CN112480275B - Modified nano-cellulose and preparation method and application thereof - Google Patents

Modified nano-cellulose and preparation method and application thereof Download PDF

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CN112480275B
CN112480275B CN201910857465.1A CN201910857465A CN112480275B CN 112480275 B CN112480275 B CN 112480275B CN 201910857465 A CN201910857465 A CN 201910857465A CN 112480275 B CN112480275 B CN 112480275B
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cellulose
preparation
nanocellulose
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CN112480275A (en
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黄勇
董西龙
吴敏
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Technical Institute of Physics and Chemistry of CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
    • C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
    • D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Food Science & Technology (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
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Abstract

The invention provides a modified nano-cellulose and a preparation method and application thereof, wherein the preparation method of the modified nano-cellulose comprises the following steps: the cellulose or the cellulose derivative and 3, 4-dichlorophenyl isocyanate are ball milled together in an aprotic polar organic solvent. The invention adopts a mechanochemical method, and applies mechanical force while utilizing 3, 4-dichlorophenyl isocyanate to carry out chemical modification on cellulose or cellulose derivatives, so as to prepare the modified nano-cellulose with water resistance and ultraviolet resistance by one step, thus being simple and efficient; and the chemical modification and the ball milling play a synergistic role, so that the diameter of the obtained modified nano-cellulose is smaller, and the transparency of the film prepared from the modified nano-cellulose is better.

Description

Modified nano-cellulose and preparation method and application thereof
Technical Field
The invention relates to the field of nanofiber materials, in particular to modified nanocellulose and a preparation method and application thereof.
Background
With the development of nanotechnology, nanocellulose has become a functional polymer material with wide application. Nanocellulose is generally a cellulose that is broken down from natural cellulose or cellulose derivatives into nano-scale cellulose by a series of physical or chemical treatments.
Due to their outstanding physical and chemical properties, such as nano-scale, excellent mechanical properties, renewability, biodegradability, etc., nanocellulose is highly desired and it is desirable to expand the use of nanocellulose by modification, for example as a water-resistant uv-resistant material.
In the prior art, most of nano-cellulose with water resistance and ultraviolet resistance is prepared by preparing cellulose into nano-cellulose and then chemically modifying the nano-cellulose, wherein the common chemical modification method comprises esterification reaction and etherification reactionThe nanocellulose is rendered hydrophobic, and is then coated with TiO2、ZnO、Al2O3And the metal oxide or other modification methods endow the nano-cellulose with ultraviolet resistance. However, such a preparation method is excessively complicated and reaction conditions are often severe.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides modified nano-cellulose and a preparation method and application thereof.
In a first aspect, the present invention provides a method for preparing a modified nanocellulose, comprising: the cellulose or the cellulose derivative and 3, 4-dichlorophenyl isocyanate are ball milled together in an aprotic polar organic solvent.
The invention adopts a mechanochemical method, and applies mechanical force while utilizing 3, 4-dichlorophenyl isocyanate to carry out chemical modification on cellulose or cellulose derivatives, so as to prepare the modified nano-cellulose with water resistance and ultraviolet resistance by one step, thus being simple and efficient; and the monoisocyanate exerts a synergistic effect on the chemical modification and the ball milling of the modified nanocellulose, so that the diameter of the obtained modified nanocellulose is smaller, about 2nm, and is much finer than the nanocellulose with the diameter of more than ten nanometers prepared in the prior art, and the modified nanocellulose is superfine fiber, so that the transparency of the prepared modified nanocellulose after being prepared into a film is better.
The cellulose in the invention refers to plant cellulose, animal cellulose and bacterial cellulose; cellulose derivatives include hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, cyanoethyl cellulose, cellulose nitrate, cellulose acetate, cellulose sulfonate and the like.
Furthermore, the molar ratio of the hydroxyl group in the cellulose or the cellulose derivative to the 3, 4-dichlorophenyl isocyanate is 10: 1-1: 10, and more preferably 1: 2.
The inventor finds that the ratio is too low, the substitution degree of cellulose is low, the diameter of nano-cellulose is large, the hydrophobicity is poor, the transparency of a film prepared from the nano-cellulose is poor, and the ratio is too high, so that the waste of reagents is caused. Under the ratio of 1:2, the nano-cellulose has high substitution degree, small diameter and high hydrophobicity, and the film prepared from the nano-cellulose has high transparency.
Further, the aprotic polar organic solvent is one or more of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, 1, 3-dimethyl-2-imidazolidinone, and N-methylpyrrolidone.
Further, the mass ratio of the cellulose or the cellulose derivative to the aprotic polar organic solvent is 0.5-10: 100.
In a preferred embodiment of the present invention, the aprotic polar organic solvent is dimethyl sulfoxide.
Further, the rotating speed of the ball mill is 100-10000 r/min, and the time is 1-3 h.
In a second aspect, the invention provides a modified nanocellulose prepared by any one of the above preparation methods.
The diameter of the modified nano-cellulose prepared by the method is about 2nm, and the modified nano-cellulose is superfine fiber and has good hydrophobicity and ultraviolet resistance.
The modified nano cellulose is dispersed in solvents such as N, N-dimethylformamide and the like, and then is subjected to suction filtration to form a film, so that the nano cellulose film with good transparency can be obtained.
In a third aspect, the invention provides an application of the modified nanocellulose in preparing an ultraviolet-resistant material, a water-resistant material, a transparent packaging material or a transparent substrate material of a flexible electronic device.
The invention adopts a mechanochemical method, and applies mechanical force while utilizing 3, 4-dichlorophenyl isocyanate to carry out chemical modification on cellulose or cellulose derivatives, so as to prepare the modified nano-cellulose with water resistance and ultraviolet resistance by one step, thus being simple and efficient; and the chemical modification and the ball milling play a synergistic role, so that the diameter of the obtained modified nano-cellulose is smaller, and the transparency of the film prepared from the modified nano-cellulose is better.
Drawings
FIG. 1 is an infrared spectrum of unmodified nanocellulose and modified nanocellulose;
FIG. 2 is an AFM image of unmodified nanocellulose and modified nanocellulose;
FIG. 3 is a graph of water contact angles for unmodified nanocellulose and modified nanocellulose;
FIG. 4 is an electron photograph of an unmodified nanocellulose membrane and a modified nanocellulose membrane;
FIG. 5 is a UV spectrum of an unmodified nanocellulose membrane and a modified nanocellulose membrane;
fig. 6 is a water contact angle graph of the modified nanocellulose in example 3.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
The embodiment provides a preparation method of modified nanocellulose, which comprises the following steps:
0.5g of bamboo pulp and 3.4819g of 3, 4-dichlorophenyl isocyanate (wherein the molar ratio of the 3, 4-dichlorophenyl isocyanate to the hydroxyl in the bamboo pulp is 2:1) are weighed and added into a ball mill, and then 20mL of dimethyl sulfoxide is added, and ball milling is carried out for 2 hours together at the rotating speed of 200 r/min.
Example 2
The embodiment provides a preparation method of modified nanocellulose, which comprises the following steps:
0.5g of corncob cellulose and 3.4819g of 3, 4-dichlorophenyl isocyanate (wherein the molar ratio of the 3, 4-dichlorophenyl isocyanate to hydroxyl in the corncob cellulose is 2:1) are weighed and added into a ball mill, then 25mL of dimethyl sulfoxide is added, and ball milling is carried out for 2 hours at the rotating speed of 300 revolutions per minute.
Example 3
The embodiment provides a preparation method of modified nanocellulose, which comprises the following steps:
0.5g of corncob cellulose and 0.1741g of 3, 4-dichlorophenyl isocyanate (wherein the molar ratio of the 3, 4-dichlorophenyl isocyanate to hydroxyl in the corncob cellulose is 1:10) are weighed and added into a ball mill, and then 20mL of dimethyl sulfoxide is added, and ball milling is carried out for 2 hours at the rotating speed of 200 r/min.
Comparative example 1
The comparative example provides a method for preparing unmodified nanocellulose, comprising the following steps:
0.5g of bamboo pulp is weighed and added into a ball mill, and then 20mL of dimethyl sulfoxide is added, and the mixture is ball milled for 2 hours together at the rotating speed of 200 r/min.
Performance testing
The modified nanocellulose obtained in example 1 and the unmodified nanocellulose obtained in comparative example 1 were subjected to a performance test, and the results were as follows:
FIG. 1 is an infrared spectrum of unmodified nanocellulose and modified nanocellulose, with the modified nanocellulose at 1720cm compared to unmodified nanocellulose-1The peak of COO ester group appears, indicating that the reaction between cellulose and 3, 4-dichlorophenyl isocyanate has been successful.
FIG. 2 is an AFM image of unmodified nanocellulose and modified nanocellulose, wherein a is an AFM image of unmodified nanocellulose, and it can be seen that the dimensions thereof are not uniform, the diameter is from several nanometers to tens of nanometers, and cellulose defibration is insufficient; and b is an AFM image of the modified nano-cellulose, and the modified nano-cellulose is uniform in size, has the diameter of about 2nm and is an ultrafine fiber.
Fig. 3 is a water contact angle graph of unmodified nanocellulose and modified nanocellulose, wherein a shows that the water contact angle of unmodified nanocellulose is only 42 °, and b shows that the water contact angle of modified nanocellulose can reach 90 °.
The preparation method of the nano cellulose membrane comprises the following steps: dispersing the nano-cellulose in N, N-dimethylformamide, and filtering to form a film. The performance of the nanocellulose membranes was tested.
Fig. 4 is an electron photograph of the unmodified nano cellulose film and the modified nano cellulose film, and it can be seen that the transparency of the unmodified nano cellulose film a is poor, and the transparency of the modified nano cellulose film b is good.
Fig. 5 is a uv spectrum of the unmodified nano cellulose film and the modified nano cellulose film, and it can be seen that the transmittance of the modified nano cellulose film in the visible light region exceeds 70%, and the transmittance in the uv region below 300nm is reduced to below 1%, while the unmodified nano cellulose film still has a higher transmittance in the uv region.
In addition, the water contact angle of the modified nanocellulose of example 3 was measured, and as a result, as shown in fig. 6, it can be seen that the contact angle was improved to some extent compared with the unmodified cellulose due to the difference in the raw material ratio in this example, but the effect was not as good as in example 1.
In conclusion, the modified nano cellulose prepared by the embodiment of the invention has the diameter of about 2nm, is a superfine fiber, has good hydrophobicity and ultraviolet resistance, and has good transparency and ultraviolet resistance after being prepared into a nano cellulose film.
Finally, the examples are only preferred embodiments and are not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. A preparation method of modified nano-cellulose is characterized by comprising the following steps: carrying out ball milling on cellulose or a cellulose derivative and 3, 4-dichlorophenyl isocyanate in an aprotic polar organic solvent, wherein the molar ratio of hydroxyl in the cellulose or the cellulose derivative to the 3, 4-dichlorophenyl isocyanate is 1: 2;
the cellulose derivative comprises hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, cyanoethyl cellulose, cellulose nitrate, cellulose acetate and cellulose sulfonate.
2. The method according to claim 1, wherein the aprotic polar organic solvent is one or more of dimethylsulfoxide, N-dimethylformamide, N-dimethylacetamide, 1, 3-dimethyl-2-imidazolidinone, and N-methylpyrrolidone.
3. The method according to claim 2, wherein the mass ratio of the cellulose or the cellulose derivative to the aprotic polar organic solvent is 0.5 to 10: 100.
4. The method according to claim 3, wherein the aprotic polar organic solvent is dimethyl sulfoxide.
5. The preparation method according to any one of claims 1 to 4, wherein the rotation speed of the ball mill is 100 to 10000 rpm and the time is 1 to 3 hours.
6. A modified nanocellulose, characterized by being produced by the production method according to any one of claims 1 to 5.
7. Use of the modified nanocellulose as claimed in claim 6 in the preparation of uv resistant materials, water resistant materials, transparent packaging materials or transparent substrate materials for flexible electronic devices.
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CN103132169A (en) * 2011-11-30 2013-06-05 中国科学院理化技术研究所 Preparation method for cellulose nano-fibers capable of dispersing stably
CN103333259A (en) * 2013-07-03 2013-10-02 福建农林大学 Method for preparing esterified nanocellulose through mechanochemical synchronization reaction
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JP2018030965A (en) * 2016-08-26 2018-03-01 株式会社ダイセル Amylose derivative and separation agent for optical isomers containing the same
CN109503724A (en) * 2018-11-05 2019-03-22 大连理工大学 The Cellulose nanocrystal of organic acid catalysis one kettle way preparation acetylation

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CN103132169A (en) * 2011-11-30 2013-06-05 中国科学院理化技术研究所 Preparation method for cellulose nano-fibers capable of dispersing stably
CN103333259A (en) * 2013-07-03 2013-10-02 福建农林大学 Method for preparing esterified nanocellulose through mechanochemical synchronization reaction
CN105885096A (en) * 2015-01-26 2016-08-24 中国科学院理化技术研究所 Hydrophobic cellulosic material and preparing method and application thereof
JP2018030965A (en) * 2016-08-26 2018-03-01 株式会社ダイセル Amylose derivative and separation agent for optical isomers containing the same
CN109503724A (en) * 2018-11-05 2019-03-22 大连理工大学 The Cellulose nanocrystal of organic acid catalysis one kettle way preparation acetylation

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