CN106084259B - A kind of preparation method of cellulose aquagel - Google Patents
A kind of preparation method of cellulose aquagel Download PDFInfo
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- CN106084259B CN106084259B CN201610616117.1A CN201610616117A CN106084259B CN 106084259 B CN106084259 B CN 106084259B CN 201610616117 A CN201610616117 A CN 201610616117A CN 106084259 B CN106084259 B CN 106084259B
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- 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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- 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
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- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
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Abstract
The invention discloses a kind of preparation methods of cellulose aquagel.Common plant fiber dissolving pulp is placed in the mixed solution being made of methanol, ethyl alcohol, N-N dimethyl acetamide, isopropanol or water two of them solvent by this method, is stirred continuously, and NaOH or KOH is then added.One or both of sodium acetate, sodium chloroacetate or sodium thioglycolate, reaction are added after reaction；Filtered fiber is dissolved in water and fiber aqueous solution is made, and solution is placed in high-speed emulsifying machine and is dispersed；Using dispersion liquid rotary evaporation to viscous pasty state as solution A.Solution B is prepared, solution B is mixed by water and NaOH and epoxychloropropane；Solution B is poured into solution A, stirring at normal temperature, drying；The method of the present invention need not use various chemical monomer materials synthesis hydrogels, use pure plant fiber element for raw material completely, in such a way that full chemistry means are handled, have the characteristics that simple process, low power consuming, environmental-friendly and at low cost.
Description
Technical field
The present invention relates to a kind of preparation methods of cellulose aquagel, use pure plant fiber completely more particularly to a kind of
Element is raw material, in a manner of the processing of full chemistry means, has simple process, low power consuming, environmental-friendly and low-cost water-setting
Glue preparation method；Can be applied to moisture condensation preventing agent biomedical, in building, conditioning agent, biological enzyme fixation, it is agriculture in guarantor
The fields such as water drought resisting.
Background technique
Hydrogel is a kind of can be water-swellable with hydrophilic radical (hydroxyl, carboxyl etc.) but not soluble in water with three dimensional network
The polymer of network structure.(temperature, PH, magnetic field, electric field etc.) can be absorbed and discharge moisture under extraneous stimulation simultaneously, can be with
Applied to moisture condensation preventing agent biomedical, in building, conditioning agent, biological enzyme fixation, it is agriculture in water conservation drought resisting etc. it is multiple
Field.It is to act on being formed by certain physical crosslinking or chemical crosslinking by water-soluble or hydrophilic macromolecule
's.The raw material sources for preparing hydrogel at present mainly have natural polymer and synthesis macromolecule two major classes.Wherein natural polymer
Include polysaccharide (starch, cellulose, alginic acid, hyaluronic acid, chitosan etc.) and polypeptide (collagen, polylysine, poly- L-
Glutamic Acid etc.).The hydrophilic high mol of synthesis includes that (polyacrylic acid, polymethylacrylic acid gather for alcohol, acrylic acid and its derivative species
Acrylamide, poly- N- are poly- for acrylamide etc.).The hydrophilic macromolecule of these synthesis needs with the derivative of PETROLEUM PROCESSING to be original
Material, greatly accelerates the consumption of these non-renewable energy resources of petroleum, while not degradable to cause pollution to environment.And it is fine
Dimension element be can with regenerated resource, have good degradation property, survivable environment, at the same with human body have well it is compatible
Property, to have received widespread attention.
Include three hydroxyls on each unit formula chain of cellulose, thus chemical modification can be carried out to cellulose, into
The reactions such as row esterification, etherificate.Traditional method for preparing cellulose aquagel is by cellulose and sodium carboxymethylcellulose low
It is dissolved separately in warm situation in the aqueous solution being made of 6wt%Na0H/4wt%Urea, then by epoxychloropropane as friendship
Join agent to prepare hydrogel.Cellulose is the mechanical strength for improving hydrogel as skeleton in this process.Crosslinking agent
Effect is exactly the carboxylic group on the hydroxyl group and carboxymethyl cellulose connected on cellulose, so that the two can become
One overall structure, to form hydrogel.
It is carried out under the cryogenic conditions of -12 DEG C of the production needs of existing cellulose aquagel, the 6wt%Na0H/ of preparation
4wt%Urea system needs to keep the time of 8h could dissolve cellulose, and technical process is harsher, while time-consuming long,
Energy consumed by freezing is larger, causes the hydrogel higher cost of preparation.
Summary of the invention
Use plant cellulose for raw material the purpose of the present invention is to provide a kind of, it is simple process, low power consuming, environmental-friendly
With the low-cost method for preparing novel cellulose aquagel handled with full chemistry means.
The principle of the invention lies in dissolving pulp is first carried out depth swollen by swollen liquid, then made again by chemical treatment
It is further dissociated, and needs to be modified fiber surface at this time, by the hydroxyl modification of fiber surface at other more hydrophilic officials
Can group, by modified, overcome the hydrogen bond force synkaingenesis that is generated between fiber by hydroxyl at functional group be more soluble in water, lead to
This partly soluble mode is crossed to realize the further separation of fiber, thus relatively fine cellulose can be obtained simultaneously with a step
And sodium carboxymethylcellulose, then using epoxychloropropane as crosslinking agent, using alkali process crosslinking agent finally by cellulose and carboxylic
Sodium carboxymethylcellulose pyce is cross-linked into an entirety, forms one using cellulose as the three dimensional hydrogel structure of bracket.Present invention preparation
Process does not need the harsh cryogenic conditions of comparison yet, can reduce system without individually dissolution cellulose and sodium carboxymethylcellulose
The production cost of standby time and product, while simple production process, provide the foundation for industrialized production in the future.Different from tradition
The method that hydrogel is prepared using NaOH/Urea system, we create -12 DEG C of low temperature item without using a large amount of electric energy
Part keeps 8h, prepares hydrogel without using expensive microcrystalline cellulose powder and CMC powder, the present invention is direct
The dissolving pulp of less expensive is used, while the time spent by whole process will be far smaller than traditional preparation side
Formula can form hydrogel in about 4 hours, it is possible to substantially reduce product cost and energy consumption.
The purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of cellulose aquagel, it is characterised in that include the following steps and process conditions:
1) dissolving pulp drying to moisture content the drying of dissolving pulp: is lower than 2%；
2) swollen of dissolving pulp: by first solvent and second solvent mixed configuration swollen liquid, the dissolving pulp after drying is added to profit
Swollen liquid obtains mixture, and control dissolving pulp oven dry weight accounts for the 0.1-5% of entire mixture weight；First solvent and second solvent are all first
The different one kind of alcohol, ethyl alcohol, N-N dimethyl acetamide, isopropyl alcohol and water；
3) it the dissociation of dissolving pulp: by the control of mixture obtained by step 2) at a temperature of 20 DEG C -50 DEG C, is added after being stirred continuously
NaOH or KOH, and continue to stir；
4) sodium acetate, sodium chloroacetate, depakine and sulphur the modification of dissolving pulp: are added in step 3) products therefrom
For one or both of sodium glycollate；Controlled at 40 DEG C -100 DEG C, 1h-10h is reacted, reaction process is stirred continuously；
5) preparation of fiber aqueous solution: washing filtering will be carried out through step 4) treated reaction solution, will then passed through
Fiber after filter is dissolved in water and fiber aqueous solution is made；
6) dispersion of fiber aqueous solution: fiber aqueous solution is placed in high-speed emulsifying machine and is dispersed；
7) concentration of fiber aqueous solution:, will be through step 6) treated dispersion liquid in Rotary Evaporators after the completion of dispersion
Rotary evaporation is carried out to viscous pasty state, as solution A；
8) preparation of solution B: water and NaOH and epoxychloropropane three being mixed, are stirred after mixing, when stirring
Between be 0.1h-5h, obtain solution B；
9) preparation of hydrogel: solution B pours into solution A, and drying box is put into after stirring at normal temperature 1h-5h, and drying box temperature is
30 DEG C -100 DEG C, drying time 1h-10h；
10) washing of hydrogel: hydrogel deionized water, dehydrated alcohol wash hydrogel, place into
Being dialysed in analysis bag to the PH of dialyzate is neutrality, and it is dry to be finally putting into drying box.
To further realize the object of the invention, it is preferable that the type of the dissolving pulp is needlebush dissolving pulp or broad-leaved
The one or both of the wooden dissolving pulp mixes；After the dissolving pulp refers to that plant cellulose removes most of lignin and hemicellulose
Part, main component are cellulose.
Preferably, drying described in step 1) is carried out under the conditions of 100 DEG C -120 DEG C.
Preferably, it according to mass ratio is that 1/8-1/2 mixes gained that the swollen liquid, which is by the first and second two kinds of solvents,.
Preferably, step 3) and stirring described in step 4) are that magnetic agitation, mechanical stirring, airflow stirring or jet stream stir
It mixes, the rate of stirring is 50-80r/min.
Preferably, the time that the control of step 3) mixture is stirred continuously at a temperature of 20 DEG C -50 DEG C is 10min-100min；
10min-100min is persistently stirred after NaOH or KOH is added；NaOH the or KOH additional amount is the 100%- of dissolving pulp quality
400%.
Preferably, the additional amount of one or both of the sodium acetate, sodium chloroacetate or sodium thioglycolate is dissociation
The 50%-500% of dissolving pulp quality afterwards；It is described controlled at 40 DEG C -100 DEG C be by water-bath, oil bath, microwave heating or
The heating of person's electric furnace is realized.
Preferably, step 6) dispersion revolving speed is 4000r/min-8000r/min, jitter time 5min-15min.
Preferably, solution B is mixed by water, NaOH and epoxychloropropane, and wherein the mass ratio of water and NaOH are 5:
3, the amount that epoxychloropropane is added is 2-5 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 the fiber aqueous solution is first added water and is matched using vacuum filtration or natural filtration mode
System；The filter tunnel is G3 G1 sand core funnel；Hydrogel preparation forming after need with bag filter carry out dialysis treatment come
Remaining small molecule and epoxychloropropane in hydrogel are removed, bag filter type used is through molecular weight 2000-7000
One of；Hydrogel is using vacuum oven or the heat set mode of drying box.
Compared with prior art, the present invention has the advantage that
1) compared to traditional by the way of various chemical monomer materials synthesis hydrogels, this method uses pure plant completely
Cellulose is raw material, prepares hydrogel, more environmentally-friendly in a manner of the processing of full chemistry means
2) a kind of preparation method of cellulose aquagel in the present invention, by the way of the processing of full chemistry means, without severe
The low-temperature treatment condition at quarter has the characteristics that simple process, low power consuming, environmental-friendly and at low cost.
Detailed description of the invention
Fig. 1 (a) is the scanning electron microscope (SEM) photograph before the processing of 1 dissolving pulp fibrous material of embodiment；
Fig. 1 (b) is 1 dissolving pulp fibrous material of embodiment treated scanning electron microscope (SEM) photograph.
Fig. 2 (a) is hydrogel pictorial diagram under 1 laser irradiation of embodiment.
Fig. 2 (b) is expansion plans after the water suction of 1 hydrogel of embodiment.
Fig. 2 (c) is the compression curve of 1 hydrogel of embodiment.
Fig. 2 (d) is 1 fiber treatment of embodiment front and back and washes the infrared waves spectrogram after washing with alcohol respectively.
Fig. 2 (e) is internal structure scanning electron microscope (SEM) photograph after the freeze-drying of 1 hydrogel of embodiment.
Specific embodiment
In order to more deeply understand the present invention, below with reference to embodiment, the present invention is further illustrated, needs to illustrate
, the scope of protection of present invention is not limited to the scope of the embodiments.
Embodiment 1
A kind of preparation method of cellulose aquagel, includes the following steps and process conditions:
(1) drying of dissolving pulp: eucalyptus dissolving pulp is dried under the conditions of 105 DEG C to moisture content and is lower than 2%；
(2) swollen of dissolving pulp: two kinds of solvents of methanol and dimethyl sulfoxide (DMSO) are mixed according to the mass ratio of 1:5
Configuration swollen liquid is closed, swollen liquid is added in the dissolving pulp after drying, obtains mixture, and control dissolving pulp oven dry weight accounts for entire mixture
The 1% of weight.
(3) dissociation of dissolving pulp: maintaining 50 DEG C for the mixture that step (2) is configured and be stirred continuously, after stirring 30min
1.5 times of dissolving pulp quality of KOH is added, and continues to stir 60min.
(4) 2 times of sodium acetate of dissolving pulp quality and the two of 1 times the modification of dissolving pulp: is added in step (3) products therefrom
Propyl-acetic acid sodium.1h is reacted under the conditions of so that solution is maintained at 40 DEG C simultaneously, reaction process needs are stirred continuously.
(5) preparation of fiber aqueous solution: washing filtering will be carried out through step (4) treated reaction solution, will then passed through
Filtered fiber is dissolved in water and fiber aqueous solution is made.
(6) dispersion of fiber aqueous solution: the fiber aqueous solution configured through step (5) is placed in high-speed emulsifying machine and is divided
It dissipates, dispersion revolving speed is 7000r/min, jitter time 5min.
(7) concentration of fiber aqueous solution:, will be through step (6) treated dispersion liquid in Rotary Evaporators after the completion of dispersion
In using 85 DEG C of progress rotary evaporation in vacuo to viscous pasty state as solution A.
(8) preparation of solution B: water and NaOH and epoxychloropropane three are mixed according to the mass ratio of 2:1:3, mixed
It is stirred after conjunction, mixing time 1h obtains solution B；
(9) preparation of hydrogel: solution B is added in solution A, and the quality of solution B is the 3/8 of solution A quality；Room temperature
Drying box is put into after stirring 3h, drying box temperature is 80 DEG C, drying time 2h.
(10) washing of hydrogel: hydrogel deionized water, dehydrated alcohol wash hydrogel, place into
Being dialysed in analysis bag (4000 molecular weight) to the PH of dialyzate is neutrality, and it is dry to be finally putting into drying box.
Hydrogel is the gel using water as decentralized medium, is a kind of macromolecule network system, and property is soft, is able to maintain certain
Shape, a large amount 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 side length is 4cm, compression stress is carried out using universal tensile machine
Strain curve test, the longitudinal axis are the variation of compressing force, and horizontal axis is the variation of compression distance.Product manufactured in the present embodiment is a kind of
Transparent three-dimensional reticular structure forms composite crosslinking network structure by cellulose and CMC and crosslinking agent, can adsorb and be equivalent to
The water that 70 times of own wt, while property is soft, compression ratio can achieve 62%.
Depth scan is carried out using microstructure of the scanning electron microscope sem technology to dissolving pulp before and after the processing, from Fig. 1 (a)
In can be seen that, dissolving pulp fiber be substantially complete structure do not occur collapse 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 very imperfect after treatment, flat structure collapse,
Find out that the phenomenon that a large amount of dissolutions occurs in fiber simultaneously.The prior art is typically all that the effect of mechanical force is utilized after pretreatment
So that big fiber is broken to lesser cellulose, mainly physical damage structure step by step.The present invention uses pure change
Processing becomes soluble in the sodium carboxymethylcellulose of water, remaining is exactly not by making few fibers carboxymethyl-modification
There is modified cellulose, then three-dimensional netted hydrogel structure is formed by the effect of crosslinking agent.Fiber by chemistry remodeling after,
Chemical group can change, and processed fiber is washed with water after washing repeatedly with alcohol respectively and is dialysed again, infrared spectrogram
Changed, as shown in Fig. 2 (d), wherein original cellulose fiber represents fibrinogen, treated
Cellulose fiber represents the fiber after reaction, and Sample-DI water is represented the filtrate after substance washing after reaction,
Sample-Ethanol is represented filtrate after reactant ethanol washing.In 1604cm‐1And 1427cm‐1There is new absorption in place
Peak, corresponding is COO‐Absorption peak, from the CMC (sodium carboxymethylcellulose) of modified generation, while by the water of generation
Sem test is carried out after gel refrigeration drying, finds to form the network-like structure being cross-linked with each other inside hydrogel, such as
Shown in Fig. 2 (e).
Hydrogel manufactured in the present embodiment is a kind of degradable cellulose aquagel material quickly prepared, without using
The experiment condition of high polymer monomer and harshness.Have good elasticity, while water absorption rate is different in different liquids,
Cellulosic material and human body have good compatibility simultaneously, will not make to generate rejection as other synthetic hydrogels,
It thus medically can be used as tissue filling agent, medicinal slow release agent.The water-retaining property of hydrogel material is fine simultaneously, and moisture is not easy
Evaporation and solidification, thus can be used as the fields such as the water conservation drought resisting in moisture condensation preventing agent, conditioning agent and agricultural in building.
Can be used as culture medium in terms of biology allows biological enzyme to be fixed in the above.
Series of processes processing by above-mentioned steps, dissolving pulp pass through swollen and dissociation, then by fiber surface
Hydroxyl be modified, after the dissociation of above dissolving pulp modified washing processing, fiber can be chemically reacted,
The hydroxyl meeting carboxy methylation on few fibers surface, the i.e. hydroxyl of cellulose surface are modified and become carboxymethyl, destroy fiber
Between the Hyarogen-bonding that is made of hydroxyl, while water is more soluble in by the functional group of modified fiber surface, this part is molten
The mode of solution enables fiber further to refine.
The pictorial diagram of the water suction of cellulose aquagel obtained by following example front and back is substantially the same manner as Example 1, electron microscope
It is similar, all it is a kind of transparent three-dimensional reticular structure, composite crosslinking network structure is formd by cellulose and CMC and crosslinking agent,
Water absorbing properties are similar, do not illustrate one by one.
Embodiment 2
A kind of preparation method of cellulose aquagel, includes the following steps and process conditions:
(1) drying of dissolving pulp: eucalyptus dissolving pulp is dried under the conditions of 105 DEG C to moisture content and is lower than 2%；
(2) swollen of dissolving pulp: two kinds of solvents of methanol and N-N dimethyl acetamide are mixed according to the mass ratio of 1:4
Swollen liquid is configured, mixture is obtained.Swollen liquid is added in dissolving pulp after drying, and control dissolving pulp oven dry weight accounts for entire mixture weight
The 2% of amount.
(3) dissociation of dissolving pulp: maintaining 30 DEG C for the mixture that step (2) is configured and be stirred continuously, after stirring 50min
1.5 times of dissolving pulp quality of KOH is added, and continues to stir 60min.
(4) 2 times of dissolving pulp quality of sodium acetate and 1 times of dipropyl second the modification of dissolving pulp: are added in step (3)
Sour sodium.5h is reacted under the conditions of so that solution is maintained at 50 DEG C simultaneously, reaction process needs are stirred continuously.
(5) preparation of fiber aqueous solution: washing filtering will be carried out through step (4) treated reaction solution, will then passed through
Filtered fiber is dissolved in water and fiber aqueous solution is made.
(6) dispersion of fiber aqueous solution: being placed in high-speed emulsifying machine for the solution configured through step (5) and disperse, point
Dissipating revolving speed is 4000r/min, jitter time 15min.
(7) concentration of fiber aqueous solution: will be through step (6) treated dispersion liquid in Rotary Evaporators after the completion of dispersion
Using 85 DEG C of progress rotary evaporation in vacuo to viscous pasty state as solution A.
(8) preparation of solution B: water and NaOH and epoxychloropropane three are mixed according to the ratio of 10:6:11,
It is stirred after mixing, mixing time 1h obtains solution B；The quality for controlling solution B is the 1/4 of solution A quality.
(9) preparation of hydrogel: solution B pours into solution A, and drying box is put into after stirring at normal temperature 3h, and drying box temperature is 80
DEG C, drying time 2h.
(10) washing of hydrogel: hydrogel deionized water, dehydrated alcohol wash hydrogel, place into
Being dialysed in analysis bag (5000 molecular weight) to the PH of dialyzate is neutrality, and it is dry to be finally putting into drying box.
Embodiment 3
A kind of preparation method of cellulose aquagel, includes the following steps and process conditions:
(1) drying of dissolving pulp: eucalyptus dissolving pulp is dried under the conditions of 105 DEG C to moisture content and is lower 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,
Swollen liquid is added in dissolving pulp after drying, obtains mixture.Control dissolving pulp oven dry weight account for mixture weight 1%.
(3) dissociation of dissolving pulp: maintaining 35 DEG C for the mixture that step (2) is configured and be stirred continuously, and stirs 40min
2 times of dissolving pulp quality of KOH is added afterwards, and continues to stir 60min.
(4) 2 times of sodium acetate of dissolving pulp quality and 1 times of sodium chloroacetate the modification of dissolving pulp: are added in step (3).
8h is reacted under the conditions of so that solution is maintained at 50 DEG C simultaneously, reaction process needs are stirred continuously.
(5) preparation of fiber aqueous solution: washing filtering will be carried out through step (4) treated reaction solution, will then passed through
Filtered fiber is dissolved in water and fiber aqueous solution is made.
(6) dispersion of fiber aqueous solution: being placed in high-speed emulsifying machine for the solution configured through step (5) and disperse, point
Dissipating revolving speed is 5000r/min, jitter time 10min.
(7) concentration of fiber aqueous solution: will be through step (6) treated dispersion liquid in Rotary Evaporators after the completion of dispersion
Using 85 DEG C of progress rotary evaporation in vacuo to viscous pasty state as solution A.
(8) preparation of solution B: water and NaOH and epoxychloropropane three are mixed according to the ratio of 10:6:15,
It is stirred after mixing, mixing time 1h obtains solution B；The quality of solution B is the 1/2 of solution A quality.
(9) preparation of hydrogel: solution B pours into solution A, and drying box is put into after stirring at normal temperature 3h, and drying box temperature is 60
DEG C, drying time 3h.
(10) washing of hydrogel: hydrogel deionized water, dehydrated alcohol wash hydrogel, place into
Being dialysed in analysis bag (3000 molecular weight) to the PH of dialyzate is neutrality, and it is dry to be finally putting into drying box.
Embodiment 4
A kind of preparation method of cellulose aquagel, includes the following steps and process conditions:
(1) drying of dissolving pulp: eucalyptus dissolving pulp is dried under the conditions of 105 DEG C to moisture content and is lower than 2%；
(2) swollen of dissolving pulp: by two kinds of solvents of isopropanol and methanol according to the mass ratio mixed configuration swollen of 1:4
Liquid, the dissolving pulp after drying are added swollen liquid, obtain mixture.Control dissolving pulp oven dry weight accounts for the 1% of mixture weight.
(3) dissociation of dissolving pulp: maintaining 40 DEG C for the mixture that step (2) is configured and be stirred continuously, after stirring 30min
2 times of dissolving pulp quality of KOH is added, and continues to stir 50min.
(4) 2 times of sodium acetate of dissolving pulp quality and 1 times of thioglycolic acid the modification of dissolving pulp: are added in step (3)
Sodium.8h is reacted under the conditions of so that solution is maintained at 60 DEG C simultaneously, reaction process needs are stirred continuously.
(5) preparation of fiber aqueous solution: washing filtering will be carried out through step (4) treated reaction solution, will then passed through
Filtered fiber is dissolved in water and fiber aqueous solution is made.
(6) dispersion of fiber aqueous solution: being placed in high-speed emulsifying machine for the solution configured through step (5) and disperse, point
Dissipating revolving speed is 5000r/min, jitter time 10min.
(7) concentration of fiber aqueous solution: will be through step (6) treated dispersion liquid in Rotary Evaporators after the completion of dispersion
Using 85 DEG C of progress rotary evaporation in vacuo to viscous pasty state as solution A.
(8) preparation of solution B: water and NaOH and epoxychloropropane three are mixed according to the ratio of 10:6:15,
It is stirred after mixing, mixing time 1h obtains solution B；The quality of solution B is the 1/8 of solution A quality.
(9) preparation of hydrogel: solution B pours into solution A, and drying box is put into after stirring at normal temperature 3h, and drying box temperature is 70
DEG C, drying time 3h.
(10) washing of hydrogel: hydrogel deionized water, dehydrated alcohol wash hydrogel, place into
Being dialysed in analysis bag (7000 molecular weight) to the PH of dialyzate is neutrality, and it is dry to be finally putting into drying box.
Embodiment 5
A kind of preparation method of cellulose aquagel, includes the following steps and process conditions:
(1) drying of dissolving pulp: eucalyptus dissolving pulp is dried under the conditions of 105 DEG C to moisture content and is lower than 2%；
(2) swollen of dissolving pulp: by two kinds of solvents of ethyl alcohol and methanol according to the mass ratio mixed configuration swollen liquid of 1:5,
Swollen liquid is added in dissolving pulp after drying, obtains mixture.Control dissolving pulp oven dry weight accounts for the 1% of mixture weight.
(3) dissociation of dissolving pulp: maintaining 50 DEG C for the mixture that step (2) is configured and be stirred continuously, after stirring 50min
2 times of dissolving pulp quality of NaOH is added, and continues to stir 40min.
(4) 1 times of sodium acetate of dissolving pulp quality and 2 times of thioglycolic acid the modification of dissolving pulp: are added in step (3)
Sodium.8h is reacted under the conditions of so that solution is maintained at 60 DEG C simultaneously, reaction process needs are stirred continuously.
(5) preparation of fiber aqueous solution: washing filtering will be carried out through step (4) treated reaction solution, will then passed through
Filtered fiber is dissolved in water and fiber aqueous solution is made.
(6) dispersion of fiber aqueous solution: being placed in high-speed emulsifying machine for the solution configured through step (5) and disperse, point
Dissipating revolving speed is 6000r/min, jitter time 15min.
(7) concentration of fiber aqueous solution: will be through step (6) treated dispersion liquid in Rotary Evaporators after the completion of dispersion
Using 80 DEG C of progress rotary evaporation in vacuo to viscous pasty state as solution A.
(8) preparation of solution B: water and NaOH and epoxychloropropane three are mixed according to the ratio of 10:6:15,
It is stirred after mixing, mixing time 4h obtains solution B；The quality for controlling solution B is the 1/2 of solution A quality.
(9) preparation of hydrogel: solution B pours into solution A, and drying box is put into after stirring at normal temperature 3h, and drying box temperature is 70
DEG C, drying time 3h.
(10) washing of hydrogel: hydrogel deionized water, dehydrated alcohol wash hydrogel, place into
Being dialysed in analysis bag (5000 molecular weight) to the PH of dialyzate is neutrality, and it is dry to be finally putting into drying box.
Embodiment 6
A kind of preparation method of cellulose aquagel, includes the following steps and process conditions:
(1) drying of dissolving pulp: eucalyptus dissolving pulp is dried under the conditions of 105 DEG C to moisture content and is lower than 2%；
(2) swollen of dissolving pulp: by two kinds of solvents of ethyl alcohol and isopropanol according to the mass ratio mixed configuration swollen of 1:5
Liquid, the dissolving pulp after drying are added swollen liquid, obtain mixture.Control dissolving pulp oven dry weight accounts for the 1% of mixture weight.
(3) dissociation of dissolving pulp: maintaining 50 DEG C for the mixture that step (2) is configured and be stirred continuously, after stirring 50min
2 times of dissolving pulp quality of NaOH is added, and continues to stir 40min.
(4) 1 times of sodium acetate of dissolving pulp quality and 2 times of thioglycolic acid the modification of dissolving pulp: are added in step (3)
Sodium.8h is reacted under the conditions of so that solution is maintained at 60 DEG C simultaneously, reaction process needs are stirred continuously.
(5) preparation of fiber aqueous solution: washing filtering will be carried out through step (4) treated reaction solution, will then passed through
Filtered fiber is dissolved in water and fiber aqueous solution is made.
(6) dispersion of fiber aqueous solution: being placed in high-speed emulsifying machine for the solution configured through step (5) and disperse, point
Dissipating revolving speed is 6000r/min, jitter time 15min.
(7) concentration of fiber aqueous solution: will be through step (6) treated dispersion liquid in Rotary Evaporators after the completion of dispersion
Using 80 DEG C of progress rotary evaporation in vacuo to viscous pasty state as solution A.
(8) preparation of solution B: water and NaOH and epoxychloropropane three are mixed according to the ratio of 10:6:15,
It is stirred after mixing, mixing time 4h obtains solution B；The quality for controlling solution B is the 1/4 of solution A quality.
(9) preparation of hydrogel: solution B pours into solution A, and drying box is put into after stirring at normal temperature 3h, and drying box temperature is 70
DEG C, drying time 5h.
(10) washing of hydrogel: hydrogel deionized water, dehydrated alcohol wash hydrogel, place into
Being dialysed in analysis bag (4000 molecular weight) to the PH of dialyzate is neutrality, and it is dry to be finally putting into drying box.
Claims (10)
1. a kind of preparation method of cellulose aquagel, it is characterised in that include the following steps and process conditions:
1) dissolving pulp drying to moisture content the drying of dissolving pulp: is lower than 2%；
2) swollen of dissolving pulp: by first solvent and second solvent mixed configuration swollen liquid, the dissolving pulp after drying is added to swollen liquid
Mixture is obtained, control dissolving pulp oven dry weight accounts for the 0.1-5% of entire mixture weight；First solvent and second solvent be all methanol,
The different one kind of ethyl alcohol, N-N dimethyl acetamide, isopropyl alcohol and water；
3) by the control of mixture obtained by step 2) at a temperature of 20 DEG C -50 DEG C, NaOH the dissociation of dissolving pulp: is added after being stirred continuously
Or KOH, and continue to stir；
4) sodium acetate and sodium chloroacetate, depakine and sulphur the modification of dissolving pulp: are added in step 3) products therefrom
For one of sodium glycollate；Controlled at 40 DEG C -100 DEG C, 1h-10h is reacted, reaction process is stirred continuously；
5) preparation of fiber aqueous solution: will carry out washing filtering through step 4) treated reaction solution, then will be after filtering
Fiber be dissolved in water fiber aqueous solution be made；
6) dispersion of fiber aqueous solution: fiber aqueous solution is placed in high-speed emulsifying machine and is dispersed；
7) concentration of fiber aqueous solution:, will treated that dispersion liquid carries out in Rotary Evaporators through step 6) after the completion of dispersion
Rotary evaporation is to viscous pasty state, as solution A；
8) preparation of solution B: water and NaOH and epoxychloropropane three are mixed, are stirred after mixing, mixing time is
0.1h-5h obtains solution B；
9) preparation of hydrogel: solution B pours into solution A, is put into drying box after stirring at normal temperature 1h-5h, and drying box temperature is 30 DEG C-
100 DEG C, drying time 1h-10h；
10) washing of hydrogel: hydrogel deionized water, dehydrated alcohol wash hydrogel, place into bag filter
Middle dialyse to the pH of dialyzate is neutrality, and it is dry to be finally putting into drying box.
2. the preparation method of cellulose aquagel according to claim 1, which is characterized in that the type of the dissolving pulp
For the mixing of the one or both of needlebush dissolving pulp or leaf wood dissolving pulp；The dissolving pulp refers to that plant cellulose removes big portion
Part after dividing lignin and hemicellulose, main component is cellulose.
3. the preparation method of cellulose aquagel according to claim 1, which is characterized in that drying described in step 1) is
It is carried out under the conditions of 100 DEG C -120 DEG C.
4. the preparation method of cellulose aquagel according to claim 1, which is characterized in that the swollen liquid is by first
Two kinds of solvents of second are 1/8-1/2 mixing gained according to mass ratio.
5. the preparation method of cellulose aquagel according to claim 1, which is characterized in that step 3) and step 4) are described
Stirring be magnetic agitation, mechanical stirring, airflow stirring or jet mixing, the rate of stirring is 50-80r/min.
6. the preparation method of cellulose aquagel according to claim 1, which is characterized in that the control of step 3) mixture exists
The time being stirred continuously at a temperature of 20 DEG C -50 DEG C is 10min-100min；10min- is persistently stirred after NaOH or KOH is added
100min；NaOH the or KOH additional amount is the 100%-400% of dissolving pulp quality.
7. the preparation method of cellulose aquagel according to claim 1, which is characterized in that the sodium acetate additional amount
It is 2 times of dissolving pulp quality after dissociation；The addition of one of the sodium chloroacetate, depakine and sodium thioglycolate
Amount is 1 times of dissolving pulp quality after dissociation；Described is by water-bath, oil bath, microwave heating controlled at 40 DEG C -100 DEG C
Or electric furnace heating is realized.
8. the preparation method of cellulose aquagel according to claim 1, which is characterized in that step 6) disperses revolving speed and is
4000r/min-8000r/min, jitter time 5min-15min.
9. the preparation method of cellulose aquagel according to claim 1, which is characterized in that in step 8), water and NaOH
Mass ratio be 5:3, the amount that epoxychloropropane is added is 2-5 times of water and NaOH gross mass；The quality of solution B is solution A matter
The 1/8-1/2 of amount.
10. the preparation method of cellulose aquagel according to claim 1, which is characterized in that the fiber aqueous solution
Preparation first using vacuum filtration or natural filtration mode add water preparation；The funnel of the filtering is the leakage of G3 G1 sand core
Bucket；It needs to carry out dialysis treatment with bag filter to remove remaining small molecule and epoxy in hydrogel after hydrogel preparation forming
Chloropropane, bag filter type used are through one of molecular weight 2000-7000.
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