CN115142263A - Cationic bamboo cellulose nanofiber and preparation method thereof - Google Patents

Cationic bamboo cellulose nanofiber and preparation method thereof Download PDF

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CN115142263A
CN115142263A CN202110340807.XA CN202110340807A CN115142263A CN 115142263 A CN115142263 A CN 115142263A CN 202110340807 A CN202110340807 A CN 202110340807A CN 115142263 A CN115142263 A CN 115142263A
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bamboo
cationic
solution
fiber
bamboo fiber
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CN115142263B (en
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徐鼎峰
李星星
李亿保
何昌飞
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Gannan Normal University
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    • 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
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01C—CHEMICAL OR BIOLOGICAL TREATMENT OF NATURAL FILAMENTARY OR FIBROUS MATERIAL TO OBTAIN FILAMENTS OR FIBRES FOR SPINNING; CARBONISING RAGS TO RECOVER ANIMAL FIBRES
    • D01C1/00—Treatment of vegetable material
    • D01C1/02—Treatment of vegetable material by chemical methods to obtain bast fibres
    • 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
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • 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 provides a preparation method of cationic bamboo cellulose nano-fibers with high lignin content, which comprises the following steps: (1) Swelling the bamboo fiber in an alkali solution to activate the hydroxyl on the bamboo fiber; (2) Reacting a cationic etherification reagent with the activated bamboo fiber, and filtering and washing a reaction product to prepare cationic bamboo cellulose nanofiber; the lignin content of the bamboo fiber is 5-25 wt%. The cationic bamboo cellulose nanofiber prepared by the method disclosed by the invention can realize that the cationic bamboo cellulose nanofiber retains lignin, is controllable in size and uniform in distribution, has the tensile strength of up to 250MPa, and has the synergistic antibacterial function of the cationic bamboo cellulose and bamboo-jade active substances.

Description

Cationic bamboo cellulose nanofiber and preparation method thereof
Technical Field
The invention relates to the technical field of polymer science, in particular to cationic bamboo cellulose nanofiber with high lignin content and a preparation method thereof.
Background
In recent years, with the rapid development of economy in China, the increasing exhaustion of non-renewable energy sources and environmental pollution bring serious influence on the living health and sustainable development realization of human beings. Therefore, the natural polymer-based composite material which is wide in source, environment-friendly, safe, nontoxic and renewable has attracted attention. Nanocellulose has recently received much attention in different fields as a renewable, degradable green nanomaterial because cellulose is the most abundant renewable biomass resource on earth, which can be derived from plants and animals such as trees, cotton, straws, bamboo on land, and seaweeds, sea squirts and the like in the sea (angew. In addition, the nano-cellulose also has the characteristics of controllable surface charge form, unique structure, excellent mechanical property, lower thermal expansion coefficient and the like (chem.Soc.Rev.2017, 46, 1510-1525), and the application of the nano-cellulose serving as a novel dreamlike nano-material can cover the aspects of biology, medicine, reinforcing agents, paper industry, food engineering field, sewage purification, photoelectric energy storage and the like.
For a long time, as for the research of nanocellulose, countries and regions such as japan, northern europe, and north america have been in the front. The cellulose nano-fiber can be divided into enzymolysis nano-cellulose with uncharged surface, TEMPO oxidized nano-cellulose with negatively charged surface and cation nano-cellulose with positively charged surface according to different preparation methods. Typically, individual cellulose fibers (typically 5-20um in diameter) are composed of bundles of nanofibers (typically 3-20nm in diameter) with a maximum length of up to 5um and an aspect ratio of over 250 (Biomacromolecules 2006,7, 1688-1691). The degradable functional polymer composite material with controllable structure and excellent performance is prepared by the method of non-covalent bond action, in-situ chemical polymerization and the like through the fine nano structure, the high specific surface area and the abundant hydroxyl and other controllable functional groups on the surface.
Currently, cationic cellulose nanofibers from wood pulp and cotton pulp have been successfully prepared (ACS Applied Materials & Interfaces 2021,13, 4463-4472), but have no antibacterial activity. Therefore, the cationic bamboo cellulose nanofiber with high lignin content and controllable size prepared by the surface chemical modification method has wide application prospect in the field of degradable functional composite materials.
Disclosure of Invention
The invention aims to provide a cationic bamboo cellulose nanofiber with high lignin content and a preparation method thereof.
Specifically, the invention provides a preparation method of cationic bamboo cellulose nanofibers, which comprises the following steps:
(1) Swelling the bamboo fiber in an alkali solution to activate the hydroxyl on the bamboo fiber;
(2) Reacting a cationic etherification reagent with the activated bamboo fiber, and filtering and washing a reaction product to prepare cationic bamboo cellulose nanofiber; the content of the bamboo fiber lignin is 5wt% -25 wt%.
Preferably, the lignin content of the bamboo fiber is 20wt% to 25wt%.
Preferably, in the step (1), the bamboo fiber is added into an alkali solution, heated at 60-100 ℃, and uniformly stirred, wherein the alkali solution is a sodium hydroxide solution or a potassium hydroxide solution; the concentration of the alkali solution is 2-8wt%; preferably 5-6wt%.
Preferably, the mass fraction of the bamboo fiber is 1-10wt%; more preferably 3 to 5wt%.
Preferably, in the step (2), the cation etherification reagent and the activated bamboo fiber are heated to react at 50-120 ℃, and the reaction product is filtered and washed to prepare the cation bamboo cellulose nanofiber; preferably, the foregoing steps are repeated 2-4 times.
Preferably, the molar ratio of the cationic etherification agent to the sugar units in the bamboo fibrils is 1-10:1; more preferably 3 to 6.
Preferably, the cationic etherification reagent comprises one or more of 2, 3-epoxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride and 2, 3-epoxypropyltriethylammonium chloride in any combination; more preferably 2, 3-epoxypropyltrimethylammonium chloride.
Preferably, the method for preparing bamboo fibrils comprises the following steps:
a. the bamboo wood is boiled with alkali to remove lignin and hemicellulose to obtain a material I, and the material I is oxidized and bleached to obtain a material II;
b. freezing and unfreezing the material II to obtain a material III, drying the material III until the water content is less than or equal to 10% to obtain a material IV, and separating the material IV to obtain the bamboo fiber.
Preferably, the bamboo material is one or more of moso bamboo, sagittaria sagittifolia, white bamboo, green bamboo, phyllostachys bambusoides, pink bamboo, green bamboo, bamboo material processing residues and pulp and paper making residues.
Preferably, in step a, the alkaline cooking conditions comprise: the raw materials are put into alkaline solution and heated at 70-160 ℃.
Preferably, the alkaline solution comprises at least one of sodium hydroxide, potassium hydroxide, sodium sulfite, sodium sulfide, sodium carbonate, sodium sulfate, sodium thiosulfate; more preferably, the alkaline solution comprises sodium hydroxide and at least one of sodium sulfite and sodium sulfide.
Preferably, the alkaline solution is 1-4mol/L NaOH and 0.1-1mol/L Na 2 SO 3 The mixed solution of (1).
Preferably, the solid-to-liquid ratio of the alkaline solution to the bamboo wood is 1:8 to 1, preferably 1: 10-1.
Preferably, in step a, the oxidative bleaching conditions comprise: and (3) adjusting the pH value of the material I to 9-12, placing the bamboo wood into an oxidant solution, heating at 60-120 ℃, and washing the bamboo wood subjected to oxidation bleaching treatment to be neutral by using water.
Preferably, the oxidizing agent comprises at least one of hydrogen peroxide, hypohalous acid or salt thereof, organic peroxyacids, sodium percarbonate, chlorine dioxide, oxygen, ozone, borohydride, dithionite; preferably any one of hydrogen peroxide, oxygen, ozone, and chlorine dioxide.
More preferably, the oxidant solution is a 1-5wt% hydrogen peroxide solution.
Preferably, the solid-to-liquid ratio of the oxidant solution to the bamboo wood is 1:8 to 1, preferably 1: 10-1.
Preferably, in the step b, the freezing temperature of the material II is-30-0 ℃, and the unfreezing temperature of the material II is 20-100 ℃.
Preferably, the material III is dried in any one of supercritical drying, freeze drying, vacuum oven drying and forced air drying.
More preferably, the material III is dried preferably by freeze drying.
Preferably, the freeze-drying further comprises a freezing medium, wherein the freezing medium is water and/or tert-butanol; more preferably tert-butanol.
The invention also provides the cationic bamboo cellulose nanofiber with high lignin content, which is prepared by the preparation method.
The inventor of the invention finds that lignin is retained when crude bamboo fibers are separated from phyllostachys edulis treated, and simultaneously, bamboo jade active components of phyllostachys edulis are retained; the cationic bamboo cellulose nanofiber prepared by the preparation method disclosed by the invention can retain lignin by the cationic bamboo cellulose nanofiber, the size of the nanofiber is controllable, the distribution is uniform, the tensile strength of the cationic bamboo cellulose nanofiber membrane is up to 250MPa, and the synergistic antibacterial function of the cationic bamboo cellulose and the bamboo jade active substances is realized.
The cationic bamboo cellulose nanofiber prepared by the preparation method disclosed by the invention has the lignin content of 5-25 wt%, the size of the nanofiber can be controlled to be 1-3 mu m, and the cationic bamboo cellulose nanofiber can be applied to the fields of antibiosis, polymer reinforced materials and the like.
Drawings
Fig. 1 is a photo of a cationic bamboo cellulose nanofiber obtained by reacting bamboo fiber with a cationizing agent for 1 time (a), 2 times (b), and 3 times (c), respectively.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of cationic bamboo cellulose nano-fibers with high lignin content, which comprises the following steps:
(1) Swelling the bamboo fiber in an alkali solution to activate the hydroxyl on the bamboo fiber;
(2) Reacting a cationic etherification reagent with the activated bamboo fiber, and filtering and washing a reaction product to prepare cationic bamboo cellulose nanofiber; the content of the bamboo fiber lignin is 5wt% -25 wt%.
Bamboo fiber with high lignin content and a cationic etherification reagent are used as raw materials, nucleophilic substitution reaction is utilized to cationize the bamboo fiber under alkaline conditions, and the molar ratio of the cationic etherification reagent to hydroxyl groups in a cellulose glucose unit is changed to control the content of cations on the nanofiber. Compared with the same wood nanocellulose, the fiber length is longer, and the active ingredients such as the bamboo jade ensure more functional applications.
According to the present invention, preferably, the bamboo fibril lignin content is 20wt% to 25wt%; the bamboo fiber with high lignin content can retain more bamboo rolling active components.
According to the invention, in the step (1), the bamboo fiber is added into the alkali solution, heated at 60-100 ℃, and uniformly stirred; under the conditions, the hydroxyl in the bamboo fiber is activated.
According to the invention, the alkali solution is selected conventionally in the invention, and the alkali solution can be sodium hydroxide solution or potassium hydroxide solution, and preferably, the concentration of the alkali solution is 2-8wt%; more preferably 5-6wt%.
According to the invention, preferably, in the alkaline solution, the mass fraction of the bamboo fibrils is 1-10wt%; more preferably 3 to 5wt%; the alkali solution of the aforementioned concentration is advantageous for activating the hydroxyl groups in the bamboo fibers.
According to the invention, preferably, in the step (2), a cationic etherification reagent reacts with the activated bamboo fibrils at the reaction temperature of 50-120 ℃, the reaction is stirred for 6-8 hours, and the reaction products are filtered and washed to prepare the cationic bamboo cellulose nanofibers; repeating the reacting step 2,3, 4, 5, 6 times, more preferably repeating the reacting step 2-4 times; bamboo fibrils can obtain bamboo nanofibers with different sizes through cationization or multiple cationization and different cation contents, and the size of the cationic bamboo cellulose nanofibers is controlled through the cation content, so that the nanofibers are uniformly distributed.
According to the invention, the molar ratio of cationic etherification agent to sugar units in the bamboo fibrils is preferably 1 to 10:1; more preferably 3-6, the size of the cationic bamboo cellulose nanofiber is controlled, and the distribution of the nanofiber is uniform.
According to the invention, preferably, the cationic etherification reagent comprises one or more of 2, 3-epoxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride and 2, 3-epoxypropyltriethylammonium chloride in any combination; more preferably 2, 3-epoxypropyltrimethylammonium chloride; the cation etherification reagent is more suitable for cationization of the bamboo fiber, and uniform distribution of the nano fiber is realized.
According to the present invention, preferably, the method for preparing bamboo fibrils with high lignin content comprises:
a. alkali cooking bamboo wood to remove lignin and hemicellulose to obtain a material I, and oxidizing and bleaching the material I to obtain a material II;
b. freezing and unfreezing the material II to obtain a material III, drying the material III until the water content is less than or equal to 10% to obtain a material IV, and separating the material IV to obtain the bamboo fiber.
Through the combination of chemical and physical methods, after most of lignin and hemicellulose are removed from the bamboo wood, the bamboo wood is frozen and unfrozen, so that parenchyma cells and fibers in the bamboo wood are effectively separated, and high-purity bamboo fibrils are prepared; the lignin content in the bamboo fiber is regulated and controlled and the bamboo phenol active components in the moso bamboo are retained by controlling the concentration of the bamboo in an alkaline solution, the cooking temperature and the cooking time, and the temperature and the time of oxidation bleaching.
According to the invention, preferably, the lignin content in the prepared bamboo fiber is more than or equal to 5wt%, and the bamboo jade active components are retained; preferably, the lignin content of the prepared bamboo fiber is 20wt%, more preferably, the lignin content in the bamboo fiber is less than or equal to 25wt%, under the condition, the preparation of the bamboo fiber is easy to realize, and more bamboo phenol active components are retained.
According to the present invention, preferably, the bamboo material is one or more of moso bamboo, arrowhead bamboo, white sandwich bamboo, stay green bamboo, pink bamboo, green bamboo, bamboo material processing residues and pulp and paper making residues.
According to the present invention, preferably, in step a, the alkaline cooking conditions comprise: the raw materials are put into alkaline solution and heated at 70-160 ℃.
According to the present invention, preferably, the alkaline solution contains at least one of sodium hydroxide, potassium hydroxide, sodium sulfite, sodium sulfide, sodium carbonate, sodium sulfate, sodium thiosulfate; more preferably, the alkaline solution comprises sodium hydroxide and at least one of sodium sulfite and sodium sulfide; by adopting the preparation method of the bamboo fiber, the prepared bamboo fiber can retain a large amount of lignin, and simultaneously retain bamboo jade active components in the moso bamboo.
More preferably, according to the invention, the alkaline solution is 1-4mol/L NaOH and 0.1-1mol/LNa 2 SO 3 The mixed solution of (1); most preferably 2.5mol/L NaOH and 0.4mol/L Na 2 SO 3 Mixing the solution; further improving the content of lignin and bamboo jade active components in the bamboo fiber.
According to the present invention, preferably, the solid-to-liquid ratio of the alkaline solution to the bamboo material is 1:8 to 1, more preferably 1: 10-1; further improving the content of lignin and bamboo jade active components in the bamboo fiber.
According to the present invention, preferably, the solid-to-liquid ratio of the oxidant solution to the bamboo material is 1:8 to 1, more preferably 1: 10-1; further improving the content of lignin and bamboo jade active components in the bamboo fiber.
According to the present invention, preferably, in step a, the oxidative bleaching conditions comprise: and (3) adjusting the pH value of the material I to 9-12, placing the bamboo wood into an oxidant solution, heating at 60-120 ℃, and washing the bamboo wood subjected to oxidation bleaching treatment to be neutral by using water.
Preferably, the oxidizing agent comprises at least one of hydrogen peroxide, hypohalous acid or salt thereof, organic peroxyacids, sodium percarbonate, chlorine dioxide, oxygen, ozone, borohydride, dithionite; preferably any one of hydrogen peroxide, oxygen, ozone and chlorine dioxide.
More preferably, the oxidant solution is a 1-5wt% hydrogen peroxide solution; further improving the contents of lignin and bamboo beautiful active components in the bamboo fiber.
According to the present invention, preferably, the solid-to-liquid ratio of the oxidant solution to the bamboo material is 1: 8-1, preferably 1: 10-1.
The reaction conditions of the freezing and thawing process are not particularly limited, as long as the acting force between the parenchyma cells and the fiber bundles in the bamboo wood can be destroyed, preferably, the freezing temperature of the material II is-30-0 ℃, and the freezing time is 1-24 h; the unfreezing temperature of the material II is 20-100 ℃; the adoption of the freezing-thawing condition can make the wet bamboo chips looser, because the volume of water expands when forming ice, the distances between the parenchyma cells and the fiber bundles are increased, and the interaction forces between the parenchyma cells and the fiber bundles are damaged, so that the parenchyma cells and the bamboo fibrils are separated.
According to the invention, the material III is dried in a manner conventional in the field, as long as water in the material III can be removed, and preferably, the drying manner is any one of freeze drying, supercritical drying, vacuum oven drying and forced air drying; more preferably, the drying method is freeze drying, and the original polyhedral structure of the parenchyma cell can be completely maintained by adopting freeze drying.
According to the invention, the step of freeze-drying further comprises placing the bamboo chips in a freezing medium, preferably, the freezing medium is one or more of water, ethanol, tert-butyl alcohol and acetone in any combination; more preferably t-butanol, the preferred freezing medium has a higher freezing point and a higher saturated vapor pressure, and the use of the preferred refrigerant is advantageous in saving freeze-drying time.
The invention also provides the cationic bamboo cellulose nanofiber with high lignin content, which is prepared by the method.
The present invention will be described in detail below by way of examples.
The mao bamboos used in the following examples and comparative examples were sampled from the demonstration base of Ganzhou Chongyi mao bamboos, and other raw materials were commercially available.
Preparation example 1
(1) Putting the moso bamboo chips into a single-neck flask, adding 2.5mol/L NaOH and 0.4mol/L Na 2 SO 3 Mixing the solution (solid-to-liquid ratio 1 2 O 2 Heating the solution (the solid-liquid ratio is 1;
(2) Placing delignified bamboo chips in a refrigerator, freezing for 1h at 0 ℃, unfreezing at 25 ℃ to obtain wet bamboo chips, placing the wet bamboo chips in tert-butyl alcohol for replacement for 12h, and then carrying out freeze drying for 12h. Finally, the mixed cells are separated by mechanical extrusion, and the bamboo fiber is washed and dried to obtain the bamboo fiber F1 (the cellulose content is 57.5%, the hemicellulose content is 19.7% and the lignin content is 22.8%).
Preparation example 2
(1) Putting the moso bamboo chips into a single-neck flask, adding 2.5mol/L NaOH and 0.4mol/L Na 2 SO 3 The mixed solution (solid-to-liquid ratio 1 2 O 2 Adding the solution (solid-liquid ratio is 1Heating for 2h, washing to neutrality, and removing mixed cells;
(2) Placing delignified bamboo chips in a refrigerator, freezing for 1h at 0 ℃, unfreezing at 25 ℃ to obtain wet bamboo chips, placing the wet bamboo chips in tert-butyl alcohol for replacement for 12h, and then carrying out freeze drying for 12h. Finally, the mixed cells are separated by mechanical extrusion, and the bamboo fiber is washed and dried to obtain the bamboo fiber F2 (the cellulose content is 63.7%, the hemicellulose content is 17.7% and the lignin content is 18.6%).
Preparation example 3
(1) Placing bamboo chips in NaOH and Na 2 S (20% alkali, 25% vulcanization degree, 1/liquid) was heated at 150 ℃ for 2 hours, washed with water to neutrality, and the bamboo chips were placed in a chamber of 4wt% H 2 O 2 And 1wt% NaOH solution, heating at 70 deg.C for 2h, washing with water to neutral to obtain delignified bamboo chips;
(2) And (3) putting the delignified bamboo chips in a refrigerator, freezing for 1h at 0 ℃, then unfreezing at 25 ℃ to obtain wet bamboo chips, putting the wet bamboo chips in tert-butyl alcohol for replacement for 12h, and then carrying out freeze drying for 12h. Finally, the mixed cells are separated by mechanical rolling, and the bamboo fiber is washed and dried to obtain the bamboo fiber F3 (the cellulose content is 86%, the hemicellulose content is 8% and the lignin content is 6%).
Practice of example 1
Placing 5.0g of the bamboo fibril F1 in the preparation example (1) into a single-neck flask, adding 95g of 5wt% NaOH solution, stirring uniformly, adding 70.21g of 2, 3-epoxypropyltrimethylammonium chloride (the molar ratio of cellulose to sugar in the bamboo fibril is 5;
the content of cationic bamboo cellulose nanofiber lignin is 21.1 percent; the tensile strength was 213.0MPa.
Example 2
Placing 5.0g of the bamboo fiber F1 in the preparation example (1) into a single-neck flask, adding 95g of 5wt% NaOH solution, uniformly stirring, adding 70.21g of 2, 3-epoxypropyltrimethylammonium chloride (the molar ratio of cellulose to sugar units in the bamboo fiber is 5;
repeating the steps for 1 time to obtain the cationic bamboo cellulose nanofiber;
the content of cationic bamboo cellulose nanofiber lignin is 20.7 percent; the tensile strength was 226.7MPa.
Example 3
Placing 5.0g of the bamboo fiber F1 in the preparation example (1) into a single-neck flask, adding 95g of 5wt% NaOH solution, uniformly stirring, adding 70.21g of 2, 3-epoxypropyltrimethylammonium chloride (the molar ratio of cellulose to sugar units in the bamboo fiber is 5;
repeating the steps for 2 times to obtain the cationic bamboo cellulose nanofiber;
the content of cationic bamboo cellulose nanofiber lignin is 20.2 percent; the tensile strength was 250.2MPa.
Example 4
Different from the example 2, the bamboo fiber F2 in the preparation example 2 is adopted as the raw material, and the rest of the operation steps are the same as the example 2;
the content of cationic bamboo cellulose nanofiber lignin is 17.3wt%; the tensile strength was 221.3MPa.
Example 5
Different from the example 2, the bamboo fiber F3 in the preparation example 3 is adopted as the raw material, and the rest of the operation steps are the same as the example 2;
the content of cationic bamboo cellulose nanofiber lignin is 5.8wt%; the tensile strength was 211.7MPa.
Example 6
Different from the embodiment 2, the cationic etherification reagent is 2, 3-epoxypropyltriethyl ammonium chloride, and the rest of the operation steps are the same as the embodiment 2;
the content of cationic bamboo cellulose nanofiber lignin is 6.3wt%; the tensile strength was 203.9MPa.
Example 7
Placing 5.0g of the bamboo fiber F1 in the preparation example (1) into a single-neck flask, adding 95g of 5wt% NaOH solution, uniformly stirring, adding 112.34g of 2, 3-epoxypropyltrimethylammonium chloride (the molar ratio of cellulose to sugar units in the bamboo fiber is 8;
repeating the steps for 1 time to obtain the cationic bamboo cellulose nanofiber;
the content of cationic bamboo cellulose nanofiber lignin is 19.4wt%; the tensile strength was 220.9MPa.
Comparative example 1
Compared with the cationic cellulose nano-fiber prepared by wood pulp (Soft Matter,2013,9, 2047-2055);
the content of the cationic cellulose nanofiber lignin is 0wt%; the tensile strength was 189MPa.
Comparative example 2
Different from the embodiment 1, the cationic etherification reagent is octadecyl trimethyl ammonium bromide, and the rest operation steps are the same as the embodiment 1;
the prepared nano bamboo cellulose nano fibers are agglomerated and cannot be dispersed.
Antibacterial testing
An antibacterial experiment is carried out according to the method in the GB/T21510-2008 standard, bacteria are inoculated into a bacteria culture medium containing cationic bamboo cellulose nano-fibers with the mass concentration of 0.5%, and the result shows that the killing rate of the cationic bamboo cellulose nano-fibers to escherichia coli is more than 99% and the killing rate to staphylococcus aureus is more than 99% in the examples 1-7.
The cationic bamboo cellulose nanofiber provided by the invention reserves lignin, can be uniformly dispersed and has a controllable size (the size can be controlled within 1-3 mu m), has high strength (the tensile strength is greater than 200MPa and the highest tensile strength is 250 MPa), and has a synergistic antibacterial function of cationic bamboo cellulose and bamboo jade active substances.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the foregoing embodiments may be combined in any suitable manner without contradiction. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (10)

1. A preparation method of cationic bamboo cellulose nanofibers is characterized by comprising the following steps:
(1) Swelling the bamboo fiber in an alkali solution to activate the hydroxyl on the bamboo fiber;
(2) Reacting a cationic etherification reagent with the activated bamboo fiber, and filtering and washing a reaction product to prepare cationic bamboo cellulose nanofiber;
the content of the bamboo fiber lignin is 5wt% -25 wt%.
2. The preparation method according to claim 1, wherein in the step (1), the bamboo fiber is added into the alkali solution, heated at 60-100 ℃ and stirred;
the mass fraction of the bamboo fiber is 1-10wt%, preferably 3-5wt%,
the concentration of the alkali solution is 2-8wt%; preferably 5-6wt%.
3. The preparation method according to claim 1, wherein in the step (2), the cationic etherification reagent and the activated bamboo fiber are heated to react at 50-120 ℃, and the reaction product is filtered and washed to prepare the cationic bamboo cellulose nanofiber;
preferably, step (2) is repeated 2-4 times.
4. The production method according to claim 1 or 3, wherein the molar ratio of the cationic etherification agent to the sugar units in the bamboo fibers is 1 to 10:1; preferably 3 to 6.
5. The preparation method according to claim 1 or 3, wherein the cationic etherification reagent comprises one or more of 2, 3-epoxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride and 2, 3-epoxypropyltriethylammonium chloride in any combination; 2, 3-epoxypropyltrimethylammonium chloride is preferred.
6. The method of claim 1, wherein the method of preparing bamboo fibrils comprises:
a. the bamboo wood is boiled with alkali to remove lignin and hemicellulose to obtain a material I, and the material I is oxidized and bleached to obtain a material II;
b. freezing and unfreezing the material II to obtain a material III, drying the material III until the water content is less than or equal to 10% to obtain a material IV, and separating the material IV to obtain the bamboo fiber.
7. The method according to claim 6, wherein the step a is a
The alkaline cooking conditions comprise: putting the raw materials into an alkaline solution, and heating at 70-160 ℃;
the oxidative bleaching conditions include: and (3) adjusting the pH value of the material I to 9-12, placing the bamboo wood into an oxidant solution, heating at 60-120 ℃, and washing the bamboo wood subjected to oxidation bleaching treatment to be neutral by using water.
8. The production method according to claim 6, wherein,
the alkaline solution contains sodium hydroxide and at least one of sodium sulfite and sodium sulfide; preferably, the alkaline solution is 1-4mol/L NaOH and 0.1-1mol/L Na 2 SO 3 The mixed solution of (1);
the oxidant comprises at least one of hydrogen peroxide, hypohalite or its salt, organic peroxy acid, sodium percarbonate, chlorine dioxide, oxygen, ozone, borohydride, dithionite; preferably any one of hydrogen peroxide, oxygen, ozone and chlorine dioxide; more preferably, the oxidant solution is a 1-5wt% hydrogen peroxide solution.
9. The production method according to claim 6, wherein,
the solid-liquid ratio of the alkaline solution to the bamboo wood is 1:8 to 1, preferably 1: 10-1;
the solid-liquid ratio of the oxidant solution to the bamboo wood is 1:8 to 1, preferably 1: 10-1.
10. A cationic bamboo cellulose nanofiber, characterized in that the cationic bamboo cellulose nanofiber is prepared by the preparation method of any one of claims 1 to 9.
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