to function nano material technology neck
Domain.
Background technology
Nano micro crystal cellulose is as a kind of natural biomaterial, because of the crystalline texture of its height, unique draw ratio
It is proved to can be applicable to the fields such as regenerative medicine, optical application, automobile application, synthetic material with the specific surface area of super large.In addition
Nanofiber is known as very high tensile strength, and high Young's modulus is that various synthetic materials reinforce filler well.Although such as
This, since the numerous hydroxyl in nano-cellulose surface determines that it cannot dissolve and be dispersed in weak polar solvent, non-aqueous well
In medium and polymeric media, its scope of application is limited so as to very big, thus, it is necessary to by chemical method to Nanowire
Dimension element is modified, to expand its application range.
In order to improve peptizaiton of the nano-cellulose in non-aqueous media, researchers employ many chemical modification skills
Art, as connected Hydrophobic small molecules, graft polymers and oligomer, adsorbing on hydrophobic compound to the hydroxyl on nano-cellulose surface
Deng.For example, king etc. carries out surface modification using acetylation, hydroxyethylation, hydroxypropylation to nano micro crystal cellulose, so as to change
The dispersibility of kind nano micro crystal cellulose, the study found that the product of dry post-modification can be in appropriate solvent by ultrasound
Dispersion, and the diameter of nano micro crystal cellulose particle do not change significantly (Front Chem Eng China, 2007,1,
228-232).Chinese patent CN105175637A is disclosed using atom transfer radical polymerization (ATRP) modified Nano microcrystalline cellulose
Ferritic improves its thermal stability and its compatibility with organic material.Jonoobi etc. carries out acetate to micron order fiber first
Change be modified, nano level acetic acid esterified cellulose has then been obtained by mechanical lapping so that it can be dispersed in acetone and
In ethyl alcohol (Cellulose, 2010,17,299-307).Lin etc. is solvent and catalyst with pyridine, to nano micro crystal cellulose
Preparing acetic acid esterified modified is carried out, has been obtained uniformly.Be scattered in dichloromethane modified production (Carbohydrate Polymers,
2011,83,1834-1842)。
In past research, for these research methods there are certain deficiency, it is anti-that some need carries out complicated chemistry
Pre-treatment should be reacted so as to destroy the structure of fiber, and in method of modifying several greatly absolutely, it will be with regard to carrying out in organic solvent, instead
Answer condition harsh, reaction route is complicated, and industrialization is of high cost.Explore environmentally protective, efficiently quick nano micro crystal cellulose
Surface-hydrophobicized method of modifying, to extending the application range of nano-cellulose and its having in the enhancing effect for improving composite material
There is important meaning.
Recently, Caruso etc. develops a kind of simple, quick, safe, cheap coating material, this coating by a step from
Assembling iron (III) and natural polyphenol class compound form, and polyphenol compound is widely present in plant, containing abundant in polyphenol
Pyrogallol, can be acted on by hydrogen bond, hydrophobic bond or covalent bond and various base materials, can be attached in nearly all substrate surface
It, forms stable clad (Science 2013,341,154).Contain abundant catechu in polyphenol-metal carbonyl coat simultaneously
Phenolic group group can effectively be combined with metal or inorganic non-metallic, and in addition under physiological environment, these groups are easily oxidized
Into quinoid structure, so as to containing mercaptan (SH), amino (NH2) or imino group (NH) organic molecule occur Michael's addition or
Schiff base reaction, so as to which functional molecular effectively is chemically bonded to material surface.Polyphenol method of modifying is easy to operate, economical
Efficiently, it is environmentally protective, it is successfully applied to the research fields such as biomaterial, water-oil separating, the energy at present.
Nevertheless, in the Research Literature and patent having disclosed, yet there are no using such method to nano microcrystalline fibre
Dimension element carries out surface-hydrophobicized modification, therefore according to fast reaction, strong adhesion and the secondary response for more utilizing metal-polyphenol layer
Hydrophobic compound under temperate condition, is efficiently quickly bonded to nano micro crystal cellulose surface, is prepared by the characteristics of active
The nano micro crystal cellulose of surface-hydrophobicized modification, so as to greatly extend its application range.This method can effectively drop
The hydrophily of low nano-cellulose improves the interface compatibility between cellulose and polymer, improves nano micro crystal cellulose pair
The enhancing effect of material.The method is easy to operate, environmentally protective, and production cost is low, is industrially with a wide range of applications.
Invention content
For above-mentioned there are problem, it is an object of the invention to overcome drawbacks described above, a kind of simple for process, green ring is provided
It protects, the hydrophobic modification method of realization nano micro crystal cellulose rapidly and efficiently, to meet the technology solution party of the object of the invention
Case is：A kind of method of nano micro crystal cellulose hydrophobic modification, the preparation method carry out according to the following steps：
A, by 1 gram of nano micro crystal cellulose ultrasonic disperse in 100 grams of deionized waters, the frequency of ultrasonic wave for 20~
50KHz is stated in dispersion liquid and is sequentially added 0.01~0.20 gram of FeCl then up3.6H2O and 0.04~0.80 gram of tannic acid,
It under the conditions of 25 DEG C~40 DEG C, is stirred to react 0.01~1 hour with the speed of 500~1500r/min, then with 0.1mol/L's
It is 7.6-9.5 that NaOH solution, which adjusts the dispersion liquid after above-mentioned reaction to pH value, and under the conditions of 25 DEG C~40 DEG C, it is anti-to continue stirring
It answers 1 hour, the dispersion liquid after reaction is subjected to centrifugation layering, discards supernatant liquor, obtain lower floor's suspension not soluble in water, point
Centrifugation layering again, repeats 3~5 times after not washing suspension with ethyl alcohol and deionized water, the suspension after cleaning is carried out cold
Jelly, which is dried to obtain surface modification, the nano micro crystal cellulose of iron-tannic acid film layer, and the temperature of freeze-drying is -80 DEG C~-40
DEG C, pressure is 10~80Pa, and the time is 5~20 hours, wherein, centrifuge speed is 7000~12000r/min；
B, by the nano micro crystal cellulose ultrasonic disperse of the iron obtained through step A-tannic acid film layer modification containing low table
Face can substance a concentration of 0.01~0.1mol/L 100mL second alcohol and waters mixed solution in, the frequency of ultrasonic wave for 20~
50KHz, the wherein volume ratio of second alcohol and water are 7:3, it is 8~10 to be adjusted above-mentioned dispersion liquid to pH value with triethylamine, 25~
Under the conditions of 40 DEG C, after being stirred to react 6~24 hours, the dispersion liquid obtained after reaction is subjected to centrifugation layering, discards supernatant liquor,
Lower floor's suspension not soluble in water is obtained, and layering is centrifuged again after washing lower floor's suspension with ethyl alcohol and deionized water respectively,
Repeat 3~5 times, by the suspension after cleaning it is freeze-dried after obtain the nano micro crystal cellulose of surface-hydrophobicized modification, it is cold
It is -80 DEG C~-40 DEG C that dry temperature, which is lyophilized, and pressure is 10~80Pa, and the time is 5~20 hours, wherein, centrifuge speed is
7000~12000r/min.
The nano micro crystal cellulose is the nanometer prepared using cotton fiber or bamboo fibre or flaxen fiber or wood pulp as raw material
One kind in microcrystalline cellulose.
The nano micro crystal cellulose shape be rodlike or ellipticity, a diameter of 10~100nm.
The low-surface energy substance is n-dodecyl mercaptan or n-octadecane base mercaptan or n-dodecylamine or octadecyl amine
In one kind.
As a result of above technical scheme, the present invention has the following advantages：
Method provided by the invention overcomes the deficiencies in the prior art, based on covalent layer-by-layer self assembly principle, tannic acid and
Iron ion quickly covalently can be self-assembly of metal-polyphenol film layer in material surface by a step can be in nearly all base material
Surface is adhered to, and forms stable clad.It, can be effective simultaneously containing abundant catechol group in polyphenol-metal carbonyl coat
Ground is combined with metal or inorganic non-metallic, and in addition under physiological environment, these groups are easily oxidized into quinoid structure, so as to
With containing mercaptan (SH), amino (NH2) or the organic molecule of imino group (NH) Michael's addition or schiff base reaction occurs, so as to
Low-surface-energy molecule is effectively firmly bound to material surface.The method of the present invention is by various nano micro crystal cellulose ultrasonic disperses
In deionized water, it after ferric chloride solution and tannic acid processing, is rapidly formed securely on nano micro crystal cellulose surface
With reference to polyphenol-metal carbonyl coat, the bionic coating have excellent anti-deformation nature, stability, reactivity and life
Object compatibility, can directly react with mercaptan or amino molecule and hydrophobic chain is covalently fixed on surface, and entire reaction process exists
It is carried out under mild alkaline condition, without adding in additional adhesive or coupling agent.The nanometer that the method for the present invention is modified is micro-
Crystalline cellulose has good hydrophobic performance, and the agglomeration of nano micro crystal cellulose particle declines, can be uniformly dispersed in
The various polarities such as N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide and 1,3- dimethyl-2-imidazolinones are molten
In agent.There is no limit for type of this method to nano micro crystal cellulose material, will not destroy the structure of nano-cellulose, product is more
Sample is widely used, and preparation process is simple, and environment is not polluted, at low cost, is suitble to large-scale production, is answered in nanometer
The fields such as reinforcing material, bio-medical material are closed to have broad application prospects.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described.A kind of hydrophobization of nano micro crystal cellulose changes
Property method, the preparation method carry out according to the following steps：
1. a kind of hydrophobic modification method of nano micro crystal cellulose, which is characterized in that the preparation method presses following step
It is rapid to carry out：
A, by 1 gram of nano micro crystal cellulose ultrasonic disperse in 100 grams of deionized waters, the frequency of ultrasonic wave for 20~
50KHz is stated in dispersion liquid and is sequentially added 0.01~0.20 gram of FeCl then up3.6H2O and 0.04~0.80 gram of tannic acid,
It under the conditions of 25 DEG C~40 DEG C, is stirred to react 0.01~1 hour with the speed of 500~1500r/min, then with 0.1mol/L's
It is 7.6-9.5 that NaOH solution, which adjusts the dispersion liquid after above-mentioned reaction to pH value, and under the conditions of 25 DEG C~40 DEG C, it is anti-to continue stirring
It answers 1 hour, the dispersion liquid after reaction is subjected to centrifugation layering, discards supernatant liquor, obtain lower floor's suspension not soluble in water, point
Centrifugation layering again, repeats 3~5 times after not washing suspension with ethyl alcohol and deionized water, the suspension after cleaning is carried out cold
Jelly, which is dried to obtain surface modification, the nano micro crystal cellulose of iron-tannic acid film layer, and the temperature of freeze-drying is -80 DEG C~-40
DEG C, pressure be 10~80Pa, the time be 5~20 hours, wherein, centrifuge speed be 7000~12000r/min, the nanometer
Microcrystalline cellulose is one in the nano micro crystal cellulose prepared using cotton fiber or bamboo fibre or flaxen fiber or wood pulp as raw material
Kind, the nano micro crystal cellulose shape be rodlike or ellipticity, a diameter of 10~100nm.
B, by the nano micro crystal cellulose ultrasonic disperse of the iron obtained through step A-tannic acid film layer modification containing low table
Face can substance a concentration of 0.01~0.1mol/L 100mL second alcohol and waters mixed solution in, the frequency of ultrasonic wave for 20~
50KHz, the wherein volume ratio of second alcohol and water are 7:3, it is 8~10 to be adjusted above-mentioned dispersion liquid to pH value with triethylamine, 25~
Under the conditions of 40 DEG C, after being stirred to react 6~24 hours, the dispersion liquid obtained after reaction is subjected to centrifugation layering, discards supernatant liquor,
Lower floor's suspension not soluble in water is obtained, and layering is centrifuged again after washing lower floor's suspension with ethyl alcohol and deionized water respectively,
Repeat 3~5 times, by the suspension after cleaning it is freeze-dried after obtain the nano micro crystal cellulose of surface-hydrophobicized modification, it is cold
It is -80 DEG C~-40 DEG C that dry temperature, which is lyophilized, and pressure is 10~80Pa, and the time is 5~20 hours, wherein, centrifuge speed is
7000~12000r/min, the low-surface energy substance for n-dodecyl mercaptan or n-octadecane base mercaptan or n-dodecylamine or
One kind in octadecyl amine.
Various nano micro crystal cellulose ultrasonic disperses in deionized water, are obtained homodisperse suspension by the method for the present invention
Liquid, by obtained dispersion liquid after iron chloride and tannic acid solution processing, iron ion is with polyphenol group in nano micro crystal cellulose
Surface carries out a step self assembly and acts on, quick to form strong bonded polyphenol-metal carbonyl coat, this clad has excellent resist
Deformation nature, stability, reactivity and biocompatibility can directly be reacted with mercaptan or amino molecule and by hydrophobic chain
Nano micro crystal cellulose surface covalently is fixed on, so as to obtain the nano micro crystal cellulose of hydrophobic modification, entire processing procedure
Additional adhesive or coupling agent or catalyst need not be added in, and used nano micro crystal cellulose can pass through document report
Method easily prepare.The nano micro crystal cellulose that the method for the present invention is modified has good hydrophobic performance, Nanowire
The agglomeration for tieing up crude granule declines, and can be uniformly dispersed in n,N-Dimethylformamide, n,N-dimethylacetamide, diformazan
In the different solution of the various polarities such as sulfoxide and 1,3- dimethyl-2-imidazolinones.This method is to nano micro crystal cellulose material
Type there is no limit, the structure of nano-cellulose will not be destroyed, product diversification is widely used, and preparation process is simple, right
Environment does not pollute, at low cost, is suitble to large-scale production, has in fields such as nano combined reinforcing material, bio-medical materials
Have broad application prospects.
Specific embodiment
Embodiment 1
The rod-like nano- crystalline cellulose ultrasonic disperse of a diameter of 10nm that 1 gram is prepared using cotton fiber as raw material is in 100
In gram deionized water, the frequency of ultrasonic wave is 20KHz, then sequentially adds 0.01 gram of FeCl3.6H2O and 0.04 gram of tannic acid,
At 25 DEG C, it is stirred to react 0.1 hour with 500r/min moral mixing speeds, it then will be after reaction with the NaOH solution of 0.1mol/L
It is 7.6 that dispersion liquid, which is adjusted to pH value, at 25 DEG C, continues stirring 1 hour, the dispersion liquid after reaction is carried out centrifugation layering, is abandoned
Remove supernatant liquor, obtain lower floor's suspension not soluble in water, and after washing suspension with ethyl alcohol and deionized water respectively again from
The heart is repeated 3 times, and will be deposited in pressure as 10Pa, at -80 DEG C after freeze-drying 5h, obtains the nanometer of iron-tannic acid film layer modification
Microcrystalline cellulose；The nano micro crystal cellulose ultrasonic disperse of iron obtained above-tannic acid film layer modification is being contained into 0.202g
In the mixed solution of the 100mL second alcohol and waters of n-dodecyl mercaptan, the frequency of ultrasonic wave is 20KHz, wherein second alcohol and water
Volume ratio is 7:3, it is 8 to adjust mixed solution pH value with triethylamine,, will be anti-after being stirred to react 6 hours under the conditions of 25 DEG C
Should after obtained dispersion liquid carry out centrifugation layering, discard supernatant liquor, obtain lower floor's suspension not soluble in water, and use second respectively
Centrifugation layering again after alcohol and deionized water washing lower floor suspension, repeats 3~5 times, wherein, centrifuge speed 7000r/
Suspension after cleaning in pressure is 10Pa, at -80 DEG C, the nanometer of surface-hydrophobicized modification is obtained after being freeze-dried 5h by min
Microcrystalline cellulose.
Embodiment 2
By 1 gram using bamboo fibre as the ellipticity nano micro crystal cellulose ultrasonic disperse of a diameter of 50nm prepared by raw material in
In 100 grams of deionized waters, the frequency of ultrasonic wave is 50KHz, then sequentially adds 0.04 gram of FeCl3.6H2O and 0.16 gram of tannin
Acid at 40 DEG C, is stirred to react 1 hour with 1000r/min moral mixing speeds, will then be reacted with the NaOH solution of 0.1mol/L
It is 9.5 that dispersion liquid afterwards, which is adjusted to pH value, at 40 DEG C, continues stirring 1 hour, and the dispersion liquid after reaction is carried out centrifugation point
Layer, discards supernatant liquor, obtains lower floor's suspension not soluble in water, after washing suspension with ethyl alcohol and deionized water respectively again
Centrifugation layering, is repeated 3 times, and in pressure is 80Pa by suspension, at -40 DEG C after freeze-drying 20h, obtains iron-tannic acid film layer
The nano micro crystal cellulose of modification；The nano micro crystal cellulose ultrasonic disperse of iron obtained above-tannic acid film layer modification is existed
In the mixed solution of 100mL second alcohol and waters containing 2.86g n-octadecane base mercaptan, the frequency of ultrasonic wave is 50KHz, wherein second
The volume ratio of alcohol and water is 7:3, it is 10 to adjust mixed solution pH value with triethylamine, under the conditions of 40 DEG C, is stirred to react 24 hours
Afterwards, the dispersion liquid obtained after reaction is subjected to centrifugation layering, discards supernatant liquor, obtain lower floor's suspension not soluble in water, and
Centrifugation layering again, repeats 3~5 times after washing lower floor's suspension with ethyl alcohol and deionized water respectively, wherein, centrifuge speed is
Suspension after cleaning in pressure is 80Pa by 12000r/min, and at -40 DEG C, freeze-drying obtains surface hydrophobicity after 20 hours
Change modified nano micro crystal cellulose.
Embodiment 3
By 1 gram using flaxen fiber as the ellipticity nano micro crystal cellulose ultrasonic disperse of a diameter of 100nm prepared by raw material in
In 100 grams of deionized waters, the frequency of ultrasonic wave is 50KHz, then sequentially adds 0.2 gram of FeCl3.6H2O and 0.8 gram of tannic acid,
It at 30 DEG C, is stirred to react 1 hour with 1500r/min moral mixing speeds, after then being reacted with the NaOH solution of 0.1mol/L
Dispersion liquid adjust to pH value be 9.5, at 30 DEG C, continue stirring 1 hour, the dispersion liquid after reaction is subjected to centrifugation layering,
Discard supernatant liquor, obtain lower floor's suspension not soluble in water, after washing suspension with ethyl alcohol and deionized water respectively again from
The heart is layered, and is repeated 3 times, and in pressure is 60Pa by suspension, at -60 DEG C after freeze-drying 15h, is obtained iron-tannic acid film layer and repair
The nano micro crystal cellulose of decorations；By the nano micro crystal cellulose ultrasonic disperse of iron obtained above-tannic acid film layer modification containing
Have in the mixed solution of 100mL second alcohol and waters of 0.269g octadecyl amines, the frequency of ultrasonic wave is 40KHz, wherein second alcohol and water
Volume ratio be 7:3, it is 9 to adjust mixed solution pH value with triethylamine,, will be anti-after being stirred to react 12 hours under the conditions of 30 DEG C
Should after obtained dispersion liquid carry out centrifugation layering, discard supernatant liquor, obtain lower floor's suspension not soluble in water, and use second respectively
Centrifugation layering again after alcohol and deionized water washing lower floor suspension, repeats 3~5 times, wherein, centrifuge speed 10000r/
Suspension after cleaning in pressure is 60Pa by min, and at -60 DEG C, freeze-drying obtains surface-hydrophobicized modification after 15 hours
Nano micro crystal cellulose.
Embodiment 4
The rod-like nano- crystalline cellulose ultrasonic disperse of a diameter of 80nm that 1 gram is prepared using wood pulp as raw material is in 100 grams
In deionized water, the frequency of ultrasonic wave is 50KHz, then sequentially adds 0.1 gram of FeCl3.6H2O and 0.4 gram of tannic acid, at 35 DEG C
Under, it is stirred to react 0.5 hour with 1500r/min moral mixing speeds, then with the NaOH solution of 0.1mol/L by point after reaction
It is 8.5 that dispersion liquid, which is adjusted to pH value, at 35 DEG C, continues stirring 1 hour, the dispersion liquid after reaction is carried out centrifugation layering, is discarded
Supernatant liquor obtains lower floor's suspension not soluble in water, centrifugation point again after washing suspension with ethyl alcohol and deionized water respectively
Layer, is repeated 3 times, and in pressure is 50Pa by suspension, at -50 DEG C after freeze-drying 20h, obtains iron-tannic acid film layer modification
Nano micro crystal cellulose；By the nano micro crystal cellulose ultrasonic disperse of iron obtained above-tannic acid film layer modification containing
In the mixed solution of the 100mL second alcohol and waters of 0.37g n-dodecylamines, the frequency of ultrasonic wave is the body of 50KHz, wherein second alcohol and water
Product is than being 7:3, it is 9 to adjust mixed solution pH value with triethylamine, under the conditions of 35 DEG C, after being stirred to react 24 hours, after reaction
Obtained dispersion liquid carries out centrifugation layering, discards supernatant liquor, obtains lower floor's suspension not soluble in water, and respectively with ethyl alcohol and
Centrifugation layering again after deionized water washing lower floor suspension, repeats 3~5 times, wherein, centrifuge speed 10000r/min,
In pressure it is 50Pa by the suspension after cleaning, at -50 DEG C, freeze-drying obtains the nanometer of surface-hydrophobicized modification after 20 hours
Microcrystalline cellulose.
Claims (4)
1. a kind of hydrophobic modification method of nano micro crystal cellulose, which is characterized in that the preparation method according to the following steps into
Row：
A, by 1 gram of nano micro crystal cellulose ultrasonic disperse in 100 grams of deionized waters, the frequency of ultrasonic wave is 20~50KHz, so
0.01~0.20 gram of FeCl is sequentially added in backward above-mentioned dispersion liquid3.6H2O and 0.04~0.80 gram of tannic acid, 25 DEG C~40
Under the conditions of DEG C, it is stirred to react 0.01~1 hour with the speed of 500~1500r/min, it then will with the NaOH solution of 0.1mol/L
It is 7.6-9.5 that dispersion liquid after above-mentioned reaction, which is adjusted to pH value, under the conditions of 25 DEG C~40 DEG C, continues to be stirred to react 1 hour, will
Dispersion liquid after reaction carries out centrifugation layering, discards supernatant liquor, obtains lower floor's suspension not soluble in water, respectively with ethyl alcohol and
Centrifugation layering again after deionized water washing suspension, repeats 3~5 times, the suspension after cleaning is freeze-dried to obtain
Surface modification has the nano micro crystal cellulose of iron-tannic acid film layer, and the temperature of freeze-drying is -80 DEG C~-40 DEG C, pressure 10
~80Pa, time are 5~20 hours, wherein, centrifuge speed is 7000~12000r/min；
B, the nano micro crystal cellulose ultrasonic disperse by the iron obtained through step A-tannic acid film layer modification is containing low-surface-energy
In the mixed solution of the 100mL second alcohol and waters of a concentration of 0.01~0.1mol/L of substance, the frequency of ultrasonic wave for 20~
50KHz, the wherein volume ratio of second alcohol and water are 7:3, it is 8~10 to be adjusted above-mentioned dispersion liquid to pH value with triethylamine, 25~
Under the conditions of 40 DEG C, after being stirred to react 6~24 hours, the dispersion liquid obtained after reaction is subjected to centrifugation layering, discards supernatant liquor,
Lower floor's suspension not soluble in water is obtained, and layering is centrifuged again after washing lower floor's suspension with ethyl alcohol and deionized water respectively,
Repeat 3~5 times, by the suspension after cleaning it is freeze-dried after obtain the nano micro crystal cellulose of surface-hydrophobicized modification, it is cold
It is -80 DEG C~-40 DEG C that dry temperature, which is lyophilized, and pressure is 10~80Pa, and the time is 5~20 hours, wherein, centrifuge speed is
7000~12000r/min.
2. a kind of hydrophobic modification method of nano micro crystal cellulose according to claim 1, it is characterised in that：It is described to receive
Rice microcrystalline cellulose is in the nano micro crystal cellulose prepared using cotton fiber or bamboo fibre or flaxen fiber or wood pulp as raw material
It is a kind of.
3. a kind of hydrophobic modification method of nano micro crystal cellulose according to claim 1, it is characterised in that：It is described to receive
Rice microcrystalline cellulose shape is rodlike or ellipticity, a diameter of 10~100nm.
4. a kind of hydrophobic modification method of nano micro crystal cellulose according to claim 1, it is characterised in that：It is described low
Surface energy substance is one kind in n-dodecyl mercaptan or n-octadecane base mercaptan or n-dodecylamine or octadecyl amine.
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| CN115894967B (en) * | 2022-12-02 | 2023-09-12 | 江苏海洋大学 | Preparation method of PVA composite hydrogel |
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