CN111978576B - Preparation method of degradable conductive composite film - Google Patents
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Abstract
The invention aims to provide a preparation method of a degradable conductive composite film, which mainly comprises the following steps: cleaning the recovered sea squirt tunic, soaking in alkaline solution for a period of time, cleaning with water to neutrality, and treating with glacial acetic acid and sodium hypochlorite to obtain sea squirt cellulose; adding sea squirt cellulose into a proper amount of distilled water, sequentially adding a proper amount of sodium bromide and 2,2,6, 6-tetramethylpiperidine-1-oxide (TEMPO), ultrasonically stirring, adding sodium hypochlorite and sodium hydroxide, reacting for a period of time to obtain a precipitate, and finally obtaining sea squirt cellulose nanocrystalline; adding the obtained sea squirt cellulose nanocrystalline, polyvinyl alcohol (PVA) and graphene into a container filled with distilled water, then adding a cross-linking agent, reacting for a period of time, and obtaining the degradable conductive composite material film by adopting a tape casting film-forming method.
Description
Technical Field
The invention belongs to the field of preparation of conductive film materials, and particularly relates to a preparation method of a degradable conductive composite material film.
Background
In recent years, flexible conductive materials have attracted research interest. The conductive medium for preparing the flexible conductive material mainly comprises: metal oxide semiconductors, polymeric conductors (e.g., polyaniline, polythiophene, polyacetylene), carbon nanotubes, graphene oxide, metal nanowires, and the like. Cellulose is a natural high molecular polymer which is rich in storage in nature, widely exists in cell membranes of plants (cotton, sisal, wood and the like), tunicates (sea squirts and the like) and fungi, and has the advantages of good thermal expansion coefficient, mechanical property, corrosion resistance and the like. Compared with the traditional flexible substrate, the cellulose has a natural porous structure, and the surface of the cellulose contains a plurality of functional groups, so that convenience is provided for the rapid transfer of substances and electrons. The cellulose nanocrystal is a nanometer high molecular polymer prepared by acid hydrolysis of natural cellulose, has higher crystallinity, larger specific surface area and higher modulus compared with cellulose, and is expected to replace the traditional electronic equipment substrate to be used for preparing flexible conductive materials.
The polymer conductive film is a conductive polymer material formed by chemical synthesis or electrochemical oxidation of a polymer having a conjugated pi bond, and the conductivity thereof can be extended from an insulator to a conductor. The typical representatives of the compound mainly comprise polyacetylene, polyaniline, polypyrrole, polythiophene and various derivatives thereof. Polyacetylene is the earliest discovered polymer with conductivity, the development of the polyacetylene is limited due to poor stability of the polyacetylene, and then conductive high molecular polymers such as polypyrrole, polyaniline, polythiophene and the like, amine and polythiophene and the like are sequentially obtained. The metal-clad copper-clad aluminum alloy can be widely applied to novel batteries, micro sensors, optical devices, semiconductor devices, invisible materials, conductive films, circuit board hole metallization and the like. The structure of polypyrrole is a conjugated structure in which carbon-carbon single bonds and carbon-carbon double bonds are alternately distributed. The carbon-carbon double bond consists of sigma electrons and pi electrons, and the sigma electrons are fixed and cannot move freely, so that covalent bonds are formed between carbon atoms. Two pi electrons in the conjugated double bond are not always on a certain carbon atom, and can move between carbon-carbon bonds, namely can spread on the whole molecular chain. This means that the overlap of pi electron clouds within a molecule creates an energy band common to the whole molecule, much like a free electron in a metal conductor. When an electric field is generated, electrons constituting pi bonds can rapidly move on the molecular chain.
The sea squirt cellulose nanocrystalline extracted from tunicate sea squirts has high crystallinity, specific surface area, excellent mechanical and corrosion resistance, and is widely applied to the fields of batteries, capacitors and other functional materials. Further, since the aspect ratio of cellulose nanocrystals extracted from ascidians is significantly higher than that of plant cellulose nanocrystals, films can be formed at room temperature at low concentrations. The sea squirt resources in China are extremely rich, the utilization of the sea squirt is limited to extracting the medicine from the internal organs of the sea squirt, and the sea squirt tunic is discarded as the waste at will. Therefore, the development and utilization of the cellulose in the sea squirt tunic have important significance for reducing environmental pollution and increasing economic benefits.
Disclosure of Invention
The invention aims to provide a preparation method of a conductive degradable composite material film, which comprises the following specific technical scheme:
cleaning the recovered sea squirt tunic, soaking in alkaline solution for a period of time, cleaning with water to neutrality, and treating with glacial acetic acid and sodium hypochlorite to obtain sea squirt cellulose; adding sea squirt cellulose into a proper amount of distilled water, sequentially adding a proper amount of sodium bromide and 2,2,6, 6-tetramethylpiperidine-1-oxide (TEMPO), ultrasonically stirring, adding sodium hypochlorite and sodium hydroxide, reacting for a period of time to obtain a precipitate, and finally obtaining sea squirt cellulose nanocrystalline; adding the obtained sea squirt cellulose nanocrystalline, polyvinyl alcohol (PVA) and graphene into a container filled with distilled water, then adding a cross-linking agent, reacting for a period of time, and obtaining the degradable conductive composite material film by adopting a tape casting film-forming method.
Preferably, the alkaline solution for soaking the sea squirt tunic is potassium hydroxide solution.
Preferably, the crosslinking agent is sodium citrate monohydrate.
The preparation method comprises the following steps:
s1: cleaning the sea squirt tunic part, then putting the sea squirt tunic part into a KOH solution with the mass fraction of 6-12 wt% for soaking for 10-20 h, then taking out the sea squirt tunic part for washing with clear water until the tunic part is neutral, then adding glacial acetic acid and sodium hypochlorite with the volume ratio of 1: 1.5-2, adding 500mL of distilled water, stirring and reacting for 8h at the temperature of 60 ℃, taking out the tunic part when the tunic part is white, washing the tunic part again to be neutral with distilled water, and then putting the tunic part into an oven for drying for 12h at the temperature of 50 ℃ to obtain sea squirt cellulose.
S2: adding the ecteinascidin obtained in the step S2 into a beaker, adding distilled water, stirring and ultrasonically treating, wherein the weight ratio of the ecteinascidin to the distilled water is 1: 3-4.5, then adding sodium bromide and 2,2,6, 6-tetramethylpiperidine-1-oxide (TEMPO) and stirring, wherein the mass ratio of the sodium bromide to the 2,2,6, 6-tetramethylpiperidine-1-oxide is 1: 0.06-0.19, then slowly dropwise adding 20g of sodium hypochlorite solution, stirring and reacting for 20min, controlling the pH value to be 10 by using 12 wt% of sodium hydroxide solution in the process, finally adding 5mL of ethanol, reacting for 5min, then stopping water washing, centrifuging, adding hydrochloric acid into the precipitate, stirring and reacting for 40min, filtering, and washing to obtain the acidified ecteinascidin nanocrystalline.
S3: adding graphene into a container filled with distilled water, performing ultrasonic stirring for 45min to fully disperse the graphene, adding polyvinyl alcohol (PVA), continuing to perform ultrasonic stirring for 30min, adding the sea squirt cellulose nanocrystal obtained in the step S2 into the container, raising the temperature to 60-90 ℃, performing ultrasonic stirring for 20min, adding sodium citrate, stirring at the temperature for 30min, then bringing the temperature to 40-50 ℃, and performing vacuum degassing to obtain a film forming solution, wherein the mass ratio of the graphene to the PVA to the sea squirt cellulose nanocrystal to the sodium citrate is 1: 2-4: 35-60: 0.75-2.
S4: and (4) uniformly pouring the film forming solution obtained in the step S3 into a glass dish by using a tape casting film forming method, drying at 60 ℃ for 2 hours, then putting into an oven at 105-130 ℃, and reacting for 10 hours to obtain the degradable conductive composite film.
Preferably, in step S2, the mass ratio of the sodium bromide to the 2,2,6, 6-tetramethylpiperidine-1-oxide (TEMPO) is 1: 0.06-0.12.
Preferably, in the step S3, the mass ratio of the graphene, the PVA, the ascidian cellulose nanocrystals and the sodium citrate is 1: 2-3: 35-50: 0.75-1.3.
The invention has the following beneficial effects:
(1) the matrix material adopted in the invention is acidified sea squirt cellulose nanocrystalline, the surface of which has carboxyl (-COOH) groups, and the matrix material can generate stronger interface interaction when being compounded with substances such as PVA, graphene and the like, thereby improving the stress transfer between the matrix material and additives, and greatly improving the performance of the composite material.
(2) The matrix material adopted in the invention is acidified sea squirt cellulose nanocrystalline, the sea squirt nano cellulose nanocrystalline belongs to animal source cellulose nanocrystalline, the molecular weight of the sea squirt nano cellulose nanocrystalline is 2-3 times of that of plant cellulose, the mechanical property of the conductive composite material film is effectively improved, meanwhile, the sea squirt cellulose nanocrystalline is used as a flexible substrate material, compared with the traditional flexible substrate, the sea squirt cellulose nanocrystalline has a natural porous structure, the surface of the sea squirt cellulose nanocrystalline contains multiple functional groups, the sea squirt tunic is convenient to rapidly transfer substances and electrons, the application of the sea squirt tunic is expanded, and the problem that a large amount of sea squirt tunic is discarded to pollute the environment can be effectively solved.
(3) The polyvinyl alcohol (PVA) and ascidian cellulose nanocrystals adopted by the invention contain a large amount of carboxyl and hydroxyl groups, have good hydrophilicity, can be distributed in aqueous solution, do not use toxic organic solvents in the preparation process, and are beneficial to environmental protection.
(4) The polyvinyl alcohol used in the invention is an environment-friendly and degradable high polymer material, and after the conductive composite material film prepared by using the material is used, the material can be effectively recycled for degradation treatment, so that the environmental pollution caused by incapability of degradation is avoided.
(5) The conductive composite material film prepared by the invention is added with graphene, and hydroxyl and carboxyl on the surfaces of polyvinyl alcohol and sea squirt cellulose nanocrystalline can form a latticed paper composite with graphene sheets, so that the conductivity of the conductive composite material film is improved, and the mechanical property and flexibility of the conductive composite material film are improved.
Drawings
FIG. 1 is a TEM (1 μm) spectrum of a degradable conductive composite film prepared in example 6 of the present invention;
FIG. 2 is a TEM (500nm) spectrum of the degradable conductive composite film prepared in example 6 of the present invention;
FIG. 3 is a TG map of a degradable conductive composite film prepared in example 6 of the present invention;
FIG. 4 is an XPS map of a degradable conductive composite film prepared in example 6 of the present invention.
Detailed Description
The following describes embodiments of the present invention in detail, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are provided, but the scope of the present invention is not limited to the following embodiments.
Example 1
A preparation method of a conductive degradable composite film comprises the following steps:
s1: cleaning the sea squirt tunic part, then putting the sea squirt tunic part into a KOH solution with the mass fraction of 6 wt% for soaking for 10h, then taking out the sea squirt tunic part for washing with clear water until the tunic part is neutral, then adding glacial acetic acid and sodium hypochlorite with the volume ratio of 1:1.5, adding 500mL of distilled water, stirring and reacting for 8h at the temperature of 60 ℃, taking out the tunic part when the tunic part is white, washing the tunic part again to be neutral with distilled water, and then putting the tunic part into an oven for drying for 12h at the temperature of 50 ℃ to obtain sea squirt cellulose.
S2: adding the ascidian cellulose obtained in the step S2 into a beaker, adding distilled water, stirring and carrying out ultrasonic treatment, wherein the weight ratio of the ascidian cellulose to the distilled water is 1:3, then adding sodium bromide and 2,2,6, 6-tetramethylpiperidine-1-oxide (TEMPO) with the mass ratio of 1:0.06, stirring, then slowly dropwise adding 20g of sodium hypochlorite solution, stirring and reacting for 20min, controlling the pH value to be 10 by using 12 wt% of sodium hydroxide solution in the process, finally adding 5mL of ethanol, reacting for 5min, then stopping washing with water, centrifuging, adding hydrochloric acid into the precipitate, stirring and reacting for 40min, filtering, and washing to obtain the acidified ascidian cellulose nanocrystal.
S3: adding graphene into a container filled with distilled water, performing ultrasonic treatment and stirring for 45min to fully disperse the graphene, adding polyvinyl alcohol (PVA), continuing to perform ultrasonic stirring for 30min, adding the ascidian cellulose nanocrystals obtained in the step S2 into the container, heating to 60 ℃, performing ultrasonic stirring for 20min, adding sodium citrate, stirring at the temperature for 30min, then heating to 40 ℃, and performing vacuum degassing to obtain a film forming solution, wherein the mass ratio of the added graphene, the PVA, the ascidian cellulose nanocrystals to the sodium citrate is 1:2:35: 0.75.
S4: and (4) uniformly pouring the film forming solution obtained in the step S3 into a glass dish by using a tape casting film forming method, drying at 60 ℃ for 2 hours, and then putting into a 105 ℃ oven for reaction for 10 hours to obtain the degradable conductive composite film.
Example 2
A preparation method of a conductive degradable composite film comprises the following steps:
s1: cleaning the sea squirt tunic part, then putting the sea squirt tunic part into a KOH solution with the mass fraction of 12 wt% for soaking for 720h, then taking out the sea squirt tunic part for washing with clear water until the tunic part is neutral, then adding glacial acetic acid and sodium hypochlorite with the volume ratio of 1:2, adding 500mL of distilled water, stirring and reacting for 8h at the temperature of 60 ℃, taking out the tunic part when the tunic part is white, washing the tunic part again to be neutral with distilled water, and then putting the tunic part into an oven for drying for 12h at the temperature of 50 ℃ to obtain sea squirt cellulose.
S2: adding the ascidian cellulose obtained in the step S2 into a beaker, adding distilled water, stirring and carrying out ultrasonic treatment, wherein the weight ratio of the ascidian cellulose to the distilled water is 1:4.5, then adding sodium bromide and 2,2,6, 6-tetramethylpiperidine-1-oxide (TEMPO) with the mass ratio of 1:0.19, stirring, then slowly dropwise adding 20g of sodium hypochlorite solution, stirring and reacting for 20min, controlling the pH value to be 10 by using 12 wt% of sodium hydroxide solution in the process, finally adding 5mL of ethanol, reacting for 5min, then stopping washing with water, centrifuging, adding hydrochloric acid into the precipitate, stirring and reacting for 40min, filtering, and washing to obtain the acidified ascidian cellulose nanocrystal.
S3: adding graphene into a container filled with distilled water, performing ultrasonic treatment and stirring for 45min to fully disperse the graphene, adding polyvinyl alcohol (PVA), continuing to perform ultrasonic stirring for 30min, adding the ascidian cellulose nanocrystals obtained in the step S2 into the container, heating to 90 ℃, performing ultrasonic stirring for 20min, adding sodium citrate, stirring at the temperature for 30min, then heating to 50 ℃, and performing vacuum degassing to obtain a film forming solution, wherein the mass ratio of the added graphene, the PVA, the ascidian cellulose nanocrystals to the sodium citrate is 1:4:60: 2.
S4: and (4) uniformly pouring the film forming solution obtained in the step S3 into a glass dish by using a tape casting film forming method, drying at 60 ℃ for 2h, and then putting into a 130 ℃ oven for reaction for 10h to obtain the degradable conductive composite film.
Example 3
A preparation method of a conductive degradable composite film comprises the following steps:
s1: cleaning the sea squirt tunic part, then putting the sea squirt tunic part into a KOH solution with the mass fraction of 7 wt% for soaking for 12h, then taking out the sea squirt tunic part for washing with clear water until the tunic part is neutral, then adding glacial acetic acid and sodium hypochlorite with the volume ratio of 1:1.6, adding 500mL of distilled water, stirring and reacting for 8h at the temperature of 60 ℃, taking out the tunic part when the tunic part is white, washing the tunic part again to be neutral with distilled water, and then putting the tunic part into an oven for drying for 12h at the temperature of 43 ℃ to obtain sea squirt cellulose.
S2: adding the ascidian cellulose obtained in the step S2 into a beaker, adding distilled water, stirring and carrying out ultrasonic treatment, wherein the weight ratio of the ascidian cellulose to the distilled water is 1:3.3, then adding sodium bromide and 2,2,6, 6-tetramethylpiperidine-1-oxide (TEMPO) with the mass ratio of 1:0.08, stirring, then slowly dropwise adding 20g of sodium hypochlorite solution, stirring and reacting for 20min, controlling the pH value to be 10 by using 12 wt% of sodium hydroxide solution in the process, finally adding 5mL of ethanol, reacting for 5min, then stopping washing with water, centrifuging, adding hydrochloric acid into the precipitate, stirring and reacting for 40min, filtering, and washing to obtain the acidified ascidian cellulose nanocrystal.
S3: adding graphene into a container filled with distilled water, performing ultrasonic treatment and stirring for 45min to fully disperse the graphene, adding polyvinyl alcohol (PVA), continuing to perform ultrasonic stirring for 30min, adding the ascidian cellulose nanocrystals obtained in the step S2 into the container, heating the temperature to 70 ℃, performing ultrasonic stirring for 20min, adding sodium citrate, stirring at the temperature for 30min, then heating the temperature to 48 ℃, and performing vacuum degassing to obtain a film forming solution, wherein the mass ratio of the added graphene, the PVA, the ascidian cellulose nanocrystals to the sodium citrate is 1:2.2:38: 0.8.
S4: and (4) uniformly pouring the film forming solution obtained in the step S3 into a glass dish by using a tape casting film forming method, drying at 60 ℃ for 2h, and then putting into a 110 ℃ oven for reaction for 10h to obtain the degradable conductive composite film.
Example 4
A preparation method of a conductive degradable composite film comprises the following steps:
s1: cleaning the sea squirt tunic part, then putting the sea squirt tunic part into a KOH solution with the mass fraction of 8 wt% for soaking for 14h, then taking out the sea squirt tunic part for washing with clear water until the tunic part is neutral, then adding glacial acetic acid and sodium hypochlorite with the volume ratio of 1:1.7, adding 500mL of distilled water, stirring and reacting for 8h at the temperature of 60 ℃, taking out the tunic part when the tunic part is white, washing the tunic part again to be neutral with distilled water, and then putting the tunic part into an oven for drying for 12h at the temperature of 50 ℃ to obtain sea squirt cellulose.
S2: adding the ascidian cellulose obtained in the step S2 into a beaker, adding distilled water, stirring and carrying out ultrasonic treatment, wherein the weight ratio of the ascidian cellulose to the distilled water is 1:3.5, then adding sodium bromide and 2,2,6, 6-tetramethylpiperidine-1-oxide (TEMPO) with the mass ratio of 1:0.10, stirring, then slowly dropwise adding 20g of sodium hypochlorite solution, stirring and reacting for 20min, controlling the pH value to be 10 by using 12 wt% of sodium hydroxide solution in the process, finally adding 5mL of ethanol, reacting for 5min, then stopping washing with water, centrifuging, adding hydrochloric acid into the precipitate, stirring and reacting for 40min, filtering, and washing to obtain the acidified ascidian cellulose nanocrystal.
S3: adding graphene into a container filled with distilled water, performing ultrasonic treatment and stirring for 45min to fully disperse the graphene, adding polyvinyl alcohol (PVA), continuing to perform ultrasonic stirring for 30min, adding the ascidian cellulose nanocrystals obtained in the step S2 into the container, heating to 80 ℃, performing ultrasonic stirring for 20min, adding sodium citrate, stirring at the temperature for 30min, then heating to 50 ℃, and performing vacuum degassing to obtain a film forming solution, wherein the mass ratio of the added graphene, the PVA, the ascidian cellulose nanocrystals to the sodium citrate is 1:2.5:40: 0.9.
S4: and (4) uniformly pouring the film forming solution obtained in the step S3 into a glass dish by using a tape casting film forming method, drying at 60 ℃ for 2h, and then putting into a 115 ℃ oven for reaction for 10h to obtain the degradable conductive composite film.
Example 5
A preparation method of a conductive degradable composite film comprises the following steps:
s1: cleaning the sea squirt tunic part, then putting the sea squirt tunic part into a KOH solution with the mass fraction of 9 wt% for soaking for 16h, then taking out the sea squirt tunic part for washing with clear water until the tunic part is neutral, then adding glacial acetic acid and sodium hypochlorite with the volume ratio of 1:1.8, adding 500mL of distilled water, stirring and reacting for 8h at the temperature of 60 ℃, taking out the tunic part when the tunic part is white, washing the tunic part again to be neutral with distilled water, and then putting the tunic part into an oven for drying for 12h at the temperature of 50 ℃ to obtain sea squirt cellulose.
S2: adding the ascidian cellulose obtained in the step S2 into a beaker, adding distilled water, stirring and carrying out ultrasonic treatment, wherein the weight ratio of the ascidian cellulose to the distilled water is 1:4, then adding sodium bromide and 2,2,6, 6-tetramethylpiperidine-1-oxide (TEMPO) with the mass ratio of 1:0.11, stirring, then slowly dropwise adding 20g of sodium hypochlorite solution, stirring and reacting for 20min, controlling the pH value to be 10 by using 12 wt% of sodium hydroxide solution in the process, finally adding 5mL of ethanol, reacting for 5min, then stopping washing with water, centrifuging, adding hydrochloric acid into the precipitate, stirring and reacting for 40min, filtering, and washing to obtain the acidified ascidian cellulose nanocrystal.
S3: adding graphene into a container filled with distilled water, performing ultrasonic treatment and stirring for 45min to fully disperse the graphene, adding polyvinyl alcohol (PVA), continuing to perform ultrasonic stirring for 30min, adding the ascidian cellulose nanocrystals obtained in the step S2 into the container, raising the temperature to 75 ℃, performing ultrasonic stirring for 20min, adding sodium citrate, stirring at the temperature for 30min, then raising the temperature to 50 ℃, and performing vacuum degassing to obtain a film forming solution, wherein the mass ratio of the added graphene, the PVA, the ascidian cellulose nanocrystals to the sodium citrate is 1:3:45: 1.
S4: and (4) uniformly pouring the film forming solution obtained in the step S3 into a glass dish by using a tape casting film forming method, drying at 60 ℃ for 2h, and then putting into a 120 ℃ oven for reaction for 10h to obtain the degradable conductive composite film.
Example 6
A preparation method of a conductive degradable composite film comprises the following steps:
s1: cleaning the sea squirt tunic part, then putting the sea squirt tunic part into a KOH solution with the mass fraction of 10 wt% for soaking for 18h, then taking out the sea squirt tunic part, washing the sea squirt tunic part by using clean water until the tunic part is neutral, then adding glacial acetic acid and sodium hypochlorite with the volume ratio of 1:1.9, adding 500mL of distilled water, stirring and reacting for 8h at the temperature of 60 ℃, taking out the tunic part when the tunic part is white, washing the tunic part by using distilled water again until the tunic part is neutral, and then putting the tunic part into an oven to dry for 12h at the temperature of 50 ℃ to obtain the.
S2: adding the ascidian cellulose obtained in the step S2 into a beaker, adding distilled water, stirring and carrying out ultrasonic treatment, wherein the weight ratio of the ascidian cellulose to the distilled water is 1:4.3, then adding sodium bromide and 2,2,6, 6-tetramethylpiperidine-1-oxide (TEMPO) with the mass ratio of 1:0.13, stirring, then slowly dropwise adding 20g of sodium hypochlorite solution, stirring and reacting for 20min, controlling the pH value to be 10 by using 12 wt% of sodium hydroxide solution in the process, finally adding 5mL of ethanol, reacting for 5min, then stopping washing with water, centrifuging, adding hydrochloric acid into the precipitate, stirring and reacting for 40min, filtering, and washing to obtain the acidified ascidian cellulose nanocrystal.
S3: adding graphene into a container filled with distilled water, performing ultrasonic treatment and stirring for 45min to fully disperse the graphene, adding polyvinyl alcohol (PVA), continuing to perform ultrasonic stirring for 30min, adding the ascidian cellulose nanocrystals obtained in the step S2 into the container, heating to 80 ℃, performing ultrasonic stirring for 20min, adding sodium citrate, stirring at the temperature for 30min, then heating to 50 ℃, and performing vacuum degassing to obtain a film forming solution, wherein the mass ratio of the added graphene, the PVA, the ascidian cellulose nanocrystals to the sodium citrate is 1:3.2:50: 1.2.
S4: and (4) uniformly pouring the film forming solution obtained in the step S3 into a glass dish by using a tape casting film forming method, drying at 60 ℃ for 2h, and then putting into a 125 ℃ oven for reaction for 10h to obtain the degradable conductive composite film.
Example 7
A preparation method of a conductive degradable composite film comprises the following steps:
s1: cleaning the sea squirt tunic part, then putting the sea squirt tunic part into a KOH solution with the mass fraction of 12 wt% for soaking for 10h, then taking out the sea squirt tunic part for washing with clear water until the tunic part is neutral, then adding glacial acetic acid and sodium hypochlorite with the volume ratio of 1:1.8, adding 500mL of distilled water, stirring and reacting for 8h at the temperature of 60 ℃, taking out the tunic part when the tunic part is white, washing the tunic part again to be neutral with distilled water, and then putting the tunic part into an oven for drying for 12h at the temperature of 50 ℃ to obtain sea squirt cellulose.
S2: adding the ascidian cellulose obtained in the step S2 into a beaker, adding distilled water, stirring and carrying out ultrasonic treatment, wherein the weight ratio of the ascidian cellulose to the distilled water is 1:3.8, then adding sodium bromide and 2,2,6, 6-tetramethylpiperidine-1-oxide (TEMPO) with the mass ratio of 1:0.11, stirring, then slowly dropwise adding 20g of sodium hypochlorite solution, stirring and reacting for 20min, controlling the pH value to be 10 by using 12 wt% of sodium hydroxide solution in the process, finally adding 5mL of ethanol, reacting for 5min, then stopping washing with water, centrifuging, adding hydrochloric acid into the precipitate, stirring and reacting for 40min, filtering, and washing to obtain the acidified ascidian cellulose nanocrystal.
S3: adding graphene into a container filled with distilled water, performing ultrasonic treatment and stirring for 45min to fully disperse the graphene, adding polyvinyl alcohol (PVA), continuing to perform ultrasonic stirring for 30min, adding the ascidian cellulose nanocrystals obtained in the step S2 into the container, heating to 90 ℃, performing ultrasonic stirring for 20min, adding sodium citrate, stirring at the temperature for 30min, then heating to 50 ℃, and performing vacuum degassing to obtain a film-forming solution, wherein the mass ratio of the added graphene, the PVA, the ascidian cellulose nanocrystals to the sodium citrate is 1:3.5:53: 1.5.
S4: and (4) uniformly pouring the film forming solution obtained in the step S3 into a glass dish by using a tape casting film forming method, drying at 60 ℃ for 2h, and then putting into a 120 ℃ oven for reaction for 10h to obtain the degradable conductive composite film.
Example 8
A preparation method of a conductive degradable composite film comprises the following steps:
s1: cleaning the sea squirt tunic part, then putting the sea squirt tunic part into a KOH solution with the mass fraction of 12 wt% for soaking for 15h, then taking out the sea squirt tunic part for washing with clear water until the tunic part is neutral, then adding glacial acetic acid and sodium hypochlorite with the volume ratio of 1:1.8, adding 500mL of distilled water, stirring and reacting for 8h at the temperature of 60 ℃, taking out the tunic part when the tunic part is white, washing the tunic part again to be neutral with distilled water, and then putting the tunic part into an oven for drying for 12h at the temperature of 50 ℃ to obtain sea squirt cellulose.
S2: adding the ascidian cellulose obtained in the step S2 into a beaker, adding distilled water, stirring and carrying out ultrasonic treatment, wherein the weight ratio of the ascidian cellulose to the distilled water is 1:4.5, then adding sodium bromide and 2,2,6, 6-tetramethylpiperidine-1-oxide (TEMPO) with the mass ratio of 1:0.12, stirring, then slowly dropwise adding 20g of sodium hypochlorite solution, stirring and reacting for 20min, controlling the pH value to be 10 by using 12 wt% of sodium hydroxide solution in the process, finally adding 5mL of ethanol, reacting for 5min, then stopping washing with water, centrifuging, adding hydrochloric acid into the precipitate, stirring and reacting for 40min, filtering, and washing to obtain the acidified ascidian cellulose nanocrystal.
S3: adding graphene into a container filled with distilled water, performing ultrasonic treatment and stirring for 45min to fully disperse the graphene, adding polyvinyl alcohol (PVA), continuing to perform ultrasonic stirring for 30min, adding the ascidian cellulose nanocrystals obtained in the step S2 into the container, heating to 90 ℃, performing ultrasonic stirring for 20min, adding sodium citrate, stirring at the temperature for 30min, then heating to 50 ℃, and performing vacuum degassing to obtain a film-forming solution, wherein the mass ratio of the added graphene, the PVA, the ascidian cellulose nanocrystals to the sodium citrate is 1:3.8:58: 1.8.
S4: and (4) uniformly pouring the film forming solution obtained in the step S3 into a glass dish by using a tape casting film forming method, drying at 60 ℃ for 2h, and then putting into a 130 ℃ oven for reaction for 10h to obtain the degradable conductive composite film.
Example 9
And (3) performance testing:
the degradable conductive composite film prepared in the example 6 is tested by TEM at 1 μm and 500nm, and the morphology is observed, as shown in the attached figures 1 and 2; the degradable conductive composite film prepared in the example 6 is subjected to thermogravimetry and XPS tests, the thermal stability and the element components of the film are observed, the thermal stability of the film can reach more than 300 ℃, and the film is proved to have better thermal stability.
In particular, the composite films prepared in the remaining examples had the same thermal stability and element composition as those of the present example.
The degradable conductive composite material films prepared in the embodiments 1 to 8 are respectively subjected to mechanical property and conductivity tests, wherein the mechanical property tests are as follows: the dried composite material was cut into a dumbbell-shaped specimen having a length of 35mm and a width of 10mm at room temperature, and the tensile strength, Young's modulus and elongation at break were measured in a universal mechanical testing machine, and as a result, as shown in Table 1, the tensile strength was 70MPa or more, the elongation at break was 4.6% or more, and the Young's modulus was 7.1GPa or more, indicating that the film was excellent in comprehensive mechanical properties.
And (3) volume resistivity measurement: cutting the material into a circular sample with the radius of 1cm under the room temperature environment, placing the circular sample on a test bench, slowly adjusting the circular disk to slightly contact the sample, repeating the measurement for 3 times, and taking an average value, wherein the volume resistivity of the composite material film is 7.1 x 10 as shown in the table 15The above shows that the composite material film has better conductivity.
TABLE 1 measurement results
Claims (3)
1. A method for preparing a degradable conductive composite film, comprising the steps of:
s1: cleaning the sea squirt tunic part, then putting the sea squirt tunic part into a KOH solution with the mass fraction of 6-12 wt% for soaking for 10-20 h, then taking out the sea squirt tunic part for washing with clear water until the tunic part is neutral, then adding glacial acetic acid and sodium hypochlorite with the volume ratio of 1: 1.5-2, adding 500mL of distilled water, stirring and reacting for 8h at the temperature of 60 ℃, taking out the tunic part when the tunic part is white, washing the tunic part again to be neutral with distilled water, and then putting the tunic part into an oven for drying for 12h at the temperature of 50 ℃ to obtain sea squirt cellulose;
s2: adding the ecteinascidin obtained in step S2 into a beaker, adding distilled water, stirring and ultrasonically treating, wherein the weight ratio of the ecteinascidin to the distilled water is 1: 3-4.5, then adding sodium bromide and 2,2,6, 6-tetramethylpiperidine-1-oxide (TEMPO) and stirring, wherein the mass ratio of the sodium bromide to the 2,2,6, 6-tetramethylpiperidine-1-oxide is 1: 0.06-0.19, then slowly dropwise adding 20g of sodium hypochlorite solution, stirring and reacting for 20min, controlling the pH value to be 10 by using 12 wt% of sodium hydroxide solution in the process, finally adding 5mL of ethanol, reacting for 5min, then stopping water washing, centrifuging, adding hydrochloric acid into the precipitate, stirring and reacting for 40min, filtering, and washing to obtain acidified ecteinascidin nanocrystalline;
s3: adding graphene into a container filled with distilled water, performing ultrasonic stirring for 45min to fully disperse the graphene, adding polyvinyl alcohol (PVA), continuing to perform ultrasonic stirring for 30min, adding the sea squirt cellulose nanocrystal obtained in the step S2 into the container, raising the temperature to 60-90 ℃, performing ultrasonic stirring for 20min, adding sodium citrate, stirring at the temperature for 30min, then bringing the temperature to 40-50 ℃, and performing vacuum degassing to obtain a film forming solution, wherein the mass ratio of the added graphene, the PVA, the sea squirt cellulose nanocrystal to the sodium citrate is 1: 2-4: 35-60: 0.75-2;
s4: and (4) uniformly pouring the film forming solution obtained in the step S3 into a glass dish by using a tape casting film forming method, drying at 60 ℃ for 2 hours, then putting into an oven at 105-130 ℃, and reacting for 10 hours to obtain the degradable conductive composite film.
2. The method of claim 1, wherein the mass ratio of the added sodium bromide to the 2,2,6, 6-tetramethylpiperidine-1-oxide (TEMPO) is 1: 0.06-0.12.
3. The method of claim 1, wherein in step S3, the mass ratio of the graphene, the PVA, the ascidian cellulose nanocrystals and the sodium citrate is 1: 2-3: 35-50: 0.75-1.3.
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