CN109280260B - Graphene-added ethylene-vinyl acetate copolymer conductive granules and preparation method thereof - Google Patents
Graphene-added ethylene-vinyl acetate copolymer conductive granules and preparation method thereof Download PDFInfo
- Publication number
- CN109280260B CN109280260B CN201811080590.8A CN201811080590A CN109280260B CN 109280260 B CN109280260 B CN 109280260B CN 201811080590 A CN201811080590 A CN 201811080590A CN 109280260 B CN109280260 B CN 109280260B
- Authority
- CN
- China
- Prior art keywords
- vinyl acetate
- graphene
- parts
- peroxide
- ethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Conductive Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
An ethylene-vinyl acetate copolymer conductive particle added with graphene and a preparation method thereof are disclosed, wherein peroxide dispersion liquid is dropwise added into graphene dispersion liquid under the condition of stirring, the mixture is uniformly stirred, ultrasonic treatment is carried out, vinyl acetate is added, the reaction is carried out at the room temperature to 140 ℃, washing and centrifuging are carried out, and the graphene filler grafted with the vinyl acetate is obtained; adding the ethylene-vinyl acetate copolymer, the vinyl acetate grafted graphene, the graphite micropowder and the auxiliary agent into a high-speed mixer for mixing, then carrying out melt extrusion in a double-screw plastic granulator, cooling and granulating the extruded materials, and then filling into a sealing bag to obtain the product. The advantages are that: vinyl acetate is grafted to the graphene nanosheet layer through a peroxide treatment method, so that the interfacial adhesion between the graphene filler and the ethylene-vinyl acetate copolymer resin in the granules is improved, and the problems of precipitation and agglomeration of graphene in the granules and the prepared products of the granules are solved.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an ethylene-vinyl acetate copolymer conductive granule added with graphene and a preparation method thereof.
Background
Ethylene-vinyl acetate copolymer resin (EVA resin), the content of Vinyl Acetate (VA) is generally 5% -40%. Compared with polyethylene, the ethylene-vinyl acetate copolymer has the advantages that the vinyl acetate monomer is introduced into the molecular chain, so that the high crystallinity is reduced, the flexibility, the impact resistance, the filler intermiscibility and the heat sealing performance are improved, and the ethylene-vinyl acetate copolymer is widely applied to the fields of foamed shoe materials, functional greenhouse films, packaging films, hot melt adhesives, electric wires and cables, toys and the like.
The ethylene-vinyl acetate copolymer resin is an insulating high molecular material, if conductive ethylene-vinyl acetate copolymer-based conductive granules are prepared, conductive fillers are added, when the conductive fillers form a continuous phase in an ethylene-vinyl acetate copolymer resin matrix, electrons can be transmitted among the conductive fillers, and the conductive function can be realized. The graphite micropowder has excellent conductivity, but the particle size of the graphite micropowder is micron-sized, a large amount of graphite micropowder needs to be added to form a continuous phase in the ethylene-vinyl acetate copolymer resin, and the mechanical toughness of the ethylene-vinyl acetate copolymer material is reduced due to the excessively high addition amount of the graphite micropowder.
The basic structure of graphene is a two-dimensional crystal composed of carbon atoms and having a thickness of only one layer, and commercially available graphene is classified into single-layer graphene, double-layer graphene, multi-layer graphene, and the like. The graphene is the thinnest novel lamellar nano filler with the greatest strength and the strongest electric and heat conducting performance, the specific surface area of the graphene is large, and if the graphene is added into the ethylene-vinyl acetate copolymer conductive granules, the contact probability of the conductive fillers can be improved, so that the use amount of the conductive graphite is reduced, and the mechanical toughness and the electric conductivity of the ethylene-vinyl acetate copolymer material are improved. However, the molecular structures of graphene and ethylene-vinyl acetate copolymer are very different, and the interfacial compatibility between graphene and ethylene-vinyl acetate copolymer is not good.
Disclosure of Invention
The invention aims to solve the technical problem of providing graphene-added ethylene-vinyl acetate copolymer conductive granules and a preparation method thereof, wherein vinyl acetate is grafted to a graphene nanosheet layer by means of peroxide treatment, so that the interfacial adhesion between graphene filler and ethylene-vinyl acetate copolymer resin in the granules is improved, and the problems of precipitation and agglomeration of graphene in the granules and prepared products thereof are solved.
The technical solution of the invention is as follows:
the graphene-added ethylene-vinyl acetate copolymer conductive granules comprise the following raw materials in parts by weight:
100 parts of ethylene-vinyl acetate copolymer;
0.001-50 parts of graphene filler grafted with vinyl acetate;
30-200 parts of graphite micro powder;
0-10 parts of an auxiliary agent;
the auxiliary agent is a mixture of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, methyl silicone oil and cumyl peroxide, or a mixture of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and methyl silicone oil.
Furthermore, the vinyl acetate content of the ethylene-vinyl acetate copolymer is 5-40%.
Further, when the auxiliary agent is a mixture of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, methyl silicone oil and cumyl peroxide, the mass ratio of the tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester to the methyl silicone oil is 1:0.2-1:6, and the mass ratio of the tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester to the cumyl peroxide is 1:0.4-1: 1; when the auxiliary agent is a mixture of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and methyl silicone oil, the mass ratio of the tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester to the methyl silicone oil is 3: 2.
Further, the graphene-added ethylene-vinyl acetate copolymer conductive granules comprise the following raw materials in parts by weight: 100 parts of ethylene-vinyl acetate copolymer, 0.003-10 parts of graphene filler branched with vinyl acetate, 50-180 parts of graphite micropowder and 0-8 parts of auxiliary agent.
Further, the purity of the graphite micropowder is 99%, and the fineness of the graphite micropowder is 500-8000 meshes.
Further, the graphene filler grafted with vinyl acetate is composed of graphene, peroxide, acid or alkali, a dispersing agent and vinyl acetate, and the raw materials comprise the following components in parts by weight:
100 parts of graphene;
1-300 parts of peroxide;
1-300 parts of acid or alkali;
1-5000 parts of dispersion liquid;
1-200 parts of vinyl acetate.
Further, the graphene filler grafted with vinyl acetate comprises the following components in parts by weight:
100 parts of graphene;
10-200 parts of peroxide;
5-200 parts of acid or alkali;
100 portions and 3000 portions of dispersion liquid;
1-180 parts of vinyl acetate.
Further, the graphene is at least one of single-layer graphene (a two-dimensional crystal composed of carbon atoms and having a thickness of only one layer), double-layer graphene and multi-layer graphene; the peroxide is at least one of hydrogen peroxide, potassium peroxide, sodium peroxide, dibenzoyl peroxide and cyclohexanone peroxide; the acid is at least one of sulfuric acid, nitric acid and phosphoric acid, and the alkali is sodium hydroxide or potassium hydroxide: the dispersion liquid is at least one of deionized water, ethanol and acetone; the purity of the vinyl acetate is more than 95%.
A preparation method of graphene-added ethylene-vinyl acetate copolymer conductive granules comprises the following specific steps:
(1) firstly, dispersing graphene in a dispersion liquid under the stirring condition to prepare a graphene dispersion liquid, dispersing peroxide, acid or alkali in the same dispersion liquid to prepare a peroxide dispersion liquid, then dropwise adding the peroxide dispersion liquid into the graphene dispersion liquid under the stirring condition to uniformly stir, treating the mixture for 10 to 120 minutes by using ultrasonic waves, directly using or centrifugally removing the dispersing agent from a product subjected to ultrasonic treatment, then adding vinyl acetate to react at the temperature of between room temperature and 140 ℃ for 0.5 to 24 hours, stopping the reaction, repeatedly washing the reaction product by using acetone, and centrifugally or filtering to remove free compounds to obtain the vinyl acetate grafted graphene filler;
(2) and preparing the graphene-added ethylene-vinyl acetate copolymer conductive granules, namely adding the ethylene-vinyl acetate copolymer, the vinyl acetate grafted graphene, the graphite micro powder and the auxiliary agent into a high-speed mixer, mixing for 5-20 minutes, then carrying out melt extrusion in a double-screw plastic granulator, cooling and granulating the extruded materials, and then filling the cooled and granulated materials into a sealing bag to obtain the graphene-added ethylene-vinyl acetate copolymer conductive granules.
Further, the rotation speed of the double-screw plastic granulator is 50-350 r/min, the first-stage temperature of the extruder is 120-.
The invention has the beneficial effects that:
(1) vinyl acetate is grafted to the graphene nanosheet layer through a peroxide treatment method, so that the interfacial adhesion between the graphene filler and the ethylene-vinyl acetate copolymer resin in the granules is improved, and the problems of precipitation and agglomeration of graphene in the granules and the prepared products of the granules are solved. The peroxide is grafted with vinyl acetate molecules on the surface of the graphene nanosheet layer to prepare the modified graphene filler, and the modified graphene filler can be uniformly dispersed in the ethylene-vinyl acetate copolymer of the granular material and is connected with the graphite micropowder to endow the granular material with excellent conductivity and mechanical property.
(2) The raw material nano-scale graphene lamellar filler is arranged in a coating layer in a laminated manner, so that the granules and the prepared products thereof have excellent mechanical properties, conductivity and corrosion resistance.
Detailed Description
Example 1
Firstly, dispersing 100 parts of multi-layer graphene in 2000 parts of deionized water under the stirring condition to prepare graphene dispersion liquid, simultaneously dispersing 200 parts of hydrogen peroxide and 200 parts of sodium hydroxide in 1000 parts of deionized water to prepare peroxide dispersion liquid, then dropwise adding the peroxide dispersion liquid into the graphene dispersion liquid under the stirring condition, uniformly stirring, treating for 120 minutes by using ultrasonic waves, centrifugally removing the deionized water from a product obtained by ultrasonic treatment, then adding 180 parts of vinyl acetate, reacting for 0.5 hour at 140 ℃, stopping the reaction, repeatedly washing the reaction product by using acetone, and centrifugally or filtering to remove free compounds to obtain the vinyl acetate grafted graphene filler.
The preparation method of the conductive granules comprises the steps of preparing 100 parts of ethylene-vinyl acetate copolymer with the Vinyl Acetate (VA) content of 24 percent, 0.003 part of graphene grafted with vinyl acetate, 180 parts of 8000 meshes of graphite micropowder and 3 parts of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester, 3 parts of methyl silicone oil, 2 parts of cumyl peroxide and the like are added into a high-speed mixer to be mixed for 20 minutes, then the mixture is melted and extruded in a double-screw plastic granulator, and the extruded material is cooled, granulated and then put into a sealing bag to be stored. The rotation speed of the double-screw plastic granulator is 50 revolutions per minute, the first-stage temperature of the extruder is 120 ℃, the second-stage temperature is 130 ℃, the third-stage temperature is 140 ℃, the fourth-stage temperature is 150 ℃, and the head temperature is 160 ℃. The conductive pellets prepared in example 1 had a resistivity of 2.2. omega. m at 20 ℃ and a tensile strength of > 3.5N/mm2And the elongation at break is more than or equal to 30 percent.
Example 2
Firstly, dispersing 100 parts of double-layer graphene in 50 parts of deionized water under the stirring condition to prepare a graphene dispersion liquid, simultaneously dispersing 10 parts of sodium peroxide and 10 parts of potassium hydroxide in 50 parts of deionized water to prepare a peroxide dispersion liquid, then dropwise adding the peroxide dispersion liquid into the graphene dispersion liquid under the stirring condition to stir uniformly, treating for 10 minutes by using ultrasonic waves, adding 1 part of vinyl acetate to react for 8 hours at 120 ℃, stopping the reaction, repeatedly washing the reaction product by using acetone, and centrifuging or filtering to remove free compounds to obtain the graphene filler grafted with the vinyl acetate.
The preparation method of the conductive granules comprises the steps of adding 100 parts of ethylene-vinyl acetate copolymer with the Vinyl Acetate (VA) content of 12%, 10 parts of graphene grafted with vinyl acetate, 50 parts of 500-mesh graphite micropowder and the like into a high-speed mixer for mixing for 5 minutes, then carrying out melt extrusion in a double-screw plastic granulator, cooling and granulating the extruded materials, and then filling the materials into a sealing bag for storage. The rotation speed of the double-screw plastic granulator is 350 r/min, the first-stage temperature of the extruder is 100 ℃, the second-stage temperature is 110 ℃, the third-stage temperature is 120 ℃, the fourth-stage temperature is 130 ℃, and the head temperature is 140 ℃. The conductive pellets prepared in example 2 had a resistivity of 2.15. omega. m at 20 ℃ and a tensile strength of > 3.5N/mm2And the elongation at break is more than or equal to 30 percent.
Example 3
Firstly, dispersing 100 parts of multi-layer graphene in 2000 parts of ethanol under the stirring condition to prepare graphene dispersion liquid, simultaneously dispersing 10 parts of dibenzoyl peroxide and 6 parts of sulfuric acid in 100 parts of ethanol to prepare peroxide dispersion liquid, then dropwise adding the peroxide dispersion liquid into the graphene dispersion liquid under the stirring condition to be uniformly stirred, treating for 60 minutes by using ultrasonic waves, adding 90 parts of vinyl acetate to react for 24 hours at 110 ℃, stopping the reaction, repeatedly washing the reaction product by using acetone, and centrifuging or filtering to remove free compounds to obtain the vinyl acetate grafted graphene filler.
The conductive granule is prepared by mixing 100 parts of ethylene-vinyl acetate containing 15% of Vinyl Acetate (VA)Copolymer, 1 part of graphene grafted with vinyl acetate, 120 parts of 2000-mesh graphite micropowder and 3 parts of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester, 2 parts of methyl silicone oil and the like are added into a high-speed mixer to be mixed for 15 minutes, then the mixture is melted and extruded in a double-screw plastic granulator, and the extruded materials are cooled, granulated and then put into a sealing bag to be stored. The rotation speed of the double-screw plastic granulator is 80 rpm, the first-stage temperature of the extruder is 110 ℃, the second-stage temperature is 130 ℃, the third-stage temperature is 140 ℃, the fourth-stage temperature is 140 ℃ and the head temperature is 150 ℃. The conductive pellets prepared in example 3 had a resistivity of 2.25. omega. m at 20 ℃ and a tensile strength of > 3.5N/mm2And the elongation at break is more than or equal to 30 percent.
Example 4
Firstly, dispersing 100 parts of single-layer graphene in 800 parts of acetone under the stirring condition to prepare a graphene dispersion liquid, simultaneously dispersing 12 parts of cyclohexanone peroxide, 3 parts of phosphoric acid and 6 parts of nitric acid in 300 parts of acetone to prepare a peroxide dispersion liquid, then dropwise adding the peroxide dispersion liquid into the graphene dispersion liquid under the stirring condition, uniformly stirring, treating for 90 minutes by using ultrasonic waves, then adding 180 parts of vinyl acetate, reacting for 24 hours at 120 ℃, stopping the reaction, repeatedly washing the reaction product by using acetone, and centrifuging or filtering to remove free compounds to obtain the vinyl acetate grafted graphene filler.
The conductive granule is prepared by mixing 100 parts of ethylene-vinyl acetate copolymer with Vinyl Acetate (VA) content of 20%, 5 parts of graphene grafted with vinyl acetate, 100 parts of 4500 mesh graphite micropowder, and 3 parts of tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester, 3 parts of methyl silicone oil, 2 parts of cumyl peroxide and the like are added into a high-speed mixer to be mixed for 20 minutes, then the mixture is melted and extruded in a double-screw plastic granulator, and the extruded material is cooled, granulated and then put into a sealing bag to be stored. The rotation speed of the double-screw plastic granulator is 200 revolutions per minute, the first-stage temperature of the extruder is 100 ℃, the second-stage temperature is 130 ℃, the third-stage temperature is 120 ℃, the fourth-stage temperature is 130 ℃, and the head temperature is 160 ℃. The conductive pellets prepared in example 4 had a resistivity of 2.4. omega. m at 20 ℃ and a tensile strength of > 3.5N/mm2And the elongation at break is more than or equal to 30 percent.
Example 5
Firstly, dispersing 100 parts of multi-layer graphene in 500 parts of ethanol under the stirring condition to prepare a graphene dispersion liquid, simultaneously dispersing 20 parts of potassium peroxide and 10 parts of sulfuric acid in 300 parts of ethanol to prepare a peroxide dispersion liquid, then dropwise adding the peroxide dispersion liquid into the graphene dispersion liquid under the stirring condition, uniformly stirring, treating for 30 minutes by using ultrasonic waves, then adding 80 parts of vinyl acetate, reacting for 3 hours at 60 ℃, stopping the reaction, repeatedly washing the reaction product by using acetone, and centrifuging or filtering to remove free compounds to obtain the vinyl acetate grafted graphene filler.
The preparation method of the conductive granules comprises the steps of preparing 100 parts of ethylene-vinyl acetate copolymer with the Vinyl Acetate (VA) content of 22%, 0.05 part of graphene grafted with vinyl acetate, 160 parts of 5000-mesh graphite micro powder and 5 parts of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester, 1 part of methyl silicone oil, 2 parts of cumyl peroxide and the like are added into a high-speed mixer to be mixed for 15 minutes, then the mixture is melted and extruded in a double-screw plastic granulator, and the extruded material is cooled, granulated and then put into a sealing bag to be stored. The rotation speed of the double-screw plastic granulator is 90 revolutions per minute, the first-stage temperature of the extruder is 120 ℃, the second-stage temperature is 130 ℃, the third-stage temperature is 140 ℃, the fourth-stage temperature is 150 ℃, and the head temperature is 150 ℃. The conductive pellets prepared in example 5 had a resistivity of 2.5. omega. m at 20 ℃ and a tensile strength of > 3.5N/mm2And the elongation at break is more than or equal to 30 percent.
Example 6
Firstly, dispersing 100 parts of multi-layer graphene in 700 parts of acetone under the stirring condition to prepare a graphene dispersion liquid, simultaneously dispersing 10 parts of hydrogen peroxide and 3 parts of sulfuric acid in 200 parts of acetone to prepare a peroxide dispersion liquid, then dropwise adding the peroxide dispersion liquid into the graphene dispersion liquid under the stirring condition, uniformly stirring, treating for 60 minutes by using ultrasonic waves, then adding 60 parts of vinyl acetate, reacting for 0.5 hour at room temperature, stopping the reaction, repeatedly washing the reaction product by using acetone, and centrifuging or filtering to remove free compounds to obtain the vinyl acetate grafted graphene filler.
The conductive granular material is prepared by mixing 100 partsEthylene-vinyl acetate copolymer with 15% Vinyl Acetate (VA), 8 parts of graphene grafted with vinyl acetate, 90 parts of 1000-mesh graphite micropowder, and 1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester, 6 parts of methyl silicone oil, 1 part of cumyl peroxide and the like are added into a high-speed mixer to be mixed for 20 minutes, then the mixture is melted and extruded in a double-screw plastic granulator, and the extruded material is cooled, granulated and then put into a sealing bag to be stored. The rotation speed of the double-screw plastic granulator is 200 revolutions per minute, the first-stage temperature of the extruder is 100 ℃, the second-stage temperature is 110 ℃, the third-stage temperature is 120 ℃, the fourth-stage temperature is 130 ℃, and the head temperature is 150 ℃. The conductive pellets prepared in example 6 had a resistivity of 2.65. omega. m at 20 ℃ and a tensile strength of > 3.5N/mm2And the elongation at break is more than or equal to 30 percent.
Example 7
Firstly, dispersing 100 parts of double-layer graphene in 600 parts of acetone under the stirring condition to prepare a graphene dispersion liquid, simultaneously dispersing 10 parts of hydrogen peroxide and 5 parts of nitric acid in 200 parts of acetone to prepare a peroxide dispersion liquid, then dropwise adding the peroxide dispersion liquid into the graphene dispersion liquid under the stirring condition, uniformly stirring, treating for 60 minutes by using ultrasonic waves, then adding 50 parts of vinyl acetate, reacting for 5 hours at 50 ℃, stopping the reaction, repeatedly washing the reaction product by using acetone, and centrifuging or filtering to remove free compounds to obtain the vinyl acetate grafted graphene filler.
The preparation method of the conductive granules comprises the steps of preparing 100 parts of ethylene-vinyl acetate copolymer with 20 percent of Vinyl Acetate (VA), 3 parts of graphene grafted with vinyl acetate, 120 parts of 5500-mesh graphite micro powder and 2 parts of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester, 3 parts of methyl silicone oil, 3 parts of cumyl peroxide and the like are added into a high-speed mixer to be mixed for 20 minutes, then the mixture is melted and extruded in a double-screw plastic granulator, and the extruded material is cooled, granulated and then put into a sealing bag to be stored. The rotation speed of the double-screw plastic granulator is 120 revolutions per minute, the first-stage temperature of the extruder is 110 ℃, the second-stage temperature is 130 ℃, the third-stage temperature is 130 ℃, the fourth-stage temperature is 130 ℃, and the head temperature is 160 ℃. The conductive pellets prepared in example 7 had a resistivity of 2.55. omega. m at 20 ℃ and a tensile strength of > 3.5N-mm2And the elongation at break is more than or equal to 30 percent.
Example 8
Firstly, dispersing 100 parts of double-layer graphene in 400 parts of ethanol under the stirring condition to prepare a graphene dispersion liquid, simultaneously dispersing 22 parts of tert-butyl hydroperoxide and 3 parts of potassium hydroxide in 100 parts of ethanol to prepare a peroxide dispersion liquid, then dropwise adding the peroxide dispersion liquid into the graphene dispersion liquid under the stirring condition, uniformly stirring, treating for 60 minutes by using ultrasonic waves, then adding 130 parts of vinyl acetate, reacting for 6 hours at 110 ℃, stopping the reaction, repeatedly washing the reaction product by using acetone, and centrifuging or filtering to remove free compounds to obtain the graphene filler grafted with the epoxy resin.
The preparation method of the conductive granules comprises the steps of preparing 100 parts of ethylene-vinyl acetate copolymer with 18 percent of Vinyl Acetate (VA), 9 parts of graphene grafted with vinyl acetate, 90 parts of 2000-mesh graphite micro powder and 2 parts of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester, 2 parts of methyl silicone oil, 2 parts of cumyl peroxide and the like are added into a high-speed mixer to be mixed for 20 minutes, then the mixture is melted and extruded in a double-screw plastic granulator, and the extruded material is cooled, granulated and then put into a sealing bag to be stored. The rotation speed of the double-screw plastic granulator is 300 revolutions per minute, the first-stage temperature of the extruder is 100 ℃, the second-stage temperature is 110 ℃, the third-stage temperature is 130 ℃, the fourth-stage temperature is 130 ℃, and the head temperature is 140 ℃. The conductive pellets prepared in example 8 had a resistivity of 2.73. omega. m at 20 ℃ and a tensile strength of > 3.5N/mm2And the elongation at break is more than or equal to 30 percent.
The above description is only exemplary of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A preparation method of ethylene-vinyl acetate copolymer conductive granules with excellent conductivity and mechanical properties is characterized by comprising the following steps:
(1) preparation of graphene filler grafted with vinyl acetate
The graphene filler grafted with the vinyl acetate comprises the following raw materials in parts by weight: 100 parts of graphene;
10-200 parts of peroxide; 5-200 parts of acid or alkali; 100 portions and 3000 portions of dispersion liquid; 1-180 parts of vinyl acetate; the preparation steps are as follows:
firstly, dispersing graphene in a dispersion liquid under the condition of stirring to prepare a graphene dispersion liquid, wherein the graphene is one of single-layer graphene, double-layer graphene and multi-layer graphene, and the dispersion liquid is one of deionized water, ethanol and acetone; simultaneously dispersing peroxide, acid or alkali in the same dispersion to prepare peroxide dispersion, wherein the peroxide is one of hydrogen peroxide, potassium peroxide, sodium peroxide, dibenzoyl peroxide and cyclohexanone peroxide; dropwise adding the peroxide dispersion liquid into the graphene dispersion liquid under the stirring condition, uniformly stirring, then carrying out ultrasonic treatment for 10-120 minutes, directly using or centrifuging the ultrasonic-treated product to remove the dispersing agent, then adding vinyl acetate, reacting for 0.5-24 hours at room temperature to 140 ℃, stopping the reaction, repeatedly washing the reaction product with acetone, and centrifuging or filtering to remove free compounds to obtain the graphene filler grafted with the vinyl acetate;
(2) the ethylene-vinyl acetate copolymer conductive granules with excellent conductivity and mechanical property are prepared
The graphene-added ethylene-vinyl acetate copolymer conductive granules comprise the following raw materials in parts by weight:
100 parts of ethylene-vinyl acetate copolymer, 0.003-10 parts of graphene filler grafted with vinyl acetate, 50-180 parts of graphite micropowder and 0-8 parts of auxiliary agent;
the auxiliary agent is a mixture of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, methyl silicone oil and cumyl peroxide, or a mixture of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and methyl silicone oil;
adding the ethylene-vinyl acetate copolymer, the vinyl acetate grafted graphene, the graphite micropowder and the auxiliary agent into a high-speed mixer for mixing for 5-20 minutes, and then carrying out melt extrusion in a double-screw plastic granulator, wherein the rotating speed of the double-screw plastic granulator is 50-350 r/min, the temperature of the first section of the extruder is 100-; and cooling and granulating the extruded materials, and filling the cooled and granulated materials into a sealing bag to obtain the ethylene-vinyl acetate copolymer conductive granules with excellent conductivity and mechanical property.
2. The method for preparing ethylene-vinyl acetate copolymer conductive pellets having excellent conductive properties and mechanical properties as claimed in claim 1, wherein: the vinyl acetate content of the ethylene-vinyl acetate copolymer is 5-40%.
3. The method for preparing ethylene-vinyl acetate copolymer conductive pellets having excellent conductive properties and mechanical properties as claimed in claim 1, wherein: when the auxiliary agent is a mixture of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, methyl silicone oil and cumyl peroxide, the mass ratio of the tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester to the methyl silicone oil is 1:0.2-1:6, and the mass ratio of the tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester to the cumyl peroxide is 1:0.4-1: 1; when the auxiliary agent is a mixture of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and methyl silicone oil, the mass ratio of the tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester to the methyl silicone oil is 3: 2.
4. The method for preparing ethylene-vinyl acetate copolymer conductive pellets having excellent conductive properties and mechanical properties as claimed in claim 1, wherein: the acid is at least one of sulfuric acid, nitric acid and phosphoric acid, and the alkali is sodium hydroxide or potassium hydroxide; the purity of the vinyl acetate is more than 95%.
5. The method for preparing ethylene-vinyl acetate copolymer conductive pellets having excellent conductive properties and mechanical properties as claimed in claim 1, wherein: the purity of the graphite micro powder is 99%, and the fineness of the graphite micro powder is 500-8000 meshes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811080590.8A CN109280260B (en) | 2018-09-17 | 2018-09-17 | Graphene-added ethylene-vinyl acetate copolymer conductive granules and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811080590.8A CN109280260B (en) | 2018-09-17 | 2018-09-17 | Graphene-added ethylene-vinyl acetate copolymer conductive granules and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109280260A CN109280260A (en) | 2019-01-29 |
| CN109280260B true CN109280260B (en) | 2021-05-18 |
Family
ID=65180915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811080590.8A Active CN109280260B (en) | 2018-09-17 | 2018-09-17 | Graphene-added ethylene-vinyl acetate copolymer conductive granules and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109280260B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110054829A (en) * | 2019-04-17 | 2019-07-26 | 华侨大学 | A kind of preparation method of EVA/ graphene composite master batch |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040714A (en) * | 2010-11-02 | 2011-05-04 | 浙江大学 | Preparation method of polymer-grafted graphene |
| CN102643470A (en) * | 2012-05-10 | 2012-08-22 | 北京科技大学 | Polymer conductive composite material with stable volume resistivity under temperature changes and preparation method thereof |
| CN102766304A (en) * | 2012-07-31 | 2012-11-07 | 上海交通大学 | Three-dimensional graphene network-contained high conductivity polymer composite material and preparation method thereof |
| CN108456359A (en) * | 2018-03-29 | 2018-08-28 | 浙江工业大学之江学院 | The preparation method of graphene power cable shield layer |
-
2018
- 2018-09-17 CN CN201811080590.8A patent/CN109280260B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040714A (en) * | 2010-11-02 | 2011-05-04 | 浙江大学 | Preparation method of polymer-grafted graphene |
| CN102643470A (en) * | 2012-05-10 | 2012-08-22 | 北京科技大学 | Polymer conductive composite material with stable volume resistivity under temperature changes and preparation method thereof |
| CN102766304A (en) * | 2012-07-31 | 2012-11-07 | 上海交通大学 | Three-dimensional graphene network-contained high conductivity polymer composite material and preparation method thereof |
| CN108456359A (en) * | 2018-03-29 | 2018-08-28 | 浙江工业大学之江学院 | The preparation method of graphene power cable shield layer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109280260A (en) | 2019-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106118018B (en) | Preparation method of high-performance polyphenyl ether/graphene nanocomposite | |
| CN110804135B (en) | High-melt-strength polypropylene and preparation method thereof | |
| JPS6234788B2 (en) | ||
| CN102504504B (en) | High-impact-resistance heat-resistant polylactic acid alloy material and preparation method thereof | |
| CN109280260B (en) | Graphene-added ethylene-vinyl acetate copolymer conductive granules and preparation method thereof | |
| CN104672613A (en) | High-temperature-resistant thermoplastic elastomer material and preparation method thereof | |
| CN104592730A (en) | Polylactic acid/polyester alloy and preparation method thereof | |
| CN102558915A (en) | Modified talcum powder and preparation method and application thereof | |
| CN106751095B (en) | Isomerism containing L-POSS crosslinking agents is modified recycling PS and preparation method thereof | |
| CN104559035B (en) | A kind of Graphene/ABS conductive plastics and its blasting stripping preparation method and purposes | |
| CN105504125B (en) | A kind of method that in-situ polymerization prepares EVA/ graphene composite materials | |
| CN106221005A (en) | A kind of impact resistance increasing tougheness PP plastics and preparation method thereof | |
| CN101781423A (en) | Glass fiber-reinforced polypropylene resin composition formula and preparation method | |
| CN105440562A (en) | Matte ABS resin composition and preparation method thereof | |
| CN110776695B (en) | Antistatic polypropylene composition and preparation method thereof | |
| CN108047535A (en) | A kind of high-tension cable conductive shield material and preparation method thereof | |
| CN109762108B (en) | Environment-friendly permanent polyolefin flame-retardant cable material and preparation method thereof | |
| Lixin et al. | Polycarbonate/polypropylene/fibrillar silicate ternary nanocomposites via two-step blending process: Degradation and morphology | |
| CN105801757A (en) | Long-chain-branch high-melt-strength polypropylene resin and preparation method thereof | |
| JPH06345899A (en) | Resin composite elastomer and its production | |
| CN110483900A (en) | A kind of rotational moulding polypropylene and preparation method thereof | |
| CN110144098A (en) | A kind of preparation method of antistatic polyether-ether-ketone composite material | |
| CN108864967A (en) | A kind of tensile property heat-resisting oil resistant insulating adhesive tape outstanding | |
| CN114672091B (en) | Method for simultaneously improving multiple properties of ethylene-vinyl acetate copolymer | |
| CN108976726A (en) | PET/PE high puncture strength material and production method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210415 Address after: 121012 No.1, Qianshan Road, Qilihe Economic Development Zone, Yi County, Jinzhou City, Liaoning Province Applicant after: LIAONING TONGYONG CABLE FACTORY Applicant after: Jinzhou fangfu Electric Power Technology Co.,Ltd. Address before: 100031 No.86, xichang'an street, Xicheng District, Xinglongtai District, Xicheng District, Beijing Applicant before: STATE GRID CORPORATION OF CHINA Applicant before: PANJIN POWER SUPPLY COMPANY OF STATE GRID LIAONING ELECTRIC POWER SUPPLY Co.,Ltd. Applicant before: State Grid Liaoning Electric Power Co., Ltd. Electric Power Research Institute Applicant before: LIAONING TONGYONG CABLE FACTORY |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |