CN105820514A - Preparation method of high-conductivity graphene-resin composite material - Google Patents

Preparation method of high-conductivity graphene-resin composite material Download PDF

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Publication number
CN105820514A
CN105820514A CN201610218633.9A CN201610218633A CN105820514A CN 105820514 A CN105820514 A CN 105820514A CN 201610218633 A CN201610218633 A CN 201610218633A CN 105820514 A CN105820514 A CN 105820514A
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CN
China
Prior art keywords
graphene
mixture
resin
resin composite
hours
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Pending
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CN201610218633.9A
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Chinese (zh)
Inventor
梁铮
***
白杨
丁荣
倪振华
梁贺君
郭喜涛
于远方
严春伟
邵悦
吕颖
吴玉广
赵宏亮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CHINA NORTH INDUSTRY NEW TECHNOLOGY PROMOTION INSTITUTE
Inner Mongolia Institute Of Graphene Materials
TAIZHOU SUNANO ENERGY CO Ltd
Original Assignee
CHINA NORTH INDUSTRY NEW TECHNOLOGY PROMOTION INSTITUTE
Inner Mongolia Institute Of Graphene Materials
TAIZHOU SUNANO ENERGY CO Ltd
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Application filed by CHINA NORTH INDUSTRY NEW TECHNOLOGY PROMOTION INSTITUTE, Inner Mongolia Institute Of Graphene Materials, TAIZHOU SUNANO ENERGY CO Ltd filed Critical CHINA NORTH INDUSTRY NEW TECHNOLOGY PROMOTION INSTITUTE
Priority to CN201610218633.9A priority Critical patent/CN105820514A/en
Publication of CN105820514A publication Critical patent/CN105820514A/en
Pending legal-status Critical Current

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    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic

Abstract

The invention provides a preparation method of a high-conductivity graphene-resin composite material. The preparation method comprises the following steps: (1) putting natural crystalline flake graphite and anhydrous ferric chloride into a vacuum tube, closing the vacuum tube, heating to 320 to 360 DEG C, and maintaining the temperature for 12 to 48 hours to obtain ferric chloride intercalated graphite; (2) commonly putting the ferric chloride intercalated graphite prepared in the step (1) and a proper amount of hydrogen peroxide into a flask, and reacting for 2 to 6 hours under room temperature to obtain few-layer of graphene; (3) mixing bisphenol-A E-51 epoxy resin with a polyether amine D230 resin curing agent according to a weight ratio of 3 to 1 to obtain a mixture; (4) adding the few-layer graphene obtained in the step (2) into the mixture obtained in the step (3) under the temperature of 12 to 18 DEG C, and stirring and mixing for 2 to 10 hours, wherein the mass percentage of the few-layer graphene is 1 to 5 percent in a total mixture; (5) curing the mixture obtained in the step (4) under a condition of 80 to 120 DEG C for 2 to 6 hours, and finally naturally cooling to room temperature. According to the graphene-resin composite material disclosed by the invention, due to the introduction of the graphene, the conductivity of the resin is improved.

Description

A kind of preparation method of high connductivity type Graphene-resin composite materials
Technical field
The invention provides the preparation method of a kind of high connductivity type Graphene-resin composite materials.The invention belongs to new Field of material technology.
Background technology
Macromolecule polymer material, due to its good insulating properties, is led in electric, communication, aviation etc. for a long time Territory is all widely used.Along with the development in epoch, every profession and trade has had increasingly for the combination property of polymer High requirement, the most prominent is exactly the requirement of antistatic property, and the existence of electrostatic makes polymeric material Tending to inflammable, explosive place causes disaster accident.On the other hand, in order to resist electromagnetic interference, polymerization The electromagnetic shielding problem of thing material is the most urgently to be resolved hurrily, and the high speed which also promotes conducting polymer based composites is sent out Exhibition.
Compared to implants such as common metal and white carbon blacks, it is big that Graphene has specific surface area, and percolation threshold is low, The advantages such as pliability is good.And the electric conductivity of conductive filler self has decision for the electric conductivity of conducting polymer The impact of property.Therefore, the present invention is from native graphite, by the few defect of graft process preparation, the lacking of high connductivity Layer graphene is as the conductive filler of composite, and then prepares high connductivity type composite with resin compounded.
Summary of the invention
Technical problem: solved by the invention technical problem is that is preparing high connductivity type Graphene-resin compounded material Material, utilizes the method for graphite intercalation and interlayer catalysis to prepare the few layer graphene of high connductivity type, then with resinous wood Material and firming agent mix, and prepare high connductivity type Graphene resin composite materials.
Technical scheme:
The preparation method of the high connductivity type Graphene resin composite materials of the present invention comprises the steps:
1) natural flake graphite and anhydrous ferric chloride are put into vacuum tube inner sealing, be heated to 320-360 DEG C, protect Hold 12-48 hour, it is thus achieved that iron chloride intercalated graphite；
2) by step 1) the iron chloride intercalated graphite for preparing puts in beaker jointly with appropriate hydrogen peroxide At room temperature reaction 2-6 hour, hydrogen peroxide is simultaneously as oxidant and reducing agent in the reaction, removes graphite and inserts Chloride ion in stratification compound and iron ion, and in course of reaction, intercalated graphite is peeled off the few layer graphite of acquisition Alkene；
3) bisphenol A-type E-51 epoxy resin is entered with the weight ratio of 3:1 with polyetheramine D230 resin curing agent Row mixing, obtains mixture；
4) at a temperature of 12-18 DEG C, toward step 3) mixture in add step 2) few layer graphene, Stirring mixing 2-10 hour, described few layer graphene mass percent in total mixture is 1-5%；
5) by step 4) mixture solidify 2-6 hour under the conditions of 80-120 DEG C, finally naturally cool to Room temperature, can obtain high connductivity type Graphene resin composite materials.
Beneficial effect: the introducing by Graphene of the Graphene resin composite materials involved by this invention, improves The electric conductivity of resin, improves the toughness of resin and anticorrosive, impact resistance the most simultaneously.It addition, compared to Graphene prepared by conventional oxidation-reduction method, it is few that the intercalated graphite alkene utilized in the present invention has defect, conduction Property advantages of higher, can realize the higher electric conductivity of resin composite materials under less filling.
Accompanying drawing explanation
Fig. 1 is electrical conductivity and the Graphene of the Graphene resin composite materials that embodiments of the invention 1-5 is obtained The relation of addition.
Detailed description of the invention
Embodiment 1
The preparation method of the high connductivity type Graphene resin composite materials of the present embodiment, comprises the steps:
1) 1 gram of natural flake graphite and 2 grams of anhydrous ferric chlorides are put into vacuum tube inner sealing, are heated to 360 DEG C, Keep 24 hours, it is thus achieved that iron chloride intercalated graphite.
2) hydrogen peroxide of the iron chloride intercalated graphite prepared Yu 100 milliliters is the most at room temperature reacted 2 Hour, intercalated graphite is peeled off and obtains few layer graphene.
3) bisphenol A-type E-51 epoxy resin is entered with the weight ratio of 3:1 with polyetheramine D230 resin curing agent Row mixing, obtains mixture.
4) at a temperature of 18 DEG C, toward step 3) mixture in add step 2) few layer of graphite obtaining Alkene, stirring mixing 6 hours, described few layer graphene mass percent in total mixture is 1%；
5) by step 4) mixture solidify 2 hours under the conditions of 100 DEG C, finally naturally cool to room temperature, High connductivity type Graphene resin composite materials can be obtained.
Embodiment 2
The preparation method of the high connductivity type Graphene resin composite materials of the present embodiment, comprises the steps:
1) 1 gram of natural flake graphite and 2 grams of anhydrous ferric chlorides are put into vacuum tube inner sealing, are heated to 320 DEG C, Keep 12 hours, it is thus achieved that iron chloride intercalated graphite.
2) hydrogen peroxide of the iron chloride intercalated graphite prepared Yu 100 milliliters is the most at room temperature reacted 4 Hour, intercalated graphite is peeled off and obtains few layer graphene.
3) bisphenol A-type E-51 epoxy resin is entered with the weight ratio of 3:1 with polyetheramine D230 resin curing agent Row mixing, obtains mixture.
4) at a temperature of 12 DEG C, toward step 3) mixture in add step 2) few layer of graphite obtaining Alkene, stirring mixing 2 hours, described few layer graphene mass percent in total mixture is 2%；
5) by step 4) mixture solidify 4 hours under the conditions of 80 DEG C, finally naturally cool to room temperature, High connductivity type Graphene resin composite materials can be obtained.
Embodiment 3
The preparation method of the high connductivity type Graphene resin composite materials of the present embodiment, comprises the steps:
1) 1 gram of natural flake graphite and 2 grams of anhydrous ferric chlorides are put into vacuum tube inner sealing, are heated to 340 DEG C, Keep 48 hours, it is thus achieved that iron chloride intercalated graphite.
2) hydrogen peroxide of the iron chloride intercalated graphite prepared Yu 100 milliliters is the most at room temperature reacted 6 Hour, intercalated graphite is peeled off and obtains few layer graphene.
3) bisphenol A-type E-51 epoxy resin is entered with the weight ratio of 3:1 with polyetheramine D230 resin curing agent Row mixing, obtains mixture.
4) at a temperature of 15 DEG C, toward step 3) mixture in add step 2) few layer of graphite obtaining Alkene, stirring mixing 10 hours, described few layer graphene mass percent in total mixture is 3%；
5) by step 4) mixture solidify 6 hours under the conditions of 120 DEG C, finally naturally cool to room temperature, High connductivity type Graphene resin composite materials can be obtained.
Embodiment 4
The preparation method of the high connductivity type Graphene resin composite materials of the present embodiment, phase basic with embodiment 1 With, difference is, step 4) in, described few layer graphene mass percent in total mixture is 4%.
Embodiment 5
The preparation method of the high connductivity type Graphene resin composite materials of the present embodiment, phase basic with embodiment 1 With, difference is, step 4) in, described few layer graphene mass percent in total mixture is 5%.
Embodiment 6
The electrical conductivity of the Graphene resin composite materials that detection embodiment 1-5 is obtained and Graphene addition Relation.
Fig. 1 is electrical conductivity and the Graphene of the Graphene resin composite materials that embodiments of the invention 1-5 is obtained The relation of addition.It will be seen from figure 1 that when the concentration of Graphene is 1%, the electrical conductivity of composite Reach 2.02*10-5Sm-1, meet the requirement of anti-static material.When the mass fraction of Graphene rises to 5% Time, the electrical conductivity of composite is further increased to 1.96*10-2Sm-1, conducting polymer and electricity can be met The requirement of magnetic shielding material.

Claims (1)

1. the preparation method of high connductivity type Graphene-resin composite materials, it is characterised in that comprise the steps:
1) natural flake graphite and anhydrous ferric chloride are put into vacuum tube inner sealing, be heated to 320-360oC, keeps 12-48 hour, it is thus achieved that iron chloride intercalated graphite；
2) iron chloride intercalated graphite step 1) prepared and appropriate hydrogen peroxide are jointly put in beaker and are at room temperature reacted 2-6 hour, intercalated graphite are peeled off and obtain few layer graphene；
3) bisphenol A-type E-51 epoxy resin is mixed with the weight ratio of 3:1 with polyetheramine D230 resin curing agent, obtain mixture；
4) at 12-18oAt a temperature of C, in the mixture of step 3) add step 2) few layer graphene, stirring mixing 2-10 hour, described few layer graphene mass percent in total mixture is 1-5%；
5) mixture of step 4) is solidified 2-6 hour under the conditions of 80-120 DEG C, finally naturally cool to room temperature, high connductivity type Graphene resin composite materials can be obtained.
CN201610218633.9A 2016-04-08 2016-04-08 Preparation method of high-conductivity graphene-resin composite material Pending CN105820514A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110117376A (en) * 2018-02-06 2019-08-13 中国科学院深圳先进技术研究院 Compound cutan and preparation method thereof
CN110229640A (en) * 2019-06-28 2019-09-13 沈阳航空航天大学 A kind of preparation from sensing composite material adhesive and its from monitoring method
CN110256985A (en) * 2019-06-28 2019-09-20 沈阳航空航天大学 A kind of epoxy group electro-and/or heat conductive adhesive and preparation method thereof
CN110785074A (en) * 2019-11-11 2020-02-11 苏州驭奇材料科技有限公司 Composite wave-absorbing material of wave-absorbing shielding film and wave-absorbing shielding film applied by composite wave-absorbing material
CN112744807A (en) * 2019-10-29 2021-05-04 中国石油化工股份有限公司 Graphite intercalation compound and graphene as well as preparation method and application thereof
CN113260241A (en) * 2021-04-13 2021-08-13 浙江大学 High-temperature-resistant high-conductivity graphene material and preparation method thereof
CN113444310A (en) * 2020-03-27 2021-09-28 中国石油化工股份有限公司 Conductive polyolefin composite material and preparation method thereof

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CN102431999A (en) * 2011-09-22 2012-05-02 中国科学院金属研究所 Method for preparing high-quality graphene
CN103030138A (en) * 2012-12-17 2013-04-10 鸿纳（东莞）新材料科技有限公司 Folding preventing less-layer graphene powder, components of composite material thereof, and application
CN103359714A (en) * 2012-03-31 2013-10-23 海洋王照明科技股份有限公司 Preparation method of graphene

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CN102431999A (en) * 2011-09-22 2012-05-02 中国科学院金属研究所 Method for preparing high-quality graphene
CN103359714A (en) * 2012-03-31 2013-10-23 海洋王照明科技股份有限公司 Preparation method of graphene
CN103030138A (en) * 2012-12-17 2013-04-10 鸿纳（东莞）新材料科技有限公司 Folding preventing less-layer graphene powder, components of composite material thereof, and application

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110117376A (en) * 2018-02-06 2019-08-13 中国科学院深圳先进技术研究院 Compound cutan and preparation method thereof
CN110229640A (en) * 2019-06-28 2019-09-13 沈阳航空航天大学 A kind of preparation from sensing composite material adhesive and its from monitoring method
CN110256985A (en) * 2019-06-28 2019-09-20 沈阳航空航天大学 A kind of epoxy group electro-and/or heat conductive adhesive and preparation method thereof
CN110229640B (en) * 2019-06-28 2021-07-23 沈阳航空航天大学 Preparation and self-monitoring method of self-sensing composite material adhesive
CN112744807A (en) * 2019-10-29 2021-05-04 中国石油化工股份有限公司 Graphite intercalation compound and graphene as well as preparation method and application thereof
CN110785074A (en) * 2019-11-11 2020-02-11 苏州驭奇材料科技有限公司 Composite wave-absorbing material of wave-absorbing shielding film and wave-absorbing shielding film applied by composite wave-absorbing material
CN113444310A (en) * 2020-03-27 2021-09-28 中国石油化工股份有限公司 Conductive polyolefin composite material and preparation method thereof
CN113260241A (en) * 2021-04-13 2021-08-13 浙江大学 High-temperature-resistant high-conductivity graphene material and preparation method thereof

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