CN106883607A - Flexible double conducing composite materials of ionization BC/PANI and its production and use - Google Patents
Flexible double conducing composite materials of ionization BC/PANI and its production and use Download PDFInfo
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Abstract
Chemical modification and modified Nano bacteria cellulose and the complex technique field of conducting polymer the invention belongs to nanometer bacteria cellulose, a kind of specific flexible pair of conducing composite materials of ionization BC/PANI and its production and use.The nanometer bacteria cellulose of ecosystem is pre-processed and purified by methods described first；Then the nanometer bacteria cellulose after pretreatment and purification is carried out chemical modification to introduce functional group；The fabricated in situ polyaniline on nanometer bacteria cellulose after chemical modification, obtains the flexible double conducing composite materials of ionization nanometer bacteria cellulose/polyaniline；Any one that the functional group that chemical modification is introduced into includes in carboxymethyl, carboxylic acid ion and sulfonate ion is carried out to the nanometer bacteria cellulose after pretreatment and purification.The composite that the present invention is prepared both had had the excellent electronic conductivity of polyaniline, further through the chemical group of modified introducing, with preferable ionic conductivity.
Description
Technical field
The invention belongs to the chemical modification and modified Nano bacteria cellulose and conducting polymer of nanometer bacteria cellulose
Complex technique field, and in particular to flexible double conducing composite materials of ionization BC/PANI and its production and use.
Background technology
Polyaniline is a kind of excellent conducting polymer, and polyaniline simple synthetic method, reaction condition is gentle, by proton
Polyaniline after acid doping has excellent electron conduction, therefore, polyaniline is widely used in coating, battery, biography at present
The fields such as sensor.But polyaniline by after common chemical synthesis into graininess, it is impossible to well shaping, therefore limit its should
Use scope.
Nanometer bacteria cellulose is a kind of by microbial fermentation generation, the natural fiber material with hyperfine network structure
Material, because of the effecting reaction avtive spot, excellent that the hydrogen bond formed between its hyperfine Nanostructure Network, great amount of hydroxy group is constituted
Heat endurance and the advantages of mechanical strength, low gas permeability so as to have as the advantageous advantage of matrix material.Perhaps
Other different materials and nanometer bacteria cellulose are answered a kind of nanometer bacteria cellulose as mould material for many researchs
Close.Bacteria cellulose/polyaniline composite material is also the more one kind of research, and polyaniline is combined by physico-chemical process
The fiber surface of bacteria cellulose, forms the bacteria cellulose composite material of polyaniline parcel, thus solves to a certain degree
Polyaniline is difficult to the problem being molded, and bacteria cellulose is had certain electron conduction.
Bacteria cellulose/polyaniline (BC/PANI) composite, SEM photograph is as shown in Figure 1.In existing bacterial fibers
In element/polyaniline composite material research, composite possesses good electron conduction, in electrolyte, amberplex, sensing
The fields such as device require that material has proton conductivity, and the proton conductivity of simple BC/PANI is very low, additionally, primary
Nanometer bacteria cellulose chemism is low, and feature is not enough, which has limited nanometer bacteria cellulose as related compound material
Using.
It is multiple the invention provides a kind of nanometer bacteria cellulose/polyaniline by functional modification based on above mentioned problem
Condensation material, it is this that both there is the excellent electronic conductivity of polyaniline by modified composite, further through modified introducing
Chemical group, with preferable ionic conductivity, extends the application of this kind of composite.
The content of the invention
Regarding to the issue above, the present invention provides a kind of flexible double conducing composite materials of ionization BC/PANI and its preparation side
Method and purposes.Preparation method of the present invention carries out chemical modification to the nanometer bacteria cellulose after pretreatment and purification, to draw
Enter any one functional group in carboxymethyl, carboxylic acid ion and sulfonate ion, then the nanometer bacteria after chemical modification
Fabricated in situ polyaniline on cellulose, obtains the flexible double conducing composite materials of ionization nanometer bacteria cellulose/polyaniline；This hair
The flexible composite of bright preparation is keeping protocorm material (nanometer bacteria cellulose of ecosystem) excellent moisture retention, retentiveness
While with mechanical property, with electrical conductivity higher, good heat endurance and biocompatibility, can be used in novel porous
Gel polyelectrolyte, amberplex, flexible wearable electronic products, implantable fuel cell, biology sensor and dyestuff
The high-end fields such as sensitization solar battery.
The present invention is achieved by the following technical solutions：
A kind of preparation method of the flexible double conducing composite materials of ionization BC/PANI, methods described is first by ecosystem
Nanometer bacteria cellulose is pre-processed and purified；Then chemistry is carried out to the nanometer bacteria cellulose after pretreatment and purification to change
Property is introducing functional group；The fabricated in situ polyaniline on nanometer bacteria cellulose after chemical modification, obtains ionization nanometer thin
The flexible double conducing composite materials of fungin/polyaniline；
Wherein, the functional group that chemical modification introducing is carried out to the nanometer bacteria cellulose after pretreatment and purification includes carboxylic
Any one in methyl, carboxylic acid ion and sulfonate ion.
Further, methods described carries out chemical modification to the nanometer bacteria cellulose after pretreatment and purification, introduces carboxylic
The method of any one functional group in methyl, carboxylic acid ion and sulfonate ion, respectively：
Introduce carboxymethyl：Carboxymethyl group is introduced the nanometer after the pretreatment and purification using alkalization-etherification method thin
Complete carboxymethyl modified in fungin, obtain carboxymethyl bacterial cellulose；
Introduce carboxylic acid ion：Carboxylate radical is introduced using step-by-step oxidation method for nanometer bacteria after the pretreatment and purification
Complete Carboxylation modified in cellulose, obtain Carboxylation bacteria cellulose；
Introduce sulfonate ion：Using sulfonated reagent, sulfonate radical is introduced into the nanometer bacteria after the pretreatment and purification
Sulfonation modifying is completed in cellulose, sulfonation nanometer bacteria cellulose is obtained.
Further, the nanometer bacteria cellulose of ecosystem is pre-processed and is purified, specially：
The nanometer bacteria cellulose film deionized water for taking ecosystem is repeatedly rinsed, except striping surface medium and impurity,
Nanometer bacteria cellulose film is soaked in the NaOH solution of 0.01~0.5mol/L again, one hour of water-bath at 60~100 DEG C
More than, removing remains in thalline and culture medium in Nanofiber Network, afterwards with the multiple soaking flushing of deionized water, until pH
The close neutrality of value, the nanometer bacteria cellulose film after being pre-processed and being purified；
Nanometer bacteria cellulose film after the pretreatment and purification is laid on hard glass plate, can be according to need
Will, uniformly cut with special round cut-off knife, obtain nanofiber plain piece, the nanometer bacteria cellulose disk that will be obtained be soaked in from
In sub- water, sealing, Cord blood；
Further, the step of introducing carboxymethyl is specially：
(1) basification：By the nanometer bacteria cellulose film after pretreatment and purification be placed in mass fraction for 20%~
In 50% isopropanol water solution, multiple exchange of solvent is carried out under magnetic agitation, every time 10~20min, filtered, obtained solvent and hand over
Nanometer bacteria cellulose after changing；
Weigh, the ethanol that the nanometer bacteria cellulose after the exchange of solvent is added slowly into NaOH at room temperature is water-soluble
In liquid, 40~60min of magnetic agitation, the nanometer bacteria cellulose film after being alkalized；
Wherein, in the ethanol water of the NaOH, NaOH is the nanometer bacteria cellulose after the exchange of solvent
9 times of dry weight, in the ethanol water, the ratio of second alcohol and water is：4:5~5:6.
(2) etherificate treatment：Take appropriate etherifying reagent to be dissolved in ethanol, the ethanol solution of etherifying reagent is obtained, by step (1)
Nanometer bacteria cellulose film after the alkalization for obtaining is slowly added in the ethanol solution of the etherifying reagent, in the feelings of stirring
45~60 DEG C of water-baths 1~24 hour are placed under condition, after taking out cooling, are cleaned repeatedly stand-by；Obtain carboxymethylated nanometer bacteria
Cellulose.
Wherein described etherifying reagent is substitution reaction can occur with the nanometer bacteria cellulose film after the alkalization, is introduced
The organic reagent of carboxymethyl；The etherifying reagent includes any one in sodium chloroacetate, monoxone, chloropropionic acid, chloropropionic acid sodium
Or any two or more combination.
Further, the step of introducing carboxylate radical is specially：
(1) oxidation processes：By the nanometer bacteria cellulose film after pretreatment and purification be placed in molar concentration for 0.02~
Lucifuge is sealed up for safekeeping 24~48 hours in the selective oxidation agent solution of 0.06mol/L, and taking-up afterwards is cleaned several times with deionized water, is obtained
To oxidation nanometer bacteria cellulose；Selective oxidant can select sodium metaperiodate, nitrogen dioxide or potassium permanganate.
(2) Carboxylation treatment：The oxidation nanometer bacteria cellulose that step (1) is prepared is put into mass fraction is
In the Carboxylation reagent of 1~10wt%, 1~15min is reacted；Take out after completion of the reaction, it is multiple repeatedly with deionized water and ethanol
Cleaning, removes residual oxidizing agent, is soaked in stand-by, the Carboxylation nanometer bacteria cellulose of acquisition in deionized water；
Wherein described Carboxylation reagent is oxidizing chemical reagent, including sodium hypochlorite, hypochlorous acid, potassium permanganate,
Any one or any two or more combination in postassium hypochlorite.
Further, the introducing sulfonate ion is specially：
(1) oxidation processes：By the nanometer bacteria cellulose film after pretreatment and purification be placed in molar concentration for 0.02~
Lucifuge is sealed up for safekeeping 24~48 hours in the selective oxidation agent solution of 0.06mol/L, and taking-up afterwards is cleaned several times with deionized water, is obtained
To oxidation nanometer bacteria cellulose；Selective oxidant can select sodium metaperiodate, nitrogen dioxide or potassium permanganate.
(2) sulfonated treatment：The oxidation nanometer bacteria cellulose that step (1) is prepared is put into mass fraction is
In the sulfonating reagent solution of 1~20wt%, between 40~80 DEG C, successive reaction 1~24 hour keeps controlling reaction temperature
Mechanical agitation；Gained nanometer bacteria cellulose film is taken out after completion of the reaction, is repeatedly cleaned repeatedly with deionized water and ethanol, removed
The unreacted sulfonating reagent of remnants is removed, product is soaked in stand-by in deionized water；The nanometer obtained after sulfonated treatment is thin
Fungin；
The sulfonated reagent is including any one or any two or more in sodium hydrogensulfite, potassium bisulfite, sulfuric acid
Combination.
Further, fabricated in situ polyaniline on nanometer bacteria cellulose fiber after modification, specially：Chemistry is changed
Property after nanometer bacteria cellulose be put into aniline hydrochloric acid solution and soak, to improve the reactivity of cellulose；
After fully immersion absorbs aniline hydrochloric acid solution, to being slowly added to appropriate initiator persulfuric acid in aniline hydrochloric acid solution
Ammonium, continues at the uniform velocity concussion reaction immediately, and control reaction is in -5~5 DEG C of low-temperature condition, until the complete coated bacteria of polyaniline
Cellulose, obtains flexible composite.
Further, the methods described also post-processing step including composite, specially：Nanometer bacteria after modification
On cellulose fibre after fabricated in situ polyaniline, with a large amount of deionized water rinsing surfaces, reagent is triggered to wash away the remaining of surface
With excessive polyaniline；
Mechanical agitation is carried out during gel mould after flushing is sequentially placed into deionized water, ethanol, is repeated 2~3 times, obtained just
Composite after step cleaning；
To be soaked in ethanol by the gel mould after preliminary cleaning, then be cleaned by ultrasonic by timing interruption, obtain depth
Flexible composite after cleaning.
The flexible double conducing composite materials of one kind ionization BC/PANI (ionize nanometer bacteria cellulose/polyaniline flexible
Double conducing composite materials), the composite includes nanometer bacteria cellulose, the nanometer after the chemical modification after chemical modification
The polyaniline of fabricated in situ on bacteria cellulose, the polyaniline is wrapped on the fiber of nanometer bacteria cellulose, forms nanometer
Sheath Rotating fields, constitute continuous conduction network；
Wherein, nanometer bacteria cellulose is introducing carboxymethyl, carboxylic acid ion and sulfonate ion after the chemical modification
In any one functional group after nanometer bacteria cellulose.
A kind of application of the flexible double conducing composite materials of ionization BC/PANI, preparation method system described in the composite
It is standby to obtain, the composite can be used in porous gel polyelectrolyte, amberplex, flexible wearable electronic products, can
The preparation of implantation fuel cell, biology sensor or DSSC.
Advantageous Effects of the invention：
(1) the flexible double conducing composite materials of the ionization BC/PANI that the present invention is prepared (ionize bacterial fibers
The double conducing composite materials of element/polyaniline) still there is nano level structure, the structural stability of composite membrane is maintained, do not change
Become distributed architecture of the polyaniline on bacteria cellulose, polyaniline is still wrapped on the fiber of nanometer bacteria cellulose, is formed
Nanometer sheath Rotating fields, constitute continuous conduction network；
(2) modified Nano bacteria cellulose prepared by the present invention still maintains the good performance of bacteria cellulose, including
Water suction, retentiveness, mechanical property, and maintain good thermodynamic stability in certain temperature range, additionally, present invention system
The standby modified Nano bacteria cellulose for obtaining has good biocompatibility, after being combined with polyaniline, the flexible compound for obtaining
Material has ion-electron electrical conductivity higher.
(3) the more unmodified nanometer bacteria cellulose of nanometer bacteria cellulose conducing composite material prepared by the present invention is combined
Film, in addition to the electronic conductivity for possessing common bacteria cellulose/polyaniline composite film, also with ionic conduction higher
Rate, and after polyaniline is compounded with, still with three-dimensional net structure specific to nanometer bacteria cellulose, pore-size distribution is equal
It is even, it is ensured that the handling capacity of ion；
(4) the double conducing composite materials of ionization bacteria cellulose/polyaniline prepared by the present invention can be used for novel porous solidifying
Glue polyelectrolyte, amberplex, flexible wearable electronic products, implantable fuel cell, biology sensor and dyestuff are quick
Change the various fields such as solar cell.
Brief description of the drawings
Fig. 1 is the SEM photograph of bacteria cellulose/polyaniline (BC/PANI) composite；
Fig. 2 is the SEM photograph of sulfonation bacteria cellulose/polyaniline (SBC/PANI) composite in embodiment 1；
Fig. 3 is the SEM photograph of Carboxylation bacteria cellulose/polyaniline (CA-BC/PANI) composite in embodiment 2；
Fig. 4 is the SEM photograph of carboxy methylation bacteria cellulose/polyaniline (CM-BC/PANI) composite in embodiment 3；
Fig. 5 hinders for the exchange of different composite material (including BC/PANI, CM-BC/PANI, CA-BC/PANI, SBC/PANI)
Anti- collection of illustrative plates.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is explained in further detail.It should be appreciated that specific embodiment described herein is used only for explaining the present invention, and
It is not used in the restriction present invention.
Conversely, the present invention covers any replacement done in spirit and scope of the invention being defined by the claims, repaiies
Change, equivalent method and scheme.Further, in order that the public has a better understanding to the present invention, below to of the invention thin
It is detailed to describe some specific detail sections in section description.Part without these details for a person skilled in the art
Description can also completely understand the present invention.
Embodiment 1
A kind of preparation method for ionizing the flexible double conducing composite materials of bacteria cellulose/polyaniline, methods described is first
The nanometer bacteria cellulose of ecosystem is pre-processed and purified；Then to the nanometer bacteria cellulose after pretreatment and purification
Chemical modification is carried out to introduce functional group；The fabricated in situ polyaniline on nanometer bacteria cellulose after chemical modification, obtain from
The flexible double conducing composite materials of sonization nanometer bacteria cellulose/polyaniline；In the present embodiment, to pretreatment and purification after receive
The functional group that rice bacteria cellulose carries out chemical modification introducing is sulfonic acid.Introduce sulfonate ion and specifically include following steps：
Step one, bacteria cellulose pretreatment and purifying technique
Take bacteria cellulose film deionized water repeatedly to rinse, except striping surface medium and impurity, then film is soaked in
In the NaOH solution of 0.01mol/L, more than hour water-bath one at 90 DEG C, afterwards with the multiple soaking flushing of deionized water, until
The close neutrality of pH value, the nanometer bacteria cellulose film after being pre-processed and being purified；
In this step, the nanometer bacteria cellulose film after the pretreatment and purification can be laid in as needed
On hard glass plate, uniformly cut with special round cut-off knife, obtain nanofiber plain piece, the nanometer bacteria cellulose disk that will be obtained
It is soaked in deionized water, sealing, Cord blood；
Step 2, oxidation processes
(or nanometer bacteria is fine for nanometer bacteria cellulose film after the pretreatment that is obtained after step 1 is processed and purification
The plain disk of dimension) it is placed in sodium periodate solution that molar concentration is 0.06mol/L and (or selects nitrogen dioxide gas or potassium permanganate
Solution is aoxidized) in lucifuge seal up for safekeeping 24 hours, taking-up afterwards is cleaned several times with deionized water, obtains oxidation nanometer bacterial fibers
Plain (or obtaining oxidation nanometer bacteria cellulose disk film)；
Step 3, sulfonation
Configuration quality fraction is the solution of sodium bisulfite of 5wt%, by step 2 gained oxidation nanometer bacteria cellulose (or
Oxidation nanometer bacteria cellulose disk film) it is put into the solution of sodium bisulfite for having configured, reaction 3 hours under 50 DEG C of water-baths, instead
Gained sulfonation nanometer bacteria cellulose film is taken out after should finishing, is repeatedly cleaned repeatedly with deionized water and ethanol, removed remaining
Sodium hydrogensulfite, product is soaked in deionized water, is obtained the nanometer bacteria cellulose after sulfonated treatment and (or is obtained sulfonation
Nanometer bacteria cellulose disk film)；
The preparation of the flexible double conducing composite materials of step 4, sulfonation nanometer bacteria cellulose/polyaniline
By nanometer bacteria cellulose (or the sulfonation nanometer bacteria cellulose disk after the sulfonated treatment obtained by step 3
Film) immersion 24h in 50mL aniline hydrochloric acid solution (AN, 0.5mol/L, HCl, 1.0mol/L) for preparing in advance is put into, it is backward
Initiator (NH is slowly added in solution4)2S2O8, at the uniform velocity concussion reaction 90 minutes is continued immediately, until polyaniline coats sulphur completely
Change nanometer bacteria cellulose, obtain the flexible double conducing composite materials of sulfonation bacteria cellulose/polyaniline.
Step 5, the post-processing step of composite are by the flexible double conducing composite materials of sulfonation bacteria cellulose/polyaniline
After taking-up, first with a large amount of deionized water rinsing surfaces, to wash away the polyaniline and ammonium persulfate ((NH on surface4)2S2O8)；Connect
And be timed during the composite after flushing is sequentially placed into deionized water, ethanol interruption ultrasonic cleaning, obtain pure answering
Condensation material.
Embodiment 2
A kind of preparation method for ionizing the flexible double conducing composite materials of bacteria cellulose/polyaniline, methods described is first
The nanometer bacteria cellulose of ecosystem is pre-processed and purified；Then to the nanometer bacteria cellulose after pretreatment and purification
Chemical modification is carried out to introduce functional group；The fabricated in situ polyaniline on nanometer bacteria cellulose after chemical modification, obtain from
The flexible double conducing composite materials of sonization nanometer bacteria cellulose/polyaniline；In the present embodiment, to pretreatment and purification after receive
The functional group that rice bacteria cellulose carries out chemical modification introducing is carboxylic acid ion, and introducing carboxylic acid ion specifically includes following
Step：
Step one, bacteria cellulose pretreatment and purifying technique
Take bacteria cellulose film deionized water repeatedly to rinse, except striping surface medium and impurity, then film is soaked in
In the NaOH solution of 0.02mol/L, more than hour water-bath one at 90 DEG C, afterwards with the multiple soaking flushing of deionized water, until
The close neutrality of pH value, the nanometer bacteria cellulose film after being pre-processed and being purified；
In this step, the nanometer bacteria cellulose film after the pretreatment and purification can be laid in as needed
On hard glass plate, uniformly cut with special round cut-off knife, obtain nanofiber plain piece, the nanometer bacteria cellulose disk that will be obtained
It is soaked in deionized water, sealing, Cord blood；
Step 2, oxidation processes
(or nanometer bacteria is fine for nanometer bacteria cellulose film after the pretreatment that is obtained after step 1 is processed and purification
The plain disk of dimension) it is placed in lucifuge in the sodium periodate solution (one kind of selective oxidation agent solution) that molar concentration is 0.04mol/L
Seal up for safekeeping 24 hours, taking-up afterwards is cleaned several times with deionized water, (or to obtain oxidation nanometer thin to obtain oxidation nanometer bacteria cellulose
Fungin disk film)；
Step 3, Carboxylation treatment
Configuration quality fraction is the liquor natrii hypochloritis of 3wt%, by step 2 gained oxidation nanometer bacteria cellulose film (or
Oxidation nanometer bacteria cellulose disk film), it is put into liquor natrii hypochloritis and reacts 5min at room temperature, after completion of the reaction by gained carboxylic
Acidifying nanometer bacteria cellulose film takes out, and is repeatedly cleaned repeatedly with deionized water and ethanol, remaining sodium hypochlorite is removed, by product
It is soaked in deionized water, obtains Carboxylation nanometer bacteria cellulose (or Carboxylation nanometer bacteria cellulose disk film).
The preparation of step 4, Carboxylation bacteria cellulose/polyaniline flexible composite
By Carboxylation nanometer bacteria cellulose disk film (or the Carboxylation nanometer bacteria cellulose disk obtained by step 3
Film), immersion 24h in 50mL aniline hydrochloric acid solution (AN, 0.5mol/L, HCl, 1.0mol/L) for preparing in advance is put into, afterwards
To being slowly added to initiator (NH in solution4)2S2O8, at the uniform velocity concussion reaction 90 minutes is continued immediately, until polyaniline is coated completely
Bacteria cellulose, obtains Carboxylation bacteria cellulose/polyaniline plural gel film.
Step 5, the cleaning treatment of composite membrane
After Carboxylation bacteria cellulose/polyaniline flexible composite is taken out, first with a large amount of deionized water rinsing tables
Face, to wash away the polyaniline and ammonium persulfate ((NH on surface4)2S2O8)；Then by the composite after flushing be sequentially placed into from
Ultrasonic cleaning is timed in sub- water, ethanol, pure flexible composite is obtained.
Embodiment 3
A kind of preparation method for ionizing the flexible double conducing composite materials of bacteria cellulose/polyaniline, methods described is first
The nanometer bacteria cellulose of ecosystem is pre-processed and purified；Then to the nanometer bacteria cellulose after pretreatment and purification
Chemical modification is carried out to introduce functional group；The fabricated in situ polyaniline on nanometer bacteria cellulose after chemical modification, obtain from
The flexible double conducing composite materials of sonization nanometer bacteria cellulose/polyaniline；In the present embodiment, to pretreatment and purification after receive
The functional group that rice bacteria cellulose carries out chemical modification introducing is carboxymethyl, introduces carboxymethyl and specifically includes following steps：
Step one, bacteria cellulose pretreatment and purifying technique
Take bacteria cellulose film deionized water repeatedly to rinse, except striping surface medium and impurity, then film is soaked in
In the NaOH solution of 0.03mol/L, more than hour water-bath one at 90 DEG C, afterwards with the multiple soaking flushing of deionized water, until
The close neutrality of pH value, the nanometer bacteria cellulose film after being pre-processed and being purified；
In this step, the nanometer bacteria cellulose film after the pretreatment and purification can be laid in as needed
On hard glass plate, uniformly cut with special round cut-off knife, obtain nanofiber plain piece, the nanometer bacteria cellulose disk that will be obtained
It is soaked in deionized water, sealing, Cord blood；
Step 2, basification
Basification：By nanometer bacteria cellulose film (or the nanometer bacteria cellulose after purification after pretreatment and purification
Disk) it is placed in the isopropanol water solution that mass fraction is 20%~50%, multiple exchange of solvent is carried out under magnetic agitation, every time
10~20min, filtering obtains the nanometer bacteria cellulose after exchange of solvent；
Nanometer bacteria cellulose after the exchange of solvent is added slowly in the ethanol water of NaOH at room temperature,
Magnetic agitation 40min, the nanometer bacteria cellulose film (or the nanometer bacteria cellulose disk after alkalization) after being alkalized；
Wherein, in the ethanol water of the NaOH, NaOH is the nanometer bacteria cellulose after the exchange of solvent
9 times of dry weight, in the ethanol water, the ratio of second alcohol and water is 1:1：
Step 3, carboxy methylation treatment
The sodium chloroacetate with the amount of the material such as NaOH is weighed, is dissolved in the ethanol solution that mass concentration is 50%, stirred
30min, afterwards by the nanometer bacteria cellulose film (or the nanometer bacteria cellulose disk after alkalization) after step 2 gained alkalization
It is slowly added in the solution；55 DEG C of water-baths 13 hours are subsequently placed in, are 50%~80% methyl alcohol with mass concentration after taking out cooling
Repeatedly washing, removes remaining sodium chloroacetate etc.；
Deionized water is repeatedly cleaned repeatedly, filtering, is neutralized with the acetic acid of mass concentration 10%~30%, to pH be 6.5~
Between 7.5, product is soaked in deionized water；(or carboxylated nanometer bacteria is fine to obtain carboxylated nanometer bacteria cellulose film
The plain disk of dimension).
The preparation of step 4, carboxy methylation bacteria cellulose/polyaniline flexible composite
Carboxylated nanometer bacteria cellulose film (or carboxylated nanometer bacteria cellulose disk) obtained by step 3 is put into
Immersion 24h in 50mL aniline hydrochloric acid solution (AN, 0.5mol/L, HCl, 1.0mol/L) for preparing in advance, backward solution in
It is slowly added to initiator (NH4)2S2O8, at the uniform velocity concussion reaction 90 minutes is continued immediately, until the complete coated bacteria fiber of polyaniline
Element, obtains carboxy methylation bacteria cellulose/polyaniline composite material.
Step 5, the cleaning treatment of composite
After carboxy methylation bacteria cellulose/polyaniline flexible composite is taken out, a large amount of deionized water rinsings are used first
Surface, to wash away the polyaniline and ammonium persulfate on surface；Then the composite after flushing is sequentially placed into deionized water, ethanol
In be timed ultrasonic cleaning, obtain pure composite.
From Fig. 1-5：Relative to unmodified bacteria cellulose/polyaniline (BC/PANI) composite (such as Fig. 1 institutes
Show), modified ionization bacteria cellulose/polyaniline composite material (as in Figure 2-4, including sulfonation bacteria cellulose/poly-
Aniline (SBC/PANI) composite, Carboxylation bacteria cellulose/polyaniline (CA-BC/PANI) composite, carboxy methylation are thin
Fungin/polyaniline (CM-BC/PANI) composite) bacteria cellulose/polyaniline (BC/PANI) is maintained well again
The three-dimensional network loose structure of condensation material, for the transmission of ion provides the passage of similar liquids electrolyte, polyaniline is uniformly coated
On ionization bacteria cellulose, continuous conduction network is formed, can effectively reduce the contact resistance and electrode between；Such as Fig. 5 institutes
Show, compared to unmodified BC/PANI, modified ionization bacteria cellulose/polyaniline composite material impedance diminishes, ion
Electrical conductivity is significantly improved.Wherein, carboxymethyl-modification is modified similar to the lifting effect of ionic conductivity with Carboxylation, and sulfonation changes
Property maximum is acted on to the raising of ionic conductivity.
Flexible composite prepared by the present invention is keeping protocorm material (nanometer bacteria cellulose of ecosystem) excellent
While water-retaining property, retentiveness and mechanical property, with electrical conductivity higher, good heat endurance and biocompatibility, energy
It is enough in novel porous gel polyelectrolyte, amberplex, flexible wearable electronic products, implantable fuel cell, biology
The high-end field such as sensor and DSSC.The composite that the present invention is prepared is in biomass fuel electricity
The aspect such as pond and biology sensor has preferable application prospect.The present invention is using the method for chemical modification to pure nanometer bacteria
Cellulose is modified, and introduces the stronger chemical group of ionizing power, is favorably improved the ionic conductivity of composite membrane.The present invention
The method of modifying for using is chemical method, but reaction condition is gentle, it is easy to controlled, safety non-toxic, with preferable operability.
Claims (8)
1. the preparation method of the flexible double conducing composite materials of a kind of ionization BC/PANI, it is characterised in that methods described first will
The nanometer bacteria cellulose of ecosystem is pre-processed and purified；Then the nanometer bacteria cellulose after pretreatment and purification is entered
Row chemical modification is introducing functional group；Fabricated in situ polyaniline, obtains ion on nanometer bacteria cellulose after chemical modification
Change the flexible double conducing composite materials of nanometer bacteria cellulose/polyaniline；
Wherein, the functional group that chemical modification introducing is carried out to the nanometer bacteria cellulose after pretreatment and purification includes carboxylic first
Any one in base, carboxylic acid ion and sulfonate ion.
2. preparation method according to claim 1, it is characterised in that methods described is to the nanometer bacteria after pretreatment and purification
Cellulose carries out chemical modification, the side of any one functional group being introduced into carboxymethyl, carboxylic acid ion and sulfonate ion
Method, respectively：
Introduce carboxymethyl：Carboxymethyl group is introduced the nanometer bacteria after the pretreatment and purification using alkalization-etherification method fine
Complete carboxymethyl modified in dimension element, obtain carboxymethyl bacterial cellulose；
Introduce carboxylic acid ion：Carboxylate radical is introduced using step-by-step oxidation method for nanometer bacteria fiber after the pretreatment and purification
Complete Carboxylation modified in element, obtain Carboxylation bacteria cellulose；
Introduce sulfonate ion：Using sulfonated reagent, sulfonate radical is introduced into the nanometer bacteria fiber after the pretreatment and purification
Sulfonation modifying is completed in element, sulfonation nanometer bacteria cellulose is obtained.
3. preparation method according to claim 2, it is characterised in that be specially the step of the introducing carboxymethyl：
（1）Basification：It is 20% ~ 50% that nanometer bacteria cellulose film after the pretreatment and purification is placed in into mass fraction
3 ~ 5 exchange of solvent are carried out in isopropanol water solution, under magnetic agitation, every time 10 ~ 20 min, filtered, after obtaining exchange of solvent
Nanometer bacteria cellulose；
Nanometer bacteria cellulose after the exchange of solvent is added slowly in the ethanol water of NaOH at room temperature, magnetic force
40 ~ 60 min of stirring, the nanometer bacteria cellulose film after being alkalized；
（2）Etherificate treatment：Take etherifying reagent to be dissolved in ethanol, the ethanol solution of etherifying reagent is obtained, by step（1）The institute for obtaining
State the nanometer bacteria cellulose film after alkalization to be slowly added in the ethanol solution of the etherifying reagent, be placed in the case of stirring
45 ~ 60 DEG C of water-baths 1 ~ 24 hour, after taking out cooling, clean stand-by repeatedly；Obtain carboxymethylated nanometer bacteria cellulose；
The etherifying reagent is including any one or any two or more in sodium chloroacetate, monoxone, chloropropionic acid, chloropropionic acid sodium
Combination.
4. preparation method according to claim 2, it is characterised in that be specially the step of the introducing carboxylate radical：
（1）Oxidation processes：It is 0.02 ~ 0.06 that nanometer bacteria cellulose film after pretreatment and purification is placed in into molar concentration
Lucifuge is sealed up for safekeeping 24 ~ 48 hours in the selective oxidation agent solution of mol/L, and taking-up afterwards is cleaned several times with deionized water, obtains oxygen
Change nanometer bacteria cellulose；
（2）Carboxylation treatment：By step（1）It is 1 ~ 10 that the oxidation nanometer bacteria cellulose for preparing is put into mass fraction
In the Carboxylation reagent of wt%, 1 ~ 15 min is reacted；Take out after completion of the reaction, repeatedly cleaned repeatedly with deionized water and ethanol, remove
Residual oxidizing agent is removed, stand-by, the Carboxylation nanometer bacteria cellulose of acquisition in deionized water is soaked in；
Wherein, the Carboxylation reagent is oxidizing chemical reagent, including sodium hypochlorite, hypochlorous acid, potassium permanganate, secondary chlorine
Any one or any two or more combination in sour potassium.
5. preparation method according to claim 2, it is characterised in that the introducing sulfonate ion is specially：
（1）Oxidation processes：Nanometer bacteria cellulose film after pretreatment and purification is placed in molar concentration for 0.02 ~ 0.06mol/
Lucifuge is sealed up for safekeeping 24 ~ 48 hours in the selective oxidation agent solution of L, and taking-up afterwards is cleaned several times with deionized water, is obtained oxidation and is received
Rice bacteria cellulose；
（2）Sulfonated treatment：By step（1）It is 1 ~ 20 that the oxidation nanometer bacteria cellulose for preparing is put into mass fraction
In the sulfonating reagent solution of wt%, between 40 ~ 80 DEG C, successive reaction 1 ~ 24 hour keeps machinery to stir to controlling reaction temperature
Mix；Gained nanometer bacteria cellulose film is taken out after completion of the reaction, is repeatedly cleaned repeatedly with deionized water and ethanol, removed remaining
Unreacted sulfonating reagent, product is soaked in stand-by in deionized water；Obtain the nanometer bacteria fiber after sulfonated treatment
Element；
The sulfonated reagent includes any one or any two or more group in sodium hydrogensulfite, potassium bisulfite, sulfuric acid
Close.
6. preparation method according to claim 1, it is characterised in that in situ on nanometer bacteria cellulose fiber after modification
Synthesized polyaniline, specially：Nanometer bacteria cellulose after chemical modification is put into aniline hydrochloric acid solution and is soaked, to improve fibre
Tie up the reactivity of element；After fully immersion absorbs aniline hydrochloric acid solution, to being slowly added to appropriate initiation in aniline hydrochloric acid solution
Agent, continues at the uniform velocity concussion reaction immediately, and control reaction is in -5 ~ 5 DEG C of low-temperature condition, until the complete coated bacteria of polyaniline is fine
Dimension element, obtains flexible composite, wherein, the initiator is ammonium persulfate.
7. a kind of to ionize the flexible double conducing composite materials of BC/PANI, the composite is according to any one of claim 1-6 institute
Preparation method is stated to prepare, it is characterised in that the composite include chemical modification after nanometer bacteria cellulose, described
After chemical modification on nanometer bacteria cellulose fabricated in situ polyaniline, the polyaniline is wrapped in the fibre of nanometer bacteria cellulose
In dimension, nanometer sheath Rotating fields are formed, constitute continuous conduction network；
Wherein, nanometer bacteria cellulose is to be introduced into carboxymethyl, carboxylic acid ion and sulfonate ion after the chemical modification
Nanometer bacteria cellulose after any one functional group.
8. the application of the flexible double conducing composite materials of a kind of ionization BC/PANI, it is characterised in that the composite is according to power
Profit require any one of 1-6 described in preparation method prepare, the composite can be used in porous gel polyelectrolyte, ion
The system of exchange membrane, flexible wearable electronic products, implantable fuel cell, biology sensor or DSSC
It is standby.
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