CN106084259A - A kind of preparation method of cellulose aquagel - Google Patents
A kind of preparation method of cellulose aquagel Download PDFInfo
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- CN106084259A CN106084259A CN201610616117.1A CN201610616117A CN106084259A CN 106084259 A CN106084259 A CN 106084259A CN 201610616117 A CN201610616117 A CN 201610616117A CN 106084259 A CN106084259 A CN 106084259A
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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
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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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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
- D21C9/005—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives organic compounds
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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
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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
- C08J2301/08—Cellulose derivatives
- C08J2301/26—Cellulose ethers
- C08J2301/28—Alkyl ethers
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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
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
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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
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/08—Cellulose derivatives
- C08J2401/26—Cellulose ethers
- C08J2401/28—Alkyl ethers
Abstract
The invention discloses the preparation method of a kind of cellulose aquagel.Common Plant fiber's dissolving pulp is placed in the mixed solution being made up of methanol, ethanol, N N dimethyl acetamide, isopropanol or water two of which solvent by the method, is stirred continuously, is subsequently adding NaOH or KOH.One or both in addition sodium acetate, sodium chloroacetate or sodium thioglycolate, reaction after reaction；Fiber after filtration is dissolved in water and makes fiber water solution, and solution is placed in high-speed emulsifying machine disperses；Using dispersion liquid rotary evaporation to viscous pasty state as solution A.Preparation solution B, solution B is mixed by water and NaOH and epoxychloropropane；Solution B is poured into solution A, stirring at normal temperature, dries；The inventive method need not use various chemical monomer materials synthesis hydrogel, and using pure plant fiber element completely is raw material, in the way of full chemical means processes, have that technique is simple, low power consuming, the feature such as environmental friendliness and low cost.
Description
Technical field
The present invention relates to the preparation method of a kind of cellulose aquagel, particularly relate to one and use pure plant fiber completely
Element is raw material, in the way of full chemical means processes, have that technique is simple, low power consuming, environmental friendliness and water-setting with low cost
Glue preparation method；Can be applicable to the condensation preventing agent in biomedicine, building, conditioning agent, the fixing of enzyme, guarantor in agricultural
The fields such as water drought resisting.
Background technology
Hydrogel is that a class has hydrophilic group (hydroxyl, carboxyl etc.) and can be water-swellable but water-fast have three dimensional network
The polymer of network structure.Under extraneous stimulation, (temperature, PH, magnetic field, electric field etc.) can absorb and discharge moisture simultaneously, permissible
It is applied to the condensation preventing agent in biomedicine, building, conditioning agent, the fixing of enzyme, water conservation drought resisting in agricultural etc. multiple
Field.It is to be formed by certain physical crosslinking or chemical crosslinking effect by water solublity or hydrophilic macromolecule
's.The raw material sources preparing hydrogel at present mainly have natural polymer and the synthesis big class of macromolecule two.Wherein natural polymer
Comprise polysaccharide (starch, cellulose, alginic acid, hyaluronic acid, chitosan etc.) and many peptides (collagen, poly-L lysine, poly-L
Glutamic acid etc.).The hydrophilic high mol of synthesis includes that (polyacrylic acid, polymethylacrylic acid gather for alcohol, acrylic acid and derivatives class thereof
Acrylamide, poly-N is poly-for acrylamide etc.).It is former that the hydrophilic macromolecule of these synthesis needs with the derivant of PETROLEUM PROCESSING
Material, is greatly accelerated the consumption of these non-renewable energy resources of oil, the most degradable thus environment is caused pollution.And it is fine
Dimension element is the resource that can regenerate, and has good degradation property, survivable environment, has the most compatible with human body simultaneously
Property, thus of great interest.
Comprise three hydroxyls on each unit formula chain of cellulose, thus cellulose can be carried out chemical modification, enter
The reactions such as row esterification, etherificate.Traditional way preparing cellulose aquagel is low by cellulose and sodium carboxymethyl cellulose
It is dissolved separately in the case of temperature in the aqueous solution being made up of 6wt%Na0H/4wt%Urea, then by epoxychloropropane as friendship
Hydrogel is prepared in connection agent.Cellulose is to improve the mechanical strength of hydrogel in this process as skeleton.Cross-linking agent
Effect connects the oh group on cellulose and the carboxylic group on carboxymethyl cellulose, exactly so that the two can become
One overall structure, thus form hydrogel.
Producing of existing cellulose aquagel is carried out under the cryogenic conditions needing 12 DEG C, the 6wt%Na0H/ of preparation
4wt%Urea system needs the time keeping 8h could dissolve cellulose, and technical process is harsher, the most long,
The energy that refrigeration is consumed is relatively big, and the hydrogel causing preparation is relatively costly.
Summary of the invention
It is an object of the invention to provide that a kind of to use plant cellulose be raw material, technique is simple, low power consuming, environmental friendliness
With the with low cost method preparing novel cellulose aquagel processed with full chemical means.
The principle of the present invention is first by swollen liquid, dissolving pulp to be carried out degree of depth swollen, is made by chemical treatment the most again
It dissociates further, now needs to be modified fiber surface, and the hydroxyl modification of fiber surface becomes other more hydrophilic officials
Can roll into a ball, by modified, the functional group overcoming the hydrogen bond force synkaingenesis one-tenth produced between fiber by hydroxyl is more soluble in water, logical
Cross this partly soluble mode and separate to realize the further of fiber, thus a step can obtain relatively fine cellulose simultaneously
And sodium carboxymethyl cellulose, then use epoxychloropropane as cross-linking agent, utilize alkali to process cross-linking agent finally by cellulose and carboxylic
Sodium carboxymethylcellulose pyce is cross-linked into an entirety, forms a three dimensional hydrogel structure with cellulose as support.Prepared by the present invention
Process is without individually dissolving cellulose and sodium carboxymethyl cellulose, it is not required that the harshest cryogenic conditions, can reduce system
Standby time and the production cost of product, production technology is simple simultaneously, provides the foundation for industrialized production in the future.It is different from tradition
The use NaOH/Urea system method of preparing hydrogel, the low temperature bar that we create 12 DEG C without using a large amount of electric energy
Part keeps 8h, and without using expensive microcrystalline Cellulose powder and CMC powder to prepare hydrogel, the present invention is direct
The dissolving pulp of less expensive, the time spent by the most whole process is used to be far smaller than traditional preparation side
Formula, just can form hydrogel in about 4 hours, it is possible to be substantially reduced product cost and energy expenditure.
The purpose of the present invention is achieved through the following technical solutions:
The preparation method of a kind of cellulose aquagel, it is characterised in that comprise the steps and process conditions:
1) dissolving pulp is dry: be dried by dissolving pulp to moisture content less than 2%；
2) swollen of dissolving pulp: by first solvent and second solvent mixed configuration swollen liquid, dried dissolving pulp joins profit
Swollen liquid obtains mixture, controls dissolving pulp oven dry weight and accounts for the 0.1 5% of whole mixture weight；First solvent and second solvent are all first
The one that alcohol, ethanol, N N dimethyl acetamide, isopropyl alcohol and water are different；
3) the dissociating of dissolving pulp: by step 2) gained mixture controls at a temperature of 20 DEG C 50 DEG C, adds after being stirred continuously
NaOH or KOH, and continuously stirred；
4) modification of dissolving pulp: in step 3) products therefrom adds sodium acetate, sodium chloroacetate, depakine and sulfur
For one or both in sodium glycollate；Controlling temperature is 40 DEG C 100 DEG C, reacts 1h 10h, and course of reaction is stirred continuously；
5) preparation of fiber water solution: by through step 4) process after reactant liquor carry out washing filtering, will pass through subsequently
Fiber after filter is dissolved in water and makes fiber water solution；
6) dispersion of fiber water solution: fiber water solution is placed in high-speed emulsifying machine and disperses；
7) concentration of fiber water solution: after having disperseed, will be through step 6) process after dispersion liquid in Rotary Evaporators
Carry out rotary evaporation to viscous pasty state, as solution A；
8) preparation of solution B: by water and NaOH and epoxychloropropane three mixing, be stirred after mixing, during stirring
Between be 0.1h 5h, obtain solution B；
9) preparation of hydrogel: solution B pours solution A into, puts into drying baker after stirring at normal temperature 1h 5h, drying baker temperature is
30 DEG C 100 DEG C, drying time is 1h 10h；
10) washing of hydrogel: hydrogel is washed by hydrogel deionized water, dehydrated alcohol, places into
The PH carrying out in analysis bag dialysing to dialysis solution is neutrality, is finally putting into drying baker and is dried.
For realizing the object of the invention further, it is preferable that the kind of described dissolving pulp is needlebush dissolving pulp or broad-leaved
The one of wood dissolving pulp or both mixing；After described dissolving pulp refers to that plant cellulose removes most of lignin and hemicellulose
Part, is mainly composed of cellulose.
Preferably, step 1) described in dry be to carry out under the conditions of 100 DEG C 120 DEG C.
Preferably, described swollen liquid is to be 1/8 1/2 mixing gained by the first and second two kinds of solvents according to mass ratio.
Preferably, step 3) and step 4) described in stirring be that magnetic agitation, mechanical agitation, airflow stirring or jet stir
Mixing, the speed of stirring is 50 80r/min.
Preferably, step 3) mixture time of controlling to be stirred continuously at a temperature of 20 DEG C 50 DEG C is 10min 100min；
Add continuously stirred 10min 100min after NaOH or KOH；Described NaOH or KOH addition is dissolving pulp quality 100%
400%.
Preferably, described one or both the addition in sodium acetate, sodium chloroacetate or sodium thioglycolate is for dissociating
50% the 500% of rear dissolving pulp quality；Described control temperature be 40 DEG C 100 DEG C be by water-bath, oil bath, microwave heating or
Person's heating by electric cooker realizes.
Preferably, step 6) dispersion rotating speed is 4000r/min 8000r/min, jitter time is 5min 15min.
Preferably, solution B is to be mixed by water, NaOH and epoxychloropropane, and wherein the mass ratio of water and NaOH is 5:
3, the amount that epoxychloropropane adds is 25 times of water and NaOH gross mass；The quality of solution B is the 1/8 1/2 of solution A quality.
Preferably, the preparation of described fiber water solution first uses vacuum filtration or natural filtration mode to add water and join
System；Described filter funnel is G3 or G1 sand core funnel；Hydrogel preparation needs after shaping to carry out dialysis treatment with bag filter
Removing little molecule and the epoxychloropropane of residual in hydrogel, bag filter kind used is through molecular weight 2,000 7000
In one；Hydrogel uses vacuum drying oven or the heat set mode of drying baker.
Compared with prior art, present invention have the advantage that
1) comparing traditional mode using various chemical monomer materials synthesis hydrogels, this method uses pure plant completely
Cellulose is raw material, prepares hydrogel in the way of full chemical means processes, more environmentally-friendly.
2) preparation method of a kind of cellulose aquagel in the present invention, uses the mode that full chemical means processes, it is not necessary to severe
The K cryogenic treatment condition carved, have that technique is simple, low power consuming, the feature such as environmental friendliness and low cost.
Accompanying drawing explanation
Fig. 1 (a) is embodiment 1 dissolving pulp fibrous material scanning electron microscope (SEM) photograph before treatment；
Fig. 1 (b) is the scanning electron microscope (SEM) photograph after embodiment 1 dissolving pulp fibrous material processes.
Fig. 2 (a) is that embodiment 1 laser irradiates lower hydrogel pictorial diagram.
Fig. 2 (b) is expansion plans after the water suction of embodiment 1 hydrogel.
Fig. 2 (c) is the compression curve of embodiment 1 hydrogel.
Infrared waves spectrogram after before and after Fig. 2 (d) is embodiment 1 fiber treatment and respectively washing and alcohol are washed.
Fig. 2 (e) is internal structure scanning electron microscope (SEM) photograph after embodiment 1 hydrogel lyophilization.
Detailed description of the invention
In order to more deeply understand the present invention, below in conjunction with embodiment, the present invention is further illustrated, needs explanation
, the scope of protection of present invention is not limited to the scope of embodiment statement.
Embodiment 1
The preparation method of a kind of cellulose aquagel, comprises the steps and process conditions:
(1) dissolving pulp is dry: be dried under the conditions of 105 DEG C by eucalyptus dissolving pulp to moisture content less than 2%；
(2) swollen of dissolving pulp: methanol and two kinds of solvents of dimethyl sulfoxide (DMSO) are mixed according to the mass ratio of 1:5
Closing configuration swollen liquid, dried dissolving pulp adds swollen liquid, obtains mixture, controls dissolving pulp oven dry weight and accounts for whole mixture
The 1% of weight.
(3) the dissociating of dissolving pulp: the mixture that step (2) is configured is maintained 50 DEG C and is stirred continuously, after stirring 30min
Add the KOH of dissolving pulp quality 1.5 times, and continuously stirred 60min.
(4) modification of dissolving pulp: add the sodium acetate and the two of 1 times of dissolving pulp quality 2 times in step (3) products therefrom
Propyl-acetic acid sodium.Reacting 1h under the conditions of making solution be maintained at 40 DEG C, course of reaction needs to be stirred continuously simultaneously.
(5) preparation of fiber water solution: the reactant liquor after step (4) processes is carried out washing filtering, will pass through subsequently
Fiber after filtration is dissolved in water and makes fiber water solution.
(6) dispersion of fiber water solution: the fiber water solution configured through step (5) is placed in high-speed emulsifying machine and carries out point
Dissipating, dispersion rotating speed is 7000r/min, and jitter time is 5min.
(7) concentration of fiber water solution: after having disperseed, will be through the dispersion liquid after step (6) processes at Rotary Evaporators
In carry out rotary evaporation in vacuo to viscous pasty state as solution A using 85 DEG C.
(8) preparation of solution B: water and NaOH and epoxychloropropane three are mixed according to the mass ratio of 2:1:3, mixed
Being stirred after conjunction, mixing time is 1h, obtains solution B；
(9) preparation of hydrogel: solution B joined in solution A, the quality of solution B is the 3/8 of solution A quality；Room temperature
Putting into drying baker after stirring 3h, drying baker temperature is 80 DEG C, and drying time is 2h.
(10) washing of hydrogel: hydrogel is washed by hydrogel deionized water, dehydrated alcohol, places into
The PH carrying out in analysis bag (4000 molecular weight) dialysing to dialysis solution is neutrality, is finally putting into drying baker and is dried.
Hydrogel is the gel with water as disperse medium, is a kind of macromolecule network system, and character is soft, can keep certain
Shape, substantial amounts of water can be absorbed.Fig. 2 (a) is hydrogel pictorial diagram, and Fig. 2 (b) is pictorial diagram after hydrogel water suction, Fig. 2 (c)
For hydrogel compression curve, hydrogel sample is cut into the cube that the length of side is 4cm, uses universal tensile machine to be compressed stress
Strain curve is tested, and the longitudinal axis is the change of compression stress, and transverse axis is the change of compression distance.Product prepared by the present embodiment is a kind of
Transparent three-dimensional network structure, is defined composite crosslinking network structure by cellulose and CMC and cross-linking agent, can adsorb and be equivalent to
The water yield that own wt is 70 times, character is soft simultaneously, and compression ratio can reach 62%.
Use scanning electron microscope sem technology that the microstructure of the dissolving pulp before and after processing is carried out depth scan, from Fig. 1 (a)
In can be seen that, dissolving pulp fiber is substantially complete structure and caves in or dissolution phenomena.After the present embodiment chemical treatment
Effect such as Fig. 1 (b) shown in, it can be seen that the form of fiber is the most imperfect after treatment, and flat structure caves in,
Find out that fiber occurs in that the phenomenon of a large amount of dissolving simultaneously.Prior art is typically all the effect utilizing mechanical force after pretreatment
Big fiber is made to be broken to less cellulose, mainly physical damage structure step by step.The present invention uses change purely
Process, and by making few fibers carboxymethyl-modification, becomes soluble in the sodium carboxymethyl cellulose of water, and remaining is exactly not
There is the cellulose of modification, then form three-dimensional netted hydrogel structure by the effect of cross-linking agent.Fiber through chemistry retrofit after,
Chemical group can change, and is washed with water respectively by the fiber processed and dialyses after washing repeatedly with alcohol again, infrared spectrogram
There occurs change, as shown in Fig. 2 (d), wherein original cellulose fiber represents fibril, treated
Cellulose fiber represents reacted fiber, and Sample DI water represents the filtrate after being washed by material after reaction,
Sample Ethanol represents filtrate after reactant washing with alcohol.At 1604cm‐1And 1427cm‐1Place occurs in that new absorption
Peak, that corresponding is COO‐Absworption peak, come from the CMC (sodium carboxymethyl cellulose) of modified generation, the water that simultaneously will generate
Carry out sem test after gel refrigeration drying, find that hydrogel has been internally formed the network-like structure being cross-linked with each other, as
Shown in Fig. 2 (e).
Hydrogel prepared by the present embodiment is the degradable cellulose aquagel material of a kind of quick preparation, it is not necessary to use
High polymer monomer and the experiment condition of harshness.Possessing good elasticity, in different liquids, water absorption rate is different simultaneously,
Cellulosic material and human body possess the good compatibility simultaneously, will not make generation rejection as other synthetic water gels,
Thus medically can be as tissue filling agent, medicinal slow release agent.The water-retaining property of hydrogel material is fine simultaneously, and moisture is difficult to
Evaporation and solidification, thus can be as fields such as the water conservation drought resistings in condensation preventing agent, conditioning agent and the agricultural in building.
As culture medium, enzyme can be fixed in the above in terms of biology.
Series of processes through above-mentioned steps is processed, and dissolving pulp passes through swollen and dissociation, then by fiber surface
Hydroxyl be modified, after the step process such as modified washing of dissociating of above dissolving pulp, fiber can occur chemical reaction,
The hydroxyl of hydroxyl the meeting carboxy methylation, i.e. cellulose surface on few fibers surface is modified and becomes carboxymethyl, destroys fiber
Between the Hyarogen-bonding that is made up of hydroxyl, be more soluble in water by the functional group of modified fiber surface simultaneously, this part is molten
The mode solved makes fiber further to refine.
Pictorial diagram before and after the water suction of example below gained cellulose aquagel is substantially the same manner as Example 1, and Electronic Speculum figure is also
Similar, it is all a kind of transparent three-dimensional network structure, cellulose and CMC and cross-linking agent defines composite crosslinking network structure,
Water absorbing properties is similar, illustrates the most one by one.
Embodiment 2
The preparation method of a kind of cellulose aquagel, comprises the steps and process conditions:
(1) dissolving pulp is dry: be dried under the conditions of 105 DEG C by eucalyptus dissolving pulp to moisture content less than 2%；
(2) swollen of dissolving pulp: methanol and two kinds of solvents of N N dimethyl acetamide are mixed according to the mass ratio of 1:4
Configuration swollen liquid, obtains mixture.Dried dissolving pulp adds swollen liquid, controls dissolving pulp oven dry weight and accounts for whole mixture weight
The 2% of amount.
(3) the dissociating of dissolving pulp: the mixture that step (2) is configured is maintained 30 DEG C and is stirred continuously, after stirring 50min
Add the KOH of dissolving pulp quality 1.5 times, and continuously stirred 60min.
(4) modification of dissolving pulp: in the middle sodium acetate adding dissolving pulp quality 2 times of step (3) and the dipropyl second of 1 times
Acid sodium.Reacting 5h under the conditions of making solution be maintained at 50 DEG C, course of reaction needs to be stirred continuously simultaneously.
(5) preparation of fiber water solution: the reactant liquor after step (4) processes is carried out washing filtering, will pass through subsequently
Fiber after filtration is dissolved in water and makes fiber water solution.
(6) dispersion of fiber water solution: the solution just configured through step (5) is placed in high-speed emulsifying machine to be disperseed, point
Scattered rotating speed is 4000r/min, and jitter time is 15min.
(7) concentration of fiber water solution: will be through the dispersion liquid after step (6) processes in Rotary Evaporators after having disperseed
Rotary evaporation in vacuo is carried out to viscous pasty state as solution A using 85 DEG C.
(8) preparation of solution B: water and NaOH and epoxychloropropane three are mixed according to the ratio of 10:6:11,
Being stirred after mixing, mixing time is 1h, obtains solution B；Control quality is solution A quality the 1/4 of solution B.
(9) preparation of hydrogel: solution B pours solution A into, puts into drying baker after stirring at normal temperature 3h, drying baker temperature is 80
DEG C, drying time is 2h.
(10) washing of hydrogel: hydrogel is washed by hydrogel deionized water, dehydrated alcohol, places into
The PH carrying out in analysis bag (5000 molecular weight) dialysing to dialysis solution is neutrality, is finally putting into drying baker and is dried.
Embodiment 3
The preparation method of a kind of cellulose aquagel, comprises the steps and process conditions:
(1) dissolving pulp is dry: be dried under the conditions of 105 DEG C by eucalyptus dissolving pulp to moisture content less than 2%；
(2) swollen of dissolving pulp: by two kinds of solvents of isopropyl alcohol and water according to the mass ratio mixed configuration swollen liquid of 1:5,
Dried dissolving pulp adds swollen liquid, obtains mixture.Control dissolving pulp oven dry weight account for mixture weight 1%.
(3) the dissociating of dissolving pulp: the mixture that step (2) is configured is maintained 35 DEG C and is stirred continuously, stirs 40min
The KOH of rear addition dissolving pulp quality 2 times, and continuously stirred 60min.
(4) modification of dissolving pulp: in the middle sodium acetate adding dissolving pulp quality 2 times of step (3) and the sodium chloroacetate of 1 times.
Reacting 8h under the conditions of making solution be maintained at 50 DEG C, course of reaction needs to be stirred continuously simultaneously.
(5) preparation of fiber water solution: the reactant liquor after step (4) processes is carried out washing filtering, will pass through subsequently
Fiber after filtration is dissolved in water and makes fiber water solution.
(6) dispersion of fiber water solution: the solution just configured through step (5) is placed in high-speed emulsifying machine to be disperseed, point
Scattered rotating speed is 5000r/min, and jitter time is 10min.
(7) concentration of fiber water solution: will be through the dispersion liquid after step (6) processes in Rotary Evaporators after having disperseed
Rotary evaporation in vacuo is carried out to viscous pasty state as solution A using 85 DEG C.
(8) preparation of solution B: water and NaOH and epoxychloropropane three are mixed according to the ratio of 10:6:15,
Being stirred after mixing, mixing time is 1h, obtains solution B；The quality of solution B is the 1/2 of solution A quality.
(9) preparation of hydrogel: solution B pours solution A into, puts into drying baker after stirring at normal temperature 3h, drying baker temperature is 60
DEG C, drying time is 3h.
(10) washing of hydrogel: hydrogel is washed by hydrogel deionized water, dehydrated alcohol, places into
The PH carrying out in analysis bag (3000 molecular weight) dialysing to dialysis solution is neutrality, is finally putting into drying baker and is dried.
Embodiment 4
The preparation method of a kind of cellulose aquagel, comprises the steps and process conditions:
(1) dissolving pulp is dry: be dried under the conditions of 105 DEG C by eucalyptus dissolving pulp to moisture content less than 2%；
(2) swollen of dissolving pulp: by isopropanol and two kinds of solvents of methanol according to the mass ratio mixed configuration swollen of 1:4
Liquid, dried dissolving pulp adds swollen liquid, obtains mixture.Control dissolving pulp oven dry weight and account for the 1% of mixture weight.
(3) the dissociating of dissolving pulp: the mixture that step (2) is configured is maintained 40 DEG C and is stirred continuously, after stirring 30min
Add the KOH of dissolving pulp quality 2 times, and continuously stirred 50min.
(4) modification of dissolving pulp: in the middle sodium acetate adding dissolving pulp quality 2 times of step (3) and the thioglycolic acid of 1 times
Sodium.Reacting 8h under the conditions of making solution be maintained at 60 DEG C, course of reaction needs to be stirred continuously simultaneously.
(5) preparation of fiber water solution: the reactant liquor after step (4) processes is carried out washing filtering, will pass through subsequently
Fiber after filtration is dissolved in water and makes fiber water solution.
(6) dispersion of fiber water solution: the solution just configured through step (5) is placed in high-speed emulsifying machine to be disperseed, point
Scattered rotating speed is 5000r/min, and jitter time is 10min.
(7) concentration of fiber water solution: will be through the dispersion liquid after step (6) processes in Rotary Evaporators after having disperseed
Rotary evaporation in vacuo is carried out to viscous pasty state as solution A using 85 DEG C.
(8) preparation of solution B: water and NaOH and epoxychloropropane three are mixed according to the ratio of 10:6:15,
Being stirred after mixing, mixing time is 1h, obtains solution B；The quality of solution B is the 1/8 of solution A quality.
(9) preparation of hydrogel: solution B pours solution A into, puts into drying baker after stirring at normal temperature 3h, drying baker temperature is 70
DEG C, drying time is 3h.
(10) washing of hydrogel: hydrogel is washed by hydrogel deionized water, dehydrated alcohol, places into
The PH carrying out in analysis bag (7000 molecular weight) dialysing to dialysis solution is neutrality, is finally putting into drying baker and is dried.
Embodiment 5
The preparation method of a kind of cellulose aquagel, comprises the steps and process conditions:
(1) dissolving pulp is dry: be dried under the conditions of 105 DEG C by eucalyptus dissolving pulp to moisture content less than 2%；
(2) swollen of dissolving pulp: by ethanol and two kinds of solvents of methanol according to the mass ratio mixed configuration swollen liquid of 1:5,
Dried dissolving pulp adds swollen liquid, obtains mixture.Control dissolving pulp oven dry weight and account for the 1% of mixture weight.
(3) the dissociating of dissolving pulp: the mixture that step (2) is configured is maintained 50 DEG C and is stirred continuously, after stirring 50min
Add the NaOH of dissolving pulp quality 2 times, and continuously stirred 40min.
(4) modification of dissolving pulp: in the middle sodium acetate adding dissolving pulp quality 1 times of step (3) and the thioglycolic acid of 2 times
Sodium.Reacting 8h under the conditions of making solution be maintained at 60 DEG C, course of reaction needs to be stirred continuously simultaneously.
(5) preparation of fiber water solution: the reactant liquor after step (4) processes is carried out washing filtering, will pass through subsequently
Fiber after filtration is dissolved in water and makes fiber water solution.
(6) dispersion of fiber water solution: the solution just configured through step (5) is placed in high-speed emulsifying machine to be disperseed, point
Scattered rotating speed is 6000r/min, and jitter time is 15min.
(7) concentration of fiber water solution: will be through the dispersion liquid after step (6) processes in Rotary Evaporators after having disperseed
Rotary evaporation in vacuo is carried out to viscous pasty state as solution A using 80 DEG C.
(8) preparation of solution B: water and NaOH and epoxychloropropane three are mixed according to the ratio of 10:6:15,
Being stirred after mixing, mixing time is 4h, obtains solution B；Control quality is solution A quality the 1/2 of solution B.
(9) preparation of hydrogel: solution B pours solution A into, puts into drying baker after stirring at normal temperature 3h, drying baker temperature is 70
DEG C, drying time is 3h.
(10) washing of hydrogel: hydrogel is washed by hydrogel deionized water, dehydrated alcohol, places into
The PH carrying out in analysis bag (5000 molecular weight) dialysing to dialysis solution is neutrality, is finally putting into drying baker and is dried.
Embodiment 6
The preparation method of a kind of cellulose aquagel, comprises the steps and process conditions:
(1) dissolving pulp is dry: be dried under the conditions of 105 DEG C by eucalyptus dissolving pulp to moisture content less than 2%；
(2) swollen of dissolving pulp: by ethanol and two kinds of solvents of isopropanol according to the mass ratio mixed configuration swollen of 1:5
Liquid, dried dissolving pulp adds swollen liquid, obtains mixture.Control dissolving pulp oven dry weight and account for the 1% of mixture weight.
(3) the dissociating of dissolving pulp: the mixture that step (2) is configured is maintained 50 DEG C and is stirred continuously, after stirring 50min
Add the NaOH of dissolving pulp quality 2 times, and continuously stirred 40min.
(4) modification of dissolving pulp: in the middle sodium acetate adding dissolving pulp quality 1 times of step (3) and the thioglycolic acid of 2 times
Sodium.Reacting 8h under the conditions of making solution be maintained at 60 DEG C, course of reaction needs to be stirred continuously simultaneously.
(5) preparation of fiber water solution: the reactant liquor after step (4) processes is carried out washing filtering, will pass through subsequently
Fiber after filtration is dissolved in water and makes fiber water solution.
(6) dispersion of fiber water solution: the solution just configured through step (5) is placed in high-speed emulsifying machine to be disperseed, point
Scattered rotating speed is 6000r/min, and jitter time is 15min.
(7) concentration of fiber water solution: will be through the dispersion liquid after step (6) processes in Rotary Evaporators after having disperseed
Rotary evaporation in vacuo is carried out to viscous pasty state as solution A using 80 DEG C.
(8) preparation of solution B: water and NaOH and epoxychloropropane three are mixed according to the ratio of 10:6:15,
Being stirred after mixing, mixing time is 4h, obtains solution B；Control quality is solution A quality the 1/4 of solution B.
(9) preparation of hydrogel: solution B pours solution A into, puts into drying baker after stirring at normal temperature 3h, drying baker temperature is 70
DEG C, drying time is 5h.
(10) washing of hydrogel: hydrogel is washed by hydrogel deionized water, dehydrated alcohol, places into
The PH carrying out in analysis bag (4000 molecular weight) dialysing to dialysis solution is neutrality, is finally putting into drying baker and is dried.
Claims (10)
1. the preparation method of a cellulose aquagel, it is characterised in that comprise the steps and process conditions:
1) dissolving pulp is dry: be dried by dissolving pulp to moisture content less than 2%；
2) swollen of dissolving pulp: by first solvent and second solvent mixed configuration swollen liquid, dried dissolving pulp joins swollen liquid
Obtain mixture, control dissolving pulp oven dry weight and account for the 0.1 5% of whole mixture weight；First solvent and second solvent be all methanol,
The one that ethanol, N N dimethyl acetamide, isopropyl alcohol and water are different；
3) the dissociating of dissolving pulp: by step 2) gained mixture controls at a temperature of 20 DEG C 50 DEG C, adds NaOH after being stirred continuously
Or KOH, and continuously stirred；
4) modification of dissolving pulp: in step 3) products therefrom adds sodium acetate, sodium chloroacetate, depakine and sulfur for second
One or both in alkyd sodium；Controlling temperature is 40 DEG C 100 DEG C, reacts 1h 10h, and course of reaction is stirred continuously；
5) preparation of fiber water solution: by through step 4) process after reactant liquor carry out washing filtering, subsequently will be after filtering
Fiber be dissolved in water and make fiber water solution；
6) dispersion of fiber water solution: fiber water solution is placed in high-speed emulsifying machine and disperses；
7) concentration of fiber water solution: after having disperseed, by through step 6) process after dispersion liquid carry out in Rotary Evaporators
Rotary evaporation is to viscous pasty state, as solution A；
8) preparation of solution B: by water and NaOH and epoxychloropropane three mixing, being stirred after mixing, mixing time is
0.1h 5h, obtains solution B；
9) preparation of hydrogel: solution B pours solution A into, puts into drying baker after stirring at normal temperature 1h 5h, drying baker temperature is 30 DEG C
100 DEG C, drying time is 1h 10h；
10) washing of hydrogel: hydrogel is washed by hydrogel deionized water, dehydrated alcohol, places into bag filter
In the PH that carries out dialysing to dialysis solution be neutrality, be finally putting into drying baker and be dried.
The preparation method of cellulose aquagel the most according to claim 1, it is characterised in that the kind of described dissolving pulp
For needlebush dissolving pulp or the one of leaf wood dissolving pulp or both mixing；Described dissolving pulp refers to that plant cellulose removes big portion
Divide the part after lignin and hemicellulose, be mainly composed of cellulose.
The preparation method of cellulose aquagel the most according to claim 1, it is characterised in that step 1) described in dry be
Carry out under the conditions of 100 DEG C 120 DEG C.
The preparation method of cellulose aquagel the most according to claim 1, it is characterised in that described swollen liquid is by first
Two kinds of solvents of second are 1/8 1/2 mixing gained according to mass ratio.
The preparation method of cellulose aquagel the most according to claim 1, it is characterised in that step 3) and step 4) described
Stirring be magnetic agitation, mechanical agitation, airflow stirring or jet mixing, the speed of stirring is 50 80r/min.
The preparation method of cellulose aquagel the most according to claim 1, it is characterised in that step 3) mixture controls
The time being stirred continuously at a temperature of 20 DEG C 50 DEG C is 10min 100min；Add continuously stirred 10min after NaOH or KOH
100min；Described NaOH or KOH addition is 100% the 400% of dissolving pulp quality.
The preparation method of cellulose aquagel the most according to claim 1, it is characterised in that described sodium acetate, chloroethene
One or both addition in acid sodium or sodium thioglycolate be dissociate after dissolving pulp quality 50% 500%；Described control
It is to be realized by water-bath, oil bath, microwave heating or heating by electric cooker that temperature processed is 40 DEG C 100 DEG C.
The preparation method of cellulose aquagel the most according to claim 1, it is characterised in that step 6) dispersion rotating speed be
4000r/min 8000r/min, jitter time is 5min 15min.
The preparation method of cellulose aquagel the most according to claim 1, it is characterised in that the mass ratio of water and NaOH is
5:3, the amount that epoxychloropropane adds is 25 times of water and NaOH gross mass；The quality of solution B is the 1/8 1/ of solution A quality
2。
The preparation method of cellulose aquagel the most according to claim 1, it is characterised in that described fiber water solution
Preparation first use vacuum filtration or natural filtration mode to add water preparation；Described filter funnel is the leakage of G3 or G1 core
Bucket；Hydrogel preparation needs to carry out dialysis treatment with bag filter and removes little molecule and the epoxy of residual in hydrogel after shaping
Chloropropane, bag filter kind used is through the one in molecular weight 2,000 7000；Hydrogel use vacuum drying oven or
The heat set mode of drying baker.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106727280A (en) * | 2016-12-08 | 2017-05-31 | 华南理工大学 | A kind of nano biological matter base anticancer sustained-release gel and preparation method thereof |
| CN107573535A (en) * | 2017-08-09 | 2018-01-12 | 华南理工大学 | A kind of preparation method of magnetic cellulose aeroge |
| CN108653383A (en) * | 2018-08-16 | 2018-10-16 | 陕西仁浩医疗器械有限公司 | A kind of medical antipyretic analgesic hydrogel |
| CN111423095A (en) * | 2020-03-05 | 2020-07-17 | 厦门大学 | Method for treating residual activated sludge |
| CN115124380A (en) * | 2022-06-09 | 2022-09-30 | 承德石油高等专科学校 | Organic-inorganic compound fertilizer with mesoporous core-shell type and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445609A (en) * | 2008-11-14 | 2009-06-03 | 武汉大学 | Hydroscopic cellulose hydrogel and preparation method thereof |
| CN105601756A (en) * | 2015-12-17 | 2016-05-25 | 华南理工大学 | Acetylation modification method for preparing nano cellulose |
-
2016
- 2016-07-29 CN CN201610616117.1A patent/CN106084259B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445609A (en) * | 2008-11-14 | 2009-06-03 | 武汉大学 | Hydroscopic cellulose hydrogel and preparation method thereof |
| CN105601756A (en) * | 2015-12-17 | 2016-05-25 | 华南理工大学 | Acetylation modification method for preparing nano cellulose |
Non-Patent Citations (1)
| Title |
|---|
| 邵自强等: ""羧甲基纤维素的环氧氯丙烷交联改性研究"", 《纤维素科学与技术》 * |
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| CN106727280A (en) * | 2016-12-08 | 2017-05-31 | 华南理工大学 | A kind of nano biological matter base anticancer sustained-release gel and preparation method thereof |
| CN106727280B (en) * | 2016-12-08 | 2019-07-16 | 华南理工大学 | A kind of nano biological matter base anticancer sustained-release gel and preparation method thereof |
| CN107573535A (en) * | 2017-08-09 | 2018-01-12 | 华南理工大学 | A kind of preparation method of magnetic cellulose aeroge |
| CN107573535B (en) * | 2017-08-09 | 2020-07-28 | 华南理工大学 | Preparation method of magnetic cellulose aerogel |
| CN108653383A (en) * | 2018-08-16 | 2018-10-16 | 陕西仁浩医疗器械有限公司 | A kind of medical antipyretic analgesic hydrogel |
| CN111423095A (en) * | 2020-03-05 | 2020-07-17 | 厦门大学 | Method for treating residual activated sludge |
| CN111423095B (en) * | 2020-03-05 | 2022-04-08 | 厦门大学 | Method for treating residual activated sludge |
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