CN114773582A - Hyperbranched polymer containing long-chain alkyl, carbon nanotube dispersion liquid and preparation method thereof - Google Patents

Hyperbranched polymer containing long-chain alkyl, carbon nanotube dispersion liquid and preparation method thereof Download PDF

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CN114773582A
CN114773582A CN202210255305.1A CN202210255305A CN114773582A CN 114773582 A CN114773582 A CN 114773582A CN 202210255305 A CN202210255305 A CN 202210255305A CN 114773582 A CN114773582 A CN 114773582A
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acid
anhydride
carbon nanotube
hyperbranched
hyperbranched polymer
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陈点
汪羽翎
吕仕铭
周永丰
杜长森
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Suzhou Sunmun Technology Co ltd
Shanghai Jiaotong University
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Suzhou Sunmun Technology Co ltd
Shanghai Jiaotong University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/127—Acids containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/005—Hyperbranched macromolecules

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Abstract

The application relates to a hyperbranched polymer containing long-chain alkyl, which comprises a core A and a chain arm B, and the structure of the hyperbranched polymer is shown as the following general formula I:

Description

Hyperbranched polymer containing long-chain alkyl, carbon nanotube dispersion liquid and preparation method thereof
Technical Field
The application relates to the technical field of hyperbranched polymers and nano materials, in particular to a hyperbranched polymer containing long-chain alkyl, a preparation method of the hyperbranched polymer containing long-chain alkyl, a carbon nanotube dispersion liquid containing the hyperbranched polymer containing long-chain alkyl and application of the hyperbranched polymer containing long-chain alkyl as a carbon nanotube dispersant.
Background
The nano material (1nm-100nm) has size effect, surface effect and macroscopic quantum tunneling effect, and the effects enable the nano material to show excellent performance in application. Carbon Nanotubes (CNTs) are one of the most representative and excellent-performance materials among nanomaterials.
Carbon Nanotubes (CNTs) are hollow tubular structures made of carbon elements, and can be considered as seamless, hollow microtubes formed by winding single-layered or multi-layered hexagonal graphite mesh planes along a chiral vector. The unique structure of the nano-material combines the excellent mechanical, electronic and optical properties of the nano-material to make the nano-material an ideal nano-material. However, since CNTs have a large surface area and a large aspect ratio, and have a strong van der waals force and pi-pi stacking between tubes, CNTs are generally present in the form of parallel bundles in a natural state, and are difficult to disperse in water and organic solvents, which requires the addition of a dispersant to enhance the dispersibility of carbon nanotubes in the solvents.
At present, the solvents of the carbon nanotube dispersion liquid are generally water and polar organic solvents, and the nonpolar organic solvents are hardly involved. Commonly used carbon nanotube dispersants are typically small molecule surfactants and linear polymers, which are generally less soluble in non-polar organic solvents. In addition, there is usually a large increase in the viscosity of the overall system after addition to the nonpolar organic solvent. Most importantly, it is substantially incapable of dispersing carbon nanotubes in non-polar organic solvents, and even exacerbates agglomeration of carbon nanotubes. To solve these problems, the research on hyperbranched polymers has attracted attention at home and abroad, and it is hoped that hyperbranched polymers replace small-molecule surfactants and linear polymers.
The research of hyperbranched polymers has been one of the hot spots in the field of polymer chemistry in recent decades. The hyperbranched polymer has a three-dimensional spherical structure, is rich in a large number of terminal functional groups on the surface, has the advantages of high reaction activity, good solubility, low viscosity and the like, and can be used in the fields of polymer processing aids, epoxy resin toughening, drug sustained release and the like.
Compared with linear polymers and small molecular surfactants, the hyperbranched polymer has a spherical molecular shape and a high branching degree, can be well dissolved in a non-polar organic solvent, has low system viscosity, and can be well coated on the surface of the carbon nanotube to form an oil-phase carbon nanotube dispersion liquid with good stability and dispersibility and small carbon nanotube particle size. The oil phase generally includes common solvents such as N-methylpyrrolidone and propylene glycol monomethyl ether acetate, and also includes liquid organic carriers such as liquid polyester and polyether, and in the present invention, the oil phase generally refers to a non-polar organic solvent. The low system viscosity can conveniently increase the content of the carbon nano-tube in the dispersion liquid and improve the service efficiency of the dispersion liquid. The oil phase carbon nano tube dispersion liquid has good stability and dispersibility, so that the subsequent application and addition process, long-term storage process and transportation process can be facilitated, and the cost is further reduced. The hyperbranched polymer has a great amount of active functional groups such as hydroxyl, carboxyl and the like at the tail end, and the terminal group of the hyperbranched polymer can be modified to enable the hyperbranched polymer to have various performances, so that the hyperbranched polymer becomes a resin with potential application value. The hyperbranched polymer is used for dispersing the oil phase carbon nano tube, so that the addition amount of the carbon nano tube can be increased, the use performance of the dispersion liquid can be improved, and meanwhile, the hyperbranched structure is beneficial to improving the dispersion liquid dispersibility and stability in the oil phase carbon nano tube dispersion liquid and reducing the cost of the subsequent application and addition process, the long-term storage process and the transportation process.
For this reason, there is a continuing need in the art to develop a hyperbranched polymer that can be used as a dispersant for carbon nanotubes.
Disclosure of Invention
Long alkyl chain polyols and hydroxy acids/polycarboxylic acids/anhydrides are several readily available, low cost materials. Has rich renewable resources from nature and petroleum products derived from fossil fuels, and has the advantages of perfect preparation process, wide sources and low cost. The polyol and hydroxy acid/polycarboxylic acid/anhydride with long alkyl chains are characterized in that the unique chemical structures of the polyol and hydroxy acid/polycarboxylic acid/anhydride have a plurality of hydroxyl and carboxyl functional groups and a special long carbon chain structure, so that the polyol and hydroxy acid/polycarboxylic acid/anhydride can be subjected to various chemical transformations to prepare low-molecular-weight and high-molecular-weight materials with multiple purposes, and have good solubility in non-polar organic solvents.
In the invention, based on a synthesis strategy of a hyperbranched polymer, the inventor synthesizes a hyperbranched carbon nanotube dispersing agent containing long alkyl chains by a body polymerization one-pot method, and uses the hyperbranched carbon nanotube dispersing agent in a high-content low-viscosity oil phase carbon nanotube dispersing solution to research the application effect of the hyperbranched carbon nanotube dispersing agent.
The present application aims to provide a hyperbranched polymer containing long-chain alkyl groups, which can be used as a carbon nanotube dispersant for high-content low-viscosity oil-phase carbon nanotube dispersions, thereby solving the above-mentioned technical problems in the prior art. The hyperbranched polymer containing long-chain alkyl comprises a core A and a chain arm B, wherein the core A is hyperbranched polyester containing hydroxyl or carboxyl at the tail end, and is connected with the chain arm B containing long-chain alkyl chain through an ester group. This particular structure makes the hyperbranched polymers containing long-chain alkyl groups described herein particularly suitable for dispersing carbon nanotubes in an oily phase solvent.
It is also an object of the present application to provide a process for the preparation of the hyperbranched polymer containing long-chain alkyl groups as described above.
It is also an object of the present application to provide an oil phase carbon nanotube dispersion comprising a hyperbranched polymer containing a long chain alkyl group as described above.
It is also an object of the present application to provide the use of the hyperbranched polymer containing long-chain alkyl groups as described above as a carbon nanotube dispersant.
In order to solve the above technical problems, the present application provides the following technical solutions.
In a first aspect, the present application provides a long-chain alkyl group-containing hyperbranched polymer, wherein the long-chain alkyl group-containing hyperbranched polymer includes a core a and a chain arm B, and the structure of the hyperbranched polymer is represented by the following general formula I:
Figure BDA0003548256080000031
the core A is hyperbranched polyester containing hydroxyl or carboxyl at the tail end, and is formed by performing polycondensation reaction on a monomer containing at least two hydroxyl groups and a monomer containing carboxyl, or by performing polycondensation reaction on a monomer containing at least two hydroxyl groups and a first anhydride;
wherein the chain arm B is monoacid, monohydric alcohol or second anhydride, and the chain arm B is connected to the terminal group of the inner core A through an ester group covalent bond.
In one embodiment of the first aspect, the monomer containing at least two hydroxyl groups is selected from one or more of pentaerythritol, glycerol, ethylene glycol, diethylene glycol, dipentaerythritol, trimethylolpropane, ditrimethylolpropane, castor oil, pentaethylene glycol, triethylene glycol, octapolyethylene glycol, heptapolyethylene glycol, hexapolyethylene glycol, tetraethylene glycol, propylene glycol, 1, 2-propanediol, butanediol, pentanediol, nonanediol, hexanediol, heptanediol, octanediol, 1, 2-octanediol, decanediol, 1, 2-decanediol, dodecanediol, and 1, 2-dodecanediol.
In one embodiment of the first aspect, the carboxyl group-containing monomer is selected from one or more of lactic acid, 3-hydroxybutyric acid, gamma-hydroxybutyric acid, 9-hydroxynonanoic acid, 3-hydroxytetradecanoic acid, 9-hydroxytetradecanoic acid, ricinoleic acid, 12-hydroxystearic acid, 2-dimethylolpropionic acid, succinic acid, sebacic acid, adipic acid, azelaic acid, malonic acid, suberic acid, phthalic anhydride, itaconic acid, glutaric acid, itaconic anhydride, benzenemalonic acid, maleic acid, undecanedioic acid, hexadecanedioic acid, dodecanedioic acid, methylmalonic acid, phenylsuccinic acid, and citric acid.
In an embodiment of the first aspect, the first anhydride is independently selected from one or more of trimellitic anhydride, maleic anhydride, succinic anhydride, glutaric anhydride, citraconic anhydride, biphenyl anhydride, methylsuccinic anhydride, pyromellitic dianhydride, 3-methylglutaric anhydride, 1, 2-cyclohexanedianhydride and 2, 2-dimethylsuccinic anhydride.
In one embodiment of the first aspect, the monoacid is selected from one or more of acetic acid, octanoic acid, nonanoic acid, linolenic acid, octadecenoic acid, oleic acid, linoleic acid, tololeic acid, arachidonic acid, ricinoleic acid, eleostearic acid, erucic acid, and trifluoroacetic acid.
In one embodiment of the first aspect, the monohydric alcohol is selected from one or more of methanol, ethanol, octanol, nonanol, isopropanol, 2-butanol, 3-pentanol, and 2,2,3, 3-tetrafluoro-1-propanol.
In one embodiment of the first aspect, the second anhydride is selected from one or more of acetic anhydride, propionic anhydride, benzoic anhydride, maleic anhydride, n-butyric anhydride, succinic anhydride, glutaric anhydride, isobutyric anhydride, trifluoroacetic anhydride, trimethylacetic anhydride.
In a second aspect, the present application provides a method for preparing a hyperbranched polymer containing long-chain alkyl groups according to the first aspect, characterized in that the method comprises the following steps:
s1: preparation of hyperbranched polyester containing hydroxyl or carboxyl at terminal
In the presence of a catalyst, carrying out a first polycondensation reaction on the monomer containing at least two hydroxyl groups and the monomer containing carboxyl groups or first acid anhydride to obtain the hyperbranched polyester with hydroxyl groups or carboxyl groups at the tail end;
s2: preparation of hyperbranched polymers containing Long-chain alkyl groups
And carrying out a second polycondensation reaction on the hyperbranched polyester with the terminal containing hydroxyl or carboxyl and the monoacid, the monohydric alcohol or the second anhydride to obtain the hyperbranched polymer containing the long-chain alkyl.
In one embodiment of the second aspect, the catalyst is selected from one or more of 4-dimethylaminopyridine, p-toluenesulphonic acid, concentrated sulphuric acid, thionyl chloride, hydrochloric acid, phosphoric acid, sodium bisulphate, ferric chloride, aluminium trichloride, zinc chloride, antimony chloride, ferric sulphate, aluminium sulphate, ferric ammonium sulphate, stannic chloride, stannous chloride, stannic laurate, copper sulphate, calcium chloride and boric acid.
In one embodiment of the second aspect, the first and second polycondensation reactions are bulk reactions.
In one embodiment of the second aspect, in step S1, the molar ratio of the monomer containing at least two hydroxyl groups to the monomer containing a carboxyl group or the first acid anhydride is charged in the range of 20:1 to 1: 40.
In one embodiment of the second aspect, in step S1, the first polycondensation reaction is performed at a reaction temperature of 120 ℃ to 250 ℃ for 0.1 to 10 hours, preferably 1 to 8 hours;
in one embodiment of the second aspect, in the step S2, the molar ratio of the monoacid, the monoalcohol, or the second anhydride to the hyperbranched polyester containing hydroxyl or carboxyl groups at the terminal is 1:1 to 100: 1.
In one embodiment of the second aspect, the reaction temperature of the second polycondensation reaction is 60 ℃ to 250 ℃ and the reaction time is 0.1 to 10 hours, preferably 0.5 to 5 hours.
In a third aspect, the present application provides an oil-phase carbon nanotube dispersion, characterized in that the carbon nanotube dispersion is prepared by the following method: dispersing the hyperbranched polymer containing long-chain alkyl and the carbon nanotubes in an oily solvent to obtain an oil-phase carbon nanotube dispersion liquid;
wherein the viscosity of the oil-phase carbon nanotube dispersion liquid at room temperature is 1000 to 10000mPa · s.
In one embodiment of the third aspect, the amount of the hyperbranched polymer containing long-chain alkyl groups added to the oil-phase carbon nanotube dispersion is 0.5% to 10% of the total mass of the oil-phase carbon nanotube dispersion.
In one embodiment of the third aspect, the carbon nanotubes in the oil-phase carbon nanotube dispersion are added in an amount of 0.5% to 10% of the total mass of the oil-phase carbon nanotube dispersion.
In one embodiment of the third aspect, the number average molecular weight of the hyperbranched polymer containing long-chain alkyl groups is 2000 to 10000.
In one embodiment of the third aspect, the fineness of the carbon nanotubes in the oil phase carbon nanotube dispersion is 10-100 μm, which can be directly tested and read by using a fineness plate according to the determination of grinding fineness of national standard GB/T1724-2019 paint, varnish and printing ink.
In one embodiment of the third aspect, the oily solvent in the oil-phase carbon nanotube dispersion is a non-polar organic solvent.
In one embodiment of the third aspect, the dispersing comprises dispersing by ball milling, the dispersion time of the ball milling dispersion preferably being 0.1 to 10 hours.
In a fourth aspect, the present application provides the use of a hyperbranched polymer containing long-chain alkyl groups as described in the first aspect as a carbon nanotube dispersant.
Compared with the prior art, the invention has the advantages that:
(1) the hyperbranched carbon nanotube dispersing agent containing the long alkyl chain has the performance advantages of good solubility in a nonpolar organic solvent, capability of effectively coating the surface of a carbon nanotube and the like.
(2) The hyperbranched carbon nanotube dispersing agent containing the long alkyl chain can be applied to uniformly and stably dispersing carbon nanotubes in a nonpolar organic solvent.
(3) The hyperbranched carbon nanotube dispersing agent containing the long alkyl chain adopts commercial polyol and hydroxy acid/polyacid/anhydride as raw materials, obtains a hyperbranched polyester core through a first bulk polymerization reaction, grafts various monoacids containing carboxyl/anhydride/hydroxyl and anhydride/monoalcohol thereof, and directly polymerizes in one pot to obtain a final product.
(4) The oil phase carbon nanotube dispersion liquid containing the long alkyl chain hyperbranched carbon nanotube dispersing agent has the advantages of high carbon nanotube adding amount, low system viscosity, high system dispersibility, high stability and the like, and can reduce the cost of a subsequent application adding process, a long-term storage process and a transportation process.
Detailed Description
Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages herein are by weight and the testing and characterization methods used are synchronized with the filing date of the present application. Where applicable, the contents of any patent, patent application, or publication referred to in this application are incorporated herein by reference in their entirety, and the equivalent family of patents is also incorporated by reference, in particular for the definitions set forth in these documents regarding synthetic techniques, product and process designs, polymers, comonomers, initiators or catalysts, and the like, in the art. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definition provided herein, the definition of the term provided herein controls.
The numerical ranges in this application are approximations, and thus may include values outside of the ranges unless otherwise specified. A numerical range includes all numbers from a lower value to an upper value, in increments of 1 unit, provided that there is a separation of at least 2 units between any lower value and any higher value. For example, if a compositional, physical or other property (e.g., molecular weight, melt index, etc.) is stated to be from 100 to 1000, it is intended that all individual values, e.g., 100, 101, 102, etc., and sub ranges, e.g., 100 to 166, 155 to 170, 198 to 200, etc., are expressly enumerated. For ranges containing a numerical value less than 1 or containing a fraction greater than 1 (e.g., 1.1, 1.5, etc.), 1 unit is considered to be 0.0001, 0.001, 0.01, or 0.1, as appropriate. For ranges containing single digit numbers less than 10 (e.g., 1 to 5), 1 unit is typically considered 0.1. These are merely specific examples of what is intended to be expressed and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application. It should also be noted that the terms "first," "second," and the like herein do not define a sequential order, but merely distinguish between different structures.
When used with respect to chemical compounds, the singular includes all isomeric forms and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively) unless expressly specified otherwise. In addition, unless explicitly stated otherwise, the use of the terms "a", "an" or "the" are intended to include the plural forms thereof.
The terms "comprising," "including," "having," and derivatives thereof do not exclude the presence of any other component, step or procedure, and are not intended to exclude the presence of other elements, steps or procedures not expressly disclosed herein. To the exclusion of any doubt, all compositions herein using the terms "comprising", "including", or "having" may include any additional additive, adjuvant, or compound, unless explicitly stated otherwise. Rather, the term "consisting essentially of … …" excludes any other components, steps or processes from the scope of any of the terms hereinafter recited, except those necessary for operational performance. The term "consisting of … …" does not include any components, steps or processes not specifically described or listed. Unless explicitly stated otherwise, the term "or" refers to the listed individual members or any combination thereof.
The embodiment of the invention provides a hyperbranched carbon nanotube dispersing agent containing long alkyl chains, which comprises a hyperbranched polymer core A and a chain arm B. And the hyperbranched polymer inner core A is hyperbranched polyester obtained by carrying out polycondensation reaction on polyol and hydroxy acid/polycarboxylic acid/anhydride, and the terminal group contains hydroxyl/carboxyl. The chain arm B is various monoacids/anhydrides/monoalcohols containing carboxyl/anhydride/hydroxyl, and is grafted to the hyperbranched core A through esterification reaction of carboxyl-terminated groups/anhydrides/hydroxyl and hydroxyl-terminated groups/carboxyl of the hyperbranched core A. In this embodiment, the hyperbranched carbon nanotube dispersant containing a long alkyl chain has a hyperbranched molecular structure and a longer alkyl chain structure, and can be widely applied to the oil-phase carbon nanotube dispersant.
In a preferred embodiment, the polyol is selected from any one or a mixture of pentaerythritol, glycerol, ethylene glycol, diethylene glycol, dipentaerythritol, trimethylolpropane, ditrimethylolpropane, castor oil, pentaethylene glycol, triethylene glycol, octapolyethylene glycol, heptapolyethylene glycol, hexapolyethylene glycol, tetraethylene glycol, propylene glycol, 1, 2-propanediol, butanediol, pentanediol, nonanediol, hexanediol, heptanediol, octanediol, 1, 2-octanediol, decanediol, 1, 2-decanediol, dodecanediol, 1, 2-dodecanediol.
In a preferred embodiment, the hydroxy acid/polycarboxylic acid/anhydride is selected from the group consisting of lactic acid, 3-hydroxybutyric acid, gamma-hydroxybutyric acid, 9-hydroxynonanoic acid, 3-hydroxytetradecanoic acid, 9-hydroxytetradecanoic acid, ricinoleic acid, 12-hydroxystearic acid, 2-dimethylolpropionic acid, succinic acid, sebacic acid, adipic acid, azelaic acid, malonic acid, suberic acid, phthalic anhydride, itaconic acid, glutaric acid, itaconic anhydride, phthalic acid, maleic acid, undecanedioic acid, hexadecanedioic acid, dodecanedioic acid, methylmalonic acid, phenylsuccinic acid, citric acid, trimellitic anhydride, maleic anhydride, succinic anhydride, glutaric anhydride, citraconic anhydride, biphenyl anhydride, methylsuccinic anhydride, pyromellitic dianhydride, 3-methylglutaric anhydride, 1, 2-cyclohexanedianhydride, 1-cyclohexanedicarboxylic anhydride, maleic anhydride, succinic anhydride, maleic anhydride, succinic anhydride, maleic anhydride, 3-methylglutaric anhydride, 1, 2-cyclohexanedianhydride, maleic anhydride, any one or mixture of 2, 2-dimethyl succinic anhydride.
In a preferred embodiment, the various types of monocarboxylic acids containing carboxyl/anhydride/hydroxyl groups and their anhydrides/monoalcohols are selected from one or a mixture of acetic acid, acetic anhydride, octanoic acid, nonanoic acid, linolenic acid, octadecenoic acid, oleic acid, linoleic acid, tolleic acid, arachidonic acid, ricinoleic acid, eleostearic acid, erucic acid, trifluoroacetic acid, methanol, ethanol, octanol, nonanol, isopropanol, 2-butanol, 3-pentanol, 2,3, 3-tetrafluoro-1-propanol.
It is to be understood that in the above examples, the polyols, hydroxy acids/polycarboxylic acids/anhydrides, various types of monocarboxylic acids containing carboxyl groups/anhydrides/hydroxyl groups and anhydrides/monohydric alcohols thereof are preferred compounds for facilitating the above reaction, and it is to be understood that the compounds listed in the above examples are not limited to those listed above, and may be other compounds known in the art, so long as the above reaction mechanism can be satisfied, and those skilled in the art can use them alternatively.
In another aspect of the embodiments of the present invention, a preparation method of a hyperbranched carbon nanotube dispersant containing a long alkyl chain is provided, which includes the following steps:
respectively adding polyhydric alcohol and hydroxy acid/polycarboxylic acid/anhydride into a reactor, and carrying out bulk polymerization reaction for 0.1-10 hours at 120-250 ℃ in the presence of a catalyst to obtain a hyperbranched polymer with a terminal hydroxyl group, wherein the preferable time is 1-8 hours; then various monoacids containing carboxyl/anhydride/hydroxyl and anhydride/monohydric alcohol thereof are added, and the mixture is subjected to bulk polymerization reaction at the temperature of 60-250 ℃ for 0.1-10 hours to obtain the hyperbranched carbon nanotube dispersing agent containing long alkyl chains, preferably for 0.5-5 hours.
In the embodiment, commercial polyhydric alcohol and hydroxy acid/polybasic carboxylic acid/anhydride are directly subjected to bulk polymerization, various monobasic acids containing carboxyl/anhydride/hydroxyl and anhydride/monohydric alcohol thereof are grafted, and the hyperbranched carbon nanotube dispersing agent containing long alkyl chains is obtained by direct one-pot polymerization. Compared with the existing preparation method, the method is mature, the direct reaction is carried out by one-step method, the post-treatment of a solvent is not needed after the reaction, the pollution is avoided, and the method can be effectively used in the industrial production and preparation process of the hyperbranched carbon nanotube dispersing agent containing long alkyl chains. It is understood that, in the above steps, the above reaction temperature and reaction time may be favorable for the formation of the product, wherein the temperature may also be 90 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, etc., and 200 ℃, 220 ℃, 240 ℃, etc., and any other point in the range, and the reaction time may also be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.8, 1,2, 3, 4, 5, 6, 8, 10 hours, etc., and can be adjusted by one skilled in the art according to the actual reaction situation.
In a preferred embodiment, the charging molar ratio of the polyalcohol and the hydroxy acid/the polycarboxylic acid/the anhydride is 20:1-1:40, and the charging molar ratio of the various types of monoacids containing the carboxyl group/the anhydride/the hydroxyl group and the anhydride/the monoacids and the hyperbranched polymer is 1:1-100: 1. In this embodiment, the charging molar ratio of the polyol and the hydroxy acid/the polycarboxylic acid/the anhydride, and the charging molar ratio of the various monocarboxylic acids containing the carboxyl group/the anhydride/the hydroxyl group and the anhydride thereof/the monohydric alcohol and the hyperbranched polymer are limited in the above range, so that the polyol and the hydroxy acid/the polycarboxylic acid/the anhydride can be effectively promoted to react to generate the hyperbranched carbon nanotube dispersant containing the long alkyl chain. It is understood that the molar ratios of the polyol and the hydroxy acid/the polycarboxylic acid/the anhydride may preferably be 5:1, 2:1, 1:1, etc., and the molar ratios of the various types of monocarboxylic acids containing a carboxyl group/the anhydride/the hydroxyl group and the anhydrides thereof/the monohydric and the hyperbranched polymer may preferably be 3:1, 6:1, 12:1, 24:1, 48:1, 96:1, etc., and may be selected by one skilled in the art within the above ranges according to actual needs.
In an alternative embodiment, the catalyst is selected from one or a mixture of 4-dimethylaminopyridine, p-toluenesulfonic acid, concentrated sulfuric acid, thionyl chloride, hydrochloric acid, phosphoric acid, sodium bisulfate, ferric chloride, aluminum trichloride, zinc chloride, antimony chloride, ferric sulfate, aluminum sulfate, ferric ammonium sulfate, stannic chloride, stannic laurate, stannous chloride, copper sulfate, calcium chloride and boric acid.
In an alternative embodiment, the catalyst is added in an amount of 0.1% to 1% of the total mass of the polyol and hydroxyacid/polycarboxylic acid/anhydride monomers. In this example, the amount of the catalyst is specifically limited, and it is understood that the catalyst mainly catalyzes the esterification reaction between the hydroxyl group and the carboxyl group/acid anhydride, and therefore, the amount of the catalyst is not too large, and only the catalytic effect is required. Within the above range, the amount of the catalyst may be 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, etc. of the total mass of the monomers, and those skilled in the art may add the catalyst according to actual reaction requirements.
In another aspect of the embodiments of the present invention, there is provided a use of the hyperbranched carbon nanotube dispersing agent containing a long alkyl chain described in the above embodiments as an additive in preparing a high-content low-viscosity oil-phase carbon nanotube dispersing liquid, including the following steps:
and carrying out ball milling dispersion on the hyperbranched carbon nanotube dispersing agent containing the long alkyl chain and the carbon nanotube in the presence of a solvent to obtain an oil-phase carbon nanotube dispersing solution.
In a preferred embodiment, the amount of the long alkyl chain-containing hyperbranched carbon nanotube dispersant added during the process of dispersing the carbon nanotubes in the non-polar organic solvent system by using the long alkyl chain-containing hyperbranched carbon nanotube dispersant is 0.5% -10%. In this embodiment, in the process of dispersing the carbon nanotubes in the non-polar organic solvent system by using the hyperbranched carbon nanotube dispersing agent containing a long alkyl chain, the added amount may also be 1%, 3%, 5%, 7%, 9%, and the like, and those skilled in the art may add the dispersing agent according to actual reaction requirements.
In a preferred embodiment, the carbon nanotubes are added in an amount of 0.5 to 10% during the dispersion of the carbon nanotubes in the non-polar organic solvent system by using the hyperbranched carbon nanotube dispersing agent containing long alkyl chains. In this embodiment, in the process of dispersing the carbon nanotubes in the non-polar organic solvent system by using the hyperbranched carbon nanotube dispersing agent containing a long alkyl chain, the added amount may also be 1%, 3%, 5%, 7%, 9%, etc., and those skilled in the art may add the dispersing agent according to actual reaction requirements.
In a preferred embodiment, the ball milling dispersion time is 0.1-10 hours during the dispersion process of the carbon nanotubes in the non-polar organic solvent system by using the hyperbranched carbon nanotube dispersing agent containing long alkyl chains. In this embodiment, in the process of dispersing the carbon nanotubes in the non-polar organic solvent system by using the hyperbranched carbon nanotube dispersing agent containing a long alkyl chain, the dispersing time of the ball milling dispersion may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.8, 1,2, 3, 4, 5, 6, 8, 10 hours, etc., and may be adjusted by a person skilled in the art according to actual reaction conditions.
The oil phase carbon nanotube dispersion liquid of the hyperbranched carbon nanotube dispersing agent containing the long alkyl chain provided by the embodiment of the invention has the performance advantages of higher addition amount of the carbon nanotube, lower system viscosity, better system dispersibility and stability and the like, can reduce the cost of the subsequent application and addition process, the long-term storage process and the transportation process, and greatly expands the application of the hyperbranched polymer in the field of oil phase carbon nanotube dispersion.
In order to more clearly and specifically describe the hyperbranched carbon nanotube dispersant containing long alkyl chains, the preparation method thereof, and the application thereof in preparing a high-content low-viscosity oil-phase carbon nanotube dispersion according to the embodiments of the present invention, the following detailed description will be made with reference to specific examples.
Examples
The technical solutions of the present application will be clearly and completely described below with reference to the embodiments of the present application. Unless otherwise specified, the reagents and starting materials used are commercially available. Experimental procedures without specifying specific conditions in the following examples were selected in accordance with conventional procedures and conditions, or in accordance with commercial instructions.
Preparation examples
Example 1
Adding 0.1mol of trimellitic anhydride, 0.2mol of octanediol and 0.20g of tin laurate into a three-neck flask, mechanically stirring and reacting at 220 ℃ for 2 hours, adding 0.3mol of acetic anhydride, reducing the temperature to 120 ℃, mechanically stirring and reacting for 2 hours, and stopping the reaction to obtain the hyperbranched carbon nanotube dispersant 1 containing long alkyl chains, wherein the yield is 92%. The number average molecular weight of the resulting hyperbranched polymer 1 was 3454.
The specific molecular structure of the hyperbranched carbon nanotube dispersant containing long alkyl chains synthesized in this example is as follows:
Figure BDA0003548256080000111
in the formula:
Figure BDA0003548256080000112
wherein denotes a bonding site.
Hyperbranched carbon nanotube containing long alkyl chain synthesized in this examplePowder of H1NMR characterization data as follows:
H1-NMR(CDCl3):δ(ppm)＝1.282-1.324(8H)；1.424-1.443(8H)；1.776-1.793(8H)；2.037-2.043(3H)；4.127-4.136(2H)；4.331-4.344(6H)；8.034-8.041(1H)；8.122-8.131(1H)；8.229-8.238(1H)。
example 2
Adding 0.1mol of glycerol, 0.3mol of dimethylolpropionic acid and 0.14g of p-toluenesulfonic acid into a three-neck flask, reacting for 3 hours at 160 ℃ by mechanical stirring, then adding 0.6mol of caprylic acid, reacting for 4 hours at 160 ℃ by mechanical stirring, and stopping the reaction to obtain the hyperbranched carbon nanotube dispersing agent 2 containing long alkyl chains, wherein the yield is 94%. The number average molecular weight of the hyperbranched polymer 2 was 2672.
The specific molecular structure of the hyperbranched carbon nanotube dispersant containing long alkyl chains synthesized in this example is as follows:
Figure BDA0003548256080000121
in the formula:
Figure BDA0003548256080000122
wherein denotes a bonding site.
H of the hyperbranched carbon nanotube dispersant containing long alkyl chain synthesized in the example1NMR characterization data as follows:
H1-NMR(CDCl3):δ(ppm)＝0.880-0.890(18H)；1.262-1.278(45H)；1.328-1.334(12H)；1.657-1.668(12H)；2.322-2.328(12H)；4.301-4.312(4H)；4.348-4.354(12H)；5.851-5.857(1H)。
example 3
Adding 0.1mol of glycerol, 0.3mol of dimethylolpropionic acid and 0.15g of p-toluenesulfonic acid into a three-neck flask, reacting for 2 hours at 160 ℃ by mechanical stirring, then adding 0.6mol of ricinoleic acid, raising the temperature to 220 ℃, reacting for 2 hours by mechanical stirring, and stopping the reaction to obtain the hyperbranched carbon nanotube dispersing agent 3 containing long alkyl chains, wherein the yield is 86%. The number average molecular weight of the obtained hyperbranched polymer 3 was 3886.
The specific molecular structure of the hyperbranched carbon nanotube dispersant containing long alkyl chains synthesized in this example is as follows:
Figure BDA0003548256080000131
in the formula:
Figure BDA0003548256080000132
wherein denotes a bonding site.
H of the hyperbranched carbon nanotube dispersant containing long alkyl chain synthesized in the example1NMR characterization data as follows:
H1-NMR(CDCl3):δ(ppm)＝0.882-0.888(18H)；1.248-1.276(69H)；1.294-1.302(12H)；1.328-1.342(24H)；1.394-1.406(12H)；1.650-1.662(12H)；1.953-1.966(6H)；2.160-2.168(12H)；2.211-2.218(6H)；2.321-2.334(12H)；3.522-3.533(6H)；4.298-4.305(4H)；4.351-4.362(12H)；4.801-4.809(6H)；5.338-5.347(12H)；5.847-5.853(1H)。
example 4
Adding 0.1mol of castor oil, 0.1mol of phthalic anhydride and 0.18g of stannous chloride into a three-neck flask, reacting for 2 hours at 220 ℃ with mechanical stirring, then adding 0.1mol of acetic anhydride, reducing the temperature to 70 ℃, reacting for 1 hour with mechanical stirring, and stopping the reaction to obtain the hyperbranched carbon nanotube dispersant 4 containing long alkyl chains, wherein the yield is 91%. The number average molecular weight of the obtained hyperbranched polymer 4 was 2396.
The specific molecular structure of the hyperbranched carbon nanotube dispersant containing a long alkyl chain synthesized in this example is as follows:
Figure BDA0003548256080000141
in the formula:
Figure BDA0003548256080000142
wherein denotes a bonding site.
H of the hyperbranched carbon nanotube dispersant containing long alkyl chain synthesized in the example1NMR characterization data as follows:
H1-NMR(CDCl3):δ(ppm)＝0.878-0.884(9H)；1.250-1.265(30H)；1.292-1.300(6H)；1.331-1.340(12H)；1.488-1.494(2H)；1.662-1.678(10H)；2.052-1.066(1H)；2.233-2.241(2H)；2.311-2.324(7H)；2.475-2.482(2H)；4.301-4.312(4H)；4.601-4.610(3H)；5.338-5.347(6H)；5.851-5.858(1H)；7.810-7.852(2H)；8.152-8.196(2H)。
example 5
0.1mol of phthalic anhydride, 0.1mol of glycerol and 0.18g of antimony chloride are added into a three-neck flask, and are mechanically stirred and reacted for 2 hours at the temperature of 200 ℃, then 0.1mol of octanoic acid is added, the temperature is reduced to 120 ℃, and the mechanical stirring and reaction are stopped for 1 hour, so that the hyperbranched carbon nanotube dispersing agent 5 containing long alkyl chains is obtained, and the yield is 87%. The number average molecular weight of the resulting hyperbranched polymer 5 was 8417.
The specific molecular structure of the hyperbranched carbon nanotube dispersant containing long alkyl chains synthesized in this example is as follows:
Figure BDA0003548256080000151
in the formula:
Figure BDA0003548256080000152
wherein denotes a bonding site.
H of hyperbranched carbon nanotube dispersant containing long alkyl chain synthesized in the example1NMR characterization data as follows:
H1-NMR(CDCl3):δ(ppm)＝0.880-0.890(3H)；1.258-1.269(6H)；1.331-1.340(2H)；1.657-1.664(2H)；2.325-2.353(2H)；4.168-4.174(1H)；4.335-4.343(1H)；4.421-4.428(1H)；4.590-4.600(1H)；5.851-5.860(1H)；7.714-7.725(2H)；8.027-8.032(2H)。
example 6
0.1mol of itaconic anhydride, 0.1mol of trimethylolpropane and 0.12g of tin laurate are added into a three-neck flask, and are mechanically stirred and reacted for 2 hours at 220 ℃, then 0.3mol of oleic acid is added, and are mechanically stirred and reacted for 2 hours at 220 ℃, and the reaction is stopped, so that the hyperbranched carbon nanotube dispersing agent 6 containing long alkyl chains is obtained, and the yield is 84%. The number average molecular weight of the obtained hyperbranched polymer 6 was 3014.
The specific molecular structure of the hyperbranched carbon nanotube dispersant containing a long alkyl chain synthesized in this example is as follows:
Figure BDA0003548256080000161
in the formula:
Figure BDA0003548256080000162
wherein denotes a bonding site.
H of the hyperbranched carbon nanotube dispersant containing long alkyl chain synthesized in the example1NMR characterization data as follows:
H1-NMR(CDCl3):δ(ppm)＝0.880-0.895(6H)；1.261-1.268(8H)；1.291-1.302(6H)；1.328-1.337(6H)；1.657-1.664(2H)；2.156-2.168(4H)；2.320-2.333(2H)；3.581-3.590(2H)；3.939-3.947(6H)；4.002-4.015(1H)；5.334-5.350(2H)；5.951-5.960(1H)。
effects of the embodiment
Example 7
The following will illustrate the application effect of the hyperbranched carbon nanotube dispersant 1-6 containing long alkyl chains obtained in examples 1-6 as a dispersant in a high-content low-viscosity oil phase carbon nanotube dispersion system by taking a nonpolar organic solvent system as an example. The obtained hyperbranched carbon nanotube dispersant 1-6 containing long alkyl chains is used as a carbon nanotube dispersant, carbon nanotube dispersion without dispersant is used as a contrast, 3% of the developed hyperbranched polymer is added on the basis of 2% of the addition of the carbon nanotubes, and the dispersion performance is shown in table 1 after ball milling for 1 hour.
Table 1: performance data for the use of the hyperbranched polymers containing Long-chain alkyl groups according to examples 1 to 6 as dispersants for carbon nanotubes
Dispersing samples viscosity/mPas Fineness/um Stability of
Dispersant free control 37000 90 After 90 days, there is settlement
Hyperbranched Polymer 1 3529 45 No sedimentation for 90 days
Hyperbranched polymer 2 7298 45 No sedimentation for 90 days
Hyperbranched Polymer 3 5139 35 No sedimentation for 90 days
Hyperbranched polymersCompound 4 1249 35 No sedimentation for 90 days
Hyperbranched Polymer 5 7254 45 No sedimentation for 90 days
Hyperbranched Polymer 6 6347 45 No sedimentation for 90 days
From the data in table 1, it can be seen that the hyperbranched carbon nanotube dispersant containing long alkyl chains has better dispersing and viscosity reducing effects on carbon nanotubes in an oily nonpolar solvent.
The molecular structure of the hyperbranched polymer provided by the invention has an anchoring group capable of adsorbing with a carbon nanotube to enhance stability, and a dissolving-assisting chain capable of interacting with a solvent to enhance solubility of the carbon nanotube. In the molecular structure of the hyperbranched carbon nanotube dispersing agent containing long alkyl chains, ester groups, benzene rings and other groups in the hyperbranched carbon nanotube dispersing agent can help the dispersing agent and the carbon nanotube to be tightly combined together, so that the hyperbranched carbon nanotube dispersing agent plays a role in anchoring groups; the long alkyl chain part can help the carbon nano tube to be well dispersed and dissolved in a non-polar organic solvent system, so that the carbon nano tube can be uniformly and stably dispersed.
The raw materials used in the application are all commercially available raw materials, are wide in source and can be produced in a large scale.
The embodiments described above are presented to enable a person having ordinary skill in the art to make and use the present application. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present application is not limited to the embodiments herein, and those skilled in the art, in light of the present disclosure, will recognize that changes may be made in the form and detail of the embodiments without departing from the scope or spirit of the application.

Claims (13)

1. The hyperbranched polymer containing long-chain alkyl is characterized by comprising an inner core A and a chain arm B, and the structure of the hyperbranched polymer is shown as the following general formula I:
Figure FDA0003548256070000011
the core A is hyperbranched polyester containing hydroxyl or carboxyl at the tail end, and is formed by performing polycondensation reaction on a monomer containing at least two hydroxyl groups and a monomer containing carboxyl, or by performing polycondensation reaction on a monomer containing at least two hydroxyl groups and a first anhydride;
wherein the chain arm B is monoacid, monoalcohol or second anhydride, and the chain arm B is connected to the terminal group of the core A through an ester group covalent bond.
2. The hyperbranched polymer of claim 1, wherein the monomer containing at least two hydroxyl groups is selected from one or more of pentaerythritol, glycerol, ethylene glycol, diethylene glycol, dipentaerythritol, trimethylolpropane, ditrimethylolpropane, castor oil, pentaethylene glycol, triethylene glycol, octapolyethylene glycol, heptapolyethylene glycol, hexapolyethylene glycol, tetraethylene glycol, propylene glycol, 1, 2-propylene glycol, butylene glycol, pentanediol, nonanediol, hexanediol, heptanediol, octanediol, 1, 2-octanediol, decanediol, 1, 2-decanediol, dodecanediol, and 1, 2-dodecanediol;
the monomer containing carboxyl is selected from one or more of lactic acid, 3-hydroxybutyric acid, gamma-hydroxybutyric acid, 9-hydroxynonanoic acid, 3-hydroxytetradecanoic acid, 9-hydroxytetradecanoic acid, ricinoleic acid, 12-hydroxystearic acid, 2-dimethylolpropionic acid, succinic acid, sebacic acid, adipic acid, azelaic acid, malonic acid, suberic acid, phthalic anhydride, itaconic acid, glutaric acid, itaconic anhydride, phthalic acid, maleic acid, undecanedioic acid, hexadecanedioic acid, dodecanedioic acid, methylmalonic acid, phenylsuccinic acid and citric acid;
the first anhydride is independently selected from one or more of trimellitic anhydride, maleic anhydride, succinic anhydride, glutaric anhydride, citraconic anhydride, biphenyl anhydride, methyl succinic anhydride, pyromellitic dianhydride, 3-methyl glutaric anhydride, 1, 2-cyclohexane dianhydride, and 2, 2-dimethyl succinic anhydride;
the monoacid is selected from one or more of acetic acid, caprylic acid, pelargonic acid, linolenic acid, octadecenoic acid, oleic acid, linoleic acid, tololeic acid, arachidonic acid, ricinoleic acid, eleostearic acid, erucic acid and trifluoroacetic acid;
the monohydric alcohol is selected from one or more of methanol, ethanol, octanol, nonanol, isopropanol, 2-butanol, 3-pentanol, and 2,2,3, 3-tetrafluoro-1-propanol;
the second anhydride is selected from one or more of acetic anhydride, propionic anhydride, benzoic anhydride, maleic anhydride, n-butyric anhydride, succinic anhydride, glutaric anhydride, isobutyric anhydride, trifluoroacetic anhydride and trimethylacetic anhydride.
3. Process for the preparation of hyperbranched polymers containing long-chain alkyl groups according to claim 1 or 2, characterized in that it comprises the following steps:
s1: preparation of hyperbranched polyester containing hydroxyl or carboxyl at terminal
In the presence of a catalyst, carrying out a first polycondensation reaction on the monomer containing at least two hydroxyl groups and the monomer containing carboxyl groups or first acid anhydride to obtain the hyperbranched polyester containing hydroxyl groups or carboxyl groups at the tail end;
s2: preparation of hyperbranched polymers containing Long-chain alkyl groups
And carrying out a second polycondensation reaction on the hyperbranched polyester with the terminal containing hydroxyl or carboxyl and the monoacid, the monohydric alcohol or the second anhydride to obtain the hyperbranched polymer containing the long-chain alkyl.
4. The method of claim 3, wherein the catalyst is selected from one or more of 4-dimethylaminopyridine, p-toluenesulfonic acid, concentrated sulfuric acid, thionyl chloride, hydrochloric acid, phosphoric acid, sodium bisulfate, ferric chloride, aluminum trichloride, zinc chloride, antimony chloride, ferric sulfate, aluminum sulfate, ferric ammonium sulfate, stannic chloride, stannous chloride, stannic laurate, copper sulfate, calcium chloride, and boric acid.
5. The method of claim 3, wherein the first polycondensation reaction and the second polycondensation reaction are bulk reactions.
6. The method according to any one of claims 3 to 5, wherein in step S1, the molar ratio of the monomer containing at least two hydroxyl groups to the monomer containing a carboxyl group or the first acid anhydride is from 20:1 to 1: 40;
the reaction temperature of the first polycondensation reaction is 120-250 ℃, and the reaction time is 0.1-10 hours, preferably 1-8 hours.
7. The method according to any one of claims 3 to 5, wherein in the step S2, the feed molar ratio of the monoacid, the monoalcohol, or the second anhydride to the hyperbranched polyester containing hydroxyl or carboxyl groups at the terminal end is 1:1 to 100: 1;
the reaction temperature of the second polycondensation reaction is 60-250 ℃, and the reaction time is 0.1-10 hours, preferably 0.5-5 hours.
8. An oil-phase carbon nanotube dispersion, characterized in that the carbon nanotube dispersion is prepared by a method comprising: dispersing the hyperbranched polymer containing long-chain alkyl groups and the carbon nanotubes of claim 1 or 2 in an oily solvent to obtain an oily-phase carbon nanotube dispersion liquid;
wherein the viscosity of the oil-phase carbon nanotube dispersion liquid at room temperature is 1000 to 10000mPa · s.
9. The oil-phase carbon nanotube dispersion of claim 8, wherein the amount of hyperbranched polymer containing long-chain alkyl groups added to the oil-phase carbon nanotube dispersion is 0.5 to 10% of the total mass of the oil-phase carbon nanotube dispersion.
10. The oil-phase carbon nanotube dispersion according to claim 8, wherein the amount of the carbon nanotubes added in the oil-phase carbon nanotube dispersion is 0.5% to 10% of the total mass of the oil-phase carbon nanotube dispersion.
11. The oil-phase carbon nanotube dispersion according to claim 8, wherein the hyperbranched polymer containing a long-chain alkyl group has a number average molecular weight of 2000 to 10000;
the fineness of the carbon nano tubes in the oil phase carbon nano tube dispersion liquid is 10-100 mu m;
the oily solvent in the oil-phase carbon nanotube dispersion liquid is a nonpolar organic solvent.
12. The oil-phase carbon nanotube dispersion according to claim 8, wherein the dispersing comprises ball milling dispersion, and the dispersion time of the ball milling dispersion is preferably 0.1 to 10 hours.
13. Use of a hyperbranched polymer containing long-chain alkyl groups as defined in claim 1 or 2 as a carbon nanotube dispersant.
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Application publication date: 20220722