CN106883607B - Ionize flexible double conducing composite materials of BC/PANI and its preparation method and application - Google Patents
Ionize flexible double conducing composite materials of BC/PANI and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to the chemical modification of nanometer bacteria cellulose and the complex technique field of modified Nano bacteria cellulose and conducting polymer, specific a kind of flexible pair of conducing composite materials of ionization BC/PANI and its preparation method and application.The nanometer bacteria cellulose of ecosystem is pre-processed and is purified first by the method；Chemical modification then is carried out to introduce functional group to the nanometer bacteria cellulose after pretreatment and purification；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；Carrying out the functional group that chemical modification is introduced into the nanometer bacteria cellulose after pretreatment and purification includes any one in carboxymethyl, carboxylic acid ion and sulfonate ion.The electronic conductivity that the composite material that the present invention prepares both had had polyaniline excellent has preferable ionic conductivity further through the modified chemical group introduced.
Description
Technical field
The invention belongs to the chemical modification of nanometer bacteria cellulose and modified Nano bacteria celluloses and conducting polymer
Complex technique field, and in particular to flexible double conducing composite materials of ionization BC/PANI and its preparation method and application.
Background technique
Polyaniline is a kind of excellent conducting polymer, and polyaniline simple synthetic method, reaction condition is mild, by proton
Polyaniline after acid doping has excellent electron conduction, and therefore, polyaniline is widely used in coating, battery, biography at present
The fields such as sensor.But polyaniline by that, at graininess, cannot form, therefore limit it and answer well after common chemical synthesis
Use range.
Nanometer bacteria cellulose is a kind of by microbial fermentation generation, the natural fiber material with hyperfine network structure
Material, it is the effecting reaction active site that is constituted by the hydrogen bond formed between its hyperfine Nanostructure Network, great amount of hydroxy group, excellent
Thermal stability and the advantages that mechanical strength, low gas permeability to have as the advantageous advantage of basis material.Perhaps
More researchs are answered other different materials and nanometer bacteria cellulose using nanometer bacteria cellulose as a kind of mould material
It closes.Bacteria cellulose/polyaniline composite material is also the more one kind of research, and polyaniline is incorporated in by physico-chemical process
The fiber surface of bacteria cellulose forms the bacteria cellulose composite material of polyaniline package, thus solves to a certain degree
Polyaniline is difficult to the problem of forming, and bacteria cellulose is also made to have certain electron conduction.
Bacteria cellulose/polyaniline (BC/PANI) composite material, SEM photograph are as shown in Figure 1.In existing bacterial fibers
In element/polyaniline composite material research, composite material has good electron conduction, in electrolyte, amberplex, sensing
The fields such as device require material to have proton conductivity, and the proton conductivity of simple BC/PANI is very low, in addition, primary
Nanometer bacteria cellulose chemical activity is low, and functional insufficient, which has limited nanometer bacteria celluloses as related compound material
Using.
Based on the above issues, it is multiple by nanometer bacteria cellulose/polyaniline of functional modification that the present invention provides a kind of
Condensation material, this electronic conductivity for both having had polyaniline excellent by modified composite material, further through modified introducing
Chemical group has preferable ionic conductivity, extends the application of such composite material.
Summary of the invention
In view of the above-mentioned problems, the present invention provides a kind of ionization BC/PANI flexible pair of conducing composite material 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, conductivity, good thermal stability and biocompatibility with higher can be used in novel porous
Gel polyelectrolyte, amberplex, flexible wearable electronic products, implantable fuel cell, biosensor 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, the method is first by ecosystem
Nanometer bacteria cellulose is pre-processed and is purified；Then chemistry is carried out to the nanometer bacteria cellulose after pretreatment and purification to change
Property is to introduce functional group；It is thin to obtain ionization nanometer for the fabricated in situ polyaniline on nanometer bacteria cellulose after chemical modification
The flexible double conducing composite materials of fungin/polyaniline；
Wherein, carrying out the functional group of chemical modification introducing to the nanometer bacteria cellulose after pretreatment and purification includes carboxylic
Any one in methyl, carboxylic acid ion and sulfonate ion.
Further, the method 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, is respectively as follows:
Introduce carboxymethyl: the nanometer after carboxymethyl group is introduced the pretreatment and purified using alkalization-etherification method is thin
It completes carboxymethyl modified in fungin, obtains carboxymethyl bacterial cellulose；
It introduces carboxylic acid ion: carboxylate radical is introduced using step-by-step oxidation method by the nanometer bacteria after the pretreatment and purification
Carboxylation modification is completed in cellulose, obtains Carboxylation bacteria cellulose；
It introduces sulfonate ion: utilizing sulfonated reagent, sulfonate radical is introduced into the nanometer bacteria after the pretreatment and purification
Sulfonation modifying is completed in cellulose, obtains sulfonation nanometer bacteria cellulose.
Further, the nanometer bacteria cellulose of ecosystem is pre-processed and is purified, specifically:
It takes the nanometer bacteria cellulose film of ecosystem repeatedly to be rinsed with deionized water, removes film surface culture 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, it removes and remains in thallus and culture medium in Nanofiber Network, later with the multiple soaking flushing of deionized water, until pH
Value is close to neutrality, 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, it can be according to need
Want, uniformly cut with special round cut-off knife, obtain nanofiber plain piece, by obtained nanometer bacteria cellulose disk be soaked in from
In sub- water, sealing, cryo-conservation；
Further, the step of introducing carboxymethyl specifically:
(1) basification: by the nanometer bacteria cellulose film after pretreatment and purification be placed in mass fraction be 20%~
In 50% isopropanol water solution, multiple exchange of solvent is carried out under magnetic agitation, every time 10~20min, filtered, obtain solvent and hand over
Nanometer bacteria cellulose after changing；
It weighs, the ethyl alcohol that the nanometer bacteria cellulose after the exchange of solvent is added slowly to 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 are as follows: 4:5~5:6.
(2) etherification process: taking appropriate etherifying reagent to be dissolved in ethyl alcohol, obtains the ethanol solution of etherifying reagent, by step (1)
Nanometer bacteria cellulose film after the obtained alkalization 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, cleaning is stand-by repeatedly；Obtain carboxymethylated nanometer bacteria
Cellulose.
Wherein the etherifying reagent is that substitution reaction can occur with the nanometer bacteria cellulose film after the alkalization, is introduced
The organic reagent of carboxymethyl；The etherifying reagent includes sodium chloroacetate, monoxone, chloropropionic acid, any one in chloropropionic acid sodium
Or any two or more combination.
Further, the step of introducing carboxylate radical specifically:
(1) oxidation processes: by the nanometer bacteria cellulose film after pretreatment and purification be placed in molar concentration be 0.02~
It is protected from light and seals up for safekeeping 24~48 hours in the selective oxidation agent solution of 0.06mol/L, taking-up later 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 processing: the oxidation nanometer bacteria cellulose that step (1) is prepared is put into mass fraction and is
In the Carboxylation reagent of 1~10wt%, 1~15min is reacted；It takes out after completion of the reaction, repeatedly repeatedly with deionized water and ethyl alcohol
Cleaning removes residual oxidizing agent, is soaked in deionized water for use, obtains Carboxylation nanometer bacteria cellulose；
Wherein the Carboxylation reagent be oxidizing chemical reagent, including sodium hypochlorite, hypochlorous acid, potassium permanganate,
Any one or any two or more combinations in postassium hypochlorite.
Further, the introducing sulfonate ion specifically:
(1) oxidation processes: by the nanometer bacteria cellulose film after pretreatment and purification be placed in molar concentration be 0.02~
It is protected from light and seals up for safekeeping 24~48 hours in the selective oxidation agent solution of 0.06mol/L, taking-up later 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 processing: the oxidation nanometer bacteria cellulose that step (1) is prepared is put into mass fraction and is
In the sulfonating reagent solution of 1~20wt%, reaction temperature is controlled between 40~80 DEG C, successive reaction 1~24 hour, is kept
Mechanical stirring；Gained nanometer bacteria cellulose film is taken out after completion of the reaction, is repeatedly cleaned, is removed repeatedly with deionized water and ethyl alcohol
Remaining unreacted sulfonating reagent is removed, product is soaked in deionized water for use；Obtain that sulfonated treated that nanometer is thin
Fungin；
The sulfonated reagent includes sodium hydrogensulfite, potassium bisulfite, any one or any two or more in sulfuric acid
Combination.
Further, fabricated in situ polyaniline on nanometer bacteria cellulose fiber after modification, specifically: chemistry is changed
Nanometer bacteria cellulose after property, which is put into aniline hydrochloric acid solution, to be impregnated, to improve the reactivity of cellulose；
After sufficiently impregnating and absorbing aniline hydrochloric acid solution, appropriate initiator persulfuric acid is slowly added into 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 method also includes the post-processing step of composite material, specifically: nanometer bacteria after modification
On cellulose fibre after fabricated in situ polyaniline, surface is rinsed with a large amount of deionized waters, causes reagent to wash away the remaining of surface
With excessive polyaniline；
Gel mould after flushing is sequentially placed into deionized water, carries out mechanical stirring in ethyl alcohol, repeats 2~3 times, obtains just
Composite material after step cleaning；
Gel mould after tentatively cleaning is soaked in ethyl alcohol, is cleaned by ultrasonic using timing interruption, obtains depth
Flexible composite after cleaning.
A kind of flexible double conducing composite materials (i.e. ionization nanometer bacteria cellulose/polyaniline flexibilities of ionization BC/PANI
Double conducing composite materials), the composite material includes nanometer bacteria cellulose, the nanometer after the chemical modification after chemical modification
The polyaniline of fabricated in situ on bacteria cellulose, the polyaniline are wrapped on the fiber of nanometer bacteria cellulose, form nanometer
Sheaths structure constitutes continuous conduction network；
Wherein, nanometer bacteria cellulose is to introduce 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 material
It is standby to obtain, the composite material can be used in porous gel polyelectrolyte, amberplex, flexible wearable electronic products, can
It is implanted into the preparation of fuel cell, biosensor or dye-sensitized solar cells.
Advantageous effects of the invention:
(1) flexible double conducing composite material (the i.e. ionization bacterial fibers of the ionization BC/PANI that the present invention is prepared
The double conducing composite materials of element/polyaniline) still there is nanoscale structure, the structural stability of composite membrane is maintained, is not changed
Become distributed architecture of the polyaniline on bacteria cellulose, polyaniline is still wrapped on the fiber of nanometer bacteria cellulose, is formed
Nanometer sheaths structure, constitutes 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 good thermodynamic stability is maintained in certain temperature range, in addition, system of the present invention
Standby obtained modified Nano bacteria cellulose has good biocompatibility, with polyaniline it is compound after, obtained flexible compound
Material ion-electron conductivity with higher.
(3) the more unmodified nanometer bacteria cellulose of nanometer bacteria cellulose conducing composite material prepared by the present invention is compound
Film, other than having common bacteria cellulose/polyaniline composite film electronic conductivity, ionic conduction also with higher
Rate, and after being compounded with polyaniline, still there is three-dimensional net structure specific to nanometer bacteria cellulose, pore-size distribution is equal
It is even, it ensure 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, biosensor and dyestuff are quick
Change the various fields such as solar battery.
Detailed description of the invention
Fig. 1 is the SEM photograph of bacteria cellulose/polyaniline (BC/PANI) composite material；
Fig. 2 is sulfonation bacteria cellulose/polyaniline (SBC/PANI) composite material SEM photograph in embodiment 1；
Fig. 3 is the SEM photograph of Carboxylation bacteria cellulose/polyaniline (CA-BC/PANI) composite material in embodiment 2；
Fig. 4 is carboxy methylation bacteria cellulose/polyaniline (CM-BC/PANI) composite material SEM photograph in embodiment 3；
Fig. 5 is that the exchange of different composite material (including BC/PANI, CM-BC/PANI, CA-BC/PANI, SBC/PANI) hinders
Anti- map.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
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.
On the contrary, the present invention covers any substitution done on the essence and scope of the present invention being defined by the claims, repairs
Change, equivalent method and scheme.Further, in order to make the public have a better understanding 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
The present invention can also be understood completely in description.
Embodiment 1
A kind of preparation method of the flexible double conducing composite materials of ionization bacteria cellulose/polyaniline, the method 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 receiving after pretreatment and purification
The functional group that rice bacteria cellulose carries out chemical modification introducing is sulfonic acid.Introduce sulfonate ion specifically includes the following steps:
Step 1: bacteria cellulose pretreatment and purifying technique
It takes bacteria cellulose film repeatedly to be rinsed with deionized water, removes film surface culture medium and impurity, then film is soaked in
In the NaOH solution of 0.01mol/L, water-bath one more than hour at 90 DEG C, later with the multiple soaking flushing of deionized water, until
PH value is close to neutrality, the nanometer bacteria cellulose film after being pre-processed and being purified；
In this step, it can according to need, the nanometer bacteria cellulose film after the pretreatment and purification be laid in
On hard glass plate, is 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, cryo-conservation；
Step 2: oxidation processes
By the obtained pretreatment after step 1 processing and the nanometer bacteria cellulose film after purification, (or nanometer bacteria is fine
Tie up plain disk) 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 be protected from light and seal up for safekeeping 24 hours, taking-up later 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 score is the solution of sodium bisulfite of 5wt%, by oxidation nanometer bacteria cellulose obtained by step 2 (or
Oxidation nanometer bacteria cellulose disk film) it is put into configured solution of sodium bisulfite, react 3 hours under 50 DEG C of water-baths, instead
Gained sulfonation nanometer bacteria cellulose film is taken out after answering, is repeatedly cleaned repeatedly with deionized water and ethyl alcohol, is removed remaining
Product is soaked in deionized water by sodium hydrogensulfite, is obtained sulfonated treated nanometer bacteria cellulose and (or is obtained sulfonation
Nanometer bacteria cellulose disk film)；
Step 4: the preparation of the flexible double conducing composite materials of sulfonation nanometer bacteria cellulose/polyaniline
By resulting sulfonated treated the nanometer bacteria cellulose of step 3 (or sulfonation nanometer bacteria cellulose disk
Film) it is put into preparatory prepared 50mL aniline hydrochloric acid solution (AN, 0.5mol/L, HCl, 1.0mol/L) and impregnates for 24 hours, it is backward
Initiator (NH is slowly added in solution4)2S2O8, continue at the uniform velocity concussion reaction 90 minutes immediately, until polyaniline coats sulphur completely
Change nanometer bacteria cellulose, obtains the flexible double conducing composite materials of sulfonation bacteria cellulose/polyaniline.
Step 5: the post-processing step of composite material is by the flexible double conducing composite materials of sulfonation bacteria cellulose/polyaniline
After taking-up, surface is rinsed with a large amount of deionized waters first, to wash away the polyaniline and ammonium persulfate ((NH on surface4)2S2O8)；It connects
The composite material after flushing is sequentially placed into deionized water, is timed interruption ultrasonic cleaning in ethyl alcohol, obtain pure answer
Condensation material.
Embodiment 2
A kind of preparation method of the flexible double conducing composite materials of ionization bacteria cellulose/polyaniline, the method 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 receiving after pretreatment and purification
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 1: bacteria cellulose pretreatment and purifying technique
It takes bacteria cellulose film repeatedly to be rinsed with deionized water, removes film surface culture medium and impurity, then film is soaked in
In the NaOH solution of 0.02mol/L, water-bath one more than hour at 90 DEG C, later with the multiple soaking flushing of deionized water, until
PH value is close to neutrality, the nanometer bacteria cellulose film after being pre-processed and being purified；
In this step, it can according to need, the nanometer bacteria cellulose film after the pretreatment and purification be laid in
On hard glass plate, is 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, cryo-conservation；
Step 2: oxidation processes
By the obtained pretreatment after step 1 processing and the nanometer bacteria cellulose film after purification, (or nanometer bacteria is fine
Tie up plain disk) molar concentration is placed in be protected from light in the sodium periodate solution (one kind of selective oxidation agent solution) of 0.04mol/L
It seals up for safekeeping 24 hours, taking-up later is cleaned several times with deionized water, and obtaining oxidation nanometer bacteria cellulose, (or to obtain oxidation nanometer thin
Fungin disk film)；
Step 3: Carboxylation processing
Configuration quality score is the liquor natrii hypochloritis of 3wt%, by oxidation nanometer bacteria cellulose film obtained by step 2 (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
It is acidified nanometer bacteria cellulose film to take out, repeatedly be cleaned repeatedly with deionized water and ethyl alcohol, 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).
Step 4: the preparation of Carboxylation bacteria cellulose/polyaniline flexible composite
By the resulting Carboxylation nanometer bacteria cellulose disk film of step 3 (or Carboxylation nanometer bacteria cellulose disk
Film), it is put into preparatory prepared 50mL aniline hydrochloric acid solution (AN, 0.5mol/L, HCl, 1.0mol/L) and impregnates for 24 hours, later
Initiator (NH is slowly added into solution4)2S2O8, continue at the uniform velocity concussion reaction 90 minutes immediately, until polyaniline coats 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, table is rinsed with a large amount of deionized waters first
Face, to wash away the polyaniline and ammonium persulfate ((NH on surface4)2S2O8)；Then by the composite material after flushing be sequentially placed into from
It is timed ultrasonic cleaning in sub- water, ethyl alcohol, obtains pure flexible composite.
Embodiment 3
A kind of preparation method of the flexible double conducing composite materials of ionization bacteria cellulose/polyaniline, the method 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 receiving after pretreatment and purification
Rice bacteria cellulose carry out chemical modification introducing functional group be carboxymethyl, introduce carboxymethyl specifically includes the following steps:
Step 1: bacteria cellulose pretreatment and purifying technique
It takes bacteria cellulose film repeatedly to be rinsed with deionized water, removes film surface culture medium and impurity, then film is soaked in
In the NaOH solution of 0.03mol/L, water-bath one more than hour at 90 DEG C, later with the multiple soaking flushing of deionized water, until
PH value is close to neutrality, the nanometer bacteria cellulose film after being pre-processed and being purified；
In this step, it can according to need, the nanometer bacteria cellulose film after the pretreatment and purification be laid in
On hard glass plate, is 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, cryo-conservation；
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, the nanometer bacteria cellulose after obtaining exchange of solvent；
Nanometer bacteria cellulose after the exchange of solvent is added slowly at room temperature in the ethanol water of NaOH,
Magnetic agitation 40min, the nanometer bacteria cellulose film (or 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 is handled
The sodium chloroacetate with the amount of the substances such as NaOH is weighed, is dissolved in the ethanol solution that mass concentration is 50%, stirring
30min, later by the nanometer bacteria cellulose film (or nanometer bacteria cellulose disk after alkalization) after alkalization obtained by step 2
It is slowly added in the solution；55 DEG C of water-baths 13 hours are subsequently placed in, are 50%~80% methanol with mass concentration after taking out cooling
Repeatedly washing removes remaining sodium chloroacetate etc.；
Deionized water is repeatedly cleaned repeatedly, is filtered, and is neutralized with the acetic acid of mass concentration 10%~30%, until pH be 6.5~
Between 7.5, product is soaked in deionized water；Obtaining carboxylated nanometer bacteria cellulose film, (or carboxylated nanometer bacteria is fine
Tie up plain disk).
Step 4: the preparation of carboxy methylation bacteria cellulose/polyaniline flexible composite
The resulting carboxylated nanometer bacteria cellulose film of step 3 (or carboxylated nanometer bacteria cellulose disk) is put into
Impregnated in preparatory prepared 50mL aniline hydrochloric acid solution (AN, 0.5mol/L, HCl, 1.0mol/L) for 24 hours, backward solution in
It is slowly added to initiator (NH4)2S2O8, continue at the uniform velocity concussion reaction 90 minutes 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 material
After carboxy methylation bacteria cellulose/polyaniline flexible composite is taken out, rinsed first with a large amount of deionized waters
Surface, to wash away the polyaniline and ammonium persulfate on surface；Then the composite material after flushing is sequentially placed into deionized water, ethyl alcohol
In be timed ultrasonic cleaning, obtain pure composite material.
From Fig. 1-5: relative to unmodified bacteria cellulose/polyaniline (BC/PANI) composite material (such as Fig. 1 institute
Show), modified ionization bacteria cellulose/polyaniline composite material (as in Figure 2-4, including sulfonation bacteria cellulose/poly-
Aniline (SBC/PANI) composite material, Carboxylation bacteria cellulose/polyaniline (CA-BC/PANI) composite material, carboxy methylation are thin
Fungin/polyaniline (CM-BC/PANI) composite material) bacteria cellulose/polyaniline (BC/PANI) is maintained well again
The three-dimensional network porous structure of condensation material provides the channel of similar liquids electrolyte for the transmission of ion, and polyaniline uniformly coats
On ionization bacteria cellulose, continuous conduction network is formed, the contact resistance between electrode can be effectively reduced；Such as Fig. 5 institute
Show, compared to unmodified BC/PANI, modified ionization bacteria cellulose/polyaniline composite material impedance becomes smaller, ion
Conductivity significantly improves.Wherein, carboxymethyl-modification is similar with promotion effect of the Carboxylation modification to ionic conductivity, and sulfonation changes
Property the raising of ionic conductivity is acted on it is maximum.
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, conductivity, good thermal stability and biocompatibility with higher, energy
It is enough in novel porous gel polyelectrolyte, amberplex, flexible wearable electronic products, implantable fuel cell, biology
The high-end fields such as sensor and dye-sensitized solar cells.The composite material that the present invention prepares is in biomass fuel electricity
Pond and biosensor etc. are with good application prospect.The present invention is using the method for chemical modification to pure nanometer bacteria
Cellulose is modified, and is introduced the stronger chemical group of ionizing power, is helped to improve the ionic conductivity of composite membrane.The present invention
The method of modifying used is chemical method, but reaction condition is mild, easily controllable, safe and non-toxic, has preferable operability.
Claims (6)
1. a kind of preparation method of the flexible double conducing composite materials of ionization BC/PANI, which is characterized in that the method first will
The nanometer bacteria cellulose of ecosystem is pre-processed and is purified；Then to the nanometer bacteria cellulose after pretreatment and purification into
Row chemical modification is to introduce functional group；Fabricated in situ polyaniline on nanometer bacteria cellulose, obtains ion after chemical modification
Change the flexible double conducing composite materials of nanometer bacteria cellulose/polyaniline；
Wherein, carrying out the functional group of chemical modification introducing to the nanometer bacteria cellulose after pretreatment and purification includes carboxylate radical
Any one in ion and sulfonate ion,
Wherein, the method carries out chemical modification to the nanometer bacteria cellulose after pretreatment and purification, introduces carboxylic acid ion
With the method for any one functional group in sulfonate ion, it is respectively as follows:
It introduces carboxylic acid ion: carboxylate radical is introduced using step-by-step oxidation method by the nanometer bacteria fiber after the pretreatment and purification
Carboxylation modification is completed in element, obtains Carboxylation bacteria cellulose；
It introduces sulfonate ion: utilizing sulfonated reagent, sulfonate radical is introduced into the nanometer bacteria fiber after the pretreatment and purification
Sulfonation modifying is completed in element, obtains sulfonation nanometer bacteria cellulose.
2. preparation method according to claim 1, which is characterized in that the step of the introducing carboxylate radical specifically:
(1) oxidation processes: by the nanometer bacteria cellulose film after pretreatment and purification be placed in molar concentration be 0.02~
It is protected from light and seals up for safekeeping 24~48 hours in the selective oxidation agent solution of 0.06mol/L, taking-up later is cleaned several times with deionized water, is obtained
To oxidation nanometer bacteria cellulose；
(2) Carboxylation processing: the oxidation nanometer bacteria cellulose that step (1) is prepared be put into mass fraction be 1~
In the Carboxylation reagent of 10wt%, 1~15min is reacted；It takes out after completion of the reaction, it is repeatedly repeatedly clear with deionized water and ethyl alcohol
It washes, removes residual oxidizing agent, be soaked in deionized water for use, obtain Carboxylation nanometer bacteria cellulose；
Wherein, the Carboxylation reagent is oxidizing chemical reagent, including sodium hypochlorite, hypochlorous acid, potassium permanganate, secondary chlorine
Any one or any two or more combinations in sour potassium.
3. preparation method according to claim 1, which is characterized in that the introducing sulfonate ion specifically:
(1) oxidation processes: by the nanometer bacteria cellulose film after pretreatment and purification be placed in molar concentration be 0.02~
It is protected from light and seals up for safekeeping 24~48 hours in the selective oxidation agent solution of 0.06mol/L, taking-up later is cleaned several times with deionized water, is obtained
To oxidation nanometer bacteria cellulose；
(2) sulfonated processing: the oxidation nanometer bacteria cellulose that step (1) is prepared be put into mass fraction be 1~
In the sulfonating reagent solution of 20wt%, reaction temperature is controlled between 40~80 DEG C, successive reaction 1~24 hour, keeps machine
Tool stirring；Gained nanometer bacteria cellulose film is taken out after completion of the reaction, is repeatedly cleaned repeatedly with deionized water and ethyl alcohol, is removed
Remaining unreacted sulfonating reagent, product is soaked in deionized water for use；Obtain sulfonated treated nanometer bacteria
Cellulose；
The sulfonated reagent includes sodium hydrogensulfite, potassium bisulfite, any one or any two or more groups in sulfuric acid
It closes.
4. preparation method according to claim 1, which is characterized in that in situ on nanometer bacteria cellulose fiber after modification
Synthesized polyaniline, specifically: the nanometer bacteria cellulose after chemical modification is put into aniline hydrochloric acid solution and is impregnated, to improve fibre
Tie up the reactivity of element；After sufficiently impregnating and absorbing aniline hydrochloric acid solution, it is slowly added to cause in right amount into 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
Cellulose obtains flexible composite, wherein the initiator is ammonium persulfate.
5. a kind of flexible double conducing composite materials of ionization BC/PANI, the composite material any one of -4 institute according to claim 1
It states preparation method to prepare, which is characterized in that the composite material includes nanometer bacteria cellulose after chemical modification, 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 sheaths structure is formed, constitutes continuous conduction network；
Wherein, nanometer bacteria cellulose is any one being introduced into carboxylic acid ion and sulfonate ion after the chemical modification
Nanometer bacteria cellulose after functional group.
6. a kind of application of the flexible double conducing composite materials of ionization BC/PANI, which is characterized in that the composite material is according to power
Benefit requires any one of 1-4 preparation method to prepare, and the composite material can be used in porous gel polyelectrolyte, ion
The system of exchange membrane, flexible wearable electronic products, implantable fuel cell, biosensor or dye-sensitized solar cells
It is standby.
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| CN108187765B (en) * | 2018-01-31 | 2020-07-28 | 河南省科学院化学研究所有限公司 | PP-ST-DVB-based cation exchange fiber and synthetic method thereof |
| CN109096752A (en) * | 2018-08-17 | 2018-12-28 | 佛山皖和新能源科技有限公司 | A kind of graphene conductive composite material and preparation method thereof |
| CN109734842B (en) * | 2018-12-04 | 2021-03-30 | 华南理工大学 | Transparent conductive flexible bacterial cellulose composite material and preparation method thereof |
| CN109575365A (en) * | 2018-12-05 | 2019-04-05 | 昆明理工大学 | The method that one-step method prepares polyaniline/cellulose nanocrystal composite membrane |
| CN111725489B (en) * | 2020-06-01 | 2021-07-16 | 华北科技学院 | Element-doped conductive composite carbonized material and preparation method and application thereof |
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