CN106188559A - Dispersant and preparation method thereof, CNT dispersion pulp and preparation method thereof - Google Patents
Dispersant and preparation method thereof, CNT dispersion pulp and preparation method thereof Download PDFInfo
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- CN106188559A CN106188559A CN201610670412.5A CN201610670412A CN106188559A CN 106188559 A CN106188559 A CN 106188559A CN 201610670412 A CN201610670412 A CN 201610670412A CN 106188559 A CN106188559 A CN 106188559A
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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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/027—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyester or polycarbonate sequences
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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- 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
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
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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
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
Abstract
The invention belongs to electrochemical material technical field, disclose a kind of CNT dispersant special with comb shape graft polymers structure and preparation method thereof, described dispersant is obtained on main chain backbone copolymer by side chain copolymer grafted, described main chain backbone copolymer is the acrylate copolymer containing grafted moiety and anchoring group, and described side chain copolymer is the linear polyester containing grafted moiety.The invention also discloses CNT dispersion pulp made from this dispersant and preparation method thereof.The dispersant of the present invention is adsorbed in carbon nano tube surface by anchoring group；The graft side chain of dispersant provides sterically hindered simultaneously, the most effectively prevents CNT from assembling, and strengthens again the compatibility between nano material and substrate polymer.Prepared CNT dispersion pulp, can improve the physical and chemical performance of the aspects such as coating or the machinery of resin base thing, weather-proof, electric, hot and anticorrosion, be with a wide range of applications.
Description
Technical field
The invention belongs to electrochemical material technical field, be specifically related to a kind of carbon with comb shape graft polymers structure and receive
Mitron dispersant special and preparation method thereof, and the CNT dispersion pulp made with this dispersant and preparation method thereof.
Background technology
Nano-carbon material because possessing various prominent physics, chemical property cause the broad interest of paint field.Nanometer
Material with carbon element has high-specific surface area, can form network structure when coating is dried, thus strengthen the adsorption of coating and substrate,
Make coating finer and close, improve the coating adhesive force to base material, meanwhile, be favorably improved the impact resistance of coating, rub resistance
Performance, heat conductivity, electric conductivity, weatherability and antiseptic property, and there is scratch resistance and slightly scratch self-repair function, it is used for making
The conductive primer of standby inner and outer decorative parts of automobile electrostatic spraying has superiority very much；Static conductive coating, antistatic coating application in
Sample has good performance.CNT (CNT) is one type nano-carbon material, has high thermal conductivity and high-specific surface area,
Can be sufficient filling with in the coating, increasing coating cooling surface area, it is possible to effectively reduce body surface and internal temperature, simultaneously by
Yu Qiguang, thermally and chemically stability are high, all can use at various extreme environments, can be used for LED heat radiation coating, industrial equipment dissipates
Hot coating, auto parts and components heat radiation coating etc..
Nano-carbon material composite coating is substantially nano composite material, the problem of most critical be intended to solve CNT and
The problem of coating film forming matter mixing, these nano materials only have well to disperse and be uniformly distributed in coating system just can fill
Its effect is waved in distribution.Nano-carbon material and fluoropolymer resin complex method substantially have three kinds: physical blending, chemical modification, in situ
Polymerization, thus realize the stable dispersion of CNT and the performance of features thereof.Physical blending is not destroying nano-carbon material
On the premise of structure, rely on physical action to be directly realized by the mixing of CNT and matrix resin, can pass through solution, emulsion,
Melting method is carried out, and is realized by the external force such as mechanical agitation or supersonic oscillations, typically requires nano material before being blended
It is modified improving and the compatibility of matrix resin, is the simplest, common method, but there is also difficult control, dispersion all
The problems such as even property is the best.Chemical modification method is in CNT and graphenic surface functionalization (hydroxyl or amino etc.), then altogether
The valency upper matrix polymer of grafting or the polymer segment compatible with matrix resin.Situ aggregation method is to add in monomer polymerization process
Entering the CNT that surface is the most processed, after mix homogeneously, the polymerization of trigger monomer forms composite again.
Incompatible due to CNT and matrix resin, it is effectively multiple that simple physical blending process is difficult to make both obtain
Closing, using effect is also had a greatly reduced quality, and usually in order to improve the compatibility of CNT and resin, needs to carry out with to CNT
Surface processes, and such as uses strong acid oxidation so that carbon nano tube surface forms the functional groups such as hydroxyl.Chemical modification method and original position are poly-
Legal is all that this process is all to CNT so that carbon nano tube surface to carry out chemical treatment and the method being modified as basis
Structure causes a certain degree of destruction, and therefore, pyroelecthc properties and mechanical performance to CNT all can cause damage, and cause
Usefulness declines.
Therefore, develop the method for the non-conjugated functionalization of a kind of CNT and realize carbon nanomaterial and high molecular polymer is multiple
Desirable justice is the most great.Non-conjugated functionalization by polymer molecule and the Van der Waals force of carbon nano tube surface, π π, CH π and
Electrostatic interaction realizes, and does not affect the structure of nanotube, and therefore the electrical characteristics of CNT and mechanical property are all without being subject to
To impact.
Summary of the invention
It is an object of the invention to provide a kind of CNT dispersant special with comb shape graft polymers structure.
It is a further object of the present invention to provide the preparation method of this dispersant.
It is a further object of the present invention to provide the CNT dispersion pulp being prepared from this dispersant.
It is a further object of the present invention to provide the preparation method of foregoing carbon nanotubes dispersion pulp.
For reaching one of above-mentioned purpose, the present invention by the following technical solutions:
A kind of dispersant with comb shape graft polymers structure, described dispersant by side chain copolymer grafted to main chain bone
Obtaining on frame copolymer, described main chain backbone copolymer is the acrylate copolymer containing grafted moiety and anchoring group, institute
Stating side chain copolymer is the linear polyester containing grafted moiety.
The molecular weight of this dispersant is 4000～100000g/mol, preferably 8000～30000g/mol.
Molecular weight is by the chromatograph of gel permeation (GPC) with refractive index detection instrument, demarcates with polystyrene PS,
Oxolane does to flow and measures mutually.
Further, described grafted moiety is at least one of epoxy radicals, hydroxyl and carboxyl.
Further, the monomer containing grafted moiety selected from 2-hydroxyethylmethacry,ate, HEMA,
2-hydroxypropyl acrylate, 2-HPMA, 3-hydroxypropyl acrylate, 3-HPMA,
4-hydroxyl butyl propyleneglycol acid esters, 4-hydroxyl butyl methyl acrylate, acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, propylene
At least one in acid glycidyl ester, glycidyl methacrylate.
The monomer containing grafted moiety content in dispersant is 5～50wt%, preferably 10～30wt%.
Further, described anchoring group is phenyl, especially Benzoylamide.
Further, the monomer containing anchoring group is selected from styrene, α-methyl styrene, phthalimide, N-first
Base aminobenzene, at least one in N-ethyl amino phenyl, N-methylbenzylamine, N-ethyl benzyl amine.
The monomer containing anchoring group content in dispersant is 5～50wt%, preferably 5～15wt%.
Anchoring group can obtain by the way of adding the monomer containing phenyl ring or rear grafting in polymerization process.
Further, described acrylic resin copolymer is by the monomer of hydroxy functional groups and acrylate or metering system
Acid ester monomer is obtained by radical polymerization.
Further, the monomer of described hydroxy functional groups is selected from 2-(Acryloyloxy)ethanol, hydroxyethyl methylacrylate, propylene
Acid-2-hydroxy propyl ester, methacrylic acid-2-hydroxy propyl ester, acrylic acid-3-hydroxy propyl ester, methacrylic acid-3-hydroxy propyl ester,
At least one in acrylic acid-4-hydroxybutyl and methacrylic acid-4-hydroxybutyl.
Further, described acrylate is selected from ethyl acrylate, propyl acrylate, isopropyl acrylate, acrylic acid fourth
Ester, Isobutyl 2-propenoate, tert-butyl acrylate, amyl acrylate, Hexyl 2-propenoate, 2-EHA, the acrylic acid moon
At least one in osmanthus ester, cyclohexyl acrylate and isobornyl acrylate；Described methacrylate is selected from methacrylic acid
Ethyl ester, propyl methacrylate, isopropyl methacrylate, n-BMA, isobutyl methacrylate, methyl-prop
Enoic acid ter-butyl ester, pentylmethacrylate, N-Hexyl methacrylate, 2-Ethylhexyl Methacrylate, lauryl
At least one in ester, cyclohexyl methacrylate, isobornyl methacrylate.
Vinyl monomer can also be added, such as vinyltoluene, styrene, Alpha-Methyl benzene second when carrying out radical polymerization
Alkene, acrylic acid and methacrylic acid etc..
The molecular weight of acrylic resin copolymer is between 1000～50000g/mol, preferably 2000～20000g/mol
Between.
Linear polyester is typically synthesized by polybasic carboxylic acid and the polycondensation of polyhydric alcohol, it is possible to gathered by cyclic ester and polyprotic acid
Closing and obtain, polyprotic acid can also change hydroxy acid into.
Polybasic carboxylic acid can be aliphatic polycarboxylic acid and/or alicyclic polycarboxylic acid and/or aromatic polycarboxylic acid；Many
Unit's carboxylic acid refers to have more than one, particular with the compound of two carboxyls；Can also replace with the derivant such as anhydride of carboxylic acid
Free polybasic carboxylic acid.
The example of polybasic carboxylic acid is adipic acid, Azelaic Acid, decanedioic acid, phthalic acid, M-phthalic acid, terephthaldehyde
Acid, 1,2,4-benzenetricarboxylic acid and hexahydro-phthalic acids.
Described hydroxy acid is selected from lactic acid, ethylene lactic acid, salicylic acid and 12-hydroxy stearic acid.
Described cyclic ester is selected from 6-caprolactone, γ-hexalactone, δ-caprolactone, gamma-valerolactone, δ-valerolactone and γ-fourth
Lactone.
Polyhydric alcohol can be aliphatic polyol and/or alicyclic polyol and/or aromatic polyol；Polyhydric alcohol refers to have
More than one, particularly there is the compound of two hydroxyls.
The example of polyhydric alcohol is butanediol, neopentyl glycol, hexanediol, bisphenol-A, hydrogenated bisphenol A, Isosorbide-5-Nitrae-hexamethylene diformazan
Alcohol, 2,2,4-trimethyl-1,3-pentanediol, trimethylolpropane and 2-butyl-2-ethyl-1,3-PD.
The molecular weight of linear polyester is between 1000～50000g/mol, preferably between 2000～10000g/mol.Line
The acid number of property polyester is 1～100mg/gKOH, preferably 10～50mg/gKOH.
Further, described side chain copolymer content in dispersant is 20～80wt%, described main chain backbone copolymerization
Thing content in dispersant is 20～80wt%.
Further, described side chain copolymer content in dispersant is 40～60wt%, and described main chain backbone is altogether
Polymers content in dispersant is 40～60wt%.
The method preparing foregoing dispersant, comprises the following steps:
S1, prepare acrylate copolymer by radical polymerization；
S2, prepare linear polyester by polycondensation reaction；
The reaction under melted or azeotropic state of S3, acrylate copolymer and linear polyester obtains dispersant.
A kind of CNT dispersion pulp, this dispersion pulp includes 1～10 parts by weight of carbon nanotubes, 1～10 parts per weight dispersing agent
With 80～98 parts by weight solvent；Described dispersant is above-mentioned dispersant.
Further, described solvent is the organic solvent known to the research worker of this area or inorganic solvent, organic solvent
Can be esters, ketone and aromatic hydrocarbons, and N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide
Deng, esters solvent such as propylene glycol methyl ether acetate；Inorganic solvent is water.
Described CNT is commercially available SWCN or multi-walled carbon nano-tubes.
The ratio of the consumption of CNT and dispersant is 10:1～1:10, preferably 2:1～1:2.
A kind of method preparing foregoing CNT dispersion pulp, specifically: CNT and solvent are mixed quiet
After putting immersion, adding dispersant, CNT obtains CNT dispersion pulp after being uniformly dispersed.
CNT can be uniformly dispersed by the way of grinding, high speed dispersion etc. are known to the research worker of this area.
Grinding is to have the grinding machine for grinding of abrasive media or at the grinding machine for grinding of non-grinding medium, abrasive media
For the combination of one or more in bead, Zirconium orthosilicate. pearl, zirconium dioxide pearl, titanium dioxide aluminium pill or steel ball；High speed dispersion is adopted
With SDF550 type dispersion sand milling stirring multiple purpose aeroplane.
The method have the advantages that
The present invention utilizes the dispersant with comb shape graft polymers structure to achieve the non-conjugated functionalization of CNT,
Dispersant is adsorbed in carbon nano tube surface by anchoring group, and this adsorption comes from anchoring group and the hexa-atomic carbon of CNT
Affinity between ring structure；The graft side chain of dispersant provides sterically hindered simultaneously, the most effectively prevents CNT from assembling, again
Strengthen the compatibility between nano material and substrate polymer.Prepared CNT dispersion pulp, joins coating or resin
Substrate can improve the physical and chemical performance of the aspects such as coating or the machinery of resin base thing, weather-proof, electric, hot and anticorrosion, has wide
General using value.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further:
Following example are prepared reaction condition (temperature, the time of main chain backbone copolymer, side chain copolymer, dispersant
Deng), material rate can adjust according to actual needs, those skilled in the art know these and conventional change.
Embodiment 1
The preparation of Carbon nano-tube dispersant A
(1) preparation of main chain backbone copolymer a-1
1000g is added in the reactor being equipped with heating mantle, thermocouple, agitator, reflux condensing tube and Dropping funnel
N-butyl acetate, is heated to backflow, the most at the uniform velocity dropping monomer mixture and initiator solution, and wherein monomer mixture contains
500g n-BMA, 500g glycidyl methacrylate and 230g hydroxyethyl methylacrylate, initiator is molten
Liquid prepares for being dissolved in 180g n-butyl acetate by 60g Vazo 67, initiated polymerization, controls rate of addition and ensures 2h dropping
Complete.When monomer solution and initiator solution drip complete, continuously add drawing of 15g Vazo 67 and 45g butyl acetate formation
Sending out agent solution, 30min adds, and keeps temperature reflux 30min, it is ensured that polyreaction completes after initiator solution dropping.?
Being 3870 to copolymer solution a-1, molecular weight Mn, molecular weight distribution mw/mn=2.36, non-volatile part is 50%.A-1 is used as system
The skeletal chain of standby comb-shaped graft copolymer dispersant.
(2) preparation of sterically hindered side chain copolymer a-2 is provided
The heating mantle reactor that nitrogen is filled is equipped with agitator, thermocouple, water knockout drum and reflux condensing tube, adds
119.5g salicylic acid, 1584g 6-caprolactone, 56.5g methanesulfonic acid and 840g dimethylbenzene, be heated to reflux.In 5h, temperature is from 141 DEG C
Rise to 162 DEG C, remove the water that reaction generates.Acid number < terminates reaction, obtains product as follows: solid part 69.6%, acid number when 15
14.81 (solid parts), molecular weight Mn is 4760, molecular weight distribution mw/mn=2.73.A-2 is used as to prepare comb-shaped graft copolymer
The sterically hindered side chain (arm) of dispersant.
(3) preparation of comb-shaped graft copolymer dispersant A
Heating mantle reactor is equipped with agitator, thermocouple and reflux condensing tube, is sequentially added into 710g backbone copolymer a-
1,132.3g phthalimide, 1200g side chain copolymer a-2, propylene glycol methyl ether acetate 200g, 40% phenyl trimethicone
The methanol solution 30g of ammonium hydroxide.Mixture is heated to 105 DEG C, and phthalimide dissolves, and reaction starts heat release.Stop
After heating, reaction temperature first rises and reduces afterwards, restarts heating and keep constant temperature 110 DEG C reaction when temperature is down to 110 DEG C
4h.When acid number is down to below 0.5, stopped reaction, now the reaction conversion ratio of carboxyl functional group and amidine functional group is not less than
95%.Obtaining the Carbon nano-tube dispersant solution A of comb-shaped graft copolymer type, molecular weight Mn is 16520, molecular weight distribution Mw/
Mn=2.98, non-volatile content is 56.5%.
Embodiment 2
The preparation of Carbon nano-tube dispersant B
(1) preparation of main chain backbone copolymer b-1
1100g is added in the reactor being equipped with heating mantle, thermocouple, agitator, reflux condensing tube and Dropping funnel
N-butyl acetate, is heated to backflow, the most at the uniform velocity dropping monomer mixture and initiator solution, and wherein monomer mixture contains
568g n-BMA, 284g glycidyl methacrylate, 260g hydroxyethyl methylacrylate and 208g benzene second
Alkene, initiator solution prepares for being dissolved in 190g n-butyl acetate by 23.4g Vazo 67, and initiated polymerization controls dropping
Speed ensures that 2h dropping is complete.When monomer solution and initiator solution drip complete, continuously add 5.8g Vazo 67 and 48g vinegar
The initiator solution that acid butyl ester is formed, 30min adds, and keeps temperature reflux 30min, it is ensured that poly-after initiator solution dropping
Conjunction reaction completes.Obtaining copolymer solution b-1, molecular weight Mn is 11350, molecular weight distribution mw/mn=2.61, and non-volatile part is
51%.B-1 is used as to prepare the skeletal chain of comb-shaped graft copolymer dispersant.
(2) preparation of sterically hindered side chain copolymer b-2 is provided
The heating mantle reactor that nitrogen is filled is equipped with agitator, thermocouple, water knockout drum and reflux condensing tube, adds
965g 12-hydroxy stearic acid, 1541g γ-hexalactone, 2.5g methanesulfonic acid and 300g dimethylbenzene, be heated to reflux.Temperature in 5h
Rise to 162 DEG C from 141 DEG C, remove the water that reaction generates.Acid number < terminates reaction, with the propylene glycol monomethyl ether acetic acid of 752g when 15
Ester dilutes, and obtains product as follows: solid part 69.5%, and acid number 14.68 (solid part), molecular weight Mn is 6950, molecular weight distribution
Mw/Mn=2.49.B-2 is used as to prepare the sterically hindered side chain (arm) of comb-shaped graft copolymer dispersant.
(3) preparation of comb-shaped graft copolymer dispersant B
Heating mantle reactor is equipped with agitator, thermocouple and reflux condensing tube, is sequentially added into 900g backbone copolymer b-
The methanol solution of 1,1000g side chain copolymer b-2, propylene glycol methyl ether acetate 200g, 40% phenyl trimethicone ammonium hydroxide
30g.Mixture is heated to 110 DEG C, and reaction starts heat release, keeps constant temperature 110 DEG C reaction 4h.When acid number is down to below 0.5, stop
Only reaction.Obtaining the Carbon nano-tube dispersant B solution of comb-shaped graft copolymer type, molecular weight Mn is 27530, molecular weight distribution
Mw/Mn=3.11, non-volatile content is 53.9%.
Embodiment 3
The preparation of Carbon nano-tube dispersant C
(1) preparation of main chain backbone copolymer c-1
1100g is added in the reactor being equipped with heating mantle, thermocouple, agitator, reflux condensing tube and Dropping funnel
N-butyl acetate, is heated to backflow, the most at the uniform velocity dropping monomer mixture and initiator solution, and wherein monomer mixture contains
568g n-BMA, 426g glycidyl methacrylate, 260g methacrylic acid-4-hydroxybutyl, cause
Agent solution prepares for being dissolved in 190g n-butyl acetate by 75g AIBN, initiated polymerization, controls rate of addition and ensures that 2h drips
Add complete.When monomer solution and initiator solution drip complete, continue to add 19g AIBN and the initiator of 45g butyl acetate formation
Solution, 30min adds, and keeps temperature reflux 30min, it is ensured that polyreaction completes after initiator solution dropping.It is total to
Copolymer solution c-1, molecular weight Mn are 2420, molecular weight distribution mw/mn=2.41, and non-volatile part is 50%.C-1 is used as preparation comb
The skeletal chain of shape graft copolymer dispersant.
(2) preparation of sterically hindered side chain copolymer c-2 is provided
The heating mantle reactor that nitrogen is filled is equipped with agitator, thermocouple, water knockout drum and reflux condensing tube, adds
965g 12-hydroxy stearic acid, 1022g adipic acid, 714g neopentyl glycol, 2.5g methanesulfonic acid and 300g dimethylbenzene, be heated to reflux.
In 5h, temperature rises to 162 DEG C from 141 DEG C, removes the water that reaction generates.Acid number < terminates reaction, with the third the two of 852g when 15
Alcohol methyl ether acetate dilutes, and obtains product as follows: solid part 69.1%, acid number 14.17 (solid part), and molecular weight Mn is 8230,
Molecular weight distribution mw/mn=2.52.C-2 is used as to prepare the sterically hindered side chain (arm) of comb-shaped graft copolymer dispersant.
(3) preparation of comb-shaped graft copolymer dispersing agent C
Heating mantle reactor is equipped with agitator, thermocouple and reflux condensing tube, is sequentially added into 800g backbone copolymer c-
1,150g phthalimide, 1200g side chain copolymer c-2, propylene glycol methyl ether acetate 200g, 40% phenyl trimethicone hydrogen
The methanol solution 30g of amine-oxides.Mixture is heated to 105 DEG C, and phthalimide dissolves, and reaction starts heat release.Stopping adds
After heat, reaction temperature first rises and reduces afterwards, restarts heating and keep constant temperature 110 DEG C to react 4h when temperature is down to 110 DEG C.
When acid number is down to below 0.5, stopped reaction, now the reaction conversion ratio of carboxyl functional group and amidine functional group is not less than
95%.Obtaining the Carbon nano-tube dispersant C solution of comb-shaped graft copolymer type, molecular weight Mn is 19340, molecular weight distribution Mw/
Mn=2.87, non-volatile content is 57.3%.
Embodiment 4
The preparation of CNT dispersion pulp A1
Commercially available for 50g multi-walled carbon nano-tubes, 400g propylene glycol methyl ether acetate are joined in round can, after being standing and soak for 2h,
With dispersion sand milling stirring multiple purpose aeroplane (the 600～800rpm) stirring under the relatively slow-speed of revolution of SDF550 type, slowly add in whipping process
Enter comb-shaped graft copolymer dispersant A 50g, continue to stir material mix homogeneously, allow dispersant and solvent abundant moistening carbon receive
Mitron, the most gradually heightens rotating speed, notes avoiding throwing away material round can when regulating rotating speed, and rotating speed is adjusted to 2000rpm, stirring
It is dispersed to CNT be uniformly dispersed, obtains the CNT dispersion pulp A1 of black half paste.
Embodiment 5
The preparation of CNT dispersion pulp B1
Commercially available for 50g multi-walled carbon nano-tubes, 400g propylene glycol methyl ether acetate are joined in round can, after being standing and soak for 2h,
With dispersion sand milling stirring multiple purpose aeroplane (the 600～800rpm) stirring under the relatively slow-speed of revolution of SDF550 type, slowly add in whipping process
Enter comb-shaped graft copolymer dispersant B 50g, continue to stir material mix homogeneously, allow dispersant and solvent abundant moistening carbon receive
Mitron, the most gradually heightens rotating speed, notes avoiding throwing away material round can when regulating rotating speed, and rotating speed is adjusted to 2000rpm, stirring
It is dispersed to CNT be uniformly dispersed, obtains the CNT dispersion pulp B1 of black half paste.
Embodiment 6
The preparation of CNT dispersion pulp C1
Commercially available for 50g multi-walled carbon nano-tubes, 400g propylene glycol methyl ether acetate are joined in round can, after being standing and soak for 2h,
With dispersion sand milling stirring multiple purpose aeroplane (the 600～800rpm) stirring under the relatively slow-speed of revolution of SDF550 type, slowly add in whipping process
Enter comb-shaped graft copolymer dispersing agent C 50g, continue to stir material mix homogeneously, allow dispersant and solvent abundant moistening carbon receive
Mitron, the most gradually heightens rotating speed, notes avoiding throwing away material round can when regulating rotating speed, and rotating speed is adjusted to 2000rpm, stirring
It is dispersed to CNT be uniformly dispersed, obtains the CNT dispersion pulp C1 of black half paste.
Embodiment 7
The preparation of CNT dispersion pulp A2
Commercially available for 50g multi-walled carbon nano-tubes, 400g propylene glycol methyl ether acetate are joined in round can, after being standing and soak for 2h,
With dispersion sand milling stirring multiple purpose aeroplane (the 600～800rpm) stirring under the relatively slow-speed of revolution of SDF550 type, slowly add in whipping process
Enter comb-shaped graft copolymer dispersant A 50g, continue to stir material mix homogeneously, allow dispersant and solvent abundant moistening carbon receive
Mitron, adds Ф 1.0～1.5mm bead and does abrasive media, and addition is 1.0～1.2 times of material gross weight, then will circle
Tank seals and tight prevents material from leakage in process of lapping, puts into SK450 type and shakes and grind in sieve instrument, sets polish process, every time
Grinding 30min, repeatedly grind and be uniformly dispersed to CNT for 4～6 times, copper mesh is filtered to remove bead and obtains black half paste
CNT dispersion pulp A2.
Embodiment 8
The preparation of CNT dispersion pulp A3
Commercially available for 50g multi-walled carbon nano-tubes, 400g propylene glycol methyl ether acetate are joined in round can, after being standing and soak for 2h,
With dispersion sand milling stirring multiple purpose aeroplane (the 600～800rpm) stirring under the relatively slow-speed of revolution of SDF550 type, slowly add in whipping process
Enter comb-shaped graft copolymer dispersant A 50g, continue to stir material mix homogeneously, allow dispersant and solvent abundant moistening carbon receive
Mitron, is then added in SGM-0.3L type horizontal sand mill grind, and takes endless form to be ground to CNT dispersion always
Uniformly, the CNT dispersion pulp A3 of black half paste is obtained.
Comparative example 1
The preparation of CNT dispersion pulp W1
Commercially available for 50g multi-walled carbon nano-tubes, 400g propylene glycol methyl ether acetate are joined in round can, after being standing and soak for 2h,
With dispersion sand milling stirring multiple purpose aeroplane (the 600～800rpm) stirring under the relatively slow-speed of revolution of SDF550 type, slowly add in whipping process
Enter commercial dispersants Disperbyk-161 50g, continue stirring by material mix homogeneously, allow dispersant and solvent abundant moistening carbon
Nanotube, the most gradually heightens rotating speed, notes avoiding throwing away material round can when regulating rotating speed, and rotating speed is adjusted to 2000rpm, stirs
Mix and be dispersed to CNT and be uniformly dispersed, obtain the CNT dispersion pulp W1 of black half paste.
Comparative example 2
The preparation of CNT dispersion pulp W2
Commercially available for 50g multi-walled carbon nano-tubes, 400g propylene glycol methyl ether acetate are joined in round can, after being standing and soak for 2h,
With dispersion sand milling stirring multiple purpose aeroplane (the 600～800rpm) stirring under the relatively slow-speed of revolution of SDF550 type, slowly add in whipping process
Enter commercial dispersants Disperbyk-2000 50g, continue stirring by material mix homogeneously, allow dispersant and the abundant moistening of solvent
CNT, the most gradually heightens rotating speed, notes avoiding throwing away material round can when regulating rotating speed, and rotating speed is adjusted to 2000rpm,
Dispersed with stirring is uniformly dispersed to CNT, obtains the CNT dispersion pulp W2 of black half paste.
Application Example
The CNT dispersion pulp of embodiment 4～8 with comparative example 1～2 preparation is pressed table 1, table 2 and table 3, joins coating
In product (the consumption unit of formula is weight portion), it is configured to the coating of carbon nanotubes.During coating used in table is
The product that mountain bridge chemical industry is on sale, wherein PO350C one-component priming paint is automobile PP bumper base paint special, PO500E one-component
Priming paint is plastic cement primer, it is adaptable to the plastic cement materials such as ABS, PC, and EP200 two component epoxy priming paint is at the bottom of special metal rust preventing
Paint, BA-01 is supporting polyamide curing agent product.
Paint template is prepared in spraying respectively.PO350C series uses ground to be PP plastic plate, and PO3500E series uses ground
For ABS plastic plate, EP200 epoxy primer uses ground to be cold-rolled steel sheet, ground used all by white spirit wiped clean and dry,
Coating is diluted to working viscosity 15～18s (being coated with-4 glasss/25 DEG C), sprays to (dope room guarantor on corresponding ground with air gun
Hold temperature 26～28 DEG C, humidity 50%～80%RH), after room temperature levelling 5min, put into 80 DEG C of * 30min bakings, paint template
Room temperature is placed 7d and is carried out correlated performance test.Electrostatic spraying experiment is carried out in application application experiment room, will be coated with corresponding priming paint
Plastic plate be fixed on dolly, use robot electrostatic rotating cup (FANUC robot/Sames revolves cup) spray paint, face used
Paint is bridge chemical industry commercially available PO880W primary colours paint and UL800 dual-component polyurethane coating varnish.
Table 1 CNT dispersion pulp application effect in PO350C priming paint
(Continued) table 1
Table 2 CNT dispersion pulp application effect in PO500E priming paint
Table 3 CNT dispersion pulp application effect in EP200 static conductive epoxy anti-corrosive primer
Adhesive force test is tested by GB/T 9286-88 standard.
Pencil hardness test is tested by GB/T 6739-96 standard.
Water resistance test: the test of PO500E and PO350 system is 40 by composite membrane (priming paint+primary colours paint+coating varnish)
± 2 DEG C are soaked 240h, observes the situation of change of paint film appearance and measure its secondary adhesive force, by GB/T 1766-95 standard
Carry out；EP200 static conductive epoxy primer is carried out by GB/T 6950-2001 standard.
Resistance to neutral salt spray test GB/T 1771-2007 standard is tested.
Paint film electric conductivity (resistance) method of testing: take the dried model of baking, place two fritter iron plates on model
(1cm × 1cm), two pieces of iron plate intervals 1～2cm, circuit tester is turned on the power, probe is coupled with the interface of resistance measurement, will
Probe is placed on two pieces of iron plates, reads resistance readings (suitably adjusting range according to resistance).
From above-mentioned test, the CNT dispersion pulp prepared by the present invention, join and coating can improve coating
Adhesive force, hardness, the index such as water-fast, salt tolerant, the performance such as the machinery of General Promotion coating, weather-proof, electric, hot and anticorrosion, have
It is widely applied value.
Embodiment 9
Commercially available for 10g SWCN, 980g N-Methyl pyrrolidone are joined in round can, after being standing and soak for 2h, uses
Dispersion sand milling stirring multiple purpose aeroplane (the 600～800rpm) stirring under the relatively slow-speed of revolution of SDF550 type, is slowly added in whipping process
Comb-shaped graft copolymer dispersing agent C 10g, continues stirring by material mix homogeneously, allows dispersant and solvent abundant moistening carbon nanometer
Pipe, the most gradually heightens rotating speed, notes avoiding throwing away material round can when regulating rotating speed, and rotating speed is adjusted to 2000rpm, stirring point
It is dissipated to CNT be uniformly dispersed, obtains the CNT dispersion pulp of black half paste.
Embodiment 10
Commercially available for 40g multi-walled carbon nano-tubes, 900g DMF are joined in round can, after being standing and soak for 2h,
With dispersion sand milling stirring multiple purpose aeroplane (the 600～800rpm) stirring under the relatively slow-speed of revolution of SDF550 type, slowly add in whipping process
Enter comb-shaped graft copolymer dispersant A 20g, continue to stir material mix homogeneously, allow dispersant and solvent abundant moistening carbon receive
Mitron, adds Ф 1.0～1.5mm zirconium dioxide pearl and does abrasive media, and addition is 1.0～1.2 times of material gross weight, then
Round can is sealed and tight prevents material from leakage in process of lapping, put into SK450 type and shake sieve instrument grinds, set polish process,
Every all over grinding 30min, grinding is uniformly dispersed to CNT for 4～6 times repeatedly, and copper mesh is filtered to remove bead and obtains black half-cream
The CNT dispersion pulp of shape.
Embodiment 11
Commercially available for 40g multi-walled carbon nano-tubes, 850g water are joined in round can, after being standing and soak for 2h, disperses by SDF550 type
Sand milling stirring multiple purpose aeroplane (600～800rpm) stirring under the relatively slow-speed of revolution, is slowly added to comb shape graft copolymerization in whipping process
Thing dispersant B 80g, continues stirring by material mix homogeneously, allows dispersant and solvent abundant moistening CNT, be subsequently adding
Grind in SGM-0.3L type horizontal sand mill, take endless form to be ground to CNT always and be uniformly dispersed, obtain black
The CNT dispersion pulp of half paste.
Embodiment 12～20 is prepares dispersant:
Embodiment 12
Main chain backbone copolymer: with 2-(Acryloyloxy)ethanol and the monomer of ethyl acrylate acrylic acid synthesizing resin copolymer,
2-hydroxyethylmethacry,ate is as the monomer containing grafted moiety；Side chain copolymer: with phthalic acid and hexanediol for synthesis
The monomer of linear polyester, glycidyl acrylate is as the monomer containing grafted moiety；Alpha-Methyl benzene is added when preparing dispersant
Ethylene is as the monomer containing anchoring group.
Embodiment 13
Main chain backbone copolymer: with 2-hydroxypropyl acrylate and isopropyl acrylate acrylic acid synthesizing resin copolymer
Monomer, 2-hydroxypropyl acrylate is as the monomer containing grafted moiety, and N-methyl amino phenyl is as the monomer containing anchoring group；
Side chain copolymer: with 1,2,4-benzenetricarboxylic acids and the monomer that butanediol is synthesizing linear polyester, itaconic acid is as containing grafted moiety
Monomer.
Embodiment 14
Main chain backbone copolymer: be total to methacrylic acid-2-hydroxy propyl ester and tert-butyl acrylate synthesizing propylene acid resin
The monomer of polymers, 3-hydroxypropyl acrylate is as the monomer containing grafted moiety；Side chain copolymer: with hexahydro-phthalic acid
With the monomer that bisphenol-A is synthesizing linear polyester, 4-hydroxyl butyl methyl acrylate is as the monomer containing grafted moiety；Preparation dispersion
N-ethyl amino phenyl is added as the monomer containing anchoring group during agent.
Embodiment 15
Main chain backbone copolymer: with acrylic acid-3-hydroxy propyl ester and Hexyl 2-propenoate acrylic acid synthesizing resin copolymer
Monomer, 4-hydroxyl butyl propyleneglycol acid esters is as the monomer containing grafted moiety；Side chain copolymer: with ethylene lactic acid and 2,2,4-front threes
Base-1,3-pentanediol is the monomer of synthesizing linear polyester, and 3-hydroxypropyl acrylate is as the monomer containing grafted moiety；Preparation point
N-methylbenzylamine is added as the monomer containing anchoring group during powder.
Embodiment 16
Main chain backbone copolymer: be total to methacrylic acid-3-hydroxy propyl ester and lauryl acrylate synthesizing propylene acid resin
The monomer of polymers, acrylic acid is as the monomer containing grafted moiety, and N-ethyl benzyl amine is as the monomer containing anchoring group；Side chain copolymerization
Thing: the monomer being synthesizing linear polyester with gamma-valerolactone and 1,4-CHDM, 2-hydroxypropyl acrylate is as containing connecing
The monomer of branch group.
Embodiment 17
Main chain backbone copolymer: be total to acrylic acid-4-hydroxybutyl and cyclohexyl methacrylate synthesizing propylene acid resin
The monomer of polymers, itaconic acid is as the monomer containing grafted moiety；Side chain copolymer: be with gamma-valerolactone and trimethylolpropane
The monomer of synthesizing linear polyester, 2-hydroxyethylmethacry,ate is as the monomer containing grafted moiety；Benzene is added when preparing dispersant
Ethylene is as the monomer containing anchoring group.
Embodiment 18
Main chain backbone copolymer: with 2-(Acryloyloxy)ethanol and the list of pentylmethacrylate acrylic acid synthesizing resin copolymer
Body, 4-hydroxyl butyl methyl acrylate is as the monomer containing grafted moiety；Side chain copolymer: with lactic acid and hexanediol as synthetic thread
The monomer of property polyester, 3-HPMA is as the monomer containing grafted moiety；Adjacent benzene two is added when preparing dispersant
Carboximide is as the monomer containing anchoring group.
Embodiment 19
Main chain backbone copolymer: with hydroxyethyl methylacrylate and propyl methacrylate acrylic acid synthesizing resin copolymer
Monomer, maleic anhydride is as the monomer containing grafted moiety, and N-methylbenzylamine is as the monomer containing anchoring group；Side chain copolymerization
Thing: the monomer being synthesizing linear polyester with gamma-butyrolacton and hydrogenated bisphenol A, 2-hydroxyethylmethacry,ate is as containing grafting base
The monomer of group.
Embodiment 20
Main chain backbone copolymer: with acrylic acid-3-hydroxy propyl ester and isobornyl methacrylate synthesizing propylene acid resin
The monomer of copolymer, glycidyl acrylate is as the monomer containing grafted moiety, and N-ethyl amino phenyl is as containing anchoring group
Monomer；Side chain copolymer: the monomer being synthesizing linear polyester with decanedioic acid and trimethylolpropane, methacrylic acid is as containing
The monomer of grafted moiety.
The above, the only detailed description of the invention of the present invention, but protection scope of the present invention is not limited thereto, and any
Belong to those skilled in the art in the technical scope that the invention discloses, the change that can readily occur in or replacement, all answer
Contain within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with scope of the claims.
Claims (10)
1. a dispersant with comb shape graft polymers structure, it is characterised in that described dispersant is connect by side chain copolymer
Branch obtains on main chain backbone copolymer, and described main chain backbone copolymer is the acrylate containing grafted moiety and anchoring group
Copolymer, described side chain copolymer is the linear polyester containing grafted moiety.
Dispersant the most according to claim 1, it is characterised in that described grafted moiety is epoxy radicals, hydroxyl and carboxyl
At least one.
Dispersant the most according to claim 2, it is characterised in that the monomer containing described grafted moiety is selected from 2-hydroxyethyl
Acrylate, HEMA, 2-hydroxypropyl acrylate, 2-HPMA, 3-hydroxypropyl
Acrylate, 3-HPMA, 4-hydroxyl butyl propyleneglycol acid esters, 4-hydroxyl butyl methyl acrylate, acrylic acid, first
At least one in base acrylic acid, itaconic acid, maleic anhydride, glycidyl acrylate, glycidyl methacrylate.
Dispersant the most according to claim 1, it is characterised in that described anchoring group is phenyl.
Dispersant the most according to claim 4, it is characterised in that the monomer containing described anchoring group selected from styrene, α-
Methyl styrene, phthalimide, N-methyl amino phenyl, in N-ethyl amino phenyl, N-methylbenzylamine, N-ethyl benzyl amine
At least one.
Dispersant the most according to claim 1, it is characterised in that described acrylic resin copolymer is by hydroxy functional groups
Monomer obtained by radical polymerization with acrylate or methacrylate monomer.
Dispersant the most according to claim 1, it is characterised in that described side chain copolymer content in dispersant is 20
~ 80wt%, described main chain backbone copolymer content in dispersant is 20 ~ 80wt%.
8. the method for the dispersant prepared described in any one of claim 1 ~ 7, it is characterised in that comprise the following steps:
S1, prepare acrylate copolymer by radical polymerization；
S2, prepare linear polyester by polycondensation reaction；
The reaction under melted or azeotropic state of S3, acrylate copolymer and linear polyester obtains dispersant.
9. a CNT dispersion pulp, it is characterised in that this dispersion pulp includes 1 ~ 10 parts by weight of carbon nanotubes, 1 ~ 10 weight portion
Dispersant and 80 ~ 98 parts by weight solvent；Described dispersant is the dispersant described in any one of claim 1 ~ 7.
10. the method for the CNT dispersion pulp that a kind is prepared described in claim 9, it is characterised in that by CNT and molten
After agent mixing is standing and soak for, adding dispersant, CNT obtains CNT dispersion pulp after being uniformly dispersed.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107417852A (en) * | 2017-07-20 | 2017-12-01 | 河南师范大学 | A kind of Carbon nano-tube dispersant and preparation method thereof and the application in cell conductive paste is prepared |
| CN108102041A (en) * | 2017-12-21 | 2018-06-01 | 上海三瑞高分子材料股份有限公司 | A kind of Carbon nano-tube dispersant and preparation method thereof |
| CN110437373A (en) * | 2018-05-03 | 2019-11-12 | 史增谦 | Carbon nano-tube dispersant and its preparation method and application |
| CN112852522A (en) * | 2020-11-30 | 2021-05-28 | 大连同康新材料科技有限公司 | Application of block type poly (methyl) acrylate polymer as dispersant of nano-copper additive in lubricating oil |
| CN114141988A (en) * | 2021-11-09 | 2022-03-04 | 远景动力技术(江苏)有限公司 | Silicon-containing negative pole piece and preparation method and application thereof |
| CN115785329A (en) * | 2022-11-29 | 2023-03-14 | 佛山市顺德区永创翔亿电子材料有限公司 | Acrylate dispersant, preparation method thereof, acrylate adhesive and termination adhesive tape |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315975A (en) * | 1998-09-02 | 2001-10-03 | 纳幕尔杜邦公司 | Polymeric pigment dipersant having propenoic acid main chain, polyester side chains, cyclic imide groups and quaternary ammonium groups |
| CN101050258A (en) * | 2007-04-28 | 2007-10-10 | 武汉大学 | An amphipathic polymer, preparation method and application |
| CN101962481A (en) * | 2010-10-19 | 2011-02-02 | 中山大桥化工集团有限公司 | Macromoleclar composite sutable of being used as solvent-based pigment dispersant |
| CN102348731A (en) * | 2009-03-13 | 2012-02-08 | 拜尔材料科学股份公司 | Method for dispersing graphite-like nanoparticles |
-
2016
- 2016-08-15 CN CN201610670412.5A patent/CN106188559A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315975A (en) * | 1998-09-02 | 2001-10-03 | 纳幕尔杜邦公司 | Polymeric pigment dipersant having propenoic acid main chain, polyester side chains, cyclic imide groups and quaternary ammonium groups |
| CN101050258A (en) * | 2007-04-28 | 2007-10-10 | 武汉大学 | An amphipathic polymer, preparation method and application |
| CN102348731A (en) * | 2009-03-13 | 2012-02-08 | 拜尔材料科学股份公司 | Method for dispersing graphite-like nanoparticles |
| CN101962481A (en) * | 2010-10-19 | 2011-02-02 | 中山大桥化工集团有限公司 | Macromoleclar composite sutable of being used as solvent-based pigment dispersant |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107417852A (en) * | 2017-07-20 | 2017-12-01 | 河南师范大学 | A kind of Carbon nano-tube dispersant and preparation method thereof and the application in cell conductive paste is prepared |
| CN108102041A (en) * | 2017-12-21 | 2018-06-01 | 上海三瑞高分子材料股份有限公司 | A kind of Carbon nano-tube dispersant and preparation method thereof |
| CN108102041B (en) * | 2017-12-21 | 2020-10-16 | 瑞固新能(上海)材料科技有限公司 | Carbon nano tube dispersant and preparation method thereof |
| CN110437373A (en) * | 2018-05-03 | 2019-11-12 | 史增谦 | Carbon nano-tube dispersant and its preparation method and application |
| CN110437373B (en) * | 2018-05-03 | 2022-08-09 | 史增谦 | Carbon nano tube dispersant, preparation method and application thereof |
| CN112852522A (en) * | 2020-11-30 | 2021-05-28 | 大连同康新材料科技有限公司 | Application of block type poly (methyl) acrylate polymer as dispersant of nano-copper additive in lubricating oil |
| CN114141988A (en) * | 2021-11-09 | 2022-03-04 | 远景动力技术(江苏)有限公司 | Silicon-containing negative pole piece and preparation method and application thereof |
| CN114141988B (en) * | 2021-11-09 | 2023-09-08 | 远景动力技术(江苏)有限公司 | Silicon-containing negative electrode piece and preparation method and application thereof |
| CN115785329A (en) * | 2022-11-29 | 2023-03-14 | 佛山市顺德区永创翔亿电子材料有限公司 | Acrylate dispersant, preparation method thereof, acrylate adhesive and termination adhesive tape |
| CN115785329B (en) * | 2022-11-29 | 2023-08-25 | 佛山市顺德区永创翔亿电子材料有限公司 | Acrylic ester dispersing agent, preparation method thereof, acrylic ester adhesive and termination adhesive tape |
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Application publication date: 20161207 |