CN115181335A - Conductive polymer and bacterial cellulose composite aerogel and preparation method thereof - Google Patents
Conductive polymer and bacterial cellulose composite aerogel and preparation method thereof Download PDFInfo
- Publication number
- CN115181335A CN115181335A CN202110361846.8A CN202110361846A CN115181335A CN 115181335 A CN115181335 A CN 115181335A CN 202110361846 A CN202110361846 A CN 202110361846A CN 115181335 A CN115181335 A CN 115181335A
- Authority
- CN
- China
- Prior art keywords
- bacterial cellulose
- conductive polymer
- composite aerogel
- mixture
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920002749 Bacterial cellulose Polymers 0.000 title claims abstract description 80
- 239000005016 bacterial cellulose Substances 0.000 title claims abstract description 80
- 239000004964 aerogel Substances 0.000 title claims abstract description 54
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 20
- 229920000767 polyaniline Polymers 0.000 claims description 18
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 14
- 238000004108 freeze drying Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000004132 cross linking Methods 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 239000002322 conducting polymer Substances 0.000 abstract description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 28
- 238000007906 compression Methods 0.000 description 16
- 239000002002 slurry Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 230000006835 compression Effects 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- -1 polyphenylenevinylene Polymers 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 3
- VBQMPXNFLQSHMH-UHFFFAOYSA-N Arlatin Chemical compound C1CC(C)(O)C2(O)CC=C(C)C2C2OC(=O)C(C)C21 VBQMPXNFLQSHMH-UHFFFAOYSA-N 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- LTOKKZDSYQQAHL-UHFFFAOYSA-N trimethoxy-[4-(oxiran-2-yl)butyl]silane Chemical compound CO[Si](OC)(OC)CCCCC1CO1 LTOKKZDSYQQAHL-UHFFFAOYSA-N 0.000 description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 239000008104 plant cellulose Substances 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000414 polyfuran Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
- C08J9/286—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0042—Use of organic additives containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
- C08J2205/026—Aerogel, i.e. a supercritically dried gel
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/04—Oxycellulose; Hydrocellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J2479/02—Polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
Abstract
The application discloses conducting polymer and bacterial cellulose composite aerogel and preparation method thereof, composite aerogel composition includes at least: conductive polymer, bacterial cellulose and water-immiscible organic solvent. The conductive polymer and bacterial cellulose composite aerogel in the application has a stable porous composite structure, has excellent mechanical properties, and solves the problems of poor mechanical strength and poor conductivity of the existing aerogel.
Description
Technical Field
The invention belongs to the technical field of aerogel preparation. In particular to a conductive polymer and bacterial cellulose composite aerogel and a preparation method thereof.
Background
Conductive polymers, also called conducting macromolecules, are polymers consisting of highly pi-conjugated polymer chains, which create the possibility of conduction by the flow of pi electrons. Common conductive polymers include polyaniline, polypyrrole, poly 3,4-ethylenedioxythiophene, polyphenylenevinylene, polythiophene, polyfuran, and the like. With the development of science and technology, conductive polymers are widely applied to a plurality of fields, such as electrochromic materials and devices, electrostatic shielding devices, temperature and humidity sensors, gas sensors, biosensors, and related electronic devices such as diodes and transistors.
The bacterial cellulose is a superfine fiber net structure high molecular polymer synthesized by microbial fermentation. The structure of bacterial cellulose is approximately the same as that of plant cellulose, and the main difference is that the bacterial cellulose does not contain hemicellulose and lignin. The bacterial cellulose has high air permeability, biocompatibility and degradability, and is an ideal raw material for preparing the aerogel. A large amount of intermolecular and intramolecular hydrogen bonds exist between molecules of the bacterial cellulose, and the structure of the bacterial cellulose is very stable due to the strong hydrogen bond effect. The bacterial cellulose has wide sources, and is a renewable and sustainable green material. Meanwhile, in combination with the staggered hierarchical structure of the fibers, the bacterial cellulose derivative and the composite material thereof are often prepared into different multifunctional aerogel materials and are widely applied to the fields of catalysis, energy storage, adsorption, sensing and the like.
For a single bacterial cellulose aerogel, the mechanical strength is often poor, and meanwhile, the conductivity of the bacterial cellulose aerogel can be generally given only after the bacterial cellulose aerogel is subjected to high-temperature carbonization treatment. Therefore, it is important to find a material which can improve the mechanical strength of the bacterial cellulose and can be compounded with the bacterial cellulose under non-extreme conditions (such as ultra-high temperature and ultra-low temperature conditions).
Disclosure of Invention
The invention provides a conductive polymer and bacterial cellulose composite aerogel and a preparation method thereof, wherein a network of the aerogel material prepared by compounding the conductive polymer and the bacterial cellulose can form a good conductive path by virtue of the conductive polymer, and effective mass transfer can be carried out by utilizing a staggered hierarchical structure of the bacterial cellulose. Meanwhile, the composite aerogel material has excellent mechanical property and stability due to the synergistic effect of the two materials, and the problems of poor mechanical strength, poor conductivity and the like of the conventional aerogel are solved.
According to one aspect of the application, a composite aerogel of a conductive polymer and bacterial cellulose is provided, wherein the composite aerogel at least comprises the following components: conductive polymer, bacterial cellulose and water-immiscible organic solvent;
optionally, the composite aerogel has a three-dimensional network structure formed by interlacing filamentous fibers of bacterial cellulose; the conductive polymer is randomly and dispersedly attached to the surfaces of the filamentous fibers in the form of particles.
Optionally, the conductive polymer is prepared by an interfacial polymerization method;
optionally, the conductive polymer is selected from at least one of polyaniline or polypyrrole.
Optionally, the mass ratio of the conductive polymer to the bacterial cellulose is: 0.1-5:1;
preferably, the lower limit of the mass ratio of the conductive polymer to the bacterial cellulose may be independently selected from 0.1; the upper limit of the mass ratio of the conductive polymer to the bacterial cellulose can be independently selected from 1:1, 2:1, 3:1, 4:1, 5:1;
optionally, the mass ratio of the bacterial cellulose to the water-immiscible organic solvent is: 0.01 to 1;
preferably, the lower limit of the mass ratio of the bacterial cellulose to the water-immiscible organic solvent can be independently selected from the group consisting of 0.01; the upper limit of the mass ratio of the bacterial cellulose to the water-immiscible organic solvent can be independently selected from the following 0.8.
According to another aspect of the present application, a method for preparing the composite aerogel at least comprises:
adding a cross-linking agent and an initiator into a mixture I containing a monomer of the conductive polymer, bacterial cellulose and an organic solvent immiscible with water to carry out cross-linking reaction to obtain pre-gel;
and (2) carrying out freeze drying treatment on the pre-gel to obtain the composite aerogel.
Optionally, the water-immiscible organic solvent is selected from at least one of carbon tetrachloride, dichloromethane and toluene.
Optionally, the temperature of the crosslinking reaction is-10 to 4 ℃, and the reaction time is 0.5 to 24 hours.
Preferably, the lower limit of the temperature of the crosslinking reaction may be independently selected from-10 ℃, -9 ℃, -8 ℃, -7 ℃, -6 ℃; the upper limit of the temperature of the crosslinking reaction may be independently selected from 0 deg.C, 1 deg.C, 2 deg.C, 3 deg.C, and 4 deg.C.
Preferably, the lower limit of the crosslinking reaction time may be independently selected from 0.5h, 1h, 3h, 5h, 7h; the upper limit of the crosslinking reaction time can be independently selected from 18h, 19h, 20h, 22h, 24h.
Optionally, the cross-linking agent is selected from at least one of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma- (2,3-glycidoxy) propyltrimethoxysilane;
optionally, the amount of the cross-linking agent is 0.3-8% of the amount of the bacterial cellulose.
Preferably, the lower limit of the amount of the cross-linking agent can be independently selected from 0.3%, 0.5%, 0.8%, 1%, 2%; the upper limit of the dosage of the cross-linking agent can be independently selected from 4%, 5%, 6%, 7% and 8% of the mass of the bacterial cellulose.
Optionally, the initiator is at least one of ammonium persulfate, potassium persulfate and azobisisobutyronitrile;
optionally, the amount of the initiator is 50-200% of the monomer mass of the conductive polymer;
preferably, the lower limit of the amount of the initiator can be independently selected from 50%, 60%, 70%, 80%, 90% of the monomer mass of the conductive polymer; the upper limit of the amount of the initiator can be independently selected from 160%, 170%, 180%, 190%, 200% of the mass of the monomer of the conductive polymer.
Preferably, the initiator is added into a hydrochloric acid aqueous solution, and a mixture A is obtained by mixing;
preferably, the concentration of the hydrochloric acid aqueous solution is 0.1-3 mmol/L;
preferably, the lower concentration limit of the hydrochloric acid aqueous solution can be independently selected from 0.1mmol/L, 0.2mmol/L, 0.3mmol/L, 0.5mmol/L and 0.6mmol/L; the upper limit of the concentration of the aqueous hydrochloric acid solution can be independently selected from 1mmol/L, 1.5mmol/L, 2mmol/L, 2.5mmol/L and 3mmol/L.
Preferably, the mixing temperature for obtaining the mixture A is-10 to 4 ℃.
Preferably, the lower limit of the mixing temperature to obtain said mixture A may be independently selected from-10 ℃, -9 ℃, -8 ℃, -7 ℃, -6 ℃; the upper limit of the mixing temperature can be independently selected from 0 deg.C, 1 deg.C, 2 deg.C, 3 deg.C, and 4 deg.C.
Alternatively, the obtaining of the mixture I comprises:
dispersing the bacterial cellulose dispersion liquid into an organic solvent immiscible with water, and mixing to obtain emulsion A;
adding monomers of the conductive polymer into the emulsion A, and mixing to obtain a mixture I;
optionally, the mixing temperature for obtaining the emulsion A is-10 to 4 ℃;
preferably, the lower limit of the mixing temperature to obtain said emulsion A is independently selected from the group consisting of-10 ℃, -9 ℃, -7 ℃, -5 ℃, -4 ℃; the upper limit of the mixing temperature can be independently selected from 0 deg.C, 1 deg.C, 2 deg.C, 3 deg.C, and 4 deg.C.
Optionally, the mixing temperature for obtaining the mixture I is-10 to 4 ℃;
preferably, the lower limit of the mixing temperature to obtain said mixture I may be independently selected from-10 ℃, -8 ℃, -6 ℃, -5 ℃, -4 ℃; the upper limit of the mixing temperature can be independently selected from-1 deg.C, 2 deg.C, 3 deg.C, and 4 deg.C.
In the application, the crosslinking reaction means that a silane crosslinking agent is hydrolyzed to form silicon hydroxyl, and the silicon hydroxyl can be physically crosslinked with a hydrogen-containing group on a conductive polymer or a hydroxyl on bacterial cellulose;
the interfacial polymerization method is a polycondensation reaction performed at an interface between two solvents (or an interfacial organic phase side) in which two monomers are dissolved, the two solvents being immiscible with each other.
The beneficial effects that this application can produce include:
1) According to the conductive polymer and bacterial cellulose composite aerogel provided by the application, a stable three-dimensional network system is provided for the aerogel by introducing the bacterial cellulose and utilizing the hydrogen bond interaction between the conductive polymer and the bacterial cellulose and the hydrogen bond interaction between a large number of hydroxyl groups in the bacterial cellulose;
2) According to the conductive polymer and bacterial cellulose composite aerogel provided by the application, by introducing the conductive polymer, not only can the gel conductivity be improved, but also a deformation signal of the gel can be converted into an electric signal, so that the application field of the gel is widened;
3) According to the conductive polymer and bacterial cellulose composite aerogel provided by the application, the aggregation phenomenon of the conductive polymer in the common polymerization process is effectively improved through an interface polymerization method, so that the conductive polymer can be randomly coated on the bacterial cellulose, and a gel system is more stable;
4) The application provides a conducting polymer and bacterial cellulose composite aerogel, not only has stable porous composite construction, has excellent mechanical properties moreover, has solved current aerogel mechanical strength difference and electric conductive property subalternation problem.
Drawings
Fig. 1 is a scanning electron microscope result image of the polyaniline and bacterial cellulose composite aerogel in example 1 of the present invention at different resolutions.
Fig. 2 is a graph of compressive stress-strain curves of polyaniline and bacterial cellulose composite aerogels with different mass ratios provided in examples 2 to 5 of the present invention;
fig. 3 is a graph of a relative resistance change versus pressure curve of the polyaniline and bacterial cellulose composite aerogel with a mass ratio of 2:1 provided in example 1 of the present invention.
Detailed Description
The invention is further illustrated with reference to the following figures and specific examples.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the test methods used in the following examples are commercially available unless otherwise specified.
The bacterial cellulose dispersion liquid adopted in the embodiment of the invention is produced by Guilin Qihong scientific and technology limited company, and the content of the bacterial cellulose is 0.65 percent; aniline, from a manufacturer of Shanghai Aladdin, >99.5wt%; carbon tetrachloride, manufacturer 99.5wt% of Tianjin Kouiou; 3-glycidylpropyltrimethoxysilane, obtained from Shanghai Arlatin, > 97% by weight.
Example 1
Weighing 20g of bacterial cellulose dispersion liquid, and stirring at a high speed for 20min; weighing 0.26 of aniline, adding the aniline into the mixed dispersion liquid, and stirring at a high speed for 20min; 0.326g of ammonium persulfate was weighed, dissolved in 50mL of hydrochloric acid (1 mol/L), and after mixing uniformly, a hydrochloric acid solution containing aniline was added to the bacterial cellulose dispersion. The whole system was reacted for 4h under ice-bath conditions. And (3) washing the reacted system with absolute ethyl alcohol and deionized water for 5 times respectively, pouring the slurry obtained after washing into a common beaker, recording the mass of the slurry, and adding deionized water to determine the mass of the whole system to be 15g so as to control the volume of the aerogel after freeze drying. And adding 80 mu L of 3-glycidylpropyltrimethoxysilane into the slurry after the water is added, stirring for 15 hours at a high speed by using a stirrer, and standing and aging for three days to obtain the pre-gel. And transferring the obtained pre-gel into a polytetrafluoroethylene beaker, and performing freeze drying treatment to obtain the final polyaniline and bacterial cellulose composite aerogel. As shown in fig. 1, wherein fig. 1 (a) is a scanning electron microscope result under a resolution condition of 400 μm, fig. 1 (b) is a scanning electron microscope result under a resolution condition of 100 μm, and fig. 1 (c) is a scanning electron microscope result under a resolution condition of 500nm, the obtained conductive polymer and bacterial cellulose composite aerogel has a staggered lamellar structure under a low resolution condition (see fig. 1 (a) and fig. 1 (b)), and the staggered pore structure formed by stacking the bacterial cellulose fibers can be clearly seen under a high resolution condition (see fig. 1 (c)). Wherein, the polyaniline exists in the bacterial cellulose in the form of insertion or adsorption coating.
Example 2
Weighing 20g of bacterial cellulose dispersion, adding into 10mL of carbon tetrachloride, and stirring at high speed for 20min; weighing 0.26g of aniline, adding the aniline into the mixed dispersion liquid, and stirring at a high speed for 20min; ammonium persulfate (0.326 g) was weighed, dissolved in 50mL of hydrochloric acid (1 mol/L), and after uniformly mixing, added to the dispersion containing bacterial cellulose and aniline. The whole system was reacted for 2h under ice-bath conditions. Washing the reacted system with absolute ethyl alcohol and deionized water for 5 times respectively, pouring the slurry obtained after washing into a common beaker, recording the mass of the slurry, and then adding deionized water to determine the mass of the whole system to be 15g so as to control the volume of the aerogel after freeze drying. Adding 50 μ L of gamma- (2,3-glycidoxy) propyl trimethoxy silane into the slurry after adding water, stirring at high speed for 12h by adopting a stirrer, and standing and aging for three days to obtain the pre-gel. And transferring the obtained pre-gel into a polytetrafluoroethylene beaker, and performing freeze drying treatment to obtain the final polyaniline and bacterial cellulose aerogel PB2-1.
Example 3
Weighing 20g of bacterial cellulose dispersion, adding the bacterial cellulose dispersion into 10mL of carbon tetrachloride, and stirring at a high speed for 20min; weighing 0.13g of aniline, adding the aniline into the mixed dispersion liquid, and stirring at a high speed for 20min; ammonium persulfate (0.163 g) was weighed, dissolved in 50mL of hydrochloric acid (1 mol/L), and added to the dispersion containing bacterial cellulose and aniline after mixing uniformly. The whole system was reacted for 2h under ice-bath conditions. And (3) washing the reacted system with absolute ethyl alcohol and deionized water for 5 times respectively, pouring the slurry obtained after washing into a common beaker, recording the mass of the slurry, and adding deionized water to determine the mass of the whole system to be 15g so as to control the volume of the aerogel after freeze drying. Adding 50 μ L of gamma- (2,3-glycidoxy) propyl trimethoxy silane into the slurry after adding water, stirring at high speed for 12h by adopting a stirrer, and standing and aging for three days to obtain the pre-gel. And transferring the obtained pre-gel into a polytetrafluoroethylene beaker, and performing freeze drying treatment to obtain the final polyaniline and bacterial cellulose aerogel PB1-1.
Example 4
Weighing 20g of bacterial cellulose dispersion, adding the bacterial cellulose dispersion into 10mL of carbon tetrachloride, and stirring at a high speed for 20min; weighing 0.065g of aniline, adding into the mixed dispersion liquid, and stirring at a high speed for 20min; 0.0815g ammonium persulfate was weighed, dissolved in 50mL hydrochloric acid (1 mol/L), mixed well, and added to the above dispersion containing bacterial cellulose and aniline. The whole system was reacted for 2h under ice-bath conditions. And (3) washing the reacted system with absolute ethyl alcohol and deionized water for 5 times respectively, pouring the slurry obtained after washing into a common beaker, recording the mass of the slurry, and adding deionized water to determine the mass of the whole system to be 15g so as to control the volume of the aerogel after freeze drying. Adding 50 μ L of gamma- (2,3-glycidoxy) propyl trimethoxy silane into the slurry after adding water, stirring at high speed for 12h by adopting a stirrer, and standing and aging for three days to obtain the pre-gel. And transferring the obtained pre-gel into a polytetrafluoroethylene beaker, and performing freeze drying treatment to obtain the final polyaniline and bacterial cellulose aerogel PB1-2.
Example 5
Weighing 20g of bacterial cellulose dispersion, adding the bacterial cellulose dispersion into 10mL of carbon tetrachloride, stirring at a high speed for 20min, weighing 0.52 parts of aniline, adding the aniline into the mixed dispersion, and stirring at a high speed for 20min; ammonium persulfate (0.652 mL) was weighed, 50mL of hydrochloric acid (1 mol/L) was added thereto, and after uniform mixing, the mixture was stirred for 2 hours under ice bath conditions. Washing the stirred system with absolute ethyl alcohol and deionized water for 5 times respectively, pouring the slurry obtained after washing into a common beaker, recording the mass of the slurry, and then adding deionized water to determine the mass of the whole system to be 15g so as to control the volume of the aerogel after freeze drying. Adding 50 μ L of gamma- (2,3-glycidoxy) propyl trimethoxy silane into the slurry after adding water, stirring at high speed for 12h by adopting a stirrer, and standing and aging for three days to obtain the pre-gel. And transferring the obtained pre-gel into a polytetrafluoroethylene beaker, and performing freeze drying treatment to obtain the final polyaniline and bacterial cellulose aerogel BC.
Example 6
The gel sample pieces prepared in examples 2 to 5 were subjected to a compression performance test in an Instron universal tester, with a compression rate of 2mm/min. And after the test is finished, corresponding compression load-displacement data is derived, and is converted into a compression stress-strain curve by using a formula. The formula for converting displacement data to compressive strain data in a compression test is:
wherein epsilon c Represents compressive strain,. L c Representing the displacement of the sample block compression, and h represents the original thickness of the sample block.
The formula for converting the compressive load to compressive stress data is:
wherein σ c Represents a compressive stress, F c Representing the compression load, S represents the base area of the cylinder block,
the specific test result is shown in fig. 2, with the increase of polyaniline, the compression performance of polyaniline and the bacterial cellulose aerogel is increased, wherein the compression performance of PB2-1 is optimal. The reason is that certain hydrogen bond interaction exists in the process of compounding polyaniline and bacterial cellulose, and the hydrogen bond interaction is increased along with the increase of the dosage of polyaniline. Meanwhile, the bacterial cellulose has strong intermolecular hydrogen bond interaction. When the gel is subjected to pressure, the gel network can take on more energy dissipation and thus the compression performance is increased.
Example 7
The aerogel blocks prepared in example 1 were selected and tested for compression sensitivity in an Instron universal tester set at a compression speed of 5mm/min. Simultaneously, a multimeter is used for recording the change delta R/R of the relative resistance value in the compression process 0 . Wherein R is 0 Representing the original resistance of the gel before testing, and Δ R represents the difference between the resistance after compression for a certain strain and the original resistance. During the compression process, the volume of the aerogel is gradually reduced along with the increase of the pressure, the conductive path formed by the polyaniline is more dense, and the resistance is gradually reduced. Therefore, the process of converting the deformation signal of the gel volume into the electric signal can be realized in the compression process.
After the test is finished, corresponding compressed data and resistance value data are exported and converted into a relative resistance value change-pressure curve by using a formula. The specific test result is shown in fig. 3, it can be seen that the relative resistance change rate (Δ R/R0)/P increases with the increase of the pressure, and when the pressure is 0-0.8 kPa, the maximum relative resistance change rate is-350.5 kPa-1, which indicates that the polyaniline and the bacterial cellulose aerogel have excellent compression sensitivity.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A composite aerogel, characterized in that the composite aerogel comprises at least: conductive polymer, bacterial cellulose and water-immiscible organic solvent.
2. The composite aerogel according to claim 1,
the composite aerogel has a three-dimensional network structure formed by interlacing filamentous fibers of bacterial cellulose;
the conductive polymer is attached to the surface of the filamentous fibers in the form of particles.
3. The composite aerogel according to claim 1,
the conductive polymer is selected from at least one of polyaniline and polypyrrole.
4. The composite aerogel according to claim 1,
the mass ratio of the conductive polymer to the bacterial cellulose is as follows: 0.1-5:1;
the mass ratio of the bacterial cellulose to the water-immiscible organic solvent is as follows: 0.01 to 1.
5. A method for preparing a composite aerogel according to any of claims 1 to 4, characterized in that it comprises at least;
(1) Adding a cross-linking agent and an initiator into a mixture I containing the monomer of the conductive polymer, bacterial cellulose and an organic solvent which is not mutually soluble with water for cross-linking reaction to obtain pre-gel;
(2) And carrying out freeze-drying treatment on the pre-gel to obtain the composite aerogel.
6. The method of claim 5,
the organic solvent immiscible with water is at least one of carbon tetrachloride, dichloromethane and toluene.
7. The method of claim 5,
the temperature of the crosslinking reaction is-10 to 4 ℃;
the crosslinking reaction time is 0.5-24 h.
8. The method of claim 5,
the cross-linking agent is at least one selected from gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane and gamma- (2,3-glycidoxy) propyltrimethoxysilane;
the dosage of the cross-linking agent is 0.3-8% of that of the bacterial cellulose.
9. The method of claim 5,
the initiator is at least one of ammonium persulfate, potassium persulfate and azobisisobutyronitrile;
the using amount of the initiator is 50-200% of the mass of the conductive polymer monomer in the step (1);
preferably, the initiator is added into a hydrochloric acid aqueous solution, and a mixture A is obtained by mixing;
preferably, the concentration of the hydrochloric acid aqueous solution is 0.1-3 mmol/L;
preferably, the mixing temperature for obtaining the mixture A is-10 to 4 ℃.
10. The method of claim 5, wherein the step (1) of obtaining the mixture I comprises:
dispersing the bacterial cellulose dispersion liquid into an organic solvent immiscible with water, and mixing to obtain emulsion A;
adding monomers of the conductive polymer into the emulsion A to form a mixture I;
preferably, the mixing temperature for obtaining the emulsion A is-10 to 4 ℃;
preferably, the mixing temperature to obtain the mixture I is-10 to 4 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110361846.8A CN115181335A (en) | 2021-04-02 | 2021-04-02 | Conductive polymer and bacterial cellulose composite aerogel and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110361846.8A CN115181335A (en) | 2021-04-02 | 2021-04-02 | Conductive polymer and bacterial cellulose composite aerogel and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115181335A true CN115181335A (en) | 2022-10-14 |
Family
ID=83511701
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110361846.8A Pending CN115181335A (en) | 2021-04-02 | 2021-04-02 | Conductive polymer and bacterial cellulose composite aerogel and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115181335A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107868161A (en) * | 2017-12-07 | 2018-04-03 | 张振 | A kind of preparation method of polymeric hollow microcapsules and its application |
| CN108467509A (en) * | 2018-03-10 | 2018-08-31 | 浙江理工大学 | A kind of preparation method for the Cellulose nanocrystal/layer/polyaniline conductive flexibility aeroge having both capacitance and sensing function |
| CN111440351A (en) * | 2020-03-13 | 2020-07-24 | 辽宁大学 | 3D supermolecule self-assembly conductive biomass aerogel, preparation method thereof and application thereof in super capacitor |
| CN112321887A (en) * | 2020-09-29 | 2021-02-05 | 浙江理工大学 | Preparation method of mechanical flexible cellulose aerogel with gradient change of wettability |
| CN112430349A (en) * | 2020-11-30 | 2021-03-02 | 桂林理工大学 | Preparation method of photothermal conversion porous material and product thereof |
-
2021
- 2021-04-02 CN CN202110361846.8A patent/CN115181335A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107868161A (en) * | 2017-12-07 | 2018-04-03 | 张振 | A kind of preparation method of polymeric hollow microcapsules and its application |
| CN108467509A (en) * | 2018-03-10 | 2018-08-31 | 浙江理工大学 | A kind of preparation method for the Cellulose nanocrystal/layer/polyaniline conductive flexibility aeroge having both capacitance and sensing function |
| CN111440351A (en) * | 2020-03-13 | 2020-07-24 | 辽宁大学 | 3D supermolecule self-assembly conductive biomass aerogel, preparation method thereof and application thereof in super capacitor |
| CN112321887A (en) * | 2020-09-29 | 2021-02-05 | 浙江理工大学 | Preparation method of mechanical flexible cellulose aerogel with gradient change of wettability |
| CN112430349A (en) * | 2020-11-30 | 2021-03-02 | 桂林理工大学 | Preparation method of photothermal conversion porous material and product thereof |
Non-Patent Citations (12)
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102212210B (en) | Method for preparing polyaniline-coated bacteria cellulose nano conductive composite by in-situ polymerization | |
| Li et al. | Flexible conductive hydrogel fabricated with polyvinyl alcohol, carboxymethyl chitosan, cellulose nanofibrils, and lignin-based carbon applied as strain and pressure sensor | |
| CN107618243B (en) | A kind of polymer modification graphene/Kynoar high-dielectric composite material and preparation method thereof | |
| CN101955631B (en) | Preparation method of polyaniline modified multi-wall carbon canotube/epoxy resin composite material | |
| CN108641099B (en) | Cellulose-based temperature-sensitive conductive hydrogel and preparation method and application thereof | |
| CN105355450A (en) | Preparation method and application of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacterial cellulose membrane material | |
| CN105199134A (en) | Polyaniline-modified graphene conductive composite film and preparation method thereof | |
| CN110808175A (en) | Electroactive biomass/polypyrrole hydrogel and preparation method and application thereof | |
| CN111636239A (en) | Preparation method of polyimide fibrid electromagnetic shielding paper | |
| CN108755126B (en) | Method for modifying surface treated carbon fiber by electrochemical polymerization and carbon fiber composite material | |
| CN112662203A (en) | Modified silicon dioxide filler, preparation method thereof and resin composition | |
| Annapurna et al. | Microbial extracellular polysaccharide-based membrane in polymer electrolyte fuel cells | |
| CN114773756B (en) | Thermo-mechanical stable supermolecular elastomer material and preparation method thereof | |
| CN114561010B (en) | Self-emulsifying nonionic aqueous polyamide imide and preparation method thereof, carbon fiber sizing agent and preparation method and application thereof | |
| CN112250890A (en) | Method for preparing chitosan/aramid nanofiber composite hydrogel by standing method | |
| CN116162318A (en) | Polyvinyl alcohol/modified glass fiber composite material and preparation method thereof | |
| CN103554909B (en) | Carbon nano tube compound material, its preparation method, prepreg and copper-clad base plate that polymer-silica is coated | |
| CN108264765B (en) | Preparation method of toughened heat-conducting insulating cyanate resin-based composite material | |
| CN113801379A (en) | Bacterial cellulose/boron nitride composite high-thermal-conductivity flexible film material and preparation method thereof | |
| CN115181335A (en) | Conductive polymer and bacterial cellulose composite aerogel and preparation method thereof | |
| CN106674558B (en) | A kind of preparation method of polyaniline/acetylbutyrylcellulose conducing composite material | |
| CN109575595A (en) | A kind of preparation method of polyetherimide/barium titanate/graphene dielectric composite material | |
| CN117534870A (en) | Preparation method and application of full biomass-based benzoxazine modified cellulose aerogel | |
| CN110627968B (en) | Aqueous organic montmorillonite modifier emulsion, preparation method and application thereof | |
| CN108910861B (en) | Preparation method of aromatic heterocyclic fiber-based carbon nanofiber aerogel material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20221014 |