CN113136053A - Preparation method of lignocellulose three-component double-crosslinking gel, gel and application - Google Patents

Preparation method of lignocellulose three-component double-crosslinking gel, gel and application Download PDF

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CN113136053A
CN113136053A CN202110346940.6A CN202110346940A CN113136053A CN 113136053 A CN113136053 A CN 113136053A CN 202110346940 A CN202110346940 A CN 202110346940A CN 113136053 A CN113136053 A CN 113136053A
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gel
lignocellulose
double
crosslinking
lignin
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CN113136053B (en
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王志国
马丽莎
张莉莉
范一民
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Nanjing Forestry University
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Nanjing Forestry University
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    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/048—Elimination of a frozen liquid phase
    • C08J2201/0484—Elimination of a frozen liquid phase the liquid phase being aqueous
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
    • C08J2205/026—Aerogel, i.e. a supercritically dried gel
    • 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
    • C08J2301/04—Oxycellulose; Hydrocellulose
    • 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
    • C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/14—Hemicellulose; Derivatives thereof
    • 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
    • C08J2497/00—Characterised by the use of lignin-containing materials

Abstract

The invention discloses a preparation method of lignocellulose three-component double-crosslinking gel, the gel and application, wherein the preparation method comprises the following steps: preparing a nano cellulose dispersion solution by using a cellulose raw material, and respectively dissolving hemicellulose and lignin in corresponding solvents to respectively obtain a hemicellulose solution and a lignin solution; uniformly mixing the raw materials to obtain a lignocellulose dispersion liquid containing three components of nano-cellulose, hemicellulose and lignin; placing the three-component lignocellulose dispersion liquid in a double-steam bath closed environment with double functions of physical crosslinking and chemical crosslinking for reaction to prepare the lignocellulose three-component double-crosslinking gel. Has the advantages that: the method adopted by the invention can effectively improve the solid content of the gel to prepare the high-strength gel, is simple to operate and easy to realize industrialization, and the obtained gel has good mechanical property and biocompatibility and can be widely applied to the fields of catalytic adsorption, biomedicine, sensors and the like.

Description

Preparation method of lignocellulose three-component double-crosslinking gel, gel and application
Technical Field
The invention relates to the technical field of gel preparation and production, in particular to a preparation method of lignocellulose three-component double-crosslinked gel, the gel and application.
Background
The three major components in the natural plant raw material lignocellulose are cellulose, hemicellulose and lignin, and the natural high molecular polymer which is rich in source, easy to obtain, easy to degrade, nontoxic and harmless plays a very important role in the production and life of human beings. The gel is a substance with a three-dimensional network structure connected through a certain function, and is widely applied to the fields of drug delivery, tissue engineering, wound dressing, water purification, catalysis, electrical elements and the like at present. In recent years, more and more researchers have used lignocellulose, which is a natural polymer, to prepare gel materials with diversified functions.
The crosslinking mode of the lignocellulose gel is divided into physical crosslinking and chemical crosslinking, the physical crosslinking depends on mutual entanglement among fibers and a large number of hydrogen bonds, van der waals force and other actions, the chemical crosslinking forms a three-dimensional network structure by generating covalent bonds, and the chemical crosslinking or double crosslinking gel has better mechanical properties than the physical gel in general.
The solid content of the gel often plays a decisive role in influencing the strength of the gel, and the lignocellulose gel prepared in a dispersion system generally has the problem of poor mechanical properties, which is caused by the fact that the solid content of the gel in the dispersion system is difficult to increase. Nguyen THM and the like add chitosan in a nano-cellulose dispersion system to prepare gel with the solid content of 0.8% at most, Sultana T adds methyl cellulose, carboxymethyl cellulose and polyethylene glycol in the nano-cellulose dispersion system to prepare gel with the solid content of 1% at most, and therefore, the improvement of the solid content of the lignocellulose gel in the dispersion system is the most main method for improving the mechanical property of the gel. In addition, there is another problem to be solved in preparing chemical gel in dispersion system, that is, it takes a certain time to blend the chemical cross-linking agent and the lignocellulose dispersion system uniformly, and if a volatile cross-linking agent is selected, it is difficult to ensure effective utilization of the cross-linking agent.
Treating lignocellulose with a steam bath to cause physical crosslinking of the gel is an emerging method of preparation. In recent years, dispersion gels represented by nanocellulose obtained by mechanical treatment or oxidation and mechanical treatment have been increasingly studied. Chinese patent CN106893116A discloses a method for preparing gel by reducing electrostatic repulsion of nanocellulose through acid vapor bath to form physical crosslinking. Xu HY and the like firstly add epichlorohydrin in nano-cellulose to form chemical crosslinking and then place the nano-cellulose in a hydrochloric acid vapor bath environment to form physical crosslinking to prepare the double-crosslinked cellulose gel, however, when the solid content of a dispersion system is higher, the crosslinking agent is difficult to be uniformly blended with the nano-cellulose, so that the maximum solid content of the gel is 1%, and the compressive strength is only 225 kPa.
In summary, it is difficult to prepare a physico-chemically double-crosslinked high solid content high strength gel in a dispersion system because the solid content of the gel is difficult to increase and the chemical crosslinking agent is difficult to be fully mixed with the dispersion liquid at a high solid content.
An effective solution to the problems in the related art has not been proposed yet.
Disclosure of Invention
Aiming at the problems in the related art, the invention provides a preparation method, gel and application of lignocellulose three-component double-crosslinking gel, so as to overcome the technical problems in the prior related art.
The invention aims to: with the increasing environmental problems and the increasing shortage of petrochemical resources, more and more attention has been paid to the strategy of synthesizing novel polymer materials by replacing petrochemical raw materials with renewable and easily degradable biomass raw materials such as lignocellulose. Based on the problem that the solid content of the lignocellulose gel in a dispersion system is difficult to improve, so that the strength is difficult to improve, the invention provides a method for preparing the lignocellulose gel with high solid content by using double vapor baths, so that the mechanical property of the lignocellulose gel is effectively enhanced, and the lignocellulose three-component double-crosslinking gel prepared by using the double vapor baths endows the gel with new functionality on the basis of keeping the original characteristics of each component, so that the application of the gel in more fields becomes possible.
Therefore, the invention adopts the following specific technical scheme:
according to one aspect of the present invention, there is provided a method for preparing a lignocellulose three-component double cross-linked gel, the method comprising the steps of:
s1, preparing nano-cellulose dispersion liquid by using a cellulose raw material, and respectively dissolving hemicellulose and lignin in corresponding solvents to respectively obtain a hemicellulose solution and a lignin solution;
s2, uniformly mixing the nano-cellulose dispersion liquid, the hemicellulose solution and the lignin solution to obtain a lignocellulose dispersion liquid containing three components of nano-cellulose, hemicellulose and lignin;
s3, placing the three-component lignocellulose dispersion liquid in a double-steam bath closed environment with double functions of physical crosslinking and chemical crosslinking for reaction to prepare the lignocellulose three-component double-crosslinking gel.
Further, the nano-cellulose is obtained by treating a cellulose raw material by a mechanical treatment method or an oxidation and mechanical treatment method, wherein the mechanical treatment method comprises high-pressure homogenization treatment, ultrasonic crushing treatment, superfine grinding treatment, colloid mill treatment, micro-jet treatment and the like, and preferably the high-pressure homogenization treatment; the oxidation treatment method is a biological oxidation method, a chemical oxidation method or the like, and is preferably TEMPO/NaBr/NaClO oxidation in the chemical oxidation method.
Further, the raw material of the hemicellulose is derived from any one or a combination of at least two of glucomannan, xylan, araban and galactan of plant raw materials, preferably glucomannan and xylan.
Further, the solvent for dissolving hemicellulose is any one of water, alkali, an alkali urea system (such as a NaOH/urea system, a NaOH/thiourea system, a LiOH/urea system), an organic solvent (such as dimethyl sulfoxide, NMMO) or a combination of at least two thereof, and is preferably water.
Further, the raw material of the lignin is any one or a combination of at least two of ground wood lignin, enzymatic hydrolysis lignin, organic solvent separation lignin, alkali lignin and lignosulfonate, preferably alkali lignin and lignosulfonate.
Further, the dissolution solvent of the lignin is any one of water, alkali urea system (such as NaOH/urea system, NaOH/thiourea system, LiOH/urea system), organic solvent (such as dimethyl sulfoxide, NMMO) or combination of at least two of them, and is preferably 0.5M NaOH.
Further, the solid content of the lignocellulose dispersion liquid is 0.5 wt% to 10.0 wt%, and preferably 1 wt% to 5 wt%.
Furthermore, the mass percentage of the cellulose raw material in the gel oven-dried raw material is 20-100%, and preferably 70-90%; the mass ratio of the hemicellulose raw material in the gel oven-dried raw material is 0-80%, preferably 10-30%; the mass ratio of the lignin raw material in the gel oven-dried raw material is 0-80%, preferably 10-30%.
Further, the vapor bath for physical crosslinking is a vapor bath for volatile physical coagulants, and the vapor bath for chemical crosslinking is a vapor bath for volatile hydroxyl crosslinking agents.
Further, the vapor bath for physical crosslinking includes volatile alcohol vapor bath, alkali vapor bath, acid vapor bath, etc., preferably ammonia water vapor bath, acetic acid vapor bath; the chemical crosslinking steam bath comprises an epichlorohydrin steam bath, a glyoxal steam bath, a glutaraldehyde steam bath and the like, and preferably the epichlorohydrin steam bath and the glutaraldehyde steam bath.
Further, the reaction temperature in the S3 is 20-90 ℃, the reaction time is 1-24 h, preferably 50-80 ℃, and 2-5 h.
According to another aspect of the present invention, there is provided a lignocellulose three-component double cross-linked gel prepared by the method for preparing the same, preferably, the methodThe lignocellulose three-component double-crosslinking gel has higher solid content and stronger mechanical property, and the storage modulus of the gel prepared under different conditions can be 9.37 multiplied by 103～1.27×107Pa。
According to another aspect of the invention, a preparation method of the lignocellulose three-component double-crosslinked aerogel is provided, wherein the lignocellulose three-component double-crosslinked gel prepared by the preparation method of the lignocellulose three-component double-crosslinked gel or the lignocellulose three-component double-crosslinked gel is subjected to freeze drying to obtain the lignocellulose three-component double-crosslinked aerogel.
According to another aspect of the invention, the lignocellulose three-component double-crosslinked aerogel is provided and is prepared by the preparation method of the lignocellulose three-component double-crosslinked aerogel.
According to a further aspect of the present invention, there is provided a use of a lignocellulosic three-component dual cross-linked gel/aerogel, such as said lignocellulosic three-component dual cross-linked gel or said lignocellulosic three-component dual cross-linked aerogel in the fields of sustained release, filtration, catalysis, adsorption or sensors.
The invention has the beneficial effects that:
1) the method for preparing the lignocellulose three-component double-crosslinked gel through double vapor baths provided by the invention can effectively solve the problem that the solid content of the lignocellulose double-crosslinked gel prepared by a dispersion system is difficult to improve, so that the gel strength is improved.
2) The method for preparing the lignocellulose three-component double-crosslinking gel through double vapor baths can effectively improve the internal crosslinking density of the gel, complete physical and chemical double crosslinking in the process of gas permeating into the gel, and ensure the crosslinking uniformity.
3) The method for preparing the lignocellulose three-component double-crosslinking gel through double steam baths provided by the invention can effectively solve the problem that a crosslinking agent is difficult to utilize efficiently. The traditional method for preparing the double-crosslinking gel by adding the crosslinking agent has lower utilization rate of the crosslinking agent, and the steam bath for physical and chemical crosslinking provided by the invention ensures that the liquid is not directly added into the dispersion liquid, thereby greatly improving the effective utilization rate of the crosslinking agent, saving energy consumption and reducing preparation cost; the method is simple and feasible to operate and easy to realize industrialization.
4) The addition of the whole lignocellulose component also improves the plasticity and toughness of the gel and endows the double-crosslinking gel with more functionality, so that the gel prepared by the method has more diversified functional applications such as catalysis, adsorption, ultraviolet resistance and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a flow chart of a method of making a lignocellulosic three-component double cross-linked gel in accordance with an embodiment of the present invention;
FIG. 2 is an appearance diagram of a lignocellulose double cross-linked gel having a solid content of 1.5 wt% in a method for preparing a lignocellulose three-component double cross-linked gel according to an embodiment of the present invention;
FIG. 3 is a graph of the viscoelastic properties of lignocellulosic two-component two-crosslinked gels of varying solids content in a process for making lignocellulosic two-component two-crosslinked gels according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings, technical process steps, specific implementation conditions and materials in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
According to the embodiment of the invention, a preparation method, gel and application of lignocellulose three-component double-crosslinked gel are provided.
According to one aspect of the present invention, as shown in fig. 1, there is provided a method for preparing a lignocellulose three-component double cross-linked gel, the method comprising the steps of:
s1, preparing nano-cellulose dispersion liquid by using a cellulose raw material, and respectively dissolving hemicellulose and lignin in corresponding solvents to respectively obtain a hemicellulose solution and a lignin solution;
s2, uniformly mixing the nano-cellulose dispersion liquid, the hemicellulose solution and the lignin solution to obtain a lignocellulose dispersion liquid containing three components of nano-cellulose, hemicellulose and lignin;
s3, placing the three-component lignocellulose dispersion liquid in a double-steam bath closed environment with double functions of physical crosslinking and chemical crosslinking for reaction to prepare the lignocellulose three-component double-crosslinking gel.
In order to better understand the technical solution, the following detailed description is made on specific embodiments of the present invention.
The lignocellulose three-component double-crosslinking gel provided by the invention can flexibly regulate and control the gel quality according to factors such as actual use environment, mold size, test requirements and the like, and the invention is explained by taking 5g as a gel preparation standard in the following examples.
Example one
Taking nano-cellulose dispersion liquid with the absolute dry mass of 0.0750g and supplementing a certain amount of distilled water, fully mixing to prepare 5g of uniform and transparent dispersion liquid, centrifuging to remove bubbles, filling the dispersion liquid into a mold, respectively placing a certain amount of ammonia water and epoxy chloropropane into a closed container to provide a gas environment capable of generating physical and chemical crosslinking, placing the dispersion liquid into a double-steam bath environment, and reacting for 3 hours at 65 ℃ to obtain the cellulose double-crosslinking gel. The cellulose double-crosslinked gel obtained had a solids content of 1.5 wt.%.
The reacted cellulose bis-crosslinked gel was transferred to a clean beaker with ethanol to stop the chemical reaction and carry out solvent displacement, and the ethanol was replaced every several hours to ensure complete solvent displacement. The cellulose double cross-linked gel was visco-elastic tested to characterize its strength.
Example two
Taking nano-cellulose dispersion liquid with the absolute dry mass of 0.0675g, dissolving 0.0075g of glucomannan in distilled water, fully mixing the two raw materials, supplementing a certain amount of distilled water to prepare 5g of uniform and transparent dispersion liquid, centrifuging to remove bubbles, filling the dispersion liquid into a mold, respectively putting a certain amount of ammonia water and epoxy chloropropane into a closed container to provide a gas environment capable of generating physical and chemical crosslinking, putting the dispersion liquid into a double-vapor bath environment, and reacting for 3 hours at 65 ℃ to obtain the lignocellulose bi-component double-crosslinking gel. The solid content of the obtained lignocellulose bi-component double-crosslinking gel is 1.5 wt%, and the mass ratio of cellulose to hemicellulose is 9: 1.
The reacted lignocellulose bi-component double-crosslinked gel is transferred to a clean beaker filled with ethanol to terminate the chemical reaction and carry out solvent replacement, and the ethanol is replaced once every several hours to ensure complete solvent replacement. Viscoelastic measurements were performed on the lignocellulosic bicomponent double cross-linked gels to characterize their strength.
EXAMPLE III
Taking nano cellulose dispersion liquid with 0.0600g of absolute dry mass, dissolving 0.0075g of glucomannan in distilled water, dissolving 0.0075g of alkali lignin in 0.5M NaOH aqueous solution, fully mixing the three raw materials, supplementing a certain amount of distilled water to prepare 5g of uniform and transparent dispersion liquid, centrifuging to remove bubbles, filling the dispersion liquid into a mold, respectively placing a certain amount of ammonia water and epoxy chloropropane in a closed container to provide a gas environment capable of generating physical and chemical crosslinking, placing the dispersion liquid in a double-steam bath environment, and reacting for 3 hours at 65 ℃ to obtain the lignocellulose three-component double-crosslinking gel. The solid content of the obtained lignocellulose three-component double-crosslinking gel is 1.5 wt%, and the mass ratio of cellulose, hemicellulose and lignin is 8:1: 1.
Transferring the reacted lignocellulose three-component double-crosslinked gel into a clean beaker filled with ethanol to stop the chemical reaction and carry out solvent replacement, and replacing the ethanol once every several hours to ensure complete solvent replacement. The lignocellulosic three-component double cross-linked gel was visco-elastic tested to characterize its strength.
The hemicellulose raw material used in the present invention is not limited to glucomannan, and glucomannan may be substituted with any of xylan, arabinan or galactan, and the present invention is illustrated by xylan in example four below.
Example four
Taking nano cellulose dispersion liquid with 0.0600g of absolute dry mass, dissolving 0.0075g of xylan in distilled water, dissolving 0.0075g of alkali lignin in 0.5M NaOH, fully mixing the three raw materials, supplementing a certain amount of distilled water to prepare 5g of uniform and transparent dispersion liquid, centrifuging to remove bubbles, filling the dispersion liquid into a mold, respectively placing a certain amount of ammonia water and epoxy chloropropane in a closed container to provide a gas environment capable of generating physical and chemical crosslinking, placing the dispersion liquid in a double-steam bath environment, and reacting for 3 hours at 65 ℃ to obtain the lignocellulose three-component double-crosslinking gel. The solid content of the obtained lignocellulose three-component double-crosslinking gel is 1.5 wt%, and the mass ratio of cellulose, hemicellulose and lignin is 8:1: 1.
Transferring the reacted lignocellulose three-component double-crosslinked gel into a clean beaker filled with ethanol to stop the chemical reaction and carry out solvent replacement, and replacing the ethanol once every several hours to ensure complete solvent replacement. The lignocellulosic three-component double cross-linked gel was visco-elastic tested to characterize its strength.
The hemicellulose solvent used in the present invention is not limited to water, and water may be replaced with any of a base, an alkali urea system, or an organic solvent. The alkali urea system provided by the present invention can be a NaOH/urea system, a NaOH/thiourea system, a LiOH/urea system, etc., and the present invention is illustrated by the NaOH/urea system in the alkali urea system in the following fifth example.
EXAMPLE five
Taking nano cellulose dispersion liquid with the absolute dry mass of 0.0600g, dissolving 0.0075g of glucomannan in NaOH/urea aqueous solution, dissolving 0.0075g of alkali lignin in 0.5M NaOH aqueous solution, fully mixing the three raw materials, supplementing a certain amount of distilled water to prepare 5g of uniform and transparent dispersion liquid, centrifuging to remove bubbles, filling the dispersion liquid into a mold, respectively placing a certain amount of ammonia water and epoxy chloropropane in a closed container to provide a gas environment capable of generating physical and chemical crosslinking, placing the dispersion liquid in a double-steam bath environment, and reacting for 3 hours at 65 ℃ to obtain the lignocellulose three-component double-crosslinking gel. The solid content of the obtained lignocellulose three-component double-crosslinking gel is 1.5 wt%, and the mass ratio of cellulose, hemicellulose and lignin is 8:1: 1.
Transferring the reacted lignocellulose three-component double-crosslinked gel into a clean beaker filled with ethanol to stop the chemical reaction and carry out solvent replacement, and replacing the ethanol once every several hours to ensure complete solvent replacement. The lignocellulosic three-component double cross-linked gel was visco-elastic tested to characterize its strength.
The lignin raw material used in the present invention is not limited to alkali lignin, and alkali lignin may be replaced by any of ground lignin, enzymatic lignin, organic solvent-separated lignin, and lignosulfonate, and the present invention will be described with lignosulfonate in the following sixth example.
EXAMPLE six
Taking nano cellulose dispersion liquid with the absolute dry mass of 0.0600g, dissolving 0.0075g of glucomannan in distilled water, dissolving 0.0075g of lignosulfonate in distilled water, fully mixing the three raw materials, supplementing a certain amount of distilled water to prepare 5g of uniform and transparent dispersion liquid, centrifuging to remove bubbles, filling the dispersion liquid into a mold, respectively putting a certain amount of ammonia water and epoxy chloropropane in a closed container to provide a gas environment capable of generating physical and chemical crosslinking, placing the dispersion liquid in a double-vapor bath environment, and reacting for 3 hours at 65 ℃ to obtain the lignocellulose three-component double-crosslinking gel. The solid content of the obtained lignocellulose three-component double-crosslinking gel is 1.5 wt%, and the mass ratio of cellulose, hemicellulose and lignin is 8:1: 1.
Transferring the reacted lignocellulose three-component double-crosslinked gel into a clean beaker filled with ethanol to stop the chemical reaction and carry out solvent replacement, and replacing the ethanol once every several hours to ensure complete solvent replacement. The lignocellulosic three-component double cross-linked gel was visco-elastic tested to characterize its strength.
The lignin solvent used in the present invention is not limited to alkali, and the alkali is replaced with any one of water, an alkali urea system, or an organic solvent. The organic solvent provided by the present invention can be dimethyl sulfoxide, dioxane, acetone, ethylene glycol, etc., and the present invention is illustrated by dimethyl sulfoxide in the organic solvent in the following seventh example.
EXAMPLE seven
Taking nano cellulose dispersion liquid with the absolute dry mass of 0.0600g, dissolving 0.0075g of glucomannan in distilled water, dissolving 0.0075g of alkali lignin in dimethyl sulfoxide, fully mixing the three raw materials, supplementing a certain amount of distilled water to prepare 5g of uniform and transparent dispersion liquid, centrifuging to remove bubbles, filling the dispersion liquid into a mold, respectively putting a certain amount of ammonia water and epoxy chloropropane in a closed container to provide a gas environment capable of generating physical and chemical crosslinking, placing the dispersion liquid in a double-vapor bath environment, and reacting for 3 hours at 65 ℃ to obtain the lignocellulose three-component double-crosslinking gel. The solid content of the obtained lignocellulose three-component double-crosslinking gel is 1.5 wt%, and the mass ratio of cellulose, hemicellulose and lignin is 8:1: 1.
Transferring the reacted lignocellulose three-component double-crosslinked gel into a clean beaker filled with ethanol to stop the chemical reaction and carry out solvent replacement, and replacing the ethanol once every several hours to ensure complete solvent replacement. The lignocellulosic three-component double cross-linked gel was visco-elastic tested to characterize its strength.
The physical vapor bath used in the present invention is not limited to the alkali vapor bath, and the alkali vapor bath may be replaced with either a volatile alcohol vapor bath or an acid vapor bath. The volatile alcohol vapor bath provided by the present invention may be a methanol vapor bath, an ethanol vapor bath, a tert-butanol vapor bath, or the like, and the present invention will be described with reference to the ethanol vapor bath in the volatile alcohol vapor bath in example eight below.
Example eight
Taking nano cellulose dispersion liquid with 0.0600g of absolute dry mass, dissolving 0.0075g of glucomannan in distilled water, dissolving 0.0075g of alkali lignin in 0.5M of NaOH aqueous solution, fully mixing the three raw materials, supplementing a certain amount of distilled water to prepare 5g of uniform and transparent dispersion liquid, adjusting the pH value of the dispersion liquid to be about 10 by using the 0.5M of NaOH aqueous solution, centrifugally removing bubbles, filling the dispersion liquid into a mold, respectively putting a certain amount of ethanol and epoxy chloropropane into a closed container to provide a gas environment capable of generating physical and chemical crosslinking, putting the dispersion liquid into a double-steam bath environment, and reacting for 3 hours at 65 ℃ to obtain the lignocellulose three-component double-crosslinking gel. The solid content of the obtained lignocellulose three-component double-crosslinking gel is 1.5 wt%, and the mass ratio of cellulose, hemicellulose and lignin is 8:1: 1.
Transferring the reacted lignocellulose three-component double-crosslinked gel into a clean beaker filled with ethanol to stop the chemical reaction and carry out solvent replacement, and replacing the ethanol once every several hours to ensure complete solvent replacement. The lignocellulosic three-component double cross-linked gel was visco-elastic tested to characterize its strength.
The chemical vapor bath used in the present invention is not limited to the epichlorohydrin vapor bath, and the epichlorohydrin vapor bath is replaced with either the glyoxal vapor bath or the glutaraldehyde vapor bath. The invention is illustrated in the following example nine by a glutaraldehyde vapor bath.
Example nine
Taking nano cellulose dispersion liquid with 0.0600g of absolute dry mass, dissolving 0.0075g of glucomannan in distilled water, dissolving 0.0075g of alkali lignin in 0.5M NaOH, fully mixing the three raw materials, supplementing a certain amount of distilled water to prepare 5g of uniform and transparent dispersion liquid, centrifuging to remove bubbles, filling the dispersion liquid into a mold, respectively placing a certain amount of hydrochloric acid and glutaraldehyde into a closed container to provide a gas environment capable of generating physical and chemical crosslinking, placing the dispersion liquid in a double-steam bath environment, and reacting for 3 hours at 65 ℃ to obtain the lignocellulose three-component double-crosslinking gel. The solid content of the obtained lignocellulose three-component double-crosslinking gel is 1.5 wt%, and the mass ratio of cellulose, hemicellulose and lignin is 8:1: 1.
Transferring the reacted lignocellulose three-component double-crosslinked gel into a clean beaker filled with ethanol to stop the chemical reaction and carry out solvent replacement, and replacing the ethanol once every several hours to ensure complete solvent replacement. The lignocellulosic three-component double cross-linked gel was visco-elastic tested to characterize its strength.
The solid content of the lignocellulose three-component double-crosslinked gel used in the present invention is not limited to 1.5 wt%, and any solid content selected from 0.5 wt% and 10 wt% is substituted for 1.5 wt%; the mass ratio of cellulose to hemicellulose to lignin is not limited to 8:1: 1. The invention is illustrated in the following examples ten and eleven with different solids contents and component mass ratios.
Example ten
Taking nano-cellulose dispersion liquid with the absolute dry mass of 0.1000g, dissolving 0.2000g of glucomannan in distilled water, dissolving 0.2000g of alkali lignin in 0.5M NaOH, fully mixing the three raw materials, supplementing a certain amount of distilled water to prepare 5g of uniform and transparent dispersion liquid, centrifuging to remove bubbles, filling the dispersion liquid into a mold, respectively putting a certain amount of ammonia water and epoxy chloropropane in a closed container to provide a gas environment capable of generating physical and chemical crosslinking, placing the dispersion liquid in a double-vapor bath environment, and reacting for 3 hours at 65 ℃ to obtain the lignocellulose three-component double-crosslinking gel. The solid content of the obtained lignocellulose three-component double-crosslinking gel is 10 wt%, and the mass ratio of cellulose, hemicellulose and lignin is 1:2: 2.
Transferring the reacted lignocellulose three-component double-crosslinked gel into a clean beaker filled with ethanol to stop the chemical reaction and carry out solvent replacement, and replacing the ethanol once every several hours to ensure complete solvent replacement. The lignocellulosic three-component double cross-linked gel was visco-elastic tested to characterize its strength.
EXAMPLE eleven
Taking nano cellulose dispersion liquid with the absolute dry mass of 0.0200g, dissolving 0.0025g of glucomannan in distilled water, dissolving 0.0025g of alkali lignin in 0.5M NaOH, fully mixing the three raw materials, supplementing a certain amount of distilled water to prepare 5g of uniform and transparent dispersion liquid, centrifuging to remove bubbles, filling the dispersion liquid into a mold, respectively putting a certain amount of ammonia water and epoxy chloropropane into a closed container to provide a gas environment capable of generating physical and chemical crosslinking, placing the dispersion liquid in a double-steam bath environment, and reacting for 3 hours at 65 ℃ to obtain the lignocellulose three-component double-crosslinking gel. The solid content of the obtained lignocellulose three-component double-crosslinking gel is 0.5 wt%, and the mass ratio of cellulose, hemicellulose and lignin is 8:1: 1.
Transferring the reacted lignocellulose three-component double-crosslinked gel into a clean beaker filled with ethanol to stop the chemical reaction and carry out solvent replacement, and replacing the ethanol once every several hours to ensure complete solvent replacement. The lignocellulosic three-component double cross-linked gel was visco-elastic tested to characterize its strength.
The preparation temperature of the lignocellulose three-component double-crosslinking gel is not limited to 65 ℃, and any temperature between 20 ℃ and 90 ℃ is used for replacing 65 ℃; the reaction time is not limited to 3 hours, and any time from 1 to 24 hours is used for replacing 3 hours. The invention is illustrated below in examples twelve and thirteen by the different reaction temperatures and times.
Example twelve
Taking nano cellulose dispersion liquid with the absolute dry mass of 0.0600g, dissolving 0.0075g of glucomannan in distilled water, dissolving 0.0075g of alkali lignin in 0.5M NaOH, fully mixing the three raw materials, supplementing a certain amount of distilled water to prepare 5g of uniform and transparent dispersion liquid, centrifuging to remove bubbles, filling the dispersion liquid into a mold, respectively placing a certain amount of ammonia water and epoxy chloropropane in a closed container to provide a gas environment capable of generating physical and chemical crosslinking, placing the dispersion liquid in a double-steam bath environment, and reacting for 24 hours at 20 ℃ to obtain the lignocellulose three-component double-crosslinking gel. The solid content of the obtained lignocellulose three-component double-crosslinking gel is 1.5 wt%, and the mass ratio of cellulose, hemicellulose and lignin is 8:1: 1.
Transferring the reacted lignocellulose three-component double-crosslinked gel into a clean beaker filled with ethanol to stop the chemical reaction and carry out solvent replacement, and replacing the ethanol once every several hours to ensure complete solvent replacement. The lignocellulosic three-component double cross-linked gel was visco-elastic tested to characterize its strength.
EXAMPLE thirteen
Taking nano cellulose dispersion liquid with the absolute dry mass of 0.0600g, dissolving 0.0075g of glucomannan in distilled water, dissolving 0.0075g of alkali lignin in 0.5M NaOH, fully mixing the three raw materials, supplementing a certain amount of distilled water to prepare 5g of uniform and transparent dispersion liquid, centrifuging to remove bubbles, filling the dispersion liquid into a mold, respectively placing a certain amount of ammonia water and epoxy chloropropane in a closed container to provide a gas environment capable of generating physical and chemical crosslinking, placing the dispersion liquid in a double-steam bath environment, and reacting for 1h at 90 ℃ to obtain the lignocellulose three-component double-crosslinking gel. The solid content of the obtained lignocellulose three-component double-crosslinking gel is 1.5 wt%, and the mass ratio of cellulose, hemicellulose and lignin is 8:1: 1.
Transferring the reacted lignocellulose three-component double-crosslinked gel into a clean beaker filled with ethanol to stop the chemical reaction and carry out solvent replacement, and replacing the ethanol once every several hours to ensure complete solvent replacement. The lignocellulosic three-component double cross-linked gel was visco-elastic tested to characterize its strength.
On the basis of the method for preparing the lignocellulose three-component double-crosslinked gel, provided by the invention, the lignocellulose three-component double-crosslinked gel is subjected to freeze-drying treatment, so that the lignocellulose three-component double-crosslinked gel aerogel can be prepared.
Example fourteen
Taking nano cellulose dispersion liquid with 0.0600g of absolute dry mass, dissolving 0.0075g of glucomannan in distilled water, dissolving 0.0075g of alkali lignin in 0.5M NaOH aqueous solution, fully mixing the three raw materials, supplementing a certain amount of distilled water to prepare 5g of uniform and transparent dispersion liquid, centrifuging to remove bubbles, filling the dispersion liquid into a mold, respectively placing a certain amount of ammonia water and epoxy chloropropane in a closed container to provide a gas environment capable of generating physical and chemical crosslinking, placing the dispersion liquid in a double-steam bath environment, and reacting for 3 hours at 65 ℃ to obtain the lignocellulose three-component double-crosslinking gel. The solid content of the obtained lignocellulose three-component double-crosslinking gel is 1.5 wt%, and the mass ratio of cellulose, hemicellulose and lignin is 8:1: 1.
And transferring the reacted lignocellulose three-component double-crosslinked gel into a clean beaker filled with ethanol to stop the chemical reaction, performing solvent replacement by using tert-butyl alcohol after the lignocellulose three-component double-crosslinked gel is stable in the ethanol for several days, and replacing the tert-butyl alcohol once every several hours to ensure that the solvent replacement is complete. And (3) carrying out freeze-drying treatment on the lignocellulose three-component double-crosslinked gel subjected to solvent replacement to obtain the lignocellulose three-component double-crosslinked gel aerogel.
The nanocellulose described in the above examples is prepared by a TEMPO/NaBr/NaClO chemical oxidation method and a high pressure homogenization treatment, but the nanocellulose used in the present invention is not limited to the preparation by this method, and may be prepared by a biological oxidation method (e.g., enzymatic oxidation), a chemical oxidation method (e.g., TEMPO/NaBr/NaClO oxidation, TEMPO/laccase/O)2Oxidation) and/or mechanical treatment (high-pressure homogenization treatment, ultrasonic crushing treatment, superfine grinding treatment, colloid mill treatment and micro-jet treatment) are all within the scope of the invention.
The examples related to the present invention are not limited to the above examples, and table 1 briefly lists the preparation method and mechanical properties of the lignocellulose three-component double-crosslinked gel related to the present invention.
TABLE 1
Figure BDA0003001027160000121
Figure BDA0003001027160000131
Viscoelastic measurements were performed on the products prepared in examples one through fourteen to characterize their strength.
Observing the product in the third example, fig. 2 is an appearance diagram of the prepared lignocellulose three-component double-crosslinked gel (a, a top view of the gel, b, a front view of the gel, c, a mechanical property performance of the gel when the gel bears 500g of weight). As can be seen from FIG. 2, the uniform lignocellulose three-component double-crosslinked gel can be successfully prepared by a simple and easy preparation method, has good shape stability and good mechanical properties, does not crack, crush, seep liquid and the like when bearing a 500g weight, does not change the shape after unloading external force, and still has good mechanical performance after repeating the steps for many times. The cellulose in the gel constructs a rigid three-dimensional network skeleton structure to endow the gel with certain internal bonding strength, and the hemicellulose and the lignin are filled in the cellulose network to endow the cellulose with certain toughness, so the lignocellulose three-component double-crosslinking gel prepared by the invention has unusual performance in the aspect of mechanical strength.
Viscoelasticity of the prepared gel (the mass ratio of the nano-cellulose to the glucomannan to the alkali lignin is 8:1:1, and the solid contents are respectively 1%, 1.25% and 1.5%) is measured to characterize the mechanical property of the gel. FIG. 3 is a diagram showing the viscoelastic properties of three lignocellulose three-component double-crosslinked gels with different solid contents, and it can be seen from FIG. 3 that the solid content of the gel plays a decisive role in the gel strength, and within a certain range, the higher the solid content of the gel is, the higher the gel strength is. In the figure, as the solid content of the gel increases, the elastic modulus and the viscous modulus of the gel both increase regularly. In the invention, the double steam baths not only solve the problems that the effective dosage of a physical coagulation bath and a chemical crosslinking agent in the traditional gel preparation method is difficult to control and difficult to recycle, but also solve the problem that the chemical crosslinking agent is difficult to be fully mixed with the gel when the solid content of the gel is high. The wood cellulose double-crosslinking gel prepared by adopting a double steam bath method effectively improves the solid content of the gel, thereby improving the mechanical property of the gel.
According to another aspect of the present invention, there is provided a lignocellulose three-component double cross-linked gel prepared by the above method, preferably, the lignocellulose three-component double cross-linked gel has a high solid content and a strong mechanical property, and the storage modulus of gels prepared under different conditions may be 9.37 × 103～1.27×107Pa。
According to another aspect of the invention, the lignocellulose three-component double-crosslinked aerogel is provided, and is prepared by freeze-drying the lignocellulose three-component double-crosslinked aerogel prepared by the preparation method of the lignocellulose three-component double-crosslinked aerogel.
According to a further aspect of the present invention, there is provided a use of a lignocellulosic three-component dual cross-linked gel/aerogel, such as said lignocellulosic three-component dual cross-linked gel or said lignocellulosic three-component dual cross-linked aerogel in the fields of sustained release, filtration, catalysis, adsorption or sensors.
In conclusion, by means of the technical scheme, the method for preparing the lignocellulose three-component double-crosslinked gel through double steam baths can effectively solve the problem that the solid content of the lignocellulose double-crosslinked gel prepared by a dispersion system is difficult to increase, so that the gel strength is increased;
in addition, the method for preparing the lignocellulose three-component double-crosslinking gel through double vapor baths can effectively improve the internal crosslinking density of the gel, complete physical and chemical double crosslinking in the process of gas permeating into the gel, and ensure the crosslinking uniformity;
in addition, the method for preparing the lignocellulose three-component double-crosslinked gel through double steam baths provided by the invention can effectively solve the problem that the crosslinking agent is difficult to utilize efficiently. The traditional method for preparing the double-crosslinking gel by adding the crosslinking agent has lower utilization rate of the crosslinking agent, and the steam bath for physical and chemical crosslinking provided by the invention ensures that the liquid is not directly added into the dispersion liquid, thereby greatly improving the effective utilization rate of the crosslinking agent, saving energy consumption and reducing preparation cost; the method is simple and feasible to operate and easy to realize industrialization;
in addition, the plasticity and toughness of the gel are improved and the double-crosslinking gel is endowed with more functionality by adding all components of the lignocellulose, so that the gel prepared by the method has more diversified functional applications such as catalysis, adsorption, ultraviolet resistance and the like.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. The preparation method of the lignocellulose three-component double-crosslinking gel is characterized by comprising the following steps:
s1, preparing nano-cellulose dispersion liquid by using a cellulose raw material, and respectively dissolving hemicellulose and lignin in corresponding solvents to respectively obtain a hemicellulose solution and a lignin solution;
s2, uniformly mixing the nano-cellulose dispersion liquid, the hemicellulose solution and the lignin solution to obtain a lignocellulose dispersion liquid containing three components of nano-cellulose, hemicellulose and lignin;
s3, placing the three-component lignocellulose dispersion liquid in a double-steam bath closed environment with double functions of physical crosslinking and chemical crosslinking for reaction to prepare the lignocellulose three-component double-crosslinking gel.
2. The method for preparing lignocellulose three-component double-crosslinked gel according to claim 1, wherein the nanocellulose is obtained by treating a cellulose raw material by a mechanical treatment method or an oxidation and mechanical treatment method, wherein the mechanical treatment method is high-pressure homogenization treatment, ultrasonic disruption treatment, superfine pulverization treatment, colloid mill treatment and micro jet treatment, and the oxidation treatment method is biological oxidation method and chemical oxidation method.
3. The method for preparing a lignocellulose three-component double cross-linked gel according to claim 1, wherein the raw material of hemicellulose is derived from any one or a combination of at least two of glucomannan, xylan, arabinan and galactan of plant raw material; the raw material of the lignin is any one or the combination of at least two of wood grinding lignin, enzymatic hydrolysis lignin, organic solvent separation lignin, alkali lignin and lignosulfonate, and the dissolving solvent of the hemicellulose and the lignin is any one or the combination of at least two of water, alkali, an alkali urea system and an organic solvent.
4. The method for preparing lignocellulose three-component double cross-linked gel according to claim 1, wherein the mass ratio of the cellulose raw material in the gel oven-dried raw material is 20-100%, the mass ratio of the hemicellulose raw material in the gel oven-dried raw material is 0-80%, the mass ratio of the lignin raw material in the gel oven-dried raw material is 0-80%, and the solid content of the lignocellulose dispersion liquid is 0.5-10.0 wt%.
5. The method of preparing a lignocellulosic three-component dual crosslinked gel according to claim 1 wherein the vapor bath of physical crosslinking is a volatile physical coagulant vapor bath and the vapor bath of chemical crosslinking is a volatile hydroxyl crosslinking agent vapor bath.
6. The method for preparing lignocellulose three-component double cross-linked gel according to claim 5, wherein the vapor bath for physical cross-linking comprises volatile alcohol vapor bath, alkali vapor bath, acid vapor bath, and the vapor bath for chemical cross-linking comprises epichlorohydrin vapor bath, glyoxal vapor bath, glutaraldehyde vapor bath.
7. The method for preparing lignocellulose three-component double cross-linked gel according to claim 1, wherein the reaction temperature in the S3 is 20-90 ℃ and the reaction time is 1-24 h.
8. The lignocellulose three-component double-crosslinked gel is characterized by being prepared by the preparation method of the lignocellulose three-component double-crosslinked gel as claimed in any one of claims 1 to 7, the lignocellulose three-component double-crosslinked gel has high solid content and strong mechanical property, and the storage modulus of the gel prepared under different conditions can be 9.37 x 103～1.27×107Pa。
9. The lignocellulose three-component double-crosslinked aerogel is characterized by being prepared by adopting the lignocellulose three-component double-crosslinked aerogel of claim 8 through freeze drying treatment.
10. Use of a lignocellulosic three-component double cross-linked gel/aerogel, characterized in that the lignocellulosic three-component double cross-linked gel according to claim 8 or the lignocellulosic three-component double cross-linked aerogel according to claim 9 is used in the field of slow release, filtration, catalysis, adsorption or sensors.
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