CN115181227A - Preparation method and application of polymer - Google Patents
Preparation method and application of polymer Download PDFInfo
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- CN115181227A CN115181227A CN202111557285.5A CN202111557285A CN115181227A CN 115181227 A CN115181227 A CN 115181227A CN 202111557285 A CN202111557285 A CN 202111557285A CN 115181227 A CN115181227 A CN 115181227A
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Abstract
The invention relates to the technical field of preparation of high molecular compounds, and particularly discloses a preparation method and application of a polymer, wherein the preparation method of the polymer comprises the following steps: step a), mixing 1,2, 4-trihydroxybenzene and halogenated octane for etherification reaction to obtain a product 1; step b), mixing the product 1 obtained in the step a) with a chloromethylation reagent for chloromethylation reaction to obtain a product 2; step c), mixing the product 2 obtained in the step b) with triphenylphosphine for substitution reaction to obtain a product 3; step d), mixing the product 3 obtained in the step c) with m-phthalaldehyde to carry out anionic polymerization reaction to obtain a product 4; step e), mixing the product 4 obtained in step d) with an aqueous solution of halogen to catalyze the anionic polymerization reaction in step d, thereby obtaining a polymer. When the polymer is used as a carbon nanotube dispersing agent, the dispersibility of the carbon nanotube can be improved on the basis of not damaging the structure of the carbon nanotube, so that the application value of the carbon nanotube is improved.
Description
Technical Field
The invention relates to the technical field of preparation of high molecular compounds, in particular to a preparation method and application of a polymer.
Background
Carbon nanotubes mainly comprise several to tens of coaxial circular tubes made of hexagonally arranged carbon atoms, exhibit various electrical, optical, chemical and physical properties, and have great potential application values, and applications of carbon nanotubes currently under study include transparent electrodes, electrostatic dispersion films, field emission devices, surface heating elements, photoelectric devices, sensors, transistors, and the like.
Although carbon nanotubes have great potential application values, carbon nanotubes are easily agglomerated due to their large aspect ratio and strong van der waals attraction between each other, which makes it difficult for carbon nanotubes to form a stable dispersion state in water or general solvents, and thus the use of carbon nanotubes is limited due to low solubility and low dispersibility.
In order to solve the problem of dispersibility of carbon nanotubes, many studies have been made on the functionalization of the surface of carbon nanotubes to modify the surface of carbon nanotubes and impart functions thereto. The carbon nanotube covalence method can effectively change the surface performance of the carbon nanotube, and further effectively improve the dispersibility of the carbon nanotube. But this process changed sp 2 The surface arrangement of carbon atoms directly affects the original physical and chemical properties of carbon nanotubes. In addition, the non-covalent functionalization of the surface of the carbon nanotube is also one of effective means for improving the dispersibility of the carbon nanotube, and the surface of the carbon nanotube is usually performed by using a surfactant, an aromatic hydrocarbon, a biomaterial, or the like as a dispersant for the carbon nanotube, and the non-covalent interaction between the carbon nanotube and the dispersant is generated to improve the dispersibility of the carbon nanotube. The non-covalent functionalization treatment of the carbon nanotube surface does not need to introduce defects into the original structure, so that the original structure and characteristics of the carbon nanotube are not easily influenced, and therefore, the non-covalent functionalization method of the carbon nanotube surface becomes a main research direction for improving the dispersibility of the carbon nanotube at present.
The inventor believes that in the process of non-covalent functionalization research on the surface of the carbon nanotube, there is room for improvement on how to further improve the dispersibility of the carbon nanotube.
Disclosure of Invention
In order to improve the dispersibility of the carbon nano tube in the research of a non-covalent functionalization method on the surface of the carbon nano tube, the application provides a preparation method of a polymer and application thereof.
In a first aspect, the present application provides a method for preparing a polymer, which adopts the following technical scheme:
a method of preparing a polymer comprising the steps of:
step a), mixing 1,2, 4-trihydroxybenzene and halogenated octane for etherification reaction to obtain a product 1;
step b), mixing the product 1 obtained in the step a) with a chloromethylation reagent for chloromethylation reaction to obtain a product 2;
step c), mixing the product 2 obtained in the step b) with triphenylphosphine for substitution reaction to obtain a product 3;
step d), mixing the product 3 obtained in the step c) with m-phthalaldehyde to carry out anionic polymerization reaction to obtain a product 4;
step e), mixing the product 4 obtained in step d) with an aqueous solution of a halogen to catalyze the anionic polymerization reaction in step d to obtain a polymer.
In the step d, an anionic polymerization reaction is carried out between the product 3 and m-phthalaldehyde to obtain a product 4 which is a polymer with an aromatic ring structure but a low molecular weight, and the anionic polymerization reaction is directionally catalyzed by adding a halogen aqueous solution serving as a catalyst, so that the molecular weight length of the product 4 is prolonged, and the conjugated polymer with a high molecular weight aromatic ring structure is obtained.
In the above reaction process, the aqueous halogen solution has poor solubility in the reaction system of step c, and thus, it is difficult for the aqueous halogen solution to directly catalyze the anionic polymerization between the product 3 and isophthalaldehyde in the reaction system of step c. The aqueous solution of halogen and the polymer product 4 with low molecular weight have good compatibility, so after the product 4 is obtained, halogen is added to catalyze anionic polymerization reaction, thereby prolonging the molecular weight of the polymer.
The carbon nano tube has a hexagonal graphite structure, the polymer obtained in the step e has a conjugated structure with an aromatic ring structure, the polymer and the carbon nano tube are interacted through pi electrons and wrap the carbon nano tube to functionalize the surface of the carbon nano tube, so that the surface performance of the carbon nano tube is changed, the carbon nano tube is uniformly and stably dispersed in a medium, and the polymer has an excellent effect of improving the dispersibility of the carbon nano tube.
In addition, a high-temperature rheological property experiment and a room-temperature overnight storage experiment of the carbon nano tube slurry show that after the polymer is added into the carbon nano tube slurry as the carbon nano tube dispersing agent, the viscosity of the carbon nano tube slurry can be obviously reduced, and the high-temperature rheological property and the viscosity stability after storage of the carbon nano tube slurry can be improved.
Preferably, the 1 to 3 equivalents of the halogenated octane are added based on the addition amount of the 1,2, 4-trihydroxybenzene in the step a). Further, the halogenated octane is 1-chlorooctane and 1-bromooctane.
Further, in the step a), 0.02-0.08 equivalent of inorganic base and 15-40 mL of organic solvent A are added in the etherification reaction by taking the adding amount of the 1,2, 4-trihydroxybenzene added in the step a) as the calculated equivalent.
The inorganic base includes ammonium carbonate, potassium carbonate, sodium carbonate, and the like.
The organic solvent A comprises an ether solvent, a nitrogen-containing solvent, ethyl acetate, toluene and xylene. Ether solvents such as tetrahydrofuran, propylene glycol methyl ether acetate, and the like. The nitrogen-containing solvent includes N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and the like.
Still further, in the step a), the etherification reaction is carried out at 70-90 ℃ for at least 4 hours.
Preferably, the chloromethyl reagent is prepared by compounding hydrochloric acid and aldehyde, wherein the equivalent weight is calculated by taking the adding amount of the 1,2, 4-trihydroxybenzene in the step a), the aldehyde is added by 0.5 to 4 equivalents, and the hydrochloric acid is added by 0.8 to 2.5 equivalents. Wherein the aldehyde is one or more of formaldehyde, acetaldehyde, propionaldehyde and butyraldehyde.
Further, the chloromethylation reaction is carried out for 3-8h at 50-90 ℃.
Still further, the equivalent weight of 1,2, 4-trihydroxybenzene added in the step a) is taken as the adding amount, and 20-40 mL of organic solvent B is also added in the step B).
The organic solvent B comprises a dioxane aqueous solution, and the mass ratio of dioxane to water in the dioxane aqueous solution is 0.5-4.
Preferably, the triphenylphosphine is added in an amount of 0.5-4 equivalents based on the amount of 1,2, 4-trihydroxybenzene added in step a).
Furthermore, 15-30 mL of organic solvent A is added in the step c) by taking the adding amount of the 1,2, 4-trihydroxybenzene in the step a) as a calculated equivalent. The kind of the organic solvent used in step c) is the same as the selection range of step a), and is not described herein.
Further, in the step c), the product 2 obtained in the step b) and triphenylphosphine are subjected to reflux reaction for 2-8 h.
Preferably, the equivalent weight of 1,2, 4-trihydroxybenzene is added in step a), and the equivalent weight of m-phthalaldehyde is added in step d) to be 1-2.5.
Further, the adding amount of the 1,2, 4-trihydroxybenzene in the step a) is taken as the calculated equivalent, and 0.05 to 0.1 equivalent of sodium ethoxide and 20 to 45mL of organic solvent D are also added in the step D).
The organic solvent D is a mixed solution of ethanol and tetrahydrofuran, wherein the mass ratio of the ethanol to the tetrahydrofuran is 1.
Further, in the step d), the anionic polymerization is carried out for 2-4 h at 40-70 ℃.
Preferably, the halogen is added in an amount of 0.5 to 3 equivalents based on the amount of 1,2, 4-trihydroxybenzene added in step a).
Furthermore, the equivalent weight of the 1,2, 4-trihydroxybenzene added in the step a) is calculated, and 10-30 mL of benzene-containing solvent is also added in the step e). Benzene-containing solvents such as benzene, toluene, xylene, and the like.
Further, in the step e), the anionic polymerization is catalyzed for 2 to 8 hours under the reflux condition.
In a second aspect, the present application provides a polymer, which adopts the following technical scheme:
a polymer having the structure:
wherein n is a positive integer, and n =50 to 170.
The polymer is prepared by the preparation method of the polymer.
Preferably, the molecular weight of the polymer is 5 to 6.5 ten thousand.
When the molecular weight of the polymer is 5-6.5 ten thousand, the polymer not only has better dispersibility on the carbon nano tube, but also has higher high-pressure change resistant degree than the commercially available carbon nano tube dispersing agent, and the cyclic voltammetry test result of the carbon nano tube shows that the carbon nano tube can keep lower resistivity and better current stability by adding the polymer into the carbon nano tube slurry, so that the economic value of the carbon nano tube in the aspect of battery application in the future is improved.
The application of the polymer is to use the polymer as a carbon nano tube dispersing agent.
The carbon nanotube slurry consists of the polymer, the carbon nanotubes and a solvent according to a mass ratio of 0.8-1.5.
By using the above polymer as a carbon nanotube dispersing agent, carbon nanotubes can be dispersed individually in a medium without being aggregated with each other to form a massive bundle, and electrochemical stability of carbon nanotubes can be improved.
The positive electrode slurry comprises the following components in percentage by mass, wherein the carbon nanotube slurry, a binder and a positive electrode active substance are 0.8-1.5.
The binder is oil-soluble binder, such as homopolymer and copolymer of polyvinylidene fluoride, and positive active material such as cobalt hydroxide, lithium salt and nickel cobalt manganese ternary active material.
In summary, the present application has the following advantages:
1. when the polymer prepared by the method is used as a dispersing agent for preparing the carbon nanotube slurry, the viscosity of the carbon nanotube slurry is obviously reduced, and the carbon nanotube slurry can be stably dispersed in a medium without mutual agglomeration to form blocks or clusters when the carbon nanotube slurry is kept stand and stored or at a higher temperature.
2. After the polymer serving as the dispersing agent is matched with the carbon nano tube in a specific proportion, the carbon nano tube slurry is not easy to reduce the dispersibility of the carbon nano tube due to the fact that the adding amount of the dispersing agent is too small, and the electrochemical stability of the carbon nano tube is not easy to reduce due to the fact that the adding amount of the dispersing agent is too large.
Drawings
FIG. 1 is a cyclic voltammogram of carbon nanotube slurries of application examples 3 to 7 and application comparative examples 1 to 2.
Detailed Description
All materials used in the following examples are commercially available, with multi-walled carbon nanotubes from Jiangsu Cnano Technology Ltd FT6120. The hydrochloric acid is commercially available concentrated hydrochloric acid with the mass fraction of 37%. Commercial dispersants PVP K15, PVDF and poly (methyl methacrylate) were purchased from sigma aldrich trade ltd, with an average molecular weight Mr of 530000 for PVDF and 97000 and an average Mw of 46000 for poly (methyl methacrylate).
In the following examples, the reaction scheme for polymer synthesis is as follows:
example 1
A method for preparing a polymer comprises the following steps:
step a, mixing 1mmol of 1,2, 4-trihydroxybenzene, 1mmol of 1-chlorooctane, 0.02mmol of potassium carbonate and 15mL of N, N-dimethylformamide uniformly, and reacting at 70 ℃ for 4 hours to obtain a product 1.
And step b, uniformly mixing the product 1 obtained in the step a, 0.5mmol of formaldehyde, 0.8mmol of hydrochloric acid and 20mL of dioxane aqueous solution, wherein the dioxane aqueous solution is prepared by mixing dioxane and water according to a mass ratio of 0.5.
And c, mixing the product 2 obtained in the step b, 0.5mmol of triphenylphosphine and 15ml of LN-methyl pyrrolidone, and refluxing for 2h to obtain a product 3.
And D, uniformly mixing the product 3 obtained in the step c, 1mmol of m-phthalaldehyde, 0.05mmol of sodium ethoxide and 20mL of organic solvent D, wherein the organic solvent D consists of ethanol and tetrahydrofuran according to a mass ratio of 1.
And e, mixing the product 4 obtained in the step d, 0.5mL of bromine water and 10mL of toluene, wherein the bromine content in the bromine water is 0.5mmol, and refluxing for 3h to obtain a polymer, which is recorded as HVD-1.
Example 2
A method for preparing a polymer comprises the following steps:
step a, mixing 1mmol of 1,2, 4-trihydroxybenzene, 3mmol of 1-bromooctane, 0.08mmol of potassium carbonate and 40mL of N-methylpyrrolidone uniformly, and reacting at 90 ℃ for 6 hours to obtain a product 1.
And step b, uniformly mixing the product 1 obtained in the step a, 4mmol of formaldehyde, 2.5mmol of hydrochloric acid and 40mL of dioxane aqueous solution, wherein the dioxane aqueous solution is prepared by mixing dioxane and water according to a mass ratio of 4.
And c, mixing the product 2 obtained in the step b, 4mmol of triphenylphosphine and 25mL of LN-methyl pyrrolidone, and refluxing for 8h to obtain a product 3.
And D, uniformly mixing the product 3 obtained in the step c, 1mmol of m-phthalaldehyde, 0.1mmol of sodium ethoxide and 45mL of an organic solvent D, wherein the organic solvent D consists of ethanol and tetrahydrofuran according to a mass ratio of 2.
And e, mixing the product obtained in the step d with 8mL of bromine water and 30mL of toluene, wherein the bromine content in the bromine water is 3mmol, and refluxing for 3h to obtain a polymer, which is recorded as HVD-2.
Example 3
A method for preparing a polymer comprises the following steps:
step a, mixing 1mmol of 1,2, 4-trihydroxybenzene, 2mmol of 1-chlorooctane, 0.05mmol of potassium carbonate and 25mL of N, N-dimethylformamide uniformly, and reacting at 90 ℃ for 4h to obtain a product 1.
And step b, uniformly mixing the product 1 obtained in the step a, 2mmol of formaldehyde, 2mmol of hydrochloric acid and 30mL of dioxane aqueous solution, wherein the dioxane aqueous solution is prepared by mixing dioxane and water according to a mass ratio of 2.
And c, mixing the product 2 obtained in the step b, 2mmol of triphenylphosphine and 25mL of LN-methyl pyrrolidone, and refluxing for 3h to obtain a product 3.
And D, uniformly mixing the product 3 obtained in the step c, 1mmol of m-phthalaldehyde, 0.08mmol of sodium ethoxide and 30mL of organic solvent D, wherein the organic solvent D consists of ethanol and tetrahydrofuran according to a mass ratio of 1.
And e, mixing the product obtained in the step d with 6mL of bromine water and 20mL of toluene, wherein the bromine content is 2mmol, refluxing for 3h to obtain a polymer, and recording as HVD-3.
Example 4
A method of preparing a polymer, differing from example 3 in that: in the step d, the product 3 obtained in the step c and 1.5mmol of m-phthalaldehyde are uniformly mixed, and other conditions are not changed. The polymer obtained in step e was designated HVD-4.
Example 5
A method of preparing a polymer, differing from example 3 in that: in the step d, the product 3 obtained in the step c and 2mmol of m-phthalaldehyde are uniformly mixed, and other conditions are not changed. The polymer obtained in step e was designated HVD-5.
Example 6
A method of preparing a polymer, differing from example 3 in that: in the step d, the product 3 obtained in the step c and 2.5mmol of m-phthalaldehyde are uniformly mixed, and other conditions are not changed. The polymer obtained in step e was designated HVD-6.
Example 7
A method of preparing a polymer, differing from example 3 in that: in the step d, the product 3 obtained in the step c and 3mmol of m-phthalaldehyde are uniformly mixed, and other conditions are not changed. The polymer obtained in step e was designated HVD-7.
Application example 1
A carbon nanotube slurry is prepared by the following steps: 6g of the polymer prepared in example 1 and 382g of N-methylpyrrolidone were taken and added together in a vertical pot and stirred until the polymer was dissolved, 12g of multiwall carbon nanotubes were then added, 400g of zirconium beads with a size of 0.3mm were then added, mechanical grinding was carried out at 25 ℃ for 4h to obtain a black dispersion containing multiwall carbon nanotubes, and finally the zirconium beads were filtered to obtain a carbon nanotube slurry which was uniformly dispersed without precipitation.
Application example 2
A carbon nanotube slurry, which is different from application example 1 in that: the polymer prepared in example 1 was replaced by an equal amount of the polymer prepared in example 2.
Application example 3
A carbon nanotube slurry, which is different from application example 1 in that: the polymer prepared in example 1 was replaced by an equal amount of the polymer prepared in example 3.
Application example 4
A carbon nanotube slurry, which is different from application example 1 in that: the polymer prepared in example 1 was replaced by an equal amount of the polymer prepared in example 4.
Application example 5
A carbon nanotube slurry, which is different from application example 1 in that: the polymer prepared in example 1 was replaced by the same amount of the polymer prepared in example 5.
Application example 6
A carbon nanotube slurry, which is different from application example 1 in that: the polymer prepared in example 1 was replaced by the same amount of the polymer prepared in example 6.
Application example 7
A carbon nanotube slurry, which is different from application example 1 in that: the polymer prepared in example 1 was replaced by the same amount of the polymer prepared in example 7.
Comparative application example 1
A carbon nanotube slurry is prepared by the following steps: 6g of the commercial dispersant PVP K15 was taken and added to a vertical tank together with 382g of N-methylpyrrolidone and stirred until the polymer dissolved, then 12g of multiwall carbon nanotubes were added, 400g of zirconium beads with a size of 0.3mm were added, mechanically ground at 25 ℃ for 4h to obtain a black dispersion containing multiwall carbon nanotubes, and finally the zirconium beads were filtered to obtain a carbon nanotube slurry which was uniformly dispersed without precipitation.
Comparative application example 2
A carbon nanotube slurry is prepared by the following steps: 6g of commercial dispersant PVDF and 382g of N-methylpyrrolidone were added together in a vertical pot and stirred until the polymer dissolved, then 12g of multiwall carbon nanotubes were added, 400g of zirconium beads with a size of 0.3mm were added, mechanically ground at 25 ℃ for 4h to obtain a black dispersion containing multiwall carbon nanotubes, and finally the zirconium beads were filtered to obtain a carbon nanotube slurry which was uniformly dispersed without precipitation.
Comparative application example 3
A carbon nanotube slurry is prepared by the following steps: 6g of poly (methyl methacrylate) and 382g of N-methylpyrrolidone are added into a vertical tank together and stirred until the polymer is dissolved, then 12g of multi-walled carbon nanotubes are added, 400g of zirconium beads with the size of 0.3mm are added, mechanical grinding is carried out for 4 hours at 25 ℃ to obtain black dispersion containing the multi-walled carbon nanotubes, and finally the zirconium beads are filtered to obtain carbon nanotube slurry which is uniformly dispersed without precipitation.
Experiment 1
NCM volume resistivity test
The conductivity of the carbon nanotube slurry samples prepared in the application examples and the application comparative examples was evaluated by evaluating the volume resistivity of the carbon nanotube slurry in the positive electrode system, so as to illustrate the influence of the polymer prepared in the examples of the present application on the conductivity of the carbon nanotube slurry.
The test method is as follows: 98.6g of nickel-cobalt-manganese ternary active material (NCM), 1g of PVDF and 0.4g of carbon nanotube slurry are uniformly mixed to obtain positive electrode slurry, then coating is carried out, baking is carried out for 60min at 120 ℃, and the body resistivity is tested by adopting a four-probe body resistivity tester. The test results are shown in table 1 below.
Experiment 2
Viscosity measurement overnight at room temperature
The test method comprises the following steps: the carbon nanotube slurry samples prepared in each application example and the application comparative example were respectively allowed to stand at 25 ℃ overnight (> 12 hours), i.e., after the slurry viscosity initially reached a steady state, and then tested at 10rpm using a rotor viscometer, and the test results are shown in table 1.
Rheology of 10S-1 after high-temperature storage for 7 days
The test method comprises the following steps: the carbon nanotube slurry sample was sealed and allowed to stand in a thermostat at 55 ℃ for 7 days, i.e., the slurry viscosity was stored at 55 ℃ and then measured for viscosity at a shear rate of 10 reciprocal seconds using an antopa rheometer, with the results shown in table 1.
TABLE 1
As can be seen from the data in table 1, after the polymer HVD1-7 prepared in the present application is added to the carbon nanotube slurry as a carbon nanotube dispersant, the carbon nanotube slurry still maintains a better viscosity after standing and storing overnight at room temperature, and still has a better rheological property after storing at high temperature for 7 days, which indicates that the polymer HVD1-7 of the present application has a good dispersibility and a good stability for the carbon nanotubes, so that the carbon nanotube slurry is not easily agglomerated during the storage process. The carbon nano tube slurry is prepared into the anode slurry, and the anode slurry also has better conductivity, which indicates that the polymer is not easy to cause adverse effect on the conductivity of the carbon nano tube after being added.
The polymer HVD1-7 and the application comparative examples 1-3 adopted in the above application examples all belong to non-covalent carbon nanotube dispersants, and by comparing the data in Table 1, the viscosity of the carbon nanotube slurry prepared in the application examples 1-7 after overnight standing and storage at room temperature is close to that of the application comparative example 1 and is obviously lower than that of the application comparative examples 2-3; after the slurry is stored at high temperature, the slurry can be agglomerated to form jelly shape when being stored at high temperature by applying comparative examples 2-3, and the rheological property of application example 1 is lower than that of application comparative example 1, but the slurry can still keep a flowing state; whereas the rheology of application examples 2-5 and 7 was similar to that of application comparative example 1, the rheology of application example 6 was significantly superior to that of application comparative example 1. The volume resistivity test result of the positive electrode slurry shows that the volume resistivity of the positive electrode slurry prepared by applying the slurry of 1-7 is close to or even more excellent than that of the positive electrode slurry prepared by applying the comparative examples 1-3. In conclusion, the polymer HVD1-7 of the present application achieves the same level of dispersibility, stability and conductivity as the current commercial non-covalent carbon nanotubes, and is even more excellent.
Cyclic voltammetry test
Cyclic voltammetry is a method of changing the potential to obtain the direction of the redox current, which is mainly performed by applying a cyclic potential, specifically, applying a constant rate from the starting point to the end point potential, and changing back to the starting potential at the same rate to complete a cycle. When scanning from low voltage to high voltage, the voltammogram shows that the analyte generates an oxidation peak of oxidation current, and the voltammogram can help to judge the potential at which oxidation reaction occurs. When the potential values were the same, the lower the current value, the more difficult the oxidation reaction was demonstrated to occur, and the more stable the analyte.
Table 2 shows the test conditions of cyclic voltammetry, wherein the scan voltage is 2-5V, the scan speed is 0.7mv/s, and the test results of the second cycle are taken.
TABLE 2
The stability of each material was demonstrated by comparing the current values at 5V voltage, which is shown in Table 3.
TABLE 3
In examples 3 to 7, m-phthalaldehyde and product 3 were reacted in different molar ratios to obtain polymers HVD3-7 with different molecular weights, and as can be seen from the data in fig. 1 and table 3, the stability of PVP K15 and PVDF in examples 3 to 7 and in comparative examples 1 to 2 using the dispersants in the following order: HVD-7 >. Therefore, when HVD-7 and HVD-5 are used as the carbon nanotube dispersing agent, not only the dispersibility of the carbon nanotubes can be improved, but also the voltage resistance stability of the carbon nanotubes can be improved.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (21)
1. A method of preparing a polymer, comprising: the method comprises the following steps:
step a), mixing 1,2, 4-trihydroxybenzene and halogenated octane for etherification reaction to obtain a product 1;
step b), mixing the product 1 obtained in the step a) with a chloromethylation reagent for chloromethylation reaction to obtain a product 2;
step c), mixing the product 2 obtained in the step b) with triphenylphosphine for substitution reaction to obtain a product 3;
step d), mixing the product 3 obtained in the step c) with m-phthalaldehyde to perform an anionic polymerization reaction to obtain a product 4;
step e), mixing the product 4 obtained in step d) with an aqueous solution of a halogen to catalyze the anionic polymerization reaction in step d to obtain a polymer.
2. The method for producing a polymer according to claim 1, characterized in that: and b), taking the adding amount of the 1,2, 4-trihydroxybenzene in the step a) as a calculated equivalent, and adding 1-3 equivalents of halogenated octane.
3. The method for producing a polymer according to claim 1, characterized in that: in the step a), 0.02-0.08 equivalent of inorganic base and 15-40 mL of organic solvent A are added in the etherification reaction by taking the addition amount of the 1,2, 4-trihydroxybenzene in the step a) as the calculated equivalent.
4. A method of preparing a polymer according to claim 3, characterized in that: the organic solvent A comprises one or more of ether solvent, nitrogen-containing solvent, ethyl acetate, toluene and xylene.
5. The method for producing a polymer according to claim 1, characterized in that: in the step a), the etherification reaction is carried out at 70-90 ℃ for at least 4h.
6. The method for producing a polymer according to claim 1, characterized in that: the chloromethyl reagent is a mixture of hydrochloric acid and aldehyde, the adding amount of the 1,2, 4-trihydroxybenzene in the step a) is taken as a calculation equivalent, the aldehyde is added by 0.5 to 4 equivalents, and the hydrochloric acid is added by 0.8 to 2.5 equivalents.
7. The method for producing a polymer according to claim 6, wherein: the aldehyde is one or more of formaldehyde, acetaldehyde, propionaldehyde and butyraldehyde.
8. The method for producing a polymer according to claim 1, characterized in that: the chloromethylation reaction is carried out for 3-8h at 50-90 ℃.
9. The method for producing a polymer according to claim 1, characterized in that: and b), taking the adding amount of the 1,2, 4-trihydroxybenzene in the step a) as a calculated equivalent, and adding 20-40 mL of dioxane aqueous solution in the step b), wherein the mass ratio of dioxane to water in the dioxane aqueous solution is 0.5-4.
10. The method for producing a polymer according to claim 1, characterized in that: and b) taking the adding amount of the 1,2, 4-trihydroxybenzene in the step a) as the calculated equivalent, and adding 0.5-4 equivalent of the triphenylphosphine.
11. The method for preparing a polymer according to claim 1 or 4, characterized in that: taking the adding amount of the 1,2, 4-trihydroxybenzene in the step a) as a calculated equivalent, and adding 15-30 mL of organic solvent A in the step c).
12. The method for producing a polymer according to claim 1, characterized in that: in the step c), the product 2 obtained in the step b) and triphenylphosphine are subjected to reflux reaction for 2-8 h.
13. The method for producing a polymer according to claim 1, characterized in that: and d) taking the adding amount of the 1,2, 4-trihydroxybenzene in the step a) as the calculated equivalent, and adding 1-2.5 equivalents of the m-phthalaldehyde in the step d).
14. The method for producing a polymer according to claim 1, characterized in that: taking the adding amount of the 1,2, 4-trihydroxybenzene in the step a) as a calculated equivalent, and adding 0.05-0.1 equivalent of sodium ethoxide and 20-45 mL of a mixed solution of ethanol and tetrahydrofuran in the step d), wherein the mass ratio of the ethanol to the tetrahydrofuran is 1.
15. The method for producing a polymer according to claim 1, characterized in that: in the step d), the anionic polymerization reaction is carried out for 2 to 4 hours at the temperature of between 40 and 70 ℃.
16. The method for producing a polymer according to claim 1, characterized in that: and b), taking the adding amount of the 1,2, 4-trihydroxybenzene in the step a) as the calculated equivalent, and adding 0.5-3 equivalents of halogen.
17. The method for producing a polymer according to claim 1, characterized in that: the adding amount of the 1,2, 4-trihydroxybenzene in the step a) is taken as the calculated equivalent, and 10-30 mL of benzene-containing solvent is also added in the step e).
18. The method for producing a polymer according to claim 1, characterized in that: in the step e), the catalytic anionic polymerization is carried out for 2 to 8 hours under the reflux condition.
19. Use of a polymer characterized by: use of any of the polymers prepared according to claims 1-18 as carbon nanotube dispersant.
20. A carbon nanotube slurry, characterized in that: consists of any one of the polymers prepared according to the claims 1 to 18, carbon nanotubes and a solvent according to a mass ratio of 0.8 to 1.5.
21. A positive electrode slurry is characterized in that: the carbon nanotube slurry of claim 20, the binder and the positive electrode active material in a mass ratio of 0.8 to 1.5.
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| CN106654282A (en) * | 2017-01-23 | 2017-05-10 | 合肥国轩高科动力能源有限公司 | Carbon nanotube positive electrode slurry and slurry synthesis method thereof |
| CN106876715A (en) * | 2017-03-30 | 2017-06-20 | 湖北金泉新材料有限责任公司 | A kind of anode sizing agent of carbon nanotubes, Preparation Method And The Use |
| CN107482220A (en) * | 2017-06-23 | 2017-12-15 | 深圳市德方纳米科技股份有限公司 | A kind of lithium ion battery conductive carbon pastes and its preparation method and application |
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| CN106654282A (en) * | 2017-01-23 | 2017-05-10 | 合肥国轩高科动力能源有限公司 | Carbon nanotube positive electrode slurry and slurry synthesis method thereof |
| CN106876715A (en) * | 2017-03-30 | 2017-06-20 | 湖北金泉新材料有限责任公司 | A kind of anode sizing agent of carbon nanotubes, Preparation Method And The Use |
| CN107482220A (en) * | 2017-06-23 | 2017-12-15 | 深圳市德方纳米科技股份有限公司 | A kind of lithium ion battery conductive carbon pastes and its preparation method and application |
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