CN109651624A - A kind of high tenacity is freeze proof/heat resistanceheat resistant/antibacterial plant polyphenol nano-cellulose conductive hydrogel preparation method - Google Patents
A kind of high tenacity is freeze proof/heat resistanceheat resistant/antibacterial plant polyphenol nano-cellulose conductive hydrogel preparation method Download PDFInfo
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
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- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
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- C08K5/00—Use of organic ingredients
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- C08K5/053—Polyhydroxylic alcohols
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
Abstract
The invention belongs to biomass functional high-polymer field of compound material, and in particular to and a kind of high tenacity is freeze proof/heat resistanceheat resistant/antibacterial plant polyphenol nano-cellulose conductive hydrogel preparation method.React the nano-cellulose of preparation pyrroles's grafting with the hydroxyl on nano-cellulose under alkaline condition using bromo pyrroles, then the nano-cellulose of pyrroles's grafting and high molecular polymer are added together in freeze proof/hot solvent system, so that it is formed multiple hydrogen bonding network cross-linked structure between nano-cellulose and high molecular polymer using plant polyphenol, pyrroles and Fe is finally added dropwise3+Solution forms conducting polymer network.The plant polyphenol nano-cellulose conductive hydrogel has good anti-microbial property, excellent mechanical performance, its every excellent properties can be still kept under conditions of extreme cold and sweltering heat.Present invention process is simple, environmentally protective, easy to operate, and low raw-material cost is easy to get, highly-safe, and economic value is high.
Description
Technical field
The invention belongs to biomass functional high-polymer field of compound material, and in particular to and a kind of high tenacity is freeze proof/heat resistanceheat resistant/
The preparation method of antibacterial plant polyphenol nano-cellulose conductive hydrogel.
Background technique
Plant polyphenol is the intracorporal complicated phenols secondary metabolites of plant, molecular structure salient feature be have it is polynary
Phenolic hydroxyl structure, common plant polyphenol have tea polyphenols, vine polyphenol, apple polyphenol etc..Plant polyphenol kind compound contains
Polyhydric phenols structure makes it have a series of unique chemical property, such as remove Characteristics of Free Radicals Produced, disinfection and sterilization, inoxidizability, with
Protein etc. combines, chelatropic reaction etc. occurs with various metals ion and its compound.Meanwhile it is rich based on containing in plant polyphenol
Rich phenolic hydroxyl group can be grafted, be copolymerized or be blended with high-molecular compound by hydrogen bond, hydrophobic bond or covalent bond, so
Also it is widely used in multifunction polymer composite material.
Nano-cellulose be cellulose through physics and chemistry processing obtain it is a kind of have excellent mechanical performance, light, high-specific surface area,
The novel nano-material of the characteristics such as renewable, biodegradable.In non-covalent bond effect, hydrogen bond intensity with higher, height
Orientation and dynamic reversibility are spent, various Polymer Systems are widely used in.The intensity of single hydrogen bond is weaker, but between multiple hydrogen bonds
It is capable of forming the combination energy that intensity is equivalent to covalent bond by synergistic effect, to be assembled into the complex with special construction
System.A large amount of hydroxyl is contained on nano-cellulose surface, can be contour by Hyarogen-bonding and plant polyphenol or containing hydroxyl, amino
Molecule aggregation objects system is self-assembly of the basis material with certain flexible three-dimensional net structure.At traditional hydrogel
In the external environment for overheating or being subcooled, hydrone can not be all stable in the presence of in hydrogel material, be preheated in use
The readily volatilized son that dries out causes hydrogel material shrivelled, and ice crystal easy to form, which is pre-chilled, causes hydrogel material to be frozen in, into
And leads to the loss of other performances of hydrogel and limit its utilization.In freeze proof/hot solvent system, due to the glycerol in antifreeze
Or the effective components such as ethylene glycol can form strong hydrogen bond action with hydrone, and hydrone is made to be difficult to form ice crystal at low temperature,
It is difficult to volatilize at high temperature to achieve the effect that freeze proof/heat.Using nano-cellulose and high molecular polymer in plant polyphenol
The coordinate bond effect of multiple hydrogen bonding combination and metal ion between each ingredient is formed under effect is formed by physics friendship
Connection makes composite hydrogel have excellent mechanical performance, and nano-cellulose not only acts as the increasing of nano-filled object in composite hydrogel
It is potent to answer, in the formation for simultaneously participating in multiple hydrogen bonding network and conducting polymer network, assign hydrogel high tenacity and good
Electric conductivity.Freeze proof/hot solvent system makes hydrogel still its item can be kept excellent under conditions of extreme cold and sweltering heat
Performance.Present invention process is simple, environmentally protective, easy to operate, and low raw-material cost is easy to get, highly-safe, can become industry
Upper production performance is excellent, a kind of new technology of the multifunctional bio composite material of low-carbon, ecology.
Summary of the invention
The purpose of the present invention is to provide a kind of high tenacity it is freeze proof/heat resistanceheat resistant/antibacterial plant polyphenol nano-cellulose conductivity water
The preparation method of gel.The plant polyphenol nano-cellulose conductive hydrogel has good anti-microbial property.With in the prior art
Common chemical cross-linking agent is compared, which leans on multiple hydrogen bonding structure and metallic ion coordination key to act on completely and be formed by physics
Crosslinking and reinforced phase nano-cellulose molecular bridge coupled action and so that composite hydrogel is had excellent mechanical performance, extreme
Its every excellent properties can be still kept under conditions of cold and hot.Present invention process is simple, environmentally protective, easy to operate,
Low raw-material cost is easy to get, highly-safe, and economic value is high.
To achieve the above object, the present invention adopts the following technical scheme:
The invention firstly uses bromo pyrroles to react preparation pyrroles's grafting with the hydroxyl on nano-cellulose under alkaline condition
Then the nano-cellulose of pyrroles's grafting and high molecular polymer are added together in freeze proof/hot solvent system for nano-cellulose,
Using resourceful and cheap plant polyphenol as functional additive, make it in nano-cellulose and high molecular polymerization
Multiple hydrogen bonding network cross-linked structure is formed between object.A certain amount of pyrroles and Fe finally is added dropwise to compound system3+Solution, make its with
The pyrroles of nano-cellulose surface grafting forms conducting polymer network.
Wherein Fe3+Being catalyzed can be with the polynary phenolic hydroxyl group and nano-cellulose or macromolecule on plant polyphenol after pyrroles polymerize
Hydroxyl on polymer surfaces forms the effect of metallic ion coordination key, further enhances the mechanical property and dynamic of composite hydrogel
Self-healing.The nano-cellulose of surface grafting pyrroles takes part in the formation of polypyrrole conductive network, thus obtains performance more
For stable polypyrrole conductive network, good electric conductivity is provided for composite hydrogel.
In freeze proof/hot solvent system, due in antifreeze glycerol or the effective components such as ethylene glycol can be formed with hydrone
Strong hydrogen bond action, makes hydrone be difficult to form ice crystal at low temperature, is difficult to volatilize at high temperature to reach freeze proof/heat
Effect makes composite hydrogel that its high tenacity, restorability can still be maintained under complicated external environment (- 50 DEG C -70 DEG C)
And electric conductivity.
A kind of high tenacity is freeze proof/heat resistanceheat resistant/antibacterial plant polyphenol nano-cellulose conductive hydrogel, preparation step is as follows:
(1) paper pulp fiber raw material is added in sulfuric acid solution, nanofiber is prepared under certain temperature and ultrasound condition
Element obtains nano-cellulose powder after freeze-dried.
(2) nano-cellulose powder is proportionally added into bromo pyrroles, be added simultaneously in n,N-Dimethylformamide solution
NaOH, centrifugal purification obtains pyrroles's engrafted nanometer cellulose after then reacting 20h at room temperature.
(3) high molecular polymer and pyrroles's engrafted nanometer cellulose are added to freeze proof/hot solvent system by a certain percentage
In, after being heated to preset temperature, insulated and stirred to high molecular polymer is completely dissolved to form uniform suspension.Again to mixing
A certain amount of plant polyphenol is added in solution system, and be sufficiently stirred makes it in high molecular polymer and nanofiber at a certain temperature
Multiple hydrogen bonding cross-linked network is formed between element.A certain amount of pyrroles and Fe finally is added dropwise to mixed system3+Solution, pyrroles is in Fe3+
Conducting polymer network is formed with the pyrroles of nano-cellulose surface grafting under catalytic action, assigns hydrogel electric conductivity.It will mix
Conjunction object is poured into after mold is cooled to room temperature standing crosslinking 12h and be can be obtained based on multiple hydrogen bonding and Fe3+The collaboration of ion coordination key is made
High tenacity under is freeze proof/heat resistanceheat resistant/antibacterial plant polyphenol nano-cellulose conductive polymer hydrogel.At this point, nano-cellulose
Multiple hydrogen bonding structure and Fe between the two are formed under the action of plant polyphenol polyhydroxy structure with high molecular polymer3+From
Sub- coordinate bond effect, forms the nano-cellulose in system " adaptive structure ", generates " superposition and collaboration " effect to have
Effect mentions composite material properties.Freeze proof/hot solvent system make hydrogel extreme cold and it is hot under conditions of still can be with
Keep its every excellent properties.
Paper pulp fiber raw material as described in step (1) be bamboo pulp, reclaimed waste paper slurry, microcrystalline cellulose, straw pulp, cotton fiber,
The mass ratio of one of agriculture and forestry organic waste material fibrous raw material, paper pulp fiber and sulfuric acid solution is 1:65, and the mass concentration of sulfuric acid is
50%-70%, sonication treatment time are 2.5 h, and ultrasonic temperature is 65 DEG C.
Bromo pyrroles described in step (2) is the compound that the hydrogen on pyrroles's nitrogen-atoms is replaced by brominated alkanes, specifically
Contain any one of the carbon atom number of alkane in all kinds of brominated alkanes between 3-12.
The dosage of NaOH described in step (2) is the 55-75wt% of bromo pyrroles mass, bromo pyrroles and nanofiber
The mass ratio of element is 6:2-5:3.
High molecular polymer described in step (3) is the water-soluble polymer containing hydroxyl or amino, further, tool
Body is agar, polyvinyl alcohol, any one in gelatin.
Plant polyphenol described in step (3) is that tea polyphenols, tannic acid, gallic acid, tannic acid, apple polyphenol, cocoa are more
It is one or more in phenol.
Freeze proof/hot solvent system described in step (3) is water/glycerol, water/ethylene glycol, in water/glycerol/ethylene glycol
Any one.Wherein the mass ratio of water and glycerol is 10:90--90:10；The mass ratio of water and ethylene glycol is 10:90--
90:10；Water/glycerol/ethylene glycol mass ratio is 10:20:70-70:20:10.
Relationship between quality of each component in conductive hydrogel is as follows in step (3): by mass fraction summation very based on, plant
Object polyphenol 5%-30%, nano-cellulose 3%-30%, high molecular polymer 10%-20%, surplus are freeze proof/hot solvent.
The preset temperature in step (3) is 40-90 according to the characteristic of used solvent and high molecular polymer
DEG C, the insulated and stirred time is 2-4h.
Pyrroles's additive amount is 0.5%-5%, Fe in step (3)3+The concentration of solution is 0.5-2mol/L, additive amount 5-
15mL。
Remarkable advantage of the invention is:
(1) china natural resources forestry products abundant are utilized -- conductive hydrogel system is added as functional additive in plant polyphenol,
Plant polyphenol is a kind of compound with polyphenol hydroxyl structure, and the phenolic hydroxyl group on molecular structure can be with the hydroxyl on nanofiber
Carbonyl, amino, carboxyl on base or macromolecule etc. form multiple hydrogen bonding structure, to play the role of crosslinking agent.
(2) nano-cellulose of surface grafting pyrroles not only acts as the humidification of nano-composite material, while participating in
In the formation of polypyrrole conductive network, the more stable polypyrrole conductive network of performance is thus obtained, is provided for composite hydrogel
Good electric conductivity.
(3) Fe3+Being catalyzed can be with the polynary phenolic hydroxyl group and nano-cellulose or macromolecule on plant polyphenol after pyrroles polymerize
Hydroxyl on polymer surfaces forms the effect of metallic ion coordination key, further enhances the mechanical property and dynamic of composite hydrogel
Self-healing.
(4) in freeze proof/hot solvent system, due in antifreeze glycerol or the effective components such as ethylene glycol can be with hydrone shape
At strong hydrogen bond action, hydrone is made to be difficult to form ice crystal at low temperature, is difficult to volatilize at high temperature to reach freeze proof/heat
Effect, make composite hydrogel that its high tenacity can still be maintained under complicated external environment (- 50 DEG C -70 DEG C), can restore
Property and electric conductivity.Freeze proof/hot solvent system makes hydrogel that can still keep its item under conditions of extreme cold and sweltering heat
Excellent properties.
(5) in addition, polyhydric phenols structure assigns a series of unique chemical property of plant polyphenol, such as there is anti-oxidant, removing
A variety of physiological activity such as interior free yl, anticancer be antitumor, disinfection and sterilization, deodorization, therefore, which leads
Electric hydrogel has good anti-microbial property simultaneously.
(6) compared with chemical cross-linking agent commonly used in the prior art, the present invention lean on completely multiple hydrogen bonding structure and metal from
Sub- coordinate bond effect is formed by the molecular bridge coupled action of physical crosslinking and reinforced phase nano-cellulose and makes compound water congealing
Glue has excellent mechanical performance, and nano-cellulose not only acts as the enhancement effect of nano-filled object in composite hydrogel, simultaneously
It participates in the formation of multiple hydrogen bonding network and conducting polymer network, assigns hydrogel high tenacity and good electric conductivity.
(7) present invention process is simple, environmentally protective, easy to operate, and low raw-material cost is easy to get, highly-safe, Ke Yicheng
For industrial production performance is excellent, a kind of new technology of the multifunctional bio composite material of low-carbon, ecology.
Specific embodiment
Further to disclose rather than the present invention is limited, the present invention is described in further detail below in conjunction with example.
Embodiment 1
(1) it is 1:65 by solid-liquid ratio, bamboo pulp fiber raw material is added in 55wt% sulfuric acid solution, it is ultrasonic under the conditions of 65 DEG C
Nano-cellulose is prepared in 2.5h, and nano-cellulose powder is obtained after freeze-dried.
(2) it takes 10g nano-cellulose powder in the n,N-Dimethylformamide solution of 500 mL, 30g bromomethyl pyrrole is added
It coughs up, while 20g NaOH is added, centrifugal purification obtains pyrroles's engrafted nanometer cellulose after then reacting 20h at room temperature.
(3) 30 g agar are dissolved in 150g water/glycerol system (in mass ratio, water: glycerol=1:1) and 15.0g pyrroles is added afterwards
The nano-cellulose powder of grafting after being heated to 60 DEG C, the tea polyphenols of 20.0 g is added to mixed system, keeps the temperature and stirs at 90 DEG C
It mixes to agar and is completely dissolved to form uniform suspension, feed the mixture into the Fe of 5.0 g pyrroles and 10mL 2mol/L3+Solution,
Mixed solution is poured into molding die after mixing evenly, is obtained after being crosslinked 12h at room temperature based on multiple hydrogen bonding and metal ion
Coordinate bond synergistic effect high tenacity it is freeze proof/heat resistanceheat resistant/antibacterial plant polyphenol nano-cellulose/agar conductive hydrogel.
Embodiment 2
(1) it is 1:65 by solid-liquid ratio, reclaimed waste paper pulp fibres raw material is added in 60wt% sulfuric acid solution, under the conditions of 65 DEG C
Nano-cellulose is prepared in ultrasonic 2.5h, and nano-cellulose powder is obtained after freeze-dried.
(2) it takes 15g nano-cellulose powder in the n,N-Dimethylformamide solution of 500 mL, 1- (the 5- bromine of 40g is added
Amyl) pyrroles, while 30g NaOH is added, centrifugal purification obtains pyrroles's engrafted nanometer fiber after then reacting 20h at room temperature
Element.
(3) 20 g polyvinyl alcohol 120g water/glycol system (in mass ratio, water: ethylene glycol=1:5) is dissolved in be added afterwards
After being heated to 90 DEG C, the cocoa polyphenol of 30.0 g is added to mixed system for the nano-cellulose powder of 10.0g pyrroles's grafting,
Insulated and stirred to polyvinyl alcohol is completely dissolved to form uniform suspension at 90 DEG C, feeds the mixture into 4.0 g pyrroles and 15mL
The Fe of 1.5mol/L3+Solution after mixing evenly pours into mixed solution in molding die, is based on after being crosslinked 12h at room temperature
Multiple hydrogen bonding and metallic ion coordination key synergistic effect high tenacity it is freeze proof/heat resistanceheat resistant/antibacterial plant polyphenol nano-cellulose/poly- second
Enol conductive hydrogel.
Embodiment 3
(1) it is 1:50 by solid-liquid ratio, microcrystalline cellulose raw material is added in 70wt% sulfuric acid solution, it is ultrasonic under the conditions of 65 DEG C
Nano-cellulose is prepared in 2.5h, and nano-cellulose powder is obtained after freeze-dried.
(2) it takes 15g nano-cellulose powder in the n,N-Dimethylformamide solution of 500 mL, the 1- (10- of 30g is added
Bromine decyl) pyrroles, while 25g NaOH is added, centrifugal purification obtains pyrroles's engrafted nanometer fibre after then reacting 20h at room temperature
Dimension element.
(3) 20 g gelatin are dissolved in 130g water/glycerol system (in mass ratio, water: glycerol=1:4) and 15.0g pyrroles is added afterwards
The nano-cellulose powder of grafting after being heated to 50 DEG C, the tannic acid of 40.0 g is added to mixed system, keeps the temperature and stirs at 90 DEG C
It mixes to gelatin and is completely dissolved to form uniform suspension, feed the mixture into the Fe of 10.0 g pyrroles and 15mL 2mol/L3+It is molten
Liquid after mixing evenly pours into mixed solution in molding die, be crosslinked after 12h at room temperature obtain based on multiple hydrogen bonding and metal from
The high tenacity of sub- coordinate bond synergistic effect is freeze proof/heat resistanceheat resistant/antibacterial plant polyphenol nano-cellulose/gelatin conductive hydrogel.
Embodiment 4
(1) it is 1:50 by solid-liquid ratio, cotton fiber raw material is added in 55wt% sulfuric acid solution, it is ultrasonic under the conditions of 65 DEG C
Nano-cellulose is prepared in 2.5h, and nano-cellulose powder is obtained after freeze-dried.
(2) it takes 20g nano-cellulose powder in the n,N-Dimethylformamide solution of 500 mL, 1- (the 4- bromine of 50g is added
Butyl) pyrroles, while 30g NaOH is added, centrifugal purification obtains pyrroles's engrafted nanometer fiber after then reacting 20h at room temperature
Element.
(3) 20 g agar are dissolved in 130g water/glycol system (in mass ratio, water: ethylene glycol=1:2) and 10.0g is added afterwards
The nano-cellulose powder of pyrroles's grafting after being heated to 60 DEG C, the tannic acid of 40.0 g is added to mixed system, keeps the temperature at 60 DEG C
Stirring is completely dissolved to form uniform suspension to agar, feeds the mixture into the Fe of 4.0 g pyrroles and 15mL 1.5mol/L3+
Solution after mixing evenly pours into mixed solution in molding die, obtains after being crosslinked 12h at room temperature based on multiple hydrogen bonding and metal
Ion coordination key synergistic effect high tenacity it is freeze proof/heat resistanceheat resistant/antibacterial plant polyphenol nano-cellulose/agar conductive hydrogel.
The different high tenacity of table 1 are freeze proof/heat resistanceheat resistant/antibacterial plant polyphenol nano-cellulose conductive hydrogel performance detection
The present invention has also investigated influence of the plant polyphenol additive amount to freeze proof/thermal conducting hydrogel mechanical performance.It investigates respectively
Plant polyphenol additive amount is 5wt%, 15wt%, 25wt%, to freeze proof/thermal conducting hydrogel mechanical property when 35wt%, 45wt%
It influences, the results showed that, under conditions of plant polyphenol each additive amount, every mechanical property of conductive hydrogel has significantly
It improves, when additive amount is between 25wt%-35wt%, tensile strength is up to 0.6-3.0 MPa, the elongation strain of conductive hydrogel
Up to 400%-700%, compressive strength and compression modulus are up to 1.5-2MPa, it is therefore preferable that plant polyphenol additive amount is 25wt%-
30wt%。
The present invention has investigated influence of the nano-cellulose dosage to freeze proof/thermal conducting hydrogel properties.It investigates respectively
Nano-cellulose additive amount is 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, to conductivity water when 40wt%
The influence of gel mechanical property.The result shows that the mechanical property of conductive hydrogel can be significant under conditions of each additive amount
Raising, when additive amount is between 20wt%-30wt%, tensile strength is answered up to 0.8-3.8MPa, the stretching of conductive hydrogel
Become reachable 500%-800%, compressive strength and compression modulus up to 2-3.5MPa, it is therefore preferable that nano-cellulose dosage is
25wt%-35wt%。
The present invention has investigated influence of pyrroles's dosage to freeze proof/thermal conducting hydrogel electric conductivity.Pyrroles has been investigated respectively to add
Dosage is 0.5wt%, 1wt%, 2wt%, 3.0wt%, 3.5wt%, 4.0wt%, 4.5wt%, to the shadow of hydrogel electric conductivity when 5.0wt%
It rings.The result shows that the electric conductivity of conductive hydrogel can be improved significantly under conditions of each additive amount, work as additive amount
When between 3.0wt%-4.0wt%, electric conductivity is up to 2 × 10-3-9×10-3 S/cm, it is therefore preferable that pyrroles's additive amount is
3.0wt%-4.0wt%。
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (10)
1. a kind of high tenacity is freeze proof/heat resistanceheat resistant/antibacterial plant polyphenol nano-cellulose conductive hydrogel preparation method, feature exists
In:
React the nanofiber of preparation pyrroles's grafting with the hydroxyl on nano-cellulose under alkaline condition first with bromo pyrroles
The nano-cellulose of pyrroles's grafting and high molecular polymer are then added in freeze proof/hot solvent system together, utilize resource by element
Abundant and cheap plant polyphenol makes its shape between nano-cellulose and high molecular polymer as functional additive
At multiple hydrogen bonding network cross-linked structure；A certain amount of pyrroles and Fe finally is added dropwise to compound system3+Solution makes itself and nanofiber
The pyrroles of plain surface grafting forms conducting polymer network.
2. high tenacity according to claim 1 is freeze proof/heat resistanceheat resistant/antibacterial plant polyphenol nano-cellulose conductive hydrogel,
Be characterized in that: specific preparation step includes:
(1) paper pulp fiber raw material is added in sulfuric acid solution, nanofiber is prepared under certain temperature and ultrasound condition
Element obtains nano-cellulose powder after freeze-dried；
(2) nano-cellulose powder is proportionally added into bromo pyrroles, be added simultaneously in n,N-Dimethylformamide solution
NaOH, centrifugal purification obtains pyrroles's engrafted nanometer cellulose after then reacting 20h at room temperature；
(3) high molecular polymer and pyrroles's engrafted nanometer cellulose are added to by a certain percentage in freeze proof/hot solvent system, are added
After heat to preset temperature, insulated and stirred to high molecular polymer is completely dissolved to form uniform suspension；Again to mixed solution
Plant polyphenol is added in system, is sufficiently stirred at a certain temperature；Pyrroles and Fe finally is added dropwise to mixed system3+Solution；It will mixing
Object pour into mold be cooled to room temperature after standing crosslinking 12h obtain high tenacity it is freeze proof/heat resistanceheat resistant/antibacterial plant polyphenol nano-cellulose is high
Molecule conductive hydrogel.
3. high tenacity according to claim 2 is freeze proof/heat resistanceheat resistant/antibacterial plant polyphenol nano-cellulose conductive hydrogel,
Be characterized in that: paper pulp fiber raw material as described in step (1) be bamboo pulp, reclaimed waste paper slurry, microcrystalline cellulose, straw pulp, cotton fiber,
The mass ratio of any one in agriculture and forestry organic waste material fibrous raw material, paper pulp fiber and sulfuric acid solution is 1:65, and the quality of sulfuric acid is dense
Degree is 50%-70%, and sonication treatment time is 2.5 h, and ultrasonic temperature is 65 DEG C.
4. high tenacity according to claim 2 is freeze proof/heat resistanceheat resistant/antibacterial plant polyphenol nano-cellulose conductive hydrogel,
Be characterized in that: bromo pyrroles described in step (2) is the compound that the hydrogen on pyrroles's nitrogen-atoms is replaced by brominated alkanes, specifically
Contain any one of the carbon atom number of alkane in all kinds of brominated alkanes between 3-12.
5. high tenacity according to claim 2 is freeze proof/heat resistanceheat resistant/antibacterial plant polyphenol nano-cellulose conductive hydrogel,
Be characterized in that: the dosage of NaOH described in step (2) is the 55-75wt% of bromo pyrroles mass, bromo pyrroles and nanofiber
The mass ratio of element is 6:2-5:3.
6. high tenacity according to claim 2 is freeze proof/heat resistanceheat resistant/antibacterial plant polyphenol nano-cellulose conductive hydrogel,
Be characterized in that: high molecular polymer described in step (3) is the water-soluble polymer containing hydroxyl or amino, specially fine jade
Rouge, polyvinyl alcohol, any one in gelatin.
7. high tenacity according to claim 2 is freeze proof/heat resistanceheat resistant/antibacterial plant polyphenol nano-cellulose conductive hydrogel,
Be characterized in that: plant polyphenol described in step (3) is that tea polyphenols, tannic acid, gallic acid, tannic acid, apple polyphenol, cocoa are more
It is one or more in phenol.
8. high tenacity according to claim 2 is freeze proof/heat resistanceheat resistant/antibacterial plant polyphenol nano-cellulose conductive hydrogel,
Be characterized in that: freeze proof described in step (3)/hot solvent system is water/glycerol, water/ethylene glycol, in water/glycerol/ethylene glycol
Any one；Wherein the mass ratio of water and glycerol is 10:90--90:10；The mass ratio of water and ethylene glycol is 10:90--
90:10；Water/glycerol/ethylene glycol mass ratio is 10:20:70-70:20:10.
9. high tenacity according to claim 2 is freeze proof/heat resistanceheat resistant/antibacterial plant polyphenol nano-cellulose conductive hydrogel,
Be characterized in that: relationship between quality of each component in conductive hydrogel is as follows in step (3): by mass fraction summation very based on,
Plant polyphenol 5%-30%, nano-cellulose 2%-20%, high molecular polymer 10%-20%, surplus are freeze proof/hot solvent.
10. high tenacity according to claim 2 is freeze proof/heat resistanceheat resistant/antibacterial plant polyphenol nano-cellulose conductive hydrogel,
Be characterized in that: the preset temperature in step (3) is 40-90 according to the characteristic of used solvent and high molecular polymer
DEG C, the insulated and stirred time is 2-4h, and the temperature after plant polyphenol is added is 40-90 DEG C；Pyrroles's additive amount is in step (3)
0.5%-5%, Fe3+The concentration of solution is 0.5-2mol/L, additive amount 5-15mL.
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