CN110164588A - A kind of denatured conductive cream and the preparation method and application thereof - Google Patents
A kind of denatured conductive cream and the preparation method and application thereof Download PDFInfo
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- CN110164588A CN110164588A CN201910494444.8A CN201910494444A CN110164588A CN 110164588 A CN110164588 A CN 110164588A CN 201910494444 A CN201910494444 A CN 201910494444A CN 110164588 A CN110164588 A CN 110164588A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
Abstract
The embodiment of the present application provides a kind of denatured conductive cream and the preparation method and application thereof, is related to conductive paste field.The raw material of denatured conductive cream includes: 1%~90% carbon-based conductive cream by mass percentage, 5%~60% carbon nanotube and 5%~50% hyperbranched polyethylene；Three-dimensional conductive network is formed between carbon-based conductive cream, carbon nanotube and hyperbranched polyethylene.Carbon-based conductive cream and organic solvent are mainly mixed to form the first solution by the preparation method of denatured conductive cream；Carbon nanotube, hyperbranched polyethylene and organic solvent are mixed, keep carbon nanotube evenly dispersed, forms the second solution；First solution and the second solution are uniformly mixed, organic solvent is removed.The conductivity of denatured conductive cream is high, at low cost, and conducting wire can be made；Preparation condition is mild, simple process, efficiently, it is environmental-friendly.
Description
Technical field
This application involves conductive paste fields, in particular to a kind of denatured conductive cream and the preparation method and application thereof.
Background technique
It is seen everywhere in life although metal material is used as conductive material, metal material is as conductive material
There is the shortcomings that can not avoiding.Such as since the current value that conducting wire unit area need to carry is very big, Gao Rong is generally all selected
Point and conducting wire is made as conductive material in the low metal of resistivity, the metal material that working process satisfies the use demand can not only disappear
It consumes many energy and environment can be caused greatly to pollute.Therefore it is excellent that easy processing, at low cost, pollution-free and electric conductivity are developed
Different material is extremely urgent.
Current research discovery carbon-based conductive cream has certain electric conductivity, and main component is adhesive in carbon-based conductive cream
And carbon material, adhesive as adhesive be it is nonconducting, carbon material plays electric action.Although carbon material is a kind of good
Non-metallic conducting material, but the conductivity principle of carbon-based conductive cream is to reach conductive mesh by the tunnel-effect between carbon material
, one layer of thin dielectric layer (adhesive) is specifically pressed from both sides between two layers of conductor (carbon material), constitutes the tunnel knot of an electronics, filler
It is not contacted between particle, there are potential barrier, experiment discovery electronics, that is, across insulating layer, can reach conductive mesh by tunnel knot
's.But the conductivity of carbon-based conductive cream is still relatively low, and when especially carbon material content is lower, the conduction of carbon-based conductive cream
Effect is very bad.
Summary of the invention
The embodiment of the present application is designed to provide a kind of denatured conductive cream and the preparation method and application thereof, denatured conductive cream
Conductivity it is high, at low cost, conducting wire can be made；Preparation condition is mild, simple process, efficiently, it is environmental-friendly.
In a first aspect, the embodiment of the present application provides a kind of denatured conductive cream, raw material includes: by mass percentage
1%~90% carbon-based conductive cream, 5%~60% carbon nanotube and 5%~50% hyperbranched polyethylene；It is carbon-based to lead
Three-dimensional conductive network is formed between electric cream, carbon nanotube and hyperbranched polyethylene.
In the above-mentioned technical solutions, carbon-based conductive cream is as conductive paste main body, carbon nanotube (CNT, Carbon
Nanotube) it is used as modified filler, hyperbranched polyethylene (HBPE, hyperbranched polyethylene) is used as dispersion and helps
Tridimensional network is collectively formed in agent.
Wherein, the electric conductivity of carbon nanotube CNT is superior, and the electric conductivity of carbon-based conductive cream can be significantly increased as filler
Can, filler of the carbon nanotube as one-dimentional structure can form three-dimensional conductive network with the carbon material in carbon-based conductive cream.Specifically
, for carbon nanotube as conductive main line, the carbon material in carbon-based conductive cream plays the role of bracket, and carbon nanotube and carbon are received
Mutually overlap joint gets up to form conductive network between mitron, and then promotes the electric conductivity of carbon-based conductive cream, especially in carbon nanometer
The electric conductivity of carbon-based conductive cream is set to be greatly improved in the case that pipe additive amount is seldom.
Inventor has found that carbon nanotube is nano-sized filler during realizing the application, when material reaches a nanometer ruler
Degree can show many nanometer size effects, such as the microscopic particles of zero dimension later, after particle size reaches nanoscale,
Its reuniting effect dramatically increases, and the mutual attractive force of aggregate endoparticle also significantly increases, and dispersion difficulty becomes larger, and shows as nanometer
The strong reuniting effect of powder.Single-root carbon nano-tube is fibrous monodimension nanometer material simultaneously, and major diameter is bigger, therefore carbon nanotube
It is easy to tangle and be bonded together, form very big aggregate.The comprehensive strong reuniting effect of nano-powder and tangling for fibrous material
Bonding phenomenon, it is known that carbon nanotube aggregate is stronger, it is evenly dispersed more difficult.Due to hyperbranched polyethylene uniqueness
Spherical racemosus structure (i.e. dendritic structure), can and carbon nanotube generate CH- π and π-π effect, thus reach removing carbon nanometer
The effect of pipe makes hyperbranched polyethylene mix dispersion in the solution with carbon nanotube, to obtain the carbon nanotube of stable dispersion
Solution.
Hyperbranched polyethylene HBPE can obtain the carbon nano-tube solution of stable dispersion not only with up-stripping carbon nanotube, more
It is important that hyperbranched polyethylene can also assist carbon nanotube stablize in carbon-based conductive cream, is evenly dispersed, i.e. hyperbranched poly
Whether the size relation of ethylene dissolution degree is uniformly dispersed in carbon-based conductive cream to carbon nanotube, because hyperbranched polyethylene both may be used
CH- π effect or π-π effect occurs with the carbon material in carbon-based conductive cream, hyperbranched polyethylene on the carbon nanotubes is adsorbed
The carbon material in carbon-based conductive cream can be also adsorbed simultaneously, and carbon material can be evenly distributed under the action of hyperbranched polyethylene at this time
The side of carbon nanotube, i.e. hyperbranched polyethylene can promote uniform and stable dispersion of the carbon nanotube in conductive paste, and formation is led
Electric bridge beam makes the conduction of denatured conductive cream so that the carbon material in carbon nanotube and carbon-based conductive cream forms tridimensional network
Performance significantly increases.
In one possible implementation, raw material includes: 72%~90% carbon-based conductive cream by mass percentage；
5%~14% carbon nanotube；And 5%~14% hyperbranched polyethylene.
In the above-mentioned technical solutions, it because hyperbranched polyethylene has not only acted as the effect of removing carbon nanotube, also functions to
The effect of auxiliary carbon nanotube stable dispersion in carbon-based conductive cream, so the difference of carbon nanotube additive amount will affect modification
The difference of the electric conductivity of conductive paste, hyperbranched polyethylene additive amount also will affect the electric conductivities of denatured conductive cream, using pressing
The raw material of mass percentage: 72%~90% carbon-based conductive cream；5%~14% carbon nanotube；And 5%~14%
The electric conductivity of hyperbranched polyethylene, obtained denatured conductive cream is relatively good.
In one possible implementation, the ingredient of carbon-based conductive cream includes adhesive and carbon material, wherein carbon material
Mass content between 30%~70%；Optionally, carbon-based conductive cream is mainly by adhesive and carbon material by grinding, dividing
It dissipates, modification obtains.
In the above-mentioned technical solutions, the carbon material in carbon-based conductive cream is the main material for playing electric action, is made carbon-based
The mass content of carbon material controls between 30%~70% in conductive paste, and carbon-based conductive cream is through carbon nanotube, hyperbranched poly second
The electric conductivity of the modified obtained denatured conductive cream of alkene is relatively good.
In one possible implementation, carbon nanotube include at least selected from single-walled carbon nanotube, double-walled carbon nano-tube,
Multi-walled carbon nanotube, highly conductive multi-walled carbon nanotube, hydroxyl carbon nano tube, carboxylic carbon nano-tube and aminated carbon nano tube
At least one of group of composition.
In the above-mentioned technical solutions, adding different types of carbon nanotube has the change of carbon-based conductive cream electric conductivity
It significantly affects, the electric conductivity of the denatured conductive cream obtained using above-mentioned carbon nanotube as modified filler is relatively good.
Second aspect, the embodiment of the present application provide a kind of preparation method of denatured conductive cream that first aspect provides,
The following steps are included:
Carbon-based conductive cream and organic solvent are mixed to form the first solution；By carbon nanotube, hyperbranched polyethylene and organic
Solvent mixing, keeps carbon nanotube evenly dispersed, forms the second solution；
First solution and the second solution are uniformly mixed, organic solvent is removed.
In the above-mentioned technical solutions, it weighs a certain amount of carbon-based conductive cream and is dissolved in corresponding organic solvent and form carbon
Base conductive paste solution (i.e. the first solution), at the same weigh again a certain amount of carbon nanotube be dissolved in hyperbranched polyethylene it is corresponding
In organic solvent, and keep carbon nanotube evenly dispersed, is formed carbon nanotube/hyperbranched polyethylene mixed solution (the second solution)；
Carbon-based conductive cream solution is mixed with carbon nanotube/hyperbranched polyethylene mixed solution again, so that carbon nanotube, hyperbranched
Polyethylene is evenly dispersed in carbon-based conductive cream, removes organic solvent, and capable of obtaining modified carbon-based conductive cream, (i.e. modification is led
Electric cream).It is the mild condition of above-mentioned preparation method, simple process, cheap, environmental-friendly, leading for carbon-based conductive cream can be improved
Electrical property efficiently prepares denatured conductive cream；The preparation method can also be recycled organic solvent, greatly reduce at
This, and avoid organic solvent volatilization and pollute the environment and cause harm to the human body.
It is evenly dispersed in carbon-based conductive cream that hyperbranched polyethylene can assist carbon nanotube, because hyperbranched polyethylene can
CH- π effect or π-π effect occurs with the carbon material in carbon-based conductive cream, hyperbranched polyethylene on the carbon nanotubes is adsorbed
The carbon material in carbon-based conductive cream can be also adsorbed simultaneously, so that the carbon material in carbon nanotube and carbon-based conductive cream forms three dimensional network
Shape structure.Denatured conductive cream is low in cost, conductivity is high, thermal conductivity is high, and can carrying out at normal temperature machine-shaping, (forming method is more
Sample and simple, can be changed its shape with mold at normal temperature), it can be recycled, solve common carbon-based conductive cream on the market
Difficult forming, conductivity are low, cannot replace the problem of plain conductor, and modified carbon-based conductive cream is applied wider
In wealthy field, such as conducting wire in low-power electric appliance can be replaced or applied in the joint of two kinds of different metal lines
It prevents from aoxidizing.
In one possible implementation, organic solvent includes at least to be selected from chloroform, tetrahydrofuran, petroleum ether and ether
At least one of group of composition；Optionally, organic solvent includes at least one of chloroform or tetrahydrofuran.
In the above-mentioned technical solutions, dissolve carbon-based conductive cream, hyperbranched polyethylene organic solvent there are many kinds of, such as chlorine
The organic solvents such as imitative, tetrahydrofuran THF, petroleum ether and ether.Hyperbranched poly is added to during modified to carbon-based conductive cream
Ethylene, dissolubility of the hyperbranched polyethylene in chloroform and tetrahydrofuran are more preferable with respect to other organic solvents, and hyperbranched poly second
The height of alkene solubility is related to the uniformity coefficient that carbon nanotube is dispersed in carbon-based conductive cream, therefore can select hyperbranched poly
At least one of the preferable chloroform of ethylene dissolution degree or tetrahydrofuran dissolve carbon-based conductive cream and over-expense as organic solvent
Change polyethylene.
In one possible implementation, carbon nanotube, hyperbranched polyethylene and organic solvent are mixed, makes carbon nanometer
Evenly dispersed method is managed as ultrasonic treatment；Optionally, the time of ultrasonic treatment is 0.5~12h.
In the above-mentioned technical solutions, ultrasonic treatment can be such that carbon nanotube is dispersed in liquid system.
It in one possible implementation, further include removal part hyperbranched poly second after keeping carbon nanotube evenly dispersed
Alkene, then the step for making carbon nanotube evenly dispersed again；
Optionally, the method for removing part hyperbranched polyethylene includes at least one of high speed centrifugation or vacuum filtration.
In the above-mentioned technical solutions, a certain amount of hyperbranched polyethylene is added to for being modified, and hyperbranched polyethylene is not only
Play the role of removing carbon nanotube, also plays the effect of auxiliary carbon nanotube stable dispersion in carbon-based conductive cream, but
It is that hyperbranched polyethylene is non-conductive, additional amount is more, and the electric conductivity of denatured conductive cream is poorer, it is therefore desirable to which removal part is super
Branched polyethylene.In addition, can not be separated since there are CH- π between hyperbranched polyethylene and carbon nanotube with π-π effect,
Part carbon nanotube is removed using at least one of high speed centrifugation or vacuum filtration method, can realize that removal part is super simultaneously
The purpose of branched polyethylene.
It in one possible implementation, is stir process by the uniformly mixed method of the first solution and the second solution；
Optionally, the time of stir process is 10~240min；
And/or the method for removing organic solvent includes at least one of revolving, purging or drying.
In the above-mentioned technical solutions, the first solution and the second solution are mixed and is continued 10~240min of stirring, can make
It is uniformly mixed, so that the carbon nanotube of stable dispersion be made uniformly to mix with carbon-based conductive cream.Due to what is selected in modifying process
It is the volatile and molten lower organic solvent of boiling point, therefore can be effectively gone using at least one of revolving, purging or drying
Except organic solvent.
The third aspect, the embodiment of the present application provide a kind of application of denatured conductive cream that first aspect provides, and modification is led
Electric cream is as conductive material for making conducting wire.
In the above-mentioned technical solutions, since to have that low in cost, filer content is low, conductivity is high etc. excellent for denatured conductive cream
Point can specifically be fabricated to low-power electric appliance conducting wire for making conducting wire with substituted metal conducting wire, or be fabricated to two kinds not
With the connector between plain conductor.
Detailed description of the invention
Technical solution in ord to more clearly illustrate embodiments of the present application will make below to required in the embodiment of the present application
Attached drawing is briefly described, it should be understood that the following drawings illustrates only some embodiments of the application, therefore should not be seen
Work is the restriction to range, for those of ordinary skill in the art, without creative efforts, can be with
Other relevant attached drawings are obtained according to these attached drawings.
Fig. 1 is a kind of preparation technology flow chart of denatured conductive cream provided by the embodiments of the present application；
Fig. 2 is the schematic illustration that hyperbranched polyethylene aid dispersion carbon nanotube forms carbon nano-tube solution；
Fig. 3 is the three-dimensional conductive network that hyperbranched polyethylene assists carbon nanotube to disperse and formed in carbon-based conductive cream
Structural schematic diagram；
Fig. 4 is not influence result schematic diagram of the same amount carbon nanotube to the electric conductivity of carbon-based conductive cream.
Specific embodiment
It, below will be in the embodiment of the present application to keep the purposes, technical schemes and advantages of the embodiment of the present application clearer
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Denatured conductive cream of the embodiment of the present application and the preparation method and application thereof is specifically described below.
In a first aspect, the embodiment of the present application provides a kind of denatured conductive cream, raw material includes: by mass percentage
1%~90% carbon-based conductive cream, 5%~60% carbon nanotube and 5%~50% hyperbranched polyethylene；It is carbon-based to lead
Three-dimensional conductive network is formed between electric cream, carbon nanotube and hyperbranched polyethylene.Optionally, raw material wraps by mass percentage
Include: 72%~90% carbon-based conductive cream, 5%~14% carbon nanotube and 5%~14% hyperbranched polyethylene；Into
Optionally, raw material includes: 72%~80% carbon-based conductive cream to one step by mass percentage, 8%~14% carbon nanotube,
And 8%~14% hyperbranched polyethylene.
In the present embodiment, there are many kinds of the selection types of carbon-based conductive cream, as an implementation, carbon-based conductive cream
Main component is adhesive and carbon material, and wherein for the mass content of carbon material between 30%~70%, carbon material content is different,
The electric conductivity of corresponding carbon-based conductive cream is also different；Optionally, adhesive is mainly passed through with carbon material and is ground by carbon-based conductive cream
Mill, dispersion, modified obtained soft shape lotion.Adhesive plays the role of gluing but non-conductive in carbon-based conductive cream, adhesive
Oil and special additive based on main component, base oil include at least one of mineral oil, synthesizing ester oil, silicone oil, spy
Different additive includes at least one of antioxidant, corrosion inhibitor, suppression arc agent.Illustratively, carbon-based conductive cream is Nanjing happiness benefit
The model DY-6 product of special adhesive Co., Ltd production, the model DDG-A product of wuhan yangtze river electromechanics production and KunLun elder brother
One of 801 product of model of logical sequence production or at least two.
In the present embodiment, there are many carbon nanotubes, and specification is available, and optionally, carbon nanotube includes at least to be selected from single wall
Carbon nanotube SWCNT, double-walled carbon nano-tube DWCNT, multi-walled carbon nanotube MWCNT, highly conductive multi-walled carbon nanotube HEMWCNT,
Hydroxyl carbon nano tube (for example, the multi-walled carbon nanotube for being connected to hydroxyl), carboxylic carbon nano-tube are (for example, be connected to the more of carboxyl
Wall carbon nano tube) and aminated carbon nano tube (for example, the multi-walled carbon nanotube for being connected to amino) composition at least one of group.
For example, carbon nanotube is single-walled carbon nanotube, double-walled carbon nano-tube, multi-walled carbon nanotube, highly conductive multi-walled carbon nanotube, hydroxyl
One of carbon nano tube, carboxylic carbon nano-tube and aminated carbon nano tube.
In the present embodiment, there are many kinds of the selection types of hyperbranched polyethylene, and illustratively, hyperbranched polyethylene can be
Using Pd-diimine catalyst ethylene, with the acquisition of one-step method " chain is removed " Mechanism of Copolymerization, specific preparation process includes
Following steps:
Under nitrogen protection, ethylene gas is added into reaction vessel and guarantees that instrument internal does not have depositing for oxygen and water
, while guaranteeing ethylene gas full of entire reaction vessel, solvent uses anhydrous grade solvent, and controls temperature at 5~35 DEG C, so
The Pd-diimine catalyst that is dissolved in anhydrous grade solvent is added afterwards, in 5~35 DEG C of temperature, 0.01~0.8MPa of ethylene pressure
Under the conditions of be stirred to react 6~72 hours, pouring into products therefrom after polymerization makes polymerization in acidified methanol, gained polymerization
Reaction mixture is through isolating and purifying to obtain hyperbranched polyethylene.
Optionally, anhydrous grade solvent includes at least selected from anhydrous methylene chloride, anhydrous chloroform or anhydrous chlorobenzene composition
At least one of combination；Optionally, the total volume of the dosage of Pd-diimine catalyst and anhydrous grade solvent be 0.5~
10.0g/L；Optionally, Pd-diimine catalyst is acetonitrile-base Pd-diimine catalystOr the six-membered cyclic Pd-diimine containing carbomethoxy
Catalyst
Isolating and purifying for above-mentioned polymerization reaction mixture can carry out in accordance with the following steps:
(a) gained polymerization reaction mixture is first removed into solvent；
(b) products therefrom is dissolved in tetrahydrofuran, acetone, which is added, precipitates product, and removal supernatant liquor obtains again
Polymerizate；It repeats the process 2~3 times；
(c) products therefrom is dissolved in tetrahydrofuran again, a small amount of hydrochloric acid and hydrogen peroxide (such as each 5~10 is added
Drop), 1~5 hour is stirred with a small amount of Pd particle contained in lysate, and methanol or acetone, which is then added, precipitates product；
(d) by products therefrom after being dried in vacuo 24~48h at 50~80 DEG C, hyperbranched polyethylene is obtained.
In the present embodiment, the hyperbranched polyethylene of variety classes, the carbon nanotube of Different adding amount and Different adding amount
The performance of denatured conductive cream can be had an impact.Wherein, the carbon nanotube for adding different parameters can be to carbon-based conductive cream electric conductivity
Can change have it is significantly different, wherein the influence factor about carbon nanotube have the type of carbon nanotube, length, conductivity,
Specific surface area, purity, outer diameter, functional group content, preparation process etc..
The embodiment of the present application also provides a kind of preparation methods of above-mentioned denatured conductive cream comprising following steps:
Step 1: carbon-based conductive cream and organic solvent are mixed to form carbon-based conductive cream solvent, i.e. the first solution.
Carbon nanotube, hyperbranched polyethylene and organic solvent are mixed, keep carbon nanotube evenly dispersed, forms carbon nanometer
Pipe/hyperbranched polyethylene mixed solution, i.e. the second solution, it is generally the case that by carbon nanotube, hyperbranched polyethylene and organic molten
Agent is uniformly mixed in the initial mixing solution formed, and the concentration of carbon nanotube is 0.5~500mg/mL, hyperbranched polyethylene and carbon
The mass ratio of nanotube is 0.005~10:1.
In the present embodiment, organic solvent includes in the group at least selected from chloroform, tetrahydrofuran, petroleum ether and ether composition
It is at least one；Optionally, organic solvent includes at least one of chloroform or tetrahydrofuran.The present embodiment is to forming the first solution
It is not specially limited with the organic solvent of the second solution, the first solution and second can be respectively formed using organic solvent not of the same race
Solution can also be respectively formed the first solution and the second solution using same organic solvent, illustratively, using chloroform, four
Hydrogen furans, petroleum ether or ether are respectively formed the first solution and the second solution as organic solvent.
Optionally, carbon nanotube, hyperbranched polyethylene and organic solvent are mixed, makes the method that carbon nanotube is evenly dispersed
For ultrasonic treatment, sonication treatment time can be 0.5~12h.Hyperbranched polyethylene is mixed in organic solvent with carbon nanotube
Merge under the auxiliary of ultrasonic wave, can get the carbon nano-tube solution of stable dispersion.
It optionally, further include removal part hyperbranched polyethylene, then make carbon nanometer again after keeping carbon nanotube evenly dispersed
Manage evenly dispersed step.Wherein, remove part hyperbranched polyethylene method include high speed centrifugation or vacuum filtration in extremely
Few one kind.Such as be ultrasonically treated mixed solution, it after keeping carbon nanotube evenly dispersed, is filtered by vacuum, filtrate is added
Organic solvent ultrasonic treatment, makes carbon nanotube evenly dispersed again；Alternatively, mixed solution is ultrasonically treated, keep carbon nanotube equal
After even dispersion, high speed centrifugation is carried out, collects the bottom solution of layering solution.
Step 2: the first solution and the second solution are uniformly mixed, wherein the first solution and the second solution are uniformly mixed
Method can for stirring 10~240min, remove organic solvent.
Optionally, the method for removing organic solvent includes at least one of revolving, purging or drying, and purging is divided into cold again
Wind sweeps, hot-air blowing.The present embodiment can use revolving, purging or drying mode to remove organic solvent, can also use
Two kinds of combinations in aforesaid way are to remove organic solvent；Illustratively, cold wind sweeping method, hot-air blowing method or vacuum are first used
After revolving method removes most of organic solvent, then by crude product and it is put into 4~48h of vacuum processing in vacuum tank, to have completely removed
Solvent.
Illustratively, Fig. 1 is a kind of preparation technology flow chart of denatured conductive cream provided in this embodiment.
When the application forms the second solution as dispersing aid using hyperbranched polyethylene, hyperbranched polyethylene is based on CH- π
It acts synergistically with π-π and non-covalent aid dispersion carbon nanotube and then obtains evenly dispersed and stable carbon nano-tube solution, formed
The schematic illustration of process is as shown in Figure 2.The structural schematic diagram of three-dimensional conductive network is as shown in figure 3, using carbon nanotube conduct
Filler, carbon nanotube is evenly dispersed in carbon-based conductive cream, mutual overlap forms conductive network, and carbon-based conductive cream itself also contains
A large amount of carbon crystal, carbon crystal, which is dispersed in around carbon nanotube, plays bridge beam action, and carbon nanotube has been connect with carbon nanotube
To form conductive network.Therefore the electric conductivity of modified carbon-based conductive cream has greatly improved, i.e. plastic at normal temperature,
Without welding, installation effectiveness is high and safer.
The embodiment of the present application also provides a kind of applications of above-mentioned denatured conductive cream, and denatured conductive cream is as conductive material
For making conducting wire.
The feature of the application and performance are described in further detail with reference to embodiments.
One, the influence using variety classes carbon-based conductive cream to properties of sample
1, sample is prepared
(1) embodiment 1 provides a kind of denatured conductive cream sample, is prepared in accordance with the following steps:
Step 1: weighing 4.5g carbon-based conductive cream at normal temperature, (carbon-based conductive cream used manufacturer is Nanjing Xi Lite
Adhesive Co., Ltd, model DY-6), and be dissolved in 30ml chloroform, form carbon-based conductive cream solution.
Step 2: weighing 0.25g carbon nanotube (carbon nanotube account for raw material total amount 5%) simultaneously, and it is dissolved in 80ml chlorine
In imitative.
Step 3: weighing 0.25g hyperbranched polyethylene (hyperbranched polyethylene account for raw material total amount 5%), and it is dissolved in
In 20ml chloroform.
Step 4: the solution of second step is mixed with the solution of third step, the ultrasound 2h in ultrasonoscope, carbon nanometer is formed
Pipe/hyperbranched polyethylene mixed solution.
Step 5: carbon nanotube/hyperbranched polyethylene mixed solution is mixed with carbon-based conductive cream solution, it is stirred,
Keep carbon nanotube evenly dispersed in carbon-based conductive cream solution, after stirring 10min, opens hair dryer and solution is purged to go
Except organic solvents, chloroform.
Step 6: crude product is placed in vacuum tank and is vacuum-treated 8h, to completely remove organic solvent to the end of chloroform volatilization
Chloroform, to obtain denatured conductive cream.
(2) embodiment 2 provides a kind of denatured conductive cream sample, the preparation method substantially phase of preparation method and embodiment 1
Together, details are not described herein, the difference is that:
Carbon-based conductive cream manufacturer used in the present embodiment is that wuhan yangtze river is electromechanical, model DDG-A, finally obtains modification and leads
Electric cream.
(3) embodiment 3 provides a kind of denatured conductive cream sample, the preparation method substantially phase of preparation method and embodiment 1
Together, details are not described herein, the difference is that:
Carbon-based conductive cream manufacturer used in the present embodiment is the Kunlun KunLun, and model 801 finally obtains denatured conductive
Cream.
2, characterization and test
Testing conductive performance
Before test in order to enable experimental data has more convincingness, need the carbon-based conductive cream of embodiment 1-3, modification
Conductive paste is respectively charged into the mold of diameter 0.5cm, long 1cm and is compacted, and conducting wire is made in correspondence, changes as made from the present embodiment
Property conductive paste plasticity is good, therefore can be formed at normal temperatures and pressures using mold to it.Carbon-based by embodiment 1-3 is led
Conducting wire made of electric cream, denatured conductive cream (i.e. modified carbon-based conductive cream), which is connected in the conducting wire of LED bulb, to be substituted
Original conducting wire, test temperature are room temperature, connect galvanic circle, can intuitively be seen very much according to the difference of LED bulb brightness
Observe the superiority and inferiority of carbon-based conductive cream, denatured conductive cream electric conductivity.
3, the comparison and analysis of test result
Embodiment 1-3 the difference is that used carbon-based conductive cream is not identical, test discovery directly adopt this three
Kind carbon-based conductive cream is as conducting wire, and brightness is all very low after being connected to LED small bulbs, illustrates existing carbon-based conductive cream electric conductivity all
It is very poor, i.e., if being unable to reach the purpose of substitution plain conductor using direct existing carbon-based conductive cream.Test discovery uses
The denatured conductive cream of embodiment 1-3 is as conducting wire, and after being connected to LED bulb, the brightness of light bulb is compared to directlying adopt corresponding carbon
The brightness of base conductive paste is obviously improved.
Analysis finds the reason for leading to unmodified carbon-based conductive cream electric conductivity difference for the conductivity principle of carbon-based conductive cream
It is that conduction is achieved the purpose that by the tunnel-effect between carbon material, its conductive effect is not very when carbon material content is lower
It is good.And denatured conductive cream conductivity it is raised the reason is as follows that: 1) add carbon nanotube electric conductivity itself it is just very excellent, can
To increase the conductivity of carbon-based conductive cream well.2) hyperbranched polyethylene can occur as a kind of auxiliary agent with carbon nanotube
CH- π effect or π-π effect up-stripping carbon nanotube obtain evenly dispersed and stable carbon nano-tube solution, while hyperbranched
Polyethylene can also assist carbon nanotube evenly dispersed in carbon-based conductive cream, because hyperbranched polyethylene can also be led with carbon-based
CH- π effect or π-π effect occur for the carbon material in electric cream, adsorb hyperbranched polyethylene on the carbon nanotubes while can also inhale
Carbon material in attached carbon-based conductive cream, so that the carbon material in carbon nanotube and carbon-based conductive cream forms tridimensional network, because
Under the action of hyperbranched polyethylene and carbon nanotube, the conductivity of carbon-based conductive cream is greatly improved for this.
Two, the influence using variety classes carbon nanotube to properties of sample
1, sample is prepared
(1) embodiment 4 provides a kind of denatured conductive cream sample, is prepared in accordance with the following steps:
Step 1: weigh at normal temperature 3.6g carbon-based conductive cream (carbon-based conductive cream used manufacturer be Nanjing happiness benefit
Special adhesive Co., Ltd, model DY-6), and be dissolved in 24ml chloroform, form carbon-based conductive cream solution.
Step 2: weigh simultaneously 0.7g single-walled carbon nanotube SWCNT (single-walled carbon nanotube accounts for the 14.3% of raw material total amount,
The parameter of single-walled carbon nanotube are as follows: outer diameter<2nm, purity>95wt%, length 5-30microns, specific surface area>490 ㎡/g are led
Electric rate > 100s/cm), and be dissolved in 224ml chloroform.
Step 3: weighing 0.7g hyperbranched polyethylene (hyperbranched polyethylene account for raw material total amount 14.3%), and it is dissolved in
In 56ml chloroform.
Step 4: the solution of second step is mixed with the solution of third step, the ultrasound 2h in ultrasonoscope, single wall carbon is formed
Nanotube/hyperbranched polyethylene mixed solution.
Step 5: single-walled carbon nanotube/hyperbranched polyethylene mixed solution is mixed with carbon-based conductive cream solution, stirred
It mixes, keeps single-walled carbon nanotube evenly dispersed in carbon-based conductive cream solution, after stirring 10min, open hair dryer and solution is carried out
Purging is to remove organic solvents, chloroform.
Step 6: crude product is placed in vacuum tank and is vacuum-treated 8h, to completely remove organic solvent to the end of chloroform volatilization
Chloroform, to obtain denatured conductive cream.
(2) embodiment 5 provides a kind of denatured conductive cream sample, the preparation method substantially phase of preparation method and embodiment 4
Together, details are not described herein, the difference is that:
Carbon nanotube used is double-walled carbon nano-tube DWCNT, the parameter of double-walled carbon nano-tube are as follows: outer diameter < 2~4nm, purity
> 60wt%, length 10-50microns, specific surface area > 340 ㎡/g, conductivity > 100s/cm finally obtain denatured conductive cream.
(3) embodiment 6 provides a kind of denatured conductive cream sample, the preparation method substantially phase of preparation method and embodiment 4
Together, details are not described herein, the difference is that:
Carbon nanotube used is multi-walled carbon nanotube MWCNT, the parameter of multi-walled carbon nanotube are as follows: outer diameter < 2~4nm, purity
>90wt%, length<10microns, 500~700 ㎡ of specific surface area/g, conductivity>100s/cm finally obtain denatured conductive
Cream.
(4) embodiment 7 provides a kind of denatured conductive cream sample, the preparation method substantially phase of preparation method and embodiment 4
Together, details are not described herein, the difference is that:
Carbon nanotube used is highly conductive multi-walled carbon nanotube HEMWCNT, the parameter of highly conductive multi-walled carbon nanotube are as follows: outer
Diameter<10~20nm, purity>90wt%, length<30microns, 230~280 ㎡ of specific surface area/g, conductivity>100s/cm, most
Denatured conductive cream is obtained afterwards.
(5) embodiment 8 provides a kind of denatured conductive cream sample, the preparation method substantially phase of preparation method and embodiment 4
Together, details are not described herein, the difference is that:
Carbon nanotube used is the multi-walled carbon nanotube MWCNT for being connected to hydroxyl, is connected to the ginseng of the multi-walled carbon nanotube of hydroxyl
Number are as follows: outer diameter<10~20nm, purity>90wt%, length<30microns, 230~280 ㎡ of specific surface area/g, conductivity>
100s/cm ,-OH content 3.06wt% finally obtain denatured conductive cream.
(6) embodiment 9 provides a kind of denatured conductive cream sample, the preparation method substantially phase of preparation method and embodiment 4
Together, details are not described herein, the difference is that:
Carbon nanotube used is the multi-walled carbon nanotube MWCNT for being connected to carboxyl, is connected to the ginseng of the multi-walled carbon nanotube of carboxyl
Number are as follows: outer diameter<10~20nm, purity>90wt%, length<30microns, 230~280 ㎡ of specific surface area/g, conductivity>
100s/cm ,-COOH content 2.00wt% finally obtain denatured conductive cream.
(7) embodiment 10 provides a kind of denatured conductive cream sample, the preparation method substantially phase of preparation method and embodiment 4
Together, details are not described herein, the difference is that:
Carbon nanotube used is the multi-walled carbon nanotube MWCNT for being connected to amino, is connected to the ginseng of the multi-walled carbon nanotube of amino
Number are as follows: outer diameter<10~20nm, purity>90wt%, length<30microns, 230~280 ㎡ of specific surface area/g, conductivity>
100s/cm ,-NH3Content 2.67wt% finally obtains denatured conductive cream.
2, characterization and test
Testing conductive performance
Referring to the test method in test one.
3, the comparison and analysis of test result
Embodiment 4-10 is the difference is that the type of added carbon nanotube is different, and embodiment 4 is using general
Logical single-walled carbon nanotube SWCNT, that embodiment 5-7 is respectively adopted is double-walled carbon nano-tube DWCNT, multi-walled carbon nanotube
MWCNT, highly conductive multi-walled carbon nanotube HEMWCNT, embodiment 8-10 is using the multi-walled carbon nanotube for being connected to functional group
MWCNT.Wherein the price of single-walled carbon nanotube SWCNT is most expensive, and modified effect is preferable, double-walled carbon nano-tube DWCNT and multi wall carbon
Nanotube MWCNT can be very good under the booster action of hyperbranched polyethylene HBPE it is compatible with carbon-based conductive cream, can very great Cheng
Degree improves the electric conductivity of carbon-based conductive cream；Highly conductive multi-walled carbon nanotube HEMWCNT relative to above several carbon nanotubes, by
In its parameter difference, the conductivity of carbon-based conductive cream can be increased substantially in the case where additive amount is seldom；It is connected to functional group
Carbon nanotube it is poor with respect to several carbon nano-tube modification effects of front because its original structure is destroyed, electric conductivity
It can be relatively poor.
Three, using not influence of the same amount nanotube to properties of sample
1, sample is prepared
(1) the denatured conductive cream sample that embodiment 1 provides, preparation method repeat no more.
(2) embodiment 11 provides a kind of denatured conductive cream sample, is prepared in accordance with the following steps:
Step 1: weighing 4.2g carbon-based conductive cream at normal temperature, and it is dissolved in 28ml chloroform, it is molten forms carbon-based conductive cream
Liquid.
Step 2: weighing 0.4g carbon nanotube (carbon nanotube account for raw material total amount 8%) simultaneously, and it is dissolved in 138ml's
In chloroform.
Step 3: weighing 0.4g hyperbranched polyethylene (hyperbranched polyethylene account for raw material total amount 8%), and it is dissolved in 32ml
Chloroform in.
Step 4: the solution of second step is mixed with the solution of third step, the ultrasound 2h in ultrasonoscope, carbon nanometer is formed
Pipe/hyperbranched polyethylene mixed solution.
Step 5: carbon nanotube/hyperbranched polyethylene mixed solution is mixed with carbon-based conductive cream solution, it is stirred,
Keep carbon nanotube evenly dispersed in carbon-based conductive cream solution, after stirring 10min, opens hair dryer and solution is purged to go
Except organic solvent.
Step 6: crude product is placed in vacuum tank and is vacuum-treated 8h to the end of organic solvent volatilization, it is organic to completely remove
Solvent, to obtain denatured conductive cream.
2, characterization and test
The test of electric conductivity
Referring to the test method in test one.
3, the comparison and analysis of test result
Embodiment 1 with embodiment 11 the difference is that the dosage of added carbon nanotube is different, the left figure in Fig. 4
For the LED bulb luminance graph of the denatured conductive cream of embodiment 1, the right figure in Fig. 4 is the LED light of the denatured conductive cream of embodiment 11
Steep luminance graph.As shown in figure 4, black group and be connected with conducting wire part be denatured conductive cream, various shapes can be molded at normal temperature
Shape, LED bulb is the brightness of light bulb in normal circuit using series circuit, therefore in the part that Fig. 4 centre circle gets up, dark
Part is the corresponding bulb brightness of denatured conductive cream；The brightness of LED bulb, observation that can be apparent in two width figures of comparison left and right
Into Fig. 4, the brightness of LED bulb is higher in right figure, i.e., with the increase of content of carbon nanotubes, the brightness of LED bulb is bigger, carbon
The electric conductivity of base conductive paste enhances.
Four, whether influence of the hyperbranched polyethylene to properties of sample is used
1, sample is prepared
(1) the denatured conductive cream sample that embodiment 1 provides, preparation method repeat no more.
(2) comparative example 1 provides a kind of denatured conductive cream sample, is prepared in accordance with the following steps:
Step 1: weighing 4.5g carbon-based conductive cream at normal temperature, and it is dissolved in 30ml chloroform, it is molten forms carbon-based conductive cream
Liquid.
Step 2: weighing 0.25g carbon nanotube simultaneously and being dissolved in the chloroform of 80ml.
Step 3: by the solution of second step in ultrasonoscope ultrasound 2h, formed carbon nano-tube solution.
Step 4: carbon nano-tube solution is mixed with carbon-based conductive cream solution, it is stirred, leads carbon nanotube carbon-based
It is evenly dispersed in electric cream solution, after stirring 10min, opens hair dryer and solution is purged to remove organic solvent.
Step 5: crude product is placed in vacuum tank and is vacuum-treated 8h to the end of organic solvent volatilization, it is organic to completely remove
Solvent, to obtain denatured conductive cream.
2, characterization and test
The test of electric conductivity
Referring to the test method in test one.
3, the comparison and analysis of test result
The difference of embodiment 1 and comparative example 1 is in comparative example 1 without using hyperbranched polyethylene as auxiliary agent, through surveying
The electric conductivity for trying the denatured conductive cream of embodiment 1 is substantially better than the denatured conductive cream of comparative example 1, while also demonstrating hyperbranched
The important function of polyethylene.
Five, using the influence to properties of sample of not same amount hyperbranched polyethylene
1, sample is prepared
(1) the denatured conductive cream sample that embodiment 7 provides, preparation method repeat no more.
(2) embodiment 12 provides a kind of denatured conductive cream sample, is prepared in accordance with the following steps:
Step 1: weighing 3.3g carbon-based conductive cream at normal temperature, and it is dissolved in 22ml chloroform, it is molten forms carbon-based conductive cream
Liquid.
Step 2: weighing the highly conductive multi-walled carbon nanotube HEMWCNT of 0.7g simultaneously, (highly conductive multi-walled carbon nanotube accounts for raw material
The 14.3% of total amount), and be dissolved in 224ml chloroform.
Step 3: weighing 1g hyperbranched polyethylene (hyperbranched polyethylene account for raw material total amount 20%), and it is dissolved in 80ml
In chloroform.
Step 4: the solution of second step is mixed with the solution of third step, the ultrasound 2h in ultrasonoscope, formed highly conductive
Multi-walled carbon nanotube/hyperbranched polyethylene mixed solution.
Step 5: highly conductive multi-walled carbon nanotube/hyperbranched polyethylene mixed solution is mixed with carbon-based conductive cream solution,
It is stirred, keeps highly conductive multi-walled carbon nanotube evenly dispersed in carbon-based conductive cream solution, after stirring 10min, open blowing
Machine purges to remove organic solvent solution.
Step 6: crude product is placed in vacuum tank and is vacuum-treated 8h to the end of organic solvent volatilization, it is organic to completely remove
Solvent, to obtain denatured conductive cream.
2, characterization and test
(1) test of electric conductivity
Referring to the test method in test one.
(2) sticky test
One of feature of denatured conductive cream is that molding is easy under normal temperature state, therefore it is required that denatured conductive cream has centainly
Viscosity and plasticity, can pass through observation denatured conductive cream flexibility.
3, the comparison and analysis of test result
Embodiment 7 is that the content of hyperbranched polyethylene is different from the difference of embodiment 12, and hyperbranched polyethylene can be auxiliary
Dispersing Nano carbon tubes are helped, form stable carbon nano tube dispersion liquid, while the viscosity of hyperbranched polyethylene is very big, can increase carbon-based
The viscosity of conductive paste.Therefore the viscosity of the denatured conductive cream of embodiment 7 is lower than the viscosity of the denatured conductive cream of embodiment 12, but real
The electric conductivity of the denatured conductive cream of example 7 is applied better than embodiment 12, reason is that while that hyperbranched polyethylene can assist
Dispersing Nano carbon tubes, and the viscosity of carbon-based conductive cream can be increased, but hyperbranched polyethylene itself is non-conductive, a large amount of addition can make
Obtain the electric conductivity decline of denatured conductive cream.
Six, the influence to properties of sample of part hyperbranched polyethylene whether is removed
1, sample is prepared
(1) the denatured conductive cream sample that embodiment 12 provides, preparation method repeat no more.
(2) embodiment 13 provides a kind of denatured conductive cream sample, is prepared in accordance with the following steps:
Step 1: weighing 3.3g carbon-based conductive cream at normal temperature, and it is dissolved in 22ml chloroform, it is molten forms carbon-based conductive cream
Liquid.
Step 2: weighing the highly conductive multi-walled carbon nanotube HEMWCNT of 0.7g simultaneously, (highly conductive multi-walled carbon nanotube accounts for raw material
The 14.3% of total amount), and be dissolved in 224ml chloroform.
Step 3: weighing 1g hyperbranched polyethylene (hyperbranched polyethylene account for raw material total amount 20%), and it is dissolved in 80ml
In chloroform.
Step 4: the solution of second step is mixed with the solution of third step, the ultrasound 2h in ultrasonoscope, formed highly conductive
Multi-walled carbon nanotube/hyperbranched polyethylene mixed solution.
Step 5: highly conductive multi-walled carbon nanotube/hyperbranched polyethylene mixed solution is filtered by vacuum.
Step 6: being reentered into the highly conductive multi-walled carbon nanotube/hyperbranched polyethylene mixed solution finished is filtered
Hui Chao is carried out in 80ml chloroform, returns 2h between time-out.
Step 7: super good highly conductive multi-walled carbon nanotube/hyperbranched polyethylene mixed solution and carbon-based conductive cream will be returned
Solution mixing, is stirred, keeps highly conductive multi-walled carbon nanotube evenly dispersed in carbon-based conductive cream solution, after stirring 10min,
Hair dryer is opened to purge to remove organic solvent solution.
Step 8: crude product is placed in vacuum tank and is vacuum-treated 8h to the end of organic solvent volatilization, it is organic to completely remove
Solvent, to obtain denatured conductive cream.
2, characterization and test
The test of electric conductivity
Referring to the test method for testing one kind.
3, the comparison and analysis of test result
The difference of embodiment 12 and embodiment 13 be embodiment 13 to carbon nanotube/hyperbranched polyethylene mixed solution into
The processing of row suction filtration, suction filtration can remove hyperbranched polyethylene most of in mixed solution, this is because hyperbranched poly second
There are CH- π and π-π to act between alkene and carbon nanotube, thus can not separate, suction filtration processing can remove part carbon nanotube and
Hyperbranched polyethylene, filter still had in treated filtrate 20% or so hyperbranched polyethylene residual.Embodiment 13
Denatured conductive cream is more superior relative to the electric conductivity of the denatured conductive cream of embodiment 12, the reason for this is that hyperbranched polyethylene is not led
Electricity, additional amount is more, and the electric conductivity of denatured conductive cream is poorer.
Seven, the influence using variety classes organic solvent to properties of sample
1, sample is prepared
(1) embodiment 14 provides a kind of denatured conductive cream sample, is prepared in accordance with the following steps:
Step 1: weighing 4.5g carbon-based conductive cream at normal temperature and being dissolved in 30ml chloroform, it is molten to form carbon-based conductive cream
Liquid.
Step 2: weighing the highly conductive multi-walled carbon nanotube HEMWCNT of 0.25g simultaneously, (highly conductive multi-walled carbon nanotube Zhan is total
The 5% of amount) and be dissolved in 80ml chloroform.
Step 3: weighing 0.25g hyperbranched polyethylene, and it is dissolved in 20ml chloroform.
Step 4: the solution of second step is mixed with the solution of third step, the ultrasound 2h in ultrasonoscope, formed highly conductive
Multi-walled carbon nanotube/hyperbranched polyethylene mixed solution.
Step 5: highly conductive multi-walled carbon nanotube/hyperbranched polyethylene mixed solution is mixed with carbon-based conductive cream solution,
It is stirred, keeps highly conductive multi-walled carbon nanotube evenly dispersed in carbon-based conductive cream solution, after stirring 10min, open blowing
Machine purges to remove organic solvents, chloroform solution.
Step 6: crude product is placed in vacuum tank and is vacuum-treated 8h to the end of chloroform volatilization, it is organic molten to completely remove
Agent, to obtain denatured conductive cream.
(2) embodiment 15 provides a kind of denatured conductive cream sample, and the preparation method of preparation method and embodiment 14 is substantially
Identical, details are not described herein, the difference is that:
Chloroform is substituted using tetrahydrofuran, finally obtains denatured conductive cream.
2, characterization and test
(1) test of solubility of the carbon-based conductive cream in different solvents:
Two parts of each 4.5g of carbon-based conductive cream are taken, are respectively charged into beaker, chloroform is taken to be respectively charged into each 30ml of tetrahydrofuran
It in two beakers, and marks, is packed into stirrer and simultaneously stirs, stirring can make carbon-based conductive cream accelerate dissolution, while with fresh-keeping
Beaker mouth is sealed the volatilization to prevent organic solvent by film, observes carbon-based conductive in beaker again after standing 1h after stirring 30min
The dissolubility of cream.
(2) test of electric conductivity
Referring to the test method for testing one kind.
3, the comparison and analysis of test result
Embodiment 14 is that used organic solvent is different from the difference of embodiment 15, and carbon-based conductive cream is deliquescent big
It is small influence whether after multi-walled carbon nanotube and carbon-based conductive cream solution mixing.Different organic solvents are being added and are stirring static
After can observe, the carbon-based conductive cream in embodiment 14 can be quickly soluble in chloroform and be formed stable solution, and
It can be observed that the dissolution of carbon-based conductive cream is relatively slow and there is the carbon-based conductive cream not being completely dissolved in the inside in embodiment 15.Pass through simultaneously
The comparison of the electric conductivity of the denatured conductive cream of embodiment 14 and embodiment 15, it is known that be better than using chloroform as organic solvent
Using tetrahydrofuran as organic solvent.
Eight, using not influence of the same amount organic solvent to properties of sample
1, sample is prepared
(1) embodiment 16 provides a kind of denatured conductive cream sample, is prepared in accordance with the following steps:
Step 1: weighing 4.5g carbon-based conductive cream at normal temperature and being dissolved in 30ml chloroform, it is molten to form carbon-based conductive cream
Liquid.
Step 2: weighing the highly conductive multi-walled carbon nanotube HEMWCNT of 0.25g simultaneously, (highly conductive multi-walled carbon nanotube accounts for original
Expect the 5% of total amount), and be dissolved in the chloroform of 80ml.
Step 3: weighing 0.25g hyperbranched polyethylene (hyperbranched polyethylene account for raw material total amount 5%), and it is dissolved in
In the chloroform of 20ml.
Step 4: the solution of second step is mixed with the solution of third step, the ultrasound 2h in ultrasonoscope, formed highly conductive
Multi-walled carbon nanotube/hyperbranched polyethylene mixed solution.
Step 5: highly conductive multi-walled carbon nanotube/hyperbranched polyethylene mixed solution is filtered by vacuum.
Step 6: being reentered into the highly conductive multi-walled carbon nanotube/hyperbranched polyethylene mixed solution finished is filtered
Hui Chao is carried out in 80ml organic solvents, chloroform, returns 2h between time-out.
Step 7: super good highly conductive multi-walled carbon nanotube/hyperbranched polyethylene mixed solution and carbon-based conductive cream will be returned
Solution mixing, is stirred, keeps highly conductive multi-walled carbon nanotube evenly dispersed in carbon-based conductive cream solution, after stirring 10min,
Hair dryer is opened to purge to remove organic solvent solution.
Step 8: crude product is placed in vacuum tank and is vacuum-treated 8h, to completely remove conduction to the end of organic solvent volatilization
Organic solvent in cream, to obtain denatured conductive cream.
(2) embodiment 17 provides a kind of denatured conductive cream sample, is prepared in accordance with the following steps:
Step 1: weighing 4.5g carbon-based conductive cream at normal temperature and being dissolved in 30ml chloroform, it is molten to form carbon-based conductive cream
Liquid.
Step 2: weighing the highly conductive multi-walled carbon nanotube HEMWCNT of 0.25g simultaneously, (highly conductive multi-walled carbon nanotube Zhan is total
The 5% of amount), and be dissolved in the chloroform of 200ml.
Step 3: weighing 0.25g hyperbranched polyethylene (hyperbranched polyethylene account for total amount 5%), and it is dissolved in 20ml chlorine
In imitative.
Step 4: the solution of second step is mixed with the solution of third step, the ultrasound 2h in ultrasonoscope, formed highly conductive
Multi-walled carbon nanotube/hyperbranched polyethylene mixed solution.
Step 5: the centrifugation by highly conductive multi-walled carbon nanotube/hyperbranched polyethylene mixed solution in 8000rad/min is fast
20min is centrifuged under rate.
Step 6: the layering solution that finishes of centrifugation is removed supernatant liquor, collect the highly conductive multi-walled carbon nanotube of bottom/
Hyperbranched polyethylene mixed solution.
Step 7: the highly conductive multi-walled carbon nanotube/hyperbranched polyethylene mixed solution and carbon-based conductive cream by collection are molten
Liquid mixing, is stirred, keeps highly conductive multi-walled carbon nanotube evenly dispersed in carbon-based conductive cream solution, after stirring 10min, beats
Hair dryer is opened to purge to remove organic solvent solution.
Step 8: crude product is placed in vacuum tank and is vacuum-treated 8h to the end of organic solvent volatilization, it is organic to completely remove
Solvent, to obtain denatured conductive cream.
2, characterization and test
The test of electric conductivity
Referring to the test method of test one.
3, the comparison and analysis of test result
The difference of embodiment 16 and embodiment 17 is in embodiment 17 that added organic solvent is more, i.e. carbon nanotube
Concentration it is lower, carbon nanotube concentration is low to be conducive to the solution that stable dispersion is formed with hyperbranched polyethylene.The mesh of centrifugal treating
It is the part hyperbranched polyethylene removed in mixed solution, most hyperbranched polyethylenes can be stayed in a solvent, specific former
Because referring to the analysis in test six about embodiment 12 and embodiment 13.The electric conductivity of the denatured conductive cream obtained in embodiment 17
It can be better than the electric conductivity of the denatured conductive cream obtained in embodiment 16.
Nine, the influence using different ultrasonic times to properties of sample
1, sample is prepared
(1) embodiment 18 provides a kind of denatured conductive cream sample, is prepared in accordance with the following steps:
Step 1: weighing 4.5g carbon-based conductive cream at normal temperature and being dissolved in 30ml chloroform, it is molten to form carbon-based conductive cream
Liquid.
Step 2: weighing the highly conductive multi-walled carbon nanotube HEMWCNT of 0.25g simultaneously, (highly conductive multi-walled carbon nanotube accounts for original
Expect the 5% of total amount), and be dissolved in the chloroform of 80ml.
Step 3: weighing 0.25g hyperbranched polyethylene (hyperbranched polyethylene account for raw material total amount 5%), and it is dissolved in
In the chloroform of 20ml.
Step 4: the solution of second step is mixed with the solution of third step, the ultrasound 8h in ultrasonoscope, formed highly conductive
Multi-walled carbon nanotube/hyperbranched polyethylene mixed solution.
Step 5: the centrifugation by highly conductive multi-walled carbon nanotube/hyperbranched polyethylene mixed solution in 8000rad/min is fast
20min is centrifuged under rate.
Step 6: the layering solution that finishes of centrifugation is removed supernatant liquor, collect the highly conductive multi-walled carbon nanotube of bottom/
Hyperbranched polyethylene mixed solution.
Step 7: the highly conductive multi-walled carbon nanotube/hyperbranched polyethylene mixed solution and carbon-based conductive cream by collection are molten
Liquid mixing, is stirred, keeps highly conductive multi-walled carbon nanotube evenly dispersed in carbon-based conductive cream solution, after stirring 10min, beats
It opens hair dryer and cold wind purging is carried out to remove organic solvent to solution.
Step 8: crude product is placed in vacuum tank and is vacuum-treated 8h to the end of organic solvent volatilization, it is organic to completely remove
Solvent, to obtain denatured conductive cream.
(2) the denatured conductive cream sample that embodiment 14 provides, preparation method repeat no more.
2, characterization and test
The test of electric conductivity
Referring to the test method for testing one kind.
3, the comparison and analysis of test result
In embodiment 18 to the ultrasonic time of mixed solution be greater than embodiment 14, and embodiment 18 to mixed solution carry out from
The heart.The extension of ultrasonic time is conducive to the combination of carbon nanotube and hyperbranched polyethylene, and the mixed solution of formation is also more equal
It is even.Carbon nanotube is stable, evenly dispersed, and the easier carbon nanotube with seldom additive amount is formed in carbon-based conductive cream and led
Electric network.Since carbon nano-tube solution is carried out centrifugal treating by embodiment 18, the electricity of the denatured conductive cream in embodiment 18
Resistance rate is lower than the denatured conductive cream in embodiment 14.
Ten, the influence using distinct methods removal organic solvent to properties of sample
1, sample is prepared
(1) embodiment 19 provides a kind of denatured conductive cream sample, is prepared in accordance with the following steps:
Step 1: weighing 4.5g carbon-based conductive cream at normal temperature, and it is dissolved in 30ml chloroform, it is molten forms carbon-based conductive cream
Liquid.
Step 2: weighing the highly conductive multi-walled carbon nanotube HEMWCNT of 0.25g simultaneously, (highly conductive multi-walled carbon nanotube Zhan is total
The 5% of amount), and be dissolved in the chloroform of 80ml.
Step 3: weighing 0.25g hyperbranched polyethylene (hyperbranched polyethylene account for total amount 5%), and it is dissolved in 20ml's
In chloroform.
Step 4: the solution of second step is mixed with the solution of third step, the ultrasound 2h in ultrasonoscope, formed highly conductive
Multi-walled carbon nanotube/hyperbranched polyethylene mixed solution.
Step 5: the centrifugation by highly conductive multi-walled carbon nanotube/hyperbranched polyethylene mixed solution in 8000rad/min is fast
20min is centrifuged under rate.
Step 6: layering solution is removed supernatant liquor, highly conductive multi-walled carbon nanotube/hyperbranched poly second of bottom is collected
Alkene mixed solution.
Step 7: the highly conductive multi-walled carbon nanotube/hyperbranched polyethylene mixed solution and carbon-based conductive cream by collection are molten
Liquid mixing, is stirred, keeps highly conductive multi-walled carbon nanotube evenly dispersed in carbon-based conductive cream solution, after stirring 10min, beats
It opens hair dryer and cold wind purging is carried out to remove organic solvent to solution.
Step 8: crude product is placed in vacuum tank and is vacuum-treated 8h, to completely remove conduction to the end of organic solvent volatilization
Organic solvent in cream, to obtain denatured conductive cream.
(2) embodiment 20 provides a kind of denatured conductive cream sample, and the preparation method of preparation method and embodiment 19 is substantially
Identical, details are not described herein, the difference is that:
It opens hair dryer and hot-air blowing is carried out to remove organic solvent to solution.To the end of organic solvent volatilization, collects and burn
Substance in cup, to obtain denatured conductive cream.
2, characterization and test
The test of electric conductivity
Referring to the test method for testing one kind.
3, the comparison and analysis of test result
Embodiment 19 is different to the processing mode of organic solvent from the difference of embodiment 20, uses in embodiment 19
Cold wind is purged and is vacuum-treated to purged crude product, and the method that solvent is removed in embodiment 20 is hot-air blowing.Implement
The electric conductivity of the denatured conductive cream of example 19 is better than the denatured conductive cream of embodiment 20, and cold wind purging removal organic solvent is time-consuming
Long, vacuum processing can further remove organic solvent；The method removal organic solvent of hot-air blowing be easy to cause carbon nanotube
Reunion, carbon nanotube, which occurs to reunite to will affect its being uniformly distributed in carbon-based conductive cream and then influence denatured conductive cream, to be led
Electrical property.Crude product is not vacuum-treated in embodiment 20, obtained denatured conductive cream has penetrating odor, reason
It is not completely removed for chloroform therein, chloroform is toxic, if failing whole removals, can bring many security risks.Therefore, implement
The treatment process in embodiment 20 is better than to the treatment process of organic solvent in example 19.
In conclusion the conductivity of the denatured conductive cream of the embodiment of the present application is high, at low cost, conducting wire can be made；Preparation
Mild condition, simple process, efficiently, it is environmental-friendly.
The above description is only an example of the present application, the protection scope being not intended to limit this application, for ability
For the technical staff in domain, various changes and changes are possible in this application.Within the spirit and principles of this application, made
Any modification, equivalent substitution, improvement and etc. should be included within the scope of protection of this application.
Claims (10)
1. a kind of denatured conductive cream, which is characterized in that its raw material includes: 1%~90% carbon-based conductive by mass percentage
Cream, 5%~60% carbon nanotube and 5%~50% hyperbranched polyethylene；The carbon-based conductive cream, the carbon nanometer
Three-dimensional conductive network is formed between pipe and the hyperbranched polyethylene.
2. denatured conductive cream according to claim 1, which is characterized in that the raw material includes: by mass percentage
72%~90% carbon-based conductive cream；5%~14% carbon nanotube；And 5%~14% it is described hyperbranched
Polyethylene.
3. denatured conductive cream according to claim 1, which is characterized in that the ingredient of the carbon-based conductive cream includes adhesive
And carbon material, wherein the mass content of the carbon material is between 30%~70%；Optionally, the carbon-based conductive cream is mainly
By the adhesive and the carbon material by grinding, dispersion, modified obtain.
4. denatured conductive cream according to claim 1, which is characterized in that the carbon nanotube includes at least to be selected from single wall carbon
Nanotube, double-walled carbon nano-tube, multi-walled carbon nanotube, highly conductive multi-walled carbon nanotube, hydroxyl carbon nano tube, carboxylated carbon are received
At least one of the group of mitron and aminated carbon nano tube composition.
5. a kind of preparation method of denatured conductive cream according to any one of claims 1 to 4, which is characterized in that it includes
Following steps:
The carbon-based conductive cream and organic solvent are mixed to form the first solution；By the carbon nanotube, the hyperbranched poly second
Alkene and organic solvent mixing, keep the carbon nanotube evenly dispersed, form the second solution；
First solution and second solution are uniformly mixed, the organic solvent is removed.
6. the preparation method of denatured conductive cream according to claim 5, which is characterized in that the organic solvent includes at least
At least one of group selected from chloroform, tetrahydrofuran, petroleum ether and ether composition；Optionally, the organic solvent includes chlorine
At least one of imitative or tetrahydrofuran.
7. the preparation method of denatured conductive cream according to claim 5, which is characterized in that by the carbon nanotube, described
Hyperbranched polyethylene and organic solvent mixing make the method ultrasonic treatment that the carbon nanotube is evenly dispersed；Optionally, described
The time of ultrasonic treatment is 0.5~12h.
8. the preparation method of denatured conductive cream according to claim 5, which is characterized in that divide the carbon nanotube uniformly
It further include the removal part hyperbranched polyethylene, then the step for making the carbon nanotube evenly dispersed again after dissipating；
Optionally, the method for removing the part hyperbranched polyethylene includes at least one of high speed centrifugation or vacuum filtration.
9. the preparation method of denatured conductive cream according to claim 5, which is characterized in that by first solution and described
The uniformly mixed method of second solution is stir process；Optionally, the time of the stir process is 10~240min；
And/or the method for removing the organic solvent includes at least one of revolving, purging or drying.
10. a kind of application of denatured conductive cream according to any one of claims 1 to 4, which is characterized in that the modification is led
Electric cream is as conductive material for making conducting wire.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112876759A (en) * | 2020-12-15 | 2021-06-01 | 浙江工业大学 | Method for preparing high-heat-dissipation polymer material by using hyperbranched polyethylene as auxiliary agent through ball milling method |
| CN115386317A (en) * | 2022-08-16 | 2022-11-25 | 浙江工业大学 | Preparation method of high-thermal-conductivity and high-electrical-conductivity composite adhesive taking graphene and carbon nano tubes as fillers |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1622224A (en) * | 2003-11-30 | 2005-06-01 | 刘金利 | Conductive paste |
| US20110247866A1 (en) * | 2008-12-10 | 2011-10-13 | Ls Cable & System, Ltd | Conductive paste containing silver-decorated carbon nanotubes |
| CN103087335A (en) * | 2012-11-09 | 2013-05-08 | 浙江工业大学 | Method for preparing graphene organic dispersion solution from hyperbranched polyethylene |
| CN104032381A (en) * | 2014-06-06 | 2014-09-10 | 浙江大学 | Method for preparing hyperbranched polyethylene fiber and hyperbranched polyethylene fiber and carbon nano tube complex fiber through electrostatic spinning |
| CN104130753A (en) * | 2014-07-15 | 2014-11-05 | 西南科技大学 | High-thermal-conductivity high-electrical-conductivity carbon nano-grade composite material and preparation method thereof |
| CN109180973A (en) * | 2018-07-11 | 2019-01-11 | 四川羽玺新材料股份有限公司 | A kind of preparation method and applications of graphene quantum dot/carbon black/resin compounded conductive film |
-
2019
- 2019-06-06 CN CN201910494444.8A patent/CN110164588B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1622224A (en) * | 2003-11-30 | 2005-06-01 | 刘金利 | Conductive paste |
| US20110247866A1 (en) * | 2008-12-10 | 2011-10-13 | Ls Cable & System, Ltd | Conductive paste containing silver-decorated carbon nanotubes |
| CN103087335A (en) * | 2012-11-09 | 2013-05-08 | 浙江工业大学 | Method for preparing graphene organic dispersion solution from hyperbranched polyethylene |
| CN104032381A (en) * | 2014-06-06 | 2014-09-10 | 浙江大学 | Method for preparing hyperbranched polyethylene fiber and hyperbranched polyethylene fiber and carbon nano tube complex fiber through electrostatic spinning |
| CN104130753A (en) * | 2014-07-15 | 2014-11-05 | 西南科技大学 | High-thermal-conductivity high-electrical-conductivity carbon nano-grade composite material and preparation method thereof |
| CN109180973A (en) * | 2018-07-11 | 2019-01-11 | 四川羽玺新材料股份有限公司 | A kind of preparation method and applications of graphene quantum dot/carbon black/resin compounded conductive film |
Non-Patent Citations (1)
| Title |
|---|
| 无: "混合使用碳纳米管提高锂电池性能的导电膏", 《硅酸盐通报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112876759A (en) * | 2020-12-15 | 2021-06-01 | 浙江工业大学 | Method for preparing high-heat-dissipation polymer material by using hyperbranched polyethylene as auxiliary agent through ball milling method |
| CN115386317A (en) * | 2022-08-16 | 2022-11-25 | 浙江工业大学 | Preparation method of high-thermal-conductivity and high-electrical-conductivity composite adhesive taking graphene and carbon nano tubes as fillers |
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