CN112142863A - Method for modifying cellulose by reactive eutectic solvent - Google Patents
Method for modifying cellulose by reactive eutectic solvent Download PDFInfo
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- CN112142863A CN112142863A CN202010967931.4A CN202010967931A CN112142863A CN 112142863 A CN112142863 A CN 112142863A CN 202010967931 A CN202010967931 A CN 202010967931A CN 112142863 A CN112142863 A CN 112142863A
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- 239000001913 cellulose Substances 0.000 title claims abstract description 118
- 229920002678 cellulose Polymers 0.000 title claims abstract description 118
- 239000002904 solvent Substances 0.000 title claims abstract description 97
- 230000005496 eutectics Effects 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 26
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 75
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000006011 modification reaction Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 79
- 239000007788 liquid Substances 0.000 claims description 30
- 238000000926 separation method Methods 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000010865 sewage Substances 0.000 claims description 3
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid group Chemical group S(N)(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001131 Pulp (paper) Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000002390 rotary evaporation Methods 0.000 abstract description 2
- 241000219000 Populus Species 0.000 description 72
- 239000000835 fiber Substances 0.000 description 52
- 238000006243 chemical reaction Methods 0.000 description 31
- 238000001035 drying Methods 0.000 description 26
- 238000012986 modification Methods 0.000 description 15
- 230000004048 modification Effects 0.000 description 15
- 238000006467 substitution reaction Methods 0.000 description 15
- 238000004061 bleaching Methods 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 230000000694 effects Effects 0.000 description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 papermaking Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(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)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 125000003535 D-glucopyranosyl group Chemical group [H]OC([H])([H])[C@@]1([H])OC([H])(*)[C@]([H])(O[H])[C@@]([H])(O[H])[C@]1([H])O[H] 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 238000009776 industrial production Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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Classifications
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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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/144—Alcohols; Metal alcoholates
- D06M13/148—Polyalcohols, e.g. glycerol or glucose
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
- D06M13/342—Amino-carboxylic acids; Betaines; Aminosulfonic acids; Sulfo-betaines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
Abstract
The invention discloses a method for modifying cellulose by using a reactive eutectic solvent, which comprises the steps of preparing the reactive eutectic solvent from sulfamic acid and glycerol, adding a cellulose raw material into the reactive eutectic solvent, and heating to 90-100 ℃ for modification reaction. The method is simple to operate, low in cost and environment-friendly; the used eutectic solvent can be recovered by methods such as rotary evaporation and the like, so that the eutectic solvent can be recycled.
Description
Technical Field
The invention belongs to the field of cellulose, and relates to a method for modifying cellulose by using a reactive eutectic solvent.
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 considered to be the most abundant natural polymer consisting of D-glucopyranose units linked by β (1 → 4) glycosidic linkages, is widely available, and can be extracted from a variety of renewable supplies of wood, algae, bacteria and more plants. Cellulose has a number of unique properties, particularly biocompatibility, biodegradability, low cost and chemical stability. These characteristics make cellulose a very promising renewable resource to replace fossil resources for the production of industrial materials, chemicals and biofuels.
In recent years, cellulose-based materials have received wide attention from many researchers, and have been widely used in the fields of food, textile, paper making, biomedical materials, and the like. However, cellulose is structurally stable and poorly soluble in most solvents, which greatly limits its applications. The cellulose modification can not only improve the solubility of the cellulose, but also enrich the application performance of the cellulose, and is one of important ways for meeting the requirements of special application. Commonly used methods for modifying cellulose are physical, chemical and biological modification. According to the research of the inventor, the physical modification can improve the dissolving performance of the cellulose, but the modification efficiency and the thermal stability are low; the chemical modification has high degree of substitution and quick reaction, but the used reagent has serious pollution to the environment; the biological modification can improve the drainage performance and the strength of the pulp, but the application range is narrow, and the biological modification is only applied to the paper making industry. These modification methods are complicated in operation and high in cost, and are not favorable for large-scale production of modified cellulose.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a method for modifying cellulose by using a reactive eutectic solvent, and the method has the advantages of simple operation, greenness, high efficiency, low cost and the like.
In order to achieve the purpose, the technical scheme of the invention is as follows:
on one hand, the application of a reactive eutectic solvent in modified cellulose is that a hydrogen bond acceptor of the reactive eutectic solvent is sulfamic acid and a hydrogen bond donor is glycerol.
The eutectic solvent is a green efficient substitute for biomass pretreatment and conversion, mainly consists of a hydrogen bond donor and a hydrogen bond acceptor, and the melting point of the eutectic solvent is lower than that of a single component, because strong hydrogen bonds formed by the hydrogen bond donor and the hydrogen bond acceptor can prevent the original component from crystallizing. The eutectic solvent has a large amount of intramolecular hydrogen bonds, and the intramolecular hydrogen bonds improve the possibility of breaking strong hydrogen bonds between biomasses, so that the eutectic solvent has high biomass solubility and good modification effect. The method for modifying cellulose by utilizing the eutectic solvent has the advantages of low cost, low toxicity and the like, and the eutectic solvent is easy to prepare, biodegradable and recyclable.
Since the object of the invention is to sulfonate cellulose, the invention selects eutectic solvents based on sulfamic acid. However, experiments show that the eutectic solvent prepared by matching hydrogen bond donors such as lactic acid and the like with sulfamic acid has the problems of side reaction, poor modification effect and the like when the cellulose is treated, so that the eutectic solvent is difficult to sulfonate and modify the cellulose. Therefore, the invention continues to carry out experiments, and the experiments show that the eutectic solvent prepared by matching glycerol as a hydrogen bond donor with sulfamic acid has better cellulose modification effect. Meanwhile, the glycerol selected by the invention is a simple natural polyol, is low in price, is biodegradable, is a green sustainable solvent, and can be easily synthesized into a eutectic solvent with sulfamic acid.
On the other hand, the method for modifying the cellulose by the reactive eutectic solvent comprises the steps of preparing the reactive eutectic solvent from sulfamic acid and glycerol, adding a cellulose raw material into the reactive eutectic solvent, and heating to 90-100 ℃ for modification reaction.
In a third aspect, modified cellulose is prepared by the above method.
In a fourth aspect, the modified cellulose is applied to the fields of chemicals, papermaking, sewage treatment and pharmacy.
The invention has the beneficial effects that:
(1) according to the invention, the eutectic solvent is adopted to modify the cellulose, no additional reagent is needed, the sulfonic acid group is grafted to the cellulose, the modification effect is good, and the product performance is excellent.
(2) The method has the advantages of simple operation, low cost and environmental protection, and the used eutectic solvent can be recovered by methods such as rotary evaporation and the like, so that the eutectic solvent can be recycled and is suitable for large-scale industrial production.
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 cellulose prepared in example 1 of the present invention.
FIG. 2 is a scanning electron micrograph of modified cellulose prepared in example 2 of the present invention.
FIG. 3 is a scanning electron micrograph of modified cellulose prepared in example 3 of the present invention.
FIG. 4 is a scanning electron micrograph of modified cellulose prepared in example 4 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.
In view of the defects of complex operation, high cost and the like of the existing method for modifying cellulose, the invention provides a method for modifying cellulose by using a reactive eutectic solvent.
The invention provides an application of a reactive eutectic solvent in modified cellulose, wherein a hydrogen bond acceptor of the reactive eutectic solvent is sulfamic acid, and a hydrogen bond donor of the reactive eutectic solvent is glycerol.
The invention continues to carry out tests, and finds that the eutectic solvent prepared by matching glycerol as a hydrogen bond donor with sulfamic acid has better modification effect on cellulose. Meanwhile, the glycerol selected by the invention is a simple natural polyol, is low in price, is biodegradable, is a green sustainable solvent, and can be easily synthesized into a eutectic solvent with sulfamic acid.
The invention further provides a method for modifying cellulose by using the reactive eutectic solvent, which comprises the steps of preparing the reactive eutectic solvent from sulfamic acid and glycerol, and adding a cellulose raw material into the reactive eutectic solvent to be heated to 90-100 ℃ for modification reaction.
In some examples of this embodiment, the molar ratio of sulfamic acid to glycerol is 1:2 to 3.
In some embodiments of the present disclosure, the reaction type eutectic solvent is prepared by heating at a temperature of 90-100 ℃ for 2-4 hours.
In some examples of this embodiment, the cellulosic feedstock is modified after drying.
In one or more embodiments, the conditions of drying are: drying for 24-26 h at 50-60 ℃.
In some examples of this embodiment, the molar ratio of cellulose to sulfamic acid is 1:10 to 20.
In some examples of this embodiment, the time for the modification reaction is 60 to 90 min.
In some examples of this embodiment, water is added after the modification reaction to terminate the reaction, and solid-liquid separation is performed to obtain a solid phase, i.e., modified cellulose.
In some examples of this embodiment, the cellulosic feedstock is bleached chemical wood pulp. When the bleached chemical poplar pulp is adopted, the cellulose content of the bleached chemical poplar pulp is 85-87%, and the effect is better.
In a third embodiment of the invention, modified cellulose is provided, which is prepared by the method.
In a fourth embodiment of the invention, the modified cellulose is applied to the fields of chemicals, papermaking, sewage treatment and pharmacy.
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 heated in an oil bath at 90 ℃ for 2h to give a clear, transparent liquid.
(3) Eutectic solvent treatment: adding the dried bleached chemical poplar pulp into the prepared eutectic solvent system, wherein the treatment temperature is 100 ℃, and the treatment time is 60min, wherein the amount of the added bleached chemical poplar pulp is calculated according to the molar ratio of the cellulose to the sulfamic acid, and the molar ratio of the cellulose to the sulfamic acid is 1: 10;
(4) and (3) bleaching chemical poplar pulp fibers after separation treatment: adding deionized water into the reaction system to terminate the reaction, then carrying out solid-liquid separation, and separating out the bleached chemical poplar pulp fiber to obtain the modified cellulose, as shown in figure 1.
The yield of the modified cellulose in the embodiment is 88.45%, the fiber length is 0.220-0.240 mm, the fiber width is 15-17 μm, the substitution degree is 0.07, and the crystallinity degree is 58.76%.
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 heated in an oil bath at 90 ℃ for 2h to give a clear, transparent liquid.
(3) Eutectic solvent treatment: adding the dried bleached chemical poplar pulp into the prepared eutectic solvent system, wherein the treatment temperature is 100 ℃, and the treatment time is 60min, wherein the amount of the added bleached chemical poplar pulp is calculated according to the molar ratio of the cellulose to the sulfamic acid, and the molar ratio of the cellulose to the sulfamic acid is 1: 15;
(4) and (3) bleaching chemical poplar pulp fibers after separation treatment: adding deionized water into the reaction system to terminate the reaction, then carrying out solid-liquid separation, and separating out the bleached chemical poplar pulp fiber to obtain the modified cellulose.
The yield of the modified cellulose is 86.82%, the fiber length is 0.260-0.280 mm, the fiber width is 14-16 μm, the substitution degree is 0.06, and the crystallinity degree is 47%.
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 heated in an oil bath at 90 ℃ for 2h to give a clear, transparent liquid.
(3) Eutectic solvent treatment: adding the dried bleached chemical poplar pulp into the prepared eutectic solvent system, wherein the treatment temperature is 100 ℃, and the treatment time is 60min, wherein the amount of the added bleached chemical poplar pulp is calculated according to the molar ratio of the cellulose to the sulfamic acid, and the molar ratio of the cellulose to the sulfamic acid is 1: 20;
(4) and (3) bleaching chemical poplar pulp fibers after separation treatment: adding deionized water into the reaction system to terminate the reaction, then carrying out solid-liquid separation, and separating out the bleached chemical poplar pulp fiber to obtain the modified cellulose.
The yield of the modified cellulose in the embodiment is 82.66%, the fiber length is 0.290-0.310 mm, the fiber width is 15-17 μm, the substitution degree is 0.07, and the crystallinity degree is 40%.
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: mixing sulfamic acid and glycerol at a molar ratio of 1:2, and heating in an oil bath at 90 ℃ for 2h to obtain a clear and transparent liquid;
(3) eutectic solvent treatment: adding the dried bleached chemical poplar pulp into the prepared eutectic solvent system, wherein the treatment temperature is 100 ℃, and the treatment time is 90min, wherein the amount of the added bleached chemical poplar pulp is calculated according to the molar ratio of the cellulose to the sulfamic acid, and the molar ratio of the cellulose to the sulfamic acid is 1: 10;
(4) and (3) bleaching chemical poplar pulp fibers after separation treatment: adding deionized water into the reaction system to terminate the reaction, then carrying out solid-liquid separation, and separating out the bleached chemical poplar pulp fiber to obtain the modified cellulose, as shown in figure 2.
The yield of the modified cellulose is 77.27%, the fiber length is 0.560-0.580 mm, the fiber width is 16-18 μm, the substitution degree is 0.11, and the crystallinity degree is 58%.
Examples 2 to 2
(1) Drying in an oven: drying bleached chemical poplar pulp in an oven at 60 ℃ for 24 hours;
(2) preparing a eutectic solvent: mixing sulfamic acid and glycerol at a molar ratio of 1:2, and heating in an oil bath at 90 ℃ for 2h to obtain a clear and transparent liquid;
(3) eutectic solvent treatment: adding the dried bleached chemical poplar pulp into the prepared eutectic solvent system, wherein the treatment temperature is 100 ℃, and the treatment time is 90min, wherein the amount of the added bleached chemical poplar pulp is calculated according to the molar ratio of the cellulose to the sulfamic acid, and the molar ratio of the cellulose to the sulfamic acid is 1: 15;
(4) and (3) bleaching chemical poplar pulp fibers after separation treatment: adding deionized water into the reaction system to terminate the reaction, then carrying out solid-liquid separation, and separating out the bleached chemical poplar pulp fiber to obtain the modified cellulose, as shown in figure 2.
The yield of the modified cellulose in the embodiment is 75.66%, the fiber length is 0.330-0.350 mm, the fiber width is 15-17 μm, the substitution degree is 0.10, and the crystallinity degree is 52.29%.
Examples 2 to 3
(1) Drying in an oven: drying bleached chemical poplar pulp in an oven at 60 ℃ for 24 hours;
(2) preparing a eutectic solvent: mixing sulfamic acid and glycerol at a molar ratio of 1:2, and heating in an oil bath at 90 ℃ for 2h to obtain a clear and transparent liquid;
(3) eutectic solvent treatment: adding the dried bleached chemical poplar pulp into the prepared eutectic solvent system, wherein the treatment temperature is 100 ℃, and the treatment time is 90min, wherein the amount of the added bleached chemical poplar pulp is calculated according to the molar ratio of the cellulose to the sulfamic acid, and the molar ratio of the cellulose to the sulfamic acid is 1: 20;
(4) and (3) bleaching chemical poplar pulp fibers after separation treatment: adding deionized water into the reaction system to terminate the reaction, then carrying out solid-liquid separation, and separating out the bleached chemical poplar pulp fiber to obtain the modified cellulose, as shown in figure 2.
The yield of the modified cellulose is 75.69%, the fiber length is 0.250-0.270 mm, the fiber width is 16-18 μm, the substitution degree is 0.17, and the crystallinity degree is 41.32%.
Example 3-1
(1) Drying in an oven: drying bleached chemical poplar pulp in an oven at 60 ℃ for 24 hours;
(2) preparing a eutectic solvent: mixing sulfamic acid and glycerol at a molar ratio of 1:3, and heating in an oil bath at 90 ℃ for 2h to obtain a clear and transparent liquid;
(3) eutectic solvent treatment: adding the dried bleached chemical poplar pulp into the prepared eutectic solvent system, wherein the treatment temperature is 100 ℃, and the treatment time is 60min, wherein the amount of the added bleached chemical poplar pulp is calculated according to the molar ratio of the cellulose to the sulfamic acid, and the molar ratio of the cellulose to the sulfamic acid is 1: 10;
(4) and (3) bleaching chemical poplar pulp fibers after separation treatment: deionized water is added into the reaction system to terminate the reaction, then solid-liquid separation is carried out, and bleached chemical poplar pulp fiber is separated out to obtain modified cellulose, as shown in figure 3.
The yield of the modified cellulose is 95.2%, the fiber length is 0.560-0.580 mm, the fiber width is 15-17 μm, the substitution degree is 0.08, and the crystallinity degree is 47.46%.
Examples 3 to 2
(1) Drying in an oven: drying bleached chemical poplar pulp in an oven at 60 ℃ for 24 hours;
(2) preparing a eutectic solvent: mixing sulfamic acid and glycerol at a molar ratio of 1:3, and heating in an oil bath at 90 ℃ for 2h to obtain a clear and transparent liquid;
(3) eutectic solvent treatment: adding the dried bleached chemical poplar pulp into the prepared eutectic solvent system, wherein the treatment temperature is 100 ℃, and the treatment time is 60min, wherein the amount of the added bleached chemical poplar pulp is calculated according to the molar ratio of the cellulose to the sulfamic acid, and the molar ratio of the cellulose to the sulfamic acid is 1: 15;
(4) and (3) bleaching chemical poplar pulp fibers after separation treatment: deionized water is added into the reaction system to terminate the reaction, then solid-liquid separation is carried out, and bleached chemical poplar pulp fiber is separated out to obtain modified cellulose, as shown in figure 3.
The yield of the modified cellulose is 94.91%, the fiber length is 0.280-0.300 mm, the fiber width is 16-18 μm, the substitution degree is 0.03, and the crystallinity degree is 54.17%.
Examples 3 to 3
(1) Drying in an oven: drying bleached chemical poplar pulp in an oven at 60 ℃ for 24 hours;
(2) preparing a eutectic solvent: mixing sulfamic acid and glycerol at a molar ratio of 1:3, and heating in an oil bath at 90 ℃ for 2h to obtain a clear and transparent liquid;
(3) eutectic solvent treatment: adding the dried bleached chemical poplar pulp into the prepared eutectic solvent system, wherein the treatment temperature is 100 ℃, and the treatment time is 60min, wherein the amount of the added bleached chemical poplar pulp is calculated according to the molar ratio of the cellulose to the sulfamic acid, and the molar ratio of the cellulose to the sulfamic acid is 1: 20;
(4) and (3) bleaching chemical poplar pulp fibers after separation treatment: deionized water is added into the reaction system to terminate the reaction, then solid-liquid separation is carried out, and bleached chemical poplar pulp fiber is separated out to obtain modified cellulose, as shown in figure 3.
The yield of the modified cellulose in the embodiment is 92.2%, the fiber length is 0.340-0.360 mm, the fiber width is 15-17 μm, the substitution degree is 0.05, and the crystallinity degree is 55.05%.
Example 4-1
(1) Drying in an oven: drying bleached chemical poplar pulp in an oven at 60 ℃ for 24 hours;
(2) preparing a eutectic solvent: mixing sulfamic acid and glycerol at a molar ratio of 1:3, and heating in an oil bath at 90 ℃ for 2h to obtain a clear and transparent liquid;
(3) eutectic solvent treatment: adding the dried bleached chemical poplar pulp into the prepared eutectic solvent system, wherein the treatment temperature is 100 ℃, and the treatment time is 90min, wherein the amount of the added bleached chemical poplar pulp is calculated according to the molar ratio of the cellulose to the sulfamic acid, and the molar ratio of the cellulose to the sulfamic acid is 1: 10;
(4) and (3) bleaching chemical poplar pulp fibers after separation treatment: deionized water is added into the reaction system to terminate the reaction, then solid-liquid separation is carried out, and bleached chemical poplar pulp fiber is separated out to obtain modified cellulose, as shown in figure 4.
The yield of the modified cellulose is 86.48%, the fiber length is 0.650-0.670 mm, the fiber width is 15-17 μm, the substitution degree is 0.09, and the crystallinity degree is 46.89%.
Example 4 to 2
(1) Drying in an oven: drying bleached chemical poplar pulp in an oven at 60 ℃ for 24 hours;
(2) preparing a eutectic solvent: mixing sulfamic acid and glycerol at a molar ratio of 1:3, and heating in an oil bath at 90 ℃ for 2h to obtain a clear and transparent liquid;
(3) eutectic solvent treatment: adding the dried bleached chemical poplar pulp into the prepared eutectic solvent system, wherein the treatment temperature is 100 ℃, and the treatment time is 90min, wherein the amount of the added bleached chemical poplar pulp is calculated according to the molar ratio of the cellulose to the sulfamic acid, and the molar ratio of the cellulose to the sulfamic acid is 1: 15;
(4) and (3) bleaching chemical poplar pulp fibers after separation treatment: deionized water is added into the reaction system to terminate the reaction, then solid-liquid separation is carried out, and bleached chemical poplar pulp fiber is separated out to obtain modified cellulose, as shown in figure 4.
The yield of the modified cellulose is 84.51%, the fiber length is 0.290-0.310 mm, the fiber width is 17-19 μm, the substitution degree is 0.09, and the crystallinity degree is 43.8%.
Examples 4 to 3
(1) Drying in an oven: drying bleached chemical poplar pulp in an oven at 60 ℃ for 24 hours;
(2) preparing a eutectic solvent: mixing sulfamic acid and glycerol at a molar ratio of 1:3, and heating in an oil bath at 90 ℃ for 2h to obtain a clear and transparent liquid;
(3) eutectic solvent treatment: adding the dried bleached chemical poplar pulp into the prepared eutectic solvent system, wherein the treatment temperature is 100 ℃, and the treatment time is 90min, wherein the amount of the added bleached chemical poplar pulp is calculated according to the molar ratio of the cellulose to the sulfamic acid, and the molar ratio of the cellulose to the sulfamic acid is 1: 20;
(4) and (3) bleaching chemical poplar pulp fibers after separation treatment: deionized water is added into the reaction system to terminate the reaction, then solid-liquid separation is carried out, and bleached chemical poplar pulp fiber is separated out to obtain modified cellulose, as shown in figure 4.
The yield of the modified cellulose is 74.83%, the fiber length is 0.250-0.270 mm, the fiber width is 17-19 μm, the substitution degree is 0.12, and the crystallinity degree is 54%.
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 lactic acid were mixed in a molar ratio of 1:2 and heated in an oil bath at 100 ℃ for 24h to give a clear, transparent liquid.
(3) Eutectic solvent treatment: adding the dried bleached chemical poplar pulp into the prepared eutectic solvent system, wherein the treatment temperature is 110 ℃, and the treatment time is 60min, wherein the amount of the added bleached chemical poplar pulp is calculated according to the molar ratio of the cellulose to the sulfamic acid, and the molar ratio of the cellulose to the sulfamic acid is 1: 10;
(4) and (3) bleaching chemical poplar pulp fibers after separation treatment: adding deionized water into the reaction system to terminate the reaction, then carrying out solid-liquid separation, and separating out the bleached chemical poplar pulp fiber to obtain the degraded cellulose.
The yield of the cellulose obtained by the comparative example treatment is 31%, most of the cellulose is degraded, the substitution degree is 0, and the eutectic solvent system has no modification effect on the cellulose.
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 lactic acid were mixed in a molar ratio of 1:3 and heated in an oil bath at 100 ℃ for 24h to give a clear, transparent liquid.
(3) Eutectic solvent treatment: adding the dried bleached chemical poplar pulp into the prepared eutectic solvent system, wherein the treatment temperature is 110 ℃, and the treatment time is 60min, wherein the amount of the added bleached chemical poplar pulp is calculated according to the molar ratio of the cellulose to the sulfamic acid, and the molar ratio of the cellulose to the sulfamic acid is 1: 10;
(4) and (3) bleaching chemical poplar pulp fibers after separation treatment: adding deionized water into the reaction system to terminate the reaction, then carrying out solid-liquid separation, and separating out the bleached chemical poplar pulp fiber to obtain the degraded cellulose.
The yield of the cellulose obtained by the comparative example treatment is 35%, most of the cellulose is degraded, the substitution degree is 0, and the eutectic solvent system has no modification effect on the cellulose.
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. The application of a reactive eutectic solvent in modified cellulose is characterized in that a hydrogen bond acceptor of the reactive eutectic solvent is sulfamic acid, and a hydrogen bond donor of the reactive eutectic solvent is glycerol.
2. A method for modifying cellulose by using a reactive eutectic solvent is characterized in that sulfamic acid and glycerol are prepared into the reactive eutectic solvent, and a cellulose raw material is added into the reactive eutectic solvent and heated to 90-100 ℃ for modification reaction.
3. The method for modifying cellulose by using the reactive eutectic solvent according to claim 2, wherein the molar ratio of sulfamic acid to glycerol is 1:2 to 3.
4. The method for modifying cellulose by using the reactive eutectic solvent as claimed in claim 2, wherein the reactive eutectic solvent is prepared by heating at 90-100 ℃ for 2-4 h.
5. The method for modifying cellulose by using the reactive eutectic solvent according to claim 2, wherein the molar ratio of the cellulose to the sulfamic acid is 1: 10-20.
6. The method for modifying cellulose by using the reactive eutectic solvent according to claim 2, wherein the modification reaction time is 60 to 90 min.
7. The method for modifying cellulose by using the reactive eutectic solvent according to claim 2, wherein the modification reaction is terminated by adding water, and the solid-liquid separation is performed to obtain a solid phase, i.e., the modified cellulose.
8. The method of claim 2, wherein the cellulose raw material is bleached chemical wood pulp.
9. A modified cellulose, which is obtained by the method according to any one of claims 2 to 8.
10. Use of the modified cellulose of claim 9 in the fields of chemicals, paper manufacture, sewage treatment, and pharmaceuticals.
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