CN109942890A - A kind of graphene-based antistatic agent and preparation method thereof with suppression hood - Google Patents

A kind of graphene-based antistatic agent and preparation method thereof with suppression hood Download PDF

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CN109942890A
CN109942890A CN201910190371.3A CN201910190371A CN109942890A CN 109942890 A CN109942890 A CN 109942890A CN 201910190371 A CN201910190371 A CN 201910190371A CN 109942890 A CN109942890 A CN 109942890A
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graphene
antistatic agent
based antistatic
preparation
suppression hood
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CN109942890B (en
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黄国波
方国忠
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TAIZHOU BRT PLASTICS ELECTRONICS CO Ltd
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TAIZHOU BRT PLASTICS ELECTRONICS CO Ltd
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Abstract

The invention discloses a kind of graphene-based antistatic agents and preparation method thereof with suppression hood, this method is that r-GO and diisocyanate cpd are added in ball mill, it is ground under conditions of logical drying nitrogen, isocyanate-modified graphene is made, add ferrocene class compound, continue to grind under conditions of logical drying nitrogen, the graphene-based antistatic agent with suppression hood is made.The antistatic modified PVC of graphene obtained by the present invention has many advantages, such as that flame-retardant smoke inhibition effect is good, mechanical strength is high, antistatic property is good, has widened PVC material in the application range of the industries such as electronic apparatus, green building material, new-energy automobile, cable.

Description

A kind of graphene-based antistatic agent and preparation method thereof with suppression hood
Technical field
The invention belongs to graphene-based antistatic agent preparation technical fields, and in particular to a kind of graphite with suppression hood Alkenyl antistatic agent and preparation method thereof.
Background technique
Preparing the common method of antistatic macromolecule material at present is that a certain amount of organic point is added in polymeric substrate Sub- antistatic agent reduces polymer surfaces resistance and volume resistance, increases electric conductivity, reaches the mesh for preventing accumulation on product 's.However since organic molecule antistatic agent and matrix poor compatibility are easy to migrate, it is easy in high temperature process and use process Being precipitated from matrix causes material antistatic property not lasting enough.Conventional inorganic antistatic agent such as carbon black, metal powder etc., though The electric conductivity of anti-static material can be effectively improved, but due to these additives and basis material poor compatibility, in high additive amount Under the premise of, the mechanical property of basis material preciousness is seriously compromised, its use scope is limited.Therefore, anti-static material is improved Electric conductivity, develop novel high-performance anti-static material, be current industrial circle facing problem.
Graphene is one of the hot spot of current conducting polymer research field as a kind of emerging nanometer additive.Graphite Alkene has the characteristics that the excellent properties such as highly conductive, high-modulus, high intensity, bigger serface, and is easy in a polymer matrix Good conductive network is formed, the conductive filler of great potential is become.When the graphene ratio added in polymeric matrix reaches To after conductivity percolation threshold values, stable conductive network will be formed, and then the conductivity of composite material can be promoted rapidly.Foreign countries have Scholar is prepared for graphene/polystyrene (PS) conducing composite material of excellent electric conductivity.Its conductivity percolation threshold values at room temperature Graphene/PS conducing composite material conductivity of only 0.1% (volume ratio), 1% volume ratio has been up to 0.1S/m, can expire Requirement of the foot as anti-static composite material conductivity.However, although graphene can the highly effective electrical property for improving polymer Can, but due to its bad dispersibility, expensive etc., it has also become the bottle that graphene is faced in polymer modification application field Neck difficult point.Anti-static material is in engineer application, it is desirable that has certain flame retardant property.Polymer/graphene nano composite material Flame retardant property is studies have shown that by intercalation or removing with the evenly dispersed graphene sheet layer in the polymer of nanoscale in two-dimensional square To barrier action, effectively completely cut off exchanging for basis material and Mass and heat transfer and the fuel gas in the external world, basis material played Good protective effect improves Flame Retardancy energy.But graphene is relatively low to the flame-retardant smoke inhibition efficiency of polymer, therefore passes through Functional modification improves graphene in the dispersibility of matrix, improves anti-while the more preferable flame-retardant smoke inhibition effect of imparting graphene The mechanical property of electrostatic material, to more preferably meet the actual needs of its engineer application.
Summary of the invention
The invention solves primary technical problem be to provide a kind of graphene-based antistatic agent with suppression hood.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of graphene-based antistatic agent with suppression hood, the graphene-based antistatic agent is graphene oxide It is made through electronation, ferrocene class compound graft modification.
The preparation method of above-mentioned graphene-based antistatic agent, includes the following steps:
(1) electronation of graphene oxide (GO)
GO is restored, redox graphene r-GO is obtained;It can be such as added in dimethylformamide (DMF) GO, ultrasound 80 minutes, are added hydrazine hydrate and ammonium hydroxide are transferred to the high pressure containing teflon lined after mixing at room temperature It in kettle, is sealed in an oven, is heated to 110 DEG C, react 6 hours;It is filtered after reaction, the no water beetle of sediment Alcohol washs 5 times, and then vacuum drying, obtains product reduced graphene (r-GO);(2) reduced graphene ferrocene class compound Graft modification reaction
R-GO and diisocyanate cpd are added in ball mill, under conditions of logical drying nitrogen grinding 30~ 100 minutes, isocyanate-modified graphene is made, adds ferrocene class compound, continues under conditions of logical drying nitrogen The graphene-based antistatic agent with suppression hood is made in grinding 60~120 minutes.
In above scheme, the quality of r-GO described in step (2), diisocyanate cpd and ferrocene class compound Than for 1:0.05~0.2:0.1~0.4.
Diisocyanate cpd described in step (2) is selected from one of the following: methyl diphenylene diisocyanate, six Asias Methyl diisocyanate, toluene di-isocyanate(TDI), isophorone diisocyanate.
Ferrocene class compound described in step (2) is selected from one of the following: ferrocenyl acetic acid, ferrocenecarboxylic acid, amino Ferrocene, methylol ferrocene.
In grinding technics condition described in step (2), 100~600 revs/min of balling drum revolving speed, ball grinder and The material of mill ball is agate or tungsten carbide, and ball load is 0.2~1.0 kilogram, and being passed through flow rate of nitrogen is 0.1~10 liter/min.
Compared with prior art, the beneficial effects of the present invention are embodied in following several respects:
1, graphene-based antistatic agent produced by the present invention can not only improve high molecular material flame retarding and smoke suppressing properties, and The mechanical property of high molecular material can be improved.Graphene is chemically modified using surface graft modification etc., by ferrocene class Compound smoke suppressant is grafted on the surface of graphene, assigns graphene flame-retardant smoke inhibition function.Organising for graphene surface changes simultaneously Property, increase the compatibility and dispersibility with macromolecule matrix, the interaction at both enhancings interface, by melt-blending process, Graphene-based antistatic agent is dispersed in polymeric matrix by situ aggregation method etc., improves antistatic macromolecule composite material Mechanics and electric conductivity;
2, graphene-based antistatic agent produced by the present invention is acted synergistically using graphene and ferrocene condensed phase suppression cigarette, Graphene-based antistatic agent flame-retardant smoke inhibition effect is substantially increased, while the ferrocene small molecule anchored on the surface of graphene is not allowed It is easily precipitated in use process, reduces the secondary pollution of smoke suppressant;
3, graphene-based antistatic agent of the present invention uses the preparation method of solvent-free solid-phase ball-milling reaction, not only makes Standby simple process, and lower production costs, reduce the discharge of energy consumption and pollutant;
4, graphene-based antistatic agent produced by the present invention has the modified functions such as self-reinforcing, flame-retardant smoke inhibition and conduction special Point, it is modified suitable for the antistatic of all kinds of high molecular materials, flame-retardant smoke inhibition, it widens high molecular material and is built in electronic apparatus, green The application range of the industries such as material, new-energy automobile, cable.
Specific embodiment
Below the technical scheme of the invention is illustrated by a specific example, but the scope of the present invention is not limited thereto:
Embodiment 1
The preparation of graphene-based antistatic agent:
(1) electronation of graphene oxide (GO)
Ultrasound 80 minutes at room temperature 1g GO are added in 100g DMF, then 1.6mL hydrazine hydrate and the dense ammonia of 7mL is being added Water (concentration 28%) is transferred to after mixing in the autoclave containing teflon lined, is sealed, is added in an oven Heat to 110 DEG C react 6 hours;Sediment is washed 5 times with anhydrous methanol, and then vacuum drying, obtains product reduced graphene (r-GO)。
(2) the compound graft modification of reduced graphene ferrocene class is reacted
1g r-GO and 0.05g methyl diphenylene diisocyanate is added to high-energy planetary formula ball mill (model: F- P2000, producer: Hunan Fu Kasi laboratory apparatus Co., Ltd) in, 600 revs/min of drum's speed of rotation, in logical dry nitrogen air-flow Rate is ground 30 minutes under conditions of being 10 liters/min, and isocyanate-modified graphene is made, adds 0.1g ferrocenyl acetic acid, Continue grinding 60 minutes under conditions of logical drying nitrogen flow rate is 10 liters/min, it is graphene-based that target product is made after separation Antistatic agent.
Embodiment 2
The preparation manipulation of reduced graphene (r-GO) is the same as step (1) in embodiment 1.1g r-GO and 0.2g toluene two is different Cyanate is added in high-energy planetary formula ball mill, 100 revs/min of drum's speed of rotation, logical drying nitrogen flow rate be 0.1 liter/ It is ground 100 minutes under conditions of minute, isocyanate-modified graphene is made, 0.4g Aminoferrocene is added, in logical drying Flow rate of nitrogen continues grinding 120 minutes under conditions of being 0.1 liter/min, and it is graphene-based antistatic that target product is made after separation Agent.
Embodiment 3
The preparation manipulation of reduced graphene (r-GO) is the same as step (1) in embodiment 1.By 1g r-GO and 0.1g isophorone Diisocyanate is added in high-energy planetary formula ball mill, and 300 revs/min of drum's speed of rotation, be 1.5 in logical drying nitrogen flow rate It is ground 60 minutes under conditions of liter/min, isocyanate-modified graphene is made, adds 0.25g methylol ferrocene, logical Drying nitrogen flow rate be 1.5 liters/min under conditions of continue grinding 80 minutes, after separation be made target product it is graphene-based resist it is quiet Electric agent.
Embodiment 4
The preparation manipulation of reduced graphene (r-GO) is the same as step (1) in embodiment 1.By 1g r-GO and 0.15g hexa-methylene Diisocyanate is added in high-energy planetary formula ball mill, and 250 revs/min of drum's speed of rotation, be 2.8 in logical drying nitrogen flow rate It is ground 50 minutes under conditions of liter/min, isocyanate-modified graphene is made, adds 0.28g ferrocenecarboxylic acid, logical dry Dry flow rate of nitrogen be 3.5 liters/min under conditions of continue grinding 100 minutes, after separation be made target product it is graphene-based resist it is quiet Electric agent.
Embodiment 5: the application of graphene-based antistatic agent
The preparation manipulation of graphene-based antistatic agent is the same as embodiment 4.To 100 parts of polyvinyl chloride (PVC), 50 parts by mass Phthalate plasticizers (DOP), 1 part of graphene-based antistatic agent, 20 parts of precipitated calcium carbonates, 2 parts of stearic acid, 6 parts of stabilizations Agent, 2 parts of anti-aging agents are added to stirrer for mixing 30min discharging, extruder are added to, in 160 DEG C~180 DEG C items of processing temperature Extruded material under part, then under the conditions of 180 DEG C~200 DEG C temperature, pressure are 10Mpa, it is antistatic to be pressed and molded obtained graphene It is as follows to measure the material properties test result for modified PVC.
Table 1
PVC anti-static composite material formula is 100 parts of PVC, 50 parts of DOP, 1 part of conductive black, 0.5 part of ferrocene, 20 parts Precipitated calcium carbonate, 2 parts of stearic acid, 6 parts of stabilizers, 2 parts of anti-aging agents, preparation of the preparation process with the antistatic modified PVC of graphene Method.
From tensile strength as can be seen that compared to the PVC anti-static composite material that conductive black is modified, stone used in the present invention Mertenyl antistatic agent has better reinforcing effect to PVC;In terms of electric conductivity angle, compared to conventional conductive black, this hair Bright graphene-based antistatic agent used has better conductive modified effect to PVC, so that more preferably antistatic effect will be obtained, Under identical additive amount, the sheet resistance of the antistatic modified PVC of graphene low number compared with PVC anti-static composite material Magnitude;From flame-retardant smoke inhibition as can be seen that comparing single ferrocene, graphene-based antistatic agent used in the present invention has PVC There is better flame-retardant smoke inhibition effect.The antistatic modified PVC of graphene obtained by the present invention good, mechanics with flame-retardant smoke inhibition effect The advantages that intensity is high, antistatic property is good, has widened PVC material in electronic apparatus, green building material, new-energy automobile, cable etc. The application range of industry.

Claims (6)

1. a kind of preparation method of the graphene-based antistatic agent with suppression hood, which comprises the steps of:
(1) electronation of graphene oxide (GO)
GO is restored, redox graphene r-GO is obtained;
(2) the compound graft modification of reduced graphene ferrocene class is reacted
R-GO and diisocyanate cpd are added in ball mill, grind 30~100 points under conditions of logical drying nitrogen Clock is made isocyanate-modified graphene, adds ferrocene class compound, continues grinding 60 under conditions of logical drying nitrogen ~120 minutes, the graphene-based antistatic agent with suppression hood is made.
2. the preparation method of the graphene-based antistatic agent with suppression hood according to claim 1, which is characterized in that The mass ratio of r-GO described in step (2), diisocyanate cpd and ferrocene class compound are 1:0.05~0.2:0.1 ~0.4.
3. the preparation method of the graphene-based antistatic agent with suppression hood according to claim 1, which is characterized in that Diisocyanate cpd described in step (2) is selected from one of the following: methyl diphenylene diisocyanate, hexa-methylene two are different Cyanate, toluene di-isocyanate(TDI), isophorone diisocyanate.
4. the preparation method of the graphene-based antistatic agent with suppression hood according to claim 1, which is characterized in that The ferrocene class compound is selected from one of the following: ferrocenyl acetic acid, ferrocenecarboxylic acid, Aminoferrocene, two cyclopentadienyl of methylol Iron.
5. the preparation method of the graphene-based antistatic agent with suppression hood according to claim 1, which is characterized in that Grinding described in step (2) refers to 100~600 revs/min of balling drum revolving speed, and the material of ball grinder and mill ball is Ma Nao or tungsten carbide, ball load are 0.2~1.0 kilogram, and being passed through flow rate of nitrogen is 0.1~10 liter/min.
6. a kind of graphene-based antistatic agent with suppression hood, which is characterized in that using such as any one of claim 1-5 institute The method stated prepares.
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CN111613454A (en) * 2020-05-29 2020-09-01 华南理工大学 Graphene/metallocene composite supercapacitor electrode material and preparation method and application thereof
CN111996611A (en) * 2020-09-03 2020-11-27 涂一淼 Antistatic agent and preparation method thereof
CN115894959A (en) * 2023-01-03 2023-04-04 深圳市今朝时代股份有限公司 Electrode active material for super capacitor and preparation method thereof

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CN111613454B (en) * 2020-05-29 2021-09-21 华南理工大学 Graphene/metallocene composite supercapacitor electrode material and preparation method and application thereof
CN111996611A (en) * 2020-09-03 2020-11-27 涂一淼 Antistatic agent and preparation method thereof
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CN115894959A (en) * 2023-01-03 2023-04-04 深圳市今朝时代股份有限公司 Electrode active material for super capacitor and preparation method thereof

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Denomination of invention: A graphene based antistatic agent with smoke suppression function and its preparation method

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