CN112267157A - Preparation method of cellulose nano-fibrils modified based on reactive eutectic solvent - Google Patents
Preparation method of cellulose nano-fibrils modified based on reactive eutectic solvent Download PDFInfo
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- CN112267157A CN112267157A CN202011185093.1A CN202011185093A CN112267157A CN 112267157 A CN112267157 A CN 112267157A CN 202011185093 A CN202011185093 A CN 202011185093A CN 112267157 A CN112267157 A CN 112267157A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
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- 238000000034 method Methods 0.000 claims abstract description 36
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- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
-
- 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
-
- 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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/02—Chemical after-treatment of artificial filaments or the like during manufacture of cellulose, cellulose derivatives, or proteins
Abstract
The invention discloses a preparation method of cellulose nanofibrils modified based on a reactive eutectic solvent, which comprises the steps of adding a paper pulp raw material into the eutectic solvent for modification pretreatment to obtain paper pulp fibers, and carrying out superfine grinding treatment on pulp slurry of the paper pulp fibers to obtain the modified cellulose nanofibrils, wherein hydrogen bond acceptors in the eutectic solvent comprise sulfamic acid. The method has the advantages of simple operation, low energy loss and small environmental pollution, and can effectively improve the preparation process of the modified cellulose nanofibrils.
Description
Technical Field
The invention belongs to the field of lignocellulose materials, and relates to a method for preparing cellulose nanofibrils based on reactive eutectic solvent modification.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Cellulose is the most abundant, renewable natural polymer on earth and can be extracted from a variety of sources, such as wood, bast fibers, grass, seed fibers, marine animals, algae, fungi, bacteria, and the like. Cellulose has the characteristics of biocompatibility, biodegradability, sustainability and the like, and is widely applied to the fields of papermaking, spinning, medicines and the like. The utilization of cellulose has great significance for the sustainable development of human beings in the future.
In recent years, the separation of Cellulose Nanofibrils (CNF) from natural cellulose has received great attention. CNF is a long entangled fiber with a diameter in the nanometer range, which is mainly composed of two parts, an amorphous region and a crystalline region. The method for extracting CNF from cellulose fiber includes: (1) mechanical treatment; (2) chemical treatment; (3) chemical treatment and mechanical treatment are combined. The CNF has excellent mechanical properties, high specific surface area, low thermal expansion coefficient, high length-width ratio and environmental benefits, and has wide application in the fields of medicine, environment, energy, textile, paper making and the like.
The CNF has abundant hydroxyl groups on its surface, which makes it well hydrophilic, but this also results in the CNF not being uniformly dispersed in most non-polar polymer media, and thus, in order to broaden the application of CNF, it is necessary to modify CNF. Common methods for modifying CNF include surface adsorption modification, chemical graft modification, and polymer graft modification. The surface adsorption modification is a method for realizing the modification of the CNF by adsorbing a functional substance on the surface of the CNF by using a physical adsorption method, and the CNF modified by using the method has poor stability under special environments such as high temperature, high salt and the like; chemical grafting modification is a method for grafting a single molecule or a polymer on the surface of CNF by using a chemical method, and the method usually occurs in the pretreatment process of hydroxyl or cellulose fiber on the surface of CNF, so that the application range is wide, and the modified CNF is relatively stable; the polymer grafting modification is a method for grafting a polymer on the surface of the CNF, and the method has wide application and is a common method for modifying the CNF, but the method has complex operation and is not beneficial to the industrial production of the modified CNF.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a method for preparing cellulose nanofibrils modified based on a reactive eutectic solvent, which has the advantages of simple operation, low energy loss and small environmental pollution, and can effectively improve the preparation process of modified CNF.
In order to achieve the technical purpose, the invention is realized by the following technical scheme.
On the one hand, the preparation method of the cellulose nanofibrils modified based on the reactive eutectic solvent comprises the steps of adding a paper pulp raw material into the eutectic solvent for modification pretreatment to obtain paper pulp fibers, and carrying out superfine grinding treatment on pulp slurry of the paper pulp fibers to obtain the modified cellulose nanofibrils, wherein hydrogen bond acceptors in the eutectic solvent comprise sulfamic acid.
According to the invention, firstly, the eutectic solvent containing sulfamic acid is used for carrying out one-step modification separation on fibers, and then the modified cellulose is treated to prepare the cellulose nanofibrils, various methods for preparing the cellulose nanofibrils are provided, such as a high-pressure homogenization method, a grinding method, a high-intensity ultrasonic method, an electrostatic spinning method and the like, however, researches show that the cellulose obtained by carrying out one-step modification separation on the fibers by using the eutectic solvent containing sulfamic acid is difficult to prepare the cellulose nanofibrils by using a conventional method such as the high-intensity ultrasonic method, and the like.
In another aspect, a sulfonated cellulose nanofibril is obtained from the above method for preparing a cellulose nanofibril modified based on a reactive eutectic solvent.
In a third aspect, the sulfonated cellulose nanofibrils are used in the fields of nanocomposites, plastics, packaging, paper making, medicines and the like.
The invention has the beneficial effects that:
(1) according to the method, the deep eutectic solvent is used for modifying and pretreating the paper pulp raw material, so that cellulose is swelled, the sulfonic acid group is grafted to cellulose molecules, the energy loss of subsequent treatment by an ultrafine pulverizer is greatly reduced, and the CNF with a good modification effect is successfully prepared.
(2) The preparation method disclosed by the invention is simple to operate, low in cost, green and environment-friendly, does not need to add other reagents, can obtain the modified CNF with high performance and high yield only through pretreatment and mechanical treatment of the eutectic solvent, reduces the energy loss, enlarges the application range of the CNF, and the used eutectic solvent can be recovered through methods such as rotary evaporation and the like, so that the CNF can be recycled, and the method is favorable for industrial production of the modified CNF.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a scanning electron micrograph of a modified CNF provided in example 1-1 of the present invention.
FIG. 2 is a scanning electron micrograph of the modified CNF provided in example 2-1 of the present invention.
FIG. 3 is a scanning electron micrograph of the modified CNF provided in example 3-1 of the present invention.
FIG. 4 is a scanning electron micrograph of the modified CNF provided in example 4-1 of the present invention.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The invention provides a preparation method of cellulose nanofibrils modified based on a reactive eutectic solvent, which is provided by the invention.
The invention provides a preparation method of cellulose nanofibrils modified based on a reaction type eutectic solvent, which comprises the steps of adding a pulp raw material into the eutectic solvent for modification pretreatment to obtain pulp fibers, and carrying out superfine grinding treatment on pulp fiber slurry to obtain the modified cellulose nanofibrils, wherein hydrogen bond acceptors in the eutectic solvent comprise sulfamic acid.
In some examples of this embodiment, sulfamic acid is used as the hydrogen bond acceptor and glycerol is used as the hydrogen bond donor in the eutectic solvent. In the binary eutectic solvent, the cellulose in the paper pulp raw material can be sulfonated and modified by the eutectic solvent prepared from sulfamic acid and glycerol.
In one or more embodiments, the molar ratio of sulfamic acid to glycerol is 1:2 to 3.
In one or more embodiments, the temperature for preparing the eutectic solvent is 90-100 ℃, and the reaction time is 2-4 hours.
In one or more embodiments, the temperature of the modification pretreatment is 90-100 ℃, and the time of the modification pretreatment is 60-90 min.
In some examples of this embodiment, the pulp feedstock is bleached chemical poplar pulp. When the cellulose content of the bleached chemical poplar pulp is 85-87%, the effect is better.
In some examples of this embodiment, the pulp feedstock is dried prior to addition of the eutectic solvent. The drying conditions were: drying for 24-26 h at 50-60 ℃.
In some examples of this embodiment, the pulp feedstock has a cellulose to sulfamic acid molar ratio of 1:10 to 20 in the modifying pretreatment.
In some examples of this embodiment, the pulp fiber slurry has a consistency of 0.7 to 1.0%.
In some examples of this embodiment, the number of times of the ultrafine pulverization treatment is 10 to 15 times.
In some examples of this embodiment, the micronization process is followed by freeze-drying.
In one or more embodiments, the freeze-drying time is 45 to 48 hours.
In another embodiment of the present invention, there is provided a sulfonated cellulose nanofibril obtained by the above method for preparing a cellulose nanofibril modified based on a reactive eutectic solvent.
In a third embodiment of the present invention, there is provided an application of the sulfonated cellulose nanofibrils in the fields of nanocomposites, plastics, packaging, paper making, medicine, and the like.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Examples 1 to 1
(1) Drying in an oven: the bleached chemical poplar pulp was oven dried at 60 ℃ for 24 h.
(2) Preparing a eutectic solvent: sulfamic acid and glycerol were mixed in a molar ratio of 1:2 and reacted at 90 ℃ for 2h by heating in an oil bath.
(3) Pretreatment of eutectic solvent: adding the dried bleached chemical poplar pulp into a eutectic solvent system, wherein the molar ratio of the bleached chemical poplar pulp cellulose to the sulfamic acid is 1:10, and treating for 60min at 100 ℃.
(4) And (3) bleaching chemical poplar pulp fibers after separation treatment: adding deionized water into the reaction system in the step (3) to stop the reaction, and then separating the pulp fibers from the mixed liquid.
(5) And (3) processing by an ultrafine pulverizer: preparing the paper pulp fiber separated in the step (4) into 1.0% thick pulp, and then carrying out crushing treatment by using an ultrafine crusher for 10 times;
(6) and (3) freeze drying: the freeze-drying time was 48 h.
The modified CNF prepared in this example has a degree of substitution of 0.07, a diameter of 60-120 nm, a Zeta potential of-33.43 mV, and a crystallinity of 54.54%, as shown in FIG. 1.
Examples 1 to 2
(1) Drying in an oven: the bleached chemical poplar pulp was oven dried at 60 ℃ for 24 h.
(2) Preparing a eutectic solvent: sulfamic acid and glycerol were mixed in a molar ratio of 1:2 and reacted at 90 ℃ for 2h by heating in an oil bath.
(3) Pretreatment of eutectic solvent: adding the dried bleached chemical poplar pulp into a eutectic solvent system, wherein the molar ratio of the bleached chemical poplar pulp cellulose to the sulfamic acid is 1:15, and treating for 60min at 100 ℃.
(4) And (3) bleaching chemical poplar pulp fibers after separation treatment: adding deionized water into the reaction system in the step (3) to stop the reaction, and then separating the pulp fibers from the mixed liquid.
(5) And (3) processing by an ultrafine pulverizer: preparing the pulp fiber separated in the step (4) into 1.0% thick pulp, and then carrying out crushing treatment by using an ultrafine crusher for 10 times.
(6) And (3) freeze drying: the freeze-drying time was 48 h.
The modified CNF prepared by the embodiment has the substitution degree of 0.06, the diameter of 30-100 nm, the Zeta potential of-33.03 mV and the crystallinity of 62.84%.
Examples 1 to 3
(1) Drying in an oven: the bleached chemical poplar pulp was oven dried at 60 ℃ for 24 h.
(2) Preparing a eutectic solvent: sulfamic acid and glycerol were mixed in a molar ratio of 1:2 and reacted at 90 ℃ for 2h by heating in an oil bath.
(3) Pretreatment of eutectic solvent: adding the dried bleached chemical poplar pulp into a eutectic solvent system, wherein the molar ratio of the bleached chemical poplar pulp cellulose to the sulfamic acid is 1:20, and treating for 60min at 100 ℃.
(4) And (3) bleaching chemical poplar pulp fibers after separation treatment: adding deionized water into the reaction system in the step (3) to stop the reaction, and then separating the pulp fibers from the mixed liquid.
(5) And (3) processing by an ultrafine pulverizer: preparing the pulp fiber separated in the step (4) into 1.0% thick pulp, and then carrying out crushing treatment by using an ultrafine crusher for 10 times.
(6) And (3) freeze drying: the freeze-drying time was 48 h.
The modified CNF prepared in the embodiment has the substitution degree of 0.07, the diameter of 40-100 nm, the Zeta potential of-31.83 mV and the crystallinity of 60.06%.
Example 2-1
(1) Drying in an oven: drying bleached chemical poplar pulp in an oven at 60 ℃ for 24 hours;
(2) preparing a eutectic solvent: sulfamic acid and glycerol were mixed in a molar ratio of 1:2 and reacted at 90 ℃ for 2h by heating in an oil bath.
(3) Pretreatment of eutectic solvent: adding the dried bleached chemical poplar pulp into a eutectic solvent system, wherein the molar ratio of the bleached chemical poplar pulp cellulose to the sulfamic acid is 1:10, and treating for 90min at 100 ℃.
(4) And (3) bleaching chemical poplar pulp fibers after separation treatment: adding deionized water into the reaction system in the step (3) to stop the reaction, and then separating the pulp fibers from the mixed liquid.
(5) And (3) processing by an ultrafine pulverizer: preparing the pulp fiber separated in the step (4) into 1.0% thick pulp, and then carrying out crushing treatment by using an ultrafine crusher for 10 times.
(6) And (3) freeze drying: the freeze-drying time was 48 h.
The modified CNF prepared in this example has a degree of substitution of 0.11, a diameter of 40-100 nm, a Zeta potential of-38.57 mV, and a crystallinity of 53.29%, as shown in FIG. 2.
Examples 2 to 2
(1) Drying in an oven: the bleached chemical poplar pulp was oven dried at 60 ℃ for 24 h.
(2) Preparing a eutectic solvent: sulfamic acid and glycerol were mixed in a molar ratio of 1:2 and reacted at 90 ℃ for 2h by heating in an oil bath.
(3) Pretreatment of eutectic solvent: adding the dried bleached chemical poplar pulp into a eutectic solvent system, wherein the molar ratio of the bleached chemical poplar pulp cellulose to the sulfamic acid is 1:15, and treating for 90min at 100 ℃.
(4) And (3) bleaching chemical poplar pulp fibers after separation treatment: adding deionized water into the reaction system in the step (3) to stop the reaction, and then separating the pulp fibers from the mixed liquid.
(5) And (3) processing by an ultrafine pulverizer: preparing the pulp fiber separated in the step (4) into 1.0% thick pulp, and then carrying out crushing treatment by using an ultrafine crusher for 10 times.
(6) And (3) freeze drying: the freeze-drying time was 48 h.
The modified CNF prepared by the embodiment has the substitution degree of 0.1, the diameter of 20-90 nm, the Zeta potential of-33.2 mV and the crystallinity of 65.22%.
Examples 2 to 3
(1) Drying in an oven: the bleached chemical poplar pulp was oven dried at 60 ℃ for 24 h.
(2) Preparing a eutectic solvent: sulfamic acid and glycerol were mixed in a molar ratio of 1:2 and reacted at 90 ℃ for 2h by heating in an oil bath.
(3) Pretreatment of eutectic solvent: adding the dried bleached chemical poplar pulp into a eutectic solvent system, wherein the molar ratio of the bleached chemical poplar pulp cellulose to the sulfamic acid is 1:20, and treating for 90min at 100 ℃.
(4) And (3) bleaching chemical poplar pulp fibers after separation treatment: adding deionized water into the reaction system in the step (3) to stop the reaction, and then separating the pulp fibers from the mixed liquid.
(5) And (3) processing by an ultrafine pulverizer: preparing the pulp fiber separated in the step (4) into 1.0% thick pulp, and then carrying out crushing treatment by using an ultrafine crusher for 10 times.
(6) And (3) freeze drying: the freeze-drying time was 48 h.
The modified CNF prepared in the embodiment has the substitution degree of 0.17, the diameter of 30-60 nm, the Zeta potential of-40.57 mV and the crystallinity of 64.03%.
Example 3-1
(1) Drying in an oven: the bleached chemical poplar pulp was oven dried at 60 ℃ for 24 h.
(2) Preparing a eutectic solvent: sulfamic acid and glycerol were mixed in a molar ratio of 1:3 and reacted at 90 ℃ for 2h by heating in an oil bath.
(3) Pretreatment of eutectic solvent: adding the dried bleached chemical poplar pulp into a eutectic solvent system, wherein the molar ratio of the bleached chemical poplar pulp cellulose to the sulfamic acid is 1:10, and treating for 60min at 100 ℃.
(4) And (3) bleaching chemical poplar pulp fibers after separation treatment: adding deionized water into the reaction system in the step (3) to stop the reaction, and then separating the pulp fibers from the mixed liquid.
(5) And (3) processing by an ultrafine pulverizer: preparing the pulp fiber separated in the step (4) into 1.0% thick pulp, and then carrying out crushing treatment by using an ultrafine crusher for 10 times.
(6) And (3) freeze drying: the freeze-drying time was 48 h.
The modified CNF prepared in this example has a degree of substitution of 0.08, a diameter of 40-110 nm, a Zeta potential of-30.03 mV, and a crystallinity of 61.65%, as shown in FIG. 3.
Examples 3 to 2
(1) Drying in an oven: the bleached chemical poplar pulp was oven dried at 60 ℃ for 24 h.
(2) Preparing a eutectic solvent: sulfamic acid and glycerol were mixed in a molar ratio of 1:3 and reacted at 90 ℃ for 2h by heating in an oil bath.
(3) Pretreatment of eutectic solvent: adding the dried bleached chemical poplar pulp into a eutectic solvent system, wherein the molar ratio of the bleached chemical poplar pulp cellulose to the sulfamic acid is 1:15, and treating for 60min at 100 ℃.
(4) And (3) bleaching chemical poplar pulp fibers after separation treatment: adding deionized water into the reaction system in the step (3) to stop the reaction, and then separating the pulp fibers from the mixed liquid.
(5) And (3) processing by an ultrafine pulverizer: preparing the pulp fiber separated in the step (4) into 1.0% thick pulp, and then carrying out crushing treatment by using an ultrafine crusher for 10 times.
(6) And (3) freeze drying: the freeze-drying time was 48 h.
The modified CNF prepared by the embodiment has the substitution degree of 0.03, the diameter of 30-100 nm, the Zeta potential of-26.23 mV and the crystallinity of 57.55%.
Examples 3 to 3
(1) Drying in an oven: the bleached chemical poplar pulp was oven dried at 60 ℃ for 24 h.
(2) Preparing a eutectic solvent: sulfamic acid and glycerol were mixed in a molar ratio of 1:3 and reacted at 90 ℃ for 2h by heating in an oil bath.
(3) Pretreatment of eutectic solvent: adding the dried bleached chemical poplar pulp into a eutectic solvent system, wherein the molar ratio of the bleached chemical poplar pulp cellulose to the sulfamic acid is 1:20, and treating for 60min at 100 ℃.
(4) And (3) bleaching chemical poplar pulp fibers after separation treatment: adding deionized water into the reaction system in the step (3) to stop the reaction, and then separating the pulp fibers from the mixed liquid.
(5) And (3) processing by an ultrafine pulverizer: preparing the pulp fiber separated in the step (4) into 1.0% thick pulp, and then carrying out crushing treatment by using an ultrafine crusher for 10 times.
(6) And (3) freeze drying: the freeze-drying time was 48 h.
The modified CNF prepared in the embodiment has the substitution degree of 0.05, the diameter of 70-120 nm, the Zeta potential of-30.87 mV and the crystallinity of 54.81%.
Example 4-1
(1) Drying in an oven: the bleached chemical poplar pulp was oven dried at 60 ℃ for 24 h.
(2) Preparing a eutectic solvent: sulfamic acid and glycerol were mixed in a molar ratio of 1:3 and reacted at 90 ℃ for 2h by heating in an oil bath.
(3) Pretreatment of eutectic solvent: adding the dried bleached chemical poplar pulp into a eutectic solvent system, wherein the molar ratio of the bleached chemical poplar pulp cellulose to the sulfamic acid is 1:10, and treating for 90min at 100 ℃.
(4) And (3) bleaching chemical poplar pulp fibers after separation treatment: adding deionized water into the reaction system in the step (3) to stop the reaction, and then separating the pulp fibers from the mixed liquid.
(5) And (3) processing by an ultrafine pulverizer: preparing the pulp fiber separated in the step (4) into 1.0% thick pulp, and then carrying out crushing treatment by using an ultrafine crusher for 10 times.
(6) And (3) freeze drying: the freeze-drying time was 48 h.
The modified CNF prepared in this example has a degree of substitution of 0.09, a diameter of 20-70 nm, a Zeta potential of-30.4 mV, and a crystallinity of 60.21%, as shown in FIG. 4.
Example 4 to 2
(1) Drying in an oven: the bleached chemical poplar pulp was oven dried at 60 ℃ for 24 h.
(2) Preparing a eutectic solvent: sulfamic acid and glycerol were mixed in a molar ratio of 1:3 and reacted at 90 ℃ for 2h by heating in an oil bath.
(3) Pretreatment of eutectic solvent: adding the dried bleached chemical poplar pulp into a eutectic solvent system, wherein the molar ratio of the bleached chemical poplar pulp cellulose to the sulfamic acid is 1:15, and treating for 90min at 100 ℃.
(4) And (3) bleaching chemical poplar pulp fibers after separation treatment: adding deionized water into the reaction system in the step (3) to stop the reaction, and then separating the pulp fibers from the mixed liquid.
(5) And (3) processing by an ultrafine pulverizer: preparing the pulp fiber separated in the step (4) into 1.0% thick pulp, and then carrying out crushing treatment by using an ultrafine crusher for 10 times.
(6) And (3) freeze drying: the freeze-drying time was 48 h.
The modified CNF prepared by the embodiment has the substitution degree of 0.09, the diameter of 20-90 nm, the Zeta potential of-29.7 mV and the crystallinity of 58.51%.
Examples 4 to 3
(1) Drying in an oven: the bleached chemical poplar pulp was oven dried at 60 ℃ for 24 h.
(2) Preparing a eutectic solvent: sulfamic acid and glycerol were mixed in a molar ratio of 1:3 and reacted at 90 ℃ for 2h by heating in an oil bath.
(3) Pretreatment of eutectic solvent: adding the dried bleached chemical poplar pulp into a eutectic solvent system, wherein the molar ratio of the bleached chemical poplar pulp cellulose to the sulfamic acid is 1:20, and treating for 90min at 100 ℃.
(4) And (3) bleaching chemical poplar pulp fibers after separation treatment: adding deionized water into the reaction system in the step (3) to stop the reaction, and then separating the pulp fibers from the mixed liquid.
(5) And (3) processing by an ultrafine pulverizer: preparing the pulp fiber separated in the step (4) into 1.0% thick pulp, and then carrying out crushing treatment by using an ultrafine crusher for 10 times.
(6) And (3) freeze drying: the freeze-drying time was 48 h.
The modified CNF prepared by the embodiment has the substitution degree of 0.12, the diameter of 20-60 nm, the Zeta potential of-33.73 mV and the crystallinity of 61.51%.
Comparative example 1
(1) Drying in an oven: the bleached chemical poplar pulp was oven dried at 60 ℃ for 24 h.
(2) Preparing a eutectic solvent: sulfamic acid and glycerol were mixed in a molar ratio of 1:2 and reacted at 90 ℃ for 2h by heating in an oil bath.
(3) Pretreatment of eutectic solvent: adding the dried bleached chemical poplar pulp into a eutectic solvent system, wherein the molar ratio of the bleached chemical poplar pulp cellulose to the sulfamic acid is 1:20, and treating for 60min at 100 ℃.
(4) And (3) bleaching chemical poplar pulp fibers after separation treatment: adding deionized water into the reaction system in the step (3) to stop the reaction, and then separating the pulp fibers from the mixed liquid.
(5) High-intensity ultrasonic treatment: preparing the paper pulp fiber separated in the step (4) into 1% thick pulp, and then carrying out ultrasonic treatment by using an ultrasonic crusher, wherein the used power is 1200w, and the treatment time is 30 min.
(6) And (3) freeze drying: the freeze-drying time was 48 h.
The cellulose prepared by the embodiment does not reach the nanometer level, a large amount of aggregation occurs, and the modified CNF cannot be prepared by combining pretreatment and ultrasonic treatment.
Comparative example 2
(1) Drying in an oven: the bleached chemical poplar pulp was oven dried at 60 ℃ for 24 h.
(2) Preparing a eutectic solvent: sulfamic acid and glycerol were mixed in a molar ratio of 1:3 and reacted at 90 ℃ for 2h by heating in an oil bath.
(3) Pretreatment of eutectic solvent: adding the dried bleached chemical poplar pulp into a eutectic solvent system, wherein the molar ratio of the bleached chemical poplar pulp cellulose to the sulfamic acid is 1:20, and treating for 60min at 100 ℃.
(4) And (3) bleaching chemical poplar pulp fibers after separation treatment: adding deionized water into the reaction system in the step (3) to stop the reaction, and then separating the pulp fibers from the mixed liquid.
(5) High-intensity ultrasonic treatment: preparing the paper pulp fiber separated in the step (4) into 1% thick pulp, and then carrying out ultrasonic treatment by using an ultrasonic crusher, wherein the used power is 1200w, and the treatment time is 30 min.
(6) And (3) freeze drying: the freeze-drying time was 48 h.
The cellulose prepared by the embodiment does not reach the nanometer level, a large amount of aggregation occurs, and the modified CNF cannot be prepared by combining pretreatment and ultrasonic treatment.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. 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 (10)
1. A preparation method of cellulose nanofibrils modified based on a reactive eutectic solvent is characterized in that a paper pulp raw material is added into the eutectic solvent for modification pretreatment to obtain paper pulp fibers, and pulp slurry of the paper pulp fibers is subjected to superfine grinding treatment to obtain the modified cellulose nanofibrils, wherein hydrogen bond acceptors in the eutectic solvent comprise sulfamic acid.
2. The method for preparing cellulose nanofibrils modified according to claim 1, wherein sulfamic acid is used as a hydrogen bond acceptor and glycerol is used as a hydrogen bond donor in the eutectic solvent;
preferably, the molar ratio of sulfamic acid to glycerol is 1: 2-3;
preferably, the temperature for preparing the eutectic solvent is 90-100 ℃, and the reaction time is 2-4 h;
preferably, the temperature of the modification pretreatment is 90-100 ℃, and the time of the modification pretreatment is 60-90 min.
3. The method for preparing cellulose nanofibrils based on reactive eutectic solvent modification according to claim 1, wherein the pulp raw material is bleached chemical poplar pulp.
4. The method for preparing cellulose nanofibrils modified according to claim 1, wherein the pulp raw material is dried before the eutectic solvent is added.
5. The method for preparing cellulose nanofibrils modified based on the reactive eutectic solvent according to claim 1, wherein in the modification pretreatment, the molar ratio of cellulose to sulfamic acid in the pulp raw material is 1: 10-20.
6. The method for preparing cellulose nanofibrils according to claim 1, wherein the concentration of the pulp fiber slurry is 0.7-1.0%.
7. The method for preparing the cellulose nanofibril modified based on the reactive eutectic solvent according to claim 1, wherein the number of times of the ultra-fine pulverization treatment is 10 to 15.
8. The method for preparing cellulose nanofibrils modified based on reactive eutectic solvent according to claim 1, wherein the microfine pulverization treatment is followed by freeze-drying;
preferably, the freeze drying time is 45-48 h.
9. A sulfonated cellulose nanofibril obtained by the method for preparing a cellulose nanofibril modified by a reactive eutectic solvent according to any one of claims 1 to 8.
10. Use of the sulfonated cellulose nanofibrils according to claim 9 in the field of nanocomposites, plastics, packaging, paper or medicine.
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