CN114573718B - Modification and application of lignocellulose - Google Patents
Modification and application of lignocellulose Download PDFInfo
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- CN114573718B CN114573718B CN202210154670.3A CN202210154670A CN114573718B CN 114573718 B CN114573718 B CN 114573718B CN 202210154670 A CN202210154670 A CN 202210154670A CN 114573718 B CN114573718 B CN 114573718B
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- 238000012986 modification Methods 0.000 title abstract description 9
- 230000004048 modification Effects 0.000 title abstract description 9
- 239000001913 cellulose Substances 0.000 claims abstract description 73
- 229920002678 cellulose Polymers 0.000 claims abstract description 73
- 238000002360 preparation method Methods 0.000 claims abstract description 36
- 230000005496 eutectics Effects 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 8
- 229920005610 lignin Polymers 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical group [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 150000001447 alkali salts Chemical class 0.000 claims description 4
- -1 quaternary ammonium salt compound Chemical class 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 238000007385 chemical modification Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 241000218631 Coniferophyta Species 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 235000012431 wafers Nutrition 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 26
- 239000006227 byproduct Substances 0.000 abstract description 10
- 235000012055 fruits and vegetables Nutrition 0.000 abstract description 8
- 239000002121 nanofiber Substances 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000012780 transparent material Substances 0.000 abstract description 5
- 239000005648 plant growth regulator Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 241000196324 Embryophyta Species 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 229920002488 Hemicellulose Polymers 0.000 description 4
- 210000002421 cell wall Anatomy 0.000 description 4
- 241000218691 Cupressaceae Species 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 241000609240 Ambelania acida Species 0.000 description 2
- 240000008790 Musa x paradisiaca Species 0.000 description 2
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 2
- 239000010905 bagasse Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 2
- 229960002218 sodium chlorite Drugs 0.000 description 2
- 239000011122 softwood Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 240000008866 Ziziphus nummularia Species 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 210000001724 microfibril Anatomy 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/20—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom three- or four-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N61/00—Biocides, pest repellants or attractants, or plant growth regulators containing substances of unknown or undetermined composition, e.g. substances characterised only by the mode of action
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P21/00—Plant growth regulators
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
- C09D101/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D197/00—Coating compositions based on lignin-containing materials
- C09D197/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2397/00—Characterised by the use of lignin-containing materials
- C08J2397/02—Lignocellulosic material, e.g. wood, straw or bagasse
Abstract
The invention provides a preparation method of thin-layer modified lignocellulose, a preparation method of modified cellulose nano-fiber, application of reaction byproduct eutectic solvent residual liquid obtained by the preparation method of thin-layer modified lignocellulose as a plant growth regulator, application of thin-layer modified lignocellulose obtained by the preparation method of thin-layer modified lignocellulose as a structural material and/or a transparent material, and application of modified cellulose nano-fiber obtained by the preparation method of modified cellulose nano-fiber in fruit and vegetable fresh-keeping and interference film preparation. The invention can realize the modification of lignocellulose under normal pressure and mild conditions, and leads the lignocellulose to be easily defibrinated into cellulose nanofibrils, and the reaction process does not need to treat byproducts, thereby achieving the characteristics of environmental protection, cost reduction and energy consumption, and the obtained lamellar modified lignocellulose, eutectic solvent residual liquid of the reaction byproducts and modified cellulose nanofibril have the characteristics of multifunction and high performance.
Description
Technical Field
The invention belongs to the field of plant fiber materials, relates to modification and application of lignocellulose, and in particular relates to a preparation method and application of thin-layer modified lignocellulose and modified cellulose nanofiber filaments.
Background
Lignocellulose is mainly derived from plant cell walls, is the biomass resource with the most abundant reserves, and has huge comprehensive utilization potential. Thanks to the multi-layer structure, the plant cell wall can be stripped and extracted from top to bottom to obtain the high-performance cellulose nanofibrillar material. The cellulose nanofibrils have the characteristics of excellent mechanical property, large specific surface area, small thermal expansion coefficient, good thermal stability, low density and the like, and have wide application prospects in the fields of nanocomposite materials, biomedical materials, optical and electrical materials and the like. However, due to the complexity of the lignocellulosic biomass component and structural stability, there are many technical challenges in efficient preparation, modification and application of cellulose nanofibrils.
Representative techniques for the preparation of conventional cellulose nanofibrillar materials are mechanical and chemical. The mechanical method is a high energy consumption process, and the chemical method needs to use a large amount of chemicals and needs to treat reaction byproducts such as acid, alkali, salt or oxidant. The two factors of energy consumption and chemical post-treatment make the cost of the cellulose nanofibrils high, and restrict large-scale application. In addition, the properties and applications of cellulose nanofibrils have not been fully explored. Lamellar structures between plant cell wall microfibrils and cellulose nanofibrils have long been neglected. Therefore, the preparation and modification technology of cellulose nanofibrils with low energy consumption and no need of post-treatment is provided, the new performance and application of the cellulose nanofibrils are provided, and the layered structure of the plant cell wall represents the development direction of lignocellulose materials.
Disclosure of Invention
A first object of the present invention is to provide a method for preparing a modified lignocellulose in the form of a thin layer, which aims at the defects existing in the prior art.
For this purpose, the above object of the present invention is achieved by the following technical solutions:
a preparation method of lamellar modified lignocellulose is characterized by comprising the following steps of: the method comprises the following steps:
1) Preparation of reactive eutectic solvent:
mixing and heating a hydrogen bond acceptor and a hydrogen bond donor in a certain stoichiometric ratio, wherein the heating temperature is 70-90 ℃ and the heating time is 15-30 minutes, so as to form a eutectic solvent;
the hydrogen bond acceptor is a quaternary ammonium salt compound containing an epoxy group; the hydrogen bond donor is a carbonamide compound;
2) Surface chemical modification of lignocellulose:
adding lignocellulose raw materials into the obtained eutectic solvent, wherein the solid-liquid ratio is 1:10-1:20, adding 0-5% of alkaline catalyst, reacting the whole reaction system at 90-120 ℃ for 30-240 min, and continuously magnetically stirring;
after the reaction is finished, diluting with water, realizing solid-liquid separation by suction filtration, preserving eutectic solvent residual liquid of a liquid phase, and washing a solid phase with a large amount of water to obtain lamellar modified lignocellulose.
The invention can also adopt or combine the following technical proposal when adopting the technical proposal:
as a preferable technical scheme of the invention: in the step 1), the hydrogen bond acceptor is 2, 3-epoxypropyl trimethyl ammonium chloride, and the hydrogen bond donor is urea.
As a preferable technical scheme of the invention: in the step 2), the lignocellulose raw material is one of conifer, broadleaf wood or grass, the cellulose content in the lignocellulose raw material is 30-95%, and the lignin content is 0.1-30%.
As a preferable technical scheme of the invention: in the step 2), the alkaline catalyst is weak acid strong alkali salt or strong alkali.
As a preferable technical scheme of the invention: the weak acid strong alkali salt is potassium carbonate or sodium carbonate; the strong base is potassium hydroxide or sodium hydroxide.
A second object of the present invention is to provide a new use of eutectic solvent raffinate, which addresses the deficiencies of the prior art.
For this purpose, the above object of the present invention is achieved by the following technical solutions:
the use of the eutectic solvent raffinate obtained according to the preparation method of the lamellar modified lignocellulose as a plant growth regulator.
A third object of the present invention is to provide a new application of modified lignocellulose in the form of a thin layer, which aims at the drawbacks existing in the prior art.
For this purpose, the above object of the present invention is achieved by the following technical solutions:
the use of the lamellar modified lignocellulose obtained according to the method for producing lamellar modified lignocellulose described above as a structural material and/or a transparent material, characterized in that: the lamellar modified lignocellulose is filtered and dried to form a sheet material with the thickness of 20-200 microns, and the sheet material is used as a structural material and/or a transparent material.
The fourth object of the present invention is to provide a method for preparing modified cellulose nanofibrils, which aims at overcoming the defects existing in the prior art.
For this purpose, the above object of the present invention is achieved by the following technical solutions:
a preparation method of modified cellulose nanofibrils is characterized by comprising the following steps: the method is based on the preparation method of the lamellar modified lignocellulose and comprises the following steps:
3) Preparation of modified cellulose nanofibrils:
and defibrating the obtained modified lignocellulose aqueous dispersion by using a wall breaking machine, wherein the solid content of the aqueous dispersion is 0.1-1.5%, the rotating speed of the wall breaking machine is 5000-30000 r/min, and the defibration time is 1-20 min, so as to obtain the modified cellulose nanofibrils.
A fifth object of the present invention is to provide a new application of modified cellulose nanofibrils, which addresses the deficiencies of the prior art.
For this purpose, the above object of the present invention is achieved by the following technical solutions:
the application of the modified cellulose nanofibrils prepared by the preparation method of the modified cellulose nanofibrils in the aspect of fruit and vegetable fresh-keeping is characterized in that: the obtained modified cellulose nanofibrillar aqueous dispersion is coated on the surface of fruits and vegetables, the concentration is 0.2%, and the fresh-keeping film is formed after drying.
It is a further object of the present invention to provide new applications of modified cellulose nanofibrils in another aspect, which address the deficiencies of the prior art.
For this purpose, the above object of the present invention is achieved by the following technical solutions:
the application of the modified cellulose nanofibrils prepared by the preparation method of the modified cellulose nanofibrils in the preparation of interference films is characterized in that: the obtained aqueous dispersion of the modified cellulose nanofibrils is coated on the surfaces of glass, metal, plastic and silicon wafers, the concentration is 0.02-0.2%, and the interference film is formed after drying, and the thickness is 0.1-2 microns.
The invention provides modification and application of lignocellulose, and provides a preparation method of thin-layer modified lignocellulose, a preparation method of modified cellulose nanofiber yarn, application of eutectic solvent residual liquid serving as a plant growth regulator, application of thin-layer modified lignocellulose serving as a structural material and/or a transparent material and application of modified cellulose nanofiber yarn obtained by the preparation method of modified cellulose nanofiber yarn in fruit and vegetable fresh-keeping and interference film preparation. The invention can realize the modification of lignocellulose under normal pressure and mild conditions, and leads the lignocellulose to be easily defibrinated into cellulose nanofibrils, and the reaction process does not need to treat byproducts, thereby achieving the characteristics of environmental protection, cost reduction and energy consumption, and the obtained lamellar modified lignocellulose, eutectic solvent residual liquid of the reaction byproducts and modified cellulose nanofibril have the characteristics of multifunction and high performance.
Drawings
Fig. 1 is a photograph showing a reactive eutectic solvent formation process.
FIG. 2 is a photograph of a eutectic solvent raffinate as a reaction byproduct.
Fig. 3 is an SEM image of the lamellar modified lignocellulose in example 1.
Fig. 4 is an SEM image of the modified cellulose nanofibrils in example 2.
FIG. 5 is a graph showing comparison of the amount of biological growth in example 3.
FIG. 6 is a stretch graph of a lamellar modified lignocellulosic sheet material in example 4.
FIG. 7 is a graph showing the transmittance of the sheet-like material of the thin-layer modified lignocellulose in example 4.
FIG. 8 is a graph showing the comparison of the weight loss of water in example 5.
FIG. 9 is a graph showing the transmittance of an interference film formed from modified cellulose nanofibrils in example 6 and a photograph of the interference film.
FIG. 10 is a stretch graph of a lamellar modified lignocellulosic sheet material in example 7.
FIG. 11 is a graph showing the transmittance of a sheet-like modified lignocellulose sheet material in example 7.
FIG. 12 is a stretch graph of a lamellar modified lignocellulosic sheet material in example 8.
FIG. 13 is a graph showing the transmittance of a sheet-like modified lignocellulose sheet material in example 8.
FIG. 14 is a stretch graph of a lamellar modified lignocellulosic sheet material in example 9.
FIG. 15 is a graph showing the comparison of tensile curves of the sheet-like modified lignocellulose sheet material of example 10 after various sub-dispersion reconstructions.
FIG. 16 is a graph showing comparison of the amount of biological growth in example 11.
FIG. 17 is a graph showing the comparison of the weight loss of water in example 12.
FIG. 18 is a graph showing the transmittance of an interference film formed from modified cellulose nanofibrils in example 13 and a photograph of the interference film.
FIG. 19 is a photograph of a self-supporting cellulose nanofibrillar interference film with a thickness of 192 to 352 nanometers in which full color domains can be displayed.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but embodiments of the present invention are not limited thereto.
The raw materials used in the invention are fully-synthesized cellulose obtained by bleaching cypress-derived sodium chlorite, the components of which are 84.0% of cellulose, 16.0% of hemicellulose and the balance of cellulose.
The components of lignocellulose obtained by bleaching cypress-derived sodium chlorite are 69.7% of cellulose, 13.3% of hemicellulose, 17.0% of lignin and the balance of lignocellulose.
Bleached kraft softwood pulp, having a composition of 86.3% cellulose, 16.7% hemicellulose, and others negligible.
Bagasse, whose component is 36.5% of cellulose, 26.1% of hemicellulose, 28.6% of lignin and 8.8% of other components.
The hydrogen bond acceptor 2, 3-epoxypropyl trimethyl ammonium chloride has the chemical structure as follows:
the chemical structure of hydrogen bond donor urea is as follows:
in the following examples, only 2, 3-epoxypropyl trimethyl ammonium chloride and urea are exemplified, but homologs in which methyl groups are substituted with ethyl groups or the like in 2, 3-epoxypropyl trimethyl ammonium chloride and homologs in which hydrogen atoms are substituted with methyl groups or the like in urea can also be effectively used for the preparation of the multifunctional biomass material.
Example 1
The preparation method of the lamellar modified lignocellulose comprises the following steps:
1) Preparation of reactive eutectic solvent:
22.2g of 2, 3-epoxypropyl trimethyl ammonium chloride and 17.8g of urea are weighed so that the molar ratio of the two is 2:1, the two are mixed in a reaction bottle, and heated for 15 minutes at 80 ℃ to form a eutectic solvent, as shown in figure 1, and figure 1 is a photograph showing the formation process of the reactive eutectic solvent.
2) Surface chemical modification of lignocellulose:
2g of cypress-derived fully-mechanized cellulose raw material is put into a eutectic solvent, reacted for 240min at 90 ℃ and continuously magnetically stirred;
after the reaction is finished, the solution is diluted by 60mL of water, solid-liquid separation is realized through suction filtration, the obtained liquid phase is eutectic solvent residual liquid of a reaction byproduct, and the solid phase is washed by a large amount of water to obtain lamellar modified lignocellulose, wherein the thickness of the lamellar modified lignocellulose is within 100 nanometers, the length is more than 100 micrometers, and the width is 2-30 micrometers as shown in figure 3.
Example 2
The preparation method of the modified cellulose nanofibrils comprises the following steps: 3) Preparation of modified cellulose nanofibrils:
the aqueous dispersion of modified lignocellulose obtained in example 1 was defibrinated with a wall breaking machine, the solid content of the aqueous dispersion was 0.5%, the rotational speed of the wall breaking machine was 18000 rpm, and the defibration time was 1 minute, to obtain modified cellulose nanofibrils.
As shown in FIG. 4, the obtained modified cellulose nanofibrils have a fibrillar structure with a high length-diameter ratio, the diameter is 3-15 nanometers, and the length is more than 1 micrometer.
Example 3
Application of eutectic solvent raffinate:
as shown in fig. 2, fig. 2 is a photograph of the residual liquid of the eutectic solvent as a reaction byproduct.
50ppm of the eutectic solvent raffinate obtained in example 1 was added to the plant broth (here, 50ppm means that the mass of the eutectic solvent represents a part of the mass of the entire solution including the plant broth), and Shanghai green was hydroponic for 14 days, and the eutectic solvent increased the biomass by 63.2% compared to the blank, as shown in fig. 5.
Example 4
Use of lamellar cellulose in structural and transparent materials:
the aqueous dispersion of lamellar cellulose was filtered and dried to form a sheet material having a thickness of 50 microns, a tensile strength of 142.5MPa and a light transmittance at 560nm of 76.6%, as shown in FIGS. 6-7.
Example 5
The application of cellulose nanofibrils in the aspect of fruit and vegetable fresh-keeping:
the aqueous dispersion of modified cellulose nanofibrils obtained in example 2 was applied to banana surface at a concentration of 0.2% and dried to form a preservative film, which was compared with the blank, and reduced in water loss by 40% within 4 days, as shown in fig. 8.
Example 6
Use of cellulose nanofibrils in interference films:
the modified cellulose nanofibrillar aqueous dispersion obtained in example 2 with a concentration of 0.06% was applied to a glass slide with a diameter of 1.5cm, and dried to form an interference film with a thickness of 192nm, and the interference film was peeled off and developed in a dark blue color, as shown in fig. 9.
Example 7
The raw material in step 2) in example 1 was changed to wood-derived lignocellulose having a lignin content of 17.0% and 2g of potassium carbonate was added as a catalyst, with the other conditions unchanged. Referring to FIGS. 10 to 11, the resulting lamellar cellulose had a tensile strength of 79.8MPa and a light transmittance at 560nm of 60.9%.
Example 8
The starting material from step 2) in example 1 was changed to bleached kraft softwood pulp and 2g of potassium carbonate was added as catalyst and the reaction temperature was raised to 120 ℃ with the other conditions unchanged. Referring to FIGS. 12 to 13, the resulting lamellar cellulose had a tensile strength of 102.5MPa and a light transmittance at 560nm of 78.5%.
Example 9
The starting material in step 2) of example 1 was changed to bagasse and 2g of potassium carbonate was added as catalyst, with the other conditions unchanged. Referring to fig. 14, the tensile strength of the resulting lamellar cellulose was 90.5MPa.
Example 10
The reaction time in step 2) in example 1 was changed to 120min, the other conditions being unchanged. The tensile strength of the obtained lamellar cellulose sheet material is 83.8MPa, and after 1, 2 and 5 times of water dispersion and reconstruction, the tensile strength can be improved to 89.0, 116.9 and 134.0MPa, and the reconstruction enhancement characteristic is shown in fig. 15.
Example 11
The amount of the residual liquid of the eutectic solvent obtained in example 1 was reduced to 10ppm (here, 10ppm means that the mass of the eutectic solvent is a part of the mass of the whole solution including the plant culture liquid), and other conditions were not changed, and the eutectic solvent increased the biomass by 44.1%, as shown in fig. 16.
Example 12
The banana in the fruit and vegetable fresh keeping application of example 5 was changed to winter jujube, the other conditions were unchanged, and the moisture loss was 27% less in 7 days compared with the blank group, as shown in fig. 17.
Example 13
The amount of aqueous cellulose nanofibrillar dispersion used in the preparation of the interference film of example 6 was increased to 0.13mL, the other conditions were unchanged, and the resulting interference film had a thickness of 230nm and a pale blue color, as shown in FIG. 18.
The above examples are part of embodiments of the invention, wherein:
comparison of example 1 with examples 7, 8, 9 as starting materials shows that: the reaction system is suitable for different raw materials, the main influencing factor is the lignin content, along with the rise of the lignin content, the reaction temperature is required to be increased or a catalyst is required to be added, and the modified lignocellulose sheet material with good mechanical strength and transparency can be obtained for different raw materials.
Example 1 is a comparison of reaction times with example 10, which shows that: the reaction time is short, the mechanical property of the obtained modified lignocellulose sheet material is reduced, but the modified lignocellulose sheet material has the reconstruction enhancing property which is not available in common paper.
Example 3 is a comparison of the amounts of eutectic solvents used as reaction byproducts in plant cultivation with example 11, which shows that: the lower concentration of 10ppm has obvious effect of promoting plant growth.
Example 5 and example 12 are comparison of fresh-keeping objects which are not used for fresh-keeping of fruits and vegetables, and the result shows that: the cellulose nanofibrils can prevent the water loss of different fruits and vegetables.
Example 6 is a comparison of the amounts of cellulose nanofibrils used in the preparation of interference films with example 13, which shows that: increasing the amount of cellulose nanofibrils increases the interference film thickness, thus changing the interference conditions and making the interference film appear different colors. As shown in FIG. 19, FIG. 19 is a photograph of a self-supporting cellulose nanofibrillar interference film with a thickness of 192 to 352 nanometers in which full color domains can be displayed. The display color of the interference film can be controlled by changing the thickness of the interference film so as to cover the full color gamut.
The above detailed description is intended to illustrate the present invention by way of example only and not to limit the invention to the particular embodiments disclosed, but to limit the invention to the precise embodiments disclosed, and any modifications, equivalents, improvements, etc. that fall within the spirit and scope of the invention as defined by the appended claims.
Claims (5)
1. The application of the modified cellulose nanofibrils in the aspect of preparing an interference film is characterized in that: coating the aqueous dispersion of the modified cellulose nanofibrils on the surfaces of glass, metal, plastic and silicon wafers, wherein the concentration is 0.02-0.2%, and forming an interference film after drying, and the thickness is 0.1-2 microns;
the modified cellulose nanofibrils are prepared by the following steps:
1) Preparation of reactive eutectic solvent:
mixing and heating a hydrogen bond acceptor and a hydrogen bond donor in a certain stoichiometric ratio, wherein the heating temperature is 70-90 ℃ and the heating time is 15-30 minutes, so as to form a eutectic solvent;
the hydrogen bond acceptor is a quaternary ammonium salt compound containing an epoxy group; the hydrogen bond donor is a carbonamide compound;
2) Surface chemical modification of lignocellulose:
adding lignocellulose raw materials into the obtained eutectic solvent, wherein the solid-liquid ratio is 1:10-1:20, adding 0-5% of alkaline catalyst, reacting the whole reaction system at 90-120 ℃ for 30-240 min, and continuously magnetically stirring;
after the reaction is finished, diluting with water, realizing solid-liquid separation through suction filtration, preserving eutectic solvent residual liquid of a liquid phase, and washing a solid phase with a large amount of water to obtain lamellar modified lignocellulose;
3) Preparation of modified cellulose nanofibrils:
and defibrating the obtained modified lignocellulose aqueous dispersion by using a wall breaking machine, wherein the solid content of the aqueous dispersion is 0.1-1.5%, the rotating speed of the wall breaking machine is 5000-30000 r/min, and the defibration time is 1-20 min, so as to obtain the modified cellulose nanofibrils.
2. Use of a modified cellulose nanofibril according to claim 1 in the preparation of an interference film, characterized in that: in the step 1), the hydrogen bond acceptor is 2, 3-epoxypropyl trimethyl ammonium chloride, and the hydrogen bond donor is urea.
3. Use of a modified cellulose nanofibril according to claim 1 in the preparation of an interference film, characterized in that: in the step 2), the lignocellulose raw material is one of conifer, broadleaf wood or grass, the cellulose content in the lignocellulose raw material is 30-95%, and the lignin content is 0.1-30%.
4. Use of a modified cellulose nanofibril according to claim 1 in the preparation of an interference film, characterized in that: in the step 2), the alkaline catalyst is weak acid strong alkali salt or strong alkali.
5. Use of the modified cellulose nanofibrils according to claim 4 in the preparation of an interference film, characterized in that: the weak acid strong alkali salt is potassium carbonate or sodium carbonate; the strong base is potassium hydroxide or sodium hydroxide.
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