CN109749520A - A kind of preparation method easily storing long-acting conductive ink - Google Patents
A kind of preparation method easily storing long-acting conductive ink Download PDFInfo
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Abstract
The invention discloses the preparation methods that one kind easily stores long-acting conductive ink, belong to conductive material preparation technical field.First pre- Modified polystyrene spheres are made with methacryloxypropyl ethylene chlorination ammonium in the present invention, then, additive are made with halogenated hydrocarbons modified sodium lignosulfonate, by the pre- Modified polystyrene spheres of additive treating, and copper sulphate and reducing agent is added, after common reaction, conductive agent is made；Finally conductive agent and acetone are mixed in blender, and crosslinking agent is added into blender, binder and curing agent are 30~40 DEG C in temperature, and revolving speed is under conditions of 300~320r/min, after being stirred 30~60min, and under conditions of frequency is 45~55kHz after 20~30min of ultrasonic disperse, conductive ink is obtained, it is produced by the present invention easily to store long-acting conductive ink with preferable storage characteristics, and conductive effect is excellent, has biggish facilitation to the art.
Description
Technical field
The invention discloses the preparation methods that one kind easily stores long-acting conductive ink, belong to conductive material preparation technology neck
Domain.
Background technique
Conductive ink is multicomponent system, is mainly made of conductive filler and multiple additives.Conductive filler General Decentralized
In aqueous or organic solvent type solution, additive is mostly wetting agent, adhesive, surfactant, defoaming agent etc., these components
Organically combine to guarantee that optimal effect can be reached after conductive ink is printed on substrate by printed apparatus.Conductive filler
Selection depend primarily on the various printing requirements of impressing pattern, such as conductive to the requirement of physical property, translucency, bending resistance
Folding endurance, fastness (being even more important for flexible print electronics), the requirement to physical and chemical performance has resistance to aggregation stability, Yi Jiyao
Meet the requirement for having compatibility with printed apparatus.
In printed electronics, functionalization printing ink is most important for the performance of electronic device.Printing ink is one
Kind contains the multicomponent system of micro Nano material, stabilizer and rheology modifier.The different component parts of printed electronic device
The ink of different performance is needed, for example, active layer uses the ink of semiconductor type in printing film transistor, electrode makes
With conductivity type ink, dielectric layer uses insulated type ink.Conductivity type ink is in stability, low cost and print with conventional inks
While brush adaptive, should have excellent carrier mobility, functional stabilization, repeatability, at the same avoid it is excessively complicated or
Extreme subsequent processing.Therefore, the process that the functionalization expanded from the transfer of the simple information of traditional printing to printed electronic manufactures,
It is closely related with the research and development of micro Nano material.Micro Nano material applied to conductive circuit mainly includes nano carbon material
Material, metal nano material, high polymer etc..Wherein, the electrical conduction mechanism of metal nanoparticle is mobile for free electron, main to use
Gold, silver, copper, 4 metalloid of aluminium.Gold and silver nanoparticle or nano wire have outstanding anti-oxidant and electric conductivity, but at high cost；Copper
It is excellent but oxidizable with aluminum nanoparticles or nano wire electric conductivity.
According to the difference of conductive filler, conductive ink can be divided into inorganic system's conductive ink, organic system conductive ink and compound
It is conductive ink.The functional unit of inorganic system's conductive ink includes metal class and non-metal kind.Non-metal kind conductive component is main
For carbon material etc., traditional carbon material is although cheap, but electric conductivity is bad, thus application range is not extensive at present.But
It is as graphene, the carbon materials such as carbon nanotube field obtain huge development in recent years, carbon material also has wide development
Prospect.There is very excellent electric property, optical property and mechanical performance if graphene and carbon nanotube, be good electricity
Son is learned and photoelectronics material.The electric conductivity of Single Carbon Nanotubes is even close to the electric conductivity of metal.But since there is complete
U.S. structure is difficult to reproduce the problems such as printed apparatus is easily blocked with high length-diameter ratio bring, and application is restricted organic system conductive ink
The functional unit of water mainly synthesizes conductive polymer material, is also referred to as intrinsically conducting macromolecule, also referred to as synthesis gold
Belong to.Conducting polymer with conjugatedπbond, backbone can have and electrochemical properties as metal phase under dopant states
Feature, and there is mechanicalness and machinability possessed by traditional polymer, it can be achieved that reducing solidification temperature, simplify molecular line
The purpose on road and device fabrication schedule, still, organic system conductive ink Conductivity Ratio are lower, and chemical property is unstable, application
It is restricted.Composite conducting ink is the important development direction of conductive ink, it is intended to give full play to inorganic system's conductive ink and have
The advantage of machine system conductive ink, inorganic conductive functional unit and organic material supporter are organically combined.Inorganic nano
Material charge mobility is much higher than organic electronic material, and performance is stablized, and organic electronic material solidification temperature is low, technique behaviour
The property made is strong.But since inorganic material and high molecular material compatibility are poor, the research and development of composite conducting ink must solve guarantee fund
The problem of metal particles keep high concentration individual particle in conductive ink and do not agglomerate.
The problem of storge quality and electric conductivity of conductive ink traditional at present can not also further increase, in the hope of exploring
Developing the conductive ink with good comprehensive performance is problem to be solved.
Summary of the invention
The present invention solves the technical problem of: it can not be into for traditional conductive ink storge quality and electric conductivity
The problem of one step is promoted provides a kind of preparation method for easily storing long-acting conductive ink.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
A kind of preparation method easily storing long-acting conductive ink, specific preparation step are as follows:
(1) pretreatment styrene is mixed with ethanol solution 1:5~1:6 in mass ratio, and pretreatment styrene quality is added
0.02~0.04 times of initiator is stirred to react under nitrogen atmosphere, obtains pre-polymer mixture, by pre-polymer mixture and first
Base acryloyl-oxy ethylene chlorination ammonium 200:1~500:1 in mass ratio mixing after being stirred to react under nitrogen atmosphere, is filtered, is done
It is dry, obtain pre- Modified polystyrene spheres；
(2) lignin sulfonic acid sodium solution is mixed with formaldehyde 20:1~25:1 in mass ratio, and is added 2~4 times of formaldehyde quality
Sodium sulfite after being stirred to react, must pre-process lignin sulfonic acid sodium solution, by pretreatment lignin sulfonic acid sodium solution and potassium iodide
The mixing of 90:1~120:1 in mass ratio, and 1, the 6- dibromo of 0.1~0.3 times of sodium lignin sulfonate solution quality of pretreatment is added
Hexane solution after being stirred to react under alkaline condition, obtains processing agent composition, and by processing agent composition extraction, filtering must be filtered
Liquid, by filtrate concentrated by rotary evaporation to get additive；(3) pre- Modified polystyrene spheres and water 1:10~1:12 in mass ratio are mixed
It closes, and the additive of 2~3 times of pre- Modified polystyrene spheres quality is added, after being stirred, obtain pre- Modified polystyrene spheres
Pre- Modified polystyrene spheres mixture is mixed with copper sulphate 15:1~15:3 in mass ratio, and pre- modification is added by mixture
The trisodium citrate and pre- Modified polystyrene spheres mixture quality 0.1 that 0.1~0.2 times of polystyrene microsphere mixture quality
~0.3 times of reducing agent is stirred to react, while with 15~35mL/min's after adjusting pH to 9.0~10.0 under nitrogen atmosphere
Rate instills the dehydrated alcohol of 8~9 times of pre- Modified polystyrene spheres mixture quality, after being stirred, filters, dry, obtains
Conductive agent；
(4) according to parts by weight, it successively weighs: 60~80 parts of acetone, 5~8 parts of crosslinking agents, 15~35 parts of binders, 5~6 parts
Curing agent and 15~25 parts of conductive agents；Conductive agent is mixed with acetone, and crosslinking agent is added, binder and curing agent, stirring mix
After conjunction, ultrasonic disperse obtains conductive ink.
Step (1) the pretreatment styrene be by styrene and mass fraction be 4~6% sodium hydroxide solution by matter
Amount can be mixed than 1:5~1:6, be evaporated under reduced pressure, obtained pretreatment styrene.
Step (1) initiator is any one in azodiisobutyronitrile or benzoyl peroxide.
Step (2) is described to mix sodium lignin sulfonate with water 1:10~1:12 in mass ratio, and adjust pH to 11.0~
11.5, obtain lignin sulfonic acid sodium solution.
Step (2) the 1,6- dibromo-hexane solution is by 1,6- dibromo-hexane and dehydrated alcohol 5:1 in mass ratio
Mixing, obtains 1,6- dibromo-hexane solution.
Step (3) reducing agent is hydrazine hydrate, any one in sodium borohydride or potassium borohydride.
Step (4) binder is epoxy resin E-20, any in epoxy resin E-44 or epoxy resin E-51
It is a kind of.
Step (4) curing agent is to mix ethylenediamine with triethylene tetramine 3:1~5:1 in mass ratio, and add
The diethylamine for entering 2~3 times of ethylenediamine quality, is stirred, obtains curing agent.
Extractant used in step (2) described extraction is petroleum ether, any one in ether or chloroform, preferably petroleum ether.
Step (4) crosslinking agent is to mix primary amine compound with isocyanates 5:1~8:1 in mass ratio, and add
The calcium bicarbonate for entering 0.1~0.2 times of primary amine compound quality after being stirred, obtains crosslinking agent, and the primary amine compound is
Any one in polyallylamine or polyethyleneimine.
The beneficial effects of the present invention are:
(1) present invention uses polystyrene microsphere as the base-material of conductive agent when preparing conductive ink, firstly, using polyphenyl second
Alkene, which prepares conductive agent for core, can make conductive agent after being added in product, since the density of polystyrene core-shell structure is relative to proof gold
Belong to smaller, therefore be not susceptible to settle after being added in product, to guarantee the dispersibility of conductive agent in the product, and then makes to produce
The storage time of product extends, secondly, polystyrene microsphere is after modification, the micro- surface of polystyrene has charge, is being added
After in product, polystyrene microsphere can be uniformly distributed in product under the action of electrostatic repulsion, to occur also in copper ion
When original reaction, the copper particle of generation is uniformly distributed in reduction system, prevents the reunion of copper, and absorption and polystyrene microsphere
Surface, and then after being added in product, copper simple substance can be uniformly distributed in together products with polystyrene microsphere, make product
Electric conductivity improves；
(2) present invention is handled pre- Modified polystyrene spheres using additive when preparing conductive ink, and conduction is made
Agent, on the one hand, there is three-dimensional net structure, and sulfomethylated lignin through the modified sodium lignin sulfonate of 1,6- dibromo-hexane in additive
It can be adsorbed under the action of electrostatic force after being mixed with pre- Modified polystyrene spheres in sour sodium containing a large amount of sulfonate groups
In pre- Modified polystyrene spheres surface, so that first the copper ion in reduction system can be fixed in reduction process, and
The layers of copper contained after reduction to pre- Modified polystyrene spheres surface is protected and is fixed, and then makes the metal in conductive agent
Ingredient is not easily runed off and is aoxidized, and product is made to have long-acting electric conductivity, and on the other hand, effective component to changing in advance in additive
Property polystyrene microsphere coated after hydrophobic side is exposed to microsphere surface, so that raising can be improved after being added in product
The dispersibility of conductive agent in the product, further increases the storge quality of product and electric conductivity.
(3) present invention is additionally added crosslinking agent when preparing conductive ink, contains primary amine compound in the crosslinking agent of addition,
Primary amine compound has carbon dioxide irritation, micro- crosslinking can occur under the action of carbon dioxide, also, in crosslinking agent
It is also added into isocyanates, water reaction can be met during storage, carbon dioxide is generated, to promote the friendship of primary amine compound
Connection, and then micro- cross-linking system is formed in the product, make conductive agent is more uniform to be distributed in product, further increases product
Storage stability.
Specific embodiment
Ethanol solution 1:5~1:6 in mass ratio that styrene and mass fraction are 90~95% will be pre-processed and be mixed in flask
In, and addition pre-processes 0.02~0.04 times of styrene quality of initiator into flask, into flask with 30~40mL/min
Rate be passed through nitrogen, in temperature be 70~75 DEG C, revolving speed be 300~320r/min under conditions of, after being stirred to react 1~2h,
Pre-polymer mixture is obtained, pre-polymer mixture is mixed with methacryloxypropyl ethylene chlorination ammonium 200:1~500:1 in mass ratio
In three-necked flask, nitrogen is passed through with the rate of 30~40mL/min into three-necked flask, is 70~80 DEG C in temperature, revolving speed is
Under conditions of 300~350r/min, after being stirred to react 22~23h, filtering obtains pre- Modified polystyrene spheres blank, will change in advance
Property polystyrene microsphere blank be 70~80 DEG C in temperature under conditions of after dry 1~3h, obtain pre- Modified polystyrene spheres；It will
Lignin sulfonic acid sodium solution and formaldehyde 20:1~25:1 in mass ratio are mixed in beaker, and formaldehyde quality 2 is added into beaker
~4 times of sodium sulfite, in temperature be 90~95 DEG C, revolving speed be 300~320r/min under conditions of be stirred to react 2~3h after,
Lignin sulfonic acid sodium solution must be pre-processed, by pretreatment lignin sulfonic acid sodium solution and potassium iodide 90:1~120:1 in mass ratio
It is mixed in four-hole boiling flask, and 1, the 6- bis- of 0.1~0.3 times of sodium lignin sulfonate solution quality of pretreatment is added in four-hole boiling flask
Bromohexane solution, the addition rate of control 1,6- dibromo-hexane solution are 8~10mL/min, at the same with mass fraction for 10~
The pH of material is 11.0~11.5 in 12% sodium hydroxide solution control four-hole boiling flask, and is 80~85 DEG C in temperature, and revolving speed is
After being stirred to react 4~5h under conditions of 230~350r/min, processing agent composition is obtained, processing agent composition petroleum ether is extracted
After taking 3~5 times, filtering, obtain filtrate, by filtrate in temperature be 60~80 DEG C, revolving speed be 120~150r/min, pressure be 500~
To get additive after 5~6h of concentrated by rotary evaporation under conditions of 600kPa；By pre- Modified polystyrene spheres and water 1:10 in mass ratio
~1:12 mixing, and pre- Modified polystyrene spheres quality 2~3 is added into the mixture of pre- Modified polystyrene spheres and water
Times additive, in temperature be 40~50 DEG C, revolving speed be 300~320r/min under conditions of, after being stirred 50~80min,
Pre- Modified polystyrene spheres mixture, by pre- Modified polystyrene spheres mixture and copper sulphate 15:1 in mass ratio~
15:3 is mixed in reaction kettle, and the lemon of 0.1~0.2 times of pre- Modified polystyrene spheres mixture quality is added into reaction kettle
The reducing agent of 0.1~0.3 times of lemon acid trisodium and pre- Modified polystyrene spheres mixture quality is 3~5% with mass fraction
After sodium hydroxide solution adjusts the pH to 9.0~10.0 of material in reactor, and into reaction kettle with the speed of 40~60mL/min
Rate is passed through nitrogen, while pre- Modified polystyrene spheres mixture quality is instilled into reaction kettle with the rate of 15~35mL/min
8~9 times of dehydrated alcohol is 30~50 DEG C in temperature, and revolving speed is stirred to react under conditions of being 300~320r/min to anhydrous second
After alcohol drop is most, filtering obtains conductive agent blank, under conditions of being 50~80 DEG C in temperature by conductive agent blank after dry 1~2h, obtains
Conductive agent；According to parts by weight, it successively weighs: 60~80 parts of acetone, 5~8 parts of crosslinking agents, 15~35 parts of binders, 5~6 parts
Curing agent and 15~25 parts of conductive agents；Conductive agent and acetone are mixed in blender, and crosslinking agent is added into blender, is glued
Agent and curing agent are tied, is 30~40 DEG C in temperature, under conditions of revolving speed is 300~320r/min, is stirred 30~60min
Afterwards, and under conditions of frequency is 45~55kHz it after 20~30min of ultrasonic disperse, obtains and easily stores long-acting conductive ink.It is described pre-
Handling styrene is that can mix styrene than 1:5~1:6 by quality with the sodium hydroxide solution that mass fraction is 4~6%, is subtracted
Pressure distillation, obtains pretreatment styrene.The initiator is any one in azodiisobutyronitrile or benzoyl peroxide.The wood
Quality sodium sulfonate solution be sodium lignin sulfonate is mixed with water 1:10~1:12 in mass ratio, and adjust pH to 11.0~
11.5, obtain lignin sulfonic acid sodium solution.The 1,6- dibromo-hexane solution is that 1,6- dibromo-hexane and dehydrated alcohol are pressed quality
It is mixed than 5:1, obtains 1,6- dibromo-hexane solution.The reducing agent is hydrazine hydrate, any one in sodium borohydride or potassium borohydride.
The binder is epoxy resin E-20, any one in epoxy resin E-44 or epoxy resin E-51.It is described solid
Agent is to mix ethylenediamine with triethylene tetramine 3:1~5:1 in mass ratio, and 2~3 times of ethylenediamine quality of diethyl is added
Amine is stirred, and obtains curing agent.The crosslinking agent is to mix primary amine compound and isocyanates 5:1~8:1 in mass ratio
It closes, and 0.1~0.2 times of primary amine compound quality of calcium bicarbonate is added, after being stirred, obtain crosslinking agent, the primary amine class
Compound is any one in polyallylamine or polyethyleneimine.
Example 1
The ethanol solution 1:6 in mass ratio that styrene and mass fraction are 95% will be pre-processed to be mixed in flask, and into flask
The initiator of 0.04 times of styrene quality of pretreatment is added, nitrogen is passed through with the rate of 40mL/min into flask, is in temperature
75 DEG C, under conditions of revolving speed is 320r/min, after being stirred to react 2h, pre-polymer mixture is obtained, by pre-polymer mixture and methyl
Acryloyl-oxy ethylene chlorination ammonium 500:1 in mass ratio is mixed in three-necked flask, into three-necked flask with the rate of 40mL/min
It is passed through nitrogen, is 80 DEG C in temperature, under conditions of revolving speed is 350r/min, after being stirred to react 23h, filtering obtains pre- modified polyphenyl
It is poly- to obtain pre- modification under conditions of being 80 DEG C in temperature by pre- Modified polystyrene spheres blank after dry 3h for ethylene microballoon blank
Phenylethylene micro ball；Lignin sulfonic acid sodium solution and formaldehyde 25:1 in mass ratio are mixed in beaker, and first is added into beaker
The sodium sulfite that 4 times of aldehyde quality is 95 DEG C in temperature, after revolving speed is stirred to react 3h under conditions of being 320r/min, must pre-process
Pretreatment lignin sulfonic acid sodium solution and potassium iodide 120:1 in mass ratio are mixed in four-hole boiling flask by lignin sulfonic acid sodium solution
In, and addition pre-processes 0.3 times of sodium lignin sulfonate solution quality of 1,6- dibromo-hexane solution, control 1,6- in four-hole boiling flask
The addition rate of dibromo-hexane solution is 10mL/min, while the sodium hydroxide solution for being 12% with mass fraction controls four mouthfuls of burnings
The pH of material is 11.5 in bottle, and is 85 DEG C in temperature, after revolving speed is stirred to react 5h under conditions of being 350r/min, obtains inorganic agent
Mixture, will processing agent composition with after petroleum ether extraction 5 times, filtering obtains filtrate, in temperature is 80 DEG C by filtrate, revolving speed is
150r/min, to get additive after concentrated by rotary evaporation 6h under conditions of pressure is 600kPa；By pre- Modified polystyrene spheres and water
The mixing of 1:12 in mass ratio, and pre- Modified polystyrene spheres matter is added into the mixture of pre- Modified polystyrene spheres and water
The additive of 3 times of amount is 50 DEG C in temperature, under conditions of revolving speed is 320r/min, after being stirred 80min, it is poly- to obtain pre- modification
Pre- Modified polystyrene spheres mixture and copper sulphate 15:3 in mass ratio are mixed in reaction kettle by phenylethylene micro ball mixture
In, and the trisodium citrate and pre- modified polyphenyl of 0.2 times of pre- Modified polystyrene spheres mixture quality is added into reaction kettle
The reducing agent of 0.3 times of ethylene mixture of microspheres quality adjusts material in reactor with the sodium hydroxide solution that mass fraction is 5%
PH to 10.0 after, and the rate into reaction kettle with 60mL/min is passed through nitrogen, while with the rate of 35mL/min to reaction
The dehydrated alcohol that 9 times of pre- Modified polystyrene spheres mixture quality is instilled in kettle, in temperature be 50 DEG C, revolving speed 320r/min
Under conditions of be stirred to react to dehydrated alcohol drop to the greatest extent after, filtering obtains conductive agent blank, by conductive agent blank in temperature be 80 DEG C
Under the conditions of after dry 2h, obtain conductive agent；According to parts by weight, it successively weighs: 80 parts of acetone, 8 parts of crosslinking agents, 35 parts of binders, 6
Part curing agent and 25 parts of conductive agents；Conductive agent and acetone are mixed in blender, and crosslinking agent is added into blender, is bonded
Agent and curing agent are 40 DEG C in temperature, under conditions of revolving speed is 320r/min, after being stirred 60min, and in frequency are
Under conditions of 55kHz after ultrasonic disperse 30min, obtains and easily store long-acting conductive ink.The pretreatment styrene is by styrene
The sodium hydroxide solution for being 6% with mass fraction can be mixed by quality than 1:6, be evaporated under reduced pressure, obtained pretreatment styrene.It is described to draw
Hair agent is azodiisobutyronitrile.The lignin sulfonic acid sodium solution is to mix sodium lignin sulfonate with water 1:12 in mass ratio,
And pH to 11.5 is adjusted, obtain lignin sulfonic acid sodium solution.The 1,6- dibromo-hexane solution be by 1,6- dibromo-hexane with it is anhydrous
Ethyl alcohol 5:1 in mass ratio mixing, obtains 1,6- dibromo-hexane solution.The reducing agent is hydrazine hydrate.The binder is ring
Oxygen resin E-20.The curing agent is to mix ethylenediamine with triethylene tetramine 5:1 in mass ratio, and ethylenediamine matter is added
The diethylamine of 3 times of amount, is stirred, obtains curing agent.The crosslinking agent be by primary amine compound and isocyanates in mass ratio
8:1 mixing, and 0.2 times of primary amine compound quality of calcium bicarbonate is added, after being stirred, obtain crosslinking agent, the primary amine class
Compound is polyallylamine.
Example 2
Lignin sulfonic acid sodium solution and formaldehyde 25:1 in mass ratio are mixed in beaker, and formaldehyde quality 4 is added into beaker
Sodium sulfite again is 95 DEG C in temperature, after revolving speed is stirred to react 3h under conditions of being 320r/min, obtains pretreatment sulfomethylated lignin
Pretreatment lignin sulfonic acid sodium solution and potassium iodide 120:1 in mass ratio are mixed in four-hole boiling flask by acid sodium solution, and four mouthfuls
1, the 6- dibromo-hexane solution of 0.3 times of sodium lignin sulfonate solution quality of pretreatment is added in flask, controls 1,6- dibromo-hexane
The addition rate of solution is 10mL/min, while the sodium hydroxide solution for being 12% with mass fraction controls material in four-hole boiling flask
PH be 11.5, and in temperature be 85 DEG C, revolving speed be 350r/min under conditions of be stirred to react 5h after, obtain processing agent composition,
Will processing agent composition with after petroleum ether extraction 5 times, it in temperature is 80 DEG C by filtrate that filtering, which obtains filtrate, revolving speed 150r/
Min, to get additive after concentrated by rotary evaporation 6h under conditions of pressure is 600kPa；By polystyrene microsphere and water in mass ratio 1:
12 mix, and the additive of 3 times of polystyrene microsphere quality is added into the mixture of polystyrene microsphere and water, are in temperature
50 DEG C, under conditions of revolving speed is 320r/min, after being stirred 80min, polystyrene microsphere mixture is obtained, polystyrene is micro-
Ball mixture and copper sulphate 15:3 in mass ratio are mixed in reaction kettle, and polystyrene microsphere mixture is added into reaction kettle
The trisodium citrate and 0.3 times of polystyrene microsphere mixture quality of reducing agent that 0.2 times of quality, the hydrogen for being 5% with mass fraction
After sodium hydroxide solution adjusts the pH to 10.0 of material in reactor, and nitrogen is passed through with the rate of 60mL/min into reaction kettle,
Instill 9 times of polystyrene microsphere mixture quality of dehydrated alcohol, Yu Wendu into reaction kettle with the rate of 35mL/min simultaneously
Be 50 DEG C, revolving speed be 320r/min under conditions of be stirred to react to dehydrated alcohol drop to the greatest extent after, filtering, obtain conductive agent blank, will lead
Under conditions of electric agent blank is 80 DEG C in temperature after dry 2h, conductive agent is obtained；According to parts by weight, it successively weighs: 80 parts of acetone,
8 parts of crosslinking agents, 35 parts of binders, 6 parts of curing agent and 25 parts of conductive agents；Conductive agent and acetone are mixed in blender, and to
Crosslinking agent, binder and curing agent are added in blender, is 40 DEG C in temperature, under conditions of revolving speed is 320r/min, stirring is mixed
After closing 60min, and obtains after ultrasonic disperse 30min under conditions of frequency is 55kHz and easily store long-acting conductive ink.It is described pre-
Handling styrene is that can mix styrene than 1:6 by quality with the sodium hydroxide solution that mass fraction is 6%, and vacuum distillation obtains
Pre-process styrene.The sodium lignin sulfonate is molten to mix sodium lignin sulfonate with water 1:12 in mass ratio, and adjusts pH
To 11.5, lignin sulfonic acid sodium solution is obtained.The 1,6- dibromo-hexane solution is that 1,6- dibromo-hexane and dehydrated alcohol are pressed matter
Amount is mixed than 5:1, obtains 1,6- dibromo-hexane solution.The reducing agent is hydrazine hydrate.The binder is epoxy resin E-20.Institute
Stating the curing agent is to mix ethylenediamine with triethylene tetramine 5:1 in mass ratio, and 3 times of ethylenediamine quality of diethyl is added
Amine is stirred, and obtains curing agent.The crosslinking agent is to mix primary amine compound with isocyanates 8:1 in mass ratio, and add
The calcium bicarbonate for entering 0.2 times of primary amine compound quality after being stirred, obtains crosslinking agent, and the primary amine compound is polyene
Propylamine.
Example 3
The ethanol solution 1:6 in mass ratio that styrene and mass fraction are 95% will be pre-processed to be mixed in flask, and into flask
The initiator of 0.04 times of styrene quality of pretreatment is added, nitrogen is passed through with the rate of 40mL/min into flask, is in temperature
75 DEG C, under conditions of revolving speed is 320r/min, after being stirred to react 2h, pre-polymer mixture is obtained, by pre-polymer mixture and methyl
Acryloyl-oxy ethylene chlorination ammonium 500:1 in mass ratio is mixed in three-necked flask, into three-necked flask with the rate of 40mL/min
It is passed through nitrogen, is 80 DEG C in temperature, under conditions of revolving speed is 350r/min, after being stirred to react 23h, filtering obtains pre- modified polyphenyl
It is poly- to obtain pre- modification under conditions of being 80 DEG C in temperature by pre- Modified polystyrene spheres blank after dry 3h for ethylene microballoon blank
Phenylethylene micro ball；Pre- Modified polystyrene spheres are mixed with water 1:12 in mass ratio, in temperature be 50 DEG C, revolving speed 320r/
Under conditions of min, after being stirred 80min, pre- Modified polystyrene spheres mixture is obtained, pre- Modified polystyrene spheres are mixed
It closes object and copper sulphate 15:3 in mass ratio is mixed in reaction kettle, and pre- Modified polystyrene spheres mixing is added into reaction kettle
The reducing agent of 0.3 times of the trisodium citrate and pre- Modified polystyrene spheres mixture quality that 0.2 times of amount of substance, uses mass fraction
After pH to 10.0 for 5% sodium hydroxide solution adjusting material in reactor, and it is logical with the rate of 60mL/min into reaction kettle
Enter nitrogen, while instilling the nothing of 9 times of pre- Modified polystyrene spheres mixture quality into reaction kettle with the rate of 35mL/min
Water-ethanol, in temperature be 50 DEG C, revolving speed be 320r/min under conditions of be stirred to react to dehydrated alcohol drop to the greatest extent after, filtering, must lead
Electric agent blank obtains conductive agent under conditions of being 80 DEG C in temperature by conductive agent blank after dry 2h；According to parts by weight, successively
It weighs: 80 parts of acetone, 8 parts of crosslinking agents, 35 parts of binders, 6 parts of curing agent and 25 parts of conductive agents；Conductive agent and acetone are mixed in
In blender, and crosslinking agent is added into blender, binder and curing agent are 40 DEG C in temperature, and revolving speed is 320r/min's
Under the conditions of, after being stirred 60min, and obtains after ultrasonic disperse 30min under conditions of frequency is 55kHz and easily store long-acting lead
Electric ink.The pretreatment styrene is that the sodium hydroxide solution for being 6% with mass fraction by styrene can be mixed by quality than 1:6
It closes, vacuum distillation obtains pretreatment styrene.The initiator is azodiisobutyronitrile.The reducing agent is hydrazine hydrate.It is described viscous
Knot agent is epoxy resin E-20.The curing agent is to mix ethylenediamine with triethylene tetramine 5:1 in mass ratio, and be added
The diethylamine that 3 times of ethylenediamine quality, is stirred, and obtains curing agent.The crosslinking agent is by primary amine compound and isocyanates
The mixing of 8:1 in mass ratio, and 0.2 times of primary amine compound quality of calcium bicarbonate is added, after being stirred, crosslinking agent is obtained, institute
Stating primary amine compound is polyallylamine.
Comparative example:
Polystyrene microsphere is mixed with water 1:12 in mass ratio, is 50 DEG C in temperature, under conditions of revolving speed is 320r/min, stirs
After mixing mixing 80min, polystyrene microsphere mixture is obtained, polystyrene microsphere mixture and copper sulphate 15:3 in mass ratio are mixed
Together in reaction kettle, and 0.2 times of polystyrene microsphere mixture quality of trisodium citrate and polyphenyl second is added into reaction kettle
The reducing agent of 0.3 times of alkene mixture of microspheres quality adjusts material in reactor with the sodium hydroxide solution that mass fraction is 5%
After pH to 10.0, and the rate into reaction kettle with 60mL/min is passed through nitrogen, while with the rate of 35mL/min to reaction kettle
The middle dehydrated alcohol for instilling 9 times of polystyrene microsphere mixture quality is 50 DEG C in temperature, and revolving speed is under conditions of 320r/min
It is stirred to react to dehydrated alcohol after dripping to the greatest extent, filtering obtains conductive agent blank, does under conditions of being 80 DEG C in temperature by conductive agent blank
After dry 2h, conductive agent is obtained；According to parts by weight, it successively weighs: 80 parts of acetone, 8 parts of crosslinking agents, 35 parts of binders, 6 parts of curing agent
With 25 parts of conductive agents；Conductive agent and acetone are mixed in blender, and crosslinking agent is added into blender, binder and solidification
Agent, in temperature be 40 DEG C, revolving speed be 320r/min under conditions of, after being stirred 60min, and in frequency be 55kHz condition
After lower ultrasonic disperse 30min, obtains and easily store long-acting conductive ink.The initiator is azodiisobutyronitrile.The reducing agent is
Hydrazine hydrate.The binder is epoxy resin E-20.The curing agent be by ethylenediamine and triethylene tetramine in mass ratio
5:1 mixing, and 3 times of ethylenediamine quality of diethylamine is added, it is stirred, obtains curing agent.The crosslinking agent is by primary amine class
It closes object to mix with isocyanates 8:1 in mass ratio, and 0.2 times of primary amine compound quality of calcium bicarbonate is added, be stirred
Afterwards, crosslinking agent is obtained, the primary amine compound is polyallylamine.
Example 1 is easily stored into long-acting conductive ink and comparative example product progress performance detection, specific inspection to example 3 is resulting
Survey method is as follows:
Using the resistivity of multimeter, the high insulation measurement instrument measurement conductive ink of ZC36 type；60 days test specimens point will be stored
It does not sample, using the resistivity of multimeter, the high insulation measurement instrument measurement conductive ink of ZC36 type.
Specific testing result is as shown in table 1:
Table 1 easily stores long-acting conductive ink performance test results
By 1 testing result of table it is found that technical solution of the present invention preparation easily stores long-acting conductive ink with excellent storage characteristics
The characteristics of energy and electric conductivity, has broad prospects in the development of conductive material technology industry.
Claims (10)
1. the preparation method that one kind easily stores long-acting conductive ink, which is characterized in that specific preparation step are as follows:
(1) pretreatment styrene is mixed with ethanol solution 1:5~1:6 in mass ratio, and pretreatment styrene quality is added
0.02~0.04 times of initiator is stirred to react under nitrogen atmosphere, obtains pre-polymer mixture, by pre-polymer mixture and first
Base acryloyl-oxy ethylene chlorination ammonium 200:1~500:1 in mass ratio mixing after being stirred to react under nitrogen atmosphere, is filtered, is done
It is dry, obtain pre- Modified polystyrene spheres；
(2) lignin sulfonic acid sodium solution is mixed with formaldehyde 20:1~25:1 in mass ratio, and is added 2~4 times of formaldehyde quality
Sodium sulfite after being stirred to react, must pre-process lignin sulfonic acid sodium solution, by pretreatment lignin sulfonic acid sodium solution and potassium iodide
The mixing of 90:1~120:1 in mass ratio, and 1, the 6- dibromo of 0.1~0.3 times of sodium lignin sulfonate solution quality of pretreatment is added
Hexane solution after being stirred to react under alkaline condition, obtains processing agent composition, and by processing agent composition extraction, filtering must be filtered
Liquid, by filtrate concentrated by rotary evaporation to get additive；(3) pre- Modified polystyrene spheres and water 1:10~1:12 in mass ratio are mixed
It closes, and the additive of 2~3 times of pre- Modified polystyrene spheres quality is added, after being stirred, obtain pre- Modified polystyrene spheres
Pre- Modified polystyrene spheres mixture is mixed with copper sulphate 15:1~15:3 in mass ratio, and pre- modification is added by mixture
The trisodium citrate and pre- Modified polystyrene spheres mixture quality 0.1 that 0.1~0.2 times of polystyrene microsphere mixture quality
~0.3 times of reducing agent is stirred to react, while with 15~35mL/min's after adjusting pH to 9.0~10.0 under nitrogen atmosphere
Rate instills the dehydrated alcohol of 8~9 times of pre- Modified polystyrene spheres mixture quality, after being stirred, filters, dry, obtains
Conductive agent；
(4) according to parts by weight, it successively weighs: 60~80 parts of acetone, 5~8 parts of crosslinking agents, 15~35 parts of binders, 5~6 parts
Curing agent and 15~25 parts of conductive agents；Conductive agent is mixed with acetone, and crosslinking agent is added, binder and curing agent, stirring mix
After conjunction, ultrasonic disperse obtains conductive ink.
2. the preparation method that one kind according to claim 1 easily stores long-acting conductive ink, it is characterised in that: step (1)
The pretreatment styrene is that the sodium hydroxide solution for being 4~6% with mass fraction by styrene can be mixed by quality than 1:5~1:6
It closes, vacuum distillation obtains pretreatment styrene.
3. the preparation method that one kind according to claim 1 easily stores long-acting conductive ink, it is characterised in that: step (1)
The initiator is any one in azodiisobutyronitrile or benzoyl peroxide.
4. the preparation method that one kind according to claim 1 easily stores long-acting conductive ink, it is characterised in that: step (2)
It is described to mix sodium lignin sulfonate with water 1:10~1:12 in mass ratio, and pH to 11.0~11.5 is adjusted, obtain sulfomethylated lignin
Acid sodium solution.
5. the preparation method that one kind according to claim 1 easily stores long-acting conductive ink, it is characterised in that: step (2)
1, the 6- dibromo-hexane solution is to mix 1,6- dibromo-hexane with dehydrated alcohol 5:1 in mass ratio, obtains 1,6- dibromo
Hexane solution.
6. the preparation method that one kind according to claim 1 easily stores long-acting conductive ink, it is characterised in that: step (3)
The reducing agent is hydrazine hydrate, any one in sodium borohydride or potassium borohydride.
7. the preparation method that one kind according to claim 1 easily stores long-acting conductive ink, it is characterised in that: step (4)
The binder is epoxy resin E-20, any one in epoxy resin E-44 or epoxy resin E-51.
8. the preparation method that one kind according to claim 1 easily stores long-acting conductive ink, it is characterised in that: step (4)
The curing agent is to mix ethylenediamine with triethylene tetramine 3:1~5:1 in mass ratio, and ethylenediamine quality 2~3 is added
Diethylamine again, is stirred, obtains curing agent.
9. the preparation method that one kind according to claim 1 easily stores long-acting conductive ink, it is characterised in that: step (2)
Extractant used in the extraction is petroleum ether, any one in ether or chloroform, preferably petroleum ether.
10. the preparation method that one kind according to claim 1 easily stores long-acting conductive ink, it is characterised in that: step (4)
The crosslinking agent is to mix primary amine compound with isocyanates 5:1~8:1 in mass ratio, and primary amine compound matter is added
The calcium bicarbonate of 0.1~0.2 times of amount after being stirred, obtains crosslinking agent, and the primary amine compound is polyallylamine or polyethylene
Any one in imines.
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| CN1186820A (en) * | 1997-11-21 | 1998-07-08 | 天津大学 | High molecular composite conductive micro-balloons |
| CN101298767A (en) * | 2008-06-06 | 2008-11-05 | 吉林中路新材料有限责任公司 | Soil solidifying agent |
| CN104542583A (en) * | 2015-01-04 | 2015-04-29 | 华南理工大学 | High-effective lignosulfonate pesticide suspension dispersing agent and preparation and applications thereof |
| CN105038501A (en) * | 2015-07-15 | 2015-11-11 | 厦门大学 | Conductive coating based on noble-metal-loaded polymer nanoparticle and preparation method of conductive coating |
| CN105153453A (en) * | 2015-07-01 | 2015-12-16 | 安徽大学 | Nano-copper/polymer hollow composite microsphere and preparation method thereof |
| CN109280423A (en) * | 2018-08-31 | 2019-01-29 | 谭亚 | A kind of preparation method of electrically conductive ink |
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2019
- 2019-02-20 CN CN201910125229.0A patent/CN109749520A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1186820A (en) * | 1997-11-21 | 1998-07-08 | 天津大学 | High molecular composite conductive micro-balloons |
| CN101298767A (en) * | 2008-06-06 | 2008-11-05 | 吉林中路新材料有限责任公司 | Soil solidifying agent |
| CN104542583A (en) * | 2015-01-04 | 2015-04-29 | 华南理工大学 | High-effective lignosulfonate pesticide suspension dispersing agent and preparation and applications thereof |
| CN105153453A (en) * | 2015-07-01 | 2015-12-16 | 安徽大学 | Nano-copper/polymer hollow composite microsphere and preparation method thereof |
| CN105038501A (en) * | 2015-07-15 | 2015-11-11 | 厦门大学 | Conductive coating based on noble-metal-loaded polymer nanoparticle and preparation method of conductive coating |
| CN109280423A (en) * | 2018-08-31 | 2019-01-29 | 谭亚 | A kind of preparation method of electrically conductive ink |
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