CN112538665A - Preparation method of graphene composite material - Google Patents

Preparation method of graphene composite material Download PDF

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Publication number
CN112538665A
CN112538665A CN201910892549.9A CN201910892549A CN112538665A CN 112538665 A CN112538665 A CN 112538665A CN 201910892549 A CN201910892549 A CN 201910892549A CN 112538665 A CN112538665 A CN 112538665A
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CN
China
Prior art keywords
graphene
molecular weight
composite material
ultra
high molecular
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CN201910892549.9A
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Chinese (zh)
Inventor
吴小莲
孔凡敏
苏豪
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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Priority to CN201910892549.9A priority Critical patent/CN112538665A/en
Publication of CN112538665A publication Critical patent/CN112538665A/en
Pending legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a preparation method of a graphene composite material, and belongs to the field of high polymer materials. The graphene-based composite material is mainly prepared from graphene, ultra-high molecular weight polyethylene, a plasticizer, a dispersing agent, a surfactant, a solvent and the like. The strength of the ultra-high molecular weight polyethylene fiber is increased, and the ultra-high molecular weight polyethylene fiber has excellent ultraviolet resistance, cutting resistance, bulletproof function and the like; the modified graphene can be well dispersed in a solvent, so that a composite material with excellent performance is obtained, and the heat resistance and impact resistance of the ultra-high molecular weight polyethylene fiber are improved, thereby widening the application range of the ultra-high molecular weight polyethylene fiber.

Description

Preparation method of graphene composite material
Technical Field
The invention relates to a preparation method of a composite material, in particular to a preparation method of a graphene composite material, and belongs to the field of high polymer materials.
Background
In 2004, enteny physicists anderley-gommy and comstein-norworth-schloff successfully prepared graphene sheets consisting of only one layer of carbon atoms by peeling graphite sheets from graphite by a special method. The breakthrough result not only proves that the graphene can exist independently, but also breaks the 'theorem' that the graphene cannot be manufactured.
Graphene has many excellent performances which are not possessed by common materials, the theoretical thickness of the graphene is 0.34 nanometer, which is only 20 ten-thousandth of hair, and is the thinnest material in the world at present, and 1 millimeter of graphite sheet can naturally strip up to 150 ten thousand pieces of graphene; it is the most portable material in the world at present, and 1 g of graphene can cover a football field; the strength of the cup is 200 times that of steel and several times that of diamond, and if a piece of graphene with the thickness as that of a food preservative film is covered on a cup, a pencil needs to be pressed on the cup by the weight of an elephant when the user wants to puncture the cup.
In graphene, the carbon atoms are arranged like a thin wire fence, and this structure also makes it very flexible, not breaking even when bent at large angles, and therefore it is the most flexible material. Graphene is a material with the highest known strength in the world at present, can be used for research and development applications of ultra-light aircrafts, infrared guide heads, laser weapons, photoelectric detection equipment, ultra-light bulletproof clothes and the like, and has wide application prospects in the aspects of military aerospace, military energy, military engines, seawater desalination, armor protection, extremely-high frequency satellite communication systems and the like.
The ultra-high molecular weight polyethylene is thermoplastic engineering plastic with excellent comprehensive performance, and plays a very important role in the fields of modern war, aviation, aerospace, sea defense equipment and the like. The ultra-high molecular weight polyethylene has the advantages of flame retardancy, chemical corrosion resistance, wear resistance, excellent electrical insulation, higher mechanical strength and the like, is widely applied to various fields, and is engineering plastic with the largest yield in the world.
Disclosure of Invention
The invention aims to provide a preparation method of a novel material, and the material is used in various fields such as protective articles, labor tools and the like.
The main technical scheme of the invention is as follows: the preparation method of the graphene composite material is characterized by comprising the following steps:
(1) dispersing ultra-high molecular weight polyethylene in a solvent to form an ultra-high molecular weight polyethylene dispersion;
(2) adding the graphene dispersion liquid into the ultra-high molecular weight polyethylene dispersion liquid, stirring and heating to obtain a spinning solution;
(3) and spinning and drafting the spinning solution to obtain the graphene composite material.
Further, the preparation method comprises the following steps:
(1) dispersing ultra-high molecular weight polyethylene in a solvent to form a uniform ultra-high molecular weight polyethylene dispersion liquid;
(2) adding graphene powder into a dispersing agent, heating, adding an emulsifying agent, and emulsifying to obtain a graphene dispersion liquid;
(3) adding the graphene dispersion liquid into the ultra-high molecular weight polyethylene dispersion liquid, stirring, heating and swelling to obtain a spinning solution;
(4) and spinning, precursor standing and hot drawing are carried out on the spinning solution to obtain the graphene composite material.
Preferably, the viscosity average molecular weight of the ultra-high molecular weight polyethylene is 500-600 ten thousand.
The concentration of the ultra-high molecular weight polyethylene is 6-8% (wt).
The concentration of the graphene is 0.12-0.4 per mill (wt).
The concentration of the dispersing agent is 0.06-0.32 per mill (wt).
The dispersant is selected from aniline trimer, aniline tetramer, aniline pentamer and aniline hexamer.
And a plasticizer is added in the preparation, and is selected from calcium stearate, magnesium stearate and aluminum stearate, and the concentration of the plasticizer is 3-6 per mill (wt).
The preparation method comprises the step of adding a surfactant selected from SDS, SDBS, SLS, CTAB, PVP and twwen80, wherein the concentration of the surfactant is 4-6 per mill (wt).
The solvent is decahydronaphthalene.
The graphene is graphene powder with a multilayer structure, the sheet diameter is 2-5 um, and the specific surface area is 600-800 m2/g。
The invention has the following remarkable characteristics: the graphene and the ultra-high molecular weight polyethylene are compounded by utilizing the respective excellent characteristics of the graphene and the ultra-high molecular weight polyethylene, so that a composite material with excellent performance is obtained, the strength of the ultra-high molecular weight polyethylene fiber is increased, and the functions of excellent cutting prevention, excellent bullet prevention and the like are achieved; the impact resistance of the ultra-high molecular weight polyethylene fiber is improved, and the composite material can be applied to military fields such as body armor, bulletproof helmets, parachutes and the like.
Detailed Description
The present invention will be described in detail with reference to examples.
The preparation method of the graphene composite material in the following embodiment includes the following steps: dispersing ultra-high molecular weight polyethylene in a solvent to form a uniform ultra-high molecular weight polyethylene dispersion liquid; adding graphene powder into a dispersing agent, heating to a certain temperature, adding an emulsifying agent, and performing emulsification treatment to obtain a graphene dispersion liquid; adding the graphene dispersion liquid into the ultra-high molecular weight polyethylene dispersion liquid, stirring, heating and swelling to obtain a spinning solution; and spinning, precursor standing and hot drawing are carried out on the spinning solution to obtain the graphene composite material.
The spinning conditions in the examples were: the swelling temperature is 97 ℃, the swelling time is 3h, the twin-screw inlet temperature is 85 ℃, the twin-screw mixing and dissolving temperature is 115 ℃/155 ℃/165 ℃/165 ℃/165 ℃/165 ℃, the melt temperature is 153 ℃, the ring cooling sleeve temperature is 208 ℃, the side blowing temperature is 120 ℃, and the side blowing air volume is 605N3H, the temperature of the channel air is 84 ℃, and the air volume of the channel air is 52N3The pre-spinning draft condition is 19.6-20.6-20.6-25.9, and the test data are shown in the table 1.
Comparison No. 1#
6 percent (wt) of ultra-high molecular weight polyethylene, 3.5 per mill (wt) of calcium stearate, 0.06 per mill (wt) of aniline trimer, 4.5 per mill (wt) of SDS and the balance of decahydronaphthalene.
Implementation No. 1#
The molecular weight is 500 ten thousand ultra-high molecular weight polyethylene 6% (wt), the sheet diameter is 2um, the specific surface area is 650m20.12 per mill (wt) of multilayer graphene, 3.5 per mill (wt) of calcium stearate, 0.06 per mill (wt) of aniline trimer, 4.5 per mill (wt) of SDS and the balance of decahydronaphthalene.
Implementation No. 2#
The molecular weight is 500 ten thousand ultra-high molecular weight polyethylene 6% (wt), the sheet diameter is 3.5um, the specific surface area is 650m2Multilayer graphene/g0.15 per mill (wt), 3.5 per mill (wt) of calcium stearate, 0.06 per mill (wt) of aniline trimer, 4.5 per mill (wt) of SDS and the balance of decahydronaphthalene.
Implementation No. 3#
The molecular weight is 550 ten thousand ultra-high molecular weight polyethylene 6% (wt), the sheet diameter is 4.5um, the specific surface area is 6000m20.18 per mill (wt) of multilayer graphene, 3.5 per mill (wt) of calcium stearate, 0.06 per mill (wt) of aniline trimer, 4.5 per mill (wt) of SDS and the balance of decahydronaphthalene.
Comparative example No. 2#
8 percent (wt) of ultrahigh molecular weight polyethylene with the molecular weight of 580 ten thousand, 3.5 per thousand (wt) of aluminum stearate, 0.10 per thousand (wt) of aniline tetramer, 4.5 per thousand (wt) of CTAB and the balance of decalin.
Implementation No. 4#
The molecular weight is 600 ten thousand ultrahigh molecular weight polyethylene 8% (wt), the sheet diameter is 2um, the specific surface area is 742m20.16 per mill (wt) of multilayer graphene, 3.5 per mill (wt) of aluminum stearate, 0.10 per mill (wt) of aniline tetramer, 4.5 per mill (wt) of CTAB and the balance of decahydronaphthalene.
Implementation 5#
The molecular weight is 550 ten thousand ultra-high molecular weight polyethylene 6% (wt), the sheet diameter is 3.3um, the specific surface area is 783m20.20 per mill (wt) of multilayer graphene, 3.5 per mill (wt) of aluminum stearate, 0.10 per mill (wt) of aniline tetramer, 4.5 per mill (wt) of CTAB and the balance of decahydronaphthalene.
Implementation 6#
The molecular weight is 600 ten thousand ultra-high molecular weight polyethylene 6% (wt), the sheet diameter is 5um, the specific surface area is 621m20.24 per thousand per gram (wt) of multilayer graphene, 3.5 per thousand per gram (wt) of aluminum stearate, 0.10 per thousand of aniline tetramer, 4.5 per thousand per gram (wt), and the balance of decahydronaphthalene.
TABLE 1 mechanical Properties of finished fibers
Breaking strength CN/dtex Elongation at Break (%) Modulus CN/dtex
Comparison No. 1# 20.31 2.07 1011.5
Implementation No. 1# 28.95 2.19 998.4
Implementation No. 2# 31.34 1.94 1253.2
Implementation No. 3# 26.79 2.05 1073.3
Comparison No. 2# 22.91 2.18 1054.4
Implementation No. 4# 28.36 2.05 1093.8
Implementation 5# 29.28 2.06 1143.8
Implementation 6# 29.71 1.92 1198.8
The result shows that the fineness and the modulus are not greatly changed after the graphite is added, the breaking strength is obviously improved, the elongation at break is reduced, the strength of the ultra-high molecular weight polyethylene fiber is increased, and the fiber has excellent functions of preventing cutting, resisting bullets and the like.

Claims (10)

1. A preparation method of a graphene composite material is characterized by comprising the following steps:
(1) dispersing ultra-high molecular weight polyethylene in a solvent to form an ultra-high molecular weight polyethylene dispersion;
(2) adding the graphene dispersion liquid into the ultra-high molecular weight polyethylene dispersion liquid, stirring and heating to obtain a spinning solution;
(3) and spinning and drafting the spinning solution to obtain the graphene composite material.
2. The method for preparing the graphene composite material according to claim 1, characterized by comprising the steps of:
(1) dispersing ultra-high molecular weight polyethylene in a solvent to form a uniform ultra-high molecular weight polyethylene dispersion liquid;
(2) adding graphene powder into a dispersing agent, heating, adding an emulsifying agent, and emulsifying to obtain a graphene dispersion liquid;
(3) adding the graphene dispersion liquid into the ultra-high molecular weight polyethylene dispersion liquid, stirring, heating and swelling to obtain a spinning solution;
(4) and spinning, precursor standing and hot drawing are carried out on the spinning solution to obtain the graphene composite material.
3. The method for preparing the graphene composite material according to claim 1 or 2, wherein the viscosity average molecular weight of the ultra-high molecular weight polyethylene is 500 to 600 ten thousand, and the concentration of the ultra-high molecular weight polyethylene is 6 to 8% (wt).
4. The method for preparing the graphene composite material according to claim 1 or 2, wherein the concentration of the graphene is 0.12-0.4 ‰ (wt).
5. The method for preparing the graphene composite material according to claim 1 or 2, wherein the concentration of the dispersant is 0.06-0.32 ‰ (wt).
6. The method for preparing the graphene composite material according to claim 1 or 2, wherein the dispersant is selected from aniline trimer, aniline tetramer, aniline pentamer, and aniline hexamer.
7. The preparation method of the graphene composite material according to claim 1 or 2, wherein a plasticizer is added during preparation, wherein the plasticizer is selected from calcium stearate, magnesium stearate and aluminum stearate, and the concentration of the plasticizer is 3-6 per mill (wt).
8. The method for preparing the graphene composite material according to claim 1 or 2, wherein a surfactant is added in the preparation, the surfactant is selected from SDS, SDBS, SLS, CTAB, PVP and twwen80, and the concentration of the surfactant is 4-6 per mill (wt).
9. The method for preparing the graphene composite material according to claim 1 or 2, wherein the solvent is decalin.
10. Method for preparing graphene composite material according to claim 1 or 2The preparation method is characterized in that the graphene is multilayer graphene powder, the sheet diameter is 2-5 um, and the specific surface area is 600-800 m2/g。
CN201910892549.9A 2019-09-20 2019-09-20 Preparation method of graphene composite material Pending CN112538665A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114150393A (en) * 2021-12-09 2022-03-08 南通强生光电科技有限公司 High-strength wear-resistant composite fiber for wires and cables and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105642184A (en) * 2014-12-02 2016-06-08 中国科学院宁波材料技术与工程研究所 Graphene dispersant and applications thereof
CN106222780A (en) * 2016-06-23 2016-12-14 常州第六元素材料科技股份有限公司 A kind of Graphene/UHMWPE composite fibre and its preparation method and application
CN106243741A (en) * 2016-08-23 2016-12-21 深圳市志海实业股份有限公司 A kind of preparation method of High-performance graphite oxide alkene modified calcium zinc stabilizer
CN108315833A (en) * 2018-01-15 2018-07-24 南通强生安全防护科技股份有限公司 The preparation method of graphene ultra-high molecular weight polyethylene composite fibre

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105642184A (en) * 2014-12-02 2016-06-08 中国科学院宁波材料技术与工程研究所 Graphene dispersant and applications thereof
CN106222780A (en) * 2016-06-23 2016-12-14 常州第六元素材料科技股份有限公司 A kind of Graphene/UHMWPE composite fibre and its preparation method and application
CN106243741A (en) * 2016-08-23 2016-12-21 深圳市志海实业股份有限公司 A kind of preparation method of High-performance graphite oxide alkene modified calcium zinc stabilizer
CN108315833A (en) * 2018-01-15 2018-07-24 南通强生安全防护科技股份有限公司 The preparation method of graphene ultra-high molecular weight polyethylene composite fibre

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114150393A (en) * 2021-12-09 2022-03-08 南通强生光电科技有限公司 High-strength wear-resistant composite fiber for wires and cables and preparation method thereof

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Application publication date: 20210323