CN108864446A - Nanofiber hydrogel, aeroge and its preparation method and application - Google Patents
Nanofiber hydrogel, aeroge and its preparation method and application Download PDFInfo
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- CN108864446A CN108864446A CN201810810952.8A CN201810810952A CN108864446A CN 108864446 A CN108864446 A CN 108864446A CN 201810810952 A CN201810810952 A CN 201810810952A CN 108864446 A CN108864446 A CN 108864446A
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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
- C08J3/02—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
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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
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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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
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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
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
Abstract
The invention belongs to the applied technical field of cellulose, it is related to a kind of nanofiber hydrogel, aeroge and its preparation method and application.The preparation method of nanofiber hydrogel of the invention, includes the following steps：(a) cellulosic material is subjected to pre-treatment, obtains nano-cellulose dispersion liquid；(b) nano-cellulose dispersion liquid is mixed with crosslinking agent, obtains composite dispersion liquid；(c) composite dispersion liquid is subjected to freeze thawing treatment, obtains nanofiber hydrogel.The present invention successfully realizes the chemical crosslinking of nano-cellulose innovatively with freeze thawing treatment, product has the characteristics that low-quality, high-strength, high resiliency, high porosity, also there are the advantages such as mild condition, strong operability simultaneously, practicable method is provided for the preparation of nano-cellulose gel, there is industrial applications prospect.
Description
Technical field
The invention belongs to the applied technical fields of cellulose, more particularly to a kind of nanofiber hydrogel, aeroge
And its preparation method and application.
Background technique
Since with the characteristics such as nontoxic, renewable, biodegradable, the polysaccharide material of chitin or cellulose base is in biology
There is stronger advantage in terms of functional material, be increasingly becoming the hot spot of countries in the world research.In the higher value application of cellulose
In the process, it is different from dissolution process, nano-cellulose receives more and more attention and becomes the important side of higher value application
Face.
Native cellulose has the characteristics such as from a wealth of sources, renewable, degradable and green non-pollution.For nano-cellulose
Utilization, hydrogel or aeroge are a kind of good platform products, and today there is also many about nanofiber hydrogel
Or the report of aeroge, but hydrogel/gas is greatly limited the characteristics of nano-cellulose physical crosslinking in existing method
The promotion of gel mechanical strength, and the universal elasticity of aerogel material prepared at present is poor, missing elasticity.It is existing to receive
Cellulose aerogels are prepared after mainly dissolving cellulose with cellulose solvent in the preparation process of rice cellulose gel again, fine
Plain aeroge is tieed up frequently with supercritical drying process, long preparation period is at high cost, complex process, is difficult to control, it is difficult to great Liang Sheng
It produces, and the performance of nano-cellulose gel obtained has to be hoisted, limits further applying for nano-cellulose gel.
In consideration of it, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of preparation method of nanofiber hydrogel；And using described
The nanofiber hydrogel that the preparation method of nanofiber hydrogel is prepared.This method is easy to operate, easy to implement,
Strong operability, nanofiber hydrogel mechanical performance obtained is excellent, has the advantage of high-intensitive, high rebound, realizes
The promotion and breakthrough of nano-cellulose hydrogel material performance.
The second object of the present invention is to provide a kind of preparation method of nano-cellulose aerogel；And using described
The nano-cellulose aerogel that the preparation method of nano-cellulose aerogel is prepared.This method is easy to operate, easy to implement,
Strong operability, nano-cellulose aerogel mechanical performance obtained is excellent, has the advantage of high-intensitive, high rebound, realizes
The promotion and breakthrough of nano-cellulose aerogel material property.
The third object of the present invention is to provide nanofiber hydrogel and/or the nanofiber described in one kind
Plain aeroge be sustained, adsorb and fix, the application in heat-insulated, noise reduction or filtration art.
To achieve the above object, the technical solution adopted by the present invention is：
According to an aspect of the present invention, the present invention provides a kind of preparation method of nanofiber hydrogel, including with
Lower step：
(a) cellulosic material is subjected to pre-treatment, obtains nano-cellulose dispersion liquid；
(b) nano-cellulose dispersion liquid is mixed with crosslinking agent, obtains composite dispersion liquid；
(c) composite dispersion liquid is subjected to freeze thawing treatment, obtains nanofiber hydrogel.
As further preferred technical solution, in step (a), pre-treatment includes mechanical treatment or mechanical treatment and pre- place
The combination of reason；
Preferably, cellulosic material is mixed with solvent, is carried out mechanical treatment, is obtained nano-cellulose dispersion liquid；
Alternatively, will be mixed by pretreated cellulosic material with solvent, mechanical treatment is carried out, nano-cellulose is obtained
Dispersion liquid.
As further preferred technical solution, the pretreatment includes any in chemical method, physical method and bioanalysis
It is a kind of or at least two combination；
And/or the mechanical treatment include homogenized, ultrasonic treatment, high-speed stirred, milling treatment of colloid, ultramicro grinding,
In microjet and high-pressure homogeneous processing any one or at least two combination；
Preferably, the chemical method includes at least one in alkali process, TEMPO oxidation, acid processing and hydrogen peroxide treatment
Kind；
Preferably, the physical method include homogenized, ultrasonic treatment, high-speed stirred, milling treatment of colloid, ultramicro grinding,
At least one of microjet and high-pressure homogeneous processing；
Preferably, the bioanalysis includes at least one of cellulase processing, glucosides enzymatic treatment and laccase treatment.
As further preferred technical solution, in step (b), the size range of nano-cellulose includes：Length is 50nm
~20 μm, width is 3nm~500nm；
Preferably, step (b) crosslinking agent is hydroxyl crosslinking agent；
Preferably, the crosslinking agent include epoxychloropropane, epoxy silane, silane coupling agent, glutaraldehyde, Geniposide and its
At least one of derivative, carbodiimide or triazine crosslinked dose of tri-alkoxy carbonylamino；
Preferably, the concentration of the crosslinking agent is 0.01%~25% (w/w)；
Preferably, the concentration of nano-cellulose dispersion liquid is 0.05%~20% (w/w) in step (b)；
Preferably, the ratio of nano-cellulose and crosslinking agent is 1~100：1(w/w).
As further preferred technical solution, in step (c) freeze thawing treatment, cryogenic temperature is -1 DEG C~-196
DEG C, the time is 6~60h, and number of freezing and thawing is 1~10 time.
As further preferred technical solution, the source of the cellulosic material includes timber, careless class, bamboo class and linen-cotton class
At least one of.
According to another aspect of the present invention, the present invention provides a kind of nanofiber hydrogel, and use is above-described
The preparation method of nanofiber hydrogel is prepared；
Preferably, the nanofiber hydrogel in water or in alcohol can be compression/rebound reciprocal 1~200 time, rebound
Rate reaches 100%, and storage modulus reaches 2.0 × 104Pa。
According to another aspect of the present invention, the present invention provides a kind of preparation method of nano-cellulose aerogel, will adopt
The nanofiber hydrogel being prepared with the preparation method of the nanofiber hydrogel or the Nanowire
Dimension hydrogel is freeze-dried, and nano-cellulose aerogel is obtained；
Alternatively, including the following steps：
(a) cellulosic material is subjected to pre-treatment, obtains nano-cellulose dispersion liquid；
(b) nano-cellulose dispersion liquid is mixed with crosslinking agent, obtains composite dispersion liquid；
(c) composite dispersion liquid is subjected to freeze-drying process, obtains nano-cellulose aerogel；
Preferably, the temperature of freeze-drying is -1 DEG C~-155 DEG C.
According to another aspect of the present invention, the present invention provides a kind of nano-cellulose aerogel, using above-mentioned nanometer
The preparation method of cellulose aerogels is prepared；
Preferably, the nano-cellulose aerogel can be compressed in air/be sprung back reciprocal 1~200 time, and compressive strength reaches
To 2000Pa.
According to another aspect of the present invention, the present invention provide a kind of nanofiber hydrogel as described above and/or
Nano-cellulose aerogel be sustained, adsorb and fix, the application in heat-insulated, noise reduction or filtration art.
Compared with prior art, the beneficial effects of the present invention are：
1), the preparation method of nano-cellulose gel provided by the invention creatively exists using nano-cellulose as raw material
Elastic hydrogel is prepared successfully with the technology of freeze thawing crosslinking under the conditions of addition crosslinking agent, and further with freeze-drying process
Elastic aerogel material is prepared, or elastic gas is prepared by freeze-drying process under conditions of adding crosslinking agent
Gel rubber material has been effectively relieved present in nanofiber hydrogel/aeroge preparation and performance in the prior art and has asked
Topic, and greatly improves the performance of nano-cellulose gel, the road that has been the applications expanding of nano-cellulose.
2), the present invention relates to nano-cellulose preparation method, the preparation of the chemical crosslinking nano-cellulose gel
Method is simple, easy to implement, strong operability, it is easy to accomplish large-scale production.
3) the nanofiber hydrogel and aeroge mechanical performance that, the present invention is prepared are excellent, have high-intensitive, high
The advantage of rebound.
4), nanofiber hydrogel and aeroge of the invention, in the base of high-intensitive, high rebound nano-cellulose gel
The extensiveness and intensiveness of its application has been widened in the developing and extension that nano-cellulose application is realized on plinth, in sustained release field, absorption
It can be widely applied in field, immobilization field, heat-insulated field, noise reduction field or filtration art etc..
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the transmission electron microscope photo for the nano-cellulose that one embodiment of the present invention provides；
Fig. 2 is the nanofiber hydrogel photo that one embodiment of the present invention provides.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiments and examples, but this field skill
Art personnel will be understood that following embodiments and embodiment are merely to illustrate the present invention, and are not construed as limiting model of the invention
It encloses.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.The person that is not specified actual conditions, according to normal conditions or manufacturer builds
The condition of view carries out.
In a first aspect, a kind of preparation method of nanofiber hydrogel is provided at least one embodiment, including with
Lower step：
(a) cellulosic material is subjected to pre-treatment, obtains nano-cellulose dispersion liquid；
(b) nano-cellulose dispersion liquid is mixed with crosslinking agent, obtains composite dispersion liquid；
(c) composite dispersion liquid is subjected to freeze thawing treatment, obtains nanofiber hydrogel.
Cellulose is the most abundant organic compound found on the earth, and due to its availability and it is sustainable production and
It is widely used.The cellulose generated every year is estimated to be 100,000,000,000 tons.Cellulose shows very attracting characteristic, such as biology
Degradability, biocompatibility, chemical and thermal stability and limited carbon footprint etc.；Cellulose is also a kind of renewable resource.And
Nanogel has many excellent characteristics because there is unique microcosmos network structure, and large specific surface area, drugloading rate are high, response
Property it is strong etc..Nano-cellulose gel combines the advantages of the two, has further expanded its application range.
The present invention breaks the confinement of those skilled in the art's conventional thought, off the beaten track, creatively proposes Nanowire
It ties up plain dispersion liquid to mix with crosslinking agent, elastic water-setting is prepared successfully with the technology that freeze thawing is crosslinked under the conditions of adding crosslinking agent
Glue, the problem of nanofiber hydrogel/aeroge preparation and performance in the prior art has been effectively relieved, and it is big
Greatly the performance of nano-cellulose gel is improved, is the applications expanding road of nano-cellulose.
The preparation method that the present invention is chemically crosslinked nano-cellulose gel is simple, easy to implement, mild condition, operability
By force, it is easy to accomplish large-scale production；Resulting nanofiber hydrogel mechanical performance is excellent, has high-intensitive, high rebound, height
The advantages such as porosity.
In a preferred embodiment, in step (a), pre-treatment includes mechanical treatment or mechanical treatment and pre- place
The combination of reason；
Preferably, cellulosic material is mixed with solvent, is carried out mechanical treatment, is obtained nano-cellulose dispersion liquid；
Alternatively, will be mixed by pretreated cellulosic material with solvent, mechanical treatment is carried out, nano-cellulose is obtained
Dispersion liquid.
According to the present invention, the preparation of nano-cellulose mainly includes two ways, first is that first carrying out to cellulosic material pre-
Processing, then mixes with solvent, and dispersion is made, and mechanical treatment is carried out, to obtain nano-cellulose dispersion liquid；Second is that straight
It connects and mixes cellulosic material with solvent, dispersion is made, carry out mechanical treatment, to obtain nano-cellulose dispersion
Liquid.
It should be noted that the present invention is not particularly limited the solvent, solvent commonly used in the art can be used,
Such as can be for water, acid etc., it is preferred to use be distilled water.
Further, the pretreatment includes any one in chemical method, physical method and bioanalysis or at least two
Combination；
And/or the mechanical treatment include homogenized, ultrasonic treatment, high-speed stirred, milling treatment of colloid, ultramicro grinding,
In microjet and high-pressure homogeneous processing any one or at least two combination；
Preferably, the chemical method includes at least one in alkali process, TEMPO oxidation, acid processing and hydrogen peroxide treatment
Kind；
Preferably, the physical method include homogenized, ultrasonic treatment, high-speed stirred, milling treatment of colloid, ultramicro grinding,
At least one of microjet and high-pressure homogeneous processing；
Preferably, the bioanalysis includes at least one of cellulase processing, glucosides enzymatic treatment and laccase treatment.
It is understood that pretreatment of the invention includes chemical method commonly used in the art, physical method and bioanalysis
In any one or in which two or three of method combination, physical method therein includes mechanical treatment process or physics
Method can be described as mechanical treatment process again.Physical method of the present invention or mechanical treatment process are method commonly used in the art,
It such as can be homogenized, ultrasonic treatment, high-speed stirred, milling treatment of colloid, ultramicro grinding, microjet, high-pressure homogeneous processing
Deng the present invention is not particularly limited the concrete operations mode of each method, and those skilled in the art can be according to the actual situation
Regulated and controled in the appropriate range.
Likewise, the present invention is for including the chemistry including alkali process, TEMPO oxidation, acid processing, hydrogen peroxide treatment
Method；Comprising the bioanalysis etc. including cellulase processing, glucosides enzymatic treatment and laccase treatment, according to the operation side of this field routine
Formula is operated, and the present invention is also not particularly limited the concrete operations mode of each method.
It should be understood that in above-mentioned preprocess method, mechanical treatment process, treatment temperature, pressure, time of each method etc.
Condition is this field routine, can be regulated and controled according to the actual situation by those skilled in the art, and the present invention is herein no longer
Detailed description.
In a preferred embodiment, in step (b), the size range of nano-cellulose includes：Length is 50nm
~20 μm, width is 3nm~500nm；It is typical but non-limiting, length for example can for 50nm, 60nm, 70nm, 100nm,
150nm, 200nm, 300nm, 400nm, 500nm, 600nm, 800nm, 900nm, 1 μm, 2 μm, 5 μm, 10 μm, 15 μm or 20 μm,
Width for example can for 3nm, 5nm, 8nm, 10nm, 20nm, 40nm, 50nm, 60nm, 80nm, 100nm, 150nm, 200nm,
300nm, 350nm, 400nm, 450nm or 500nm.
Preferably, step (b) crosslinking agent is hydroxyl crosslinking agent；
Preferably, the crosslinking agent include epoxychloropropane, epoxy silane, silane coupling agent, glutaraldehyde, Geniposide and its
At least one of derivative, carbodiimide or triazine crosslinked dose of tri-alkoxy carbonylamino；
It is highly preferred that the crosslinking agent is epoxychloropropane；Using such crosslinking agent to hydroxyl cross-linking efficiency height, cost
It is low, good application effect.
Preferably, the concentration of the crosslinking agent be 0.01%~25% (w/w), preferably 0.1%~20% (w/w), into
One step is preferably 0.5~15% (w/w), typical but non-limiting, the concentration of crosslinking agent for example can for 0.01%,
0.02%, 0.05%, 0.1%, 0.2%, 0.3%, 0.5%, 0.6%, 0.8%, 1%, 1.5%, 2%, 3%, 5%, 6%,
8%, 10%, 12%, 15%, 16%, 18%, 20%, 22% or 25% (w/w).
Preferably, in step (b) nano-cellulose dispersion liquid concentration be 0.05%~20% (w/w), preferably 0.1%
~15% (w/w), further preferably 0.5~10% (w/w), it is typical but non-limiting, nano-cellulose dispersion liquid it is dense
Degree for example can for 0.05%, 0.06%, 0.08%, 0.1%, 0.2%, 0.3%, 0.5%, 0.6%, 0.8%, 1%,
1.5%, 2%, 3%, 5%, 6%, 8%, 10%, 12%, 14%, 15%, 16%, 18% or 20% (w/w).
Preferably, the ratio of nano-cellulose and crosslinking agent is 1~100：1 (w/w), preferably 1~80：1 (w/w), into
One step is preferably 1~50：1 (w/w), typical but non-limiting, the ratio of nano-cellulose and crosslinking agent for example can be 1：
1,2：1,3：1,4：1,5：1,6：1,8：1,10：1,12：1,14：1,15：1,16：1,18：1,20：1,25：,30：1,40：1,
45：1,50：1,60：1,70：1,80：1,90：1 or 100：1(w/w).
It, can by the limitation of concentration, nano-cellulose concentration, the ratio of nano-cellulose and crosslinking agent to crosslinking agent etc.
To optimize cross-linking effect, the excellent composite dispersion liquid of dispersion effect is obtained at low cost, is additionally beneficial to subsequent freeze thawing treatment.
In a preferred embodiment, in step (c) freeze thawing treatment, cryogenic temperature is -1 DEG C~-196
DEG C, the time is 6~60h, and number of freezing and thawing is 1~10 time；It is typical but non-limiting, cryogenic temperature for example can for -1 DEG C, -
2℃,-5℃,-6℃,-8℃,-10℃,-15℃,-20℃,-25℃,-30℃,-40℃,-50℃,-60
DEG C, -80 DEG C, -100 DEG C, -120 DEG C, -150 DEG C, -160 DEG C, -180 DEG C or 196 DEG C, the time for example can for 6h, 8h,
10h, 12h, 16h, 18h, 20h, 22h, for 24 hours, 28h, 32h, 36h, 40h, 48h, 50h, 55h or 60h, number of freezing and thawing for example can be with
It is 1 time, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times or 10 times.
Preferably, cryogenic temperature is -1 DEG C~-150 DEG C, and the time is 6~50h, and number of freezing and thawing is 1~8 time；
Preferably, cryogenic temperature is -5 DEG C~-100 DEG C, and the time is 6~48h, and number of freezing and thawing is 1~5 time.
Have many advantages, such as that elasticity is good, mechanical strength is big using hydrogel material made from freeze-thaw method, by freeze thawing temperature,
The optimization of time, number of freezing and thawing etc. can further promote freeze thawing effect, improve the performance of material obtained.
In a preferred embodiment, the source of the cellulosic material includes timber, careless class, bamboo class and linen-cotton class
At least one of.
It is understood that the present invention is not particularly limited the source of cellulosic material, such as cellulosic material
Source can come from timber, careless class, bamboo class, any one or more in linen-cotton class.Do not have for the way of purification of cellulose yet
Have specifically limited, can be purified using the processing mode of this field routine, commercially available fibre after purification also can be directly used
Tie up plain raw material.
It should be understood that the content being not described in detail in the explanation of above-mentioned raw materials and preparation method, is this field skill
The Common Parameters that art personnel are readily apparent that, therefore can be omitted detailed description thereof.
Second aspect provides a kind of nanofiber hydrogel, using above-mentioned Nanowire at least one embodiment
The preparation method of dimension hydrogel is prepared.
The nanofiber hydrogel mechanical performance that the present invention is prepared is excellent, has high-intensitive, high rebound, toughness
Advantages, the application ranges such as good, high porosity are wider.
Preferably, the nanofiber hydrogel in water or in alcohol can be compression/rebound reciprocal 1~200 time, rebound
Rate reaches 100%, and storage modulus reaches 2.0 × 104Pa。
Fig. 1 is the transmission electron microscope photo for the nano-cellulose that one embodiment of the present invention provides；Fig. 2 is that the present invention is a kind of
The nanofiber hydrogel photo that embodiment provides.
From the above, it can be seen that elasticity is good for the nano-cellulose hydrogel material being prepared using the method for the present invention, tool
There is excellent mechanical performance.
The third aspect provides a kind of preparation method of nano-cellulose aerogel at least one embodiment, will use
The nanofiber hydrogel or above-mentioned nanofiber that the preparation method of above-mentioned nanofiber hydrogel is prepared
Hydrogel is freeze-dried, and nano-cellulose aerogel is obtained；
Alternatively, including the following steps：
(a) cellulosic material is subjected to pre-treatment, obtains nano-cellulose dispersion liquid；
(b) nano-cellulose dispersion liquid is mixed with crosslinking agent, obtains composite dispersion liquid；
(c) composite dispersion liquid is subjected to freeze-drying process, obtains nano-cellulose aerogel.
It is understood that the preparation method of nano-cellulose aerogel of the invention includes two kinds：One is will be above-mentioned
The hydrogel being prepared carries out freeze-drying process to get the nano-cellulose aerogel；Another kind is by nanofiber
The composite dispersion liquid that plain dispersion liquid obtains after mixing with crosslinking agent carries out freeze-drying process directly to get the nano-cellulose
Aeroge.
Preferably, the temperature of freeze-drying be -1 DEG C~-155 DEG C, preferably -1 DEG C~-155 DEG C, further preferably
It is -1 DEG C~-155 DEG C；Typical but unrestricted, the temperature of freeze-drying for example can be -1 DEG C, -2 DEG C, -5 DEG C, -6
℃,-8℃,-10℃,-15℃,-20℃,-25℃,-30℃,-40℃,-50℃,-60℃,-80℃,-100
DEG C, -120 DEG C, -140 DEG C, -150 DEG C or -155 DEG C.
It is understood that the preparation method of the nano-cellulose aerogel and nanofiber hydrogel above-mentioned
Preparation method be based on the same inventive concept, thus at least have advantage identical with aforementioned hydrogel preparation method, this hair
It is bright that details are not described herein.
Fourth aspect provides a kind of nano-cellulose aerogel at least one embodiment, using above-mentioned Nanowire
The preparation method for tieing up plain aeroge is prepared.
Preferably, the nano-cellulose aerogel can be compressed in air/be sprung back reciprocal 1~200 time, and compressive strength reaches
To 2000Pa.As can be seen that it is good using the nano-cellulose aerogel elastic properties of materials that the method for the present invention is prepared, have excellent
Mechanical performance.
5th aspect, provides a kind of nanofiber hydrogel as described above at least one embodiment and/or receives
Rice cellulose aerogels be sustained, adsorb and fix, the application in heat-insulated, noise reduction or filtration art.
Nanofiber hydrogel of the invention and aeroge, on the basis of high-intensitive, high rebound nano-cellulose gel
On realize nano-cellulose application developing and extension, widened its application extensiveness and intensiveness, sustained release field, absorption neck
It can be widely applied in domain, immobilization field, heat-insulated field, noise reduction field or filtration art etc..For example, nano-cellulose
Gel rubber material applies the absorption of heavy metal ion, the absorption to deleterious particle in air in polluted-water, or applies
Thermal insulation material etc. in building.
Combined with specific embodiments below, the invention will be further described.
Embodiment 1
A kind of preparation method of nanofiber hydrogel, includes the following steps：
(1) processing of cellulosic material：It using wood-cellulose as raw material, discongests through machinery to flocculence, weighs the sample
Beaker is added in dry weight 1g, NaBr0.1g, TEMPO0.016g and 100mL distilled water, stirs evenly, and sufficiently dissolves.Add into system
Enter 6mmol sodium hypochlorite, it is 10 that 5M hydrochloric acid, which is added dropwise, and adjusts total system pH, starts to aoxidize.Use autotitrator automatic dripping
It is 10 that 0.5M sodium hydroxide, which maintains total system pH,.After system hardly consumes sodium hydroxide solution, a small amount of ethanol solution is added dropwise
Plantation reaction, is added a small amount of 0.5M hydrochloric acid for pH and is adjusted to neutrality.Eccentric cleaning oxycellulose takes insoluble matter to be placed in 4 DEG C of refrigerators
It saves.
(2) preparation of nano-cellulose：It takes 0.2g dry weight oxidation wood-cellulose that 100mL distilled water is added to be homogenized,
Ultrasound procedure recycles 5~6 times, solution clear, and centrifugation removal precipitating, supernatant is nano-cellulose obtained
Dispersion liquid.
(3) preparation of nanofiber hydrogel：The nano-cellulose being prepared using above-mentioned steps first will as raw material
Nano-cellulose adjusts solids level concentration to 0.4%, then with nano-cellulose/glutaraldehyde mass ratio for 1：1 condition addition penta
Dialdehyde crosslinking agent and with acetic acid tune pH to 5, mixing to be mixed is placed on -20 DEG C of refrigerator overnights, finally melts at room temperature and obtains
Nanofiber hydrogel.
Embodiment 2
A kind of preparation method of nanofiber hydrogel, includes the following steps：
(1) processing of cellulosic material：Using flaxen fiber element as raw material, take 1g dry weight flaxen fiber element and 64% sulfuric acid in solid-liquid
Than being 1：3h is reacted in 60 DEG C of processing under the conditions of 30, and team's material is thoroughly washed and dialyses to obtain acidolysis flaxen fiber to the end of reacting
Element.
(2) preparation of nano-cellulose：It takes 0.5g dry weight acidolysis flaxen fiber element that 100mL distilled water is added to be homogenized, surpass
Sound operation, recycles 5~6 times, solution clear, and centrifugation removal precipitating, supernatant is nano-cellulose point obtained
Dispersion liquid.
(3) preparation of nanofiber hydrogel：The nano-cellulose being prepared using above-mentioned steps first will as raw material
Nano-cellulose adjusts solids level concentration to 0.4%, then with nano-cellulose/epoxychloropropane mass ratio for 1：1 condition adds
Add epichlorohydrin crosslinker and with sodium hydroxide tune pH to 9, mixing to be mixed is placed on -20 DEG C of refrigerator overnights, finally in room
Lower melt of temperature obtains nanofiber hydrogel.
Embodiment 3-4
A kind of preparation method of nano-cellulose aerogel, includes the following steps：
The nanofiber hydrogel that embodiment 1-2 is prepared is prepared under the conditions of -50 DEG C with freeze-drying
To nano-cellulose aerogel.
Embodiment 5
A kind of preparation method of nano-cellulose aerogel, includes the following steps：
(1) processing of cellulosic material：It using grass fiber element as raw material, discongests through machinery to flocculence, weighs the sample
Beaker is added in dry weight 1g, NaBr0.1g, TEMPO0.016g and 100mL distilled water, stirs evenly, and sufficiently dissolves.Add into system
Enter 6mmol sodium hypochlorite, it is 10 that 5M hydrochloric acid, which is added dropwise, and adjusts total system pH, starts to aoxidize.Use autotitrator automatic dripping
It is 10 that 0.5M sodium hydroxide, which maintains total system pH,.After system hardly consumes sodium hydroxide solution, a small amount of ethanol solution is added dropwise
Plantation reaction, is added a small amount of 0.5M hydrochloric acid for pH and is adjusted to neutrality.Eccentric cleaning oxycellulose takes insoluble matter to be placed in 4 DEG C of refrigerators
It saves.
(2) preparation of nano-cellulose：It takes 0.2g dry weight oxycellulose that 100mL distilled water is added to be homogenized, ultrasound
Operation recycles 5~6 times, solution clear, centrifugation removal precipitating, and supernatant is nano-cellulose dispersion obtained
Liquid.
(3) preparation of nano-cellulose aerogel：The nano-cellulose being prepared using above-mentioned steps first will as raw material
Nano-cellulose adjusts solids level concentration to 1.0%, then with nano-cellulose/silane coupling agent mass ratio for 2：1 condition adds
Add even object for appreciation coupling agent, mixing to be mixed is placed on -10 DEG C of conditions and stands for 24 hours, is finally freeze-dried and obtains under the conditions of -50 DEG C
Nano-cellulose aerogel material.
Embodiment 6
A kind of preparation method of nano-cellulose aerogel, includes the following steps：
(1) processing of cellulosic material：Using wood-cellulose as raw material, 1g dry weight wood-cellulose and 64% sulfuric acid is taken to exist
Solid-to-liquid ratio is 1：2h is reacted in 60 DEG C of processing under the conditions of 30, is thoroughly washed to the end of reacting to material and dialyses to obtain acidolysis fibre
Dimension element.
(2) preparation of nano-cellulose：Take acidolysis cellulose be raw material with distilled water be configured to 1% dispersion carry out it is even
Slurry, ultrasound procedure recycle 5~6 times, and to solution clear to be centrifuged removal precipitating, supernatant is nanofiber obtained
Plain dispersion liquid.
(3) preparation of nano-cellulose aerogel：The nano-cellulose being prepared using above-mentioned steps first will as raw material
Nano-cellulose adjusts solids level concentration to 1.0%, then with nano-cellulose/glutaraldehyde mass ratio for 2：1 condition addition penta
Dialdehyde crosslinking agent and with hydrochloric acid tune pH to 5, mixing to be mixed is placed on -20 DEG C of refrigerator overnights, finally cold under the conditions of -50 DEG C
Jelly is dried to obtain nano-cellulose aerogel material.
Embodiment 7
A kind of preparation method of nano-cellulose aerogel, includes the following steps：
(1) preparation of nano-cellulose：It takes 1.0g microcrystalline cellulose that 100mL distilled water is added and carries out high-pressure homogeneous processing 15
It is secondary to obtain nano-cellulose dispersion liquid.
(2) preparation of nano-cellulose aerogel：The nano-cellulose being prepared using above-mentioned steps first will as raw material
Nano-cellulose adjusts solids level concentration to 2.0%, then with nano-cellulose/Geniposide mass ratio for 3：1 condition adds capital
The flat crosslinking agent of Buddhist nun and with acetic acid tune pH to 5, mixing to be mixed is placed on -10 DEG C of conditions processing for 24 hours, finally melts at room temperature
Obtain nanofiber hydrogel.
(3) the nanofiber hydrogel obtained using above-mentioned steps is freeze-dried under the conditions of -50 DEG C as raw material and is received
Rice cellulose aerogels material.
Embodiment 8
A kind of preparation method of nano-cellulose aerogel, includes the following steps：
(1) preparation of nano-cellulose：It takes 1.0g microcrystalline cellulose that 100mL distilled water is added and carries out high-pressure homogeneous processing 15
It is secondary to obtain nano-cellulose dispersion liquid.
(2) preparation of nano-cellulose aerogel：The nano-cellulose being prepared using above-mentioned steps first will as raw material
Nano-cellulose adjusts solids level concentration to 2.0%, is then with nano-cellulose/tri-alkoxy carbonylamino triazine mass ratio
3：1 condition adds triazine crosslinked dose of tri-alkoxy carbonylamino (TACT) and with acetic acid tune pH to 5, and mixing to be mixed is placed on-
10 DEG C of condition processing for 24 hours, finally melt at room temperature and obtain nanofiber hydrogel.
(3) the nanofiber hydrogel obtained using above-mentioned steps is freeze-dried under the conditions of -50 DEG C as raw material and is received
Rice cellulose aerogels material.
The nano-cellulose aerogel of nanofiber hydrogel and section Example to above-described embodiment carries out mechanical
Performance test, test result are as shown in table 1.
Test method is：Hydrogel is made having a size of 9mm (diameter) × 9mm (height) cylindrical type gel sample with mold
Product carry out Mechanics Performance Testing using rheometer to the hydrogel, hydrogel axial compressive force 0.1N or so are kept when test,
Gel is performed a scan under the conditions of 0.1 to 100；Aerogel material after freeze-drying is compressed with tensilon
Rebound test.
The performance test results of the 1 gentle gel of nanofiber hydrogel of table
As can be seen from Table 1, the nanofiber hydrogel and aeroge mechanicalness being prepared using the method for the present invention
Can be excellent, there is the advantage of high-intensitive, high rebound.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, those skilled in the art should understand that：Its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of preparation method of nanofiber hydrogel, which is characterized in that include the following steps：
(a) cellulosic material is subjected to pre-treatment, obtains nano-cellulose dispersion liquid；
(b) nano-cellulose dispersion liquid is mixed with crosslinking agent, obtains composite dispersion liquid；
(c) composite dispersion liquid is subjected to freeze thawing treatment, obtains nanofiber hydrogel.
2. the preparation method of nanofiber hydrogel according to claim 1, which is characterized in that in step (a), preceding place
Reason includes mechanical treatment or mechanical treatment and pretreated combination；
Preferably, cellulosic material is mixed with solvent, is carried out mechanical treatment, is obtained nano-cellulose dispersion liquid；
Alternatively, will mix by pretreated cellulosic material with solvent, mechanical treatment is carried out, obtains nano-cellulose dispersion
Liquid.
3. the preparation method of nanofiber hydrogel according to claim 2, which is characterized in that the pretreatment packet
Include in chemical method, physical method and bioanalysis any one or at least two combination；
And/or the mechanical treatment includes homogenized, ultrasonic treatment, high-speed stirred, milling treatment of colloid, ultramicro grinding, micro- penetrates
Stream and high-pressure homogeneous processing in any one or at least two combination；
Preferably, the chemical method includes at least one of alkali process, TEMPO oxidation, acid processing and hydrogen peroxide treatment；
Preferably, the physical method includes homogenized, ultrasonic treatment, high-speed stirred, milling treatment of colloid, ultramicro grinding, micro- penetrates
At least one of stream and high-pressure homogeneous processing；
Preferably, the bioanalysis includes at least one of cellulase processing, glucosides enzymatic treatment and laccase treatment.
4. the preparation method of nanofiber hydrogel according to claim 1, which is characterized in that in step (b), nanometer
The size range of cellulose includes：Length is 50nm~20 μm, and width is 3nm~500nm；
Preferably, step (b) crosslinking agent is hydroxyl crosslinking agent；
Preferably, the crosslinking agent includes epoxychloropropane, epoxy silane, silane coupling agent, glutaraldehyde, Geniposide and its derivative
At least one of object, carbodiimide or triazine crosslinked dose of tri-alkoxy carbonylamino；
Preferably, the concentration of the crosslinking agent is 0.01%~25% (w/w)；
Preferably, the concentration of nano-cellulose dispersion liquid is 0.05%~20% (w/w) in step (b)；
Preferably, the ratio of nano-cellulose and crosslinking agent is 1~100：1(w/w).
5. the preparation method of nanofiber hydrogel according to claim 1, which is characterized in that step (c) jelly
Melt in processing, cryogenic temperature is -1 DEG C~-196 DEG C, and the time is 6~60h, and number of freezing and thawing is 1~10 time.
6. the preparation method of described in any item nanofiber hydrogels according to claim 1~5, which is characterized in that described
The source of cellulosic material includes at least one of timber, careless class, bamboo class and linen-cotton class.
7. a kind of nanofiber hydrogel, which is characterized in that use the described in any item nano-celluloses of claim 1~6
The preparation method of hydrogel is prepared；
Preferably, the nanofiber hydrogel in water or in alcohol can be compression/rebound reciprocal 1~200 time, and rebound degree reaches
To 100%, storage modulus reaches 2.0 × 104Pa。
8. a kind of preparation method of nano-cellulose aerogel, which is characterized in that will be using described in any one of claim 1~6
Nanofiber hydrogel the nanofiber hydrogel that is prepared of preparation method or nanometer as claimed in claim 7
Cellulose aquagel is freeze-dried, and nano-cellulose aerogel is obtained；
Alternatively, including the following steps：
(a) cellulosic material is subjected to pre-treatment, obtains nano-cellulose dispersion liquid；
(b) nano-cellulose dispersion liquid is mixed with crosslinking agent, obtains composite dispersion liquid；
(c) composite dispersion liquid is subjected to freeze-drying process, obtains nano-cellulose aerogel；
Preferably, the temperature of freeze-drying is -1 DEG C~-155 DEG C.
9. a kind of nano-cellulose aerogel, which is characterized in that using the system of nano-cellulose aerogel according to any one of claims 8
Preparation Method is prepared；
Preferably, the nano-cellulose aerogel can be compressed in air/be sprung back reciprocal 1~200 time, and compressive strength reaches
2000Pa。
10. nanofiber hydrogel as claimed in claim 7 and/or nano-cellulose aerogel as claimed in claim 9
Be sustained, adsorb and fix, the application in heat-insulated, noise reduction or filtration art.
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